Note: Descriptions are shown in the official language in which they were submitted.
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Alkyl Toluene Sulfonate Deter,~ents
This Application claims priority to: US Provisional patent application
''x0/227,795 filed August 25, 2000 and U. S. Provisional Application No.
60/178,823
filed 01/28/00, which are both currently still pending; 09/174,891 filed
10/19/98; co-
pending application serial number 08/879,745, filed June 20, 1997, (which is a
divisional of serial number 08/598,695, filed February 8, 1996, now U. S.
Patent
5,770,782); and is a continuation-in-part application of co-pending
application serial
numbers: 09/616,568 filed 7/14/00; 09/559,841 filed April 26, 2000, the
contents of
all which are expressly incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates generally to detergent compositions and cleaning
compositions haviilg enhanced detergency and cleaning capabilities. It relates
more
particularly to detergent and cleaning compositions containing the 2-tolyl
isomer of
linear allcyltoluene sulfonates in concentrations higher than were previously
available
in the prior art, owing to the discovery of the revolutionary catalyst and
process for
producing such isomers in high concentration, as detailed herein. According to
a
preferred form of the invention, an alkylated benzene, such as toluene or
ethylbenzene, are utilized as an aromatic compound that is further allcylated
and
sulfonated to provide a surfactant useful in detergent formulations.
Chemical compounds useful for removing grease, oils, dirt and other foreign
matter from various surfaces and objects have been known for some time,
including
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the simple soaps which are manufactured by the saponification of oils
(including
animal fats and vegetable oils). Saponification is essentially a process
whereby
aqueous alkali metal hydroxide is mixed with an ester (such as an animal fat
or
vegetable oil) to cause de-esterification of the ester with the formation of
the alkali
salts) of the carboxylic acids) from which the ester was derived, which salts)
axe
typically very soluble in aqueous media. Importantly, the anon portions of
such
alkali salts of the carboxylic acids) include as part of their molecular
structure a
hydrophilic portion, i.e., the caxboxylate function, which is highly attracted
to water
molecules. Such salts also include a hydrophobic portion as part of their
molecular
structure, which is typically a hydrocarbon-based portion containing between
about 12
and 22 carbon atoms per molecule. Such salts are commonly refeiTed to by those
spilled in the art as "salts of fatty acids", and by laypersons as "soap".
Aqueous
solutions of salts of fatty acids are very effective at causing grease, oils,
and other
normally water-insoluble materials to become soluble and thus capable of being
rinsed away, thus leaving behind a clean substrate which may typically
comprise a
tabletop, countertop, article of glassware or dinnerware, flatware, clothing,
architecture, motor vehicle, human skin, human hair, etc.
While the industries for the production of such soaps from fats and oils are
well-established, saponification chemists and other worlcers have continuously
sought
improved chemistry for rendering materials which axe not normally soluble in
aqueous media to become soluble therein. Towards this end, a wide variety of
materials have been identified by those slcilled in the art, with the common
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denominator of such materials being that the materials all contain a
hydrophobic
portion and a hydrophilic portion in their molecular structures.
One family of materials that have been identified as suitable soap substitutes
are the linear allcylbenzene sulfonates ("LAB sulfonates"). The LAB sulfonates
in
general are exemplified as comprising a benzene ring structure having a
hydrocarbyl
substituent (or "allcyl substituent") and a sulfonate group bonded to the ring
in the para
position with respect to one another. The length of the hydrocarbon chain of
the alkyl
substituent on the ring is selected to provide a high level of detergency
characteristics
while the linearity of the hydrocarbon chain enhances the biodegradability
characteristics of the LAB sulfonate. The hydrocarbyl substituent may
typically'
contain 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms (the "detergent
range") in a
substantially linear arrangement, and may be attached to the benzene ring by
means of
a conventional Friedel-Crafts alkylation process using a corresponding olefin
and
employing a Lewis acid catalyst such as aluminum chloride and conditions known
to
those skilled in the art as useful for such alkylations. Various alkylation
processes
useful for production of allcylbenzenes are described in US Patent numbers
3,342,888;
3,478,118; 3,631,123; 4,072,730; 4,301,316; 4,301,317; 4,467,128; 4,503,277;
4,783,567; 4,891,466; 4,962,256; 5,012,021; 5,196,574; 5,302,732; 5,344,997;
and
5,574,198, as well as European patent application 353813 and Russian patent
739,046, the entire contents of which are incorporated herein by reference
thereto.
Once a hydrocarbyl radical has been appended to a benzene ring in accordance
with the foregoing, the resulting linear alkylbenzene must subsequently be
sulfonated
in order to produce a finished detergent material that is capable of
solubilizing grease,
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oils, dirt, and the like from various substrates, such as dishes, motorized
vehicles, hard
surfaces, architecture, and fabrics, to name but a few. Sulfonation is a
lcnown
chemical process whose reactants and conditions are known to those slcilled in
the
chemical arts. Through the process of sulfonation, a sulfonate group is caused
to
become chemically bonded to a carbon atom in the benzene ring structure of the
linear
allcylbenzene, thus providing the molecule as a whole with a hydrophilic
sulfonate
group in addition to the hydrophobic hydrocarbyl portion.
It is ltnown that during the course of mono-allcylation of the benzene ring to
introduce a hydrocarbon tail into the molecular structure, several structural
isomers
are possible in which the benzene ring is attached to various points along the
hydrocarbon chain used. It is generally believed that steric effects of the
mono-olefin
employed play a role in the distribution of isomers in the mono-alkylated
product, in
addition to the catalyst characteristics and reaction conditions. Thus, it is
possible for
a single benzene ring to become attached to, say, the 2, 3, 4, or 5 positions
in a 10
carbon atom linear mono-olefin, with a different allcylbenzene isomer being
produced
in each such case. Sulfonation of such different materials results in as many
different
allcylbenzene sulfonates, each of which have different solubilization
capabilities with
respect to various oils, grease, and dirt, etc.
The sulfonates of the 2-phenyl alkyl isomers are regarded by those skilled in
the art as being very highly desirable materials, as sulfonated linear
allcylbenzene
detergent materials made from sulfonation of the 2-phenyl alkyl materials have
superior cleaning and detergency powers with respect to the sulfonation
products of
other isomers produced during the alkylation. This is believed to be due in
part to the
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greater degree of separation of the hydrophobic and hydroplulic portions of
the
molecule in the 2-phenyl isomer than in the other isomers present. The most
desired
2-phenyl alkyl isomer products may be represented structurally, in the case of
the
allcylbenzenes, as:
H3C
(CHa)n CH3
which in a preferred embodiment has n equal to any integer selected from the
group
consisting of: 5, 6, 7, 8, 9, 10, 11, and 12. Since the Friedel-Crafts type
alkylation
employed to produce 2-phenyl alkyl isomers according to the invention may
often
utilize a mixture of olefins in the detergent range (C8 to C15), a
distribution of various
allcylbenzenes results from such alkylation.
These same considerations as above relating to linear allcylbenzenes are also
applicable to the linear alkyltoluenes of this invention. The present
invention is
therefore in one broad respect concerned with the use of sulfonated 2-toluyl
alkyltoluenes derived from the alkylation of toluene, preferably using olefins
having a
carbon number distribution in the detergent range, in detergent formulations.
In the case of benzene allcylation using a detergent range olefin, a 2-phenyl
allcylbenzene is but one possible structural isomer resulting from the
allcylation of
benzene with an olefin, and a mixture of 2-phenyl alkylbenzenes results from
the
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alkylation of benzene using as reactants a feed which includes a mixture of
olefins in
the detergent range. This may be due to resonance stabilization which permits
effective movement of the double bond in an activated olefin/Lewis acid
complex.
Generally speaking, the collection of all isomeric products produced from the
alkylation of benzene with a mixture of olefins in the detergent range is
commonly
referred to by those of ordinary skill in the art as "linear allcylbenzenes",
or "LAB'S".
Frequently, those skilled in the art use "linear alkylbenzenes" or "LAB'S"
interchangeably with their sulfonates. It is common for people to say LAB's
when
they are actually referring to sulfonated LAB's useful as detergents. These
same
considerations apply to linear alkyltoluenes as well, and lineax alkyltoluenes
may be
referred to as "LAT's".
Typically, LAB's are manufactured commercially using classic Friedal-Crafts
chemistry, employing catalysts such as aluminum chloride, or using strong acid
catalysts
such as hydrogen fluoride, for example, to alkylate benzene with olefins.
While such
methods produce high conversions, the selectivity to the 2-phenyl isomer in
such
reactions as known in the prior art is low, generally being about 30% or less.
LAB's
with a high percentage of the 2-phenyl isomer are highly desired because such
compounds when sulfonated have long "tails" which provide enhanced solubility
and
detergent properties.
While the alkylation of benzene to provide alkylbenzenes that are further
sulfonated to afford surfactants has served the industry well for decades,
there are
disadvantages associated with the use of benzene. For example, benzene is a
toxic
material which requires specialized equipment for its safe handling, and which
is traded
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under stringent regulation by various governmental bodies. Thus, mere handling
and
health aspects have provided a motivation for chemists to seek alternative
surfactants
wluch are effective, but are not based on benzene.
Further, the price of benzene is generally higher than other aromatic
compounds
which may be suitable candidates from which surfactants may ultimately be
derived,
such as toluene and ethylbenzene.
One of the most important aspects of a surfactant that is intended to be
utilized
in aqueous solution is its solubility. Formulations need good solubility in
order to
perform well. As mentioned, surfactant molecules generally comprise a
hydrophobic
portion and a hydrophilic portion. As the hydrophobic group increases in
molecular
weight (the hydrophilic group being held the same), the surfactant becomes
less soluble
in water. Similarly, for the same hydrophobic group, the surfactant becomes
more water
soluble as the hydrophilic group becomes more water soluble.
Surfactants exhibit behavioral characteristics which differ from those
exhibited
by most other organic molecules. The solubility of most chemical compounds in
water
increases as the temperature of the water is increased. The solubility of
ionic surfactants
increases dramatically above a certain temperature known as the Krafft point.
When the
solubility of an ionic surfactant is plotted against temperature, a complex
graph results.
The solubility slowly increases as the temperature rises up to the Krafft
temperature,
after which there is seen a very rapid rise in solubility with only moderate
increases in
temperature, and it is at the Krafft temperature at which micelles are formed.
Below the
Krafft temperature, solubility is limited as no micelles are formed. Thus, a
surfactant
having a KrafFt temperature that is above the temperature at which the
surfactant is
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intended to be used will not have sufficient solubility at the use temperature
to be
effective as a surfactant.
Thus, providing a surfactant material having an sufficiently high Krafft
temperature to enable its use at ordinary temperatures, and which surfactant
is not
benzene-derived, represents a very desirable goal. To provide such a material
having
higher 2-phenyl isomer content over that available in the art so as to
increase its
detergency characteristics would be a huge step forward in the art of
detergents.
SUMMARY OF THE INVENTION
According to the present invention, linear alkyltoluene sulfonate surfactants
are
provided, wherein the aromatic ring of the toluene nucleus is appended to a
detergent
range allcyl chain in its 2-position. Since the methyl group in toluene is an
ortho, para
director for aromatic substitution, the detergent range olefin may attach
itself in either an
ortho or para position with respect to the methyl group. Subsequent
sulfonation of such
a mixture of ortho and para linear alkyltoluenes results iiz a wide range of
possible
isomeric products, because each of the methyl group on the ring and the
detergent range
alkyl group on the ring are themselves ortho, para directors. Thus, the
following
isomeric structures of linear all~yltoluene sulfonates are possible:
M+
I.
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M+
II.
III.
[~/~+ , O' , O
IV.
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M+
V.
Tn one aspect the present invention provides a method and catalyst for LAT
(linear alkyltoluene) production having high substrate olefin conversion, high
selectivity
to 2-toluyl isomer LAT production, and employing a catalyst having long
lifetimes and
easy handling. Through use of this aspect of the invention, 2,-toluyl
allcyltoluenes may
be readily produced in yields in excess of 70.0 %, and indeed often in excess
of 80.0
%, on the basis of catalyst selectivity.
Tmportantly, the present invention provides detergent compositions and
cleaning formulations made with a component that comprises a mixture of
sulfonated
alkyltoluenes in which the hydrocarbon groups that are bonded to the toluene
nucleus
may comprise any number of carbon atoms in the detergent range, and in one
embodiment in which at least 70.0% (weight basis) of the sulfonated
allcyltoluene
isomers present have the toluyl group attached to the hydrocarbon group in the
2
position of the hydrocarbon group, and in another embodiment in which at least
80.0% (weight basis) of the sulfonated alkyltoluene isomers present have the
phenyl
group attached to the hydrocarbon group in the 2 position of the hydrocarbon
group.
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The invention further provides detergent compositions and formulations which
axe formed from an surfactant component that comprises a mixture of the
following:
1 ) a first allcyltoluene sulfonate component comprising 2-toluyl alkyltoluene
sulfonates in which 2-toluyl allcyltoluene sulfonate isomers comprise any
percentage
between 40.0% and 80.0%, including every hundredth percentage therebetween, of
all
allcyltoluene sulfonate isomers present in said first alkyltoluene sulfonate
component;
and 2) a second surfactant component which may comprise: a) alkylbenzene
sulfonates in which isomers having the benzene ring attached to a linear alkyl
group at
a position other than the alkyl group's 2 position comprise at least 60 % of
all
alkylbenzene sulfonate isomers present; b) alkylbenzene sulfonates in which
isomers
having the benzene ring attached to a linear alkyl group at a position other
than the
alkyl group's 2 position comprise at least 70 % of all alkylbenzene sulfonate
isomers
present; or c) branched alkylbenzene sulfonates, or a combination thereof; or
d)
allcyltoluene sulfonates in which isomers having the toluene nucleus attached
to a
linear allcyl group at a position other than the allcyl group's 2 position
comprise at least
60 % of all allcyltoluene sulfonate isomers present; e) alkyltoluene
sulfonates in which
isomers having the toluene nucleus attached to a linear alkyl group at a
position other
than the alkyl group's 2 position comprise at least 70 % of all alkyltoluene
sulfonate
isomers present; or f) branched alkyltoluene sulfonates, or a combination
thereof.
