Canadian Patents Database / Patent 1099656 Summary

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(12) Patent: (11) CA 1099656
(21) Application Number: 254838
(54) English Title: MANUFACTURE OF GASOLINE
(54) French Title: TRADUCTION NON-DISPONIBLE
(52) Canadian Patent Classification (CPC):
  • 196/104
(51) International Patent Classification (IPC):
  • C10G 3/00 (2006.01)
(72) Inventors :
  • CHANG, CLARENCE D. (United States of America)
  • LANG, WILLIAM H. (United States of America)
  • SILVESTRI, ANTHONY J. (United States of America)
(73) Owners :
  • MOBIL OIL CORPORATION (United States of America)
(71) Applicants :
(74) Agent: KIRBY EADES GALE BAKER
(45) Issued: 1981-04-21
(22) Filed Date: 1976-06-15
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
592,434 United States of America 1975-07-02

English Abstract


8715 MANUFACTURE OF GASOLINE

ABSTRACT OF THE DISCLOSURE
Reacting mixtures of difficultly convertible
aliphatic organic oxygenate compounds, such as short chain
aldehydes, carboxylic acids or carbohydrates with easily con-
vertible aliphatic alcohols, ethers, acetals and analogs
thereof over a crystalline aluminosilicate zeolite having
a silica to alumina ratio of at least about 12 and a constraint
index of about 1 to 12, at elevated temperatures, 0.5 to 50
LHSV and 1 to 200 atmospheres to produce a product comprising
water, full range highly aromatic hydrocarbon gasoline and
light aliphatic hydrocarbon gases having an improved production
of C6 to C10 monocyclic aromatic hydrocarbons.


Note: Claims are shown in the official language in which they were submitted.


The embodiments of the invention in which an exclusive
property or privilege is claimed is defined as follows:
1. In a process of converting lower aliphatic oxygen
containing organic compounds of the empirical formula
CnHm-2p?pH2O where n is the number of carbon atoms up to
about 8, p is the number of oxygen atoms and m is the number of
hydrogen atoms in the feed, to a product comprising water
and hydrocarbons, said hydrocarbons containing a preponderance
of the carbon of said organic compounds, by contacting such
feed with a crystalline aluminosilicate zeolite catalyst
having a silica to alumina ratio of at least about 12 and a
constraint index of about 1 to 12 at an elevated temperature
of at least about 500°F, and a space velocity of about 0.5 to
50 LHSV; the improvement, which comprises providing as said
feed a mixture of a difficultly convertible said organic
compound having a value of Image of up to 1 and an easily
convertible said organic compound having no carboxylic acid
groups and having a value of R greater than 1, said mixture
having a cumulative value of R of greater than 1 and a
stoichiometric deficiency of carboxylic acid groups, whereby
a hydrocarbon product of increased aromaticity is obtained.
2. The improved process claimed in claim 1 wherein said
feed mixture comprises at least a carboxylic acid and a
monohydric alcohol.
3. The improved process claimed in claim 1 wherein said
product hydrocarbons consist essentially of C? light
aliphatics and C? full boiling range, highly aromatic
gasoline.


21



4. The improved process claimed in claim 1 wherein
said feed comprises as said difficultly convertible compounds
at least one member selected from the group consisting of C1
or C2 aldehydes, polyhydric alcohols, carboxylic acids, car-
bohydrates and carboxylic acid anhydrides, and as said
easily convertible compounds at least one member of the group
consisting of alcohols, ethers, ketones, esters of carboxylic
acids and C? aldehydes.


5. The improved process claimed in claim 1 carried
out at about 600 to 900°F.


6. The improved process claimed in claim 1 using
a ZSM-5 zeolite as the catalyst.


7. The improved process claimed in claim 2 wherein
said difficultly convertible material is selected from the
group consisting of acetic acid, acetaldehyde and a
formaldehyde moiety.


8. The improved process claimed in claim 1
including converting a mixture of acetic acid and methanol
to a product comprising toluene.

-22-

Note: Descriptions are shown in the official language in which they were submitted.

