Note: Descriptions are shown in the official language in which they were submitted.
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1
IMPROVED PROCESSES FOR MAKING SURFACTANTS VIA ADSORPTIVE
SEPARATION AND PRODUCTS THEREOF
1o FIELD OF THE INVENTION
The present invention is in the field of processes for making surfactants
useful in
cleaning products. Preferred processes comprise particular combinations of
adsorptive
separation steps to separate certain hydrocarbons using specific means.
Preferably these
means include combinations of two or more particular adsorbent beds and two or
more of
particular types of rotary valves, as well as specified types of porous
adsorbents having
pore sizes in excess of those used in conventional linear alkylbenzene
manufacture.
Preferred processes further employ particular alkylation steps having
specified internal
isomer selectivities, or particular OXO reaction steps. The invention is also
in the field of
products of such processes, including certain modified alkylbenzenes, of
modified
2o alkylbenzenesulfonate surfactants, of detergent alcohols and surfactants
derivable
therefrom, and of consumer cleaning products, especially laundry detergents,
containing
them. Preferred processes herein employ unconventional sequences of adsorptive
separation steps to secure certain branched hydrocarbon fractions which are
then used in
additional process steps as alkylating agents for arenes or for other useful
surfactant-
making purposes, such as OXO reactions to form particular detergent alcohols,
followed
by alkoxylation, sulfation or the like. Surprisingly, such fractions can even
be derived from
effluents from current linear alkylbenzene manufacture.
BACKGROUND OF THE INVENTION
Historically, highly branched alkylbenzenesulfonate surfactants, such as those
based
on tetrapropylene (known as "ABS" or "TPBS") were used in detergents. However,
these
were found to be very poorly biodegradable. A long period followed of
improving
manufacturing processes for alkylbenzenesulfonates, making them as linear as
practically
possible ("LAS"). The overwhelming part of a large art of linear
alkylbenzenesulfonate
surfactant manufacture is directed to this objective. Large-scale commercial
alkylbenzenesulfonate processes in use in the U.S. today are directed to
linear
alkylbenzenesulfonates. However, linear alkylbenzenesulfonates are not without
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limitations; for example, they would be more desirable if improved for hard
water cleaning
properties.
In the petroleum industry, various processes have recently been developed, for
example for producing low viscosity tube oil or high-octane gasoline, which
the inventors
s have now found provide useful new insight on how to delinearize hydrocarbons
to a
limited and controlled extent. Such deliberate delinearization, however, is
not a feature of
any current commercial processes in the different field of
alkylbenzenesulfonate surfactant'
manufacture for consumer products. This is not surprising, in view of the
overwhelming
volume of LAS surfactant art teaching toward making linear compounds and away
from
delinearization.
The majority of commercial processes for making alkylbenzenes rely on HF or
aluminum chloride catalyzed alkylation of benzene. Quite recently, it has been
discovered
that certain zeolite catalysts can be used for alkylation of benzene with
olefins. Such a
process step has been described in the context of otherwise conventional
processes for
manufacture of linear alkylbenzenesulfonates. For example, the DETAL~ process
of UOP
uses a zeolite alkylation catalyst. The DETAL~ process and all other current
commercial
processes for alkylbenzenesulfonate manufacture are believed to fail to meet
the internal
isomer selectivity reduirements of the preferred inventive process and
alkyiation catalyst
defined hereinafter. Moreover, the DETAL~ process catalyst or catalysts are
believed to
lack the moderate acidity and intermediate pore size of alkylation catalysts
used in the
preferred processes of the present invention. Other recent literature
describes the use of
mordenite as an alkylation catalyst, but no such disclosure makes the
combination of
specific process steps reduired by the instant invention. Moreover, in view of
the linearity
desired in alkylbenzenesulfonate products of conventionally known processes,
they also
generally include steps directed to the provision or making of a substantially
linear
hydrocarbon, not a delinearized one, prior to the alkylation. Possible
exceptions are in US
5,026,933 and US 4,990,718. These and other known processes have numerous
shortcomings from the standpoint of the detergent industry in terms of cost,
catalyst
limitations in the propylene oiigomerization or olefin dimerization stage,
presence of large
3o volumes of distillation fractions that would need to be discarded or find
non-detergent
customers, and limited range of product compositions, including mixtures of
chainlengths
attainable. Such developments by the petroleum industry are, in short, not
optimal from
the standpoint of the expert formulator of detergent products.
It is also known in the art how to make linear alkylbenzenes using particular
adsorptive separation processes. See US 2,985,589. Such processes as described
hitherto
however do not provide branched alkylbenzenesulfonates.
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It is also known in the art to prepare long-chained methyl paraffins for use
as
industrial solvents by processes which include urea clathration and separation
on
"molecular sieves". See Chemical Abstracts, 83:100693 and JP 49046124 B4. This
process assertedly involves double urea adduction, for example treating a
petroleum
fraction once with urea to remove n-alkanes as complexes, and then a second
time with
excess urea to obtain adducts of mixed n-alkanes and long-chained monomethyl
para~ns.
While this process may have some limited usefulness and may be included in the
overall
processes of the invention as most broadly defined, its limitations are
considerable. This
process, despite dating from 1974, is not known to have been incorporated into
any overall
to process for making surfactants such as the modified alkylbenzenesulfonates
described
herein.
As further described in the Background Art section hereinafter, it is also
known
how to make various OXO alcohols and to make surfactants therefrom. However,
the
currently available OXO alcohols have shortcomings, such as in producing
surfactants
which are less soluble at a given chainlength than might be desired for the
increasingly
popular low wash temperatures or in relying on relatively expensive processes
such as
olefin oligomerization, isomerization and disproportionation; or in still
having a relatively
high content of linear material.
BACKGROUND ART
2o WO 97/39090, WO 97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO
97/38972, WO 97/39089, US 2,985,589; Chemical Abstracts, 83:100693; JP
49046124
B4 12/07/74; EP 803,561 AZ 10/29/97, EP 559,510 A 9/8/93; EP 559,510 B1
1/24/96;
US 5,026,933; US 4,990,718; US 4,301,316; US 4,301,317; US 4,855,527; US
4,870,038; US 2,477,382; EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR
2,697,246,
4/29/94; SU 793,972, 1/7/81; US 2,564,072; US 3,196,174; US 3,238,249; US
3,355,484;
US 3,442,964; US 3,492,364; US 4,959,491; WO 88/07030, 9/25/90; US 4,962,256,
US
5,196,624; US 5,196,625; EP 364,012 B, 2/15/90; US 3,312,745; US 3,341,614; US
3,442,965; US 3,674,885; US 4,447,664; US 4,533,651; US 4,587,374; US
4,996,386;
US 5,210,060; US 5,510,306; WO 95/17961, 7/6/95; WO 95/18084; US 5,510,306; US
5,087,788; US 4,301,316; US 4,301,317; US 4,855,527; US 4,870,038; US
5,026,933;
US 5,625,105 and US 4,973,788 are useful by way of background to the
invention. Cited
documents EP 559,510 A and B in particular relate to making high-octane
gasolines by
recycling streams to an isomerization reactor. Grafted porous materials of EP
559,510
and grafting of zeolites, e.g., by tin alkyls, are useful in the present
invention. US
5,107,052 likewise relates to improving octane ratings of gasoline and
describes separating
C4-C6 methyl paraflins using various molecular sieves such as A1P04-5, SSZ-24,
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MgAPO-5 and/or MAPSO-5 containing less than 2% water. These sieves are
assertedly
capable of selectively adsorbing dimethyl paraffins and not adsorbing
monomethyl and
normal paraffins.
The manufacture of alkylbenzenesulfonate surfactants has recently been
reviewed.
See Vol. 56 in "Surfactant Science" series, Marcel Dekker, New York, 1996,
including in
particular Chapter 2 entitled "Alkylarylsulfonates: History, Manufacture,
Analysis and
Environmental Properties", pages 39-108 which includes 297 literature
references. This
work provides access to a great deal of literature describing various
processes and process
steps such as dehydrogenation, alkylation, alkylbenzene distillation and the
like. See also
to "Detergent Alkylate" in Encyclopedia of Chemical Processing and Design,
Eds. Mc.Ketta
and Cunningham, Marcel Dekker, N.Y., 1982.; especially pages 266-284.
Adsorption
processes such as UOP's Sorbex process and other associated processes are also
described
in Kirk Othmer's Encyclopedia of Chemical Technology, 4'". Edition, Vol. 1,
see
"Adsorption and Liquid Separation", including pages 583-598 and references
cited therein.
See also publications by UOP Corp., including the "Processing Guide" available
from UOP
Corp., Des Plaines, Illinois. Commercial paraffin isolation and separation
processes using
molecular sieves include MOLEX~ (UOP Inc.), a liduid-phase process, and
ISOSIV~
(Union Carbide Corp.) as well as ENSORB~ (Exxon Corp.) and TSF~ or Texaco
Selective Finishing process, which are vapor-phase processes. All these
processes are
' 2o believed to use 5 Angstrom molecular sieves as porous media. Where not
noted herein,
the operating temperatures, pressures and other operating conditions and
apparatus for any
process step are conventional, that is, as already well known and defined in
the context of
manufacturing linear alkylbenzenesulfonate surfactants. Documents referenced
herein are
incorporated in their entirety.
US 3,732,325 issued May 8, 1973 describes a process for sorptive separation of
aromatic hydrocarbons.
US 3,455,815 issued July 15, 1969, US 3,291,726 issued December 13, 1966, US
3,201,491 issued August 17, 1965 and US 2,985,589 issued May 23, 1961 describe
simulated moving bed sorptive separation processes for hydrocarbons.
3o US 5,780,694 issued July 14, 1998 and WO 98/23566 published June 4, 1998
incorporated herein by reference relate to certain branched detergent alcohols
and to
surfactants derivable therefrom. These documents include a description of the
well-known
OXO process and of catalysts suitable for hydroformylation. See especially
'694 columns
10 and 11.
US 5,510,564 issued April 23, 1996 incorporated herein by reference describes
processes for purifying hydrocarbons, especially in the context of aromatics
removal.
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US 5,276,231 issued Jan 04, 1994 describes aromatics removal from hydrocarbons
by means of sulfolane extraction.
US 4,184,943 issued Jan 22, 1980 describes sorptive hydrocarbon separations.
US 4,006,197 issued Feb O1, 1977 describes sorptive hydrocarbon separations of
5 n-paraffins.
US 5,220,099 issued June 15,1993 and US 5,171,923 issued December 15, 1992
describe purifying parai~ns by removal of aromatics, sulfur, nitrogen and
oxygen
containing compounds, and color bodies by magnesium Y or Na-X zeolite
sorption.
Surfactant Science Series, Volume 7, "Anionic Surfactants", Part 1, MarceI
to Dekker, N.Y., Ed. W. Linfield, 1976, Chapter 2 "Petroleum-Based Raw
Materials for
Anionic Surfactants", pages 11-86 provides general background including for
the OXO
process (see pp. 71 and following) and for certain feedstocks (see p 60 and
following). To
be noted, this reference under the heading "branched-chain olefins" at page 65
and
following does not describe branched-chain olefins suitable for use in the
instant process
the identified "branched-chain" olefins being unsuitable biologically "hard"
types. The
OXO process discussion at pp. 72 and following shows conversion of linear
olefin to
mixtures of "branched" and linear aldehydes and/or alcohols. Again, this usage
of the term
"branched" differs from the present invention - processes herein all involve
use of at least
partially mid-chain methyl-branched feedstocks as the principal source of
branching, the
2o OXO reactions herein providing specific methyl-branched primary alcohols
wherein only
secondary aspects of any branching are due to OXO reaction.
Separately, the reference immediately supra and references cited therein also
describe the UOP OLEX ~ process and sorbents useful therein, see for example
pages 60-
63 making reference to Cu- or Ag-doped zeolites. See more particularly US
3,969,276
issued July I3, 1976 for X- or Y- type zeolites doped with silver. See also
D.B.
Broughton and R.C. Berg, Hydrocarbon Process, Vo(. 48(6), 115 (1969); D.B.
Broughton
and R.C. Berg, National Petroleum Refiners Association, 1969 Annual Meeting,
March
23, 1969, technical paper AM-69-38; D.B. Broughton and R.C. Berg, Chemical
Engineering, January 26, 1970, page 86, article entitled "Two processes team
up to make
linear monoolefins".
Kirk Othmer's Encyclopedia of Chemical Technology, 4~'. Edition, Vol. 1, pages
893-913 ( 1991 ), article entitled "Alcohols, Higher Aliphatic", sub-heading
"Synthetic
Processes" describes an OXO reaction to form detergent alcohols, see
especially
"Modified Cobalt Catalyst, One-Step, Low Pressure Process", at pages 904-906.
Note
once again that the diagrams showing methyl-branched alcohols, see for example
page
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904, are exclusively made from linear precursors and the OXO-branching is in
the 2-
position (as in the above-identified reference).
See also Surfactant Science Series, Volume 56, "Anionic Surfactants", Marcel
Dekker, N.Y., Ed. W. Linfield, 1996, Chapter 1 "Raw Materials for Anionic
Surfactant
Synthesis", pages 1-142 incorporated by reference, for additional description
of feedstocks
common in detergent manufacture, for description of known processes for
sorptive and
other separations, for descriptions of detergent alkylation, and for
description of OXO or
hydroformylation process steps (see for example pp. 23-25).
OXO process literature includes also "New Syntheses with Carbon Monoxide",
to Ed. J. Falbe, Springer-Verlag, New York, 1980.
Commercial practice for making detergent alcohols which differ from those
accessible herein is currently understood to include the seduence: isolation
of linear
parai~ns from kerosene by sorptive separation, dehydrogenation by the PACOL ~
process
(or similar) to linear internal olefins, isolation of the olefin from paraffin
by the OLEX
process (or similar), and OXO reaction in one of two ways, either by a
conventional OXO
catalyst to give a 2-alkyl substituted primary alcohol, e.g., as in ENI's LIAL
~ alcohols, or
by isomerization of the olefin to the terminal position followed by terminal
OXO addition,
as practiced by the ShelUMitsubishi process.
See also W097/01521 A1 published January 16, 1997 and 95 ZA - 0005405
2o published June 25, 1995. See also various technical bulletins and
publications of Sasol
andlor Sastech of South Africa, especially in relation to already known or
available OXO
alcohols made or makable by the OXO processes proprietary to these companies.
BRIEF DESCRIPTION OF THE DRAWINGS
Figs. 1 - 18 are schematic drawings of some processes in accordance with the
invention. Fig. 8 shows in more detail a configuration of two adsorptive
separation units,
each individually being of a type as found in the first two adsorptive
separation steps of
Fig. 1 and Fig. 2. Note that the Fig. 8 interconnections are as shown in Fig.
1., but differ
from those shown in Fig. 2.
Solid lines are used for essential process steps and process streams. Dashed
lines
3o identify steps and streams which may not be essential in the processes as
most broadly
defined but which are present in various preferred process embodiments.
Rounded
rectangles identify process steps, stages or units. Numbered lines identify
feedstocks,
intermediate process streams and products. "SOR" identifies an adsorptive
separation
step. "4/S" identifies that the adsorptive separation uses small-pore zeolite,
especially Ca
zeolite SA, which is completely conventional in linear alkylbenzene
manufacture. "5/7"
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identifies that the adsorptive separation uses a porous material such as SAPO-
11 or any
equivalent porous material having the ability to adsorb
~ monomethyl branched para~ns and/or
~ monomethyl branched monoolefins and/or
~ nongeminal dimethyl paraffns and/or
~ nongeminal dimethyl olefins
white rejecting geminal dimethyl hydrocarbons, cyclic (five-, six- or higher
membered ring) hydrocarbons or higher branched hydrocarbons, whether aromatic
or
aliphatic. The term "geminal dimethyl" as used herein means that there are two
methyls
1o attached to an internal carbon atom of a hydrocarbon, as in:
Only sorptive stage SOR 4/5 and/or sorptive stage SOR 5/7 herein are of the
type used in
stage (a) of modified alkylbenzene manufacture or stage (A) of modified
primary OXO
alcohol manufacture as described hereinafter.
The large-pore porous materials herein should not adsorb such hydrocarbons. In
contrast,
the following hydrocarbons should be adsorbed. They are illustrative of what
is meant by
the term "nongeminal dimethyl" hydrocarbons:
v v v v v v
Note that any methyl moieties at the ends of the main chain are not counted in
defining the
term "nongeminal dimethyl" as used herein. Further, consistent with this
convention, the
following hydrocarbon should be adsorbed by the large-pore porous material. It
is a
"monomethyl" hydrocarbon:
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Large-pore porous materials suitable for use herein are more fially and more
generally described in the specification hereinafter. "DEH" identifies a step
of at least
partial dehydrogenation of a stream (partial dehydrogenation being typical in
conventional
s linear alkylbenzene manufacture though complete dehydrogenation can also be
used
herein), and "ALK" identifies an alkylation step. Any step, stage or unit
identified by a
rounded rectangle can in practice comprise only the essential step or can,
more typically;
include within it an additional step or steps which may be optional in the
invention as most
broadly defined, or which may be essential only in a preferred embodiment.
Such
to additional steps not shown include, for example, distillation steps of
types commonly
practiced in the art.
In Figs. 9 - 18, "DIST" where present identifies a distillation step, "SOR O /
P"
where present identifies a sorptive olefin / paraffin separation step, for
example OLEX
process of UOP as used in stage (C) of modified primary OXO alcohol
manufacture
15 described in detail hereinafter and "OXO" where present identifies a
hydroformylation
process step. Such process steps are well-known in the art: see the
"Background Art"
section.
With the aforementioned conventions in mind, it will be seen that Fig. 1
illustrates a
process having, in sequence, two adsorptive separations, collectively in
accordance with
2o adsorptive separation stage (a) of the invention as defined hereinafter;
followed by a
dehydrogenation step (step (b) hereinafter); optionally followed by an
alkylation step (step
(c) hereinafter). While step (c) is optional in the invention as most broadly
defined, it is
present in all preferred embodiments which relate to making modified
alkylbenzenes in
accordance with the invention and, when making modified alkylbenzenesulfonate
25 surfactants, is typically followed by (d) sulfonation, (e) neutralization
and (f) mixing to
formulate into a consumer cleaning product. Steps (d) though (f) use
conventional means
and are not explicitly shown in Figs. 1-8.
In the Fig. 1 process, a hydrocarbon feed 1 passes to the first adsorptive
separation
step, for example a step in conformity with US 2,985,589, which uses a bed of
4-5
3o Angstrom zeolite. A linear hydrocarbon stream is discarded as a reject
stream 6. For
comparison, in conventional linear alkylbenzene manufacture, stream 6,
comprising a high
proportion of linear hydrocarbons, would pass to DEH while step SOR S/7 and
associated
streams would be absent. In the present process according to Fig. 1, an
intermediate
branched-enriched hydrocarbon stream is retained 2 and passes to a second
adsorptive
35 separation. The second adsorptive separation uses a particular type of
porous media and
produces a branched-enriched stream 3 (product of stage (a) as defined
hereinafter) which
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passes to the dehydrogenation reactor (DEH); as well as a reject stream 7. The
particular
type of porous media is preferably a "large-pore" zeolite, such zeolite herein
being
characterized by a pore size larger than that of the zeolites used in making
linear
alkylbenzenes, and very preferably, a pore size of from above about 5 Angstrom
to about 7
Angstrom though larger pore materials can be used and their pore sizes can be
"tuned
down", for example by use of tin alkyls. Stream 4 represents dehydrogenated
branched
enriched hydrocarbon; stream 8 represents recycled branched paraffns. Also
shown is an
alkylation step according to the invention which is included in a preferred
embodiment of
the invention. Output from the alkylation step is a modified alkylbenzene as
defined
to elsewhere herein.
Fig. 2 is a schematic drawing identifying steps in another embodiment of the
present process. While generally similar to the process of Fig. l, the Fig. 2
process has
important differences, especially in that the adsorptive separation steps are
reversed with
respect to pore sizes in the adsorbent beds.
Fig. 4 is a schematic drawing identifying an embodiment of the invention which
starts with a hydrocarbon feedstock 23 such as branched effluent from a
conventional
linear alkylbenzene manufacturing process, or from a conventional linear
detergent alcohol
process. An adsorptive separation step using particular porous media is used
to produce a
reject stream 27 and a branched-enriched stream 24. The latter is
dehydrogenated in the
2o step marked DEH. The particular type of porous media is preferably a
zeolite having pore
size larger than that of the zeolites used in making linear alkylbenzenes, and
very
preferably has pore size of from above about 5 Angstrom to about 7 Angstrom.
The
dehydrogenated hydrocarbon stream 25 passes to an alkylation step ALK from
which
passes a modified alkylbenzene product 26. An optional recycle stream is
identified as 28.
Fig. 3 is a schematic drawing identifying an embodiment of the invention
similar to
that of Fig. 4 but using substantially different feedstock and intermediate
process stream
compositions. For example, Fig. 3 can utilize as feed 17 a C 10-C 14 paraffin
fraction
having the intrinsic linear/branched paraffin ratio as received, and from
which cyclics,
aromatics, gem-dimethyl, ethyl- or higher-than-ethyl branched hydrocarbons are
removed
3o as part of the present process.
When comparing Fig. 3 and Fig. 4 it may appear in view of the apparently
identical
configuration of steps that the processes illustrated therein are identical.
This is not the case in view of the very different results achieved in
consequence of
changing the hydrocarbon feed. Fig. 4 uses as hydrocarbon feed 23 an effluent
stream
from a linear alkylbenzene manufacturing facility and produces a modified
alkylbenzene 26
which is predominantly branched. The Fig. 4 process could be built as an "add-
on" to a
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standard linear alkylbenzene manufacturing plant. In contrast, Fig. 3 uses as
hydrocarbon
feed a mixture of linear and branched paraffins of the kind intrinsically
present in, say, a
jet/diesel cut derived from kerosene which has not been processed in a linear
alkylbenzene
manufacturing facility. The Fig. 3 process produces a modified alkylbenzene
which
s contains a mixture of methyl-branched (unconventional, in accordance with
the invention)
and linear (conventional) alkylbenzenes. The Fig. 3 process can be built as a
"stand-alone"
facility requiring no connection to a conventional linear alkylbenzene
manufacturing
facility. These observations are intended to better illustrate the present
process and should
not be taken as limiting.
to Fig. 5, Fig. 6 and Fig. 7 are schematic drawings identifying additional
embodiments
of the invention to accommodate other different hydrocarbon feeds. More
specifically,
these Figures illustrate processes which accommodate mixed parafFn/olefin
feeds.
Fig. 8 shows in more detail the particular configuration of adsorptive
separations
which is found in other process illustrations, e.g., in Fig. 1 and Fig. 6.
Each block
represents an adsorptive separation unit. Within each block, a vertical array
of adsorptive
separation beds (AC in the left of each block) is controlled by a rotary valve
(RV). The
adsorptive separation is accompanied by distillations in columns RC and EC.
The streams
marked "Feed", "Extract" and "Raffinate" of the leftmost adsorptive separation
correspond with the streams marked "I ", "6" and "2" in Fig. 1. The raffinate
stream of the
2o first adsorptive separation (and not the extract as would be the case in
conventional linear
alkylbenzene manufacture) becomes the feed for the second adsorptive
separation. The
raffinate of the second adsorptive separation in Fig. 8 corresponds with
stream 7 in Fig. 1.
The extract of the second adsorptive separation in Fig. 8 corresponds with
stream 3 in Fig.
1: this is the stream which in the present process is dehydrogenated and/or
alkylated.
Fig. 8, as noted, also serves to illustrate in more detail individual
adsorptive
separations herein. Thus, while the connections are not as shown in Figs. 2,
3, 4, 5 and 7,
any single adsorptive separation of Figs. 2, 3, 4, S and 7 can be represented
in more detail
using an appropriate interconnection of the detailed units illustrated in
either block of Fig.
8.
The convention is used in Figs. 1-7 to depict hydrocarbon fractions adsorbed
by
the porous media as exiting above the adsorptive separations marked "SOR"
while
fractions not adsorbed are shown as exiting below the adsorptive separations
marked
"SOR". The fraction exiting "above" is sometimes in the art referred to as an
"adsorbate"
or "extract" and the fraction exiting "below" is sometimes referred to as a
"raffnate" or
"effluent". The "above" and "below" conventions used here are intended to make
reading
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11
the process Figures more convenient and should not be taken as limiting the
practical
executions of the present process to any particular geometrical arrangement.
