CA1180309A - Shape selective reactions with cadmium-modified zeolite catalysts - Google Patents
Shape selective reactions with cadmium-modified zeolite catalystsInfo
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- CA1180309A CA1180309A CA000371534A CA371534A CA1180309A CA 1180309 A CA1180309 A CA 1180309A CA 000371534 A CA000371534 A CA 000371534A CA 371534 A CA371534 A CA 371534A CA 1180309 A CA1180309 A CA 1180309A
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Abstract
ABSTRACT
A process for the conversion of aromatic compounds to dialkylbenzene compounds rich in the 1,4-dialkylbenzene isomer. The reaction is carried out in the presence of a particular type of zeolite catalyst having a silica to alumina mole ratio of at least 12 and a constraint index of about 1-12, said catalyst having been modified by treatment with one or more compounds of cadmium, and optionally phosphorus, to deposit a minor proportion of such elements on the zeolite.
A process for the conversion of aromatic compounds to dialkylbenzene compounds rich in the 1,4-dialkylbenzene isomer. The reaction is carried out in the presence of a particular type of zeolite catalyst having a silica to alumina mole ratio of at least 12 and a constraint index of about 1-12, said catalyst having been modified by treatment with one or more compounds of cadmium, and optionally phosphorus, to deposit a minor proportion of such elements on the zeolite.
Description
3U3~
0533 S~PF SF.LECTIVE P~EACTIO~S T~IT~ CAD~IIU~1- ODIFIE~
ZT.OLI~E CATALYSTS
BACKGROU~1~ OF TY.E I~1VE~1TION
Field of_the ~nvention The invention disclosed herein relates to the prod~ction of dial~ylbenzene compounds utilizing a modified crystalline zeolite catalyst to yield a product mixture in which the 1,4-dialkylbenzene isomer is substantially in excess of its nor~al equilihriu~ concentration.
Description of the Prior Art The disproportionation of aromatic hydrocarbons in the presence of zeolite catalysts has been described hy Grandio et al. in the ~IL Ai`lD GAS JOUR~AL, Vol. 69, ~1umber 48(1971).
U.S. Patents Nos. 3,126,422; 3,413,374;
3,598,878; 3,598,879 and 3,607,961 sho~ vapor-phase dis-proportionation of toluene over various catalysts.
In these prior art processes, the dimethylbenzene product produced has the equilibrium composition of approximately 24 percent of 1,4-, 54 percent of 1,3- and 22 percent of 1,2-isomer. Oc the dimethylbenzene isomers, 1,3-dimethylbenzene is normally the least desired product, ~ith 1,2- and 1,4-dimethylbenzene bein.o, the more useful products.
1,4-~imethylhenzene is or particularl value hein~, useful in the manufacture o- terephthalic acid ~hich is an ~asi~3~s intermediate in the manufacture of synthetic fibers such as "Dacron".~ Mixtures of dimethylbenzene isomers, either alone or in further admixture with ethylbenzene, have previously been separated by expensive superfractionation and multistage refrigeration steps. Such process, as will be realized, involves high operation costs and has a limited yield.
Various modified zeolite catalysts have been developed to alkylate or disproportionate toluene with a ~reater or lesser degree of selectivity to 1,4-dimethyl-benzene isomer. Hence, U.S. Patents 3,972,832, 4,034,053, 4,128,592 and 4,137,195 disclose particular zeolite catalys~s which have heen treate~ with compounds of phos-phorus andlor magnesium. Boron-containing zeolites are shown in U.S. Patent 4~067,920 and antimony-containing zeolites in U.S. Patent 3,979,472. Similarly, U.S. Patents 3,965,208 and 4,117,026 disclose other modified zeolites useful for shape selective reactions.
t~hile the above-noted prior art is considered of interest in connection with the subject matter of the present invention, the conversion process described herein, utilizing a crystalline zeolite catalyst of specified characteristics which has undergone the particular treatment disclosed, has not, insofar as is known, been previously described.
`~4 .
3~
SU~RY OF THE INVENTIO~l In accordance with the present invention, there has now been discovered a novel process for conversion of organic compounds (e.g., hydrocarbon compounds) in the presence of a particular type of modified zeolite catalyst.
An especially advantageous element of the invention comprises the selective production of the 1,4-isomer of dialkylated benzene compounds. The process involves contacting an alkylated aromatic compound, either alone or in admixture with a suitable alkylatin~ agent such as methanol or ethylene, with a particular type of ~odified crystalline zeolite catalyst and under suitable conversion conditions to ef~ect disproportionation or transalkylation of alkylbenzene compounds or alkylation of aromatic compounds to selectively produce the 1,4-dial~ylbenzene isomer in excess of its normal equilibrium concentration.
The particular type of crystalline zeolite cata-lysts utilized herein are zeolite materials having a silica to alumina ratio of at least about 12, a constraint index within the approximate range of 1 to 12 and which have been modified by initial treatment with a compound derived from the element cadmium to yield a composite containing a minor proportion of an oxide of that element. In addition to treatment of the catalyst with one or more cadmium-containing compounds, the zeolite may also be treated with a phosphorus-containing compound to deposit a minor proportion of an oxide of phosphorus thereon.
An embodiment of the disclosed invention is a process for the alkylation of aromatic compounds, in the presence of the herein described modified zeolite catalysts~
with selective production of the 1,4-dialkylbenzene isomer in preference to the 1,2- and 1,3- isomers thereof.
Especially preferred embodiments involve the selective production of 1,4-dimethylbenzene from toluene and methanol and 1-e~hyl-4-methylbenzene from toluene and ethylene.
Another embodiment contemplates the selective disproportionation or transalkylation of alkylbenæene and polyalkylbenzene compounds in the presence of the disclosed catalysts, thereby yielding 1,4-disubstituted benzenes in excess of their normal equilibrium concentration. For example, under appropriate conditions of temperature and pressure, toluene will disproportionate in the presence of these catalysts to produce benzene and dimethylbenzenes rich in th~e desirable 1,4-isomer.
DESCRIPTIO~ OE SPECIFIC E~BODI~E~TS
The crystalline zeolites utilized herein are members of a novel class of zeolitic materials wnich e~hibit unusual properties. Although these zeolites have unusually low alumina contents, i.e. high silica to alumina mole ratios, they are very active even when the silica to alumina mole ratio exceeds 30. The activity is surprising since catalytic activity is ~enerally attributed to framework aluminum atoms and/or cations associated with these aluminum atoms. These zeolites retain their crystallinity for long ~ ~L8~'3r~
periods in spite of the presence of steam at high temperature which induces irreversible collapse of the framework of other zeolites, e.g. of the X and A type.
Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temperatures to restore activity. These zeolites, used as catalysts, generally have low coke-forming activity and therefore are conducive to long times on stream between regenerations by burning carbonaceous deposits with oxygen-containing gas such as air.
An important characteristic of the crystal structure of this novel class of zeolites is that it provides a selective constrained access to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate b &ween the small pore Linde ~ and the large pore Linde X, i.e. the pore windo~s of the structure are of about a size such as would be provided by 10-membered rings of silicon atoms interconnected by oxygen atoms. It is to be understood, of course, that these rings are ehose formed by the regular disposition of the tetrahedra making up the anionic frameworX of the crystalline zeolite, the oxygen atoms themselves being bonded to the silicon (or aluminum, etc.) atoms at the centers of the tetrahedra.
The silica to alumina mole 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 frameworX of the zeolite crystal and to exclude c)~
aluminum in the binder or in cationic or other form within the channels. Although zeolites with silica to alumina mole ratios of at least l~ are useful, it is preferred in some instances to use zeolites having substantially hi~her silica/alumina ratios, e~g., 1600 and above. In addition, zeolites as otherwise characterized herein but which are substantially free of aluminum, that is having silica to alumina mole ratios of up to infinity, are found to be useful and even preferable in some instances. Such "high silica" or "highly siliceous" zeolites are intended to be included within this description. Also included within this definition are substantially pure silica analogs of the useful zeolites described herein, thac is to say those zeolites having no measurable amount of aluminu~ (silica to alumina mole ratio of infinity) but which otherwise embody the characteristics disclosed.
The novel class of zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e. they exhibit "hydrophobic" properties. This hydrophobic character can be used to advanta~e in some applications.
The novel class of zeolites useful herein have an effective pore size such as to freely sorb normal hexane.
In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a kno~n crystal structure ~hether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum ~8~3C~
a~oms, then access by molecules of larger cross~section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-memhered rings are preferred, although in some instances excessive puc~ering of the rings or pore blockage may render these zeolites inefective, Although 12-membered rings in theory would not offer sufficient constraint to produce advantageous conversions, it is noted that the puckered 12-ring structure of T~A offretite does show some constrained access. Other 12-ring structures may exist which may be operative for other reasons and, therefore, it is not the present intention to entirely judge the usefulness of a particular zeolite solely from theoretical structural considerations.
Rather than attempt to judge from crystal structure whether or not a zeolite possesses the necessary constrained access to molecules of larger cross-section than normal paraffins, a simple determination of the "Constraint Index" as herein defined may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a sample 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 540C for at least 15 minutes. The zeolite is then flushed with helium and the temperature is adjusted betueen ~aooC and 510C to give an overall conversion of between 10/, and 60%. The mixture of 3~ ~
hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 volume of liquid hydrocarbon per volume of zeolite per hour) over the zeolite with a helium dilution to give a helium to (total) hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchan~ed for each of the two hydrocarbons.
While the above experimental procedure will enable one to achieve the desired overall conversion of 10 to 60%
for most zeolite sampLes and represents preferred condieions, it may occasionally be necessary to use somewhat more severe conditions for samples of very low aceivity, such as those having an exceptionally high silica to alumina mole ratio. In those instances, a temperature of up to about 540C and a liquid hourly space velocity of less than one, such as 0.1 or less, can be employed in order to achieve a minimum total conversion of about 10,',.
The "Constraint Index" is calculated as follows:
Constraint Index =
~1o (fraction of hexane remainino) log1o (fraction of 3-methylpentane remaining) The Constraint Index approximates the ratio of the cracking rate constants for the two hydrocarbons. Zeolites suitable for the present invention are those having a Constraint Index of 1 to 12. Constraint Index (CI) values for some typical materials are:
~-a ~?3,~
C.I.
ZS~1-4 0.5 ZSM-5 8.3 ZSM-l1 8.7 ZSM-23 9.1 ZS~I-35 ~-5 ZS~-38 2 ZS~1-48 3-4 T~ Offretite 3.7 Clinoptilolite 3.4 Beta 0.6 H-Zeolon (mordenite) 0.4 ~ REY 0.4 Amorphous Silica-Alumina 0.6 Erionite 38 The above-described Constraint Index is an impor-tant and even critical definition of those zeolites which are useful in the instant invention. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeoli~e can be tested under somewhat different conditions and thereby exhibit different Constraint Tndices. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders.
Likewise, other variables such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the constraint index. Therefore, it will be appreciated that it may be possible to so select test conditions as to establish more than one value in the range of 1 to 12 for the Constraint Index of a particular zeolite.
Such a zeolite exhibits the constrained access as herein define~ and is to be regarded as having a Constraint Index in the range of 1 to l2. Also contemplated herein as having a Constraint Index in the range of 1 to 12 and therefore within the scope of the defined novel class of highly )3L~g silicPous ~eolites are those zeolites which, when tested under two or more sets of conditions ~ithin the above-specified rang~s of temperature and conversion/ produce a value of the Constraint Index slightly less than 1, e.g.
0.9, or somewhat greater than 12, e.g. 14 or 15, with at least one other value within the range of l to 12. Thus, it should be understood that the Constraint Index value as used herein i5 an inclusive rather than an exclusive va~ue.