1~99~56

This invention relates to the synthetic production
of gasoline. It more particularly refers to an improved
method of converting simple organic chemicals, particularly
certain mixtures thereof to hydrocarbons boiling in the
gasoline boiling range.
Gasoline, as such term is used in the instant
specification, and as such term is commonly used in the
petroleum industry, is a motor fuel for internal combustion
engines. It is hydrocarbon in nature being composed ôf
various aliphatic and aromatic hydrocarbons having a full
boiling range of about C5 to about 280 to 430F. depending
upon the exact blend used and the time of the year. Although
gasoline is predominantly hydrocarbon in nature, various
additives which are not necessarily exclusively hydrocarbon
are often included. Additives of this type are usually
present in very small proportions, e.g. less than 1% by
volume of the total gasoline. It is also not uncommon for
various gasolines to be formulated with non-hydrocarbon
components, particularly alcohols and/or ethers, as significant
although not major, constituents thereof. Such alcohols,
~ 20~ ~ ethers and the like have burning qualities in internal com-
- busion engines which are similar to those of hydrocarbons
; in the gasoline boiling range. For purposes of this applica~
tion, the term "gasoline" is used to mean a mixture of
hydrocarbons boiling in the aforementioned gasoline boiling
range and is not intended to mean the above-referred to
additives and/or non-hydrocarbon constituents.
It is generally known that various specific hydro-
carbon compounds or isomeric mixtures of h~drocarbon compounds


--2--
.. ~,

.. .. . ~, . ,., .... . .. .... ~ . ....... ... , ..... _ . ..... ......... . .... .... .. .. .. .. .. .. . . . . . .

1~99656

8715 boiling in the gasoline boiling range can be made by
converting various appropriate organic chemicals using
specific processes particularly adapted to the particularly
desired conversion. Thus7 for example, acetone can be con-
verted to mesitylene over many different acid catalysts,
including acid zeolites. Propylene can be converted to
2-ethyl hexane by a combination of hydroformylation, hydrogena-
tion and Aldol condensation, using ametal catalyst in a basic
system, through an aldehyde and/or alcohol intermediate (butyr-
aldehyde and 2-ethyl hexanol). Sirnilarly, acetaldehyde can
be converted to iso-octane by Aldoling and hydrogenolysis.
Methanol can be converted to toluene by alkylation of benzene
using an acid zeolite catalyst.
It 1~ clear, however, that all of the known
processes of this type do not produce a wide range of hydro-
carbon products, and do not even produce significant quan-
tities of full range gasoline. U.S. Patent 2,950,332,
Mattox, discloses the use of crystalline alumin~ilicate
zeolites as catalysts to convert ketones to aromatics, particu-
~20 larly acetone to mesitylene. In particular, rather low silica
to alumina ratio zeolites, such as Y, were employed by this
patentee. His reaction temperatures were about 300 to 900~.
and he produced as much as about 43% Cg~ aromatics from
acetone at 500~.
U.S. Patent 3,728,408, Tobias, carried this
conversion over into the use of high silica to alurnina
ratio zeolites, such as dealuminized Y and ZSM-5. Tobias
insisted upon a minimum silica to alumina ratio of 10 and
showed a 25~ conversion of acetone to mesitylene and mesityl
oxide using a 17 to 1 silica to alumina ratio ZSM-5 at 200C.