Using principles similar to those used in Figs. 1-8, Fig. 9 illustrates a
process for
the production of modified primary OXO alcohols using mid-chain methyl-
branched
internal olefins having carbon numbers suitable for detergent application as
intermediates
and in which the OXO catalyst largely pre-isomerizes the internal olefin to an
alpha-olefin
and then hydroformylates predominantly at the terminal carbon atom. In more
detail,
crude hydrocarbon feed 51 is distilled using distillation column DIST to
secure a
hydrocarbon feed suitable for the remainder of the process. Feed 1 can
desirably be a
to narrow-carbon range paraffin cut. A light distillation cut 52 and a heavy
distillation cut 53
are also obtained but not further used for making the instant OXO alcohols.
Hydrocarbon
feed 1 is passed through a simulated moving bed sorptive separation system
comprising
units SOR 4/S followed by SOR 5/7, each suitably of MOLEX ~ type, connected in
the
order shown. The configuration is set such that a linear-enriched stream (an
adsorbate)
rich in linear paraffn and identified as 6 in Fig. 9 is rejected from unit SOR
4/5. An
intermediate branched-enriched stream (a raffinate) 2, which is enriched in
methyl-
branched paraffins, proceeds to unit SOR 5/7. Reject stream 7 from SOR 5/7
which
contains unwanted cyclics, aromatics, ethyl-branched and higher-branched
paraffins is
discarded. Branched-enriched stream 3 from SOR 5/7 now a purified methyl-
branched
2o paraffin stream, proceeds to dehydrogenator DEH, for example of PACOL ~
type where
up to 20% of it is converted predominantly to the corresponding mono-olefins.
Branched-
enriched stream (olefinic) 4, containing said mono-olefins together with
unreacted
paraffins and some diolefin impurity, proceeds to SOR O/P, which is a
simulated moving-
bed adsorptive separation system configured to use OLEX ~ or similar
approaches for the
separation of olefins from paraflins. Suitably, for example, the adsorbent is
copper or
silver on zeolites X or Y. From SOR O/P, a purified olefinic branched-enriched
stream
(the adsorbate) 55, now mostly methyl-branched olefins, proceeds to an OXO
reactor.
Recycle stream 8 is predominantly methyl-branched paraffins. The OXO reactor
is
configured for what is termed in the art as a "one-step low-pressure OXO
process" using a
3o catalytic metal other than iron, said metal being modified with bulky
phosphine ligands (see
the references in Background). Crude modified primary OXO alcohol, product
stream 58,
is separated from recyclable material using distillation and other ancilliary
means not
shown and the clean modified primary OXO alcohol, now freed from recyclable
material,
emerges as stream 57. See the table hereinafter for more detailed description
of the
composition of each stream.
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Fig. 10 is similar to Fig. 9 with the exception that it incorporates one or
more
treatment steps after the dehydrogenation step, to hydrogenate diolefin
impurity produced
in the dehydrogenator and convert it back to mono-olefin. This is typically a
DEFINE
type stage licensable from UOP Corp. Additionally present can be one or more
additional
aromatic removal steps, for example the PEP ~ process of UOP, principally to
remove
aromatic impurities formed during the dehydrogenation.
Fig. 11 is similar to Fig. 10 except that it is simplified in that it uses an
olefin/parafl7n mixture as feed to the OXO reactor and in that recycle stream
8 is now a
large fraction ( > 70%) of the OXO reactor output.
to Fig. 12 is similar to Fig. 10 except that units SOR 4/5 and SOR 5/7 have a
reverse
configuration.
Fig. 13 is similar to Fig. 1 I except that units SOR 4/S and SOR 5/7 have a
reverse
configuration.
Fig. 14 is similar to Fig. 12 except that SOR 4/5 is removed such that a
mixture of
linear and methyl-branched compounds proceeds through the process. The final
product is
a mixed linear and methyl-branched primary OXO alcohol.
Fig. 1 S is similar to Fig. I 3 except that SOR 4/S is removed such that a
mixture of
linear and methyl-branched compounds proceeds through the process. The final
product is
a mixed linear and methyl-branched primary OXO alcohol.
2o Fig. 16 is similar to Fig. 10 except that the plant is fitted such that the
olefinic
branched-enriched stream, 55, can be used to make either modified alkylbenzene
and/or
modified primary OXO alcohols.
Fig. 17 is similar to Fig. 1 I except that the plant is fitted such that
methyl-branched
olefin stream 54 can be used to make either modified alkylbenzene and/or
modified primary
OXO alcohols.
Fig. 18 is similar to Fig. 14 except that the plant is fitted such that methyl-
branched
and linear olefin stream 61 can be used to make product comprising modified
alkylbenzene
and/or modified primary OXO alcohols along with the corresponding linear
counterparts.
SUMMARY OF THE INVENTION
3o In preferred embodiments, this invention relates to processes for preparing
modified alkylbenzenesulfonate surfactants or modified primary OXO alcohols
and
surfactants derivable therefrom, or even combinations of these different
surfactant types.
The processes start from hydrocarbon feeds defined in more detail elsewhere
herein.
"Modified" connotes a very particular type of branching. Specifically, for
example, in the
context of the OXO alcohols herein, "modified" means that there is methyl
branching in
positions other than the usual OXO position, while substantially avoiding
branching in
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13
positions or of types that would adversely affect biodegradation. Preferred
"modified"
refers to mid-chain positioned, mono-lower alkyl, especially monomethyl
substitution of
the OXO alcohol. The processes comprise (a) a particularly defined adsorptive
separation
stage and, when making modified alkylbenzenes and/or alkylbenzenesulfonates,
(c) an
s alkylation stage. Of significant utility for the manufacturer of detergents,
the hydrocarbon
feed can be an adsorptive separation raffinate or effluent deriving from a
linear
alkylbenzene manufacturing process or conventional linear detergent alcohol
process,
though other feeds, such as jet/diesel or olefins can be used.
When the feed is paraffinic, process embodiments typically and preferably
further
to include (b) a dehydrogenation stage inserted in the sequence between the
adsorptive
separation and the alkylation and, when a modifed alkylbenzene is the desired
product, (c)
an alkylation stage. When the feed is olefin, quite evidently, dehydrogenation
is not
essential. In general, the alkylation stage is preferably followed by (d)
suIfonation; (e)
neutralization; and (f) formulation into consumer cleaning products by mixing,
15 agglomeration, compaction, spray-drying and the like. Any stage can have
more than one
step and include options such as distillation, provided that it includes at
least the specified
minimum.
When making a modified alkylbenzene, stage (a), adsorptive separation,
comprises
at least partially separating the hydrocarbon feed selected from olefinic
feeds, paraffinic
2o feeds and mixed olefinic / paraffinic feeds, into at least one branched-
enriched stream
comprising an increased proportion (e.g., in relative terms at least about SO%
higher, and
in absolute terms, that is in terms of percentage by weight, at least about
l0% by weight)
of branched acyclic hydrocarbons relative to said hydrocarbon feed and
typically, one or
more additional streams, for example at least one linear-enriched stream
comprising an
25 increased proportion (e.g., in relative terms at least about SO% higher,
and in absolute
terms at least about 10% by weight) of linear acyclic aliphatic hydrocarbons
relative to said
hydrocarbon feed. Other streams present in the process can vary in
composition. Such
streams include reject streams, in which cyclic and/or aromatic undesirable
components
from the feeds are present at levels generally exceeding those of the feed;
recycle streams
30 and the like can also be present.
In more detail, the adsorptive separation part, (a), of the process has one or
more
steps comprising first, providing the hydrocarbon feed, then at least one step
selected from
adsorptive separation using porous media (preferred), clathration using a
clathrating
compound selected from urea, thiourea and alternative clathrating amides; and
35 combinations thereof. This stage uses simulated moving bed adsorptive
separation means
known from the art (see in particular US 2,98S,S89 incorporated herein in its
entirety)
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1 ~1
comprising both of at least one bed holding said porous media or clathrating
compound
(see, for example Figure 1 of US 2,985,589 and the associated description) and
a device,
typically a rotary valve of a highly specialized design, for simulating motion
of said porous
media or clathrating compound countercurrent to a hydrocarbon stream in said
bed. (see in
s particular US 2,985,589 Figure 2).
Particularly unusual and novel in the context of the present process is that,
at
minimum, the simulated moving-bed adsorptive separation herein is used to
obtain an-
essential branched-enriched stream, that is, the exact opposite of the
practice used in linear
alkylbenzenesulfonate surfactant manufacture. This essential dii~'erence is
also associated
to with having a different content of the bed as compared to conventional
practice, that is,
there is at least one bed containing porous media differing from the 4-s
Angstrom zeolites
normally used for linear alkylbenzene manufacture by having larger pore size
and
reconfiguring the process equipment, notably said bed and said device, so that
they
connect differently with the associated process steps. More specifically,
these means are
is configured such that the branched stream is passed on through the process,
while any
linear-enriched streams, however useful for other purposes, are either
rejected from the
present process or are present in accompaniment of branched-enriched streams.
Moreover, stage (a) of the instant process (or stage (A), when making modified
primary
OXO alcohols) suitably comprises use of at least one porous medium selected
from the
2o group consisting of porous media having a minimum pore size at least larger
than the pore
size required for selective adsorption of linear acyclic hydrocarbons, said
pore size not
exceeding about 20 Angstroms, more preferably not exceeding about 10
Angstroms.
When said hydrocarbon feed comprises more than about 10% of paraffins, and
invariably with higher levels, e.g., about 11% to 90% or higher of paraffins,
the present
2s process preferably includes an additional step, (b), of at least partially
dehydrogenating
said branched-enriched stream. Dehydrogenation can be done using known
catalysts and
conditions.
When making modified alkylbenzenes, regardless of the type of feed, the
present
process preferably comprises (c) reacting a branched-enriched stream prepared
by one or
3o both of the preceding steps (adsorptive separation optionally with
dehydrogenation
provided that the branched -enriched stream ultimately comprises olefin,
typically at least
about 5%, more typically at least about 15% of olefins, generally 5% to 90% or
higher)
with an aromatic hydrocarbon selected from benzene, toluene and mixtures
thereof in the
presence of an alkylation catalyst. The preferred alkylation step herein has a
low internal
35 isomer selectivity of from 0 to no more than about 40, preferably no more
than about 20,
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and is described and defined more fully elsewhere herein. Such low selectivity
alkylations
are believed novel in their own right in the context of modified alkylbenzene
manufacture.
Preferred processes herein further preferably meet at one least one, and more
preferably both, of the following requirements: As the first requirement, said
stage (a)
5 means comprise one, two or more of said devices and at least two of said
beds, at least one
of said beds comprising porous media differentiated relative to the contents
of another of
said beds by an increased capacity to retain methyl-branched acyclic aliphatic
hydrocarbons. For example, zeolites having pore size of above about 5 to no
more than
about 7 Angstrom are especially preferred. As the second requirement, when
making
to modified alkylbenzenes, said step (c) has an internal isomer selectivity of
from 0 to no
more than about 40, preferably lower as further defined hereinafter.
Preferred processes herein operate in a manner contradictory to and
inconsistent
with conventional practice for making alkylbenzenesulfonate surfactants, which
accept
linear materials for further processing and reject most branched materials.
Further, in
15 order to achieve this reversal, it is found necessary to make use of an
unconventional
interconnection of adsorptive separation operations as further described and
illustrated in
the Figures of this specification.
Also in preferred processes herein, said simulated moving bed adsorptive
separation means in said stage (a) comprise not one, but two of said devices.
The number
of devices taken in conjunction with their configuration is of especial
importance in
accomplishing the manufacture of the preferred compositions of the invention
and
increases specific types of branching in the hydrocarbon streams.
Further, in certain preferred processes having two of said beds, each
comprises a
diiFerent member of said porous media, each of said beds being controlled by
one of said
devices, and each of said devices having a minimum of eight ports (as defined
in US
2,985,589) for achieving simulated movement of said porous media in said beds.
Each of
said beds is further preferably divided into a vertically positioned array of
at least eight
sub-beds. (See Figure 1 in US 2,985,589). Also preferably, stage (a) uses
exclusively
porous media, rather than clathrating compounds, in said beds.
3o Processes herein when making modified alkylbenzenes, can have one or more
steps
following the alkylation step. Such steps can include the additional step of
(d) sulfonating
the product of step (c).
Sulfonation can be followed by the additional step of (e) neutralizing the
product of step
(d). Such steps can be followed by (f) mixing the product of step (d) or (e)
with one or
more cleaning product adjunct materials; thereby forming a cleaning product.
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The present invention also encompasses modified alkylbenzene produced by any
of
the processes herein; as well as modified alkylbenzenesulfonic acid or
modified
alkylbenzenesulfonate surfactant in any known salt form such as the sodium
form, the
potassium form, the ammonium form, the substituted ammonium form or the like,
produced by any of the processes herein; as well as consumer cleaning products
produced
by any of the processes herein.
Likewise, when producing anionic surfactants from modified primary OXO
alcohols as taught herein, all the above identified salt forms of the
surfactants are
encompassed by the invention.
to Cleaning product embodiments herein, whether they incorporate the modified
alkylbenzene sulfonates and/or any of the modified primary OXO alcohol derived
surfactants taught herein, include laundry detergents, dishwashing detergents,
hard surface
cleaners and the like. In such embodiments, the content of modified
surfactants produced
by the instant process is from about 0.0001 % to about 99.9%, typically from
about 1 % to
about 50%, and the composition further comprises from about 0.1 % to about
99.9%,
typically from about 1% to about 90%, of cleaning product adjunct materials
such as
cosurfactants, builders, enzymes, bleaches, bleach promoters, activators or
catalysts, and
the like.
The present invention also has alternate embodiments using paraffnic
hydrocarbon
2o feeds, in which two adsorptive separations, particularly configured in much
the same
manner as stage (a) described herein for modified alkylbenzene production, are
followed
by additional steps other than benzene alkylation step (c), and lead to useful
cleaning
surfactants. Such steps replacing the step (c) alkylation can include at least
one step
selected from: dehydrogenation, chlorination, sulfoxidation, oxidation to a C8-
C20 alcohol
and oxidation to a C8-C20 carboxylic acid or salt thereof, optionally followed
by one of
glucosamidation, conversion to a nonsaccharide-derived amide surfactant (for
example a
monoethanolamide surfactant or any such amide not having a glucose moiety),
and
sulfonation as ester. Other alternative embodiments use a hydrocarbon feed
comprising
20% or more of methyl-branched olefins; again, this process has the
particularly
3o configured stage (a) adsorptive separations. Subsequent steps can include
alkylation with
benzene or toluene optionally followed by sulfonation; alkylation with phenol
followed by
at least one of alkoxylation, sulfation, sulfonation or combinations thereof;
hydroformylation to alcohol optionally followed at least one of alkoxylation,
glycosylation,
sulfation, phosphation or combinations thereof; sulfonation; epoxidation;
hydrobromination followed by amination and oxidation to amine oxide; and
phosphonation.
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The invention also encompasses the surfactants produced by such processes and
the cleaning products produced by such processes. The present invention
moreover
includes especially useful embodiments wherein the adsorptive separations of
stage (a)
comprise at least one separation step using an organometallic-grafted
mordenite such as a
tin-grafted mordenite. The invention also encompasses a method comprising use
of a
grafted mordenite for manufacturing detergent surfactants and any of the
corresponding
surfactants and consumer products produced by use of these specific porous
media in any
of the above-defined processes.
The present invention has many other important embodiments and ramifications.
l0 Thus the present invention encompasses a process comprising: (A) a stage of
at least
partially separating a hydrocarbon feed comprising branched aliphatic
hydrocarbons, more
particularly, paraffinic hydrocarbons, having from about 8 to about 20 carbon
atoms, into
at least one branched-enriched stream comprising an increased proportion of
branched
acyclic hydrocarbons relative to said hydrocarbon feed and optionally, one or
more of
- a linear-enriched stream comprising an increased proportion of linear
aliphatic hydrocarbons relative to said hydrocarbon feed; and
- a reject stream comprising cyclic and/or aromatic and/or ethyl- or higher-
branched hydrocarbons;
wherein said stage (A) comprises:
- providing said hydrocarbon feed; and
- adsorptive separation of said feed into said streams using porous media;
said stage (A) using simulated moving bed adsorptive separation means
comprising
both of:
- at least one bed holding said porous media; and
- a device for simulating motion of said porous media countercurrent to a
hydrocarbon stream in said bed; followed by further stages (B), (C) and
(D) (any of which can have one or more steps) as follows:
(B) (i) at least partially dehydrogenating the branched-enriched stream of
stage (A) thereby
forming an olefinic branched-enriched stream comprising mono-olefin
(optionally large
3o proportions, up to 80% or higher of paraffns may also be present along with
impurities
such as diolefins and/or aromatic impurities), optionally followed by one or
more of {ii)
treating said olefinic branched-enriched stream to diminish the content
therein of diolefin
impurities and (iii) treating said olefinic branched-enriched stream to
diminish the content
therein of aromatic impurities; (C) optionally, at least partially
concentrating said mono-
olefins in said olefinic branched-enriched stream of stage (B) by means of
sorptive
separation using a known sorbent or porous media provided that said sorbent or
porous
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18
media are nonidentical with the porous media of stage (A) and are adapted for
olefin /
paraffin separations (such as, for example, is the case for copper-treated or
silver-treated
zeolite X or Y} and, optionally, concurrently recycling paraffins to said
dehydrogenation
stage (B);
and
(D) reacting said olefinic branched-enriched stream produced in stage (B) or,
optionally, as
further concentrated in stage (C), with carbon monoxide and hydrogen in the
presence
of an OXO catalyst, thereby forming a modified primary OXO alcohol.
In the description of processes herein, the term "stage" refers to a
collectively
1o identifiable group of one or more process steps. For example, (A) is an
adsorptive
separation stage, essentially a modified MOLEX ~ stage which can be licensed
from UOP
Corp., here unconventionally configured to enrich (rather than decrease as in
normal
practice) the branched content of the hydrocarbons. It can optionally include
as part of the
same stage ancilliary steps such as distillation, addition or removal steps
with lower boiling
hydrocarbons to wash adsorbent, etc., all as known in the art. (B) is a
dehydrogenation
stage, comprising, at minimum, a dehydrogenation step but often including
other optional
steps such as those specifically mentioned supra. Essential process technology
for (B) can
be licensed from UOP Corp., for example as the PACOL ~ process. (C) is
essentially a
conventional OLEX ~ stage, again available from UOP Corp. (D) is preferably an
OXO
2o stage of the kind referred to in the art as a "one-step low pressure OXO"
and is well
known in the art. As with the other stages of this process, stage (D) can be
complemented
by other optional steps, for example, catalyst removal, etc. Unless otherwise
indicated, the
convention herein will be to use capitals (A, B, C . . . ) when referring to
stages of the
present process embodiments wherein the process includes making a modified
primary
OXO alcohol.
Surfactants derivable from these new modified primary OXO alcohols and the
aforementioned alkylbenzenes have significant advantages, such as in being
more soluble at
a given chainlength / carbon number which is important in view of the growing
popularity
of low wash temperatures; and in having unexpectedly high rates of dissolution
when
3o incorporated into detergent granules. Thus the OXO alcohols and the
alkylbenzenes
themselves have exceptional utility to the manufacturer of cleaning
compositions such as
heavy-duty laundry detergents, dishwashing liquids and the like. All
percentages, ratios
and proportions herein are by weight, unless otherwise specified. All
temperatures are in
degrees Celsius (oC) unless otherwise specified. All documents cited are in
relevant part,
incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
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In one embodiment, the present invention relates to a process for preparing a
modified alkylbenzenesulfonate surfactant from a hydrocarbon feedstock. The
equivalent
terms "feed" and/or "feedstock" are used herein to identify any hydrocarbon
useful as a
starting material in the present process. In contrast, the term "stream" is
typically used to
identify hydrocarbon which has undergone at least one process step. The
hydrocarbon
feed herein in general contains usefi~l proportions of acyclic aliphatic
hydrocarbons,
whether olefinic or paraf~nic, or may include mixtures of such olefins and
paraffins. The-
raw feedstock further typically includes varying amounts of cyclic and/or
aromatic
impurities, as found for example in kerosene, jet/diesel (middle distillate)
hydrocarbon
to cuts. In the feedstock, the olefins and paraffins generally occur in both
branched and linear
forms. Moreover, m general, the branched forms in the feedstock can be either
undesirable
or desirable for the present purposes. The present purposes of providing
cleaning
products differ markedly, for example, from gasoline manufacture in which a
high degree
of polymethyl-branched hydrocarbons is desirable for increasing octane rating.
The
present invention provides processes for separating particular desired forms
of the
hydrocarbon feeds for cleaning product purposes, and of incorporating them
into
surfactants (especially certain modified alkylbenzene sulfonates and/or
surfactants based on
modified primary OXO alcohols) and into cleaning products and useful
surfactant
intermediates for such products.
The term "modified" as applied in connection with any product of the present
process means that the product contains a very particular type of branching
and
surprisingly departs from the linear structure which is now commonly taught to
be
preferred and used for cleaning product surfactants. The term "modified" is
further used
to differentiate the products herein from conventional highly-branched
cleaning surfactant
structures, such as those found in tetrapropylene benzene sulfonates, and from
all other
conventional branched structures such as "two-tailed" or "Guerbet" or aldol-
derived
branched structures.
Hydrocarbon feeds herein can in general vary quite widely, but typically
include
methyl branches such as monomethyl, dimethyl (including gem-dimethyl),
trimethyl,
3o polymethyl, ethyl, and higher alkyl branches. The hydrocarbon feeds may
contain
quaternary carbon atoms. However, tolerance for quaternary carbon atoms in the
feeds is
much superior when the present processes include an alkylation stage as taught
hereinafter.
Preferred feeds herein in embodiments of the invention which have an OXO
process stage
and do not have an alkylation stage are essentially free from quaternary
carbon atoms. The
desirable components for the present purposes include monomethyl-branched,
dimethyl-
branched other than gem-dimethyl-branched, and to some extent, especially at
carbon
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contents in excess of about 14, some proportion of trimethyl-branched. The
hydrocarbon
feeds include useful proportions, e.g., S%-40% or more, of acyclic
hydrocarbons having in
general from about 9 to about 20 carbon atoms depending on the desired type of
cleaning
product surfactant or the cleaning product use of the modified surfactant
being produced.
5 More preferably, when making modified alkylbenzenes and modified -
alkylbenzenesulfonates the acyclic aliphatic hydrocarbons of the feedstock
comprise from
about 10 to about 16, more preferably from about 11 to about 14 carbon atoms.
The present processes comprise a particularly defined adsorptive separation
stage
and, for the purposes of making modified alkylbenzenes and
alkylbenzenesulfonates, an
l0 alkylation stage is also essential. When the feedstock is paraffnic,
process embodiments
typically and preferably fi~rther include a dehydrogenation stage inserted in
the sequence
between the adsorptive separation and the alkylation, or, when making modified
primary
OXO alcohols, between the adsorptive separation of type referred to as SOR 4/S
or SOR
5/7 in the Figures, and the OXO process stage. In general, the alkylation or
OXO stage
15 can be followed by additional steps such as sulfonation, typically followed
by
neutralization and formulation into consumer cleaning products by mixing,
agglomeration,
compaction, spray-drying and the like. Also in general, any stage can have
more than one
step provided that it includes at least the minimum of one step.
Stage (a), adsorptive separation, comprises at least partially separating the
2o hydrocarbon feed selected from olefinic feeds, parafFnic feeds and mixed
olefinic /
paraffinic feeds into at least one branched-enriched stream comprising an
increased
proportion (e.g., in relative terms compared to the feed at least about SO%
higher, more
preferably at least about 100% higher, typically treble, quadruple or more and
in absolute
terms, that is in terms of percentage by weight, at least about 10% by weight,
typically at
least 20%, more preferably from 30% to about 90% or more) of branched acyclic
hydrocarbons (especially the desired types identified supra, particularly
methyl-branched
paraffins or methyl-branched mono-olefins) relative to said hydrocarbon feed
and
optionally, one or more of a linear-enriched stream comprising an increased
proportion
(e.g., in relative terms at least about 50% higher, more preferably at least
about 100%
3o higher, typically treble, quadruple or more and in absolute terms at least
about 10% by
weight, typically at least 20%, more preferably from 30% to about 90% or more)
of linear
acyclic aliphatic hydrocarbons relative to said hydrocarbon feed; and a reject
stream
comprising cyclic and/or aromatic hydrocarbons or other impurities such as gem-
dimethyl
hydrocarbons, ethyl-branched hydrocarbons or higher-branched hydrocarbons.
Other streams present anywhere in the present process can vary in composition.
Such streams include reject streams, in which cyclic and/or aromatic
undesirable
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21
components from the feeds are present at levels generally exceeding those of
the feed;
recycle streams having compositions depending on the parts of the process they
connect,
and the like. Known processes, such as that of US 5,012,021 or US 4,520,214
both
incorporated by reference, can be used herein to convert impurities, such as
certain
diolefins, back to monoolefins using a selective catalyst. Other processes
which can
optionally be incorporated herein to selectively remove aromatic by-products
formed in
paraffin dehydrogenation include those of US 5,300,715 and US 5,276,231
involving the
use of one or more aromatic removal zones and/or extractants for aromatics
which may
include, for example, sulfolane and/or ethylenediamine.