Branched alkyltoluene sulfonates may be introduced into a formulated product
according to the invention in one of two ways. First, a portion of the linear
olefin
feedstoclc used in the allcylation reaction of the toluene nucleus may be
replaced by
branched olefin(s), to provide an alkyltoluenes mixture for sulfonation in
which the
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allcyltoluenes contain a selected amount of branched alkylate. The second
method of
providing branched allcyltoluene sulfonates in a finished formulation
according to the
invention is when branched allcyltoluenes are used as a blending component in
the
production of a finished product according to the invention. Thus, by either
blending
or providing branching in the alkylation reaction product, it is possible to
provide a
wide range of the amount of branched allcyltoluene sulfonates in a finished
formulation according to the invention; however, it is preferable that the
branched
isomers comprise any amount less than 50.0 % of the total alkyltoluene
sulfonate
isomers present in a given formulation according to the invention. In another
preferred form of the invention, branched isomers comprise any amount less
than
15.00% of the total alkyltoluene sulfonate isomers present in a given
formulation
according to the invention. In yet another preferred form of the invention,
branched
isomers comprise any amount less than 2 .00% of the total alkyltoluene
sulfonate
isomers present in a given formulation according to the invention.
In one preferred form of the invention, lower activity isomers (isomers other
than the 2-phenyl isomers) of linear allcylbenzenes or linear alkyltoluenes
are present
in the second surfactant component in any amount between 0.00% and 70.00%,
including every hundredth percentage therebetween, by weight based upon the
total
weight of the second surfactant component.
In a preferred form of the invention, the second surfactant component may
comprise alkyltoluene sulfonates or allcylbenzene sulfonates in which isomers
having
the benzene ring attached to a linear allcyl group at a position other than
the alkyl
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group's 2 position comprise at least 50 % of all allcylbenzene sulfonate
isomers
present.
In another preferred form of the invention, the second surfactant component
may comprise allcyltoluene sulfonates or alkylbenzene sulfonates in which
isomers
having the benzene ring attached to a linear allcyl group at a position other
than the
alkyl group's 2 position comprise at least 40 % of all alkylbenzene sulfonate
isomers
present.
In another preferred form of the invention, the second alkylbenzene sulfonate
component may comprise alkyltoluene sulfonates or allcylbenzene sulfonates in
which
isomers having the benzene ring attached to a linear allcyl group at a
position other
than the alkyl group's 2 position comprise at least 30 % of all alkylbenzene
sulfonate
isomers present.
Thus, an alkylbenzene sulfonate component according to yet another
embodiment of the invention may contain sulfonated 2-phenyl alkyltoluenes in
an
amount of at least 30.00 % by weight based upon the total weight of the
sulfonated
allcyltoluene component. In another form of the invention, an alkyltoluene
sulfonate
component may contain sulfonated 2-phenyl allcyltoluenes in an amount of at
least
40.00 % by weight based upon the total weight of the sulfonated phenyl
alkyltoluene
component. In yet another form of the invention, an alkyltoluene sulfonate
component may contain sulfonated 2-phenyl alkyltoluenes in an amount of at
least
50.00 % by weight based upon the total weight of the sulfonated alkyltoluene
component. In yet another form of the invention, an allcyltoluene sulfonate
component may contain sulfonated 2-phenyl alkyltoluenes in an amount of at
least
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60.00 % by weight based upon the total weight of the sulfonated alkyltoluene
component. In yet another form of the invention, an alkyltoluene sulfonate
component may contain sulfonated 2-phenyl allcyltoluenes in an amount of at
least
70.00 % by weight based upon the total weight of the sulfonated phenyl
alkyltoluene
component. In yet another form of the invention, an alkyltoluene sulfonate
component may contain sulfonated 2-phenyl allcylbenzenes in an amount of at
least
80.00 % by weight based upon the total weight of the sulfonated alkyltoluene
component.
By admixture with conventional mixtures of sulfonated linear allcylbenzene
detergents, a mixture of sulfonated alkylbenzenes and sulfonated alkyltoluenes
useful
as components in detergent formulations having any desired content of the
total
amount of 2-phenyl alkylbenzene or 2-phenyl alkyltoluene isomers, or
combination
of these, in the range of between about 18.00 % and 82.00 %, including every
hundredth percentage therebetween, may be produced using the materials
provided
according to the invention. Such mixtures of sulfonated alkylbenzenes with
sulfonated allcyltoluenes are useful as a component in forming detergent and
cleaning
compositions useful in a wide variety of applications as later illustrated in
the
examples.
It has also been found that a catalyst according to this invention may be used
in
combination with an existing aluminum chloride or hydrogen fluoride alkylation
facility
to afford LAB or LAT having a higher 2-phenyl or 2-toluyl isomer content than
would
otherwise be available from such plant using conventional catalysts. Thus, an
existing
facility may be retrofitted to include one or more reactors containing the
fluorine-
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containing mordeiute of this invention. In this manner, a slip stream of
reactants may be
sent to the mordenite with effluent therefrom being introduced back into the
conventional allcylation system. This embodiment has several advantages. For
example, the cost of capital is minimized since conventional equipment will
already be
in place. Also, the retrofitted plant can produce higher 2-phenyl isomer LAB
or LAT at
the discretion of its operator, depending on need. That is, the plant need not
produce
strictly high 2-phenyl isomer LAB or LAT and can instead produce high 2-phenyl
isomer at its discretion. In one embodiment, a slip stream of reactant is
drawn and sent
to one or more reactors containing fluorine-containing mordenite catalyst. The
effluent
from the fluorine-containing mordenite reactor may then be combined with
effluent
from the HF or aluminum chloride reactor to provide a product having a higher
level of
2-phenyl isomer LAB or LAT than would otherwise be present in product from an
HF
or aluminum chloride reactor.
The invention, in one broad respect, is directed at cleaning formulations
designed to cleanse a wide variety of surfaces or substrates and which possess
increased
tolerance to water hardness, wherein the formulations comprise an
allcyltoluene
sulfonate component having a much higher 2-phenyl isomer content than
formulations
previously available commercially, and other components known to be useful in
formulating soaps, detergents, and the like, including conventional linear
alkylbenzene
sulfonate detergents.
The invention, in another broad respect is a process useful for the production
of
mono-alkyltoluene, comprising: contacting toluene with an olefin containing
from about
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8 to about 30 carbons in the presence of fluorine-containing mordenite under
conditions
such that linear monoallcyltoluene is formed.
In another broad respect, this invention is a process for the production of
linear
alkyltoluene, comprising: a) contacting toluene and an olefin having about 8
to about
30 carbons in the presence of a fluorine-containing mordenite to form a first
linear
alkyltoluene stream; b) contacting toluene and an olefin having about 8 to
about 30
carbons in the presence of a conventional linear allcylbenzene allcylation
catalyst to
form a second linear alkyltoluene stream; and c) combining the first linear
alkyltoluene stream and the second linear alkyltoluene stream form a third
linear
allcyltoluene stream, as well as the mono-sulfonation product made from this
process.
In another broad respect, this invention is a process useful for the
production of
linear alkyltoluene, comprising: combining a product from a conventional
linear
alkylbenzene alkylation reactor with a product from a linear alkyltoluene
alkylation
reactor containing fluorine-containing mordenite.
In yet another broad respect, this invention is a process for the production
of
linear alkyltoluene, comprising: a) dehydrogenating a paraffin to form an
olefin; b)
sending a primary feed stream of toluene and the olefin through a conduit to a
conventional linear allcylbenzene alkylation reactor; c) contacting the
primary feed
stream in the conventional linear alkylbenzene alkylation reactor with a
conventional
linear allcylbenzene allcylation catalyst under conditions effective to react
the toluene
and olefin to form a first linear alkyltoluene product; d) withdrawing a
portion of the
primary feed stream from the conduit and contacting the portion with a
fluorine-
containing mordenite under conditions effective to react the toluene and
olefin to form
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a second linear allcyltoluene product; e) combiung the first and second linear
alkyltoluene products to form a crude linear allcyltoluene stream; and f)
distilling the
crude lineax allcyltoluene stream in a first distillation column to separate
toluene that
did not react and to form a toluene-free linear allcyltoluene stream.
Such process may optionally include the steps of: g) distilling the toluene-
free
linear allcyltoluene stream in a second distillation column to separate any
olefin and to
form a linear allcyltoluene stream; and h) distilling the second olefin-free
alkyltoluene
stream in a third distillation column to provide an overhead of a purified
linear
allcyltoluene product and removing a bottoms stream containing any heavies.
In another broad respect, this invention is a process useful for the
production of
monoallcyltoluene, comprising: introducing a feed comprising olefin having
about 8 to
about 30 carbons and toluene into a fluorine-containing mordenite catalyst bed
under
conditions such that monoalkyltoluene is produced, allowing toluene, olefin,
and mono-
allcyltoluene to descend (fall) into a reboiler from the catalyst bed,
removing
monoalkyltoluene from the reboiler, and heating the contents of the reboiler
such that
toluene refluxes to further contact the fluorine-containing mordenite.
In yet another broad aspect, this invention relates to mordenite useful for
alkylating toluene with olefin having a silica to alumina molar ratio of about
10:1 to
about 100:1; wherein the mordenite has been treated with an aqueous hydrogen
fluoride
solution such that the mordenite contains from about 0.1 to about 4 percent
fluorine by
weight.
In yet another broad respect, the invention relates to a chemical mixture that
contains linear allcyltoluenes produced using the processes) and/or catalysts)
taught
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herein, which chemical mixture is useful for producing a mixture of sulfonated
linear
allcyltoluenes which mixture contains a higher concentration of sulfonated 2-
toluyl
allcyltoluenes than previously available using prior art methods and
catalysts.
In another broad respect, the invention comprises formulations for finished
consumer and iildustrial strength compositions useful in or as: all-purpose
cleaners, pine
oil microemulsions, liquid dishwashing soaps, enzyme-based powdered and liquid
laundry detergents, enzyme-free powdered laundry detergents, and the lilce, as
it has
been found that the use of sulfonated LAT mixtures having a higher content of
the 2-
phenyl isomer with respect to what has been heretofore available from the
teachings of
the prior art unproves the effectiveness and cleaning action of all cleaning
compositions
which contain conventional sulfonated alkylbenzene detergents, be they linear
or
branched. This is true whether all or only a portion of the linear
allcylbenzene sulfonate
in the formulations of prior art are replaced by the linear alkyltoluene
sulfonates of this
invention having enhanced 2-phenylallcyl concentration (any percentage between
30.00% and 80.00%, including every hundredth percentage therebetween) over the
materials available according to the prior art.
In another broad respect, the invention is a method useful for the preparation
of
fluorine-containing mordenite, comprising contacting a mordenite having a
silica to
alumina molar ratio in a range from about 10:1 to about 100:1 with an aqueous
hydrogen fluoride solution having a concentration of hydrogen fluoride in the
range of
from about 0.1 to about 10 percent by weight such that the mordenite
containing
fluorine is produced, collecting the fluorine-containing mordenite by
filtration, and
drying.
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The fluorine treated mordenite catalyst advantageously produces high
selectivities to the 2-phenyl isomer in the preparation of LAB and LAT,
generally
producing selectivities of about 70 percent or more. Also, the fluorine
treated mordenite
enjoys a long lifetime, preferably experiencing ony a 25 percent or less
decrease in
activity after 400 hours on stream. A process operated in accordance with the
apparatus
depicted in FIGS. 1 and 2 has the advantage that rising toluene from the
reboiler
continuously cleans the catalyst to thereby increase lifetime of the catalyst.
In addition,
this invention advantageously produces only low amounts of dialkyltoluene,
which is
not particularly as useful for detergent manufacture, as well as only low
amounts of
tetralin derivatives.
In another aspect the invention provides solid salts of alkyltoluene
sulfonates,
which solid salts may contain various cations necessary for charge balance.
In another aspect the invention comprises finished detergent compositions
useful for cleaning fabrics, dishes, hard surfaces, and other substrates that
is formed
from components comprising: a) an alkyltoluene sulfonate surfactant component
present in any amount between 0.25 % and 99.50 % by weight based upon the
total
weight of the finished detergent composition, said component characterized as
comprising any amount between 26.00 % and 82.00 % by weight based upon the
total
weight of the component, and including every hundredth percentage
therebetween, of
water-soluble sulfonates of the 2-phenyl isomers of allcyltoluenes described
by the
general formula:
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H3C CH CH2 CH3
n
R1 / R5
R2 Y ~R4
R3
wherein n is equal to any integer between 4 and 16, wherein one and only one
of R1,
R2, R3, R4 and RS is a sulfonate group, and wherein one and only one of Rl,
R2, R3, R4
and RS is a substituent group selected from the group consisting of methyl and
ethyl;
and b) any amount between 0.50 % and 99.75 % of other components known to be
useful in formulating soaps, detergents, and the like, wherein at least one of
said other
components is selected from the group consisting of: fatty acids, alkyl
sulfates, an
ethanolamine, an amine oxide, alkali carbonates, water, ethanol, isopropanol,
pine oil,
sodium chloride, sodium silicate, polymers, alcohol allcoxylates, zeolites,
perborate
salts, alkali sulfates, enzymes, hydrotropes, dyes, fragrances, preservatives,
brighteners, builders, polyacrylates, essential oils, alkali hydroxides, ether
sulfates,
alkylphenol ethoxylates, fatty acid amides, alpha olefin sulfonates, paraffin
sulfonates,
betaines, chelating agents, tallowamine ethoxylates, polyetheramine
ethoxylates,
ethylene oxide/propylene oxide block copolymers, alcohol ethylene
oxide/propylene
oxide low foam surfactants, methyl ester sulfonates, alkyl polysaccharides, N-
methyl
glucamides, allcylated sulfonated diphenyl oxide, and water soluble
allcylbenzene
sulfonates or allcyltoluene sulfonates having a 2-phenyl isomer content of
less than
26.00 %.