-3-

~ )99656

(392F.). The ratio of mesifyl oxide to mesitylene in -
Tobias' product was reported to be 9 to 1. This calculates
out to a yield of 2.07% (by wt) mesitylene based upon ace~one
~eed. As noted in the prosecution of the above-re~erred to
parent application. consideration of the gas chromatograph of
Tobias' product fails to show the production of any aromatic
hydrocarbon, or in fact any hydrocarbon, other than mesitylene.
U.S. Patent 2,456,584 is also worthy of note, for
reasons which will become apparent below, becuase it dis-
closes the conversion of dimethylether to hydrocarbongasoline using a silica alumina catalyst. This reference
indicates that while dimethyl ether by itself is poorly
converted to gasoline, in admixture with isobutane, the mix-
ture converts very nicely to aromatic gasoline.
With all~this prior art at his disposal, the
routineer in the chemical arts still does not know how to
convert relatively simple hetero-atom containing organic
chemicals directly to hydrocarbon gasoline, particularly full ~ .
range gasoline, of commercial quality and in commercial
quantity.
~ t is, therefore, an ob~ect of this invention to
provide an improved means of convertlng relatively simple organic
campounds to gasoline.
Thus the present invention relates to a process
of converting lower aliphatic oxygen containing organic
compounds of the empirical formula CnHm_2p pH20 where _ is
the number of carbon atoms up to about 8, p is the number of
oxygen atoms and _ is the number of hydrogen atoms in the
feed, to a product comprising water and hydrocarbons, said
hydrocarbons containing a preponderance of the carbon of
- 4

,.~

lU99~i56

said organic compounds, by contacting such feed with a
crystalline aluminosilicate ziolite catalyst having a silica
to alumina ratio of at least about 12 and a constraint index

of about 1 to 12 at an elevated temperature of at least about
500F, and a space velocity of about 0.5 to 50 LHSV. The
novel feature relates to an improvement whereby the aromaticity
of the hydrocarbon product is increased by a method which
comprises providing as said feed a mixture of a difficulty
convertible said organic compound having a value of R=m-2p
of up to 1 and an easily convertible said organic compound
having no carboxylic acid groups and having a value of R of
greater than 1, said mixture having a cumulative value of R of
greater than l and a stoichiometric deficiency of carboxylic
acid groups.
It will be appreciated that within the ranges of
operatlng parameters recited will exist certain combinations
of conditions which will direct the conversion toward specific
types of products.
Therefore, it is appropriate to indicate that ln
addition to the temperature specified above as a critical
variable, there is also a critical variable in the severity
of operation as well as a preferred critical variable in the
mode of operation. Within the operating parameters specified
above, there are a number of combinations of temperature and
residence time, sometimes reported as space velocity in a
continuous system, which in combination define the severity
required to achieve a given desired result. Since there is
no generally accepted unit or numerical designation for severity,
it is believed appropriate in this situation to define severity




~3

1~9965~
, .


in terms of product composition; that is that combination of
temperature, pressure and contact time which will yield a product
in which the major proportion, based on the carbon contained
in the feed, of the carbon is in the form of hydrocarbons, the
preponderant components of which are C6 to C10 monocyclic
aromatic hydrocarbons.
Consideration of the data presented in this specifi-
cation indicates that a wide variety of hydrocarbon compounds
~ are produced by the process hereof and that some if not most~
of them are not predictable from the specified reactant by any
classical chemical conversion theory or mechanism.
It is remarkable that when carrying out the process
of this invention under any given set of reaction conditions,
it does not seem to partlcularly matter what reactant or
reactant mixture is chosen, the product slate seems to be
just about the same, e.g. ethyl acetate gives just about the
same products as does acetone. This appears to be a qualitative
fact, that is that the product slate produced is substantially
equivalent. There are differences in proportion of individual
constituents of the product slate as a function of the parti-
cular reactant conditions chosen, but the product slate appears
to remain substantially unaltered. In fact, it would appear
that the product slate is not a function of any specific
reactant. Under equivalent operating conditions, substantially
the same product results regardless of which specific reactants
are used.