1o In more detail, the adsorptive separation stage or part of the process used
to enrich
the content of branched hydrocarbons in the feed has one or more steps
comprising at least
one step selected from providing a suitable hydrocarbon feed and at least one
step selected
from adsorptive separation using porous media, clathration using a clathrating
compound
selected from urea, thiourea and alternative clathrating amides, and
combinations thereof.
Very preferably, when using combinations, at least one step is an adsorptive
separation
using porous media of the larger-pore type described more fully hereinafter.
Stage (a) (or
stage (A) when making modified primary OXO alcohols) uses simulated moving bed
adsorptive separation means well known from the art (see in particular US
2,985,589
incorporated herein in its entirety) comprising both of at least one bed
holding said porous
2o media or clathrating compound (see, for example US 2,985,589 Figure 1 and
the
associated description) and a device for simulating motion of said porous
media or
clathrating compound countercurrent to a hydrocarbon stream in said bed. (See
in
particular US 2,985,589 Figure 2 and the associated description, or variants
in current
commercial use for the production of linear alkylbenzenesulfonates). The
device in
question is typically a rotary valve of a highly specialized design. In
general, types of such
valves as used in current linear alkylbenzene manufacture can be used herein.
Adsorptive
separation conditions, e.g., pressures, temperatures and times, can be as used
in the art.
See, for example, US 2,985,589.
What is particularly unusual and novel in the context of the present process
is that,
3o at minimum, the simulated moving-bed adsorptive separation herein is used
to obtain an
essential branched-enriched stream, that is, the exact opposite of the
practice used in linear
alkylbenzenesulfonate surfactant manufacture. This essential difference is
also associated
with changing the contents of the bed so that it contains porous media
differing from the
4-5 Angstrom zeolites normally used for Linear alkylbenzene manufacture, and
reconfiguring the process equipment, notably said bed and said device, so that
they
connect differently with the associated process steps. More specifically,
these means are
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22
configured such that the branched stream is passed on through the process,
while any
linear-enriched streams, however useful for other purposes, are either
rejected from the
present process or are present in accompaniment of branched-enriched streams.
When said hydrocarbon feed comprises less than about 5% of olefins, the
present
process preferably includes an additional stage, (b), or stage (B) when making
modified
primary OXO alcohols, of at least partially dehydrogenating the product of
stage (a).
Dehydrogenation can be done using any known dehydrogenation catalyst, such as
the De-
H series from UOP, and are further illustrated hereinafter. Dehydrogenation
conditions
are similar to those used in current linear alkylbenzenesulfonate manufacture.
to When making modified alkylbenzenes, regardless of the type of feedstock
treated,
the present process preferably comprises (c) reacting the product of stage
(a), or when
stage (b) is also present in the foregoing steps, the product of stage (a}
followed by stage
(b), with an aromatic hydrocarbon selected from benzene, toluene and mixtures
thereof in
the presence of an alkylation catalyst. The preferred alkylation step herein
has a low
I5 internal isomer selectivity of from 0 to about 40, preferably not more than
about 20, more
preferably not more than about 10, as described and defined more fully
elsewhere herein.
Such low internal isomer selectivities are believed novel in their own right.
In one mode, the alkylation step herein is run in the presence of excess
paraffin,
which is then recovered and recycled to the dehydrogenator. In another mode,
the
2o alkylation step is run in presence of 5 x to 10 x excess of arene. Any
combination of such
modes is possible.
Note that when the final branched-enriched stream, i.e., the product of stage
(a),
has appreciable olefin content, e.g., more than about 5% olefins in total,
this stream can
proceed directly to the alkylation step (c), then recovered paraffns can be
recycled to a
25 dehydrogenation reactor for at least partial conversion to olefin. See, for
example, Figs. 5,
6, 7.
Of great importance to the present invention, preferred processes herein
further
preferably meet at one least one, and more preferably both, of the following
requirements:
As the first requirement, said stage (a) means (or, when making modified
primary OXO
3o alcohols, stage (A) means) comprise one, two or more of said devices (e.g.,
the
aforementioned rotary valves or any equivalent means) and at least two of said
beds, at
least one of said beds comprising porous media dii~erentiated relative to the
contents of
another of said beds by an increased capacity to retain methyl-branched
acyclic aliphatic
hydrocarbons. For example, zeolites having pore size at least in excess of
sizes used in
35 conventional linear alkylbenzene manufacture and up to about 20 Angstrom,
more
preferably up to about 10 Angstrom, more preferably still up to about 7
Angstrom, or
CA 02341224 2001-02-20
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23
other porous media such as certain silicoaluminophosphates or Mobil MCM-type
materials
are suitable herein provided that the pore sizes are as noted. When using
porous materials
having pore sizes above about 7 Angstrom, it is often highly desirable to
"tune down" the
pore openings, for example by grafting of tin alkyls at the pore openings. See
EP 559,510
A incorporated herein by reference in its entirety. As the second reduirement,
when
making modified alkylbenzenes, said step (c) has an internal isomer
selectivity of from 0 to
no more than about 40, preferably lower, as noted supra and as further defined
in detail -
hereinafter.
In other preferred processes, at least one of said beds comprises porous media
to conventional for the manufacture of linear alkylbenzenes; said beds being
connected into
said process in a manner consistent with at least partially increasing the
proportion of
methyl-branched acyclic aliphatic hydrocarbons in streams passing to step (c)
of said
process, and at least partially decreasing the proportion of linear acyciic
aliphatic
hydrocarbons passing to step (c) of said process, said linear acyclic
aliphatic hydrocarbons
being at least partially removed as reject stream in stage (a). In other
words, preferred
processes herein operate in a manner contradictory to and inconsistent with
conventional
practice for making alkylbenzenesulfonate surfactants, which reject branched
materials and
accept linear materials for further processing. Further, in order to achieve
this reversal, it
is found necessary to make use of an unconventional interconnection of
adsorptive
2o separation operations as already briefly described and as further
illustrated in the Figures
herein.
Also of great importance, in preferred .processes herein, said simulated
moving bed
adsorptive separation means in said stage (a) (or stage (A) when making
modified primary
OXO alcohols) comprise not one, but two of said devices, or a single device
capable of
simulating movement of said porous media in at least two independent beds. In
other
words, for all preferred processes herein, using a single device, for example
a device as
taught in US 2,985,589, will not since. The number of devices taken in
conjunction with
their configuration is of especial importance in accomplishing the manufacture
of the
preferred compositions of the invention. Thus, in a hypothetical not known
from the art,
3o an increasing purification of a linear hydrocarbon might be accomplished by
two devices
and two beds connected in series. A highly linear adsorbate of the first stage
might
proceed to a second stage adsorptive separation process inlet for further
purification.
Such a configuration is outside the present invention on account of its
incorrect connection
of the stages, which lead to increasing the linearity and purity of a
hydrocarbon. The
present processes, as has already been noted, involve passing branched streams
though the
CA 02341224 2001-02-20
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2=4
various steps or stages, requiring a connection of the devices which is
consistent with the
objective. This increases specific types of branching in the hydrocarbon
streams herein.
Further of great importance in preferred processes herein, there are two of
said
beds, each comprising a different member of said porous media, each of said
beds being
controlled by one of said devices, and each of said devices having a minimum
of eight
ports for achieving simulated movement of said porous media in said beds. Each
of said
beds is further preferably divided into a vertically positioned array of at
least eight sub-
beds. Also preferably, stage (a) uses exclusively porous media in said beds.
Thus, the
invention can make use of conventional beds and devices of the general type
described in
l0 US 2,985,589; but their number and connection into the present process is
novel and
unprecedented in alkylbenzenesulfonate manufacturing plants.
Also, the better to illustrate what has already been described, in certain
embodiments of preferred processes herein, said linear-enriched stream is
present in stage
(a) and stage (a) comprises: (a-i) adsorptive separation of said hydrocarbon
feed into said
linear-enriched stream and an intermediate branched-enriched stream and
rejection of said
linear-enriched stream for essential purposes of said process, by means of one
of said
simulated moving beds; followed by (a-ii) adsorptive separation of said
intermediate
branched-enriched stream into said branched-enriched stream comprising an
increased
proportion of branched (more particularly methyl-branched) acyclic aliphatic
hydrocarbons
2o relative to said linear-enriched stream, and a reject stream comprising at
least an increased
proportion of cyclic and/or aromatic hydrocarbons relative to said branched -
enriched
stream, by means of another of said simulated moving beds.
Said reject stream in said step (a-ii) can further comprise undesired branched
hydrocarbons selected from gem-dimethyl branched hydrocarbons, ethyl branched
hydrocarbons and higher than ethyl branched hydrocarbons; and wherein the
acyclic
aliphatic hydrocarbons of said intermediate branched-enriched stream and said
branched-
enriched stream comprise a reduced proportion of said gem-dimethyl branched
hydrocarbons, ethyl branched hydrocarbons and higher than ethyl branched
hydrocarbons
relative to said hydrocarbon feed. In terms of tolerance .of these various
components in the
3o intermediate branched-enriched stream, ethyl branched hydrocarbons are much
more
acceptable than are gem-dimethyl, cyclic and aromatic components. In general,
a
minimum of "increasing proportion", "decreasing proportion", or "enriching" of
any
component in any step herein corresponds to any increase (enrichment) or
decrease in
proportion useful for the practically stated purposes of the invention. Such
amounts are
well illustrated throughout the specification.
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Also in said process, said stream compositions can be achieved by selecting as
said
porous media: a member selected from the group consisting of 4-5 Angstrom pore-
size
zeolites in said step (a-i) and a member selected from the group consisting of
porous media
having a pore size at least greater than about the maximum pore size of said
step {a-i)
5 zeolite and at most about 10 Angstrom in said step {a-ii).
In another preferred embodiment, stage (a) comprises: (a-i) adsorptive
separation
of said hydrocarbon feed into an acyclic aliphatic hydrocarbon-enriched stream
comprising
linear- and branched (such as the desirable types described supra) acyclic
aliphatic
hydrocarbons and a first reject stream comprising at least an increased
proportion of cyclic
to and/or aromatic hydrocarbons relative to said hydrocarbon feed, followed by
(a-ii)
adsorptive separation of said acyclic aliphatic hydrocarbon-enriched stream
into said
branched-enriched stream and said linear-enriched stream; wherein said
adsorptive
separations are accomplished using said simulated moving bed adsorptive
separation
means. Unless otherwise noted herein, the "branched-enriched stream" is the
final stream
15 of stage or step (a); additional qualifiers such as "intermediate" will
otherwise be prefixed
on the name to indicate that the stream, though enriched in branched
hydrocarbons,
requires further treatment before proceeding from the adsorptive separation
stages of the
instant process to other stages. Also to be noted, stage (a), the adsorptive
separation
stage, can freely include other conventional, optional steps, such as
distillation, provided
20 that adsorptive separation is conducted. Thus, current commercial MOLEX~
plants will
typically further include distillation in this stage and can be useful herein.
The invention further encompasses a process wherein said first reject stream
in said
step (a-i) further comprises undesired branched hydrocarbons selected from gem-
dimethyl
branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl
branched
25 hydrocarbons; and wherein said acyclic aliphatic hydrocarbon-enriched
stream and said
branched-enriched stream each comprises a reduced proportion of said gem-
dimethyl
branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl
branched
hydrocarbons relative to said hydrocarbon feed. In such embodiments, stream
compositions can be achieved by selecting as said porous media: a member
selected from
3o the group consisting of 4-S Angstrom pore-size zeolites in said step (a-ii)
and a member
selected from the group consisting of porous media having a pore size at least
greater than
about the maximum pore size of said step (a-ii) zeolite and at most about 10
Angstrom in
said step (a-i).
More generally, the invention relates to a process wherein stage (a) comprises
use
of at least one porous medium selected from the group consisting of porous
media having
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2G
a minimum pore size larger than the pore size required for selective
adsorption of linear
acyclic hydrocarbons, said pore size not exceeding about 20 Angstroms.
As noted, preferred processes herein include those wherein said alkylation
step, (c),
has an internal isomer selectivity of from 0 to 20; also, a preferred
alkylation step, (c) uses
an alkylation catalyst consistent with said internal isomer selectivity, and
wherein said
alkylation catalyst is selected from the group consisting of: at least
partially acidic
mordenites and at least partially acidic zeolite beta. Preferred alkylation
catalysts include
H-mordenites and H-beta, more preferably H-mordenite, which is at least
partially
dealuminized.
to With respect to making modified alkylbenzenes and modified
alkylbenzenesulfonates, the invention also preferably includes the process
wherein said
hydrocarbon feed comprises at least about 10% methyl-branched parafFns having
molecular weight of at least about 128 and no more than about 282; said
process having
said dehydrogenation step (b). More preferably in such embodiments, said
hydrocarbon
feed comprises at least about 20% methyl-branched paraffins having molecular
weight of
at least about 128 and no more than about 226; said process having said
dehydrogenation
step (b) and having alkylation step (c); and also preferably includes the
process wherein
said hydrocarbon feed comprises at least about 10% methyl-branched olefins
having
molecular weight of at least about 126 and no more than about 280. More
preferably in
such embodiments, the hydrocarbon feed comprises at least about 50% methyl-
branched
olefins having molecular weight of at least about 126 and no more than about
224; said
process having no dehydrogenation step (b).
For the corresponding processes wherein a modified primary OXO alcohol is
made, the above ranges can be extended somewhat, consistent with going to a
total carbon
number of up to about C20 or higher. More preferably, the upper-end para~n
molecular
weight of 226 supra is extended to about 254, and the upper-end olefin
molecular weight
of 224 supra is extended to about 252.
Of significant utility for the manufacturer of detergents, the hydrocarbon
feed or
feedstock herein can be an adsorptive separation raffinate or effluent
deriving from a linear
3o alkylbenzene manufacturing process, or from a conventional linear detergent
alcohol
process.
Processes herein can have one or more steps following the alkylation step.
Such
steps can include the additional step of (d) sulfonating the product of step
(c).
Sulfonation can be followed by the additional step of (e) neutralizing the
product of step
(d). Such steps can be followed by (f) mixing the product of step (d) or (e)
with one or
more cleaning product adjunct materials; thereby forming a cleaning product.
CA 02341224 2001-02-20
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27
Thus the process herein includes highly preferred embodiments having all of
the
additional steps of (d) sulfonating the modified alkylbenzene product of step
(c); (e)
neutralizing the modified alkylbenzenesulfonic acid product of step (d); and
(fj mixing the
modified alkylbenzenesulfonic acid or modified alkylbenzenesulfonate
surfactant product
of steps (d) or (e) with one or more cleaning product adjunct materials;
thereby forming a
cleaning product. In one such embodiment, prior to said sulfonation step,
modified
alkylbenzene which is the product of said step (c) is blended with a linear
alkylbenzene
produced by a conventional process. In another such embodiment, in any step
subsequent
to said sulfonation step, modif ed alkylbenzene sulfonate which is the product
of said step
(d) is blended with a linear alkylbenzene sulfonate produced by a conventional
process. In
these blended embodiments, a preferred process has a ratio of modified
alkylbenzene to
linear alkylbenzene of from about 1:100 to about 100:1. When a relatively more
linear
product is desired, a preferred ratio is from about 10:90 to about 50:50. When
a relatively
more branched product is desired, a preferred ratio is from about 90:10 to
about 51:49.
The present invention also encompasses modified alkylbenzene produced by any
of
the processes herein; as well as modified alkylbenzenesulfonic acid or
modified
alkylbenzenesulfonate surfactant in any known salt form such as the sodium
form, the
potassium form, the ammonium form, the substituted ammonium form or the like,
produced by any of the processes herein; as well as consumer cleaning product
produced
2o by any of the processes herein.
Cleaning product embodiments herein include laundry detergents, dishwashing
detergents, hard surface cleaners and the like. In such embodiments, the
content of
modified alkylbenzenesulfonate, or content of any surfactant derived from
modified
primary OXO alcohols, etc., herein and produced by the instant process, is
from about
0.0001% to about 99.9%, typically from about 1% to about 50%, and the
composition
further comprises from about 0.1% to about 99.9%, typically from about 1% to
about
50%, of cleaning product adjunct materials such as cosurfactants, builders,
enzymes,
bleaches, bleach promoters, activators or catalysts, and the like.
Preferred consumer cleaning products produced by these processes suitably
3o comprise from about 1% to about SO% of said modified surfactant and from
about
O.OOOI% to about 99% of cleaning product adjunct materials selected from
enzymes,
nonphosphate builders, polymers, activated bleaches, catalyzed bleaches,
photobleaches
and mixtures thereof.
Alternate Process Embodiments
The present invention has alternate embodiments in which two particularly
configured adsorptive separations are followed by additional steps which lead
to useful
CA 02341224 2001-02-20
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28
cleaning surfactants. Thus, there is encompassed herein a process comprising:
(I)
separating a hydrocarbon feedstock into a branched hydrocarbon-enriched stream
comprising, more preferably consisting essentially of, at least about 85% of
saturated
acyclic aliphatic hydrocarbons having a carbon content of from about C8 to
about C20,
said branched hydrocarbon-enriched stream comprising at least about 10% of
paraffns
having methyl branches, said methyl branches being distributed in said
paraffins such that
any para$in molecule has from 0 to no more than about 3 of said methyl
branches and said-
branches being positioned within said paraffins to an extent that at least
about 90% of said
branches occupy positions other than those forming gem-dimethyl and/or
quaternary
to moieties; wherein said separation is conducted by means including at least
two adsorptive
separation steps using simulated moving bed adsorptive separation means and at
least two
porous media having different pore sizes; and (II) converting said branched
hydrocarbon
enriched stream to a surfactant by further steps including at least one step
selected from:
dehydrogenation, chlorination, sulfoxidation, oxidation to a C8-C20 alcohol
and oxidation
to a C8-C20 carboxylic acid or salt thereof, optionally followed by one of
glucosamidation, conversion to a nonsaccharide-derived amide surfactant and
sulfonation
as ester.
Further by way of alternate embodiments, there is encompassed herein a process
comprising: (I) separating a hydrocarbon feedstock into a olefinic branched
hydrocarbon-
2o enriched stream comprising, preferably consisting essentially of, mixtures
of olefinic
acyclic aliphatic hydrocarbons having a carbon content of from about C8 to
about C20 or
mixtures thereof with their saturated analogs, said branched hydrocarbon-
enriched stream
comprising at least about 10% of the sum of said olefins and their saturated
analogs having
methyl branches, said methyl branches being distributed in said mixtures such
that any of
said acyclic aliphatic hydrocarbon molecules has from 0 to no more than about
3 of said
methyl branches and said branches being positioned within said acyclic
aliphatic
hydrocarbon molecules to an extent that at least about 90% of said branches
occupy
positions other than those forming gem-dimethyl moieties; wherein said
separation is
conducted by means including at least two adsorptive separation steps using
simulated
moving bed adsorptive separation means and at least two porous media having
different
pore sizes; and (II) converting said olefinic branched hydrocarbon enriched
stream to a
surfactant by further steps including at least one step selected from:
alkylation with
benzene or toluene optionally followed by sulfonation; alkylation with phenol
followed by
at least one of alkoxylation, sulfation, sulfonation or combinations thereof;
hydroformylation optionally followed at least one of alkoxylation,
alkoxylation combined
with oxidation, glycosylation, sulfation, phosphation or combinations thereof;
sulfonation;
CA 02341224 2001-02-20
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29
epoxidation; hydrobromination followed by amination and oxidation to amine
oxide; and
phosphonation.
In view of the alternate processes encompassed, the invention also encompasses
the surfactants produced by such processes and the cleaning products produced
by such
processes.
Aspects of the invention will now be discussed and illustrated in more detail.
Modified Alkylbenzenes and Alkylbenzenesulfonate Products
As noted in summary, the present invention includes a process for preparing
modified alkylbenzenesulfonate surfactants suitable for use in cleaning
products such as
to laundry detergents, hard surface cleaners, dishwashing detergents and the
like.
The terms "modified alkylbenzenesulfonate surfactant" and "modified
alkylbenzene" refer products of the processes herein. The term "modified" as
applied
either to the novel alkylbenzenesulfonate surfactants or to the novel
alkylbenzenes (MAB)
is used to indicate that the product of the present process is compositionally
different from
is that of all alkylbenzenesulfonate surfactants hitherto used in commerce in
consumer
cleaning compositions. Most particularly, the instant compositions differ
compositionally
from the so-called "ABS" or poorly biodegradable alkylbenzenesulfonates, and
from the
so-called "LAS" or linear alkylbenzenesulfonate surfactants. Conventional LAS
surfactants are currently commercially available through several processes
including those
2o relying on HF-catalyzed or aluminum chloride-catalyzed alkylation of
benzene. Other
commercial LAS surfactants include LAS made by the DETAL~ process. Preferred
alkylbenzenesutfonate surfactants herein made using the preferred low-internal
isomer
selectivity alkylation step herein are also compositionally different from
those made by
alkylating linear olefins using fluoridated zeolite catalyst systems, believed
also to include
25 fluoridated mordenites. Without being limited by theory, it is believed
that the modified
alkylbenzenesulfonate surfactants herein are uniquely lightly branched. They
typically
contain a plurality of isomers and/or homologs. Often, this plurality of
species (often tens
or even scores) is accompanied by a relatively high total content of 2-phenyl
isomers, 2-
phenyl isomer contents of at the very least 25% and commonly 50% or even 70%
or
3o higher being attained. Moreover the modified alkylbenzenesulfonate products
herein differ
in physical properties from known alkylbenzenesulfonate surfactants, for
example by
having improved surfactant efficiency and low tendency to phase-separate
internal isomers
from solution, especially in presence of water hardness.
Feeds and Streams of the Process
35 The term "feed" is used herein to identify a material which has not yet
been
processed by the present process. The term feed" however may also be used when
a step
CA 02341224 2001-02-20
WO 00/12451 PCT/US99/20124-
which is optional in the present process (e.g., adsorptive separation over S
Angstrom Ca-
zeolite) has been applied to such a material, provided that such treatment
occurs before the
first essential step of the present process.
The term "stream" is used herein to identify materials which have undergone at
5 least one step of the present process.
The term "branched-enriched stream" herein unless more particularly noted,
refers
to any processed hydrocarbon fraction containing at least the smaller of the
following:
(i) in relative terms, an increase of at least about 10%, preferably at least
100% (that is, a doubling), more preferably a trebling, quadrupling or more,
10 of branched acyclic C8 to about C20 hydrocarbons, compared to a parent
fraction or feed which has not been processed in the present process; or
(ii) in absolute terms, at least about 5%, preferably 10% or more, of branched
acyclic C8 to about C20 hydrocarbons, more preferably of
about C 10 to about C 14 hydrocarbons when the process produces modified
15 alkylbenzenes or modified alkylbenzenesulfonates.
The branched hydrocarbons referred to can be olefinic, paraffinic or mixed
olefin/paraffin
in any proportion unless otherwise more particularly noted. (Certain preferred
processes
involving making modified primary OXO alcohols as illustrated in Figures 9 and
higher
start from parafl;inic feeds, though, more generally, variations of these
processes can use
20 olefinic feeds). The branches are preferably monomethyl branches or
isolated (non-
geminal) dimethyl branches.
The term "linear-enriched stream" herein unless more particularly noted,
refers to
any processed hydrocarbon fraction which contains a higher percentage by
weight of
normal (n-) acyclic hydrocarbons than does a parent fraction or feed which has
not been
25 processed in the present process.
More particularly, linear-enriched" refers to any processed hydrocarbon
fraction
containing at least the smaller of the following:
(iii) in relative terms, an increase of at least about 10%, preferably at
least
100% (that is, a doubling), more preferably a trebling, quadrupling or more,
30 of linear acyclic C8 to about C20 hydrocarbons, compared to a parent
fraction or feed which has not been processed in the present process; or
(iv) in absolute terms, at least about 5%, preferably 10% or more, of linear
acyclic C8 to about C20 hydrocarbons.
The linear hydrocarbons can be olefinic, paraffinic or mixed olefin/paraffin
in any
proportion, unless otherwise more particularly identified.
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31
Qualifiers such as "intermediate" when used in connection with a branched-
enriched stream are used to identify that the branched-enriched stream to
which is being
referred has not completed passage through the adsorptive separation stage (a)
of the
present process. Other qualifiers such as "olefinic" or "paraffinic" may be
used to identify
whether the stream contains a preponderance of olefinic or of paraffinic
hydrocarbons.