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The mordenite catalyst of the present invention is useful as a catalyst in the
production of LAT's in accordance with the process of manufacturing LAT's of
this
invention. LAT is useful as starting material to produce sulfonated LAT, which
itself is
useful as a surfactant.
Certain terms and phrases have the following meanings as used herein:
"Meq/g" means milliequivalents of titratable acid per gram of catalyst, wluch
is
a unit used to describe acidity of the catalysts. Acidity is generally
determined by
titration with a base, as by adding excessive base, such as sodium hyckoxide,
to the
catalyst and then back titrating the catalyst.
"Cony." and "Conversion" mean the mole percentage of a given reactant
converted to product. Generally, olefin conversion is about 95 percent or more
in the
practice of this invention.
"Sel." and "Selectivity" mean the mole percentage of a pauticular component in
the product. Generally, selectivity to the 2-phenyl isomer is about 70 % or
more in the
practice of this invention.
"Detergent range" means a molecular species which contains an alkyl group that
comprises any number of carbon atoms: 8, 9, 10, 11, 12, 13, 14 or 15 per alkyl
group,
and includes LAB, LAB sulfonates, LAT, LAT sulfonates, and mono-olefins.
"Substantially linear" when refeiTing to a hydrocarbon or alkyl chain that is
part
of an alkylbenzene or allcyltoluene, whether the alkylbenzene or alkyltoluene
is
sulfonated or not, means a hydrocarbon comprising between 7 and 16 carbon
atoms
linked to one another to form a straight chain, wherein the carbon atoms of
said straight
chain may have only hydrogen atoms or a methyl group bonded to them as
appendages.
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"Branched allcyl" when referring to a hydrocarbon or alkyl chain that is part
of
an allcylbenzene or allcyltoluene, whether the allcylbenzene or allcyltoluene
is sulfonated
or not, means a hydrocarbon comprising between 4 and 16 carbon atoms linlced
to one
another to form a straight chain, wherein one or more of the carbon atoms of
said
straight chain may have a hydrogen atom acid any allcyl group other than a
methyl group
(including without limitation ethyl, propyl and butyl groups), bonded to them
as
appendages.
"Branched allcylbenzene" means a molecular spacies which comprises a
branched alkyl chain appended to a benzene ring.
"Branched alkyltoluene" means a molecular species which comprises a branched
alkyl chain appended to a the ring portion of a toluene molecule, regardless
of the
respective positions of the methyl group of the toluene and the branched alkyl
chain.
"Branched allcylbenzene sulfonate" means a water-soluble salt of a branched
alkylbenzene that has been sulfonated.
"Branched alkyltoluene sulfonate" means a water-soluble salt of a branched
alkyltoluene that has been sulfonated, regardless of the isomeric position of
the sulfonate
group and the allcyl group with respect to the methyl group.
"2-phenyl alkylbenzenes" means a benzene ring having at least one alkyl
group attached to it, wherein the alkyl group comprises any number of carbon
atoms
between 7 and 16 (including every integral number therebetween) linked to one
another so as to form a substantially linear chain and wherein the benzene
ring is
attached the alkyl group at a carbon atom that is adjacent to the terminal
carbon of the
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substantially linear chain. Thus, the carbon atom that is attached to the
benzene ring
has a methyl group and another alkyl group attached to it in a 2-phenyl
allcylbenzene.
"2-phenyl allcyltoluenes" means a toluene molecule having, in addition to its
methyl group, at least one other alkyl group attached to it, wherein the other
alkyl
group comprises any number of carbon atoms between 7 and 16 (including every
integral number therebetween) linked to one another so as to form a
substantially
linear chain and wherein the ring portion of the toluene molecule is attached
the alkyl
group at a carbon atom that is adjacent to the terminal carbon of the
substantially
linear alkyl chain. Thus, the carbon atom that is attached. to the ring of the
toluene has
a methyl group and another alkyl group attached to it in a 2-phenyl
allcyltoluene. 2-
phenyl allcyltoluene is synonymous with2-tolyl alkylbenzene.
"2-tolyl alkylbenzene" means a toluene molecule having, in addition to its
methyl group, at least one other alkyl group attached to it, wherein the other
alkyl
group comprises any number of carbon atoms between 7 and 16 (including every
integral number therebetween) linked to one another so as to form a
substantially
linear chain and wherein the ring portion of the toluene molecule is attached
the alkyl
group at a carbon atom that is adjacent to the terminal carbon of the
substantially
linear allcyl chain. Thus, the carbon atom that is attached to the ring of the
toluene has
a methyl group and another alkyl group attached to it in a 2-phenyl
allcyltoluene.
"Sulfonated 2-phenyl alkylbenzenes" means 2-phenyl allcylbenzenes as
defined above which further comprise a sulfonate group attached to the benzene
ring
of a 2-phenyl alkylbenzene as described above, regardless of the position of
the
sulfonate group on the ring with respect to the location of the alkyl group;
however, it
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is most common and preferred that the sulfonate group is attached to the
benzene ring
in the para-position with respect to the alkyl group.
"Sulfonated 2-phenyl allcyltoluenes" means 2-phenyl allcyltoluenes as defined
above which further comprise a sulfonate group attached to the aromatic ring
of a 2-
phenyl allcyltoluene as described above, regardless of the positions of the
sulfonate
group, the methyl group, and the alkyl group with respect to one another;
however, it
is most preferred that the sulfonate group is attached to the benzene ring in
the para-
position with respect to the alkyl group.
"LAB" means a mixture linear allcylbenzenes wluch comprises a benzene ring
appended to any carbon atom of a substantially linear alkyl chain in the
detergent range.
"LAT" means a mixture linear allcyltoluenes which comprises a toluene
molecule having its aromatic ring appended to any carbon atom of a
substantially linear
allcyl chain in the detergent range.
"LAB sulfonates" means LAB which has been sulfonated to include an acidic
sulfonate group appended to the benzene rings (thus forming a parent acid),
and
subsequently rendered to a form more soluble to aqueous solution than the
parent acid
by neutralization using any of alkali metal hydroxides, alkaline earth
hydroxides,
ammonium hydroxides, allcylammonium hydroxides, or any chemical agent lcnown
by
those spilled in the art to react with linear alkylbenzene sulfouc acids to
form water-
soluble linear alkylbenzene sulfonates.
"LAT sulfonates" means LAT which has been sulfonated to include an acidic
sulfonate group appended to the aromatic ring of the LAT (thus forming a
parent acid),
and subsequently rendered to a form more soluble to aqueous solution than the
parent
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acid by neutralization using any of alkali metal hydroxides, allcaline earth
hydroxides,
ammonium hydroxides, allcylammonium hydroxides, or any chemical agent known by
those skilled in the art to react with linear allcylbenzene sulfonic acids to
foam water-
soluble linear allcylbenzene sulfonates.
"2-phenyl isomer" means LAB or LAT sulfonates of 2-phenyl allcylbenzenes,
as warranted by the context.
"sulfonated aromatic alkylate" means a chemical compound which comprises a
benzene ring having a sulfonate group attached to a carbon atom of the ring
structure
and at least one alkyl group in the detergent range attached to a carbon atom
of the
ring structure; hence LAT and LAB materials fall within this classification.
All percentages set forth in this specification and its appended claims are
expressed in temps of weight percent, unless specifed otherwise.
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BRIEF DESCRIPTION OF THE DRAWINGS
FIG.1 shows a representation of a first continuous reactive distillation
column
employed in the practice of this invention;
FIG. 2 shows a representation of a second continuous reactive distillation
column
employed in the practice of this invention;
FIG. 3 shows a representative process scheme for one embodiment of this
invention
where a conventional LAB alkylation reactor (that is also useful in producing
LAT) is
shown in combination with a fluorine-containing mordenite reactor of this
invention
wherein a slip stream of reactant to the conventional reactor is sent to the
mordeiute
reactor and wherein the flow of high 2-phenyl isomer LAB or LAT, as the case
may be,
from the mordente reactor may be adjusted to vary the 2-phenyl isomer LAB or
LAT
content of the effluent from the conventional LAB all~ylation reactor.
FIG. 4 shows another representative process scheme for one embodiment of tlus
invention where a first conventional LAB allcylation reactor (also useful in
LAT
production) is shown in combination with a fluorine-containing mordeute
reactors of
this invention whereiil a slip stream of reactant to the conventional reactor
is sent to one
or both of a pair of mordenite reactor and wherein the LAT or LAB effluent
from the
first LAB allcylation reactor and the effluent from the one or both mordenite
reactors are
combined and flowed into a second conventional LAB allcylation reactor.
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FIG. 5 shows graphic data of a total detergency study conducted on cloth
swatches
using detergents having allcylbenzenes of differing 2-phenyl isomer content.
FIG. 6 shows the turbidity of solutions containing conventional alkylbenzene
surfactant
in aqueous solutions of differing hardness;
FIG. 7 shows the turbidity of solutions containing alkylbenzene surfactant
having a 2-
phenyl isomer content of about 80% in aqueous solutions of differing hardness;
FIG. 8 shows the turbidity of aqueous solutions having a constant water
hardness in the
presence of different mixtures which each contain different amounts of linear
alkylbenzene sulfonates and linear alkyltoluene sulfonates in which the 2-
pheny isomer
content of the allcylbenzene sulfonates and the alkyltoluene sulfonates is
greater than
80% by weight based upon the total weight of all sulfonates present.
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DETAILED DESCRIPTION OF THE INVENTION
The catalysts used to prepare the linear allcyltoluenes of this invention is a
fluorine-containing mordenite. Mordenite is a type of zeolite. The catalyst of
this
invention is prepared from hydrogen mordenite (typically having 0.1 percent or
less of
sodium) having a silica-alumina molar ratio of from about 10:1 to about 100:1.
More
typically, the starting mordenite has a silica/alumina molar ratio of from
about 10:1 to
about 50:1. The starting hydrogen mordenite, which is connnonly available
commercially, is treated with an aqueous solution of hydrogen fluoride ("HF")
to
produce the active, long-life and highly selective catalyst of the invention.
In the course
of such HF treatment, as well as during subsequent calcination of said HF-
treated
mordenite, the silica/alumina molar ratio typically increases. The finished
catalysts of
this invention show a fluorine content of from about 0.1 to about 4 percent by
weight,
more typically about 1 percent.
The aqueous solution used to treat the mordenite may contain a range of HF
concentrations. Generally, the HF concentration is a minimum of about 0.1
percent by
weight. Below such minimum concentration, the effect of the fluorine treatment
significantly decreases, resulting in the undesirable need for repeated
treatments.
Generally, the HF concentration on the upper end is about 10 percent by weight
or less.
Above a concentration of about 10 percent by weight, the HF is so concentrated
that it is
difficult to prevent HF from destroying the crystallinity of the mordenite,
thereby
detrimentally affecting its efficacy as a catalyst for LAB and LAT production.
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The aqueous HF solution may be prepared by diluting commercially available
48% HF solutions to the desired concentration. Alternatively, HF can be
sparged into
water to provide an aqueous HF solution.
Typically, the treatment is carried out by adding mordeute powder or pellets
to
a stirred aqueous HF solution at a temperature of from about 0 ° C to
about 50 ° C. The
stirring and contacting is continued for a time sufficient to achieve the
desired level of
fluorine in the mordenite. This time may vary depending on factors such as HF
concentration, amount of HF solution relative to the amount of mordenite being
treated,
speed of agitation is employed, and temperature. After treatment, the
mordenite can be
recovered by filtration, and then dried. It is also possible to impregnate the
mordenite to
incipient wetness with a given HF solution, as well as to treat the mordenite
with
gaseous hydrogen fluoride. Preferably said fluoride-treated mordenite would be
calcined
in air prior to use in allcylation service. The preferred calcination
temperature would be
in the range from about 400 ° C to about 600 ° C. Alternative
mordenite fluorinating
agents to hydrofluoric acid and hydrogen fluoride include ammonium fluoride,
fluorided
silicon compounds and fluorided hydrocarbons.
The HF-treated mordenite of this invention generally has about 0.1 percent by
weight or more of fluorine based on the total weight of the mordenite.
Typically, the
fluorine-containing mordenite contains about 4 percent by weight or less
fluorine. The
fluorine-containing mordenite most typically contains about 1 percent by
weight of
fluorine.
The mordenite can be used in the practice of this invention as a powder, in
pellet form, as granules, or as extrudates. The mordenite can be formed into
pellets or
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extrudates using binders well known to those of skill in the art, such as
alumina, silica
or mixtures thereof.
Reactants for L~iT Production
In the practice of this invention, toluene is allcylated with olefin to form
LAT.
These reactants can be handled and purified as is generally performed by those
of
ordinazy slcill in the art. In this regard, it is preferred that the
reacta~.its are water and
alcohol free The olefins employed in the practice of this invention have from
about 8 to
about 30 carbons, preferably from about 10 to about 14 carbons, such as is
available
commercially or produced as dehydrogenated paraffin feed stocks. It is
preferred that
the olefin be monounsaturated. It is most preferred that the olefin be an
alpha-olefin
containing a terminal ethylenic unit.
Olefins in the 10 to 14 carbon number range are typically available from the
dehydrogenation of a C,o to C,d paraffin mixture using methods knoml to those
skilled
in the art. Dehydrogenation of such paraffms provides a mixture of mono-
olefins
having a double bond at the terminal carbon in the chain and its neighboring
carbon
atom, and leaves some of the paraffins unconverted. Thus, the effluent of a
dehydrogenation reactor into which was fed a C,o to C,ø mixture typically
comprises a
mixture which is predominantly paraffms and has an olefin content of about 5
to 20%,
and is readily available. Often, the olefin content of said olefin-parafFn
mixture may be
8 to 10 weight %.