That is, a crystalline zeolite when identified by any com-bination of conditions within the testing definition set forth herein as having a Constrain~ Index in the range of 1 to 12 is intended to be included in the instant novel zeolite definition whether or not the same identical zeo-lite, when tested under other of the defined conditions, may give a Constraint Index value outside of the range of 1 to 12.
The novel class of zeolites define~ herein is exemplified by ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar materials.
ZSM-5 is described in greater detail in U.S. Patents No. 3,702,886 and Re 29,948.
ZSM-ll is described in U.S. Patent No. 3,709,979.
3g?3~
ZSM-12 is described in U.S. Patent No. 3,832,449.
ZSM-23 is described in U.S. Patent No. 4,076,842.
ZSM-35 is described in U.S. Patent No. 4,016,245.
ZSM-38 is more particularly described in U.S.
Patent No. 4,046,859.
ZSM-48 can be identified, in terms of moles of anhydrous oxides per 100 moles of silica, as follows:
(0-15)RN : (0-1.5)M2/nO : (0.2)A12O3 : (lOO)SiO2 wherein:
M is at least one cation having a valence n; and RN is a Cl-C20 organic compound having at least one amine functional ~roup of PKa ' 7-l; It is recognized that, particularly when the composition contains tetrahedral, framework aluminum, a fraction of the amine functional groups may be protonated.
The doubly protonated form, in conventional notation, would he (RNH)2O and is equivalent in stoichiometry to 2RN + H2O.
.~ ,, ~L131'3~;~
The characteristic X-ray diffraction pattern of the synthetic zeolite ZSM-48 has the following significant lines Characteristic Lines of ZS~-48 5 d (Anostroms) Relative Intensity 11 .~ W-S
l0.2 ~:J
7.2 t~
5.9 W
4.2 ~S
3.6 ll
0533 S~PF SF.LECTIVE P~EACTIO~S T~IT~ CAD~IIU~1- ODIFIE~
ZT.OLI~E CATALYSTS
BACKGROU~1~ OF TY.E I~1VE~1TION
Field of_the ~nvention The invention disclosed herein relates to the prod~ction of dial~ylbenzene compounds utilizing a modified crystalline zeolite catalyst to yield a product mixture in which the 1,4-dialkylbenzene isomer is substantially in excess of its nor~al equilihriu~ concentration.
Description of the Prior Art The disproportionation of aromatic hydrocarbons in the presence of zeolite catalysts has been described hy Grandio et al. in the ~IL Ai`lD GAS JOUR~AL, Vol. 69, ~1umber 48(1971).
U.S. Patents Nos. 3,126,422; 3,413,374;
3,598,878; 3,598,879 and 3,607,961 sho~ vapor-phase dis-proportionation of toluene over various catalysts.
In these prior art processes, the dimethylbenzene product produced has the equilibrium composition of approximately 24 percent of 1,4-, 54 percent of 1,3- and 22 percent of 1,2-isomer. Oc the dimethylbenzene isomers, 1,3-dimethylbenzene is normally the least desired product, ~ith 1,2- and 1,4-dimethylbenzene bein.o, the more useful products.
1,4-~imethylhenzene is or particularl value hein~, useful in the manufacture o- terephthalic acid ~hich is an ~asi~3~s intermediate in the manufacture of synthetic fibers such as "Dacron".~ Mixtures of dimethylbenzene isomers, either alone or in further admixture with ethylbenzene, have previously been separated by expensive superfractionation and multistage refrigeration steps. Such process, as will be realized, involves high operation costs and has a limited yield.
Various modified zeolite catalysts have been developed to alkylate or disproportionate toluene with a ~reater or lesser degree of selectivity to 1,4-dimethyl-benzene isomer. Hence, U.S. Patents 3,972,832, 4,034,053, 4,128,592 and 4,137,195 disclose particular zeolite catalys~s which have heen treate~ with compounds of phos-phorus andlor magnesium. Boron-containing zeolites are shown in U.S. Patent 4~067,920 and antimony-containing zeolites in U.S. Patent 3,979,472. Similarly, U.S. Patents 3,965,208 and 4,117,026 disclose other modified zeolites useful for shape selective reactions.
t~hile the above-noted prior art is considered of interest in connection with the subject matter of the present invention, the conversion process described herein, utilizing a crystalline zeolite catalyst of specified characteristics which has undergone the particular treatment disclosed, has not, insofar as is known, been previously described.
`~4 .
3~
SU~RY OF THE INVENTIO~l In accordance with the present invention, there has now been discovered a novel process for conversion of organic compounds (e.g., hydrocarbon compounds) in the presence of a particular type of modified zeolite catalyst.
An especially advantageous element of the invention comprises the selective production of the 1,4-isomer of dialkylated benzene compounds. The process involves contacting an alkylated aromatic compound, either alone or in admixture with a suitable alkylatin~ agent such as methanol or ethylene, with a particular type of ~odified crystalline zeolite catalyst and under suitable conversion conditions to ef~ect disproportionation or transalkylation of alkylbenzene compounds or alkylation of aromatic compounds to selectively produce the 1,4-dial~ylbenzene isomer in excess of its normal equilibrium concentration.
The particular type of crystalline zeolite cata-lysts utilized herein are zeolite materials having a silica to alumina ratio of at least about 12, a constraint index within the approximate range of 1 to 12 and which have been modified by initial treatment with a compound derived from the element cadmium to yield a composite containing a minor proportion of an oxide of that element. In addition to treatment of the catalyst with one or more cadmium-containing compounds, the zeolite may also be treated with a phosphorus-containing compound to deposit a minor proportion of an oxide of phosphorus thereon.
An embodiment of the disclosed invention is a process for the alkylation of aromatic compounds, in the presence of the herein described modified zeolite catalysts~
with selective production of the 1,4-dialkylbenzene isomer in preference to the 1,2- and 1,3- isomers thereof.
Especially preferred embodiments involve the selective production of 1,4-dimethylbenzene from toluene and methanol and 1-e~hyl-4-methylbenzene from toluene and ethylene.
Another embodiment contemplates the selective disproportionation or transalkylation of alkylbenæene and polyalkylbenzene compounds in the presence of the disclosed catalysts, thereby yielding 1,4-disubstituted benzenes in excess of their normal equilibrium concentration. For example, under appropriate conditions of temperature and pressure, toluene will disproportionate in the presence of these catalysts to produce benzene and dimethylbenzenes rich in th~e desirable 1,4-isomer.
DESCRIPTIO~ OE SPECIFIC E~BODI~E~TS
The crystalline zeolites utilized herein are members of a novel class of zeolitic materials wnich e~hibit unusual properties. Although these zeolites have unusually low alumina contents, i.e. high silica to alumina mole ratios, they are very active even when the silica to alumina mole ratio exceeds 30. The activity is surprising since catalytic activity is ~enerally attributed to framework aluminum atoms and/or cations associated with these aluminum atoms. These zeolites retain their crystallinity for long ~ ~L8~'3r~
periods in spite of the presence of steam at high temperature which induces irreversible collapse of the framework of other zeolites, e.g. of the X and A type.
Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temperatures to restore activity. These zeolites, used as catalysts, generally have low coke-forming activity and therefore are conducive to long times on stream between regenerations by burning carbonaceous deposits with oxygen-containing gas such as air.
An important characteristic of the crystal structure of this novel class of zeolites is that it provides a selective constrained access to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate b &ween the small pore Linde ~ and the large pore Linde X, i.e. the pore windo~s of the structure are of about a size such as would be provided by 10-membered rings of silicon atoms interconnected by oxygen atoms. It is to be understood, of course, that these rings are ehose formed by the regular disposition of the tetrahedra making up the anionic frameworX of the crystalline zeolite, the oxygen atoms themselves being bonded to the silicon (or aluminum, etc.) atoms at the centers of the tetrahedra.
The silica to alumina mole 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 frameworX of the zeolite crystal and to exclude c)~
aluminum in the binder or in cationic or other form within the channels. Although zeolites with silica to alumina mole ratios of at least l~ are useful, it is preferred in some instances to use zeolites having substantially hi~her silica/alumina ratios, e~g., 1600 and above. In addition, zeolites as otherwise characterized herein but which are substantially free of aluminum, that is having silica to alumina mole ratios of up to infinity, are found to be useful and even preferable in some instances. Such "high silica" or "highly siliceous" zeolites are intended to be included within this description. Also included within this definition are substantially pure silica analogs of the useful zeolites described herein, thac is to say those zeolites having no measurable amount of aluminu~ (silica to alumina mole ratio of infinity) but which otherwise embody the characteristics disclosed.
The novel class of zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e. they exhibit "hydrophobic" properties. This hydrophobic character can be used to advanta~e in some applications.
The novel class of zeolites useful herein have an effective pore size such as to freely sorb normal hexane.
In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a kno~n crystal structure ~hether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum ~8~3C~
a~oms, then access by molecules of larger cross~section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-memhered rings are preferred, although in some instances excessive puc~ering of the rings or pore blockage may render these zeolites inefective, Although 12-membered rings in theory would not offer sufficient constraint to produce advantageous conversions, it is noted that the puckered 12-ring structure of T~A offretite does show some constrained access. Other 12-ring structures may exist which may be operative for other reasons and, therefore, it is not the present intention to entirely judge the usefulness of a particular zeolite solely from theoretical structural considerations.
Rather than attempt to judge from crystal structure whether or not a zeolite possesses the necessary constrained access to molecules of larger cross-section than normal paraffins, a simple determination of the "Constraint Index" as herein defined may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a sample 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 540C for at least 15 minutes. The zeolite is then flushed with helium and the temperature is adjusted betueen ~aooC and 510C to give an overall conversion of between 10/, and 60%. The mixture of 3~ ~
hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 volume of liquid hydrocarbon per volume of zeolite per hour) over the zeolite with a helium dilution to give a helium to (total) hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchan~ed for each of the two hydrocarbons.
While the above experimental procedure will enable one to achieve the desired overall conversion of 10 to 60%
for most zeolite sampLes and represents preferred condieions, it may occasionally be necessary to use somewhat more severe conditions for samples of very low aceivity, such as those having an exceptionally high silica to alumina mole ratio. In those instances, a temperature of up to about 540C and a liquid hourly space velocity of less than one, such as 0.1 or less, can be employed in order to achieve a minimum total conversion of about 10,',.
The "Constraint Index" is calculated as follows:
Constraint Index =
~1o (fraction of hexane remainino) log1o (fraction of 3-methylpentane remaining) The Constraint Index approximates the ratio of the cracking rate constants for the two hydrocarbons. Zeolites suitable for the present invention are those having a Constraint Index of 1 to 12. Constraint Index (CI) values for some typical materials are:
~-a ~?3,~
C.I.
ZS~1-4 0.5 ZSM-5 8.3 ZSM-l1 8.7 ZSM-23 9.1 ZS~I-35 ~-5 ZS~-38 2 ZS~1-48 3-4 T~ Offretite 3.7 Clinoptilolite 3.4 Beta 0.6 H-Zeolon (mordenite) 0.4 ~ REY 0.4 Amorphous Silica-Alumina 0.6 Erionite 38 The above-described Constraint Index is an impor-tant and even critical definition of those zeolites which are useful in the instant invention. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeoli~e can be tested under somewhat different conditions and thereby exhibit different Constraint Tndices. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders.
Likewise, other variables such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the constraint index. Therefore, it will be appreciated that it may be possible to so select test conditions as to establish more than one value in the range of 1 to 12 for the Constraint Index of a particular zeolite.
Such a zeolite exhibits the constrained access as herein define~ and is to be regarded as having a Constraint Index in the range of 1 to l2. Also contemplated herein as having a Constraint Index in the range of 1 to 12 and therefore within the scope of the defined novel class of highly )3L~g silicPous ~eolites are those zeolites which, when tested under two or more sets of conditions ~ithin the above-specified rang~s of temperature and conversion/ produce a value of the Constraint Index slightly less than 1, e.g.