Feeds and streams in the present process both with respect to embodiments
comprising alkylation and with respect to embodiments comprising OXO reaction
(or
concurrent utilization of both) are further illustrated in the following
Table. The numbers
in the leftmost column refer to the feeds and streams identified in Fig. l
throur~h Fis. 18
StreamStream Type Exemplary Sources Predominant Components)
/ (for Feeds)
Name or com ositions (for
streams)
1 Hydrocarbon Jet / Kerosene cats,b-paraffin / I-paraffin
Feed preferably
from light cntdes
For process
embodiments making
modified
OXO alcohols, preferred
feeds
are narrow cuts (e.g.,
3, 2, 1 or
carbon spread, or
nonintegral
narrow-cut)
2 Branched-enrichedMainly branched paratlins;b-parafTin
still
Stre<~m includes cyclics,
aromatics
{lntennediate)
3 Branched-enrichedMainly methyl branchedb-paraffin
Stream arafBns
4 Branched-enrichedMainly methyl branchedb-paraffin / b-olefin
Stream (Olefinic)parafrns; methyl-branched
olefins (e.g., at
up to about
20%); possibly diolefin
im urities will also
be resent.
5 Modified Mainly methyl-branchedModified Alkylbenzenes
Alkylbenzene alkylbenzenes produced by Fig.
1 process
with alkvlation
ste
6 Linear-enrichedMainly linear paratiinsI-parafrn
Stream
7 Reject Cyclics. aromatics,
ethyl and
Stream(Cyclics/Arhigher branched paratlins
omatics)
8 Recycle StreamMainly methyl-branchedb-paratlin
arafFns
9 Hydrocarbon Jct / Kerosene cuts,b-paraffin / I-paraffin
Feed preferably
from li ht cnides
Branched-enrichedMainly methyl branchedb-paraffin / !-paraffin
and
Stream linear paraffins
(Intermediate)
11 Branched-enrichedMainly methyl branchedb-paratTin
Stream araffins
12 Branched-enrichedMainly methyl branchedb-paraffin / b-olefin
Stream (Olefinic)paratTins; methyl-branched
olefins must be present,
e.g., at
a to about 20%
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32
13 Modified Mainly methyl-branchedModified Alkylbenzenes
Alkylbenzene alkylbcnzenes produced by Fig.
2 process
with alkvlation
ste
14 Reject C~clics, aromatics,
ethyl- and
Stream(CyclicslArhigher branched
paraffins
omatics)
15 Linear-enrichedMainly linc~~r paraffinsl-paraffin
Stream
16 Recycle StreamMainly methyl-branchedb-paraffin
arms
17 Hydrocarbon Jet / Kerosene cuts,b-paraffin / 1-paraffin
Feed preferably
from li ht crudes
18 Branched-enrichedMainly methyl branchedb-par~tflin / I-paraffin
and
Stream linear araffins
19 Branched-enrichedMainly methyl-branchedb-paraffin / I-paraffin
and / b-
Stream (Olefinic)linear paraflins; olefin / I-olefin
must have some
linear and methyl
branched
olefins
20 Linear and Mainly methyl-branchedLinear and Modified
and
Modified linear alkylbcnzenesAlkylbenzene mixture
Alkvlbenzene roduced b Fi .
3 rocess
21 Reject StreamCyclics, aromatics,
ethyl and
hi her branched
arailins
22 Recycle StreamMainly methyl-branchedb-paraffin
and
linear araffins 1- araffin
23 Hydrocarbon Mixture of branchedb-paraffin
Feed par~ins
and cyclics and
aromatics,
sourced from conventional
LAB
plant effluent,
e.g., MOLEX~
eiTluent.
24 Branched-enrichedMainly methyl branchedb-paraffn
Stream ara~ns
25 Branched-enrichedMainly methyl branchedb-paraffin / b-olefin
Stream (OleBnic)paraffins; methyl-branched
olefins must be
present, e.g.,
at
a to about 20%
26 Modified Mainly methyl-branchedModified Alkylbenzenes
A1 lbenzene alkylbenzenes roduced b Fi .
4 rocess
27 Reject StreamCyclics, aromatics,
ethyl and
hi her branched
araffillS
28 Recycle StreamMainly methyl-branchedb-paraffin
araflins
29 Hydrocarbon F.T. gasoline, higherb-olefin / 1-olefin
Feed cuts; / b-
crackate from slackparaffin / 1-paraffin
wax;
crackate from Flexicoker
or
Fluidcoker
30 Branched-enrichedMainly methyl-branchedb-olefin / 1-olefin
and / b-
SVeam linear olefins; paraffin / 1-paraffin
usually have some
(Intermediate)linear and methyl
branched
arafGns
31 Branched-enrichedMainly methyl branchedb-olc6n / b-paraffin
olefins
Stream and methyl branched
para((ins;
variable ratio
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33
32 Branched-enrichedMainly methyl branchedb-paratTin / b-olefin
Stre<~m (Olefinic)parlffins; methyl
branched
olefins will be present,
e.g., at
a to 20%
33 Modified Mainly methyl-branchedModified Alkylbenzenes
Alkvlbenzenealkylbenzenes roduced by Fi .
S rocess
34 Reject StreamCyclics, aromatics,
ethyl- and
(Cyclics/Aromaticshigher branched hydrocarbons
35 Linear-enrichedMainly linear olefins1-olefin / I-parallin
and linear
Stream paratlins
(may include
C~clics/Aromatics)
36 Recycle StreamMainly methyl-branchedb-parailin
ara~ns
37 Hydrocarbon F.T. gasoline, higherb-olefin / 1-olefin
Feed cuts; / b-
crackate from slack paraffin / 1-par~in
wax;
crackate from Flexicoker
or
Fluidcoker
38 Branched-enrichedBranched olefins, b-olefin / b-paraffin
branched
Stream parailins, cyclics
and aromatics
(Intermediate)
39 Branched-enrichedMainly methyl branchedb-olefin / b-paraffin
olefins
Stream and methyl branched
paralrns;
variable ratio
40 Branched-enrichedMainly methyl branchedb-parafrn / b-olefin
Stream (Olefinic)parallins; methyl
branched
olefins will be present,
e.g., at
a to 20%
41 Modified Mainly nlcth~~l-branchedModified Alkylbenzenes
A1 (benzene alkylbenzenes roduced by Fi .
6 rocess
42 Linear-enrichedMainly linear olefins1-olefin / I-parlffin
and linear
Stream arafiins
43 Reject Cyclics, aromatics,
ethyl- and
Siream(Cyclics/Arhigher branched hydrocarbons
OIlIatICS)
44 Recycle StreamMainly methyl-branchedb-paraffin
ara~ns
45 Hydrocarbon F.T. gasoline, higherb-olefin / 1-olefin
Feed cuts; / b-
crackate from slack paraffin / 1-paraffin
wax;
crackate from Flexicoker
or
Fluidcoker
46 Branched-enrichedMainly methyl-branchedb-olefin / I-olefin
and / b-
Stre<~m linear olefins; usuallyparaiBn / I-paraffin
have some
linear and methyl
branched
araffins
47 Branched-enrichedMainly linear and b-paraffin / 1-paraffin
methyl- / b-
Stream (Olcfinic)branched parafFuls; olefin / i-olefin
will have
some linear and methyl
branched olefins
48 Modified Mainly methyl-branchedModified Alkylbenzenes
and
Alkvlbenzenelinear alkvlbcnzenesroduced by Fi .
7 rocess
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34
49 Reject Cyclics, aromatics,
ethyl- and
Stream(Cyclics/Arhigher branched hydrocarbons
omatics)
50 Recycle StreamMainly methyl-branchedb-paraffin
and
linear araftins 1- arafFn
51 Cmde hydrocarbonKerosene-range paraffins;b-paraffin
360 -
feed 500F (182 - 277C) 1-paraffin
preferably from light
parallinic
cn~des.
52 Light distillationLight cuts - e.g.,
360F to
cuts (not product cut.
used for
nuking OXO
alcohol or
modified
LAB)
53 Heavy disti4ationHeavy cuts - e.g.,
from top of
cuts (not product cut to 530F
used for
making OXO
alcohol or
modified
LAB)
54 Branched-enrichedMainly methyl-branchedb-paraffins
stream (Olefinic)paruftins and methyl-branchedb-olefins
(De-diolefinized)olefins will be present
e.g., up to
about 20% (essentially
free of
diolefins and/or
aromatics)
55 Branched-enrichedMainly methyl-branchedb-olefins
olefins
stream (Olefinic)
(De- araffinized)
56 Modified primaryMainly modified primarymodified primary
OXO OXO
OXO alcohols alcohols plus trace alcohols
parafl-ms
57 Modified primaryModified primary modified primary
OXO alcohols OXO
OXO alCOllOIS a1C011015
(freed from
recyclable
materials
58 Crude modifiedMainly modified primarymodified primary
OXO OXO
primary OXO alcohols plus some alcohols
alpha-,
alcohols omega- diols, plus
trace
parafTins
59 modified Mainly methyl-branchedb-paraflins
alkylbenzenesparaiTins plus up modified alkylbenzenes
plus to about 30%
parafTns modified alkylbcnzenes
GO Modified primaryMainly methyl-branchedb-paratTn
OXO alcohols paralTins plus up modified primary
plus to about 25% OXO
parafTns modified primary alcohols
OXO alcohols
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61 linear plus Mainly line'~r paraffinsb-paraffins
methyl- and
branched methyl-branched para~ns,1-paraffns
olefins
in
parutlins linear olefins and b-olefins
methyl-
branched olefins I-olefins
will be present,
e.g., at up to about
20%
(essentially free
of diolefins
and/or aromatics)
(The linear compounds
effectively "dilute"
the
branched)
62 linear and Mainly linear olefinsb-olefins
methyl- and
branched methyl-branched olefinsI-olefins
olefins
63 mixture of Mainly conventional modified primary
OXO OXO
modified alcohols and modifiedalcohols
primary primary
OXO alcoholsOXO alcohols, plus linear OXO alcohols
and trace
conventionalOXOparlffins
alcohols
64 another mixtureMainly conventional modified primary
of OXO OXO
modified alcohols and modifiedalcohols
primary primary
OXO alcoholsOXO alcohols, withoutliner OXO alcohols
and trace
conventionalOXOparafftns
alcohols
65 mixture in Mainly linear parall'tnsb-paraflms
and
paraffins methyl-branched paraffinsI-paraffins
of plus
modified up to about 25% conventionalmodified primary
primary OXO
OXO alcoholsOXO alcohols (the alcohols
and primary
conventionalOXO alcohol type linear OXO alcohols
OXO formed from
alcohols OXO reaction on a
linear
feedstock) and modified
primary
OXO alcohols
66 mixture in Mainly linear paraffinsb-paraffins
and
paraffins methyl-branched paraffinsI-paraffins
of plus
mixtures up to about 30% linearmodified alkylbenzenes
of
modified alkylbenzenes and I-alkylbenzenes
modified
alkylbenzenesalkylbenzenes
and
linear
alkylbenzenes
The hydrocarbon feeds exemplified in the table hereinabove should of course be
viewed as illustrative and not limiting of the present invention. Any other
suitable
hydrocarbon feed may be used. For example, crackates of petroleum waxes
including
crackates of Fischer-Tropsch waxes. These waxes are from Tube oil distillate
fractions and
5 melt in the relatively low range up to about 72°C, e.g., in the range
from about 50°C to
about 70°C and contain from about 18 to about 36 carbon atoms. Such
waxes preferably
contain 50% to 90% normal alkanes and 10% to 50% of monomethyl branched
alkanes
and low levels of various cyclic alkanes. Such crackate feeds are especially
useful in
alternate embodiments of the invention as further described in detail
hereinafter, and are
to described in "Chemical Economics Handbook", published by SRI, Menlo Park,
California.
See, for example, "Waxes", S595.5003 L, published 1995. Paraffin waxes are
also
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3G
described in Kirk Othmer's Encyclopedia of Chemical Technology, 3'd. Edition,
(1984),
Volume 24. See "Waxes" at page 473. Any equivalent alternative hydrocarbon
feeds or
more preferably shorter-chain equivalents in the C 10-C20 range and having
appreciable
monomethyl-branching in any position on the chain, for example from Fischer-
Tropsch
synthesis, are also suitable.
Hydrocarbon feeds herein can contain varying amounts ofN,O,S impurity. Certain
preferred hydrocarbon feeds, especially if derived from sulfur- and/or
nitrogen-containing
fractions, are desulfurized and/or freed from nitrogenous matter using
conventional
desulfurization or "de-NOS' technology.
to Hydrocarbon feeds herein can be separated before use in the present
processes so
that the maximum amount of hydrocarbons having specific chainlengths and/or
degrees of
branching are most ei~ectively utilized to make modified alkylbenzenes and/or
modified
primary OXO alcohols. For example, though not specifically illustrated in the
Figures, it
may be desirable to use two para~n cuts from kerosene for two essentially
parallel
processes, each as described herein, one including an alkylation stage to form
modified
alkylbenzene, and one including an OXO stage to form modified primary OXO
alcohols.
In such a dual process, it might typically be preferred to use a cut having
overall lower
carbon number for the modified alkylbenzene manufacturing (for example a cut
rich in
C11-C13 hydrocarbons), while a heavier cut, for example one richer in C14-C17
2o hydrocarbons might be used for making modified OXO alcohols. Other process
permutations include using multiple hydrocarbon streams or cuts for
concurrently
manufacturing both modified and non-modified (conventional) alkylbenzenes
and/or OXO
alcohols.
Adsorptive Separation Step(sl
In general, separation techniques in stage (a) or stage (A) of the instant
processes
rely on adsorption on porous media and/or use of clathrates. A landmark patent
on
adsorptive separation is US 2,985,589 which illustrates devices, adsorbent
beds and
process conditions of temperature and pressure generally suitable for use
herein. '589 does
not describe critical modifications, especially pore sizes for specific
separations and
3o connection of steps, that are part of the present invention.
Adsorptive separation steps herein can, in general, be conducted in the vapor
phase
or the liquid phase, and may or may not employ any of the commercialized
process
equipment as identified in the background of the invention.
Porous media used as adsorbents can in general be dried or non-dried.
Preferred
embodiments include those wherein the adsorbents are dried and contain less
than about
2% free moisture.
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37
Any adsorptive separation step according to the present invention may, or may
not
use a desorbent or displacing agent. In general, any desorption means, such as
pressure-
swing or other means, can be used. However, preferably such desorbing agent is
used, in
other words, solvent displacement is a preferred method of desorbing streams
from the
porous media used herein. Suitable desorbents or displacing agents include a
lower- -
molecular weight n-paraffin such as heptane, octane or the like, or a polar
desorbent such
as ammonia. It should be understood that, irrespective of their presence, such
well-known
desorbents, being fully conventional, are not explicitly included in
identifying any of the
streams or their compositions in the processes herein, and can be recycled at
will using
to desorbent recycle steps not explicity shown in Figs. 1-18.
In the present process, stage (a) can use a MOLEX~ process step of UOP,
subject to the difference that the present process must have at least one
adsorptive
separation using a porous material which has larger pores than the usual 5
Angstrom
zeolite as used in linear alkylbenzene manufacture. MOLEX~ is discussed in the
hereinabove-identified Surfactant Science Series Vol. 56, including for
example pages 5-
10. Vapor-phase processes such as Union Carbide' s IsoSiv process (see the
same
reference) are also useful but less preferred.
Apparatus and operating conditions for the MOLEX~ process in any version used
herein are well-known; see, for example the above-identified reference at page
9 showing
2o the process and its various streams including raffnate and absorbent in
detail.
Porous Media (Larger-pore Types)
Porous media required in stage (a) or stage (A) herein are larger-pore types.
By
"larger-pore" is specifically meant porous media having pores large enough to
retain
mono-methyl-branched linear olefinic or paraffinic hydrocarbons and dirnethyl-
branched or
trimethyl-branched linear olefinic or paraffinic hydrocarbons other than gem-
dimethyl
hydrocarbons, while being small enough to at least partly exclude gem-
dimethyl, ethyl and
higher-branched hydrocarbons as well as cyclic (e.g., 5-, 6-membered rings)
and aromatic
hydrocarbons. Such pore sizes large enough to retain appreciable amounts of
methyl-
branched hydrocarbons are invariably not used in conventional linear
alkylbenzene
3o manufacture and in general are far more rarely used in any commercial
processes than are
the more familiar 4 - 5 Angstrom pore size zeolites. The larger-pore porous
media are
those used in Figs. 1-7 in the adsorptive separation units marked as "SOR
5/7".
Porous media essential in stage (a) or stage (A) herein accordingly have a
minimum
pore size larger than the pore size reduired for selective adsorption of
linear acyclic
hydrocarbons, i.e., in excess of those used in conventional linear
alkylbenzene
manufacture, said pore size not exceeding about 20 Angstroms, more preferably
not
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38
exceeding about 10 Angstroms and very preferably, from above about 5 Angstroms
to
about 7 Angstroms on average. When specifying minimum pore size for the so-
called
"larger-pore" porous materials herein, it should be recognized that such
materials often
have elliptical pores, for example SAPO-11 has a pore size of 4.4 by 6.7
Angstrom. (5.55
Angstrom average). See S. Miller, Microporous Materials, Vol. 2., pages 439-
449 (1994).
When comparing such a material with a "smaller-pore" zeolite such as a 4-S
Angstrom
uniform-pore zeolite, the convention herein is to look to the aver a of
elliptical
dimensions or the lamer elliptical dimension - in any event not to the smaller
elliptical
dimension - when making the size comparison. Thus the SAPO-11 material herein
by
1o definition has a pore size larger than a 5 Angstrom, uniform-pore zeolite.
Porous media having the larger pores essential in stage (a) or stage (A)
herein can
be either zeolites (aluminosilicates) or non-zeolites.
Suitable non-zeolites include the silicoaluminophosphates, especially SAPO-11
though other silicoaluminophosphates, e.g., SAPO 31 or 41, can be used if the
average
pore size is greater than about S Angstroms or if elliptical pores are present
with at least
one elliptical dimension above 5 Angstroms.
Another technique suitable for adsorptive separation herein is sorption using
pyrolyzed poly(vinylidene chloride) i.e., pyrolyzed SARAN, for example
manufactured
according to Netherlands Application NL 7111508 published October 25, 1971.
Preferred
2o materials have sieve diameter of from 4-7 Angstrom. When using such
material as the
essential adsorbent, a pore size above about 5 Angstrom will be used.
Use of Or~anometallic-crafted Mordenites and other grafted zeolites as Porous
Media in Sta~~(a) or Stag~A)
The present invention also includes especially useful embodiments wherein the
adsorptive separations of stage (a) or stage (A) comprise at least one
separation step using
an organometallic-grafted mordenite. Especially suitable as the "large-pore"
porous ,
media herein are grafted mordenites such as a tin-grafted mordenite. Likewise,
and more
generally, the invention encompasses a method comprising use of a grafted
mordenite for
manufacturing detergent surfactants and any of the corresponding surfactants
and
3o consumer products produced by use of these specific porous media in any of
the above-
defined processes. See EP 559,510 A 9/8/93 incorporated by reference in its
entirety. The
practitioner will select those grafted mordenites of EP 559,510 which are
clearly
identifiable from the Examples thereof to be best suited for separations of
linear and
monomethyl-branched hydrocarbons from gem-dimethyl and polymethyl
hydrocarbons.
Other grafted zeolites useful as the porous media herein include those of US
5,326,928, also incorporated by reference in its entirety. In such embodiments
of the
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39
instant invention, it is especially preferred to integrate into a single
process the use both of
the above-identified grafted mordenite in stage (a), and the use of an at
least partially
dealuminized H-mordenite in step (c), the alkylation step defined elsewhere
herein.
On this basis, using the terminology of US 5,326,928 to describe the process
s module containing the grafted component and combining therewith the
preferred alkylation
step as defined herein, the present invention also encompasses a process for
making
modified alkylbenzenes and/or modified alkylbenzenesulfonates, said process
comprising:
(a) at least one stage of separating aliphatic parafFns having varying degrees
of branching
in a hydrocarbon charge containing molecules of 9 to 14 carbon atoms into at
least one
to first effluent comprising less branched (linear and monomethyl, optionally
some dimethyl-
branched} paraf~ns and at least one second effluent comprising more branched
parafftns
(trimethyl and higher-branched parafFns and optionally cyclic and/or aromatic
impurities),
said separation comprising contacting the hydrocarbon charge with at least one
adsorbent
bed comprising at least one microporous solid (as defined in US 5,326,928)
having grafted
15 in the pores thereof an organometallic compound of a quantity and shape
sufficient to yield
pores selective for entry of the less branched paraffins but not the more
branched paraf~ns;
(b) at least one stage of alkylating a less branched effluent of stage (a),
preferably in an
alkylation having internal isomer selectivity of from 0 to 40, and more
preferably still,
using an at least partially dealuminized, at least partially acidic H-
mordenite as catalyst;
2o and (c) at least one stage of sulfonating the product of stage (b) using
any conventional
sulfonating agent. The resulting modified alkylbenzenesulfonic acid can be
neutralized and
incorporated into cleaning products as taught elsewhere herein.
In stage (a) or stage (A) of the present process, there is a preference to use
zeolites
or other porous media in such a form that they do not actively promote
chemical reactions
25 of the feedstock., e.g., cracking, polymerization. Thus, acidic mordenite
is preferably
avoided in stage (a) or stage (A). See in contrast alkylation catalysts
hereinafter, in which
at least partial acid-form is preferred.
Porous Media (Smaller-pare Tvaes)
Smaller-pore zeolites optionally useful in stage (a) or stage (A) herein, for
example
3o those used in processes such as those of the adsorptive separation unit
identified as "SOR
4/5" in Figs. l, 2, 5, 6, 9, etc. are those which selectively adsorb linear
hydrocarbons and
which do not adsorb methyl-branched hydrocarbons appreciably. Such porous
materials
are well-known and include, for example, Calcium Zeolites with 4-5 Angstrom
pores.
Such materials are further illustrated in US 2,985,589 and are those in
current commercial
35 use for manufacture of linear alkylbenzenes.
Porous Media (e.g.. OLEX ~ or similar processes)
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When making modified primary OXO alcohols herein, it may be desirable to
conduct an olefin/paraffin separation step in stage (C) to concentrate mono-
olefins. See
"SOR O / P" in the Figures and stage (C) in the claims. Suitable porous media
for this
stage include copper- or silver- treated zeolite X or zeolite Y. See, for
example, US
5 5,300,71 S or US 4,133,842, and references cited therein. See also US
4,036,744 and US
4,048,11 I . Alternatively, UOP Corp., a technology licenser, has an entire
process known
as OLEX ~ available for license.
Clathration
Urea clathration can also be used herein in stage (a) for separating n-
paraffins from
to branched paraffins, as is well known in the art. See, for example,
Surfactant Science
Series, Marcel Dekker, N.Y., 1996, Vol. 56, , pages 9-10 and references
therein. See also
"Detergent Manufacture Including Zeolite Builders and other New Materials, Ed.
Sittig.,
Noyes Data Corp., 1979, pages 25-30 and especially US 3,506,569 incorporated
in its
entirety which uses solid urea and no chlorocarbon solvents. More generally
but less
15 preferably, processes according to US 3,162,627 may be used.
Dehydrogenation
In general, dehydrogenation of the olefin or olefin/paraffin mixtures in the
instant
process can be accomplished using any of the well-known dehydrogenation
catalyst
systems, including those described in the Surfactant Science Series references
cited in the
2o background as well as in "Detergent Manufacture Including Zeolite Builders
and Other
New Materials", Ed. Sittig, Noyes Data Corp., New Jersey, 1979 and other
dehydrogenation catalyst systems, for example those commercially available
though UOP
Corp. Dehydrogenation can be conducted in presence of hydrogen gas and
commonly a
precious metal catalyst (e.g., DeH-5 ~, DeH-7 ~ , DeH-9 ~ available from UOP)
is
25 present though alternatively non-hydrogen, precious-metal free
dehydrogenation systems
such as a zeolite/air system can be used with no precious metals present.
More specifically, dehydrogenation catalysts useful herein include a catalyst
supported
on Sn-containing alumina and having Pt: O.I6%, Ir: 0.24%, Sn: 0.50%, and Li:
0.54% as
described in US 5,012,027 incorporated by reference. This catalyst, when
contacted with
3o a C9-C14 paraffin mixture (believed to be linear) at 500°C and 0.68
atm. produces olefinic
products (38h on stream) with 90.88% selectivity and 11.02% conversion and is
believed
to be very suitable for at least partially dehydrogenating branched-enriched
streams of
paraffins herein. See also US 4,786,625; EP 320,549 Al 6/21/89; Vora et al.,
Chem. Age
India (1986), 37(6), 415-18;
35 As noted supra, dehydrogenation can be complete or partial, more typically
partial.
When partial, this step forms a mixture of olefin (e.g., about 10% though this
figure is
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41
illustrative and should not be taken as limiting) and the balance unreacted
paraffin. Such
mixture is a suitable feed for the alkylation step of the instant process.