099~;56
,~ . . . ' .. . . . .
.... . . . .
.. , :. . ' .. ,' . . - . ' :. -
. . . ..,. , . .. . , :
- -
. ~, ,
.
.The speciaI zeol-ite cakalysts referred ko herein
. utilize members of a special class of zeolites exhibiting some
unusual properties.' These zeolites inauce profound trans-
formations of aliphakic'hydrocarbons to aromakic hydrocarbons
in commercially desirable yields and are generally highly
- . , - . . . . .
~ ~ ef~ective ln alkylation, isomerization, disproporkionakion
~ - I
' ' and other reactions involving aro~atic hydrocarbons. Alt~ou~h
.
' they have unusually low alumina contents, i.e. high silica to
' ' alumina ratios, they are very active even with silica to
10; alumina rakios exceeding 30. This activity is surprising since
' catalytic activity of zeolites is generally attributed to
''" ~xamework aluminum akoms and cations associaked wikh these
, ., .,. . - . i
- ' aluminum atoms. These zeolites retain their crys~allinity
or''lo~g periods in spike of khe presence of s~eam e~en a~
.. , ~, ~ . , ,
~15 ~ high temperakures which induce irreversible collapse of the
crystal ~ramework of okhèr zeolites, e.g. of the X and'A kype.
Furthermore, carbonaceous deposits, when formed, may be
' removed by burning ak higher than usual temperatures to restore
- ,~:: - ; ,
act~ity~ In many environmenks, khe zeolites of this class
' exhibit Yery low coke forming capabiliky, conducive ko very
long times on stream between burning regenerations.
An important characteristic of the crystal structure
of th~s class of zeolites ~s that it pro~des cons~rained
' access to~ and egress from, the intra-crystalline free

,

..
.
-7- ~-
t . r~

.. .. .. ..

1G~99656

space by virtue of having a pore dimension greater than about
5 Angstroms and pore windo~s of about a size as would
be provided by lO-membered rings of oxygen atoms. It is
to be understood~ of course, that these rings are those formed
by the regular disposition of the tetrahedra making up the
anionic framework of the crystalline aluminosilicate, the
oxygen atoms themselves being bonded to the silicon or
aluminum atoms at the centers of the tetrahedra. Briefly,
the preferred zeolites useful as catalysts in this invention
possess, in combination: a silica to alumina ratio of at
least about 12; and a structure providing constrained access
to the crystalline free space.
The silica to alumina ratio referred to may be
determined by conventional analysis. This ratio is meant to
represent, as closely as possible, the ratio in the rigid
anionic framework of the zeolite crystal and to exclude
aluminum in the binder or in cationic or other form within
the channels. Although zeolites with a silica to alumina
ratio of at least 12 are useful, it is preferred to use
zeolites having higher ratios of at least about 30. Such
zeolites, after activation, acquire an intracrystalline
sorption capacity for noraml hexane which is greater than
.~
that for water, i.e. they exhibit "hydrophobic" properties.
It is believed that this hydrophobic character is advantageous
i the present invention.
The zeolites useful as catalysts in this invention
~reely sorb normal hexane and have a pore dimension greater
than about 5 Angstroms. In addition, their structure must
provide constrained access to some larger molec~les. It is
sometimes possible to judge from a known crystal structure

--8--

99~iS6

whether such constrained access exists. For example,.if the
only pore windows in a crystal are formed by 8-membered rings
of oxygen atoms, then access by molecules of larger cross-
section than normal hexane is substantially excluded and the
zeolite is not of the desired type. Zeolites with windows
of 10-membered rings are preferred, although excessive
puckering or pore blockage may render these zeolites
substantially ineffective. Zeolites with windows of twelve-
membered rings do not generally appear to offer sufficient
constraint to produce the advantageous conversions desired
in the instant invention, although structures can be conceived,
due to pore blockage or other cause, that may be operative.
Rather than attempt to judge from crystal structure
whether or not a zeolite possesses the necessary constrained
access, a simple determination of the "constraint index" may
be made by continuously passing a mixture of equal weight of
normal hexane and 3-methylpentane over a small sample, approx-
imately 1 gram or less, of zeolite at atmospheric pressure
; according to the following procedure. A sample of the
zeolite, in the form of pellets or extrudate, is crushed to
a particle size about that of coarse sand and mounted in a
glass tube. Prior to testing, the zeolite is treated with a
stream of air at 1000F for at least 15 minutes. The zeolite
is then flushed with helium and the temperature adjusted
between 550F and 950F to give an overall conversion between
10% and 60%. The mixture of hydrocarbons is passed at 1
liquid hourly space velocity (i.e., 1 volume of liquid hydro-
carbon per volume of catalyst per hour) over the zeolite with
a helium dilution to give a helium to total hydrocarbon mole