0.9, or somewhat greater than 12, e.g. 14 or 15, with at least one other value within the range of l to 12. Thus, it should be understood that the Constraint Index value as used herein i5 an inclusive rather than an exclusive va~ue.
That is, a crystalline zeolite when identified by any com-bination of conditions within the testing definition set forth herein as having a Constrain~ Index in the range of 1 to 12 is intended to be included in the instant novel zeolite definition whether or not the same identical zeo-lite, when tested under other of the defined conditions, may give a Constraint Index value outside of the range of 1 to 12.
The novel class of zeolites define~ herein is exemplified by ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar materials.
ZSM-5 is described in greater detail in U.S. Patents No. 3,702,886 and Re 29,948.
ZSM-ll is described in U.S. Patent No. 3,709,979.
3g?3~
ZSM-12 is described in U.S. Patent No. 3,832,449.
ZSM-23 is described in U.S. Patent No. 4,076,842.
ZSM-35 is described in U.S. Patent No. 4,016,245.
ZSM-38 is more particularly described in U.S.
Patent No. 4,046,859.
ZSM-48 can be identified, in terms of moles of anhydrous oxides per 100 moles of silica, as follows:
(0-15)RN : (0-1.5)M2/nO : (0.2)A12O3 : (lOO)SiO2 wherein:
M is at least one cation having a valence n; and RN is a Cl-C20 organic compound having at least one amine functional ~roup of PKa ' 7-l; It is recognized that, particularly when the composition contains tetrahedral, framework aluminum, a fraction of the amine functional groups may be protonated.
The doubly protonated form, in conventional notation, would he (RNH)2O and is equivalent in stoichiometry to 2RN + H2O.
.~ ,, ~L131'3~;~
The characteristic X-ray diffraction pattern of the synthetic zeolite ZSM-48 has the following significant lines Characteristic Lines of ZS~-48 5 d (Anostroms) Relative Intensity 11 .~ W-S
l0.2 ~:J
7.2 t~
5.9 W
4.2 ~S
3.6 ll
2.85 ~J
These values were determined by standard techniques. The radiation was the K-alpha doublet of copper, and a scintillation counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart.
From these, the relative intensities, lOO I/Io, where Io is the intensity of the strongest line or peak, and d (obs.), the interplanar spacing in angstroms, corresponding to the recorded lines, were calculated. In the foregoing table the relative intensities are given in terms of the symbols W =
weak, VS = very strong and W-S = weak-to-strong. Ion exchange of the sodium ion with cations reveals subseantially the same pattern with some minor shifts in ~ ~q,!3~
interplanar spacing and variation in relative intensity.
Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample, as well as if it has been subjected to thermal treatment.
The ZS~1-48 can be prepared from a reaction mixture containing a source of silica, water, P~1, an alkali metal oxide (e.g. sodium) and optionally alumina. The reactLon mixture should have a composition, in terms of mole ratios of oxides, falling within the following ranges:
REACTA~ITS BROAD PREFERRED
Al2O3/siO2 - 0 to 0.02 0 to 0,01 ~a/SiO2 = 0 to 2 0.l to 1.0 ~I/SiO2 = 0.0l to 2.0 0.05 to 1.0 OH-/SiO2 = 0 to 0.25 0. to 1.0 H2O/siO2 = 10 to 100 20 to 70 H+(added)/SiO = 0 to 0.2 0 to 0.05 wherein ~l is a Cl-C20 organic compound having amine functional group of pKa>7~ The mixture is maintained at 80-250C until crystals of the material are formed.
H+(added) is moles acid added in excess of the moles of hydroxide added. In calculating H+(added) and OH values, the term acid (Y+) includes bo~h hydronium ion, whether free or coordinated, and aluminum. Thus aluminum sulfate, for example, would be considered a mixture of aluminum oxide, sulfuric acid, and water. An amine hydrochloride would be a mixture of amine and HCl. In preparing the highly siliceous form of 7SM-48 no alumina is added. Thus, the only aluminum present occurs as an impurity in the reactants.
These values were determined by standard techniques. The radiation was the K-alpha doublet of copper, and a scintillation counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart.
From these, the relative intensities, lOO I/Io, where Io is the intensity of the strongest line or peak, and d (obs.), the interplanar spacing in angstroms, corresponding to the recorded lines, were calculated. In the foregoing table the relative intensities are given in terms of the symbols W =
weak, VS = very strong and W-S = weak-to-strong. Ion exchange of the sodium ion with cations reveals subseantially the same pattern with some minor shifts in ~ ~q,!3~
interplanar spacing and variation in relative intensity.
Other minor variations can occur depending on the silicon to aluminum ratio of the particular sample, as well as if it has been subjected to thermal treatment.
The ZS~1-48 can be prepared from a reaction mixture containing a source of silica, water, P~1, an alkali metal oxide (e.g. sodium) and optionally alumina. The reactLon mixture should have a composition, in terms of mole ratios of oxides, falling within the following ranges:
REACTA~ITS BROAD PREFERRED
Al2O3/siO2 - 0 to 0.02 0 to 0,01 ~a/SiO2 = 0 to 2 0.l to 1.0 ~I/SiO2 = 0.0l to 2.0 0.05 to 1.0 OH-/SiO2 = 0 to 0.25 0. to 1.0 H2O/siO2 = 10 to 100 20 to 70 H+(added)/SiO = 0 to 0.2 0 to 0.05 wherein ~l is a Cl-C20 organic compound having amine functional group of pKa>7~ The mixture is maintained at 80-250C until crystals of the material are formed.
H+(added) is moles acid added in excess of the moles of hydroxide added. In calculating H+(added) and OH values, the term acid (Y+) includes bo~h hydronium ion, whether free or coordinated, and aluminum. Thus aluminum sulfate, for example, would be considered a mixture of aluminum oxide, sulfuric acid, and water. An amine hydrochloride would be a mixture of amine and HCl. In preparing the highly siliceous form of 7SM-48 no alumina is added. Thus, the only aluminum present occurs as an impurity in the reactants.
3~
Preferably, crystallization is carried out under pressure in an autoclave or static bomb reactor, at ~0C to 250C. Thereafter, the crystals are separated from the liquid and recovered. The composition can be prepared ueilizing materials which supply the appropriate oxide.
Such compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, ~I, sodium hydroxide, sodium chloride, alumin~m sulfate, sodium aluminate, aluminum oxide, or aluminum itself. RN is a Cl-C20 organic compound containing at least one amine functional group of pka>7~ as defined ahove, and includes such compounds as C3-C1~
primary, secondary, and tertiary amines, cyclic amine (such as piperdine, pyrrolidine and piperazine), and polyamines such as NH2-CnH2n-NH2 wherein m is 4-12.
The original cations can be subsequently replaced, at least in part, by calcination and/or ion exchange with another cation. Thus, the original cations are exchanged into a hydrogen or hydrogen ion precursor form or a form in which the original cation has been replaced by a metal of Groups II through ~III of the Periodic Table. Thus, for example, it is contemplated to exchange the original cations with ammonium ions or with hydronium ions. Catalytically active forms of these would include, in particular, hydrogen, rare earth metals, aluminum, manganese and other metals of Groups II and VIII of the Periodic Table.
It is to be understood that by incorporating by reference the foregoing patents to describe example3 of specific members of the novel class with greater particularity, it is intended that identification of the !3 ~ ~
therein disclosed crystalline zeolites be resolved on the basis of their respective X-ray diffraction patterns. As discussed above, the present invention contemplates utilization of such catalysts wherein the mole ratio of silica to alumina is essentially unbounded. The incorporation of the identified patents should therefore not be construed as limiting the disclosed crystalline zeolites to those having the specific silica-alumina ~ole ratios discussed therein, it now bein~ known that such zeolites may be substantially aluminum-free and yet, having the same crystal structure as the disclosed materials, may be useful or even preferred in some applications. It is the crystal structure, as identified by the X-ray diffraction "fingerprint", which establishes the identity of the specific crystalline zeolite material.
The specific zeolites described, when prepared in the presence of organic cations, are substantially catalytically inactive, possibly hecause the intra-crystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540C for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 540C in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of this type zeolite; however, the presence of these cations does appear .o favor the formation of this special class of zeolite. ~ore generally, it is desirable to activate this type catalyst by base )3~)~
exchange with ammonium salts followed by calcination in air at about 540C for from about 15 minutes to about 24 hours.
~atural zeolites may sometimes be converted to zeolite structures of the class herein identified by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination, alone or in combinations. ~1atural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite.
The preferred crystalline zeolites for utilization herein include ZSM-5, ZSM-11, ZSM-12, 2SM-23, ZSM-35, ZSM-38, and ZSM-48, with ZSM-5 being particularly preferred.
In a preferred àspect o~ this invention, the zeolites hereof are selected as those providing among other things a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centineter.
It has been found that zeolites which satisfy all three of the discussed criteria are most desired for several reasons.
When hydrocarbon produces or by-products are catalytically formed, for e~ample, such zeolites tend to maximize the production of gasoline boiling range hydrocar~on products.
Therefore, the preferred zeolites useful with respect to this invention are those having a Constraint Index as defined above of about 1 to about 12, a silica to alumina mole ratio of at least ahout 1~ and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for kno~n structures may be calculated from the ~8'~;33~9 number of silicon plus aluminum atoms per l000 cubic Angstroms, as given, e.g., on Page l9 of the article ZEOLITE ST~UCTURE by W. M. Meier. This paper is included in PROCEEDINGS OF THE CONFE~ENCE ON MOLECULA~ SIEVES, (London, ~pril 1967) published by the Society of Chemical Industry, London, 1968.
When the crystal structure is un~no~Jn, the crystal framework density may be determined by classical pycnometer techniques. For example, it may be determined by immersing the dry hydrogen for~ of the zeolite in an organic solvent which is not sorbed by the crystal. Or, the crystal density may be determined by mercury porosimetry, since mercury ~ill fill the interstices between crystals but will not penetrate the intracrystalline free space.
It is possible that the unusual sustained activity and stability of this special class of zeolites is associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density must necessarily be associated with a relatively small amount of free space within the crystal 9 which might be expected to result in more stable structures.
This free space, however, is important as the locus of catalytic activity.
Crystal framework densities of some typical zeolites, including so~e which are no~ within the purview of this invention, are:
~8~31~9 Vold Framework Volume _ I~ensity Ferrierite 0.28 cc/cc 1.76 g/cc Mordenite .28 1.7 ZSM-5, -11 .29 1.79 ZSM-12 - 1.8 ZS~1-23 - 2.0 Dachiardite .32 1.72 L .32 1.61 Clino~tilolite .34 1,71 Laumontite ,34 1,77 ZSM-4 (Omega) .38 1.65 Heulandite .39 1.69 P .41 1.57 Offretite .40 1.55 Levynite ,40 1.54 Erionite ,35 1,51 Gmelini~e .44 1.46 Chabazite ,47 1,45 2n A .5 1.3 Y .4~ 1.27 ~ hen synthesized in the alkali metal form, the zeolite is convenient~y cont~erted to the hydrogen form, generally by intermediate formation of the ammonium form as 25^ a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. In addition to the hydrogen form, other forms of the zeolite wherein the original alkali metal has been reduced to less than about 1.5 percent by weight may be used. Thus, the original al~ali metal of the zeolite may be replaced by ion exchange with other suitable metal cations of Groups I through VIII
of the Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare earth metals.
In practicing a particularly desired cnemical as conversion process, it may be useful to incorporate the above-described crystalline zeolite with a matrix comprising another material resistant to the temperature and other conditions employed in the process. Such matrix material l)30~
is useful as a binder and imparts greater resistance to the catalyst for the severe temperature, pressure and reactant feed stream velocity conditions encountered in many cracking processes.