Other useful dehydrogenation systems readily adapted into the present
invention
include those of US .4,762,960 incorporated by reference which discloses a Pt-
group metal
containing dehydrogenation catalyst having a modifier metal selected from the
group
consisting of Sn; Ge, Re and their mixtures, an alkali metal, an alkaline
earth metal or their
mixtures, and a particularly defined refractory oxide support.
Alternative dehydrogenation catalysts and conditions useful herein include
those of US
4,886,926 and of US 5,536,695.
to A1 lation
Important embodiments of the present invention further include alkylation,
which takes
place after delinearization by separative enrichment of lightly branched
paraffn and at least
partial dehydrogenation of the delinearized olefin or olefin/paraffm mixtures.
Alkylation is
conducted with an aromatic hydrocarbon selected from benzene, toluene and
mixtures
thereof.
Internal Isomer Selectivity and Selection of Alkylation Step
Preferred embodiments of the present processes require an alkylation step
having
internal isomer selectivity in the range from 0 to 40, preferably from 0 to
20, more
preferably still from 0 to 10. The Internal Isomer Selectivity or "IIS" as
defined herein is
2o measured for any given alkylation process step by conducting a test
alkylation of benzene
by 1-dodecene at a molar ratio of 10:1. The alkylation is conducted in the
presence of an
alkylation catalyst to a conversion of dodecene of at least 90% and formation
of
monophenyldodecanes of at least 60%. Lnternal isomer selectivity is then
determined as:
IIS = 100 * ( 1- amount of terminal phenyldodecanes )
amount of total phenyldodecanes
wherein amounts are amounts of the products by weight; the amount of terminal
phenyldodecanes is the amount of the sum of 2-phenyldodecane and 3-
phenyldodecane
3o and the amount of total phenyldodecanes is the amount of the sum of 2-
phenyldodecane
and 3- phenyldodecane and 4-phenyldodecane and S- phenyldodecane and 6-
phenyldodecane and wherein said amounts are determined by any known analytical
technique for alkylbenzenesulfonates such as gas chromatography. See
Analytical
Chemistry, Nov. 1983, 55 (13), 2120-2126, Eganhouse et al, "Determination of
long-chain
alkylbenzenes in environmental samples by argentation thin-layer
chromatography - high
resolution gas chromatography and gas chromatography / mass spectrometry". In
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42
computing IIS according to the above formula, the amounts are divided before
subtracting
the result from 1 and multiplying by 100. It should of course be understood
that the
specific alkenes used to characterize or test any given alkylation step for
suitability are
reference materials permitting a comparison of the alkylation step herein with
known
alkylation steps as used in making linear alkylbenzenes and permitting the
practitioner of
the invention to decide if a given known alkylation step is, or is not, useful
in the context
of the series of process steps constituting the present invention. In the
process of the
invention as practiced, the hydrocarbon feedstock for alkylation actually used
is of course
that which is specified on the basis of the preceding process steps. Also to
be noted, all
to the current commercial processes for LAS manufacture are excluded from
preferred
embodiments of the present invention solely on the basis of the IIS for the
alkylation step.
For example, LAS processes based on aluminum chloride, HE and the like all
have IIS
outside of the range specified for the instant process. In contrast, a few
alkylation steps
described in the literature but not currently applied in commercial
alkylbenzenesulfonate
production do have suitable IIS and are useful herein.
The better to assist the practitioner in determining IIS and in deciding
whether a
given alkylation process step is suitable for the purposes of the present
invention, the
following are more particular examples of IIS determination.
As noted, test alkylation of benzene by 1-dodecene is conducted at a mole
ratio of
10:1 benzene to 1-dodecene and the aikylation is conducted in the presence of
an
alkylation catalyst to a conversion of dodecene of at least 90% and formation
of
monophenyldodecanes of at least 60%. The alkylation test must in general be
conducted
in a reaction time of less than 200 hours and at a reaction temperature of
from about
ISoC to about SOOoC, preferably from about 20oC to 500oC. Pressure and
catalyst
concentration relative to 1-dodecene can vary widely. No solvent other than
benzene is
used in the test alkylation. The process conditions used to determine the IIS
for the
catalyst or alkylation step in question can be based on the literature. The
practitioner will
use generally appropriate conditions based on a large body of well-documented
data for
alkylations. For example, appropriate process conditions to determine if an
AlCl3
3o alkylation can be used herein are exemplified by a reaction of 5 mole %
A1C13 relative to
1-dodecene at 20-40oC for 0.5-1.0 hour in a batch reactor. Such a test
demonstrates that
an A1C13 alkylation step is unsuitable for use in the present process. An IIS
of about 48
should be obtained. In another example, an appropriate test of alkylation
using HF as a
catalyst should give an IIS of about 60. Thus, neither AICl3 alkylation nor HF
alkylation
is within the scope of this invention. For a medium-pore zeolite such as a
dealuminized
mordenite, process conditions suitable for determining IIS are exemplified by
passing 1-
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dodecene and benzene at a mole ratio of 10:1 across the mordenite catalyst at
a WHSV of
30 Hr-1 at a reaction temperature of about 200oC and a pressure of about 200
psig which
should give an IIS of about 0 for the mordenite catalyst. The temperatures and
pressures
for the exemplary mordenite alkylation test (see also the detailed examples of
the instant
process hereinafter) are expected to be more generally useful for testing
zeolites and other
shape-selective alkylation catalysts. Using a catalyst such as H-ZSM-4 one
should obtain
an IIS of about 18. Clearly both the dealuminized mordenite and H-ZSM-4
catalyzed
alkylations give acceptable IIS for the invention, with the mordenite being
superior.
Without intending to be limited by theory, it is believed that the low-IIS
alkylation
to step practiced using H-mordenites herein is capable bath of alkylating
benzene with the
branched-enriched hydrocarbon, but very usefully also of scrambling the
position of a
methyl branch attached to the hydrocarbon chain.
Alkwlation Catalyst
Accomplishing the required IIS in the alkylation process step is made possible
by a
is tightly controlled selection of alkylation catalysts. Numerous alkylation
catalysts are
readily determined to be unsuitable. Unsuitable alkylation catalysts include
the DETAL~
process catalysts, aluminum chloride, HF, HF on zeolites, fluoridated
zeolites, non-acidic
calcium mordenite, and many others. Indeed no alkylation catalyst currently
used for
alkylation in the commercial production of detergent linear
atkylbenzenesulfonates has yet
2o been found suitable.
In contrast, suitable alkylation catalyst herein is selected from shape-
selective
moderately acidic alkylation catalysts, preferably zeolitic. The zeolite in
such catalysts for
the alkylation step (step (b)) is preferably selected from the group
consisting of mordenite,
ZSM-4, ZSM-12, ZSM-20, offretite, gmelinite and zeolite beta in at least
partially acidic
25 form. More preferably, the zeolite in step (b) (the alkylation step) is
substantially in acid
form and is contained in a catalyst pellet comprising a conventional binder
and further
wherein said catalyst pellet comprises at least about 1 %, more preferably at
least 5%,
more typically from SO% to about 90%, of said zeolite.
More generally, suitable alkylation catalyst is typically at least partially
crystalline,
3o more preferably substantially crystalline not including binders or other
materials used to
form catalyst pellets, aggregates or composites. Moreover the catalyst is
typically at least
partially acidic. Fully exchanged Ca-form mordenite, for example, is
unsuitable whereas
H-form mordenite is suitable. This catalyst is useful for the alkylation step
identified as
step (b) in the claims hereinafter: these correspond to Step 7 in Fig. 1.
35 The pores characterizing the zeolites useful in the present alkylation
process may
be substantially circular, such as in cancrinite which has uniform pores of
about 6.2
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44
angstroms, or preferably may be somewhat elliptical, such as in mordenite. It
should be
understood that, in any case, the zeolites used as catalysts in the alkylation
step of the
present process have a major pore dimension intermediate between that of the
large pore
zeolites, such as the X and Y zeolites, and the relatively small pore size
zeolites ZSM-5
and ZSM-11, and preferably between about 6A and about 7A. Indeed ZSM-5 has
been
tried and found inoperable in the present invention. The pore size dimensions
and crystal
structures of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE
TYPES by W. M. Meier and D. H. Olson, published by the Structure Commission of
the
International Zeolite Association ( 1978 and more recent editions) and
distributed by
1o Polycrystal Book Service, Pittsburgh, Pa.
The zeolites useft~l in the alkylation step of the instant process generally
have at
least 10 percent of the cationic sites thereof occupied by ions other than
alkali or alkaline-
earth metals. Typical but non-limiting replacing ions include ammonium,
hydrogen, rare
earth, zinc, copper and aluminum. Of this group, particular preference is
accorded
ammonium, hydrogen, rare earth or combinations thereof. In a preferred
embodiment, the
zeolites are converted to the predominantly hydrogen form, generally by
replacement of
the alkali metal or other ion originally present with hydrogen ion precursors,
e.g.,
ammonium ions, which upon calcination yield the hydrogen form. This exchange
is
conveniently carried out by contact of the zeolite with an ammonium salt
solution, e.g.,
2o ammonium chloride, utilizing well known ion exchange techniques. In certain
preferred
embodiments, the extent of replacement is such as to produce a zeolite
material in which at
least 50 percent of the cationic sites are occupied by hydrogen ions.
The zeolites may be subjected to various chemical treatments, including
alumina
extraction (dealumination) and combination with one or more metal components,
particularly the metals of Groups IIB, III, IV, VI, VII and VIII. It is also
contemplated
that the zeolites may, in some instances, desirably be subjected to thermal
treatment,
including steaming or caicination in air, hydrogen or an inert gas, e.g.
nitrogen or helium.
A suitable modifying treatment entails steaming of the zeolite by contact with
an
atmosphere containing from about 5 to about 100 percent steam at a temperature
of from
3o about 250°C to 1000°C. Steaming may last for a period of
between about 0.25 and about
100 hours and may be conducted at pressures ranging from sub-atmospheric to
several
hundred atmospheres.
In practicing the desired alkylation step of the instant process, it may be
useful to
incorporate the above-described intermediate pore size crystalline zeolites in
another
material, e.g., a binder or matrix resistant to the temperature and other
conditions
employed in the process. Such matrix materials include synthetic or naturally
occurring
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substances as well as inorganic materials such as clay, silica, and/or metal
oxides. Matrix
materials can be in the form of gels including mixtures of silica and metal
oxides. The
latter may be either naturally occurring or in the form of gels or gelatinous
precipitates.
Naturally occurring clays which can be composited with the zeolite include
those of the
5 montmorillonite and kaolin families, which families include the sub-
bentonites and the
kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others
in
which the main mineral constituent is halloysite, kaolinite, dickite, nacrite
or anauxite.
Such clays can be used in the raw state as originally mined or initially
subjected to
calcination, acid treatment or chemical modification.
to In addition to the foregoing materials, the intermediate pore size zeolites
employed
herein may be compounded with a porous matrix material, such as alumina,
silica-aiumina,
silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-
titania, as well as
ternary combinations, such as silica-alumina-thoria, silica-alumina-zirconia,
silica-alumina-
magnesia and silica-magnesia-zirconia. The matrix may be in the form of a
cogel. The
15 relative proportions of finely divided zeolite and inorganic oxide gel
matrix may vary
widely, with the zeolite content ranging from between about 1 to about 99
percent by
weight and more usually in the range of about 5 to about 80 percent by weight
of the
composite.
A group of zeoIites which includes some useful for the alkylation step herein
have a
2o silica:alumina ratio of at least 10:1, preferably at least 20:1. The
silica:alumina ratios
referred to in this specification are the structural or framework ratios, that
is, the ratio for
the Si04 to the A104 tetrahedra. This ratio may vary from the silica:alumina
ratio
determined by various physical and chemical methods. For example, a gross
chemical
analysis may include aluminum which is present in the form of rations
associated with the
25 acidic sites on the zeolite, thereby giving a low silica:alumina ratio.
Similarly, if the ratio is
determined by thermogravimetric analysis (TGA) of ammonia desorption, a low
ammonia
titration may be obtained if cationic aluminum prevents exchange of the
ammonium ions
onto the acidic sites. These disparities are particularly troublesome when
certain
treatments such as the dealuminization methods described below which result in
the
3o presence of ionic aluminum free of the zeolite structure are employed. Due
care should
therefore be taken to ensure that the framework silica:alumina ratio is
correctly
determined.
Zeolite beta suitable for use herein (but less preferred than H-mordenite) is
disclosed in U.S. Pat. No. 3,308,069 to which reference is made for details of
this zeolite
35 and its preparation. Such a zeolite in the acid form is also commercially
available as
Zeocat PB/H from Zeochem.
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4G
When the zeolites have been prepared in the presence of organic cations they
are
catalytically inactive, possibly because the intracrystalline free space is
occupied by organic
cations from the forming solution. They may be activated by heating in an
inert atmosphere
at 540°C. for one hour, for example, followed by base exchange with
ammonium salts
followed by caicination at 540°C. in air. The presence of organic
cations in the forming
solution may not be absolutely essential to the formation of the zeolite; but
it does appear
to favor the formation of this special type of zeolite. Some natural zeolites
may sometimes -
be converted to zeolites of the desired type by various activation procedures
and other
treatments such as base exchange, steaming, alumina extraction and
calcination. The
1o zeolites preferably have a crystal framework density, in the dry hydrogen
form, not
substantially below about 1.6 g.cm -3. The dry density for known structures
may be
calculated from the number of silicon plus aluminum atoms per 1000 cubic
Angstroms, as
given, e.g., on page 19 of the article on Zeolite Structure by W. M. Meier
included in
"Proceedings of the Conference on Molecular Sieves, London, April 1967",
published by
the Society of Chemical Industry, London, 1968. Reference is made to this
paper for a
discussion of the crystal framework density. A further discussion of crystal
framework
density, together with values for some typical zeolites, is given in U. S.
Pat. No. 4,016,218,
to which reference is made. When synthesized in the alkali metal form, the
zeolite is
conveniently converted to the hydrogen form, generally by intermediate
formation of the
2o ammonium form as a result of ammonium ion exchange and calcination of the
ammonium
form to yield the hydrogen form. It has been found that although the hydrogen
form of the
zeolite catalyzes the reaction successfully, the zeolite may also be partly in
the alkali metal
form.
EP 466,558 describes an acidic mordenite type alkylation catalyst also of
possible
use herein having overall Si/AI atomic ratio of 15-85 ( I S-60), Na weight
content of less
than 1000 ppm (preferably less than 250 ppm), having low or zero content of
extra-
network Al species, and an elementary mesh volume below 2,760 nm3.
US 5,057,472 useful for preparing alkylation catalysts herein relates to
concurrent
dealumination and ion-exchange of an acid-stable Na ion-containing zeolite,
preferably
3o mordenite effected by contact with a 0.5-3 (preferably 1-2.5) M HN03
solution containing
su~cient NH4N03 to fully exchange the Na ions for NH4 and H ions. The
resulting
zeolites can have an Si02:A12O3 ratio of 15-26 (preferably 17-23):1 and are
preferably
. calcined to at least partially convert the NH4/H form to an H form.
Optionally, though not
necessarily particularly desirable in the present invention, the catalyst can
contain a Group
VIII metal (and optionally also an inorganic oxide) together with the calcined
zeolite of
'472.
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47
Another acidic mordenite catalyst useful for the alkylation step herein is
disclosed
in US 4,861,935 which relates to a hydrogen form mordenite incorporated wish
alumina,
the composition having a surface area of at least 580 m2 /g. Other acidic
mordenite
catalysts useful for the alkylation step herein include those described in US
5,243,116 and
US 5,198,595. Yet another alkylation catalyst useful herein is described in US
5,175,135
which is an acid mordenite zeolite having a silica/alumina molar ratio of at
least 50:1, a
Symmetry Index of at least 1.0 as determined by X-ray diffraction analysis,
and a porosity
such that the total pore volume is in the range from about 0.18 cc/g to about
0.45 cc/g
and the ratio of the combined meso- and macropore volume to the total pore
volume is
to from about 0.25 to about 0.75.
Particularly preferred alkylation catalysts herein include the acidic
mordenite
catalysts ZeocatT"' FM-8/25H available from Zeochem; CBV 90 A available from
Zeolyst
International, and LZM-8 available from UOP Chemical Catalysts.
Most generally, any alkylation catalyst may be used herein provided that the
alkylation step meets the internal isomer selectivity requirements identified
supra.
Most generally, any alkylation catalyst may be used herein provided that the
alkylation step meets the internal isomer selectivity requirements identified
supra.
Distillation of Modified Al>~lbenzenes or Modified Prima~r r OXO Alcohols
Optionally, depending on feedstock and the precise sequence of steps used, the
present
2o process can include distillation of modified alkylbenzenes or modified
primary OXO
alcohols, for example to remove unreacted starting materials, paraffins,
excesses of
benzene and the like. Any conventional distillation apparatus can be used. The
general
practice is similar to that used for distillation of commercial linear
alkylbenzenes (LAB) or
OXO alcohols. Suitable distillation steps are described in the hereinabove-
referenced
Surfactant Science Series, e.g., the review of alkylbenzenesulfonate
manufacture.
Sulfonation / Sulfation and Workua
In general, sulfonation of the modified alkylbenzenes or sulfation of modified
primary OXO alcohols (or their alkoxylates) in the instant process can be
accomplished
using any of the well-known sulfonation systems, including those described in
the
3o hereinabove-referenced volume "Detergent Manufacture Including Zeolite
Builders and
Other New Materials" as well as in the hereinabove-referenced Surfactant
Science Series
review of alkylbenzenesulfonate manufacture. Common sulfonation systems
include
sulfuric acid, chlorosulfonic acid, oleum, sulfur trioxide and the like.
Sulfur trioxide/air is
especially preferred. Details of sulfonation using a suitable air/sulfur
trioxide mixture are
provided in US 3,427,342, Chemithon. Sulfonation processes are further
extensively
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48
described in "Sulfonation Technology in the Detergent Industry", W.H. de
Groot, Kluwer
Academic Publishers, Boston, 199 l .
Any convenient workup steps may be used in the present process. Common
practice is to neutralize after sulfonation with any suitable alkali. Thus the
neutralization
step can be conducted using alkali selected from sodium, potassium, ammonium,
magnesium and substituted ammonium alkalis and mixtures thereof. Potassium can
assist
solubility, magnesium can promote soft water performance and substituted
ammonium can
be helpful for formulating specialty variations of the instant surfactants.
The invention
encompasses any of these derivative forms of the modified
alkylbenzenesulfonate
to surfactants, or of the sulfated modified primary OXO alcohols, or of the
alkoxylated,
sulfated modified primary OXO alcohols as produced by the present process and
their use
in consumer product compositions.
Alternately the acid form of the present surfactants can be added directly to
acidic
cleaning products, or can be mixed with cleaning ingredients and then
neutralized.
Post-alkylation steps
As noted, the modified alkylbenzene manufacturing process herein includes
embodiments having steps that take place subsequent to the alkylation step
(c). These
steps preferably include (d) sulfonating the product of step (c); and one or
more steps
selected from (e) neutralizing the product of step (d); and (fj mixing the
product of step
(d) or (e) with one or more cleaning product adjunct materials; thereby
forming a cleaning
product.
Blended Embodiments
In one preferred embodiment, prior to said sulfonation step, modified
alkylbenzene
which is the product of said step (c) is blended with a linear alkylbenzene
produced by a
conventional process. In another such embodiment, in any step subsequent to
said
sulfonation step, modified alkylbenzene sulfonate which is the product of said
step (d) is
blended with a linear alkylbenzene produced by a conventional process. In
these blended
embodiments, a preferred process has a ratio of modified alkylbenzene to
linear
alkylbenzene of from about 10:90 to about 50:50.
Corresponding blending schemes are of course likewise applicable to modified
primary
OXO alcohol processes herein. Moreover, any blends can be made of the
different types
of surfactant, or their precursors, herein. For example, the practitioner can
freely blend
modified alkylbenzene with modified primary OXO alcohol as made herein,
alkoxylate the
mixture using ethylene oxide, propylene oxide, etc., and then sulfate /
sulfonate the
resulting mixture. Moreover, since in general, modified OXO alcohols can be
separated by
distillation and various other OXO alcohols including linear OXO alcohol types
are known
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49
from the art, the present invention also includes processes of blending any of
the modified
or branched OXO alcohols attainable herein with any known linear OXO alcohol
in any
proportion, such as from about 1:100 to about 100:1 by weight branched:linear
OXO
alcohol, and of converting any of such OXO alcohol blends to surfactants
useful for
detergents.
Other Process Embodiments
The present invention also encompasses a process for beneficiating an effluent
stream from the manufacture of linear alkylbenzenesulfonate surfactants useful
in cleaning
products, said process comprising (i) at least partially separating an
isoparaffin into a
to normal paraffin enriched stream and an effluent stream having the form of
an isoparaffin
(especially methyl branched paraffin) enriched stream comprising at least
about 10%
isoparaffin and having molecular weight of at least about 128 and no more than
about 282
wherein said separation comprises at least one step selected from clathration
by means of
urea and separation by means of sorption and wherein said steps are integral
in a process
for linear alkylbenzene manufacture; (ii) at least partially further enriching
the isoparaffin
content of said effluent stream by at least one step selected from urea
clathration and
adsorptive separation; wherein said step is additional to and follows step
(i); and (iii) a step
of at least partially dehydrogenating the isoparaffin enriched stream of said
step (ii).
More generally, it is contemplated that the hydrocarbons produced herein can
be
2o useful not only in modified alkylbenzenesulfonate surfactants as
nonlimitingly illustrated
herein but also in modified surfactants other than alkylbenzenesulfonates
(such as alkyl
sulfates). Thus the present invention also encompasses a process for
beneficiating a
branched paraffinic effluent stream comprising (i) at least partially
separating an isoparaffin
into a normal paraffin enriched stream and an effluent stream having the form
of an
isoparaffin enriched stream comprising at least about 10% isoparaffin wherein
said
separation comprises at least one step selected from clathration by means of
urea and
separation by means of sorption; (ii) at least partially further enriching the
isoparaffin
content of said effluent stream by at least one step selected from urea
clathration and
adsorptive separation; wherein said step is additional to and follows step
(i); and (iii) a step
of at least partially dehydrogenating the isoparaf~n enriched stream of said
step (ii).
In such embodiments, the isoparaffin enriched stream may vary from about C10
to
about C20 in overall carbon content and the nonlinear fraction of said
enriched stream
comprises an average of from about one to about two methyl side chains other
than
terminal methyl side-chains per molecule and further, the nonlinear fraction
of said
enriched stream preferably comprises less than about 30%, more preferably less
than about
10%, more preferably still less than about 1% of molecules having quaternary
carbon
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i0
atoms and less than 50%, preferably less than about 10%, more preferably less
than about
1% of molecules having gem-dimethyl substitution.
Process Embodiments incorporating hydroformylation OXO reaction)
As noted in the summary, the present invention also has process embodiments
involving converting hydrocarbons, via certain sorptive separation selections,
into new and
useful modified primary OXO alcohols which can be used to make exceptionally
soluble
sulfates, poly(alkoxy)sulfates, and poly(alkoxylates). These are only
illustrative. The
modified versions of any other surfactant types known in the art to be
derivable from OXO
alcohols are, of course, included in the present invention. With respect to
such a process
1o embodiment, broadly defined in the summary, a preferred process herein has
in stage (A)
means comprising one, two or more of said devices and at least two of said
beds, at least
one of said beds comprising said porous media differentiated relative to the
porous media
contents of another of said beds by an increased capacity to retain methyl-
branched acyclic
aliphatic hydrocarbons. Moreover, preferably, said stage (D) comprises a one-
step OXO
stage wherein said OXO catalyst is a phosphine-coordinated transition metal
other than
iron.
In more detail, in such a preferred process, at least one of said beds
comprises
porous media conventional for the manufacture of linear alkylbenzenes; said at
least one
bed having a connection into said process suitable for at least partially
increasing the
2o proportion of methyl-branched acyclic aliphatic hydrocarbons in streams
passing to said
stage (B) of said process, and suitable for at least partially decreasing the
proportion of
linear acyclic aliphatic hydrocarbons passing to said stage (B) of said
process, said linear
acyclic aliphatic hydrocarbons being at least partially being removed as the
linear-enriched
stream in said stage (A).
Conveniently, in one such process embodiment, said simulated moving bed
adsorptive separation means in said stage (A) comprise - one of said device,
provided that
said device is capable of simulating movement of said porous media in at least
two of said
at least one bed; or- at least two of said device.