The process of this invention for producing the 2-phenyl isomer of the LAT
having the formula previously set forth above can be carried out using the
continuous
reactive distillation column depicted in FIG.1. In FIG.1, a feed mixture of
toluene and
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olefin, generally at a toluene-to-olefin molar ratio range of about 1:1 to
100:1 flows
from feed pump 10 to feed inlet 14 via line 12. The feed mixture falls to
packed
mordenite catalyst bed 32 where alkylation in the presence of the fluorine-
containing
mordenite occurs. Alternatively, while not depicted in FIG.1, the toluene and
olefin
can be introduced separately into the bed with mixing occurring in the bed, or
the
reactants can be mixed via an in-line mixer prior to introducing the reactants
into the
catalyst bed, or the reactants can be injected separately above the bed with
mixing
affected by use of standard packing above the bed, or the reactants can be
sparged into
the chamber above the bed. The catalyst bed 32 depicted in FIG.1 for
laboratory scale
may be made of two lengths of 1.1 inch internal diameter tubing, the lengths
being 9.5
inches and 22 inches. In the catalyst bed 32, the falling feed mixture also
contacts rising
vapors of unreacted toluene which has been heated to reflux in reboiler 42 by
heater 40.
Such rising vapors pass over thermocouple 38 which monitors temperature to
provide
feedbaclc to heater 40. The rising vapors of toluene and/or olefin also pass
through
standard packing 36 (e.g., 7.5 inches of goodloe packing). The rising vapors
heat
thermocouple 30 which connects to bottoms temperature controller 28 which
activates
heater 40 when temperature drops below a set Ievel.
Prior to startup, the system may be flushed with nitrogen which enters via
line
54 and which flows through line 58. After startup, a nitrogen blanket is
maintained over
the system. Also prior to startup and during nitrogen flush, it may be
desirable to heat
catalyst bed 32 so as to drive off water from the fluorine-containing
mordenite.
Residual water from the feed mixture or which otherwise enters the system is
collected in water trap 24 upon being liquefied at condenser 21 (along with
benzene
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vapor). If the feed is very dry (free of water) the water trap 24 may not be
needed.
Removing water leads to longer catalyst lifetime. Hence, the water trap 24 is
optional.
The same applies to FIG. 2. Condenser 21 is cooled via coolant such as water
entering
condenser 21 via port 22 and exiting via port 20. As needed, water in water
trap 24 may
be drained by opening drain valve 26.
As needed, when LAT content in reboiler 42 rises to a desired level, the
bottoms
LAT product may be removed from the system via line 47, using either gravity
or
bottoms pump 48 to withdraw the product. When product is so withdrawn, valve
44 is
opened.
In FIG.1, dip tube 46, which is optional, is employed to slightly increase the
pressure in reboiler 42 to thereby raise the boiling point of benzene a degree
or two.
Likewise, a pressure generator 56 may be optionally employed to raise the
pressure of
the system. Other standard pressure increasing devices can be employed.
Pressure can
thus be increased in the system such that the boiling point of toluene
increases up to
about 200 ° C.
In FIG.1, control mechanisms for heat shutoff 50 and pump shutoff 52 are
depicted which serve to shut off heat and pump if the liquids level in the
system rises to
such levels. These control mechanisms are optional and may be included so that
the
catalyst bed does not come into contact with the bottoms of the reboiler. Line
60
connects pump shutoff 52 to the system above condenser 21.
In the practice of this invention in the alkylation of toluene, a wide variety
of
process conditions can be employed. In this regard, the temperature in the
catalyst bed
may vary depending on reactants, rate of introduction into the catalyst bed,
size of the
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bed, and so forth. Generally, the bed is maintained at the reflux temperature
of toluene
depending on pressure. Typically, the temperature of the catalyst bed is above
about
100 ° C, and most lilcely about 110° to 130°C or more in
order to have reasonable
reaction rates, and about 250 ° C or less to avoid degradation of
reactants and products
and to avoid deactivation of the catalyst by coke build-up. Preferably, the
temperature is
in the range from about 120 ° C to about 200 ° C. The process
may be operated at a
variety of pressures during the contacting step, with pressures of about
atmospheric
most typically being employed. When the process is operated using a system as
depicted in FIGS.1 and 2, the reboiler temperature is maintained such that
toluene and
olefin vaporize, the temperature varying depending on olefin, and generally
being from
about 110 ° C to about 300 ° C for olefins having 10 to 14
carbons. The composition of
the reboiler will vary over time, but is generally set initially to have a
toluene-to-olefin
ratio of about 5:1, with this ratio being maintained during the practice of
this invention.
The rate of introduction of feed into the catalyst bed may vary, and is
generally at a
liquid hourly space velocity ("LHSV") of about 0.05 hr-1 to about 10 hr-',
more typically
from about 0.05 hr-' to about 1 hr-1. The mole ratio of toluene to olefin
introduced into
the catalyst bed is generally from about 1:1 to about 100:1. In commercial
toluene
alkylation operations, it is common to run at mole ratios of from about 2:1 to
about 20:1,
which can suitably be employed in the practice of this invention, and to
charge said
olefins as an olefin-paraffin mixture comprising 5% to 20% olefin content.
Said olefin-
paraffin mixtures are normally generated commercially through dehydrogenation
of the
corresponding paraffin starting material over a noble metal catalyst.
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Another continuous reactive distillation apparatus is depicted in FIG. 2. In
FIG. 2, the feed mixture enters the reactor via feed inlet 114. The feed
mixture falls
through the column into catalyst bed 132, wherein allcylation to form LAT
occurs. A
thermowell 133 monitors the temperature of said catalyst bed 132. The catalyst
bed 132
may be optionally heated externally and is contained within 1-1/4 inch
stainless steel
tubing. Goodloe packing is positioned at packing 136 and 137. LAT product, as
well as
unreacted toluene and olefin, fall through packing 136 into reboiler 142. In
reboiler 142,
electric heater 140 heats the contents of reboiler 142 such that heated vapors
of toluene
and olefin rise from the reboiler 142 to at least reach catalyst bed 132. As
needed, the
bottoms LAB product may be removed from reboiler 142 by opening bottoms valve
144
after passing through line 147 and filter 145. Residual water from the feed
mixture, or
which otherwise enters the system, may be condensed at condenser 121 which is
cooled
with coolant via outlet line 122 and inlet line 120. The condensed water falls
to water
trap 124, which can be drained as needed by opening drain valve 126.
Temperature in
the system is monitored via thermocouples 138, 130, and 165. The system
includes
pressure release valve 166. A nitrogen blanket over the system is maintained
by
introduction of nitrogen gas via inlet line 154. Level control activator 150
activates
bottoms level control valve 151 to open when the liquids level in the reboiler
rises to the
level control activator 150. Line 160 connects level control activator 150 to
the system
above condenser 121.
While the systems depicted in FIG.1 and FIG. 2 show single catalyst bed
systems, it may be appreciated that multi-catalyst bed reactors are within the
scope of
this invention, as well as multiple ports for inlet feeds, water traps,
product removal
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lines, and so forth. Moreover, the process may be run in batch mode, or in
other
continuous processes using plugflow designs, tricl~le bed designs, and
fluidized bed
designs.
It is believed that as average molecular weight of olefins increases,
particularly
when the average number of carbons exceed 14, the selectivity and conversion
to LAT,
especially LAT with the 2-isomer, may incrementally decrease. If desired, the
product
of the allcylation using HF-treated mordenite may be sent to a second,
fnustiing catalyst
bed to improve yield. This procedure is optional and is believed to be
dependent on the
needs and desires of the end user. An example of such a second catalyst is HF-
treated
clay such as montmorillonite clay having about 0.5% fluoride. Such a catalyst
may also
serve to lower the bromine number of the allcylate product below about 0.1,
depending
on conditions.
l~ariable 2 plze>zyl Isozne>' Coutezzt of Product Usi>zg the Mordezzite of
tl:e
IfzV~fZtIOIZ I>z Couzbihatiou with Conveutiozzal LATAlkylatiou
The fluorine-containing mordenite of this invention generally produces LAT
having high 2-phenyl isomer content, such as higher than about 70%. Currently,
LAT
purchasers who make detergents would prefer to use LAT having a 2,-phenyl
isomer
content in the range from about 30 to about 40 percent, but this level is not
available in
the marketplace. Conventional LAT alkylation technology do not achieve these
higher
2-phenyl isomer levels. HF, which is currently the most widely used catalyst
for
production of LAT on a commercial scale, produces about 16-18 percent of the 2-
phenyl
isomer in the product stream from the reactor. Aluminum chloride, in contrast,
produces
about 26-28 percent of the 2-phenyl isomer. The present inventors recognized
that a
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need exists for a process which produces a 2-phenyl isomer product in the
desired
range.
It has now been found that the mordenite of this invention can be used in
combination with conventional LAB allcylation catalysts, such as HF and
aluminum
chloride allcylation catalysts. This may be affected by withdrawing a slip
stxeam of
reactant that is being sent to the conventional LAB reactor, and directing the
slip stream
to the mordenite reactor. Since conventional LAB catalysts produce product
having a 2-
phenyl isomer content much less than that from mordenite of this invention,
combining
the LAT products from each catalyst results in a product having a higher 2-
phenyl
isomer content than that from the conventional LAB alkylation catalyst. For
example,
while the catalyst of this invention typically produces a 2-phenyl isomer
content of 70%
or more, a typical HF process produces about 16-18% of the 2-phenyl isomer. By
combining effluent from each catalyst at given proportions, the resulting
mixture will
have any desired 2-phenyl isomer content in the range between the 2-phenyl
isomer
contents of the HF catalyst product and the mordenite catalyst product. Thus,
the levels
of 2-phenyl isomer may be adjusted by the amount of reactants sent to the
mordenite
catalyst and/or by storing 2-phenyl isomer product from the mordenite catalyst
for later
mixing with the product of from the conventional LAB alkylation catalyst to
thereby
achieve any desired level of 2-phenyl isomer content in the final product. An
advantage
of this invention pertains to the ability to retrofit an existing,
conventional LAB system
with a reactor containing fluorine-treated mordenite of this invention. This
enables
existing users of the conventional LAB technology to augment their existing
facilities
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without interrupting their production. Tlus provides a considerable cost
advantage to
the producer.
The conventional LAB catalysts used most frequently are HF allcylation
reactors and aluminum chloride alkylation catalysts. Other alkylation
catalysts
include various zeolites, alumina-silica, various clays, as well as other
catalysts.
FIG. 3 depicts a representative, non-limiting scheme for practice of this
invention wherein the fluorine-treated mordenite is used in combination with a
HF
allcylation reactor to afford LAT having high 2-phenyl isomer contents
relative to that
produced from the HF reactor alone. The scheme of FIG. 3 is shown in the
context of
LAT alkylation based on a feed from a paraffin dehydrogenation facility. Prior
to this
invention, the plant depicted in FIG. 3 would be operated conventionally
without use
of mordenite reactor 220.
Thus, in conventional operation, fresh paraffin is fed to conventional
dehydrogenation apparatus 210 via line 211, with recycled paraffin being
introduced
from the paraffin column 250 via line 252. Dehydrogenated paraffin from the
dehydrogenation apparatus 210 is then pumped into a conventional allcylation
reactor
230 containing conventional LAB catalyst, such as HF, via conduit 214. The
dehydrogenated paraffin feed may of course be supplied from any provider. The
source of dehydrogenated paraffin (olefin) is not critical to the practice of
this
invention. LAT product from alkylation unit 230 may thereafter be purified by
a
series of distillation towers.
In this regard, alkylation effluent is delivered to a toluene column 240 by
way
of line 231. It should be appreciated that the alkylation product may be sent
offsite
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for purification. Further, the particular purification scheme used is not
critical to the
practice of this invention, but is depicted in FIG. 3 as representative of a
typical
commercial operation. In FIG. 3, unreacted toluene is distilled off from the
crude
LAT product. Toluene is then recycled to the alkylation reactor 230. The
toluene-
free LAT crude product from the toluene column 240 is pumped through line 241
to
paraffin column 250 where any paraffin present is distilled off, with the
distilled
paraffin being recycled to paraffin dehydrogenation unit 210 via line 252.
Paraffm-
free crude LAT allcylate from the paraffin column 250 is transported to a
refining
column 260 where purified LAT is distilled and removed via line 262. Heavies
(e.g.,
diallcylates and olefin derivatives) are withdrawn from refining column 260
via
conduit 261.
In the practice of this invention, a fluorine-treated mordenite containing
reactor 220 is used in conjunction with the conventional alkylation reactor
230. In the
embodiment of this invention depicted in FIG. 3, a slip stream of
toluene/dehydrogenated paraffin feed is taken from line 214 and pumped through
mordenite reactor 220 where high 2-phenyl isomer production is achieved. LAT
product from reactor 220, high in 2-phenyl isomer, is then introduced back
into line
214 via line 222. Alternatively mordenite reactor 220 may be fed toluene and
dehydrogenated paraffin (olefin) directly, rather than by way of a slip stream
from line
221. In addition, effluent from reactor 220 may, in the alternative if no
unreacted
olefin is present, be sent directly to toluene column 240, for later
combination with
conventional alkylation reactor 230 product or transported and tied into
conduit 231,
which feeds toluene column 240. It should be appreciated that columns 240,
250, and
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260 may be maintained at conditions (e.g., pressure and temperature) well
lcnown to
those of slcill in the art and may be packed with conventional materials if
desired.
FIG. 4 depicts an alternative configuration to that shown in FIG. 3. In FIG.
4, dual mordenite beds 320, 321 are used in conjunction with conventional
allcylation
reactors 330, 340. Conveniently, one of the mordenite reactors may be in
operation
while the other reactor is down for catalyst regeneration. For example, during
operation, olefin feed (dehydrogenated paraffin) is supplied via line 301,
with toluene
or other aromatic feed stock being provided via line 302. The admixed
reactants may
flow to standaxd alkylation reactor 330 via line 304b after passing through
heat
exchanger 303. A portion of the mixed stream may be withdrawn via line 304a
for
supply to the mordenite reactor. The extent of the mixed feed stream being
withdrawn may be vaxied depending on the desired level of 2-phenyl isomer in
the
final product. In another embodiment, the product from the reactor containing
mordeute 320, 321 may be fed to the first alkylation reactor 330, paz-
ticularly if the
second alkylation reactor 34 is not employed in the process.
The slip stream reactants may optionally be sent to dewatering unit 317 by
application of pump 306 after passing through heat exchanger 305. In the
dewatering
unit 317, water is distilled from the reactants in dewatering tower 310.