Useful matrix materials include both synthetic and naturally occurring substances, as well as inorganic materials such as clay, silica and/or metal o~ides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-7irconia. The matrix may be in the form of a cogel. The relative proportions of zeolite component and inorganic oxide gel matrix, on an anhydrous basis, may vary '3~
~idely with the zeolite content ranging from between about 1 eo about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the dry composite.
~he above crystalline zeolites employed are, in accordance with the present invention, contacted with a solution of one or more compounds of the element cadmium (Cd). Solutions of such compounds may be in any suitable solvent which is inert with respect to the metal-containing compound and the zeolite. Non-limiting examples of some suitable solvents include water, aliphatic and aromatic hydrocarbons, alcohols, org2nic acids (such as acetic acid, formic acid, propionic acid and so forth), and inorganic acids (such as hydrochloric acid, sulfuric acid and nitric acid). Other commonly available solvents such as halogenated hydrocarbons, ketones, ethers, etc. may al~o be useful to dissolve some metal compounds or complexes.
Generally, the most useful solvent will be found to be water. However, the solvent of choice for any particular compound will, of course, be determined by the nature of that compound and for that reason the foregoing list should not be considered exhaustive of all of the suitable possibilities.
Representative cadmium-containing compounds include cadmium acetate, cadmium bromide, cadmium chloride, cadmium fluoride, cadnium iodide, cadmium formate, cadmium fumarate, cadmium lactate, cadmium maleate, cadmium nitrate, cadmium oxalate, cadmium phosphate, cadmium oxide, cadmium !3 D~
sulfide, cadmium sulfate, cadmium iodate, cadmium chlorate, cadmium carbonate, cadmium benzoate, cadmium ammonium sulfate, cadmium ammonium chloride and cadmium cyanide.
This listing is not to be taken as encompassing all of the utili~able cadmium-containing compounds. It is merely intended to be illustrative of some of the representative metal compounds which those in the art will find useful in practicing the disclosed invention. The knowledgeable reader will readily appreciate that there are numerous other known cadmium salts and complexes which would prove useful herein to provide solutions containing cadmium suitable for combination with the zeolite in the manner hereinafter described.
Reaction of the zeolite with the treating cadmium compound is effected by contacting the zeolite with such compound. ~1here the treating compound is a liquid, such compound can be in solution in a solvent at the eime contact with the zeolite is effected. Any solvent relatively inert with respect to the treating cadmium compound and the zeolite may be employed. Sùitable solvents include water and aliphatic, aromatic or alcoholic liquid. The treating compound may also be used without a solvent, i.e. may be used as a neat liquid. ~rhere the treating compound is in the gaseous phase, it can be used by itself or in admixture with a gaseous diluent relatively inert to the treating compound and the zeolite (such as helium or nitrogen) or with an organic solvent such as octane or toLuene. ~.eating of the cadmium compound impregnated catalyst subsequent to preparation and prior to use is preferred, and heating can be carried out in the presence of oxygen - for example, in air.
Although heating can be at a temperature of about 150C, higher temperatures, e.g. up to about 500C, are preferred. Heating is generally carried out for 1-5 hours but may be extended to 24 hours or longer. While heating temperatures above about 500C
may be employed, they are generally not necessary, and at tem-peratures of about 1000C the crystal structure of the zeolite tends to deteriorate. After heating in air at elevated temper-atures, and without being limited by any theoretical consider-ations, it is contemplated that the cadmium is actually present in the zeolite in an oxidized state, such as Cdo.
The amount of cadmium oxide incorporated in the zeolite composite should be at least 0.25 percent by weight, lS calculated on the basis of elemental cadmium. ~owever, it is preferred that the amount be at least about 2.0 percent by weight, calculated on the basis of elemental cadmium, particu-larly when the zeolite is combined with a binder, e.g., 35 weight percent of alumina. The amount of cadmium oxide can be as high as about 40 percent by weight of composite or more, calculated on the basis of elemental cadmium, depending on the amount and type of binder present. Preferably the amount of cadmium oxide added to the zeolite composite will be between about 2 and about 35 percent by weight, calculated on the basis of elemental cadmium.
The amount of cadmium incorporated with the zeolite by reaction with elemental cadmium or cadmium containing compound will depend upon several factors. One of these is the reaction time, i.e., the time that the zeolite and the cadmium-.. ~ .
'3~
containing source are maintained in contact with each other.
r~ith greater reaction times, all other factors being equal, a greater amount of metal is incorporated with the zeolite.
Other factors upon which the amount of cadmium incorporated with the zeolite is dependent include reaction temperature, concentration of the treating compound in the reaction mixture, the degree to which the zeolite has been dried prior to reaction with the metal-containing compound, the conditions oE drying of the zeolite a~ter reaction with the treating compound, and the amount and type of binder incorporated with the zeolite.
A further embodiment of this invention includes addit-ional modification of the above metal oxide - zeolite composites with phosphorus, whereby from about 0.25 weight percent to about 30 wei~ht percent of an oxide of phosphorus, calculated as ele-mental phosphorus, is combined with the zeolite. The preferredamount of phosphorus oxide will be between about 1 weight percent and about 25 weight percent, based on the weight of the treated zeolite composite, and calculated on the basis of elemental phosphorus. The phosphorus treatment of the zeolite catalyst will preferably be carried out before the previously described modification with one or more of the specified metals.
Reaction of the zeolite compound with the phosphorus-containing compound is carried out essentially as described above with respect to the metal-containing compounds and it is preferred that the total amount of oxides combined with the zeolite, i.e.
the phosphorus oxides plus the metal oxides, fall within the approximate range of 2 percent to 40 percent by weight, based on the weight of the treated æeolite composite, and calculated on the basis of elemental cadmium plus elemental phosphorus.
31)g Representative phosphorus-containing compounds ~hich may be used include derivatives of groups represented by PX3, RPX2, R2PX, R3P, X3PO, (XO) 3PO, (XO) 3P, R3P=O, R3P=S, RPO2, RPS2, RP (O) (OX) 2 . RP (S) (SX) 2 . R2P (O)OX, R2P (S) SX, RP (SX) 2, ROP (OX) 2 . RSP (SX) 2, (RS) ~)PSP (SR) 2. and (R0)2POP~OR)2, where R is an alkyl or aryl, such as a phenyl radical and Y~ is hydrogen, R, or halide. These compounds include primary, RPH2, secondary, R2PH and tertiary, R3P, phosphines such as butyl phosphine; the tertiary phosphine oxides R3PO, such as tributylphosphine oxide, the tertiary phosphine sulfides, R3PS, the primary, RP(O) (OX)2, and secondary, R2P(O)OX, phosphonic acids such as benzene phosphonic acid; ehe corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters of the phosphonic acids such as diethyl phosphonate, (P~0)2P(O)M, dialkyl alkyl phosphonates, (RO)2P(O)R, and alkyl dialkylphosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphosphinous acid, primary, (RO)P(OX)2, secondary, (RO~2POX, and tertiary, (RO)3P, phosphites;
and esters thereof such as tne monopropyl ester, alkyl dialkylphosphinites, (RO)PR2, and dialkyl alkyl-phosphinite, (RO) 2PR esters. Corresponding sulfur derivatives may also be employed including (P~S)2P(S)H, (RS)2P(S)R, (RS)P(S)R2, R2PSX, (RS)P(sx)2~ (RS)2PSX~ (RS)3P~
(RS)PR2 and (P~S)2PR. E~amples of phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite; and pyrophosphites such as tetraethylpyrophosphite. The alkyl oroups in the mentioned compounds contain from one to four carbon atoms.
`3~)~
Other suitable phosphorus-containing compounds include the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichlorid-i~es, (RO)PC12, dialkyl phosphorochloridites, (RO)2PCl, dialkylphosphinochloridites, R2PCl, alkyl alkylphosphono-chloridates, (RO)(R)P(O)Cl, dialkyl phosphinochloridates, R2P(O)Cl and RP(O)Cl~. Applicable corresponding sulfur derivatives include (RS)PCl2, (RS)2PCl, (RS)(R)P(S)Cl and R2P(S)Cl.
Preferred phosphorus-containing compounds include diphenyl phosphine chloride, trimethylphosphite and phosphorus trichloride, phosphoric acid, phenyl phosphine oxychloride, trimethylphosphate, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid phosphate and other 21cohol-P20s reaction products.
Particularly preferred are ammonium phosphates, including ammonium hydrogen phosphate, (NH4)2HP04, and ammonium dihydrogen phosphate, NH4H2P04.
Still another modifying treatment entails steam-ing of the zeolite by contact with an atmosphere containingfrom about 5 to about 100 percent steam at a tempera.ure of from about 250 to about 1000C for a period of between about 15 minutes and about 100 hours and under pressures ranging from sub-atmospheric to several hundreA atmospheres.
Preferably, steam treatment is effected at a temperature of between about 400C and about 700C for a period of beeween about 1 and about 24 hours.
. .
.
~ 3~ 9 Another modifying treatment involves precoking of t.he catalyst to deposit a coating of between about 2 and about 75, and preferably between about 15 and about 75, weight percent of coke thereon. Precoking can be accom-plished by contacting the catalyst with a hydrocarbon charge, e~g. toluene, under high severity conditions or alternatively at a reduced hydrogen to hydrocarbon concen-tration, i.e. 0 to 1 mole ratio of hydrogen to hydrocarbon, for a sufficient time to deposit the desired amount of coke io thereon.
It is also contemplated that a combination of steaming and precoking of the catalyst under the above conditions may be employed to suitably modify the crystalline zeolite catalyst.
Alkylation of aromatic compounds in the presence of the above-described catalyst is effected by contact of the aromatic with an alkylating agent. A pareicularly preferred embodiment involves the alkylation of toluene wherein the alkylating agents employed comprise methanol or other well known methylating agents or ethylene. The reaction is carried out at a ~emperature of between about 250C and about 75QC, preferably between about 300C and 650C. At higher temperatures, the zeolites of high silica/alumina ratio are preferred. For example, ZSM-5 having a SiO2~A12O3 ratio of 30 and upwards is exceptionally stable at high temperatures. The reaction Oenerally takes place at atmospheric pressure, but pressures within the .?3C~
approximat~ ran~e of 105 ~1/m2 to 107 N/m2 (1-100 atmospheres) may be employed.
Some non-limiting examples of suitable alkylatin~
agents would include olefins such as, for example, ethylene, propylene, butene, decene and dodecene, as well as formaldehyde, alkyl halides and alcohols, the alkyl portion thereof having from 1 to 1~ carbon atoms. ~lumerous other aliphatic compounds having at least one reactive alkyl radical may be u~ilized as alkylating agents.
Aromatic compounds which may be selectively alkylated as described herein would include any alkylatable aromatic hydrocarbon such as, for example, benzene, ethylbenzene, toluene, dimethylbenzenes, diethylbenzenes, methylethylbenzenes, propylbenzene, isopropylbenzene, isopropylmethylbenzenes, or substantially any mono- or di-subs~ituted benzenes which are alkylatable in the
Preferably, crystallization is carried out under pressure in an autoclave or static bomb reactor, at ~0C to 250C. Thereafter, the crystals are separated from the liquid and recovered. The composition can be prepared ueilizing materials which supply the appropriate oxide.
Such compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, ~I, sodium hydroxide, sodium chloride, alumin~m sulfate, sodium aluminate, aluminum oxide, or aluminum itself. RN is a Cl-C20 organic compound containing at least one amine functional group of pka>7~ as defined ahove, and includes such compounds as C3-C1~
primary, secondary, and tertiary amines, cyclic amine (such as piperdine, pyrrolidine and piperazine), and polyamines such as NH2-CnH2n-NH2 wherein m is 4-12.