Also encompassed herein is the process wherein there are two of said at Least
one
3o bed, each comprising a different member of said porous media, each of said
at least one
bed being controlled by one of said device, and each of said device having a
minimum of
eight ports for achieving simulated movement of said porous media in said at
least one
bed. See, for example, Fig. 9 wherein unit SOR 4/5 comprises one type of
porous media
as defined in more detail elsewhere herein, and unit SOR 5/7 comprises another
type. The
"devices" referred to can especially be chosen from special rotary valve
devices, as
described in detail in various patents identified in the "Background Art"
section. See also
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51
Fig. 8 which, though it illustrates more particularly a process having an
alkylation step,
more detail of a suitable arrangement of sorptive separation units, rotary
valves and
ancilliary equipment is shown. It should therefore be understood that the
devices, sorption
media and equipment are all individually known; it is rather the selection of
devices and
how they should be connected which is essential for the present inventive
purposes to
arrive at superior OXO alcohols and the derivative surfactants.
The present invention accordingly also encompasses a process of the OXO-
alcohol -
producing type wherein said linear-enriched stream is present in said stage
(A) and said
stage (A) comprises: (A-i) adsorptive separation of said hydrocarbon feed into
said Iinear-
to enriched stream and an intermediate branched-enriched stream and rejection
of said linear-
enriched stream by means of one of said simulated moving bed adsorptive
separation
means; followed by (A-ii) adsorptive separation of said intermediate branched-
enriched
stream into said branched-enriched stream comprising an increased proportion
of branched
acyclic aliphatic hydrocarbons relative to said intermediate branched-enriched
stream, and
said reject stream comprising at least an increased proportion of cyclic
and/or aromatic
hydrocarbons relative to said branched -enriched stream, by means of another
of said
simulated moving bed adsorptive separation means.
Preferably in such embodiment, all of said beds comprises porous media not
conventional for the manufacture of linear alkylbenzenes (for example a SAPO-
11
2o containing unit SOR 5/7 or other equivalent molecular sieve of a pore size
larger than is
used in making linear alkylbenzenes) said porous media having pore sizes
suitable for, and
being connected into said process, in a manner consistent with at least
partially increasing
the proportion of methyl-branched plus linear acyclic aliphatic hydrocarbons
in streams
passing to said step (B) of said process, and at least partially decreasing
the proportion of
cyclic, aromatic and/or ethyl-branched or higher, aliphatic hydrocarbons
passing to said
step (B) of said process, said hydrocarbons other than said linear- and methyl-
branched
hydrocarbons being at least partially being removed as a reject stream in said
stage (A).
Suitably in the OXO-alcohol making embodiments of the present process, said
hydrocarbon feed comprises at least about 10% methyl-branched paraffins having
3o molecular weight of at least about 128 and no more than about 282. See the
tables
elsewhere herein for additional description of suitable feeds.
Crude feed materials in the OXO-alcohol processes herein are desirably
distilled
before use. For example as non-limitingly illustrated by the distillation unit
at the
beginning of the processes shown in Figs. 9-18. In this example the
hydrocarbon feed (as
it proceeds from such a distillation unit into the remainder of the process)
comprises a
narrow cut of not more than about three carbon atoms (preferably not more than
about
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52
two carbon atoms) in the range CIO to C17. Such cuts can be single carbon
cuts, two-
carbon cuts, three-carbon cuts, or cuts comprising a nonexact range of carbon
numbers,
such as a one-and-one-half carbon cut. Suitable cuts are further illustrated
by a C11-C13
cut, a C 14-C 15 cut, and a C I S-C 17 cut, though it is not intended to
exclude other cuts
such as a C 16.5 cut. Such cuts designated by nonintegral carbon numbers can
be
generated by any means, such as blending shorter and longer single carbon
number
fractions. Thus a C16.5 cut can be made by blending C16 and C17 or by blending
C14
and C 17, etc. Preferred cuts have narrower "spread" of carbon numbers in a
blend.
Alternatively, the distillation could be performed directly on the olefinic
branced enriched
to stream just before the oxo reaction on the olefinic branced enriched stream
to produce the
desired cut.
It should of course be understood and appreciated for practical purposes that
when
distilling hydrocarbons herein, the desirable methyl-branched hydrocarbons
will be
generally lower in boiling-point than the linear hydrocarbons having equal
carbon number.
Therefore, a preferred cut boiling in a range intermediate between a linear
C15 and a linear
C16 para~n (and thus apparently a cut having nonintegral carbon number) will
be
relatively rich in methyl-branched isomers having a tote) of 16 carbon atoms
which are
desirable for the present process.
Very unusually, if not uniquely, for an OXO-alcohol making process, said
hydrocarbon feedstock is an adsorptive separation raffinate deriving from a
linear
alkylbenzene manufacturing process ar from a conventional linear detergent
alcohol
process. In other words, the present invention opens up all manner of new
possibilities for
combining linear alkylbenzene manufacturing and/or conventional linear
detergent alcohol
process and OXO alcohol manufacturing in a manner not hitherto accomplished.
This
results in better utilization of the feeds. Moreover, when using the invention
as taught
herein, new alkylbenzenes and OXO alcohols are accessible. These can be made
on their
own, or can be made in any permutation with conventional linear alkytbenzenes
and/or
OXO alcohols by configuring the plant appropriately using the steps taught
herein.
Once the modified primary OXO alcohol has been made, it can of course be
3o converted in the same plant or at a remote facility to another useful
derivative. For
example, the present process can have the additional stage or stages in
sequence selected
from: (E) sulfating and neutralizing the product of said stage (D);(F)
alkoxylating the
product of said stage (D); and (G) alkoxylating, sulfating and neutralizing
the product of
said stage (D).
Moreover once surfactant derivatives of the above kinds have been made, they
can
readily be incorporated into all manner of cleaning compositions. For this
purpose,
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53
colocated in the same facility or remotely situated, the present process can
have the
additional step of (H) mixing the product of the preceding stages with one or
more
cleaning product adjunct materials; thereby forming a cleaning product.
Although as will be seen from the Background Art section, various OXO alcohols
are already well known, see for example the Shell and/or Sasol processes, it
has not
previously been suggested to apply the kinds of specific sorptive separation
prior to the
OXO stage which are specifically identified here. Moreover it has not been
suggested to
use, at least with respect to detergents, hitherto unuseful parts of streams
available from
linear alkylbenzene manufacture. From either the crude feed selection, or the
use of the
specific sorptive separation stages, or both, the composition of the resulting
OXO alcohols
is changed relative to the Shell and Sasol processes and makes them very
useful for the
manufacture of surfactants, especially for low wash temperature, demanding
solubility
(compact granules, tablets) or high water hardness applications. All of this
is
accomplished with great economy. In view of the compositional changes imparted
to the
OXO alcohols, the invention also encompasses modified primary OXO alcohol
produced
by any of the present processes.
Likewise the invention encompasses any consumer cleaning product produced by
the above-described processes that include the specific OXO alcohol
manufacture shown
herein, followed by a stage comprising admixing at least one cleaning product
adjunct
ingredient.
In other variations, the processes herein include those in which prior to said
OXO
stage, (D), the product of said stage (B) or (C) is blended with a
conventional detergent
olefin; or wherein the product of any of said stages (E), (F) or (G) are
blended with a
conventional detersive surfactant.
Although there are many configurations in which the present process makes it
possible to prepare concurrently or in alternate processing cycles both
modified
alkylbenzenes and modified primary OXO alcohols, one such nonlimiting process
according to the invention further comprising at least one stage of reacting
the product of
stage (A) with an aromatic hydrocarbon selected from the group consisting of
benzene,
3o toluene and mixtures thereof in the presence of an alkylation catalyst; for
making modified
(crystallinity-disrupted) alkylbenzenes, said alkylation catalyst has an
internal isomer
seiectivity of from 0 to 40. Ramifications include providing means are
provided to route
the product of stage (C) to stage (D), to said alkylation step, or to both of
said stages in
parallel. See the Figures for further illustration.
More generally, the invention also encompasses a detergent or cleaning
composition comprising (a) an effective amount of a detersive surfactant
selected from
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s4
alkyl sulfates, alkylpoly(alkoxy)sulfates, alkylpoly(alkoxylates) and mixtures
thereof, said
surfactant incorporating (preferably in an amount of up to one mole of, more
preferably,
about one mole of) the R-O- radical of an R = C9-C20 detergent alcohol of
formula ROH,
wherein R is mixtures of methyl branched and some linear chains and said
alcohol is
further characterized in that it comprises the product of at least one Fischer-
Tropsch
process stage or an oligomerization or dimerization or skeletal isomerization
stage or
olefin and/or paraffin provision stage (e.g., via the above adsorptive
separations or
alternate processes such as wax hydroisomerization / cracking, Flexicoking ~,
Fluidcoking
~ etc.) and at least one OXO process stage; provided that in at least one
stage prior to
to said OXO process stage there is present a sorptive separation stage having
the effect of
increasing the proportion of methyl-branched olefin used as feed in said OXO
process
stage; and (b) one or more adjuncts at least partially contributing to the
useful properties
of the composition.
Also encompassed herein is a detergent or cleaning composition comprising (a)
an
effective amount of a detersive surfactant selected from alkyl sulfates,
alkylpoly(alkoxy)sulfates, alkylpoly(alkoxylates) and mixtures thereof, said
surfactant
incorporating (preferably in an amount of up to one mole of, more preferably
about one
mole of) the R-O- radical of an R = C9-C20 detergent alcohol of formula ROH,
wherein R
is mixtures of methyl branched and some linear chains and said alcohol is
further
2o characterized in that it comprises the product of any of the hereinabove-
described modified
primary OXO alcohol making processes; and (b) one or more adjuncts at least
partially
contributing to the useful properties of the composition.
Cleaning Product Embodiments
Cleaning product embodiments of the present invention include laundry
detergents,
dishwashing detergents, hard surface cleaners and the like. In such
embodiments, the
content of modified alkylbenzenesulfonate or surfactant derived from modified
primary
OXO alcohol produced by the instant process is from about 0.1 % to about
99.9%,
typically from about 1 % to about 50%, and the composition further comprises
from about
0.1% to about 99.9%, typically from about I% to about 50%, of cleaning product
adjunct
3o materials such as cosurfactants, builders, enzymes, bleaches, bleach
promoters, activators
or catalysts, and the like.
The present invention also encompasses a cleaning product formed by the
instant
process comprising:
(a) from about 0.1 % to about 99.8%, more typically up to about 50%, of
modified
alkylbenzenesulfonate surfactant or modified primary OXO alcohol derived
surfactant
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such as modified alkyl sulfate, modified poly(alkoxy)sulfate etc., as prepared
herein
and
(b) from about 0.00001 %, more typically at least about 1 %, to about 99.9% of
one or
more of said cleaning product adjunct materials.
5 Adjunct materials can vary widely and accordingly can be used at widely
ranging
levels. For example, detersive enzymes such as proteases, amylases,
cellulases, lipases and
the like as well as bleach catalysts including the macrocyclic types having
manganese or
similar transition metals all useful in laundry and cleaning products can be
used herein at
very low, or less commonly, higher levels.
to Other cleaning product adjunct materials suitable herein include bleaches,
especially the
oxygen bleach types including activated and catalyzed forms with such bleach
activators
as nonanoyfoxybenzenesulfonate and/or tetraacetylethylenediamine and/or any of
its
derivatives or derivatives of phthaloylimidoperoxycaproic acid or other imido-
or amido-
substituted bleach activators including the lactam types, or more generally
any mixture of
15 hydrophilic and/or hydrophobic bleach activators (especially acyl
derivatives including
those of the C6-C16 substituted oxybenzenesulfonates); preformed peracids
related to or
based on any of the hereinbefore mentioned bleach activators, builders
including the
insoluble types such as zeolites including zeolites A, P and the so-called
maximum
aluminum P as wei) as the soluble types such as the phosphates and
polyphosphates, any
20 of the hydrous, water-soluble or water-insoluble silicates, 2,2'-
oxydisuccinates, tartrate
succinates, glycolates, NTA and many other ethercarboxylates or citrates,
chelants
including EDTA, S,S'-EDDS, DTPA and phosphonates, water-soluble polymers,
copolymers and terpolymers, soil release polymers, cosurfactants including any
of the
known anionic, cationic, nonionic or zwitterionic types, optical brighteners,
processing
25 aids such as crisping agents and/fillers, solvents, antiredeposition
agents, silicone/silica and
other suds suppressors, hydrotropes, perfumes or pro-perfumes, dyes,
photobleaches,
thickeners, simple salts and alkalis such as those based on sodium or
potassium including
the hydroxides, carbonates, bicarbonates and sulfates and the like. When
combined with
the modified alkylbenzenesulfonate surfactants of the instant process, any of
the
30 anhydrous, hydrous, water-based or salvent-borne cleaning products are
readily accessible
as granules, tablets, powders, flakes, gels, extrudates, pouched or
encapsulated forms or
the like. Accordingly the present invention also includes the various cleaning
products
made possible or formed by any of the processes described. These may be used
in discrete
dosage forms, used by hand or by machine, or may be continuously dosed into
all suitable
35 cleaning appliances or delivery devices.
Cleaning Products in Detail
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SC
References cited herein are incorporated by reference. The surfactant
compositions prepared by the processes of the present invention can be used in
a wide
range of consumer cleaning product compositions including powders, granules,
gels,
pastes, tablets, pouches, bars, types delivered in dual-compartment
containers, spray or
foam detergents and other homogeneous or multiphasic consumer cleaning product
forms.
They can be used or applied by hand and/or can be applied in unitary or freely
alterable
dosage, or by automatic dispensing means, or are useful in appliances such as
washing-
machines or dishwashers or can be used in institutional cleaning contexts,
including for
example, for personal cleansing in public facilities, for bottle washing, for
surgical
to instrument cleaning or for cleaning electronic components. They can have a
wide range of
pH, for example from about 2 to about 12 or higher, and they can have a wide
range of
alkalinity reserve which can include very high alkalinity reserves as in uses
such as drain
unblocking in which tens of grams of NaOH equivalent can be present per 100
grams of
formulation, ranging through the 1-10 grams of NaOH equivalent and the mild or
low-
alkalinity ranges of liquid hand cleaners, down to the acid side such as in
acidic hard-
surface cleaners. Both high-foaming and low-foaming detergent types are
encompassed.
Consumer product cleaning compositions are described in the "Surfactant
Science
Series", Marcel Dekker, New York, Volumes 1-67 and higher. Liquid compositions
in
particular are described in detail in the Volume 67, "Liquid Detergents", Ed.
Kuo-Yann
Lai, 1997, ISBN 0-8247-939!-9 incorporated herein by reference. More classical
formulations, especially granular types, are described in "Detergent
Manufacture including
Zeolite Builders and Other New Materials", Ed. M. Sittig, Noyes Data
Corporation, 1979
incorporated by reference. See also Kirk Othmer's Encyclopedia of Chemical
Technology.
Consumer product cleaning compositions herein nonlimitingly include:
Light Duty Liquid Detergents (LDL~ these compositions include LDL
compositions having surfactancy improving magnesium ions (see for example WO
97/00930 A; GB 2,292,562 A; US 5,376,310; US 5,269,974; US 5,230,823; US
4,923,635; US 4,681,704; US 4,316,824; US 4,133,779) and/or organic diamines
and/or
various foam stabilizers and/or foam boosters such as amine oxides (see for
example US
4,133,779) and/or skin feel modifiers of surfactant, emollient and/or
enzymatic types
including proteases; and/or antimicrobial agents; more comprehensive patent
listings are
given in Surfactant Science Series, Vol. 67, pages 240-248.
Heavy Duty Liduid Deterrents ~HDLO these compositions include both the so
called "structured" or multi-phase (see for example US 4,452,717; US
4,526,709; US
4,530,780; US 4,618,446; US 4,793,943; US 4,659,497; US 4,871,467; US
4,891,147;
US 5,006,273; US 5,021,195; US 5,147,576; US 5,160,65.5) and "non-structured"
or
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57
isotropic liquid types and can in general be aqueous or nonaqueous (see, for
example EP
738,778 A; WO 97/00937 A; WO 97/00936 A; EP 752,466 A; DE 19623623 A; WO
96/10073 A; WO 96/10072 A; US 4,647,393; US 4,648,983; US 4,655,954; US
4,661,280; EP 225,654; US 4,690,771; US 4,744,916; US 4,753,750; US 4,950,424;
US
5,004,556; US 5,102,574; WO 94/23009; and can be with bleach (see for example
US
4,470,919; US 5,250,212; EP 564,250; US 5,264,143; US 5,275,753; US 5,288,746;
WO
94/11483; EP 598,170; EP 598,973; EP 619,368; US 5,431,848; US 5,445,756)
and/or
enzymes {see for example US 3,944,470; US 4,111,855; US 4,261,868; US
4,287,082; US
4,305,837; US 4,404,11 S; US 4,462,922; US 4,529,5225; US 4,537,706; US
4,537,707;
to US 4,670,179; US 4,842,758; US 4,900,475; US 4,908,150; US 5,082,585; US
5,156,773; WO 92/19709; EP 583,534; EP 583,535; EP 583,536; WO 94/04542; US
5,269,960; EP 633,31 1; US 5,422,030; US 5,431,842; US 5,442,100) or without
bleach
and/or enzymes. Other patents relating to heavy-duty liquid detergents are
tabulated or
listed in Surfactant Science Series, Vol. 67, pages 309-324.
IS Heaw Duty Granular Deter_~ents (HDG~ these compositions include both the so-
called "compact" or agglomerated or otherwise non-spray-dried, as well as the
so-called
"flufl~y" or spray-dried types. Included are both phosphated and nonphosphated
types.
Such detergents can include the more common anionic-surfactant based types or
can be
the so-called "high-nonionic surfactant" types in which commonly the nonionic
surfactant
2o is held in or on an absorbent such as zeolites or other porous inorganic
salts. Manufacture
of HDG's is, for example, disclosed in EP 753,571 A; WO 96/38531 A; US
5,576,285;
US 5,573,697; WO 96/34082 A; US 5,569,645; EP 739,977 A; US 5,565,422; EP
737,739 A; WO 96/27655 A; US 5,554,587; WO 96/25482 A; WO 96/23048 A; WO
96/22352 A; EP 709,449 A; WO 96/09370 A; US 5,496,487; US 5,489,392 and EP
25 694,608 A.
"Softer~ents" STW): these compositions include the various granular or liquid
(see for example EP 753,569 A; US 4,140,641; US 4,639,321; US 4,751,008; EP
315,126; US 4,844,821; US 4,844,824; US 4,873,001; US 4,911,852; US 5,017,296;
EP
422,787) softening-through-the wash types of product and in general can have
organic
30 (e.g., quaternary) or inorganic (e.g., clay) softeners.
Hard Surface Cleaners (HSC~: these compositions include a(I-purpose cleaners
such as cream cleansers and liquid all-purpose cleaners; spray all-purpose
cleaners
including glass and tile cleaners and bleach spray cleaners; and bathroom
cleaners including
mildew-removing, bleach-containing, antimicrobial, acidic, neutral and basic
types. See,
35 for example EP 743,280 A; EP 743,279 A. Acidic cleaners include those of WO
96/34938
A.
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Bar Soaps and/or Laundry Bars (BS&HW~ these compositions include personal
cleansing bars as well as so-called laundry bars (see, for example WO 96/35772
A);
including both the syndet and soap-based types and types with softener (see US
5,500,137
or WO 96/01889 A); such compositions can include those made by common soap-
making
techniques such as plodding and/or more unconventional techniques such as
casting,
absorption of surfactant into a porous support, or the like. Other bar soaps
(see for
example BR 9502668; WO 96/04361 A; WO 96/04360 A; US 5,540,852 ) are also
included. Other handwash detergents include those such as are described in GB
2,292,155
A and WO 96/01306 A.
1o Shampoos and Conditioners yS&Cl: (see, for example WO 96/37594 A; WO
96/17917 A; WO 96/17590 A; WO 96/17591 A). Such compositions in general
include
both simple shampoos and the so-called "two-in-one" or "with conditioner"
types.
Liquid Soaps (LS): these compositions include both the so-called
"antibacterial"
and conventional types, as well as those with or without skin conditioners and
include
types suitable for use in pump dispensers, and by other means such as wall-
held devices
used institutionally.
Special Purpose Cleaners (SPCI: including home dry cleaning systems (see for
example WO 96/30583 A; WO 96/30472 A; WO 96/30471 A; US 5,547,476; WO
96/37652 A); bleach pretreatment products for laundry (see EP 751,210 A);
fabric care
2o pretreatment products (see for example EP 752,469 A); liquid fine fabric
detergent types,
especially the high-foaming variety; rinse-aids for dishwashing; liquid
bleaches including
both chlorine type and oxygen bleach type, and disinfecting agents,
mouthwashes, denture
cleaners (see, for example WO 96/19563 A; WO 96/19562 A), car or carpet
cleaners or
shampoos (see, for example EP 751,213 A; WO 96/15308 A), hair rinses, shower
gels,
foam baths and personal care cleaners (see, for example WO 96/37595 A; WO
96/37592
A; WO 96/37591 A; WO 96/37589 A; WO 96/37588 A; GB 2,297,975 A; GB 2,297,762
A; GB 2,297,761 A; WO 96/17916 A; WO 96/12468 A) and metal cleaners; as well
as
cleaning auxiliaries such as bleach additives and "stain-stick" or other pre-
treat types
including special foam type cleaners (see, for example EP 753,560 A; EP
753,559 A; EP
753,558 A; EP 753,557 A; EP 753,556 A) and anti-sunfade treatments (see WO
96/03486 A; WO 96/03481 A; WO 96/03369 A) are also encompassed.
Detergents with enduring perfume (see for example US 5,500,154; WO 96/02490)
are increasingly popular.
Process Integration
The present process can be integrated with current LAB manufacturing processes
or with conventional linear detergent alcohol process in any convenient
manner. For
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example, conventional erected plant can be switched to produce the modified
alkylbenzenes and/or modified primary OXO alcohols in their entirety.
Alternately,
depending on volumes desired or feedstocks available, for example as effluents
from the
LAB process or conventional linear detergent alcohol process or based on
proximity of
feedstock sources from the petrochemical industry, plant for the manufacture
of the instant
modified alkylbenzenes and/or modified primary OXO alcohols may be erected as
an add-
on or complement to an existing LAB facility, or as a stand-alone.
Both batch and continuous operation of the present process are envisaged.
In one add-on mode, the present invention encompasses steps of making
vinylidene
olefrn and from the vinylidene olefin, modified alkylbenzene or alkyltoluene
and/or
modified primary OXO alcohol using the steps described in detail hereinabove.
The
modified alkylbenzene or alkyltoluene is blended at a ratio of from about
1:100 to 100:1,
more typically from about 1:10 to about 10:1, for example about 1:5, into a
conventional
linear alkylbenzene, for example a C 1 I .8 average alkylbenzene or any
alkylbenzene
produced by the DETAL~ process. The blend is then sulfonated, neutralized and
incorporated into consumer cleaning product compositions. Parallel process
stages or
alternate process stages lead to modified primary OXO alcohol.
The present invention should not be considered limited by the specifics of its
illustration in the specification including the examples given for
illustration hereinafter.
Most generally, the present invention should be taken to encompass any
consumer cleaning
composition comprising any surfactant product of any type wherein the
hydrophobe of the
surfactant has been modified by an approach using the essential teachings of
the instant
process. The present teachings, especially with respect to the delinearization
approach, are
believed to be reapplicable, for example, to the manufacture of modified alkyl
sulfates and
other surfactants.
EXAMPLE I
Modified alkylbenzenesulfonate prepared via branched hydrocarbon-containing
feeds
sourced from jet/diesel; with separation over SAPO-11; dehydrogenation;
alkylation over
H-mordenite; sulfonation using sulfur trioxide/air; and neutralization
3o A suitable feed is obtained in the form of a jet/diesel distillation cut
from kerosene.
This feed contains paraffinic branched and linear hydrocarbons, wherein the
linear
hydrocarbons are of suitable chainlen5th for LAB manufacture and wherein the
branched
hydrocarbons include at least about 10% of methyl branched paraffins; along
with cyclic
hydrocarbons, aromatics and other impurities. This stream is passed
continuously to two
adsorptive separation units, connected as shown in Fig. 8 and Fig. 1 wherein
unit AC1 of
detail Fig. 8 is loaded with 5 Angstrom Ca zeofite as used in conventional
linear
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GO
alkylbenzene manufacture and unit AC2 of detail Fig. 8 is loaded with the
silicoaluminophosphate SAPO-l1. The units AC1 and AC2 along with the
associated
rotary valve devices, raf~inate columns and extract columns (RC and EC) and
condensers
(shown as unlabelled horizontal tanks in Fig. 8.) and other means shown,
though
connected in unique manner, are of construction generally in accordance with
units
licensable and commercially available through UOP Corp. (MOLEX~ units). The
adsorbate (extract) from the Ca zeolite adsorptive unit AC 1 is rejected and
the ra~nate is
passed continuously to the second adsorptive separation unit AC2 containing
the SAPO-
11. The branched-enriched stream taken from unit AC2 as adsorbate or extract
is passed
to to a standard commercial LAB process dehydrogenation unit provided by UOP
Corp.