Rising vapor
exits via line 311a and passes through heat exchanger 312 wherein condensation
occurs. Effluent from heat exchanger 312 is advanced to water trap 318 via
line 311b.
Water is removed from water trap 318 via line 313, with the bottom organic
layer
being returned to the dewatering tower 310. Dewatered reactants may be removed
via
line 316 and conveyed to either line 316a or line 316b. Some of the dewatered
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reactant may be withdrawn by conduit 314b, sent through heat exchanger 315 and
returned to the tower 310 via line 314a. In this regard, heat exchanger 315
may serve
as a reboiler.
After reaction in either reactor 320 or 321, LAT product is sent to lines 322
and 331 from either line 322a or 322b after passing through heat exchanger
323.
When desired, one of the catalyst beds may be regenerated, as by calcination
for
example, through use of regeneration heater 350, which may be connected to the
reactor of choice by dotted line 351 through valuing and hardware that axe not
shown.
The reactors 320 and 321 may optionally be run simultaneously. The reactors
320
and 321 may be loaded with mordenite catalyst in any fashion, as would be
apparent
to one of skill in the art. Typically, a plugged flow arrangement is used. The
amount
of catalyst employed may vary depending on a variety of considerations such as
type
and flow rate of reactants, temperature and other variables. The combined
effluents
from conventional reactor 330 and mordeute reactors 320 or 321 may be fed to a
second conventional reactor 340, or optionally may be sent to a purification
section
directly if no unreacted olefin is present (the conventional reactor serves to
complete
reaction of any olefin that is not converted in the mordenite reactors 320,
321). In
FIG. 4, effluent from the second conventional alkylation reactor is advanced
to a
purification section. The second alkylation reactor may be used to react
unreacted
feed stoclc from reactors 330, 320 and 321 to thereby reduce recycle loads.
It should be appreciated that a wide variety of conf gurations are
contemplated, and the figures should not be construed as limiting this
invention or
claims hereto. Additional reactors and other equipment may, for example, be
used.
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The following examples are illustrative of the present invention and are not
intended to be construed as limiting the scope of the invention or the claims.
Unless
otherwise indicated, all percentages are by weight. In the examples, all
reactants were
commercial grades and used as received. The apparatus depicted in FIG.1 was
employed for examples 2-4. The apparatus depicted in FIG.1 was used for
example 5.
While the examples herein relate to the allcylation of benzene according to
the
invention to provide LAB having enhanced 2-phenyl isomer content, the same
catalysts
and equipment may be used to provide LAT using toluene as a starting material
in the
stead of benzene, using the temperatures mentioned above for LAT production.
It may be noted that example 2 illustrates LAB production from paraffin
dehydrogenate using the fluoride-treated mordenite catalyst of example B,
where good
catalyst life (250+ hrs) is achieved without catalyst regeneration, while
maintaining a 2-
phenyl isomer selectivity of >70% and high LAB productivity without
significant loss
of fluoride. Comparative example 1, on the other hand, using untreated
mordenite, with
no fluoride added, shows a rapid decline in LAB production. In addition,
examples 3
and 4 illustrate LAB production using a 5:1 molar benzene/C,o C,a olefin feed
mix and
the fluoride-treated mordenite catalysts of Example B when operating at
different
LHSV's in the range of 0.2-0.4 hr-'. Catalyst life may exceed 500 hours.
Example 5
illustrates LAB production with the fluoride-treated mordenite catalyst where
the
allcylation is conducted at higher temperatures and under pressure. Examples 6-
8
illustrate the performance of three HF-treated mordenite catalysts with
different fluoride
loadings. Example 9 shows how virtually no alkylation activity is observed
with a
highly-fluorinated mordenite.
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EXAMPLE A
Tlus example illustrates the preparation of a hydrogen fluoride-modified
mordenite.
To 30 g of acidified mordeiute (LZM-8, Si02/A1203 ratio 17; Na20 wt% 0.02,
surface area 517 mz/g, powder, from Union Carbide Corp.) was added 600 ml of
0.4%
hydrofluoric acid solution, at room temperature. After 5 hours the solid
zeolite was
removed by filtration, washed with distilled water, dried at 120 ° C
overnight, and
calcined at 538 ° C.
EXAMPLE B
The example illustrates the preparation of a hydrogen fluoride-modified
mordenite.
To 500 g of acidified, dealuminized, mordente (CBV-20A from PQ Corp.;
Si02/A1203 molar ratio 20; Na20, 0.02 wt%; surface area 550 m2/g, 1/16"
diameter
extrudates, that had been calcined at 538 ° C, overnight) was added a
solution of 33 ml of
48% HF solution in 1633 ml of distilled water, the mix was cooled in ice,
stirred on a
rotary evaporator overnight, then filtered to recover the extruded solids. The
extrudates
were further washed with distilled water, dried in vacuo at 100 ° C,
and then calcined at
53 8 ° C, overnight.
Analyses of the treated mordenite showed:
F: 1.2%; Acidity: 0.49 meq/g
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EXAMPLE 1
This example illustrates the preparation of linear allcylbenzenes using a
hydrogen fluoride-modified mordenite catalyst.
To a 500 ml flask, fitted with condenser and Dean Starlc Trap was added 100 ml
of benzene (reagent grade) plus 10 g of hydrogen fluoride-modified mordenite
zeolite,
prepared by the method of Example A. The mix was refluxed for 15-20 nunutes to
remove small amounts of moisture, then a combination of benzene (50 ml) plus 1-
dodecene (10 g) was injected into the flask and the solution allowed to reflux
for 3
hours.
Upon cooling, the modified mordenite catalyst was removed by filtration, the
filtrate liquid flashed to remove unreacted benzene, and the bottoms liquid
analyzed by
gas chromatography.
Typical analytical data are summarized in Table 1.
DODECENE LAB HEAVIES LINEAR LAB (LLAB)
CONY. ISOMER (%) (%)
(%) DISTRIBUTION
(%)
2-Ph
3-Ph
4-Ph
5-Ph
6-Ph
99.7 79.9 16.6 0.8 1.3 1.3 0.2 95.9
Table 1
EXAMPLE 2
This example illustrates the preparation of linear alkylbenzenes fiom para~n
dehydrogenate using a hydrogen fluoride-treated mordenite catalyst.
In example 2, benzene was alkylated with a sample of Clo C,4 paraffin
dehydrogenate containing about 8.5% C,o C,a olefins. Alkylation was conducted
in a
process unit as shown in FIG. 1.
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Allcylation was conducted by f rst charging 500 ml of a benzene/paraffin
dehydrogenate mix (10:1 molar ratio, benzene/C,o-C14 olefin) to the reboiler
and 250 cc
of the HF-treated mordenite of example B to the 1.1" i.d. reaction zone. The
mordenite
was held in place using Goodloe packing. The reboiler liquid was then heated
to reflux
a~.ld a benzene plus Clo C,4 paraffin dehydrogenate mix (10:1 molar ratio,
benzene/Clo-
Cl~ olefin) continuously introduced into the unit above the catalyst column at
the rate of
100 cc/hr: (LHSV=0.4 hr-').
Under steady state, reflux, conditions liquid product was continuously
withdrawn from the reboiler and water continuously taken off from the water
trap. The
crude liquid product was periodically analyzed by gas chromatography. The
reboiler
temperature was typically in the controlled range of 97-122 ° C. The
column head
temperature variability was 78-83 ° C. A summary of the analytical
results may be
found in Table 2.
After 253 hours on stream, the recovered HF-treated mordenite catalyst showed
by analysis: F: 1.1%; Acidity: 0.29 meq/g; H20: 0.3%
Time on Stream SampleAlkylate Conc. 2-Phenyl Sel.(%)C~H6 Conc.
(Hrs) (%) (%)
0 0 1.4 32.3
2 1 3.4 19.7
4 2 5.8 74.9 16.6
6 3 6.6 75.8 . 25.2
32 4 7.9 80:7 27.0
56 I 5 I 7.8 I 82.7 I 27.0
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Time on Stream Sample Alkylate Conc.2-Phenyl Sel.(%)C6H6 Conc.
(Hrs) (%) (%)
69 6 7.3 81.4 27.4
94 7 6.5 82.0 27.8
118 8 6.0 78.4 27.7
142 9 5.9 81.3 26.9
166 10 5.4 81.5 27.3
207 11 5.3 81.3 26.1
229 12 5.1 81.1 27.4
253 13 4.9 81.4 28.1
Table 2
Comparative Example 1
This example illustrates the preparation of linear alkylbenzene from paraffin
dehydrogenate using an untreated mordeute catalyst. Following the procedures
of
Example 9, the alkylation unit was charged with 250 cc of untreated, calcined,
mordenite, (the staring mordenite of Example B), and the Liquid feed comprised
benzene plus C,o-Cl~ paraffin dehydrogenate mix in a 10:1 molar ratio of
benzene/Clo-
Clø olefin.
Typical results are summarized in Table 3
The recovered mordenite showed by analysis: Acidity: 0.29 meq/g; HzO: 2.1
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Time on Stream Sample Alkylate Conc.(%)2-Phenyl sel.(%)C~H~ Conc.
(Hrs) (%)
0 0 11.2
2 1 6.50 9.9
4 2 7.16 73.2 17.1
6 3 7.09 73.1 26.4
22 ' 4 8.61 73.9 26.6
31 5 10.49 67.4 15.8
46 6 7.39 75.0 27.7
70 7 6.39 75.1 28.5
93 8 6.08 73.6 23.0
144 9 5.21 73.6 15.8
157 10 4.40 73.9 26.2
I 80 11 3.06 69.6 27.1
204 12 1.32 19.5
228 13 1.32 33.3
Table 3
EXAMPLE 3
This example also illustrates the preparation of linear alkylbenzene from
paraffin
dehydrogenate using a hydrogen fluoride-treated mordenite catalyst.
Following the procedures of Example 2, the alkylation unit was charged with
250 cc of the HF-treated mordenite of Example B, and the liquid feed comprised
a
benzene plus Clo C,4 paraffin dehydrogenate mix in a 5:1 molar ratio of
benzene/Cl°-Cla
olefin, the reboiler temperature was typically in the range of 122-188
° C, the column
head temperature 78-83 ° C. Typical analytical results are summarized
in Table 4.
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After 503 hours on stream, the recovered HF-treated mordenite catalyst showed
on analysis: F: 1.0%; Acidity: 0.35 meq/g; HzO: 0.1%
Time on Stream Sample Allcylate2-Phenyl C~H~ Correcteda Alkylate
(Hrs) Conc. Sel. (%) Conc. Conc. (%)
(%) (%)
0 0 1.0 8.9 1.1
2 1 3.5 61.8 0.3 3.5
4 2 7.1 72.1 0 7.1
6 3 6.8 76.7 7.2 7.3
34 4 8.4 79.7 14.3 9.8
71 5 7.2 81.8 14.6 8.5
96 6 6.5 80.8 15.5 7.7
119 7 6.3 80.6 15.1 7.4
643 8 6.0 81.0 14.3 7.0
168 9 5.9 80.7 14.4 6.9
239 10 5.0 78.2 8.8 5.5
263 11 5.3 79.2 13.5 6.2
288 12 5.0 79.6 16.5 6.0
311 13 5.4 79.4 4.1 5.6
335 14 5.5 79.2 8.2 6.0
408 15 4.9 79.4 13.1 5.6
432 16 4.7 78.8 14.4 5.5
456 17 4.4 78.5 14.1 5.1
479 18a 4.7 78.6 2.7b 4.8
488 19b 4.9 78.5 2.4~ 5.0
503 206 5.1 78.9 0.6 5.1
Table 4
a Corrected for benzene in effluent sample.
b Applied pressure 8" H20
Applied pressure 12" Ha0
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Example 4
This example also illustrates the preparation of linear allcylbenzenes from
paraffin dehydrogenate using a hydrogen fluoride-treated mordenite catalyst.
Following the procedures of Example 2, allcylation was conducted in the
glassware unt of FIG. 1 complete with catalyst column, reboiler, condenser and
controls. To the reaction zone was charged 500 cc of HF-treated mordenite of
Example
B. The liquid feed comprised a benzene plus Clo C,4 paraffin dehydrogenate mix
in a 5:1
molar ratio of benzene /Clo Cl~ olefin. The feed rate was 100 cc/hr (LHSV:0.2
hr-')
Under typical steady state, reflux, conditions, with a reboiler temperature
range
of 131-205 ° C and a head temperature of 76-83 ° C, typical
results are summarized in
Table 5.
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PressureReboilerTime SampleAlkylate2-PhenylC~H6 Correcteda
(Inch Temp. on Conc. Sel. Conc. Alkylate
Hz0) (C) Stream (%) (%) (%) Conc. (%)
(Hrs)
12 205 2 1 8.2 74.3 0.5 8.3
193 4 2 9.2 75.0 0.4 9.2
175 6 3 10.0 74.8 2.3 10.3
204 21 4 12.7 78.7 0.3 12.7
146 44 5 11.7 81.0 10.4 12.9
136 68 6 11.5 81.8 10.0 12.7
2-3 Cb 11.6 81.4 9.4 12.7
days
136 93 7 11.3 82.6 10.8 12.5
4-5 C-16 11.0 81.8 11.0 12.2
days
142 165 8 10.4 83.0 11.4 11.5
142 189 9 10.2 83.4 10.5 11.2
146 213 10 9.7 80.2 11.2 10.7
139 238 11 9.6 83.4 11.1 10.7
143 261 12 9.9 81.9 11.0 11.0
133 333 13 9.2 83.4 11.3 10.3
138 356 14 8.9 83.5 11.1 9.9
138 381 15 8.8 83.0 11.3 9.8
131 405 16 8.7 82.8 11.2 9.7 '
Table 5
a Corrected for benzene in effluent sample
b Composite product
EXAMPLE 5
This example illustrates the preparation of linear alkylbenzenes from paraffin
dehydrogenate using a hydrogen fluoride-treated mordenite catalyst.