The original cations can be subsequently replaced, at least in part, by calcination and/or ion exchange with another cation. Thus, the original cations are exchanged into a hydrogen or hydrogen ion precursor form or a form in which the original cation has been replaced by a metal of Groups II through ~III of the Periodic Table. Thus, for example, it is contemplated to exchange the original cations with ammonium ions or with hydronium ions. Catalytically active forms of these would include, in particular, hydrogen, rare earth metals, aluminum, manganese and other metals of Groups II and VIII of the Periodic Table.
It is to be understood that by incorporating by reference the foregoing patents to describe example3 of specific members of the novel class with greater particularity, it is intended that identification of the !3 ~ ~
therein disclosed crystalline zeolites be resolved on the basis of their respective X-ray diffraction patterns. As discussed above, the present invention contemplates utilization of such catalysts wherein the mole ratio of silica to alumina is essentially unbounded. The incorporation of the identified patents should therefore not be construed as limiting the disclosed crystalline zeolites to those having the specific silica-alumina ~ole ratios discussed therein, it now bein~ known that such zeolites may be substantially aluminum-free and yet, having the same crystal structure as the disclosed materials, may be useful or even preferred in some applications. It is the crystal structure, as identified by the X-ray diffraction "fingerprint", which establishes the identity of the specific crystalline zeolite material.
The specific zeolites described, when prepared in the presence of organic cations, are substantially catalytically inactive, possibly hecause the intra-crystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540C for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 540C in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of this type zeolite; however, the presence of these cations does appear .o favor the formation of this special class of zeolite. ~ore generally, it is desirable to activate this type catalyst by base )3~)~
exchange with ammonium salts followed by calcination in air at about 540C for from about 15 minutes to about 24 hours.
~atural zeolites may sometimes be converted to zeolite structures of the class herein identified by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination, alone or in combinations. ~1atural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite.
The preferred crystalline zeolites for utilization herein include ZSM-5, ZSM-11, ZSM-12, 2SM-23, ZSM-35, ZSM-38, and ZSM-48, with ZSM-5 being particularly preferred.
In a preferred àspect o~ this invention, the zeolites hereof are selected as those providing among other things a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centineter.
It has been found that zeolites which satisfy all three of the discussed criteria are most desired for several reasons.
When hydrocarbon produces or by-products are catalytically formed, for e~ample, such zeolites tend to maximize the production of gasoline boiling range hydrocar~on products.
Therefore, the preferred zeolites useful with respect to this invention are those having a Constraint Index as defined above of about 1 to about 12, a silica to alumina mole ratio of at least ahout 1~ and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for kno~n structures may be calculated from the ~8'~;33~9 number of silicon plus aluminum atoms per l000 cubic Angstroms, as given, e.g., on Page l9 of the article ZEOLITE ST~UCTURE by W. M. Meier. This paper is included in PROCEEDINGS OF THE CONFE~ENCE ON MOLECULA~ SIEVES, (London, ~pril 1967) published by the Society of Chemical Industry, London, 1968.
When the crystal structure is un~no~Jn, the crystal framework density may be determined by classical pycnometer techniques. For example, it may be determined by immersing the dry hydrogen for~ of the zeolite in an organic solvent which is not sorbed by the crystal. Or, the crystal density may be determined by mercury porosimetry, since mercury ~ill fill the interstices between crystals but will not penetrate the intracrystalline free space.
It is possible that the unusual sustained activity and stability of this special class of zeolites is associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density must necessarily be associated with a relatively small amount of free space within the crystal 9 which might be expected to result in more stable structures.
This free space, however, is important as the locus of catalytic activity.
Crystal framework densities of some typical zeolites, including so~e which are no~ within the purview of this invention, are:
~8~31~9 Vold Framework Volume _ I~ensity Ferrierite 0.28 cc/cc 1.76 g/cc Mordenite .28 1.7 ZSM-5, -11 .29 1.79 ZSM-12 - 1.8 ZS~1-23 - 2.0 Dachiardite .32 1.72 L .32 1.61 Clino~tilolite .34 1,71 Laumontite ,34 1,77 ZSM-4 (Omega) .38 1.65 Heulandite .39 1.69 P .41 1.57 Offretite .40 1.55 Levynite ,40 1.54 Erionite ,35 1,51 Gmelini~e .44 1.46 Chabazite ,47 1,45 2n A .5 1.3 Y .4~ 1.27 ~ hen synthesized in the alkali metal form, the zeolite is convenient~y cont~erted to the hydrogen form, generally by intermediate formation of the ammonium form as 25^ a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. In addition to the hydrogen form, other forms of the zeolite wherein the original alkali metal has been reduced to less than about 1.5 percent by weight may be used. Thus, the original al~ali metal of the zeolite may be replaced by ion exchange with other suitable metal cations of Groups I through VIII
of the Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare earth metals.
In practicing a particularly desired cnemical as conversion process, it may be useful to incorporate the above-described crystalline zeolite with a matrix comprising another material resistant to the temperature and other conditions employed in the process. Such matrix material l)30~
is useful as a binder and imparts greater resistance to the catalyst for the severe temperature, pressure and reactant feed stream velocity conditions encountered in many cracking processes.
Useful matrix materials include both synthetic and naturally occurring substances, as well as inorganic materials such as clay, silica and/or metal o~ides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-7irconia. The matrix may be in the form of a cogel. The relative proportions of zeolite component and inorganic oxide gel matrix, on an anhydrous basis, may vary '3~
~idely with the zeolite content ranging from between about 1 eo about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the dry composite.
~he above crystalline zeolites employed are, in accordance with the present invention, contacted with a solution of one or more compounds of the element cadmium (Cd). Solutions of such compounds may be in any suitable solvent which is inert with respect to the metal-containing compound and the zeolite. Non-limiting examples of some suitable solvents include water, aliphatic and aromatic hydrocarbons, alcohols, org2nic acids (such as acetic acid, formic acid, propionic acid and so forth), and inorganic acids (such as hydrochloric acid, sulfuric acid and nitric acid). Other commonly available solvents such as halogenated hydrocarbons, ketones, ethers, etc. may al~o be useful to dissolve some metal compounds or complexes.
Generally, the most useful solvent will be found to be water. However, the solvent of choice for any particular compound will, of course, be determined by the nature of that compound and for that reason the foregoing list should not be considered exhaustive of all of the suitable possibilities.
Representative cadmium-containing compounds include cadmium acetate, cadmium bromide, cadmium chloride, cadmium fluoride, cadnium iodide, cadmium formate, cadmium fumarate, cadmium lactate, cadmium maleate, cadmium nitrate, cadmium oxalate, cadmium phosphate, cadmium oxide, cadmium !3 D~
sulfide, cadmium sulfate, cadmium iodate, cadmium chlorate, cadmium carbonate, cadmium benzoate, cadmium ammonium sulfate, cadmium ammonium chloride and cadmium cyanide.
This listing is not to be taken as encompassing all of the utili~able cadmium-containing compounds. It is merely intended to be illustrative of some of the representative metal compounds which those in the art will find useful in practicing the disclosed invention. The knowledgeable reader will readily appreciate that there are numerous other known cadmium salts and complexes which would prove useful herein to provide solutions containing cadmium suitable for combination with the zeolite in the manner hereinafter described.
Reaction of the zeolite with the treating cadmium compound is effected by contacting the zeolite with such compound. ~1here the treating compound is a liquid, such compound can be in solution in a solvent at the eime contact with the zeolite is effected. Any solvent relatively inert with respect to the treating cadmium compound and the zeolite may be employed. Sùitable solvents include water and aliphatic, aromatic or alcoholic liquid. The treating compound may also be used without a solvent, i.e. may be used as a neat liquid. ~rhere the treating compound is in the gaseous phase, it can be used by itself or in admixture with a gaseous diluent relatively inert to the treating compound and the zeolite (such as helium or nitrogen) or with an organic solvent such as octane or toLuene. ~.eating of the cadmium compound impregnated catalyst subsequent to preparation and prior to use is preferred, and heating can be carried out in the presence of oxygen - for example, in air.
Although heating can be at a temperature of about 150C, higher temperatures, e.g. up to about 500C, are preferred. Heating is generally carried out for 1-5 hours but may be extended to 24 hours or longer. While heating temperatures above about 500C
may be employed, they are generally not necessary, and at tem-peratures of about 1000C the crystal structure of the zeolite tends to deteriorate. After heating in air at elevated temper-atures, and without being limited by any theoretical consider-ations, it is contemplated that the cadmium is actually present in the zeolite in an oxidized state, such as Cdo.
The amount of cadmium oxide incorporated in the zeolite composite should be at least 0.25 percent by weight, lS calculated on the basis of elemental cadmium. ~owever, it is preferred that the amount be at least about 2.0 percent by weight, calculated on the basis of elemental cadmium, particu-larly when the zeolite is combined with a binder, e.g., 35 weight percent of alumina. The amount of cadmium oxide can be as high as about 40 percent by weight of composite or more, calculated on the basis of elemental cadmium, depending on the amount and type of binder present. Preferably the amount of cadmium oxide added to the zeolite composite will be between about 2 and about 35 percent by weight, calculated on the basis of elemental cadmium.
The amount of cadmium incorporated with the zeolite by reaction with elemental cadmium or cadmium containing compound will depend upon several factors. One of these is the reaction time, i.e., the time that the zeolite and the cadmium-.. ~ .
'3~
containing source are maintained in contact with each other.
r~ith greater reaction times, all other factors being equal, a greater amount of metal is incorporated with the zeolite.
Other factors upon which the amount of cadmium incorporated with the zeolite is dependent include reaction temperature, concentration of the treating compound in the reaction mixture, the degree to which the zeolite has been dried prior to reaction with the metal-containing compound, the conditions oE drying of the zeolite a~ter reaction with the treating compound, and the amount and type of binder incorporated with the zeolite.
A further embodiment of this invention includes addit-ional modification of the above metal oxide - zeolite composites with phosphorus, whereby from about 0.25 weight percent to about 30 wei~ht percent of an oxide of phosphorus, calculated as ele-mental phosphorus, is combined with the zeolite. The preferredamount of phosphorus oxide will be between about 1 weight percent and about 25 weight percent, based on the weight of the treated zeolite composite, and calculated on the basis of elemental phosphorus. The phosphorus treatment of the zeolite catalyst will preferably be carried out before the previously described modification with one or more of the specified metals.
Reaction of the zeolite compound with the phosphorus-containing compound is carried out essentially as described above with respect to the metal-containing compounds and it is preferred that the total amount of oxides combined with the zeolite, i.e.
the phosphorus oxides plus the metal oxides, fall within the approximate range of 2 percent to 40 percent by weight, based on the weight of the treated æeolite composite, and calculated on the basis of elemental cadmium plus elemental phosphorus.
31)g Representative phosphorus-containing compounds ~hich may be used include derivatives of groups represented by PX3, RPX2, R2PX, R3P, X3PO, (XO) 3PO, (XO) 3P, R3P=O, R3P=S, RPO2, RPS2, RP (O) (OX) 2 . RP (S) (SX) 2 . R2P (O)OX, R2P (S) SX, RP (SX) 2, ROP (OX) 2 . RSP (SX) 2, (RS) ~)PSP (SR) 2. and (R0)2POP~OR)2, where R is an alkyl or aryl, such as a phenyl radical and Y~ is hydrogen, R, or halide. These compounds include primary, RPH2, secondary, R2PH and tertiary, R3P, phosphines such as butyl phosphine; the tertiary phosphine oxides R3PO, such as tributylphosphine oxide, the tertiary phosphine sulfides, R3PS, the primary, RP(O) (OX)2, and secondary, R2P(O)OX, phosphonic acids such as benzene phosphonic acid; ehe corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters of the phosphonic acids such as diethyl phosphonate, (P~0)2P(O)M, dialkyl alkyl phosphonates, (RO)2P(O)R, and alkyl dialkylphosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphosphinous acid, primary, (RO)P(OX)2, secondary, (RO~2POX, and tertiary, (RO)3P, phosphites;
and esters thereof such as tne monopropyl ester, alkyl dialkylphosphinites, (RO)PR2, and dialkyl alkyl-phosphinite, (RO) 2PR esters. Corresponding sulfur derivatives may also be employed including (P~S)2P(S)H, (RS)2P(S)R, (RS)P(S)R2, R2PSX, (RS)P(sx)2~ (RS)2PSX~ (RS)3P~
(RS)PR2 and (P~S)2PR. E~amples of phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite; and pyrophosphites such as tetraethylpyrophosphite. The alkyl oroups in the mentioned compounds contain from one to four carbon atoms.