_ g _
X

1(t996S~


ratio of 1~:1. After 20 minutes on stream~ a sample of the
e~fluent is taken and analyzed, most conveniently by gas
chromatography~ to determine the fraction remainlng unchanged
for each of the two hydrocarbons.
The "constraint index" is calculated as follows:
Constraint Index = log (fraction of n-hexane remaining)
loglO ~fraction of 3-methylpentane
remaining)

The constraint index approximates the ratio of the
cracking rate constants for the two hydrocarbons. Catalysts
suitable for the present invention are those which employ a
zeolite having a constraint index from 1.0 to 12Ø Constraint
Index (CI) values for some typical zeolites including some
not within the scope of this invention are:

i 15 CAS C.I.
ZS~-5 8.3
ZSM-ll 8 7
ZSM-35 4 5
TMA Offretite 3.7
ZSM-12 2
ZSM-38 2
Beta o.6
ZSM-4 0 5
Acid Mordenite 0.5
~25~ REY 0.4
Amorphous
Silica-alumina o.6
Erionite 38
The above-described Constraint Index is an important
and even critical, definition of those zeolites which are
useful to catalyze the instant process. The very nature of
this parameter and the recited technique by which it is deter-
mined~ however, admit of the possibility that a given zeolite
can be tested under somewhat different conditions and thereby
have different constraint indexes. Constraint Index seems to


--10--

.

g~6S6

vary somewhat with severity of operation (conversion). There-
fore, it will be appreciated that it may be possible to so
select test conditions to establish multiple constraint indexes
for a particular given zeolite which may be both inside and
outside the above defined range of 1 to 12.
Thus, it should be understood that the "Constraint
Index" value as used herein is an inclusive rather than an
exclusive value. That is, a zeolite when tested by any
combination of conditions within the testing definition set -~
forth herein above to have a constraint index of 1 to 12 is
intended to be included in the instant catalyst definition
regardless that the the same identical zeolite tested under
other defined conditions may give a constraint index value
outside of 1 to 12.
The class of zeolites defined herein is exemplified
by ZSM-5, ZSM-ll, ZSM-12, ZSM-21, ZSM-35, ZSM-38, and other

similar material. U.S. Patent 3,702,886 issued November 14, 1972
describes and claims ZSM-5.
ZSM-ll is more particularly describad in U.S. Patent
3,709,979, issued January 9, 1973.
ZSM-12 is more particularly described in U.S. Patent
3,832,449, issued August 27, 1974.
U.S. Patent 4,016,245 issued April 5, 1977, describes
a zeolite composition including a method of making it. This
composition is designated ZSM-35 and is useful in this
invention.
U.S. Patent 4,046,859 issued September 6, 1977, describes
a zeolite composition including a method of making it. This
composition is designated ZSN-38 and is useful in this
invention.

1099656


The specific zeolites described, when prepared in
the presence of organic cations, are substantially catalytically
inactive, possibly because the intracrystalline free space is
occupied by organic cations from the forming solution. They
may be activated by heating in an inert atmosPhere at 100F
for one hour, for example, followed by base exchange with
ammonium salts followed by calcination at 1000F in air. The
presence of organic cations in the forming solution may not be
absolutely essential to the formation of this special type
zeolite; however, the presence of these aations does appear
to favour the formation of this special type of zeolite.
More generally, it is desirable to activate this type zeolite
by base exchange with ammonium salts followed by calcination
in air at about 100 for from about 15 minutes to about 24
hours.
Natural zeoli-es may sometimes be converted to this