Following the procedures of Example 2, alkylation of benzene with C,o C,4
paraffin dehydrogenate was conducted using the stainless-steel unit of FIG. 2,
complete
with catalyst column, reboiler, condenser, and controls. About 250 cc or HF-
treated
mordenite of Example B was charged to the column. The liquid feed comprised
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benzene plus Clo C14 paraffin dehydrogenate mix in a 10:1 molar ratio of
benzene/Clo-
C14 olefin. The LHSV varied from 0.2 to 0.4 hr-I.
Alkylation was conducted over a range of column and reboiler temperatures and
a range of exit pressures. Typical results are summarized in Table 6.
Column Pressure Pot Time SampleAlleylate2- C~H6
Temp DIFF Temp. (hr) (#) Conc. PhenylConc.
(C) EXIT (C) (%) Sel. (%)
(psi) (%)
(psi)
149-129 0.1 0 188 4 1 3.8 6.3
1S2-126 0 0 200 20 2 1.8 32.7
195-108 0 0 199 25 3 5.7 8.7
218-111 0 0 201 28 4 0.8 67.5
212-118 0 0 201 44 5 8.8 71.7 4.5
209-114 0.2 0 198 52 6 2.4 47.3
228-116 0 0 197 68 7 6.9 72.6 12.4
187-107 0.5 0 197 76 8 2.9 74.6 44.1
76 9a 4.8 72.9 25.3
9C6 6.8 72.2 1.0
174-107 0 0 178 6 10 4.1 79.2 54.9
170-106 0 0 172 22 11 2.0 59.8
28 12$ 6.6 76.8 26.8
142-107 0 0 136 31 13 4.8 67.9 18.9
141-110 0 0 138 47 14 4.4 65.9 16.9
142-110 0 0 136 55 15 5.0 63.9 16.6
168-111 0 0 131 71 16 4.1 64.8 16.7
170-108 0 0 150 79 17 5.0 72.0 8.8
175-113 0 0 143 95 18 5.9 68.1 15.2
145-106 0 S.2 188 14 19 3.2 60.2 9.0
149-108 0 4.2 186 20 20 4.8 66.3 12.0
160-118 0 11.7 213 29 21 4.2 6.7
160-119 0 9.3 210 44 22 5.2 6.6
Table 6
a Composite product
b Stripped composite product
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EXAMPLES 6-8
These examples illustrate the preparation of linear allcylbenzene using
hydrogen
fluoride-modified mordenite catalysts with different fluoride treatment
levels.
Following the procedures of Example 1, the allcylation unit was charged with
benzene (100 ml), a 10 g sample of hydrogen fluoride-modified mordenite
prepared by
the procedure of Example B, plus a mix of benzene (50 ml) and 1-decene (10 g).
Three
HF-treated mordenites were tested, having the composition:
Catalyst "C" 0.25% HF on mordenite (CBV-20A)
Catalyst "D" 0.50% HF on mordenite (CBV-20A)
Catalyst "E" 1.0% HF on mordenite (CBV-20A)
In each experiment samples of the bottoms liquid fraction were withdrawn at
regular periods and subject to gas chromatography analyses. The results are
summarized in Table 7.
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CATALYST TIME %LLAB %ISOS %HVY %2Ph %3Ph %4Ph %5Ph %6&7Ph
D 10 11.75 0.14 0 73.36 21.87 2.89 0.94 1.02
20 12.43 0.21 0 72.97 21.96 3.14 1.13 0.81
30 12.88 0.21 0 72.67 22.13 3.03 1.16 1.01
40 12.27 0.22 0 73.02 21.92 2.85 1.06 1.14
50 12.15 0.98 0 72.46 21.67 3.21 1.17 1.49
50 12.24 1.01 0 72.53 21.63 3.23 1.12 1.44
60 12.28 0.21 0 72.96 22.07 2.93 1.14 0.91
60 11.98 0.21 0 72.97 22.21 2.93 1.17 0.83
C 10 12.2 0.18 0 72.54 22.46 3.21 0.98 0.82
20 12.7 0.39 0 71.51 22.61 2.91 1.02 2.13
30 12.52 0.21 0 71.96 22.68 2.96 1.04 1.36
40 12.75 0.21 0 71.84 22.67 3.22 1.02 1.25
50 12.98 0.21 0 71.57 22.81 3.16 1.08 1.39
60 12.54 0.21 0 71.45 22.81 3.19 1.12 1.44
60 12.33 0.21 0 71.61 22.87 2.92 1.05 1.31
E 10 10.56 0.05 0 75.19 19.41 2.18 3.22
20 12.95 0.15 0 74.36 19.23 3.01 3.4
30 13.44 0.18 0 74.11 19.42 3.2 3.27
40 13.16 0.15 0 074.1619.38 3.12 3.34
50 13.1 0.15 0 74.43 19.16 3.21 3.28
60 12.83 0.15 0 74.28 19.49 2.88 3.35
60 12.87 0.16 0 73.82 19.97 2.8 3.2
Table 7
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Example 9
This example illustrates the inactivity of a heavily loaded hydrogen-fluoride
modified mordenite catalyst.
Following the procedures of Example 2, the allrylation unit was charged with
100 cc of a hydrogen fluoride-treated mordenite (CBV-20A) prepared by the
method of
Example B but having a much higher loading of HF (fluoride content 4.8%). The
acidity of said HF-treated mordenite was 0.15 meq/g.
No significant amount of allcylated product was detected by gas
chromatography.
EXAMPLE 10
Preparation of high 2-position isomer C12-alkyltoluene
C12-Linear allcyltoluene (LAT) is prepared by using mordenite, CBV20A, a
mordenite catalyst available from Zeolyst, Inc. of Conshohocken, Pennsylvania.
The
reaction was conducted in a 2L round-bottom flaslc equipped with a mechanical
stirrer, condenser, and a Dean-Stark trap to remove water from the reaction
mixture.
About 50 grams of freshly calcined (1000° F) CBV20A mixed with 920
grams of
reagent grade toluene and stirred under moderate agitation, with heating to
reflux.
About 25 ml of cloudy toluene is collected into the trap and is removed from
the trap
to make the reaction anhydrous. About 168 grams of alpha dodecene is added
slowly
over 15 minutes and continued stirring for about one hour at 130-135°C.
The reaction
mixture was cooled, filtered, and the excess toluene is distilled off obtain
the crude
allcyltoluene. The crude material is distilled under vacuo at 150-155°C
at 1-2 mm
pressure. Gas chromatography analysis showed a mixture of 2-tolyl isomer
(84.20%),
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3-tolyl isomer (15.77%) consisting of ortho, para, and meta isomers, with the
para
isomer being predominant.
EXAMPLE 11
Preparation of high 2-position isomer C10-alkyltoluene
C10-linear alkyltoluene (LAT) is prepared by using mordenite, CBV20A,
catalyst with/without fluoride. The reaction apparatus is the same as the one
used in
Example 10 above. About 50 grams of freshly calcined (1000° F) catalyst
is stirred
with 500 grams of reagent grade toluene and heated to reflux with moderate
mechanical stirring. About 25 ml of toluene is collected into the trap to make
the
reaction mixture anhydrous. About 140 grams of C10-alpha olefin is added over
15
minutes and heated with stirring at 120-130°C for 30 mints., cooled and
filtered.
Excess toluene is removed by distillation, and the crude allcyltoluene is
distilled under
vacuo at 145-150°C at 1-2 mm. Gas chromatography analysis of the
distilled fraction
showed a mixture of 2-tolyl isomer (84.04%), 3-tolyl isomer (15 .78%), each
containing paralortho/meta isomers, with predominant isomers being the para
isomers.
Example 12
Preparation of high 2-position isomer Li hg t alkyltoluenes
Linear light alkyltoluene (LLAT) is prepared by using mordenite CBV20A
catalyst. The reactor setup is the same as for Example 10 above. About 50
grams of
freshly calcined (1000°F) CBV20A is mixed with 400 grams of reagent
grade toluene
and heated to reflux with moderate mechanical stirring at 120-125°C.
About 25 ml of
toluene azeotrope is removed to make the reaction completely anhydrous. About
600
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grams of a hydrocarbon mix containing about 10% olefins and 90 % paraffins is
added slowly over 30 minutes, and heating continued for about 2 hours at 130-
135°C.
The reaction mixture is cooled, filtered, and the excess toluene is removed to
obtain a
crude allcyltoluene / paraffin mixture. Paraffin is removed by distillation up
to 250°C.
The final product is distilled at 145-155C at 1-2mm pressure. Gas
chromatography
analysis of distilled product showed a mixture of C10-C13 alkyltoluenes, with
only 2
and 3 phenyl isomers containing para/ortho/meta isomers.
Compositions Having Enhanced Water HardfZess TolerafZCe
A surprising observation of increased water hardness tolerance was
unexpectedly observed when using LAB sulfonates having a high 2-phenyl isomer
content in various cleaning formulations, as set forth below. As is well-known
to those
of ordinary skill in the chemical arts, most ordinary "tap" water contains
varying
amounts of cations of the alkaline earth metals calcium and magnesium. These
metals
are well known to form relatively insoluble complexes (a.k.a. "soap scum")
with most
soap and detergent molecules, including the LAB sulfonate materials of the
prior art.
Such complexation frequently results in precipitation of the salts formed by
the union of
the above-mentioned canons with materials commonly used as soaps, and such
complexation results in precipitation of the complex with an attendant
effective decrease
of the total concentration of detergent in solution. This is an especially
troubling
problem in areas such as parts of Texas where the local water supply may
contain as
much as 0.10 % of calcium and magnesium hardness, which render some soaps and
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detergents essentially useless. To reduce the effects of hardness, formulators
must often
add a chelating agent such as borax, zeolites, citric acid, or EDTA or one of
its sodium
salts, to fornl stable, soluble complexes with hardness minerals, thus masking
and
effectively reducing the effective concentration of the hardness minerals.
Tt was unexpectedly discovered that ionic metallic species such as alkaline
earth
metal cations wluch normally hinder detergent activity by complexation as
described
above do not form insoluble complexes with the LAB sulfonates having a high 2-
phenyl
isomer content as provided herein as readily as they do with LAB sulfonates in
formulations provided by a prior art. The net result of the reluctance of such
ionic
metallic species to form insoluble complexes with LAB sulfonates having a high-
2-
phenyl isomer provided by the invention and the formulations described herein
is that an
effectively higher concentration of such active detergent components is
present in
solution and available for solubilization of oils and general cleaning of
exposed
substrates. This result is astounding, siilce hardness minerals have forever
been an issue
in the f~imulation of every detergent and cleaning composition because of
their
propensity to form insoluble salts with surface active agents. Thus, the
formulations of
this invention are pioneering insomuch as they represent a first major step
away from
considering alkaline earth cations as being an issue in the formulation of
detergents and
the like.
However, the LAB sulfonates of this invention which have a higher 2-phenyl
isomer content than were previously available from the teachings of the prior
art also
have a Krafft temperature which is in the range of between about 15°C
to 30° C,
depending upon the length of the alkyl chain. In cases where such high I~rafft
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temperatures are undesirable, these LAB's may not be the material of choice,
all things
considered. However, the LAT sulfonates of this iizvention wluch have a 2-
phenyl
isomer content in the range of between about 30.00% and 80.00 % have been
observed
to have much lower I~rafft temperatures, typically less than 10° C, and
more typically in
the range of between -5°C and +5° C. These lower Krafft
temperatures are beneficial in
providing the micellular structures necessary for acceptable detergency
characteristics in
most applications; however, the water harcliless tolerance of the high 2-
toluyl isomer
LAT materials is particularly dependent upon the alkyl chain length in the LAT
materials. As is evident from FIG. 10, when the average alkyl chain length of
the LAT
material is below about 10.8, the water hardness tolerance is superior to LAB
material.
However, when the average alkyl chain length is greater than about 11, then
the water
hardness tolerance is inferior to LAB material. Thus it has been found
beneficial in
some formulations to employ mixtures of the high 2-phenyl isomer LAT materials
and
high 2-phenyl isomer LAB materials, in order to arrive at a component useful
in
detergent formulations which has enhanced detergency characteristics at lower
temperatures and a high degree of water hardness tolerance.
Through use of the components having a high 2-phenyl isomer content as
provided herein, formulators may in many instances omit a chelating agent from
their
formulations, or at the least, only moderate, reduced amounts would be
required. Since
such chelants are relatively costly, a savings in manufacture from the
standpoints of
blending and raw material quantities may be passed on to the public.
Cleaning compositions which utilize an allcylbenzene sulfonate of this
invention
having a 2-phenyl isomer content of about 80% in the stead of those having a 2-
phenyl
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isomer content of less than about 50% are in general are possessive of much
greater
cleaning strength. The increase in cleaning performance provided by the
liilear
allcylbenzene sulfonates of this invention having a 2-phenyl isomer content of
about
80% ("Super High 2-Phenyl") is illustrated by the data set forth in FIG. 5
below. In
FIG. 5, the total detergency of a blend comprising a conventional linear
allcylbenzene
sulfonate (denoted as A225 that comprises a 2-phenyl isomer content of about
16 % to
18% of the total alkylbenzene sulfonates present; A225 is available from
Huntsman
Petrochemical Corporation located at 7114 North Lamar Blvd., Austin, Texas.)
containing various added amounts of Super High 2-Phenyl is illustrated as
performance
from laundry testing data. For this series of tests, Super High 2-Phenyl was
blended
with A225 holding the total amount of actives constant at 10%. The samples
were
tested in a 6 pot Terg-o-tometer~ (I1S Testing Corporation) at 2 grams per
liter of
detergent at 100 degrees Fahrenheit, using a 150 ppm hard water with a 15
minute wash
cycle followed by a 5 minute rinse. Standardized soil swatches were used to
assess the
detergency. Results were obtained by measuring the reflectance of the swatches
both
before and after cleaning using a Hunter Lab Color Quest reflectometer using
the L-A-B
scale. All swatches were run in triplicate and the results averaged. Soil
swatches used
were: dirty motor oil, dust sebum, grass stain, blood/milk/ink stain, olive
oil (EMPA),
clay, and clean white swatches to measure redeposition. Both cotton and
polyester/cotton blends were evaluated for all soils. The results show that
the cleaning
performance increases with increasing percentage of 2-phenyl isomer content in
the
blend. The results for the detergent which employed 100 % of material
containing a
high 2-phenyl isomer content were as much as 50 % higher than the conventional
linear
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allcylbenzene sulfonate ("LAS"). In all solutions employed herein for hardness
testing, a
calcium to magnesium ratio of 2 to 1 was employed.