`3~)~
Other suitable phosphorus-containing compounds include the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichlorid-i~es, (RO)PC12, dialkyl phosphorochloridites, (RO)2PCl, dialkylphosphinochloridites, R2PCl, alkyl alkylphosphono-chloridates, (RO)(R)P(O)Cl, dialkyl phosphinochloridates, R2P(O)Cl and RP(O)Cl~. Applicable corresponding sulfur derivatives include (RS)PCl2, (RS)2PCl, (RS)(R)P(S)Cl and R2P(S)Cl.
Preferred phosphorus-containing compounds include diphenyl phosphine chloride, trimethylphosphite and phosphorus trichloride, phosphoric acid, phenyl phosphine oxychloride, trimethylphosphate, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid phosphate and other 21cohol-P20s reaction products.
Particularly preferred are ammonium phosphates, including ammonium hydrogen phosphate, (NH4)2HP04, and ammonium dihydrogen phosphate, NH4H2P04.
Still another modifying treatment entails steam-ing of the zeolite by contact with an atmosphere containingfrom about 5 to about 100 percent steam at a tempera.ure of from about 250 to about 1000C for a period of between about 15 minutes and about 100 hours and under pressures ranging from sub-atmospheric to several hundreA atmospheres.
Preferably, steam treatment is effected at a temperature of between about 400C and about 700C for a period of beeween about 1 and about 24 hours.
. .
.
~ 3~ 9 Another modifying treatment involves precoking of t.he catalyst to deposit a coating of between about 2 and about 75, and preferably between about 15 and about 75, weight percent of coke thereon. Precoking can be accom-plished by contacting the catalyst with a hydrocarbon charge, e~g. toluene, under high severity conditions or alternatively at a reduced hydrogen to hydrocarbon concen-tration, i.e. 0 to 1 mole ratio of hydrogen to hydrocarbon, for a sufficient time to deposit the desired amount of coke io thereon.
It is also contemplated that a combination of steaming and precoking of the catalyst under the above conditions may be employed to suitably modify the crystalline zeolite catalyst.
Alkylation of aromatic compounds in the presence of the above-described catalyst is effected by contact of the aromatic with an alkylating agent. A pareicularly preferred embodiment involves the alkylation of toluene wherein the alkylating agents employed comprise methanol or other well known methylating agents or ethylene. The reaction is carried out at a ~emperature of between about 250C and about 75QC, preferably between about 300C and 650C. At higher temperatures, the zeolites of high silica/alumina ratio are preferred. For example, ZSM-5 having a SiO2~A12O3 ratio of 30 and upwards is exceptionally stable at high temperatures. The reaction Oenerally takes place at atmospheric pressure, but pressures within the .?3C~
approximat~ ran~e of 105 ~1/m2 to 107 N/m2 (1-100 atmospheres) may be employed.
Some non-limiting examples of suitable alkylatin~
agents would include olefins such as, for example, ethylene, propylene, butene, decene and dodecene, as well as formaldehyde, alkyl halides and alcohols, the alkyl portion thereof having from 1 to 1~ carbon atoms. ~lumerous other aliphatic compounds having at least one reactive alkyl radical may be u~ilized as alkylating agents.
Aromatic compounds which may be selectively alkylated as described herein would include any alkylatable aromatic hydrocarbon such as, for example, benzene, ethylbenzene, toluene, dimethylbenzenes, diethylbenzenes, methylethylbenzenes, propylbenzene, isopropylbenzene, isopropylmethylbenzenes, or substantially any mono- or di-subs~ituted benzenes which are alkylatable in the
4-position of the aromatic ring.
The molar ratio of alkylating agent to aromatic compound is generally bet~een about 0.05 and about 5. For instance, when methanol is employed as the methylating agent and toluene is the aromatic, a suitable molar ratio of methanol to toluene has been found to be approximately 1-0.1 moles of methanol per mole of toluene. Reaction is suitably accomplished utilizina a feed weight hourly space velocity (~SV) of between about 1 and about 1000, and preferably between about 1 and about 200. ~he reaction product, consisting predominantly of the l,4-dialkyl isomer, e.g.
1,4-dimethvlbenzene, 1-ethyl-4-methylbenzene, etc., or a ~q~3~3~
mixture of the 1,4- and 1,2- isomers together with comparatively smaller amounts of 1,3-dialkylbenzene isomer, may be separated by any suitable means. Such means may include, for exampie, passing the reaction product stream throu~h a water condenser and subsequently passing the organic phase through a colu~n in which chromatographic separation of the aromatic isomers is accomplished.
When transalkylation is to be accomplished, transalkylating agents are alkyl or polyalkyl aromatic hydrocarbons wherein alkyl may be composed of from 2 to about 5 carbon atoms, such as, for example, toluene, xylene, trimethylbenzene, triethylbenzene, dimethylethylbenzene, ethylbenzene, diethylbenzene, ethyltoluene, and so forth.
Another aspect of this invention involves the selective disproportionation cf alkylated aromatic compounds to produce dialkylben~enes wherein the yield of 1,4-dialkyl isomer is in excess of the normal equilibrium concentration.
In this context, it should be noted that disproportionation is a special case of transalkylation in which the alkylatable hydrocarbon and the transalkylating agent are the same compound, for example when toluene serves as the donor and acceptor of a transferred methyl group to produce benzene and xylene.
The transalkylation and disproportionation reactions are carried out by contacting the reactants with the above described modified zeolite catalyst at a temperature of between about 250C and 750C at a pressure of between atmospheric (105 ~/m2) and about 100 atmospheres (107 ~1/m2). The reactant feed ~HS~ will normally fall 3ri~
within t~e range of about 0.1 to about 50. Preferred alkylated aromatic compounds suitable for utilization in this embodiment comprise toluene, ethylbenzene, propylbenzene or substantially any mono-substituted a1kylbenzene. These aromatic compounds are selectively converted to, respectively, 1,4-dimethylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, or other 1~4-dialkylbenzene, as appropriaee, with benzene being a primary side product in each instance. The product is recovered from the reactor effluent by conventional means, such as distillation to remove the desired products of benzene and dialkylbenzene, and any unreacted aromatic component is recycled for further reaction.
The hydrocarbon conversion processes described herein may be carried out as a batch type, semi-continuous or continuous operation utilizing a fixed or moving bed catalyst system. The catalyst after use in a moving bed reactor is conducted to a regeneration zone w~erein coke is burned from the catalyst in an oxygen-containing atmosphere, e.g. air, at an elevated temperature, after which the regenerated catalyst is recycled to the conversion zone for further contact with the charge stock. In a fixed bed reactor, regeneration is carried out in a conventional manner where an inert gas containing a small amount of oxygen (0.5-2%) is used to burn the coke in a controlled manner so as to limit the temperature to a maximum of around 500-550C.
'`~ - -: - . - : ., .
;:~fj~
The following examples will serve to illustrate certain specific embodiments of the hereindisclosed invention. These examples should not, however, be construed as limiting the scope of the novel invention as there are many variations which may be made thereon without departing from the spirit of ~he disclosed invention, as those of skill in ~he art will recognize.
EXAMP~F. 1A
- ~Alkylation reaction with unmodified ZSM-5]
Five grams of HZSM-5 (silica/alumina mole ratio =
70; 65V/, on alumina binder) were placed in a quartz flow reactos and heated to various temperatures between 350C and 500C. A ~ixture of toluene and methanol, at a 4/1 molar ratio, was passed thru the zeolite catalyst at a weight hourly space velocity (~SV) of 10. The reactor effluent was monitored and the results obtained at the various temperatures are shown below.
TemperaturePercent toluenePercent para-isomer C conversion in xvlenes 350 47.2 24.8 400 58.0 24.4 450 6~.0 24.3 500 87.6 24.2 3~, ~
In a similar manner, toluene was alkylated with ethylene by passing toluene and ethylene, at ~SV of 7.0 and 0.5, respectively, over the unmodified zeolite. The results at various temperatures are shown below.
Temperature Percent tolueneIsomer ratios of C conversionethyltoluene __ _ o 400 76.4 29.9 58.5 11.6 425 76.4 29.9 57.5 12.7 450 79.0 29.6 57.1 13.4 [Disproportionation reaction with unmodified ZSM-5]
Toluene was passed over a 6.0g sample.of ~ZSM-5 (SiO2/Al203 mole ratio = 70; 65% on alumina binder) at a feed ~SV of 3.5-3.6 and at temperatures between 450C and 600C. The results are summarized below.
3~j9 ~ o~
O ~ O ~n ,_~
o o o o ~n O~ I ~
r~e o ~ 3 :~
o 0~
~n ~ ~ ~ ~ ~
cO ~ ~, ~ u~
o a~ v- N (D
Ul ut X rt ~ co ~ ~n ~ ~:
3 s ~ ~l--:
n 3 ` _ ., ~ : ... . .'' ¢~3~
EX~MPLE 3 IPreparation of Cd-modified zeolite]
To a solution of 5,0g cadmium acetate in 5.0 ml water heated at 80C was added 3.0g HZSM-5 (SiO2/Al203 =
70). The mixture was maintained at ~0C for 2 hours. After filtration and drying at about 90C for 16 hours, the residue was calcined at 500C for 2 hours to give 3.65g of Cd-ZS~-5. The content of cadmium was analyzed to be 21.3C~,.
EX~PLE 4A
~Alkylation reaction with Cd-modlfied zeolite]
Alkylation of toluene with methanol was carried out by passing a toluene/methanol mixture tmolar ratio of 411) over 1.1g of the Cd-ZSM-5 catalyst of Example 3 at ~SV
of 10 and 500C, Toluene conversion was 19.67, and selectivity to p-xylene in xylenes was 64.3~/,, Under substantially the same conditions the unmodified ZSM-5 (Example lA) resulted in only 24,2% selectivity to para-isomer, E~PLE 4B
In a si~ilar manner, ethylation of toluene was carried out by passing toluene (at ~HSV = 7) and ethylene at (WHSV = 0,5) over 1,1g of the Cd-ZS~-5 catalyst of Example 3 at 400C, Conversion of toluene was 40.3% and selectivity to p-ethyltoluene in ethyltoluenes was 89.5%.
.
3~
[Disproportionation reaction with Cd-modified zeolite]
Disproportionation of toluene was carried out by passing toluene over 1.1g of the Cd-ZSM-5 catalyst of Example 3 at l~SV = 3.5 and 50~C. Toluene conversion was 7.1% and selectivity eo p-xylene in ~ylene was 68.9V/~. This represen~s a very significant increase in para-selectivity compared to the 24.5~/, selectivity shown for the unmodified zeolite under the same conditions of reaction (Example 2).
F.XAMPLE 6 ~Preparation of P-modified zeolite]
Two hundred grams of ammonium-ZSM-5 (65% on alumina binder) were added to a solution of 80g of diammoni~lm hydrogen phosphate in 300 ml of ~2 at about 90C. After standing at about 90C for 2 hours, the zeolite was filtered, dried at 90C for 2 hours and then calcined at 500C for another 2 hours. The recovered P-ZS~-5 zeolite contained 3.43 wt.% phosphorus.