(PACOL~ process) charged with a standard LAB dehydrogenation catalyst (DeH 5~
or
DeH 7~ or similar) proprietary to UOP Corp. After dehydrogenation under
conventional
LAB-making process conditions, the hydrocarbons are passed continuously to an
alkylation unit which is otherwise conventional but is charged with H-
mordenite
(ZEOCAT ~ FM 8/25 H) where alkylation proceeds continuously at a temperature
of
about 200°C with discharge on reaching a completion of at least about
90%, that is, a
conversion of the input hydrocarbon (olefins) of at least about 90%. This
produces a
modified alkylbenzene. In optional variations, the above procedure can be
repeated except
with discharge on reaching a conversion (based on olefin) to the desired
modified
alkylbenzene of at least about 80%. A recycle of paraffins is obtained by
distillation at the
back-end of the alkylation unit and the recycle is passed back to the
dehydrogenator. The
process to this point includes the steps and streams of Fig. 1. The modified
alkylbenzene
can be further purified by additional conventional distillation (such
distillative steps are not
shown in Fig. 1 ). The distilled modified alkylbenzene mixture is sulfonated
batchwise or
continuously, at a remote facility if desired, using sulfur trioxide as
sulfonating agent.
Details of sulfonation using a suitable air/sulfur trioxide mixture are
provided in US
3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product of the
preceding
step is neutralized with sodium hydroxide to give modified alkylbenzene
sulfonate, sodium
salt mixture.
3o EXAMPLE 2
Modified alkylbenzenesulfonate prepared via hydrocarbon feed sourced from
MOLEX
effluent, separation over SAPO-1 l, dehydrogenation using standard UOP method,
alkylation over H-mordenite, sulfonation using sulfur trioxide/air, and
neutralization
A suitable feedstock is obtained in the form of effluent or raffinate from an
LAB plant,
specifically the MOLEX ~ process unit of such a plant. This raffinate contains
a high
proportion of branched paraffinic hydrocarbons along with undesirable cyclic
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G1
hydrocarbons, aromatics and other impurities. This raflinate is passed
continuously to an
adsorptive separation unit constructed conventionally, e.g., after the manner
of a
MOLEX~ unit, but having a charge of SAPO-11. This unit operates under
conditions
generally similar to the MOLEXc~ unit as used in linear alkylbenzene
manufacture and
resembles the unit AC2 described in Example 1. The raf~nate or effluent from
the SAPO-
11 adsorptive unit is rejected and the adsorbate or extract now meeting the
invention
definition of a branched-enriched stream is passed continuously to a standard
commercial
LAB process dehydrogenation unit provided by UOP Corp. (PACOL~ process)
charged
with a standard LAB dehydrogenation catalyst (e.g., DeH 7 ~) proprietary to
UOP Corp.
l0 After dehydrogenation under conventional LAB-making process conditions, the
hydrocarbons are passed continuously to an alkylation unit which is otherwise
conventional but is charged with H-mordenite (ZEOCAT ~ FM 8/25 H) where
alkylation
proceeds continuously at a temperature of about 200°C with discharge on
reaching an
alkylating agent conversion of at least about 90%. The modified alkylbenzene
mixture is
purified by conventional distillation and branched paraffns are recycled to
the
dehydrogenation unit. Steps in the process to this point follow Fig. 4.
The distilled modified alkylbenzene mixture produced in process to this point
is
sulfonated batchwise or continuously, at a remote facility if desired, using
sulfur trioxide
as sulfonating agent. Details of sulfonation using a suitable air/sulfur
trioxide mixture are
2o provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid
product of
the preceding step is neutralized with sodium hydroxide to give modified
alkylbenzene
sulfonate, sodium salt mixture.
EXAMPLE 3
Modified alkytbenzenesulfonate prepared via hydrocarbon feed sourced from
MOLEX
effluent, separation over pyrolyzed poly(vinylidene chloride), dehydrogenation
using
standard UOP method, alkylation over H-ZSM-12, sulfonation using sulfur
trioxide/air and
neutralization
A suitable feedstock is obtained in the form of rafl~inate from an LAB plant,
specifically
the MOLEX~ process unit of such a plant. This raffinate contains branched
paraffinic
3o hydrocarbons along with cyclic hydrocarbons, aromatics and other undesired
impurities.
This raffinate is passed continuously to an adsorptive separation unit of
conventional
construction, e.g., MOLEX type, not conventionally being incorporated in LAB
plant
design and hereinafter termed the "SARAN ~ unit" having a charge of pyrolyzed
poly(vinylidene chloride), sieve diameter >_5 Angstrom, manufactured according
to
Netherlands Application NL 7111508 published October 25, 1971. The "SARAN
unit"
operates under conditions similar to the MOLEX unit. The raflinate from the
"SARAN
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unit" is rejected and the adsorbate is passed continuously to a standard
commercial LAB
process dehydrogenation unit provided by UOP Corp. {PACOL~ process) charged
with a
standard LAB dehydrogenation catalyst such as DeH 7 ~ proprietary to UOP Corp.
After
dehydrogenation under conventional LAB-making process conditions, the
hydrocarbons
are passed continuously to an alkylation unit which is otherwise conventional
but is
charged with H-ZSM 12 where alkylation proceeds continuously at a temperature
of about
200°C with discharge on reaching a conversion of the input hydrocarbon
of at least about
90%. The modified alkylbenzene mixture produced in the preceding step is
distilled and
sulfonated batchwise or continuously using sulfur trioxide as sulfonating
agent. Details of
sulfonation using a suitable air/sulfur trioxide mixture are provided in US
3,427,342,
Chemithon. The modified alkylbenzenesulfonic acid product of the preceding
step is
neutralized with sodium hydroxide to give modified alkylbenzene sulfonate,
sodium salt
mixture.
EXAMPLE 4
Modified alkylbenzenesulfonate prepared via hydrocarbon feed from urea
clathration,
separation over SAPO-I 1, dehydrogenation using Pt catalyst, alkylation over
acidic zeolite
beta, sulfonation using sulfur trioxide/air and neutralization
A suitable feedstock is obtained from kerosene by urea clathration which is
used to
remove a fraction rich in the more commercially valuable linear hydrocarbons.
See US
3,506,569. The low-grade branched effluent from the urea clathration stage is
a suitable
hydrocarbon feed for the present process. It is stripped of any activator
solvent such as
methanol, if present, and is passed continuously to an adsorptive separation
unit
constructed in any conventional manner, for example after the fashion of
MOLEX~
process units, but differently charged, having a charge of SAPO-11. The SAPO-
11 unit
operates under conditions similar to a standard MOLEX~ process unit. The
raf~inate
from the SAPO-I 1 unit is rejected and the adsorbate is passed continuously to
a standard
commercial LAB process dehydrogenation unit provided by UOP Corp. (PACOL~
process) charged with a nonproprietary Platinum dehydrogenation catalyst.
After
dehydrogenation under conventional LAB-making process conditions, the
hydrocarbons
3o are passed continuously to an alkylation unit which is otherwise
conventional but is
charged with Zeocat PB/H~' where alkylation proceeds continuously at a
temperature of
about 200°C with discharge on reaching a conversion of the input
hydrocarbon of at least
about 90%. The modified alkylbenzene mixture produced in the preceding step is
sulfonated batchwise or continuously using sulfur trioxide as sulfonating
agent. Details of
sulfonation using a suitable air/sulfur trioxide mixture are provided in US
3,427,342,
Chemithon. The modified alkylbenzenesulfonic acid product of the preceding
step is
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G3
neutralized with sodium hydroxide to give modified alkylbenzene sulfonate,
sodium salt
mixture.
EXAMPLE 5
Modified alkylbenzenesulfonate prepared via hydrocarbon feed from kerosene cut
from a
high paraffinic petroleum source, separation over grafted nonacidic zeolite,
dehydrogenation using DeH 9 ~ catalyst, alkylation over H-mordenite,
sulfonation using
chlorosulfonic acid, and neutralization
A jet/kerosene cut is taken from a low-viscosity crude, e.g., Brent light.
This is passed
continuously to an adsorptive separation unit constructed in any conventional
manner, for
to example after the fashion of MOLEX~ process units, but differently charged,
having a
charge of grafted zeolite prepared in accordance with US 5,326,928. The unit
operates
under conditions similar to a conventionally charged MOLEX~ unit. The
raffinate from
this unit is rejected and the adsorbate is passed continuously to a standard
commercial
LAB process dehydrogenation unit provided by UOP Corp. (PACOL~ process)
charged
with a standard LAB dehydrogenation catalyst DeH 9 ~ proprietary to UOP Corp.
After
dehydrogenation under conventional LAB-making process conditions, the
hydrocarbons
are passed continuously to an alkylation unit which is otherwise conventional
but is
charged with H-mordenite (ZEOCAT FM 8/25 H) where alkylation proceeds
continuously
at a temperature of about 200°C with discharge on reaching a conversion
of the input
2o hydrocarbon of at least about 90%. The modified alkylbenzene mixture
produced in the
preceding step is sulfonated batchwise or continuously using sulfur trioxide
as sulfonating
agent. Details of sulfonation using a suitable air/sulfur trioxide mixture are
provided in US
3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product of the
preceding
step is neutralized with sodium hydroxide to give modified alkylbenzene
sulfonate, sodium
salt mixture.
EXAMPLE 6
Cleaning product composition
10% by weight of modified alkylbenzenesulfonate sodium salt product of any of
the
foregoing exemplified processes is combined with 90% by weight of an
agglomerated
3o compact laundry detergent granule.
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EXAMPLE 7
Cleaning Product Compositions
In this Example,
the following abbreviation
is used for a modified
alkylbenzene sulfonate,
sodium salt form
or potassium salt
form, prepared according
to any of the preceding
process examples:
MAS
The following abbreviations
are used for cleaning
product adjunct
materials:
Cxy Amine Oxide Alkyldimcthylamine N-Oxide RN(O)Mc2 of given
chainlength
Cay where average total carbon range of
the non-methyl alkyl
moiety R is from 10+x to 10+y
Amylase Antylolytic enzyme of activity GOKNU/g sold
by NOVO
Industries A/S under the tradenamc Termantyl
GOT.
Alternatively, the amylase is selected from:
Fungamyl~;
Durantyl~~; BANS; and a amylase enzymes
described in
W095/2G397 and in co-pending application
by Novo Nordisk
PCT/DK 9G/0005G.
APA C8-CIO amido propyl dimcthyl amine
Cty Betaine AlkyldintethJt Bctaine having an average
total carbon range of
alkyl moiety front 10+x to 10+y
Bicarbonate Anhydrous sodium bicarbonate with a particle
size distribution
bchvecn 400ftm and 1200Etm
Borax Na tetraborate decahvdrate
BPP Butoay - propoay - propanol
Brightener 1 Disodium a,~l'-bis(2-sulphostyi)I)biphenyl
Brightener 2 Disodium ~.~1'-bis(.~-aniliuo-G-morpholino-1.3.5-triazin-2-
yl)amino) stilbcnc-2:2'-disulfonate
CaCl2 Calcium chloride
Carbonate NaZC03 anhydrous, 200Eun - 900Eun
Cellulase Cellulolytic enzyme, 1000 CEVU/g, NOVO,
Carezyme~
Citrate Trisodium citrate dihydralc, 8G.4%,425Etm
- 850 ltm
Citric Acid Citric Acid, Anhydrous
CMC Sodium carboyntethyl cellulose
CayAS All.~1 sulfate, Na salt or other salt if
specified having an average
total carbon range of alkyl moiety from
10+x to 10+y
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Gi
CxyEz Conunercial linear or branched alcohol
cthoxylate (not having
mid-chain methyl branching) and having
an average total
carbon range of alkyl moiety from 10+x
to 10+y average z
moles of elhvlenc oxide
CayEzS Alkyl ethoaylate sulfate, Na salt (or
other salt if specified)
having an average total carbon range
of alkyl moiety from 10+x
to 10+y and an average of z moles of
ethylene oxide
Diamine Alkyl diamine, e.g., l,3 propancdiaminc,
Dytck EP, Dytek A,
(Dupont) or selected from: dimelhyl aminopropyl
amine; 1,G-
hcxane diaminc; 1,3 propane diamine:
2-methyl 1,5 pentane
diaminc; 1,3-pentanediaminc: 1-methyl-diaminopropane;
1,3
cyclohcxanc diaminc; 1,2 cyclohcxanc
diamine
Dimethicone 40(gum)/GO(tluid) w. Blend of SE-7G dimcthicone
gum (G.E
Silicones Div.) / dimethicone fluid of
viscosity 350 eS.
DTPA Dicthylenc triaminc pentaacctic acid
DTPMP Diethylene triamine pcnta (mcthylcnc
phosphonate), Monsanto
(Deducst 2060)
Endolase Endoglucanase, activity 3000 CEVU/g,
NOVO
EtOH Ethanol
Fatty Acid (C12/18)C12-C18 fatty acid
Fatty Acid (C12/14)C12-C14 fatty acid
Fatty Acid (C14/18)Cl-1-CI8 fatty acid
Fatty Acid (RPS)Rapeseed fart)' acid
Fatty Acid (TPK)Topped palm kernel fatty acid
Formate Formatc (Sodium)
HEDP 1,1-hydrovycthane diphosphonic acid
Hydrotrope selected from sodium, potassium, Magnesium,
Calcium,
anunonium or water-soluble substituted
ammonium salts of
toluene sulfonic acid, naplUhalene sulfonic
acid, cumene
sulfonic acid, a~~lene sulfonic acid.
Isofol 12 X12 (avertgc) Guerbet alcohols (Condea)
Isofol IG C1G (average) Gucrbct alcohols (Condca)
LAS Linear Alkylbenzene Sulfonate (e.g.,
C1 1.8, Na or K salt)
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GG
Lipase Lipolytic enzyme , 100kLU/g, NOVO, Lipolase~. Alternatively,
the lipase is selected from: Amano-P; M I Lipase;
LIpOtllax~;
D9GL - lipolytic enzyme variant of the native lipase
derived from
Humicola lanuginosa as described in US Serial No.
08/341,826;
and the Humicola lanuginosa strain DSM 4106.
LMFAA Cl2-14 alkyl N-methyl glucamide
MA/AA Copolymer 1:4 maleic/acn~lic acid, Na s<~lt, avg.
mw. 70,000.
MBA~cEy Mid-chain branched primary, alkyl ethovylate (average
total
carbons = x; average EO = y)
MBAaEyS Mid-chain branched or modified primary alkyl ethoaylate
sulfate, Na salt (average total carbons = x; average
EO = y)
according to the invention (see Example 9)
MBAyS Mid-chain branched primarv_ alkyl sulfate. Na salt
(average total
carbons = y)
MEA Monocthanolaminc
Cxy MES Alkyl methyl ester sulfonate, Na salt having an
average total
carbon range of alkyl moiety from 10+x to 10+y
MgCly Magnesium chloride
MnCAT Macrocyclic Manganese Bleach Catalyst
as in EP 544,440 A or, preferably, use [Mn(Bcyclam)C12]
wherein
Bcyclam = 5,12-dimethyl-I,S,R,l2-tetraaza-bicyclo[6.6.2]hexadecane
or
a comparable bridged tetra-aza macrocycle
NaDCC Sodium dicltloroisocvanurale
NaOH Sodium hydroxide
Cay NaPS Paraffin sulfonate, Na salt having an average
total carbon range
of alkyl moiety from 10+x to 10+y
NaSKS-G Crystalline layered silicate of formula
ti -Na2Si20~
NaTS Sodium toluene sulfonate
NOBS Nonanoyloaybenzene sulfonate, SOdlnlll Salt
LOBS C12 oaybcnzencsulfonate, sodium salt
PAA Polyacrylic Acid (nnv = 4500)
PAE Elhoxylated Ictraethylene pcntaminc
PAEC Methyl quaternizcd cthoaylatcd dihcxylene
triamine
PB1 Anhydrous sodium pcrborate bleach of nominal
formula
NaB02.H202
PEG Polyethylene glycol (mw=4600)
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Percarbonate Sodium Percarbonate of nominal formula
2Na2C03.3H202
PG Propanediol
Photobleach Sulfonated Zinc Plrihalocyanine encapsulated
in dewrin soluble
polymer
PIE Ethoaylated polyethyleneimine, water-soluble
Protease Proteolytic enzy7ne, 4KNPU/g, NOVO, Savinase~~.
Alternatively, the protease is selected
from: Maaatase~;
Maaacal~; Maxapem 15~~; subtilisin BPN
and BPN ; Protease
B: Protease A; Protease D; Primase~; Durazym~;
Opticlean~;and Optimase~; and Alcalase
W
QAS R2.N+(CH3)~((C2H;10)fH)z with R2 = C8
- C18
s+z=3,e=Oto3,z=Oto3,y= I to 15.
Cxy SAS Secondary alkyl sulfate, Na s<~It having
ar average total carbon
range of alkyl moiety from 10+x to 10+y
Silicate Sodium Silicate, amorphous (Si02:Na20;
2.0 ratio)
Silicone antifoamPolydimcthylsiloxane foam controller +
sifoxane-ovyalkylene
copolymer as dispersing agent; ratio of foam
controller:dispcrsing agent = 10:1 to 100:1; or, combination of
finned silica and high viscosip' polfdimcthylsiloxane (optionally
chemically modified)
Solvent nonaqueous Solent e.g., heaylcne glycol,
see also propylene
glycol
SRP 1 Sulfobcnzoyl end capped esters with oaycthylene
oay and
terephthaloyl backbone
SRP 2 Sulfonatcd ethoaylated tereplUhalate polymer
SRP 3 Methyl capped etho~ylated tercplnhalate
polymer
STPP Sodium tripolyphosphate, anhydrous
Sulfate Sodium sulfate, anhydrous
TAED Tetraacctylcthylencdiamine
TFA CIG-18 allc~'I N-methyl glucamide
Zeolite A Hydrated Sodium Aluminosilicate, Nal2(A102Si02)12~
27H20; 0.1 - 10 pm
Zeolite MAP Zeolite (Maximum aluminum P) detergent grade (Crosfield)
Typical ingredients often referred to as "minors" can include perfumes, dyes,
pH trims etc.
The following example is illustrative of the present invention, but is not
meant to
limit or otherwise define its scope. All parts, percentages and ratios used
are expressed as
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GA
percent weight unless otherwise noted. The following laundry detergent
compositions A
to F are prepared in accordance with the invention:
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A B C D E F
MAS 22 16.5 1 1 l - I 0 - 5-35
5.5 25
Any Combination 0 1 - 1 1 16.5 0 - 5 0-10
of 5.5
C45AS
C45E1S
LAS
C26 SAS
C47 NaPS
C48 MES
MBA16.SS
MBA15.SE2S
QAS 0-2 0-2 0-2 0-2 0-4 0
C23E6.5 or C45E7 1.5 1.5 1.5 I .5 0 - 4 0 - 4
Zeolite A 27.8 0 27.8 27.8 20 - 30 0
Zeolite MAP 0 27.8 0 0 0 0
STPP 0 0 0 0 0 5-65
PAA 2.3 2.3 2.3 2.3 0 - 5 0 - 5
Carbonate 27.3 27.3 27.3 27.3 20 - 30 0 - 30
Silicate 0.6 0.6 0.6 0.6 0 - 2 0 - 6
PB 1 I 1. 0 0-10 0-10 0 - I 0 - 20
. 0
0
NOBS 0- 0-1 0-1 0.1 0. 5-3 0 - 5
I
LOBS 0 0 0-3 0 0 0
TAED 0 0 0 2 0 0-5
MnCAT 0 0 0 0 2 m 0 - 1
Protease 0-0.50-0.5 0-0.5 0-0.5 0-0.5 0- 1
Cellulase 0 0 - 0 - 0 - 0 - 0.5 0 - 1
- 0.3 0.3 0.3
0.3
Am lase 0-0.50-0.5 0-0.5 0-0.5 0- 1 0- 1
SRP 1 orSRP2 0.4 0.4 0.4 0.4 0-1 0-5
Bri htener 1 or 0.2 0.2 0.2 0.2 0 - 0.3 0 -5
2
PEG 1.6 1.6 1.6 1.6 0-2 0-3
Silicone Antifoam0.42 0.42 0.42 0.42 0 - 0.5 0 - 1
Sulfate, Water, to to
Minors to 100%
to
to
to
100%
100%
100%
100%
100%
Density (g/L) 400- 600- 600- 600- 600 - 450-
700 700 700 700 700 750
EXAMPLE 8
Cleaning Product Compositions
The following liquid laundry detergent compositions A to E are prepared in
accord with
the invention. Abbreviations are as used in the preceding Examples.
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_A B C D E
MAS 1 -7 7- 12 12- 17 17-22 1 -35
Any combination of: 15 - 10 - 5 - 10 0 - 0 -
C25E1.8-2.SS 21 15 S 25
MBA15.SE1.8S
MBA15.SS
C25AS (linear to high
2-alkyl)
C47 NaPS
C26 SAS
LAS
C26 MES
LMFAA 0-3.5 0-3.5 0-3.S 0-3.S 0-8
C23E9orC23E6.5 0-2 0-2 0-2 0-2 0-8
APA 0-0.5 0-0.5 0-0.5 0-0.5 0-2
Citric Acid 5 5 S 5 0 -
8
Fatt Acid (TPK or C 2 2 2 2 0 -
I 2/ 14) 14
EtOH 4 4 4 4 0 -
8
PG 6 6 6 6 0-10
MEA I 1 1 I 0-3
NaOH 3 3 3 3 0 -
7
H drotro a or NaTS 2.3 2.3 2.3 2.3 0 -
4
Formate 0.1 0.1 0.1 0.1 0 -
I
Borax 2. 5 2.5 2. S 2.5 0 -
5
Protease 0.9 0.9 0.9 0.9 0 -
1.3
Li ase 0.06 0.06 0.06 0.06 0 -
0.3
Am lase 0.15 0. I 0. I 0.15 0 -
S 5 0.4
Cellulase 0.05 0.05 0.05 0.05 0 -
0.2
PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5
PIE 1.2 1.2 1.2 1.2 0-2.5
PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2
SRP2 0.2 0.2 0.2 0.2 0-0.5
Bri htener 1 or 2 0. I 0.15 0. I 0. I 0 -
5 5 5 0.5
Silicone antifoam 0.12 0.12 0.12 0.12 0 -
0.3
Fumed Silica 0.0015 0.0015 0.0015 0.0015 0-0.003
Perfume 0.3 0.3 0.3 0.3 0 -
0.6
D a 0.0013 0.0013 0.0013 0.0013 0-0.003
Moisture/minors BalanceBalanceBalance BalanceBalance
Product H (10% in D1 7.7 7.7 7.7 7.7 6 -
water 9.5
EXAMPLE 9
In the present Example, a branched-enriched hydrocarbon stream is made and it
is
dehydrogenated, subjected to hydroformylation to make a modified primary OXO
alcohol,
5 ethoxylated and sulfated.
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A suitable crude hydrocarbon feed is obtained in the form of a jet/diesel or
kerosene
distillation cut. This feed is low in sulfur, nitrogen and aromatics (to the
extent that these
are known to have some adverse effect on lifetime of MOLEX ~ and OLEX ~
adsorbent
beds) and contains paraffinic branched and linear hydrocarbons, wherein the
linear
hydrocarbons are of suitable chainlength for detergent manufacture and wherein
the
branched hydrocarbons include at least about 10% of methyl branched paraffns;
along
with cyclic hydrocarbons, aromatics and other impurities.
The crude hydrocarbon feed is distilled to obtain a two-carbon cut at about
C14 - C15.
This forms a suitable hydrocarbon feed for the rest of the process. See Fig.
10, stream 1.
to The distilled hydrocarbon feed is passed continuously to two adsorptive
separation
units, connected as shown in Fig. 10 wherein unit SOR 4/S is loaded with 5
Angstrom Ca
zeolite as used in conventional linear alkylbenzene manufacture, and unit SOR
5/7 is
Loaded with the silicoaluminophosphate SAPO-11. The general construction of
the units
SOR 4/5 and SOR 5/7 and ancilliary equipment not shown in Fig. 10 is in
accordance with
units licensable and commercially available through UOP Corp. (MOLEX~ units).