As mentioned above, detergents formulated using Super High 2-Phenyl exhibit
an increased tolerance to water hardness with respect to those formulated
using
conventional, commercially-available linear alkyl benzene sulfonate detergent
components. FIG. 6 below provides turbidity data to evidence the hardness
tolerance of
conventional LAS surfactant A225 present at about 1 % aqueous at various
levels of
water hardness, as measured in NTU units (using a turbidimeter from Orbeco-
Helige of
Farmingdale, N~, the use of which is well known to those of ordinary skill in
the art.
In FIG. 6, the point at which the solution turbidity first undergoes a
dramatic increase is
the point approximately corresponding to the solubility limit of the complex
formed by
the hardness minerals found in the water used and the detergent component.
Thus,
formulations which employ conventional linear allcylbenzene sulfonate
components
similar to A225 begin to experience a decrease in the effective concentration
of a main
ingredient at a water hardness level of around 750 ppm. Of course such efFect
will be
more pronounced for consumers wishing to ration detergents by using less soap
in a
given volume of water than the recommended amount, since the amount of total
hardness with respect to available sulfonate will be greatly increased which
may in some
cases bind up more than half of the sulfonate present.
FIG. 7 provides data for the same hardness tolerance data as was gathered for
FIG. 6 present at about 1 % aqueous; however, the LAS used for gathering these
data
was the Super High 2-Phenyl LAS. From the data in FIG. 7, it is evident that
significant amounts of water-insoluble compounds are not formed until a
hardness level
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of about 1500 ppm is reached, which is about twice the hardness tolerance of
conventional materials. Since the formulations according to the invention
contain high
amounts of the 2-phenyl isomer of linear allcylbenzene sulfonates, they not
only have
increased detergency power, but are also more tolerant to water hardness.
Thus, less
active chemical may be used in a formulation to give it equal cleaning power
to prior a~.-t
formulations which contain greater amounts of linear allcylbenzene sulfonates.
Lowering the amount of active chemical in the formulation saves in raw
material costs,
blending operations, and transportation costs, which savings may be passed on
to the
public.
FIG. 8 provides data for the same hardness tolerance data as was gathered for
FIGS. 6 and 7; however the surfactant concentration was reduced to about 0.1
aqueous to show the effect of reduced surfactant concentration, since the
point at which
precipitates begin to form is dependent upon the total amount of surfactant
present. In
FIG. 8, both A225 and an alkylbenzene sulfonate provided according to the
invention
having a 2-phenyl isomer are compared. From these data, it is evident that
significant
amounts of water-insoluble compounds are formed at hardness levels of about 25
ppm
using the conventional A225 material while the Super High 2-phenyl material
does not
show any precipitation until the hardness level of four time this amount or
about 100
ppm is achieved.
FIG. 9 illustrates an unexpected synergy discovered with respect to blends
containing linear alkylbenzene sulfonates and linear alkyltoluene sulfonates,
in wluch
both of these sulfonated aromatic alkylates have a 2-phenyl isomer content
greater than
75%. The data on the graph are NTU turbidity values for a 0.10% aqueous
solution
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WO 02/24845 PCT/USO1/29396
(hardness of 300 ppm, Ca/Mg = 2:1) to which blends containing these linear
allcylbenzene sulfonates (SLAS) and linear allryltoluene sulfonates (SLATS)
are present
in varying amounts. For each data point, the total combined amount of
surfactant is the
same at 0.10 % of the total solution. From the graph can be observed the
unexpected
minimum when the amount of allcyltoluene sulfonates present are between about
15%
and 55% of the total amount of surfactant present.
Since such a large number of formulations of various cleaning compositions
contain linear allcylbenzene sulfonates as a main detergent component, the
breadth of
applicability of the discoveries according to this invention is great indeed.
Thus, all
cleaning compositions l~nown in the prior art which contain sulfonated linear
allcylbenzenes can be increased in effectiveness and cleaning strength by
being
reformulated to replace at least a portion of the sulfonated linear
alkylbenzenes currently
used with a sulfonated linear allcyltoluene surfactant provided by this
invention that have
an increased percentage of 2-phenyl alkyltoluene isomers over what was
previously
available. Further, since it is possible to blend an LAT sulfonate having a
high 2-phenyl
isomer content produced in accordance with the present invention (on the order
of about
82 %) with conventional LAB or LAT sulfonates, it is also possible according
to the
invention to provide a mixed LAB/LAT sulfonate component useful for forming a
detergent composition or cleaning formulation in which the component has a 2-
phenyl
isomer content of any selected value between about 18% and 82 % by weight
based
upon the total combined weight of all isomers of LAB and LAT sulfonates
present. As
shown in Table 5, allcylbenzenes that contain amounts of the 2-phenyl isomer
u~ excess
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of 80% may be readily produced according to the instant process using the
instant
catalyst.
Formulators of finished detergents would prefer to use LAB based surfactants
having a 2-phenyl isomer content in the range from about 30 to 40 percent, but
this level
has not heretofore been available in commercial quantities. Through use of the
instant
invention, a wide variety of cleaning products comprising LAB and LAT
sulfonates
having between 30% and 40%of 2-phenyl isomer are easily achieved for the first
time
on a commercial scale. Below are set forth examples of some superior
formulations
which employ sulfonated linear alkylbenzenes as surfactants. In each example,
the
LAB sulfonate and the LAT sulfonate used are sulfonates produced in accordance
with table 2, and having 2-phenyl isomer contents of about 81 %. In the
examples,
the term "LAB sulfonate having 80% 2-phenyl content" means an LAB sulfonate
having a 2-phenyl isomer content of 80 % based upon the total of alI LAB
sulfonate
isomers present in the LAB sulfonate. The term "LAT sulfonate having 80% 2-
phenyl
content" means an LAT sulfonate having a 2-phenyl isomer content of 80 % based
upon
the total of all LAT sulfonate isomers present in the LAT sulfonate. In each
of the
Examples given below, all of the ingredients were combined with one another
and
mixed until homogeneous. Then, in each case, the final mixtures were adjusted
, as is
done according to a preferred form of the invention, to a pH in the range of
10-11 using
aqueous NaOH and HCI, as needed. However, any final pH level in the range of
about 7
-12 is may be aclueved. In liquid dishwashing liquids, a pH in the range of
about 7-8
is most desirable.
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It will be seen in the examples below that there are components in each of the
formulas other than the allcylbenzene surfactant component having a high 2-
phenyl
isomer content. These other components are lcnown by those of ordinary skill
in this art
to be useful in formulating soaps, cleaning compositions, hard surface
cleaners, laundry
detergents, and the like. For purposes of this invention and the appended
claims, the
words "other components known to be useful in formulating soaps, detergents,
and the
life" means any material which a formulator of ordinary skill in the soap or
detergent
arts recognizes as adding a benefit to the physical performance, aroma, or
aesthetics of a
combination that is intended to be used as a cleaning composition, regardless
of the
substrate that is intended to be cleansed. Such includes every material that
has been
lcnown in the prior art to be useful in soap and detergent formulations.
In each of the Examples which follow, all percentages are given on a percent
by weight basis based on the total weight of the finished composition, unless
noted
otherwise.
Example 13 - All Purpose Cleaner
LAT sulfonate having 80% 2-phenyl1.3
content
LAB sulfonate having 80% 2-phenyl2.0
content
alkyl sulfate 1.6
coconut fatty acid 1.8
monoethanolamine 1.5
SURFONIC~ L 12-6 12.4
Amine oxide 0.9
Soda ash 0.7
Water 77.8
Total 100
Example 14 - All Purpose Cleaner
LAT sulfonate having 80% 2-phenyl content 0.66
LAB sulfonate having 80% 2-phenyl content 2.64
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alkyl sulfate 1.6
coconut fatty acid 1.8
monoethanolamine 1.5
SURFONIC~ L 12-6 12.4
Amine oxide 0.9
Soda ash 0.7
Water 77.8
Total 100
Example 15 - All Purpose Cleaner
LAT sulfonate having 80% 2-phenyl content 0.66
LAB sulfonate having 2-phenyl content between 2.64
12.0 % and 30.0%
alkyl sulfate 1.6
coconut fatty acid 1.8
monoethanolamine 1.5
SURFONIC~ L12-6 12.4
Amine oxide 0.9
Soda ash 0.7
Water 77.8
Total 100
Example 16 - Pine Oil Microemulsion
Pine Oil 20.0
SURFONIC~ L12-8 4.7
LAT sulfonate having 80% 2-phenyl3.12
content
LAB sulfonate having 80% 2-phenyl4.68
content
Isopropanol 11.0
Triethanolamine 4.7
Water 51.8
Total 100
Example 17 - Pine Oil Microemulsion
Pine Oil 20.0
SURFONIC~ L12-8 4.7
LAT sulfonate having 80% 2-phenyl1.56
content
LAB sulfonate having 80% 2-phenyl6.24
content
Isopropanol 11.0
Triethanolamine 4.7
Water 51.8
Total 100
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Example 18 - Pine Oil Microemulsion
Pine Oil 20,0
SURFONIC~ L12-8 4.7
LAT sulfonate haviilg 80% 2-phenyl content 1.56
LAB sulfonate having 2-phenyl content between 12.0% and 30.0% 6.24
Isopropanol 11.0
Triethanolamine 4.7
Water 51.8
Total 100
Example 19 - Value Brand Powdered Laundry Detergent
LAB sulfonate having 80% 2-phenyl3.9
content
LAT sulfonate having 80% 2-phenyl2.6
content
SURFONIC~ N-95 4.3
Soda ash 29.8
Sodium chloride 45.7
Sodium silicate 11.6
Polymer 2.1
Example 20 - Value Brand Powdered Laundry Deter,_
LAB sulfonate having 80 %2-phenyl5.2
content
LAT sulfonate having 80% 2-phenyl1.3
content
SURFONIC~ N-95 4.3
Soda ash 29.8
Sodium chloride 45.7
Sodium silicate 11.6
Pol~nner 2.1
Example 21- Value Brand Powdered Laundry Detergent
LAB sulfonate having 2-phenyl content between 3.9
12.0% and 30.0%
LAT sulfonate having 80% 2-phenyl content 2.6
SURFONIC~ N-95 4.3
Soda ash 29.8
Sodium chloride 45.7
Sodium silicate 11.6
Polymer 2.1
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WO 02/24845 PCT/USO1/29396
Example 22 - Premium Brand Powdered Laundry Detergent
LAB sulfonate having 80% 2-phenyl5.68
content
LAT sulfonate having 80% 2-phenyl1.42
content
Sodium alkyl sulfate 13.3
Alcohol ethoxylate 2.6
Zeolites 34.7
Soda ash 19.6
Sodium silicate 1.0
Sodium perborate 0.9
TAED 0.5
Sodium sulfate 19.3
Protease enzyme 0.5
Cellulase enzyme 0.5
Total 100
Example 23 - Premium Brand Powdered Laundr~Deter~ent
LAB sulfonate having 80% 2-phenyl4.26
content
LAT sulfonate having 80% 2-phenyl2.84
content
Sodium all~yl sulfate 13.3
Alcohol ethoxylate 2.6
Zeolites 34.7
Soda ash 19.6
Sodium silicate I.0
Sodium perborate 0.9
TAED 0.5
Sodium sulfate 19.3
Protease enzyme 0.5
Cellulase enzyme '
0.5
Total 100
Example 24 - Premium Brand Powdered Laundry Deter,_gent
LAB sulfonate having 2-phenyl content between 4.26
12.0% and 30.0%
LAT sulfonate having 80% 2-phenyl content 2.84
Sodium alkyl sulfate ~ 13.3
Alcohol ethoxylate 2.6
Zeolites 34.7
Soda ash 19.6
Sodium silicate 1.0
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Sodium perborate 0.9
TAED 0.5
Sodium sulfate 19.3
Protease enzyme 0.5
Cellulase enzyme 0,5
Total 100
Example 25 - Value Brand Laundr~Concentrate
LAB sulfonate having 80% 2-phenyl11.1
content
LAT sulfonate having 80% 2-phenyl7.4
content
SURFONIC~ N-95 75.00
Monoethanolamine 6.50
Total 100
Example 26 - Value Brand Laundry Concentrate
LAB sulfonate having 80% 2-phenyl14.8
content
LAT sulfonate having 80% 2-phenyl3.7
content
SURFONIC~ N-95 75.00
Monoethanolamine 6.50
Total 100
Example 27 - Value Brand Laundry Concentrate
LAB sulfonate having 2-phenyl content between 12.0% and 30.0% 14.8
LAT sulfonate having 80% 2-phenyl content 3.7
SURFONIC~ N-95 75.00
Monoethanolamine 6.50
Total 100
Example 28 - Value Brand Laundry Detergent
Concentrate from Example 22, 7.0000
23, or 24
Water (well) 92. I68
Optical Brightener 0.0100
Salt 0.1352
Salt 0.6148
Preservative 0.0100
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Dye 0.0020
Fragrance 0.0600
Total 100
Example 29 - Value Brand Laundry Concentrate
LAB sulfonate having 80% 2-phenyl10.44
content
LAT sulfonate having 80% 2-phenyl7.00
content
SURFONIC~ N-95 34.8
SURFONIC~ T-15 17.4
POGOL~ 300 8.0
Monoethanolamitie 2.4
Water 20.0
Total 100
Example 30 - Value Brand Laundry Concentrate
LAB sulfonate having 80% 2-phenyl13.92
content
LAT sulfonate having 80% 2-phenyl3.48
content
SURF'ONIC~ N-95 34.8
SURFONIC~ T-15 17.4
POGOL~ 300 8.0
Monoethanolamine 2.4
Water 20.0
Total 100
Example 31- Value Brand Laundry Concentrate
LAB sulfonate having 2-phenyl content between 13.92
12.0% and 30.0%
LAT sulfonate having 80% 2-phenyl content 3.48
SURFONIC~ N-95 34.8
SURFONIC~ T-15 17.4
POGOL~ 300 8.0
Monoethanolamine 2.4
Water 20.0
Total 100
Example 32 - Value Brand Laundry Deter. ent
Concentrate from Example 26, 27, or 28 50.000
Water 44.245
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Optical brightener A 0.15
Sodium chloride 0.500
Polyacrylate A 2.500
Chelating agent 1.00
NaOH (50.0% aq.) 0.220
Fragrance 0.300
Preservative 0.080
Melaleuca oil 0.005
Total 100
Example 33 - Premium Laundry Detergent with Enzymes
Concentrate from Example 30, 30.0000
31, or 32
Water (well) 56.2632
Optical brightener 0.0500
Calcium dichloride 0.1000
Sodium chloride 0.6148
Preservative 0.0100
Dye 0.0020
Fr agrance 0.0600
Propylene glycol 10.0000
Borax 2.0000
Protease enzyme 0.7000
Lipase enzyme 0.2000
Total 100
Example 34 - Premium Liduid Dishwashing Formulation I
LAB sulfonate having 80% 2-phenyl 15.44
content
LAT sulfonate having 80% 2-phenyl 10.31
content
De-iouzed water 16.316
Magnesium hydroxide 1.133
Sodium hydroxide (38% aq.) 3.591
SURFONIC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate (3 14.286 (molecular weight
moles EO, 70 % aq.) = 440)
Cocoamidopropyl betaine (38 % aq.)15.789
Ethanol 0.0300
Tetrasodium EDTA 0.1500
Preservative 0.2000
Dye (0.8% aq.) 1.0000
Fragrance 0. 5 000
Total 100
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Example 35 - Premium Liquid Dishwashing Formulation
LAB sulfonate having 80% 2-phenyl20.59
content
LAT sulfonate having 80% 2-phenyl5.16
content
De-ionized water 16.316
Magnesium hydroxide I.I33
Sodium hydroxide (38% aq.) 3.591
SURFONIC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate(3 14.286 (molecular weight
moles EO, 70 % aq.) = 440)
Cocoamidopropyl betaine (38 % 15.789
aq.)