EX~MPLE 7A
[Alkylation reaction wtih P-modified zeolite]
Alkylation o~ toluene with methanol was carried out by passing a toluene/methanol feed stream (molar ratio =
4/1) over 5.0g of the P-ZSM-5 zeolite of Example 6. The feed I~SV was 10 and the reactor temperature was varied between 400C and 600C. The result3 obtained are summarized belo~.
, ._ ~ ~ - . . ...
33~9 TemperaturePercent ToluenePercent para-isomer C Conversion in Xylenes 400 43.6 66.6 450 54.4 57.7 500 70.4 53.7 550 85.~ 52.0 600 ~5.2 58.0 EX~PLE 7B
In a similar manner, ethylation of toluene was accomplished utilizing a feed stream of toluene (T.~SV = 7.0) and ethylene (~SV - 0.5) in the presence of the P-ZSM-5 catalyst at 400C. Conversion of toluene was 74.8/~ and selectivity to the para-isomer of ethyltoluene was 55.57~.
E ~MPLE 8 [Disproportionation reaction with P-modified zeolite]
Toluene disproportionation was tested by passing a stream of toluene over the P-ZSM-5 catalyst of Example 6 at a feed I~HSV of 3.5 at temperatures of between 475C and 550C. The results are sumT~arized below.
~13q'3~
1 ~3 o~
~n ~ O _ C~ ~
o ~n O ~n tt P~
C
~3 C
~ _ _, ~ ~
o ~ ~o , o ~ w ~ 1~ ~o I ~D ~D
~n _ (o ~_ (D
~o ~ ~ ~ ~ X~
- O ~ V- ~D ~ p~
rD r~
_ ~ ~
3~
EXA~LE 9 [Preparation of Cd-P-modified ~eolite]
To a solution of 8.0g cadmium acetate in lO ml ~Jater heating at approximately 80C was added 6.0g of the P-ZSM-5 of Example 6, and the mixture maintained at 80-90C
to 2 hours. After filtration and drying at about 90C, the residue was calcined at 500C for 2 hours to give 6.81g Cd-P-ZSM-5. Analysis showed the content of cadmiu~ to be 17.8% and that of phosphorus to be 2.03/,.
EX~IPLE lOA
[Alkylation reaction with Cd-P-modified zeolite]
Alkylation of toluene with methanol was carried out by passing a toLuene/methanol mixture (molar ratio of 4/1) over l.lg of the Cd-P-ZS~-5 catalyst of Example 9 at ~SV of 10 and 400C. Toluene conversion was 6.8% and selectivity to p-xylene in xylenes was 94.6%. This is a dramatic increase over the selectivity of the catalyst modified with phosphorus alone 1Example 7A].
E~-~IPLE lOB
In a similar manner, ethylation of toluene was made by passing toluene (at ~SV = 7) and ethylene (at ~SV
= 0.5) over l.lg of the Cd-P-ZSM-5 catalyst of Example 9 at 400C. Conversion of toluene was 2.1% and selectivity to p-ethyltoluene in ethyltoluene was over 99%. Again, a startling increase in selectivity compared to the P-ZSM-5 alone [Example 73].
3C!9~
E.YAMPLE 11 [Disproportionation reaction with Cd-P-modified zeolite]
Disproportionation of toluene was carried out by passing toluene over l~lg of the Cd-P-ZSM-5 catalyst of Example 9 at I~SV = 3.5 and 500C ~ Toluene conversion was 6~5% and selectivity to p-xylene in ~ylene was 96~/,. 3y contrast, disproportionation of toluene with P-ZSM-5 (Example 8) resulted in only 35~1% selectivity to para-isomer under the same conditions.
E ~PLE 12A
[Alkylation reaction with unmodified ZSM-11]
A toluene/methanol feed stream, havin~ a 4/1 molar ratio of the respective reactants, was passed over unmodified HZSM-ll zeolite (SiO2/A12O3 = 70) at 400-600C
and a feed ~SV of 10. The results are sho~m below.
Temperature Percent Toluene Percent para-xylene _C Conversion in Xylenes 400 ~ 67.6 23.4 500 -90~4 24~0 600 157.~ 22.7 '3~
A toluene/ethylene feed stream was similarly brought into contact with the unmodified HZSM-11. The feed ~HSV was 7.5 and 0.55, respectively, and the temperature of reaction 400-450C. The results are summarized below.
Temperature Percent Toluene Isomer ratios of _C Conversion eth~ltoluene P _ o 400 80.2 27.3 58.4 14.3 450 81.9 27.~ 57.~ 14.9 EX~MPLE 13 [Disproportionation reaction with unmodified ZSM-11]
A 1.0g portion of unmodified HZSM-11 zeolite (silica to alumina mole ratio = 70) was placed in a quartz flow reactor and heated to tem-perature. Toluene was passed over the zeolite at ~HSV of 3.8 and various temperatures between 400C and 600C. The results are summarized below.
. .
:~, - - ' . - .
3rj~
a~ ~n ~n ~ ~ 1 l o~a O Vl O ~ O C~
O O O O O ~
~O . C
_ O 3 ~' n ~D
U~
_ O _l N
e~
~ CO O _ tD ~_ ca ~ ~D ~I
W W W ,c~
rcl, p~
- ` _ - ` `, . -'3`~
EX~MPLE 14 [Preparation of Cd-modified ZSM-ll]
To a solution of 4.09 cadmium acetate in 5 ml water heated at 80C was added 1.59 HZSM-ll (SiO2/A1203 = 70). The mixture was maintained at 80 - 90C for 2 hours. After filtration and drying at about 90PC for 16 hours, the residue was calcined at 500C
for 2 hours to give 2.19 Cd-ZSM-ll. The content of cadmium was analyzed to be 26.2%.
Example 15A
[Alkylation reaction with Cd-m~dified ZSM-ll]
Alkylation of toluene with methanol was carried out by passing a toluene/methanol mixture (molar ratio of 4/1) over 1.19 of the Cd-ZSM-ll catalyst of Example 14 at WHSV of 10 and 400~C.
Toluene conversion was 27.6% and selectivity to p-xylene in xylenes was 31.0%
In a similar manner, ethylation of toluene was carried out by passing toluene (at W~SV = 7) and ethylene at (W~SV = 0.5) oYer 1.19 of the Cd-ZSM-ll catalyst of Example 14 at 400C. Conversion Of toluene was 15.1% and selectivity to p-ethyltoluene in ethyltoluene was 45.0%.
As the foregoing ably demonstrate, modification of the ZSM-ll zeolite with cadmium as herein described results in significant increases in para-selectivity as compared to the 2~ activity of the unmodified zeolite (Example 12).
~-a~3~
EX~` LE 16 [Disproportionation reaction with Cd-modified ZSM-11]
Disproportionation of toluene was carried out by passing toluene over 1.lg o_ the Cd-ZSM-11 catalyst of Example 14 at ~SV = 3.S and 4jOC. Toluene conversion was 1.3% and selectivity to p-xylene in xylene was 48.1%. This represents approximately twice the level of para-selectivity shown by the unmodified ZSM-11 zeolite in the same reaction [Example 13].
It is to be understood that the foregoing is ineended to be merely illustrative of certain specific embodiments of the disclosed invention. As those of skill in the art will readily appreciate, there are many variations which may be made on these specific embodiments without departing from the spirit of the herein described invention and such variations are clearly to be encompassed within ambit of the following claims.
~.
- , - - - ,- : ., .
The molar ratio of alkylating agent to aromatic compound is generally bet~een about 0.05 and about 5. For instance, when methanol is employed as the methylating agent and toluene is the aromatic, a suitable molar ratio of methanol to toluene has been found to be approximately 1-0.1 moles of methanol per mole of toluene. Reaction is suitably accomplished utilizina a feed weight hourly space velocity (~SV) of between about 1 and about 1000, and preferably between about 1 and about 200. ~he reaction product, consisting predominantly of the l,4-dialkyl isomer, e.g.
1,4-dimethvlbenzene, 1-ethyl-4-methylbenzene, etc., or a ~q~3~3~
mixture of the 1,4- and 1,2- isomers together with comparatively smaller amounts of 1,3-dialkylbenzene isomer, may be separated by any suitable means. Such means may include, for exampie, passing the reaction product stream throu~h a water condenser and subsequently passing the organic phase through a colu~n in which chromatographic separation of the aromatic isomers is accomplished.
When transalkylation is to be accomplished, transalkylating agents are alkyl or polyalkyl aromatic hydrocarbons wherein alkyl may be composed of from 2 to about 5 carbon atoms, such as, for example, toluene, xylene, trimethylbenzene, triethylbenzene, dimethylethylbenzene, ethylbenzene, diethylbenzene, ethyltoluene, and so forth.
Another aspect of this invention involves the selective disproportionation cf alkylated aromatic compounds to produce dialkylben~enes wherein the yield of 1,4-dialkyl isomer is in excess of the normal equilibrium concentration.
In this context, it should be noted that disproportionation is a special case of transalkylation in which the alkylatable hydrocarbon and the transalkylating agent are the same compound, for example when toluene serves as the donor and acceptor of a transferred methyl group to produce benzene and xylene.
The transalkylation and disproportionation reactions are carried out by contacting the reactants with the above described modified zeolite catalyst at a temperature of between about 250C and 750C at a pressure of between atmospheric (105 ~/m2) and about 100 atmospheres (107 ~1/m2). The reactant feed ~HS~ will normally fall 3ri~
within t~e range of about 0.1 to about 50. Preferred alkylated aromatic compounds suitable for utilization in this embodiment comprise toluene, ethylbenzene, propylbenzene or substantially any mono-substituted a1kylbenzene. These aromatic compounds are selectively converted to, respectively, 1,4-dimethylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, or other 1~4-dialkylbenzene, as appropriaee, with benzene being a primary side product in each instance. The product is recovered from the reactor effluent by conventional means, such as distillation to remove the desired products of benzene and dialkylbenzene, and any unreacted aromatic component is recycled for further reaction.
The hydrocarbon conversion processes described herein may be carried out as a batch type, semi-continuous or continuous operation utilizing a fixed or moving bed catalyst system. The catalyst after use in a moving bed reactor is conducted to a regeneration zone w~erein coke is burned from the catalyst in an oxygen-containing atmosphere, e.g. air, at an elevated temperature, after which the regenerated catalyst is recycled to the conversion zone for further contact with the charge stock. In a fixed bed reactor, regeneration is carried out in a conventional manner where an inert gas containing a small amount of oxygen (0.5-2%) is used to burn the coke in a controlled manner so as to limit the temperature to a maximum of around 500-550C.
'`~ - -: - . - : ., .
;:~fj~
The following examples will serve to illustrate certain specific embodiments of the hereindisclosed invention. These examples should not, however, be construed as limiting the scope of the novel invention as there are many variations which may be made thereon without departing from the spirit of ~he disclosed invention, as those of skill in ~he art will recognize.
EXAMP~F. 1A
- ~Alkylation reaction with unmodified ZSM-5]
Five grams of HZSM-5 (silica/alumina mole ratio =
70; 65V/, on alumina binder) were placed in a quartz flow reactos and heated to various temperatures between 350C and 500C. A ~ixture of toluene and methanol, at a 4/1 molar ratio, was passed thru the zeolite catalyst at a weight hourly space velocity (~SV) of 10. The reactor effluent was monitored and the results obtained at the various temperatures are shown below.
TemperaturePercent toluenePercent para-isomer C conversion in xvlenes 350 47.2 24.8 400 58.0 24.4 450 6~.0 24.3 500 87.6 24.2 3~, ~
In a similar manner, toluene was alkylated with ethylene by passing toluene and ethylene, at ~SV of 7.0 and 0.5, respectively, over the unmodified zeolite. The results at various temperatures are shown below.