Not
shown are the desorbent systems and ancilliary distillation and recovery
columns. The
linear-enriched stream (stream 6 in Fig. 10, rich in linear hydrocarbon) from
the Ca zeolite
MOLEX ~ unit SOR 4/S is rejected and the intermediate branched-enriched stream
(stream 2 in Fig. 10, enriched in branched hydrocarbon) is passed continuously
to the
2o second adsorptive separation unit SOR 5/7 containing the SAPO-11. The
branched-
enriched stream taken from unit SOR 5/7 as adsorbate or extract (stream 3 in
Fig. 10,
more branched hydrocarbon) is passed to a standard commercial LAB process
dehydrogenation unit (DEH in Fig. 10) provided by UOP Corp. (PACOL ~ process)
charged with a standard dehydrogenation catalyst (DeH 5 ~ or DeH 7 ~ or
similar)
proprietary to UOP Corp. After partial dehydrogenation (up to about 20%) under
conventional LAB olefin feed preparation process conditions, the branched-
enriched
olefin/paraf~in mixtures (stream 4 in Fig. 10) are passed continuously to
DEFINE ~ and
PEP ~ process units licensed from UOP Corp. These units hydrogenate diolefin
impurity
to monoolefin and help reduce the content of aromatic impurities,
respectively. The
3o resulting purified olefin/paraffin stream (54 in Fig. 10) now passes to an
OLEX ~ process
unit licensed from UOP, charged with olefin separation sorbent proprietary to
UOP Corp.
After olefin separation from unreacted paraffins (the latter are recycled as
stream 8 in Fig.
10), the branched-enriched olefinic hydrocarbons (stream 55 in Fig. 10) are
passed
continuously to an OXO reaction unit operating with a 2-2.5:1 H2:C0 ratio and
using a
pressure of from about 60-90 atm. and a temperature of about 170°C -
about 210°C and
charged with a cobalt organophosphine complex. OXO proceeds continuously with
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72
discharge on reaching a selectivity to the modified primary OXO alcohol of at
least about
90%, and essentially all the olefin of the input stream has reacted. This
produces a
modified primary OXO alcohol according to the invention. A small amount of
reduction
also occurs to form paraffin. The paraffins are separated by distillation and
can be
recycled to the dehydrogenator. The process to this point includes the steps
and streams
of Fig. I0. The modified primary OXO alcohol (stream 57 in Fig. 10) is
ethoxylated to an
average of one mole of ethylene oxide content. Alternatively ethoxylation,
propoxylation
etc. can be done using differing amounts of alkylene oxide to produce the
desired
alkoxylate. This is done batchwise or continuously, at a remote facility if
desired, using
to ethylene oxide and the usual base catalyst (see Schonfeldt, Surface Active
Ethylene Oxide
Adducts, Pergamon Press, N.Y., 19G9). Now the ethoxylated modified OXO alcohol
is
treated batchwise or continuously with sulfur trioxide as sulfating agent (See
"Sulphonation Technology in the Detergent Industry", W, de Groot, Kluwer
Academic
Publishers, London, I991 ). The product of the preceding step is neutralized
with sodium
hydroxide to give modified alkyl ethoxysulfate, sodium salt, according to the
invention. In
variations of the above example, alkyl chain length of the hydrocarbon can be
varied so as
to produce the desired chainlength modified OXO alcohol derived surfactants as
used in
the formulation Examples. In a further variation, the modified OXO alcohol can
be
sulfated without any prior alkoxylation.
2o EXAMPLE 10
A non-limiting example of bleach-containing nonadueous liduid laundry
detergent
is prepared having the composition as set forth in the following Table:
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73
TABLE
Component Wt. /. Range (% w1.)
Liquid Phase
LAS 25.0 18-35
C24E5 or MBA14.3E5 (Example13.G 10-20
9)
Solvent or He~ylene glycol 27.3 20-30
Perfume 0.4 0-1.0
MBA14.4EIS (Example 9) 2.3 I-3.0
Solid Phase
Protease 0,4 0_l.p
Citrate 4.3 3-G
PB 1 3.~1 2-7
NOBS 8.0 2-12
Carbonate 13.9 5-20
DTPA 0.9 0-1.5
Brightener I 0,4 0_
Silicone antifoam 0.1 0-0.3
Minors Balance ----
The resulting composition is an anhydrous
heavy duty
liquid laundry
detergent
which provides excellent soil removal mance when used in normal
stain and perfor fabric
laundering operations.
EXAMPLE 11
Lictuid detereent compositions are made acrnrrl;no tn the fnllnmina
A B C D
MBA14.4E1S (Exam le 9) 2 8 7 5
MBA14.4S (Exam le 9) 1> 12 IU 8
C24 Amine Oaide _ _ - 2
C25AS G 4 G 8
LMFAA 0-5 0-4 0-3 0-3
C24E5 G I 1 1
Fat acid (12/18) I I 4 4 3
Citric acid 1 3 3 2
DTPMP 1 1 1 0.5
MEA 8 i 5 2
NaOH 1 2.5 1 1.5
Solvent or PG 1=4, 13.1 10.0 g
i
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74
EtOH 1.8 4.7 5.4 1
Am lase 0.3 0.3 0.4 0.4
Li ase 0.15 0.1 0. 0.15
S I
5
Protease 0.5 0.5 0.5 0.5)
Endolase 0.05 0.05 0.05 0.05
Cellulase 0.09 0.09 0.09 0.09
SRP3 0.5 - 0.3 0.3
Borax 2.4 2.8 2.8 2.4
H drotro a - 3 _ -
Isofol 12 1 1 1 I
Silicone antifoam 0.3 0.3 0.3 0.3
Water & minors U to
100%
The above liquid detergent compositions (A-D) are found to be very efficient
in the
removal of a wide range of stains and soils from fabrics under various usage
conditions.
EXAMPLE 12
The following compositions (E to J) are heavy duty liquid laundry detergent
COmDOSltlons according to the present invention
Exam le #: E F G H I J
MBA14.4E0.8S 17 15 7.0 7.0 12 12
xam le 9)
C35E3S / C25E3S2.0 9.0 - - 7.0 7.0
C25E2.SS - - 12.0 12.0 -
LMFAA G.0 5.0 0 0 4.0 0
C35E7 G.0 1.0 - - - _
C23E9 - - 2.0 1.0 5.0 5.0
APA - 1.5 - 2.0 - 2.5
Fatty Acid 7.5 i.l 2.0 4.0 5.0 5.0
(C12/C14)
Fatty Acid 3.0 3.5 - _ _ _
C14/C18)
Citric Acid 1.0 3.i 3.0 3.0 3.0 3.0
Protease O.G O.G 0.9 0.9 1.2 1.2
Li ase 0.1 0.1 0.1 0.1 0.2 0.2
Am lase 0.1 0.1 O.l 0.1 - 0.1
Cellulase 0.03 0.03 0.05 0.05 0.2 0.2
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Endolase 0.1 0.1 - - _ _
Bri htener 0.1 0. I - - - _
2
Borax 3.0 3.0 3.5 3.5 4.0 4.0
MEA 8.0 4.0 I.0 l.i 7.0 7.0
NaOH 1.0 4.0 3.0 2.5 1.0 1.0
PG 12.0 12.0 7.~ 7.5 7.0 7.0
EtOH I .0 1.0 3.5 3. i 6.0 6.0
Hvdrotro - - 2.5 2.i - -
Minors BalanceBalance BalanceBalance BalanceBalance
EXAMPLE 13
Aqueous based heavy duty liquid laundry detergent compositions K to O which
comprise
the mid-chain branched surfactants of the present invention are presented
below-
In redient K L _ M ~ N O
MBA14.4E0.8S (Exam le 10 12 14 16 20
9) _
C25E1.8S 10 8 6 4 0
_
C23E9 2 2 2 2 2
LMFAA S 5 S ~ 0
Citric acid 3 3 3 3 5
Fa acid (TPK, RPS or 2 2 2 2 0
C12/14)
PAE 1 1 1.2 1.2 0.5
PG 8 8 8 8 4.5
EtOH 4 4 4 4 2
Borax 3.~ 3.5 3.~ 3.5 2
H drotro a 3 3 2 3 0
H = 8.0 8.0 8.0 8.0 7.0
water and minors balancebalancebalance balancebalance
100% 100% 100% 100% 100%
EXAMPLE 14
The following aqueous liquid laundry detergent compositions P to T are
prepared
in accord with the invention:
P Q R S T
MBA14.4E1S and / or 1 - 7 - 12 - l7 - 1 -
7 12 17 22 35
MBA14.4S (Exam Ic 9)
Any combination of: 1 s 10 - 5 - 0 - 0 -
- 21 15 10 5 25
C25E 1.8-2.5 S
C25AS (linear to hi8h
2-alkyl)
C47 NaPS
C26 SAS
LAS
C26 MES
LMFAA 0-3.~ U-3.i 0-3.i 0-5 0-8
C23E9orC23E6,> 0-2 0-2 0-2 0-2 0-8
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7G
APA 0.5 1 1 1.5 0.5 -
2
Citric Acid S 5 5 5 0 - 8
Fat Acid (TPK, RPS or 2 2 2 10 0 - 14
C12/14
EtOH 4 4 4 4 0 - 8
PG G G G G 0-10
MEA I 1 1 1 0-3
NaOH 3 3 3 3 0 - 7
H drotro a 2.5 2 1.5 1 0 - 4
Borax 2.5 2.5 2.5 2.5 0 - 5
Protease 0.5 0.7 0.9 0.9 0 - 1.3
Li ase 0.0 O.OG 0.15 0.3 0 - 0.3
Am lase 0.15 0.2 0.25 0.3 0 - 0.4
Cellulase 0.0i 0.05 0.2 0.3 0 - 0.2
P~ 0-O.G 0-O.G 0-O.G 0-O.G 0-2.5
P~ 1.2 1.2 1.2 i.2 0 - 2,5
PAEC 0-O.:l 0-0.4 0-0.4 0-0.4 0-2
SItP 2 0.2 0.2 0.2 0.2 0 - 0.5
Bri htener 1 or 2 0. I 0.15 0.15 0.15 0 - 0.5
5
Silicone antifoam 0.12 0.12 0.12 0.12 0 - 0.3
Water and minors BalanceBalanceBalance BalanceBalance
Product H (10% in DI 7.7 7.7 7.7 7.7 6 - 9.5
water)
EXAMPLE I S
Light-duty liduid dishwashing detergent compositions comprising the modified
primary OXO alcohol derived surfactants of the present invention are prepared:
- lngrodient Wt.% Wt.% Wt.% Wt.%
A B C D
MBA13.SEO.GS (Exam le 9) 5 10 20 30
MBA12.SE9 (Exam le 9) 1 1 I 1
C23E1S 25 20 10 0
LMFAA 4 4 4 4
C24 Amine Oxide 4 4 4 4
EO/PO Block Co- olvmer - Tetronic~t0.5 0.5 0.5 0.5
70.1
EtOH _ G G 6
G
H drotro a (Calcium w~lene 5 5 5 5
sulfonate)
Ma nesium++ (added as chloride3.0 3.0 3.0 3.0
Water and minors balance balancebalancebalance
H (cry, 10% (as made) 7.5 7.5 7.5 7.5
E F_ G H I 1
H 10% 9.3 8.5 I 1 10 9 9.2
MBA13.SEO.GS 10 1 > 10 27 27 20
or
MBA13.SS
(Exam le 9)
C25PS 10 0 0 p 0 p
LAS 5 I S 12 0 0 0
C26 Betainc 3 1 0 2 2 0
C24 Amine Oxide0 0 0 2 5 7
LMFAA ~ ~ 0 1 2 0 0
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CilE8 0 0 20 I~ 0 2
H drotro a 0 0 0 _ 0 g
0
Diamine 1 5 7 2 2 5
M ++ (as M C12 1 0 0 .3 0 0
Ca+-+ (as Calcium0 0.5 0 0 0.1 0.1
lene sulfonate)
Protease 0.1 0 0 0.05 O.OG 0.1
Am lace 0 0.07 0 0.1 0 0.05
Li ase 0 0 0.025 0 0.05 0.05
DTPA 0 0.3 0 0 0.1 0.1
Citrate 0.65 0 0 0.3 0 0
Water and Minors(to
100%)
EXAMPLE 16
The following laundry detergent compositions K to O are prepared in accord
with the
invention:
_ K L M N O
MBA14.4EO.SS (Example22 1G.5 11 I - 5.5 10
9 -
25
Any Combination 0 1 - 5.5 11 1G.5 0 -
of: 5
C45AS
C45E1S
LAS
C2GSAS
C47 NaPS
C48 MES
AS 0-2 0-2 0-2 0-2 0-4
C23EG.5 or C45E7 I .5 1.5 1.5 1.5 0 -
4
Zeolite A 27.8 27.8 27.8 27.8 20
-
30
PAA 2.3 2.3 2.3 2.3 0 -
5
Carbonate 27.3 27.3 27.3 27.3 20
-
30
Silicate O.G O.G 0.G O.G 0 -
2
PB 1.0 1.0 1.0 1.0 0 -
3
Protease 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5
Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5
Am lase 0-0.5 0-0.5 0-0.5 0-0.5 0-1
SRP 1 0.4 0.4 0.4 0.4 0 -
1
Bri htener 1 or 0.2 0.2 0.2 0.2 0 -
2 0.3
PEG I.G 1.6 I.G 1.6 0 -
2
Sulfate 5.5 5.5 5.5 5.5 0 -
6
Silicone Alitlf0alll0.42 0.42 0.42 0.42 0 -
0.5
Moisture & Minors ---Balance---
Density (g/L) GG3 GG3 GG3 GG3 G00
-
700
EXAMPLE 17
The following laundry detergent compositions P to T are prepared in accord
with the
invention:
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78
P R S T
MBA14.4E0.4S IG.S 12.5 8.5 4 1 -
xam le 9 25
Any Combination 0 - G 10 I=4 18.5 0 -
of 20
C45AS
C45E1S
LAS
C26 SAS
C47 NaPS
C48 MES
AS 0-2 0-2 0-2 0-2 0-4
TFAA 1.G I.G 1.G I.G 0 -
4
C24E3, C23EG.5 5 5 5 5 0 -
or 6
MBA14.SE5 (Exam
le 9)
Zeolite A IS 15 15 IS 10 -
30
NaSKS-G l I 1 I 1 I 11 5 -
15
Citrate 3 3 3 3 0 -
8
MA/AA 4.8 4.8 4.8 4.8 0 -
8
HEDP 0. S 0.5 0. 5 0. 5 0 -
1
Carbonate 8.5 8.5 8.5 8.5 0 -
15
Percarbonate or 20.7 20.7 20.7 20.7 0 -
PB 1 25
TAED 4.8 4.8 4.8 4.8 0 -
8
Protease 0.9 0.9 0.9 0.9 0 -
1
Li ase 0.15 0.15 0.15 0.15 0 -
0.3
Cellulase 0.2G 0.2G 0.2G 0.2G 0 -
0.5
Am lase 0.3G 0.36 0.3G 0.3G 0 -
0.5
SRP 1 0.2 0.2 0.2 0.2 0 -
0.5
Bri htener 1 or 0.2 0.2 0.2 0.2 0 -
2 0.4
Sulfate 2.3 2.3 2.3 2.3 0 -
25
Silicone Antifoam 0.4 0.4 0.4 0 -
1
Moisture & Minors---Balance---
Densi ( ) 850 850 800 850 850
EXAMPLE 18
The following high density detergent formulations U to X, according to the
present
invention, are prepared:
U V W X
A lomerate
C45AS 11.0 4.0 0 14.0
MBA14.3EO.SS 3.0 10.0 17.0 3.0
(Exam 1e 9)
Zeolite A 15.0 I5.0 I5.0 10.0
Carbonate 4.0 4.0 4.0 8.0
PAA or MA/AA 4.0 4.0 4.0 2.0
CMC 0.5 0.5 0.5 0.5
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DTPMP 0.4 0.4 0.4 0.4
S ra On
MBA14.SE5 5.0 5.U 5.0 5.0
(Exam le 9)
Perfinne 0.5 0.5 0.5 0.5
D Adds
C45AS G.0 G.0 3.0 3.0
HEDP 0.5 0.5 0.5 0.3
SKS-G 13.0 13.0 13.0 6.0
Citrate 3.0 3.0 3.0 1.0
TAED 5.0 5.0 5.0 7.0
Pcrcarbonate 20.0 20.0 20.0 20.0
SRP I 0.3 0.3 0.3 0.3
Protease 1.4 1.4 1.4 1.4
Li ase 0.4 0.4 0.4 0.4
Cellnlase O.G O.G O.G O.G
Amylase O.G O.G O.G 0.6
Silicone antifoam 5.0 5.0 5.0 5.0
Bri htener 1 0.2 0.2 0.2 0.2
Bri htener 2 0.2 0.2 0.2 -
Balance (Water/Miscellaneons)100 100 100 100
Densi itre) 850 850 Bill 850
The present process can use many different hydrocarbon feeds, as already
illustrated herein. Alternate hydrocarbon feeds that can be used in this
process include
mixtures of specific types of paraffins and/or mono-olefins. These hydrocarbon
mixtures
can be selected from:
A. mixtures of paraffins conforming to the formula:
R R' R'
I I I
CH~(CH~)",C H(CH~~CH(C H~)~ C H(CH~)~ CHI
wherein the total number of carbon atoms in the branched primary alkyl moiety
of this
formula (including the R, Rl, and R2 branching) is from 8 to 20, preferably 10
to 20;
preferably from about 10 to about 18; R, Rl, and R2 are each independently
selected from
hydrogen, C l-C3 alkyl, and mixtures thereof with minor proportions of
impurities such as
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C3-C~ cycloalkyl, aryl, arylalkyl and alkaryl, provided preferably from H and
C1-C3 alkyl
(more preferably methyl), provided R, Rl, and R2 are not all hydrogen and,
when z is 0, at
least R or RI is not hydrogen; w, x, y, z are each independently integers from
0 to 13,
subject to the limitation on total carbon number stated supra and w + x + y +
z is
5 preferably from 8 to 14.
More highly preferred paraflins have only H, methyl, ethyl, propyl or butyl in
R, ,
R1, and R2, more preferably only H and methyl, provided R, RI, and R2 include
at least
one alkyl moiety; and methyl, when present, is preferably internal, that is,
removed as
much as possible from the 1-, 2- and preferably even 3- carbon positions in
the longest
to countable chain.
The hydrocarbons herein also encompass:
B. mixtures of mono-olefins. These mono-olefins are related to the paraffins
of A.
above, in that any of the suitable mono-olefins can be made by dehydrogenating
any of the paraffins of A. above. (In practice, one can first isolate suitable
15 olefins, then hydrogenate them to the parafFns). The preferred olefins are
mono-olefins, though in general, up to about 10% by weight of the olefinic
hydrocarbon can be diolefins, after dehydrogenation of suitable paraffins.
Like the paraffins, the olefins herein can vary widely in structure, for
example,
possible mono-olefins are:
20 , /,
H H
H H
or
These structures are of course illustrative and are not to be taken as
limiting.
The hydrocarbons herein also encompass:
C. mixtures of the paraffins of A. and the olefins of B.
25 These hydrocarbon mixtures herein can be in any possible combination, and
can, for
example, be a result of combining compositions containing only paraffins, only
olefins, or
paraffin/olefin mixtures in any proportion. The mixtures can be derived
"inherently" as a
conseduence of the hydrocarbon coming from a natural, e.g., geologically
sourced
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8t
petroleum raw material (e.g., light crude or kerosene or jet/diesel fuels
distilled therefrom),
typically with some treatment of such material (for example by fractionation,
selective
sorption, distillation, clathration etc.) to isolate preferred hydrocarbon
mixtures.
Alternately, the mixtures can be made up by progressively mixing more complex
mixtures
from a series of compositionally simple hydrocarbons. The present hydrocarbon
mixtures
can also derive from any synthetic transformation known in petroleum
chemistry, for
example cracking, hydrocracking, hydroisomerisation, hydrogenation,
dimerization,
dehydrogenation, isomerization, disproportionation, and the like. Moreover,
equivalent
compositions can more painstakingly be built up by means of known organic
synthetic
1o schemes, for example those involving Grignard reactions. Catalytic
isomerizations on
zeolites and modified zeolites can be particularly useful.
Hydrocarbon mixtures useful herein can further include:
D. mixtures of the paraflins of A. and the olefins of B. with other known
olefins and/or
paraffins (especially linear ones) in the same or, less preferably, different
carbon
number range;
And the hydrocarbons herein also encompass:
E. mixtures of A.-D. with benzene or other non-aliphatic hydrocarbons. This
includes the
use of other solvents such as cyclohexane, pentane, toluene, etc.
One group of preferred paraffns have the formula selected from:
CHI
(II) CH~(CH~)"CH(CH~)~,CH;
CHI CH3
(III) CH3(CHz)dCH(CH,)~CHCH~
or mixtures thereof; wherein a, b, d, and a are integers, a+b is from 10 to
16, d+e is from 8
to 14 and wherein further
when a + b = 10, a is an integer from 2 to 5 and b is an integer from S to 8;
when a + b = 11, a is an integer from 2 to 5 and b is an integer from 6 to 9;
when a + b = 12, a is an integer from 2 to 6 and b is an integer from 6 to 10;
when a + b = 13, a is an integer from 2 to 6 and b is an integer from 7 to 11;
when a + b = 14, a is an integer from 2 to 7 and b is an integer from 7 to 12;
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when a + b = 15, a is an integer from 2 to 7 and b is an integer from 8 to 13;
when a + b = 16, a is an integer from 2 to 8 and b is an integer from 8 to 14;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
when d + a = 9, d is an integer from 2 to 8 and a is an integer from 1 to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from 1 to 8;
when d + a = 1 l, d is an integer from 2 to 10 and a is an integer from 1 to
9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
when d + a = 13, d is an integer from 2 to 12 and a is an integer from 1 to
11;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12.
to The present hydrocarbon compositions can accommodate varying amounts of
impurities (say up to about 20%, preferably below about 1 %), such as
impurities in which
one or more ether or alcohol oxygen atoms are present or interrupt the carbon
chain(so
called "oxygenated" impurities); or impurities in which moieties such as aryl,
arylalkyl or
alkaryl are attached to the carbon chain as the branches, or impurities in
which quaternary
carbon atoms are present, or diolefins, or impurities in which nonhydrogen
moieties are
attached to adjacent carbon atoms. Such impurities are of course not desired.
It is
especially preferred to limit any impurities known to adversely affect
biodegradation or to
produce malodors. For greatest mass efficiency, a minimum of the total carbon
content is
placed in any of the side-chains, provided that the resulting hydrocarbon
preferably still has
2o at least one carbon atom in a side-chain. Preferred parat~ns and/or olefins
herein may
contain varying amounts of nonalkylbenzene aromatic, cycloalkyl and alkyl
cycloalkyl
impurities, though these are more desirably removed, for example by known
sorption
steps. Preferred paraffins and/or olefins herein can contain some sulfur
and/or nitrogen,
but these can produce objectionable odors and for this or other reasons are
preferably
removed by any of the desulfurization and/or nitrogen removal techniques well
known in
the petroleum industry.
Preferred olefins are closely related to the paraftins above: they have
structures
formed by dehydrogenating any of the paraf~ns in any accessible position to
form the
corresponding mono-olefin. Especially preferred olefins are monomethyl-
branched and
3o dimethyl-branched, particularly monomethyl-branched.
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It should be understood and appreciated that the underlying concept being
taught
for how to select preferred paraftins and olefins for best results herein
involves several
features including:
(a) making a deliberate selection of mixtures of C 10-C 18 hydrocarbons having
typicatiy_
one or two alkyl substituents, these preferably being as short as possible,
and being
positioned at least in a manner consistent with avoiding biodegradation
issues. Thus the
present hydrocarbons clearly differ substantially from the very non-
biodegradable
tetrapropylene type; and
(b) preferably having at least some methyl moieties which are not in the 2-
position of the
to longest hydrocarbon chain.
Without intending to be limited by theory, it is believed that some of the
more
complex mixtures within the defined ranges have especially superior
characteristics for
forming hydrophobes for highly soluble hardness resistant , cold water
tolerant "modified"
surfactants including the alkylbenzenes and oxo alcohols.
Additionally, these hydrocarbon mixtures can be broadly used in the production
of
modified surfactants. They can be used to prepare the modified alkyl sulfates,
alkyl
alkoxylates, alkylalkoxy sulfates or alkylaryl sulfonates, such as
alkylbenzene sulfonates.
The alkyl sulfates, alkyl alkoxylates, alkylalkoxy sulfates are prepared by
first converting
the hydrocarbon mixtures in to the corresponding alcohol and then optionally
sulfating
2o and/or alkoxylating the alcohol. The alcohol can be formed by any
conventional means,
such as by the oxo process. And similarly the sulfation and/or alkoxylation
can be by
conventional means. The alkylbenzene sulfonates are formed by alkylating
benzene with
the olefinic containing hydrocarbon mixtures and then sulfonating the ~
resulting
alkylbenzene. The alkyl benzene sulfonates formed are the so-called "modified
alkyl
benzene sulfonate".