Ethanol 0.0300
Tetrasodium EDTA 0.1500
Preservative 0.2000
Dye (0.8% aq.) 1.0000
Fragrance 0.5000
Total 100
Example 36 - Premium Liquid Dishwashing Formulation
LAB sulfonate having 2-phenyl content between20.59
12.0% and 30.0%
LAT sulfonate having 80% 2-phenyl content 5.16
De-ionized water 16.316
Magnesium hydroxide 1.133
Sodium hydroxide (38% aq.) 3.591
SURFONIC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate (3 moles EO, 14.286 (mw
70 % aq.) =440)
Cocoamidopropyl betaine (38 % aq.) 15.789
Ethanol 0.03 00
Tetrasodium EDTA 0.1500
Preservative 0.2000
Dye (0.8% aq.) 1.0000
Fragrance 0.5000
Total 100
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Example 37 - Premium Liquid Dishwashing Formulation
LAB sulfonate having 80% 2-phenyl6.12
content
LAT sulfonate having 80% 2-phenyl4.08
content
De-ionized water 35.567
Magnesium hydroxide 1.133
Sodium hydroxide (38 % aq.) 1.250
SURFOMC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate (40%20.000 (molecular weight
aq.) = 440)
All~yl polyglycoside (50% aq.) 6.000
Fatty acid MEA amide 3.000
Tetrasodium EDTA 0.150
Preservative 0.200
Fragrance 0.500
Total 100
Example 38 - Premium Liquid Dishwashing Formulation
LAB sulfonate having 80% 2-phenyl8.16
content
LAT sulfonate having 80% 2-phenyl2.04
content
De-ionized water 35.567
Magnesium hydroxide 1.133
Sodium hydroxide (38 % aq.) 1.250
SURFONIC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate (40%20.000 (molecular weight
aq.) = 440)
Alkyl polyglycoside (50% aq.) 6.000
Fatty acid MEA amide 3.000
Tetrasodium EDTA 0.150
Preservative 0.200
Fragrance 0.500
Total 100
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Example 39 - Premium Liduid Dishwashing Formulation
LAB sulfonate having 2-phenyl content between 8.16
12.0% and 30.0%
LAT sulfonate having 80% 2-phenyl content 2.04
De-ioiuzed water 35.567
Magnesium hydroxide 1.133
Sodium hydroxide (38 % aq.) 1.250
SURFONIC~ SXS-40 (40% aq.) 15.000
Propylene glycol 6.000
Sodium lauryl ether sulfate (40% aq.) 20.000
(molecular weight = 440)
Alkyl polyglycoside (50% aq.) 6.000
Fatty acid MEA amide 3.000
Tetrasodium EDTA 0.150
Preservative 0.200
Fragrance 0.500
Total 100
Example 40 - Powdered Aircraft Cleaner
Metso pentabead 20 (sodium metasilicate)30.0
Sodium tripolyphosphate 30.0
Ammonium bifluoride 8.0
Tetrasodium pyrophosphate 20.0
LAB sulfonate having 80% 2-phenyl content4.0
LAT sulfonate having 80% 2-phenyl content8.0
Example 41- Powdered Aircraft Cleaner
Metso pentabead 20 (sodium metasilicate)30.0
Sodium tripolyphosphate 30.0
Ammonium bifluoride 8.0
Tetrasodium pyrophosphate 20.0
LAB sulfonate having 80% 2-phenyl content8.0
LAT sulfonate having 80% 2-phenyl content4.0
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Example 42 - Powdered Aircraft Cleaner
Metso pentabead 20 (sodium metasilicate)30.0
Sodium tripolyphosphate 30.0
Ammonium bifluoride 8.0
Tetrasodium pyrophosphate 20.0
LAB sulfonate having 80% 2-phenyl content8.0
LAT sulfonate having 80% 2-phenyl content4.0
Example 43 - Dairy Cleaner
Sodium hexametaphosphate 20.00
Sodium Sulfate 20.00
LAB sulfonate having 80% 2-phenyl content 30.00
LAT sulfonate having 80% 2-phenyl content 10.00
Example 44 - Dairy Cleaner
Sodium hexametaphosphate 20.00
Sodium Sulfate 20.00
LAB sulfonate having 80% 2-phenyl content 10.00
LAT sulfonate having 80% 2-phenyl content 30.00
Example 45 - Powdered Dairy Cleaner
LAB sulfonate having 80% 2-phenyl content 3.00 - 50.00
LAT sulfonate having 80% 2-phenyl content 3.00 - 50.00
Sodium sulfate 0.00 - 20.00
Sodium metasilicate 0.00 - 30.00
Nonionic surfactant 5.00
Example 45 - Powdered Neutral Dairy Cleaner
LAB sulfonate having 80% 2-phenyl content x (where x = 0.00 to 33.00)
LAT sulfonate having 80% 2-phenyl content 33-x
Non-ionic surfactant 1.00
Monsanto Phosphate STP/A 33.00
Monsanto Phosphate SAPP/A 33.00
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Example 46 - Vehicle Wash, Powder
Sodium tripolyphosphate 36.00
Tetrasodium pyrophosphate 30.00
Sodium metasilicate, anhydrous 20.00
LAT sulfonate having 80% 2-phenyl 5.00
content
Shell Chemical Co. Neodol 91-6 8.00
Monsanto Co. bequest 2006 phosphonate1.00
Examule 47 - Aluminum Vehicle Wash, Powder
Sodium tripolyphosphate 36.00
Tetrasodium pyrophosphate 30.00
Sodium metasilicate, anhydrous 20.00
LAB sulfonate having 80% 2-phenyl 5.00
content
Shell Chemical Co. Neodol 91-6 8.00
Monsanto Co. bequest 2006 phosphonate1.00
The above examples are intended to be exemplary of the versatility of the
compositions produced according to the invention with respect to the
formulation of
household and commercial cleaning formulations, and are not intended to be
delimitive
thereof in any way whatsoever. Any formulation of a soap, detergent, cleaning
composition, whether liquid or solid, regardless of its intended use, that in
its common
use formulation contains a LAB sulfonate as a component can be increased in
effectiveness by having the current commercial LAB sulfonate component used in
its
formulation removed and a component comprising an LAB sulfonate component
having
an elevated 2-phenyl isomer content and an LAT sulfonate component having an
elevated 2-phenyl isomer content substituted therefor. The present invention
thus
represents a revolutionary advance in the detergent arts, since the preferred
2-phenyl
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isomers of aromatic alkylates may now be produced in high yield, e~ n2asse,
for
approximately the same cost as inferior prior art LAB sulfonate mixtures.
In the foregoing formulations, the relative proportions of the LAB sulfonates
to
the LAT sulfonates is in the range of 1.5:1 to 4:1. This is because of an
unexpected
synergy we have discovered in relation to the relative amounts of LAB to LAT
sulfonates present in aqueous detergent solutions which contain these
materials. Our
discovery is depicted pictorially in FIG. 9.
It has also been discovered that salts of alkylbenzene sulfonates having a 2-
phenyl isomer content greater than about 60 % may be isolated as solids at
room
temperature. This result is surprising since salts of alkylbenzene sulfonates
have
heretofore been believed to exist only in liquid form. Thus, by the present
invention, it
is now possible to provide dry powder formulations comprising alkylbenzene
sulfonates, such as dry laundry detergents, dry dishwashing detergents, etc.
Such dry
formulations may be provided using existing blending techniques, including the
use of
conventional dry processiizg equipment such as ribbon blenders, etc., and also
include
detergent tablets for laundry use.
To produce a solid alkylbenzene salt according to a preferred form of the
invention, one begins with the sulfonic acid mixture which is produced from
sulfonating
an alkylbenzene mixture prepared in accordance with the invention, such as any
of
samples 4 through 7 of table 2 above, which contain more than about 80.0 % of
the 2-
phenyl isomers. Such sulfonic acids are then dissolved in water to a
concentration of
about 10.0 % by weight, and neutralized by slow addition of an alkaline
aqueous
solution of the desired cation, such as through the use of alkali hydroxides,
until
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stoichiometric neutralization has occurred, which in the case of sodium and
potassium is
when a pH of about 10.5 is reached. Finally, the water is removed by
evaporation or by
other means known to those skilled in the chemical arts, such as through the
use of a
ROTOVAP~ evaporator or the lilce, spray dryer, turbodryer, etc. thus leaving
crystals of
the allcylbenzene sulfonate salt. Such crystals may be conveniently purified
further by
recrystallization from ethanol. The sodium and potassium salts of
allcylbenzene
sulfonate according to sample 4 of table 2 have a melting point in the range
of about 50°
to ~0° C, depending upon the all~yl chain length, with longer chain
length materials
having a lugher melting point. The test method used is differential scanning
calorimetry according to ASTM specification D-3417.
Cationic surfactants may also function as a canon in forming a stable, solid
salt
of an allcylbenzene sulfonate. ' Cationic surfactants are well known in the
art as being
surfactants with a positively-charged ionic group in their molecular
structure, such as
the as quaternary ammonium compounds. Cationic surfactants are known to
function
together with other parts of a formulated detergent system to lower the
water's surface
tension. They are typically used in wash, rinse and dryer-added fabric
softeners.
Thus, when a cationic surfactant is employed for providing charge balance in a
solid
allcylbenzene sulfonate salt according to the invention, a formulator using
such a salt
is able to reap added benefit from the presence of both a cationic surfactant
and an
anionic surfactant in the same solid material, which may be powdered. Such
salts
therefore may reduce the costs associated with storage and blending of
different
materials, as is currently common in the art owing to the presence of both a
surfactant
and a detergent in the same molecule.
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Owing to the unexpected finding that certain salts of the alkylbenzene
sulfonates having sufficient 2-phenyl isomer content are solids at room
temperature,
the present invention also comprises as formulations useful for cleaning
latmdry
which comprise solid tablets, as well as solid bars of soap comprising the
solid
allcylbenzene sulfonates as an active detergent component.
Detergent tablets are described, for example, in GB 911 X04 (Unilever), U.S.
Pat. No. 3,953,350 (I~ao), JP 60 015 SOOA (Lion), JP 60 135 497A (Lion) and JP
60
135 498A (Lion); and are sold commercially in Spain. Detergent tablets are
generally
made by compressing or compacting a detergent powder, as is well-known in the
art.
Thus, the present invention contemplates substitution of at least a portion
of, and more
preferably all of, the active detergent component of a conventional laundry
tablet of
the prior art with a salt of an alkylbenzene sulfonate having sufficiently
high 2-phenyl
isomer to cause such salt to exist in the form of a solid at room temperature.
Such
substitution is readily made by providing such solid sulfonate in the stead of
the
conventional detergent component of the conventional laundry tablet during
laundry
tablet manufacture.
Bars of soap are made by various means knomn to those in the art including
the pouring into molds of a caustic/oil mixture prior to its full
saponification, or the
use of "soap noodles" in a press with or without the aid of heat and pressure.
Soaps
typically include fatty acid carboxylates, perfumes, dyes, preservatives,
bactericides,
fillers such as talc, and other additives. The present invention contemplates
substitution of at least a portion of, and more preferably all of, the active
cleaning
component of a conventional bar of soap of the prior art with a salt of an
alkylbenzene
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sulfonate having sufficiently high 2-phenyl isomer to cause such salt to exist
in the
form of a solid at room temperature. Such substitution is readily made by
providing
such solid sulfonate in the stead of the conventional detergent component of
the
conventional bar of soap during soap manufacture. Thus, a bar of soap
according to
the invention may comprise only the Super High 2-phenyl allcylbenzene
sulfonate
according to the invention, in combination with sufficient binders, perfumes,
dyes,
etc. to form a solid bar of soap, using in one form of the invention the same
general
compression techniques useful for producing laundry tablets.
Although the present invention has been shown and described with respect to
ceutain preferred embodiments, it is obvious that equivalent alterations and
modifications will occur to others skilled in the art upon the reading and
understanding of the specification. The present invention includes all such
equivalent
alterations and modifications, and is limited only by the scope of the claims
which
now follow.
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