` - 12 -

- 1~99656


type zeolite by various activation procedures and other
treatments such as base exchange, stearning, alumina extrac-
tion and calcination, alone or in combinations. Natural
minerals which may be so treated include ferrierite, brewsterite,
stilbite, dachiardite, epistilbite, heulandite and clinoptiolo-
lite. The preferred crystalline aluminosilicates are ZSM-5,
ZSM-ll, ZSM-12, ZSM-21, ZSM-35 and ZSM-38, with ZSM-5 particularl~
preferred.
The zeolites used as catalysts in this invention
may be in the hydrogen form or they may be base exchanged or
impregnated to contain ammonium or a metal cation complement.
It is desirable to calcine the zeolite after base exchange.
The metal cations that may be present include any of the
cations of the metals of Groups I through ~III of the periodic
table. However, in the case of Group IA metals, the cation
content should in no case be so large as to substantially
eliminate the activity of the zeolite for the catalysis being
employed in the instant invention. For example, a completely
sodium exchanged H-ZSM-5 appears to be largely inactive for
shape selective conversions required in the present invention.
In a preferred aspect of this lnvention, the
zeolites useful as catalysts herein are selected as those
having a crystal framework density, in the dry hydrogen form,
of not substantially below about 1.6 grams per cubic centi-
meter. It has been found that zeolites which satisfy all
three of these criteria are most desired. Therefore, the
preferred catalysts of this invention are those comprising
zeolites having a constraint index as defined abo~e of about
1 to 12, a silica to alumina ratio of at least about 12 and a


' '' ' 1 '

.....

~99656


dried crystal density of not substantially less than about 1.6
grams per cubic centimeter. The dry density for known
structures may be calculated from the number of silicon plus
aluminum atoms per 1000 cubic Angstroms, as given,e.g. on
page 19 of the article on Zeolite Structure by W.M. Neier.
This paper is included in "Proceedings of the Conference on
Molecular Sieves, London, April 1967", published by the
Society of Chemical Industry, London, 1968. When the crystal
structure is unknown, the crystal framework density may be
determined by classical pyknometer techniques. For example,
it may be determined by immersing the dry hydrogen form of
the zeolite in an organic solvent which is not sorbed by the
crystal. It is possible that the unuuual sustained activity
and stability of this class of zeolites in associated with
its high crystal anionic framework density of not less than
about 1.6 grams per cubic centimeter. This high density -
of course must be associated with a relatively small amount
of free space within the crystal, which might be expected to
result in more stable structures. This free space, however,
seems to be important as the locus of catalytic activity.
Crystal framework densitites of some typical
zeolites including some which are not within the purview
this invention are:




- 14 -

11~9965~i

Void Fr~mework
Zeolite Volume Density
~'errierite 0.28 cc/cc 1.76 g/cc
Mordenite .28 1.7
ZSM-5, -11 .29 1.79
Dachiardite .32 1.72
L .,32 1.61
Clinoptilolite .3/-~ 1.71
Laumontite .34 1 77
ZSM-4 (Omega? .38 1 65
Heulandite .39 1.69
P .41 1-57
Offretite .4O 1.55
Levynite .4O 1.54
Erionite .35 1.51
Gmelinite .44 1.46
Chabazite .47 1.45
: A .5 1.3
; Y .48 1.27
I-t has been noted in the abo.ve-referred to parent
application that carbonyl containing lower organic compounds
in general convert according to the process of this
invention to products comprising aromatic gasoline. It has
now been discovered that short chain aldehydes (one or two
carbon atoms), carboxylic acids and anhydrides, glycols,
glycerin, and carbohydrates, although they do convert to
: highly aromatic gasoline, convert in a less satisfactory
manner with poorer catalyst cycle life. It has been found,
and it is a most important aspect of this invention, that
~30 these difficulty convertible feeds can be converted to
: desired product mixtures, particularly highly aromatic full
range gasoline, in a synergistically better manner if the
conversion is carried out as aforesaid but with a mixture of
these difficulty convertible oxygenates and an easily
`~ converted oxygenate such as alcohols, ethers, esbers, long
chain aldehydes, ketones and their analogues.
The difficulty convertible oxygenate feeds seem to
fall into certain categories of organic compounds. This


- 15 -

1099656
-I

categorization is empirlcal rather than theoretical. As
noted, carboxylic acids and anhydrides, carbohydrates such
as starch and sugars, lower glycols, glycerin, and other
polyols and short chain aldehydes seem to be difficult to
convert to a desirable product with an acceptable catalyst
life. Organic carboxylic acids of any chain length are
difficultly convertible.
Organic oxygenates use~ul in this invention have
an empirical formula which can be written:
C Hm_2p P 2

where n is the number of carbon atoms in the moleule, _ is
the number of oxygen atoms in the molecule and m is the number
of hydrogen atoms in the molecule. Difficultly convertible
~ 15 oxygenates, as the term is used herein, are those in which
! the relation:
R = m-2p

is equal to or less than 1. Easily convertible oxygenates, as
the term is used herein, are those in which this relation R
is greater than 1.
These criteria are separate and distinct, not
~cumulative. That is if an aliphatic organic oxygenate is
either an acid or has value of R up to 1, it is considered to
be difficultly convertible. Easily convertible aliphatic
organic oxygenates are non-carboxylic acids having a value of
R greater than 1. These criteria are ~cumulative in that the
compound must satlsfy both criteria. The preferred embodiment
of this invention requires the conversion o~ a mixture of



-16-


.. ..

9~6S~


aliphatic organic oxygenates having a -total cumulatlve
value of R o~ greater than a stoichiometric deficiency of
carboxylic acids. In a preferred embodiment of this
invention, monocarboxylic acids are -the difficultly convert-
ible oxygenates and monohydric alcohols are the easily con-
verted oxygenates. With a mixture o~ methanol and acetic
acid, the feed should have a mole ratio of the former to the
latter greater than 1, most preferably greater than 2.
Carrying out this conversion using a mixed feed as
aforesaid not only improves the catalyst cycle life and
yields of gasoline boiling range, particularly aromatic
products obtainable from the difficultly convertible reactant,
but it actually increases the yield of gasoline boiling range,
partlcularly aromatic products at the expense of the C4 portion
of the product usually obtained from the conversion o~ the
desirable, e.g. alcoholj reactant. Put more succinctly in
perspective, the conversion o~ acetic acid at 500 to 1000F
over a ZSM-5 zeolite will give a product which comprises in
the organic portion C4 aliphatics and C5 aromatics and
aliphatics. It also cokes and chars the catalyst in a shorter
than expected time. The conversion of methanol or dimethyl
ether under the same conditions gives excellent yields of
hydrocarbon products and exhibits long catalyst life with
little coke slowly building up on the catalyst. The hydro-
~5 carbon products are predominantly in the gasoline boiling range
with some C~ aliphatics.
It would, of course, be desirable to car~y out
this conversion in such a manner as to increase the yield of
gasoline bolling range hydrocarbons at the expense of the
lighter, C~ products. It is truly an unexpected ad-~antage


-17-

, .,,,,. - - ~' ~:

lU9965~


o~ co-converting lower alcohols and/or ethers e-tc. with acids,
lower aldehydes and/or carbohydrates that no-t only is the con- t,
~ersion of these latter compounds improved, but the proportion
of the hydrocarbon product which is gasoline as compared to
lighter hydrocarbons is significantly increased even with
respect to the already high yields of gasoline obtained from
alcohol and ether conversion.
It is an important ~eature of this aspect of this
invention therefore to co-convert easily converted and
dif~icultly converted lower aliphatic organic compounds con- ¦
taining hetero atoms in order to improve the overall yield
o~ desired full range gasoline with respect to that which
is obtainable from either reactant type alone. In this
re~ard, it is an important feature to use mixtures o~ single
compounds, e.g. dimethyl ether and acetic acid, as the feed
to this process. It is also an important ~eature o~ this
invention to use multi-component mixtures~ which contain
more t~han one easily converted and/or more than one difficultly
converted reactant. In fact, it may be most preferred to
1 20 use a ~ully mixed feed such as that obtained by the controlledpartial oxidation of propane, butane or naphtha in the vapor
or liquid phases. Other sources o~ such mixtures o~ various
.
light oxygenates include the Fischer-Tropsch process wheren ~nthesis
gas, carbon mono~ide and hydrogen, are catalytically converted
to a mixture of lower aliphatic organic oxygenated compounds
including alcohols, ethers, aldehydes, ketones, etc.
These aspects of this invention will be illustrated
by the ~ollowing Examples in which parts and percenta~es are
by weight unless expressly stated to be on some other bas-is.
The followlng Table sets ~orth the results obtained in four


-18-

~39~56


(4) comparative tests run slde by side under substantially
identical conditions. The temperature was 700F; the
pressure was 1 Atmosphere, the space velocity was 1 LHSV;
and the catalyst was H-ZSM-5 with 35~ A1203 binder.




:., . :
.
. `

. .
. .




-19 -

. ... ,.. ~ ... . . , . , .~ . ... . .. ... . .. . ... . . . .

S~; fl



8715 E,xample No 1 2 3 4
~'eed (Mol %) CH30EI(100) CH30H(80) CH O~I(67) CH oH(80)
S-Tri- Acetalde- Ac~tic
oxane ~0) hyde (33) Acid (20)
Product Dlstribution
Hydrocarbons (wt %) 45.66 38.02 46.29 38.72
Oxygenates 0.03 0.11 0.13 0.02
Water 57.76 50.62 50.40 55.72
Carbon oxides 0.25 11.20 2.36 4.44
Hydrogen 0.03 0.05 0.02 0.01
Product Distribution
Hydrocarbon portion
Methane 0.42 1.99 1.03 1.15
Ethane 0.47 o.84 0.77 o.48
Ethylene 0.45 0.56 o.66 1 18
Propane 15.50 16.46 9.73 5 64
Propylene 1.27 1.16 o.89 0.80
i-Butane 19.16 12.05 7.00 3.40
n-Butane 5-29 3.93 2.96 1.32
Butenes 1.21 0.77 o.87 o.63
i-Pentane 9.40 3.82 3.00 2.30
n-Pentane 1.34 o.66 0.75 0.42
Pentenes 0.19 0.13 0.29 0.33
C6 PON 6.02 2.19 2.7Q 2.47
C7+PON 1.78 o.63 o.98 0.86
Benzene 0~90 1.66 2.23 1.91
Toluene 7.34 10.32 12.92 11.05
Ethylbenzene 0.93 o.80 1.88 2.26
Xylenes 15.57 22.13 26.05 25.64
Ag 9.72 14.45 18.69 26.01
: Alo 2.95 4.93 6.58 10.29
All+ 0.09 0.54 - 1.86
Carbon Selectivity* 99.8 89.2 98.1 96.3



*Carbon in hydrocarbon product x 100
Carbon in feed




-20-

1(~99~5~ 1


8715In the following Exa~nple 5, a mixture comprising 57
Cl-C6 alkanols, 3~ C2 Cl~ alkanals, 11% C3-C6 alkanones and 29
C2-C5 alkanoic acids was converted to a mixed hydrocarbon
product, as indicated, using an HZSM-5 catalys-t. Conditions
5were 1 Atm. pressure, 1 LHSV, 700F and 3 hours total time on
stream.
TOTAL PRODUCT, Wt%
Eydrocarbons 58.14
Oxygenates 0.03
- 10 H 0 39.55
- C2~2 2.93
CO 1.53
2 0.03
102.21
HYDROCARBONS, Wt%
Methane 0.11
Ethane o.68
Ethylene 0.89
Propane 8.74
Prop~lene 1.35
i-Butane 7-5
n-Butane 3.41
Butenes 1.13
i-Pentane 2.76
n-Pentane 1.12
Pe~tenes 0.31
C~ PON 4.25
Benzene 3.30
Toluene 16.48
Ethylbenzene 2.53
Xylene 21.49
Ag 15.3
A 7.59

A + 1.00
11
; TOTAL C5+ 76.19
TOTAL AROMATICS 67.75




-20a-

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Title Date
Forecasted Issue Date 1981-04-21
(22) Filed 1976-06-15
(45) Issued 1981-04-21
Expired 1998-04-21

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Filing $0.00 1976-06-15
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Current Owners on Record
MOBIL OIL CORPORATION
Past owners on record shown in alphabetical order.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.

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