Temperature Percent tolueneIsomer ratios of C conversionethyltoluene __ _ o 400 76.4 29.9 58.5 11.6 425 76.4 29.9 57.5 12.7 450 79.0 29.6 57.1 13.4 [Disproportionation reaction with unmodified ZSM-5]
Toluene was passed over a 6.0g sample.of ~ZSM-5 (SiO2/Al203 mole ratio = 70; 65% on alumina binder) at a feed ~SV of 3.5-3.6 and at temperatures between 450C and 600C. The results are summarized below.
3~j9 ~ o~
O ~ O ~n ,_~
o o o o ~n O~ I ~
r~e o ~ 3 :~
o 0~
~n ~ ~ ~ ~ ~
cO ~ ~, ~ u~
o a~ v- N (D
Ul ut X rt ~ co ~ ~n ~ ~:
3 s ~ ~l--:
n 3 ` _ ., ~ : ... . .'' ¢~3~
EX~MPLE 3 IPreparation of Cd-modified zeolite]
To a solution of 5,0g cadmium acetate in 5.0 ml water heated at 80C was added 3.0g HZSM-5 (SiO2/Al203 =
70). The mixture was maintained at ~0C for 2 hours. After filtration and drying at about 90C for 16 hours, the residue was calcined at 500C for 2 hours to give 3.65g of Cd-ZS~-5. The content of cadmium was analyzed to be 21.3C~,.
EX~PLE 4A
~Alkylation reaction with Cd-modlfied zeolite]
Alkylation of toluene with methanol was carried out by passing a toluene/methanol mixture tmolar ratio of 411) over 1.1g of the Cd-ZSM-5 catalyst of Example 3 at ~SV
of 10 and 500C, Toluene conversion was 19.67, and selectivity to p-xylene in xylenes was 64.3~/,, Under substantially the same conditions the unmodified ZSM-5 (Example lA) resulted in only 24,2% selectivity to para-isomer, E~PLE 4B
In a si~ilar manner, ethylation of toluene was carried out by passing toluene (at ~HSV = 7) and ethylene at (WHSV = 0,5) over 1,1g of the Cd-ZS~-5 catalyst of Example 3 at 400C, Conversion of toluene was 40.3% and selectivity to p-ethyltoluene in ethyltoluenes was 89.5%.
.
3~
[Disproportionation reaction with Cd-modified zeolite]
Disproportionation of toluene was carried out by passing toluene over 1.1g of the Cd-ZSM-5 catalyst of Example 3 at l~SV = 3.5 and 50~C. Toluene conversion was 7.1% and selectivity eo p-xylene in ~ylene was 68.9V/~. This represen~s a very significant increase in para-selectivity compared to the 24.5~/, selectivity shown for the unmodified zeolite under the same conditions of reaction (Example 2).
F.XAMPLE 6 ~Preparation of P-modified zeolite]
Two hundred grams of ammonium-ZSM-5 (65% on alumina binder) were added to a solution of 80g of diammoni~lm hydrogen phosphate in 300 ml of ~2 at about 90C. After standing at about 90C for 2 hours, the zeolite was filtered, dried at 90C for 2 hours and then calcined at 500C for another 2 hours. The recovered P-ZS~-5 zeolite contained 3.43 wt.% phosphorus.
EX~MPLE 7A
[Alkylation reaction wtih P-modified zeolite]
Alkylation o~ toluene with methanol was carried out by passing a toluene/methanol feed stream (molar ratio =
4/1) over 5.0g of the P-ZSM-5 zeolite of Example 6. The feed I~SV was 10 and the reactor temperature was varied between 400C and 600C. The result3 obtained are summarized belo~.
, ._ ~ ~ - . . ...
33~9 TemperaturePercent ToluenePercent para-isomer C Conversion in Xylenes 400 43.6 66.6 450 54.4 57.7 500 70.4 53.7 550 85.~ 52.0 600 ~5.2 58.0 EX~PLE 7B
In a similar manner, ethylation of toluene was accomplished utilizing a feed stream of toluene (T.~SV = 7.0) and ethylene (~SV - 0.5) in the presence of the P-ZSM-5 catalyst at 400C. Conversion of toluene was 74.8/~ and selectivity to the para-isomer of ethyltoluene was 55.57~.
E ~MPLE 8 [Disproportionation reaction with P-modified zeolite]
Toluene disproportionation was tested by passing a stream of toluene over the P-ZSM-5 catalyst of Example 6 at a feed I~HSV of 3.5 at temperatures of between 475C and 550C. The results are sumT~arized below.
~13q'3~
1 ~3 o~
~n ~ O _ C~ ~
o ~n O ~n tt P~
C
~3 C
~ _ _, ~ ~
o ~ ~o , o ~ w ~ 1~ ~o I ~D ~D
~n _ (o ~_ (D
~o ~ ~ ~ ~ X~
- O ~ V- ~D ~ p~
rD r~
_ ~ ~
3~
EXA~LE 9 [Preparation of Cd-P-modified ~eolite]
To a solution of 8.0g cadmium acetate in lO ml ~Jater heating at approximately 80C was added 6.0g of the P-ZSM-5 of Example 6, and the mixture maintained at 80-90C
to 2 hours. After filtration and drying at about 90C, the residue was calcined at 500C for 2 hours to give 6.81g Cd-P-ZSM-5. Analysis showed the content of cadmiu~ to be 17.8% and that of phosphorus to be 2.03/,.
EX~IPLE lOA
[Alkylation reaction with Cd-P-modified zeolite]
Alkylation of toluene with methanol was carried out by passing a toLuene/methanol mixture (molar ratio of 4/1) over l.lg of the Cd-P-ZS~-5 catalyst of Example 9 at ~SV of 10 and 400C. Toluene conversion was 6.8% and selectivity to p-xylene in xylenes was 94.6%. This is a dramatic increase over the selectivity of the catalyst modified with phosphorus alone 1Example 7A].
E~-~IPLE lOB
In a similar manner, ethylation of toluene was made by passing toluene (at ~SV = 7) and ethylene (at ~SV
= 0.5) over l.lg of the Cd-P-ZSM-5 catalyst of Example 9 at 400C. Conversion of toluene was 2.1% and selectivity to p-ethyltoluene in ethyltoluene was over 99%. Again, a startling increase in selectivity compared to the P-ZSM-5 alone [Example 73].
3C!9~
E.YAMPLE 11 [Disproportionation reaction with Cd-P-modified zeolite]
Disproportionation of toluene was carried out by passing toluene over l~lg of the Cd-P-ZSM-5 catalyst of Example 9 at I~SV = 3.5 and 500C ~ Toluene conversion was 6~5% and selectivity to p-xylene in ~ylene was 96~/,. 3y contrast, disproportionation of toluene with P-ZSM-5 (Example 8) resulted in only 35~1% selectivity to para-isomer under the same conditions.
E ~PLE 12A
[Alkylation reaction with unmodified ZSM-11]
A toluene/methanol feed stream, havin~ a 4/1 molar ratio of the respective reactants, was passed over unmodified HZSM-ll zeolite (SiO2/A12O3 = 70) at 400-600C
and a feed ~SV of 10. The results are sho~m below.
Temperature Percent Toluene Percent para-xylene _C Conversion in Xylenes 400 ~ 67.6 23.4 500 -90~4 24~0 600 157.~ 22.7 '3~
A toluene/ethylene feed stream was similarly brought into contact with the unmodified HZSM-11. The feed ~HSV was 7.5 and 0.55, respectively, and the temperature of reaction 400-450C. The results are summarized below.
Temperature Percent Toluene Isomer ratios of _C Conversion eth~ltoluene P _ o 400 80.2 27.3 58.4 14.3 450 81.9 27.~ 57.~ 14.9 EX~MPLE 13 [Disproportionation reaction with unmodified ZSM-11]
A 1.0g portion of unmodified HZSM-11 zeolite (silica to alumina mole ratio = 70) was placed in a quartz flow reactor and heated to tem-perature. Toluene was passed over the zeolite at ~HSV of 3.8 and various temperatures between 400C and 600C. The results are summarized below.
. .
:~, - - ' . - .
3rj~
a~ ~n ~n ~ ~ 1 l o~a O Vl O ~ O C~
O O O O O ~
~O . C
_ O 3 ~' n ~D
U~
_ O _l N
e~
~ CO O _ tD ~_ ca ~ ~D ~I
W W W ,c~
rcl, p~
- ` _ - ` `, . -'3`~
EX~MPLE 14 [Preparation of Cd-modified ZSM-ll]
To a solution of 4.09 cadmium acetate in 5 ml water heated at 80C was added 1.59 HZSM-ll (SiO2/A1203 = 70). The mixture was maintained at 80 - 90C for 2 hours. After filtration and drying at about 90PC for 16 hours, the residue was calcined at 500C
for 2 hours to give 2.19 Cd-ZSM-ll. The content of cadmium was analyzed to be 26.2%.
Example 15A
[Alkylation reaction with Cd-m~dified ZSM-ll]
Alkylation of toluene with methanol was carried out by passing a toluene/methanol mixture (molar ratio of 4/1) over 1.19 of the Cd-ZSM-ll catalyst of Example 14 at WHSV of 10 and 400~C.
Toluene conversion was 27.6% and selectivity to p-xylene in xylenes was 31.0%
In a similar manner, ethylation of toluene was carried out by passing toluene (at W~SV = 7) and ethylene at (W~SV = 0.5) oYer 1.19 of the Cd-ZSM-ll catalyst of Example 14 at 400C. Conversion Of toluene was 15.1% and selectivity to p-ethyltoluene in ethyltoluene was 45.0%.
As the foregoing ably demonstrate, modification of the ZSM-ll zeolite with cadmium as herein described results in significant increases in para-selectivity as compared to the 2~ activity of the unmodified zeolite (Example 12).
~-a~3~
EX~` LE 16 [Disproportionation reaction with Cd-modified ZSM-11]
Disproportionation of toluene was carried out by passing toluene over 1.lg o_ the Cd-ZSM-11 catalyst of Example 14 at ~SV = 3.S and 4jOC. Toluene conversion was 1.3% and selectivity to p-xylene in xylene was 48.1%. This represents approximately twice the level of para-selectivity shown by the unmodified ZSM-11 zeolite in the same reaction [Example 13].
It is to be understood that the foregoing is ineended to be merely illustrative of certain specific embodiments of the disclosed invention. As those of skill in the art will readily appreciate, there are many variations which may be made on these specific embodiments without departing from the spirit of the herein described invention and such variations are clearly to be encompassed within ambit of the following claims.
~.
- , - - - ,- : ., .
Claims (14)
1. A process for para-selective conversion of aromatic compounds via alkylation, transalkylation or disproportionation to form a dialkylbenzene compound mixture rich in the 1,4-dialkylbenzene isomer, said process comprising contacting said aromatic compounds with a zeolite catalyst at a temperature of between 250°C and 750°C and a pressure within the approximate range of 105N/m2 to 107N/m2, said catalyst comprising a zeolite characterized by a silica to alumina mole ratio of at least 12 and a constraint index within the approximate range of 1 to 12, said catalyst having undergone prior modification by treatment with one or more cadmium compounds to deposit thereon at least about 0.25 weight percent of cadmium, said cadmium being present in said catalyst in the form of cadmium oxide.
2. The process of claim 1 wherein said temperature is between 300°C
and 650°C.
and 650°C.
3. The process of claim 1 wherein cadmium comprises between 2 and }5 weight percent of the modified zeolite catalyst.
4. The process of claim 1 wherein said catalyst is also modified by treatment with a phosphorus compound to deposit thereon at least 0.25 weight percent of phosphorus, said phosphorus being present in the form of an oxide of phosphorus.
5. The process of claim 1, 3 or 4 wherein said zeolite is admixed with a binder therefor.
6. The process of claim 1, 3 or 4 wherein said conversion is the alkylation of an aromatic compound by contacting said compound with an alkylating agent to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration.
7. The process of claim 1, 3 or 4 wherein said conversion is the transalkylation of aromatic compounds to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration.
8. The process of claim 1, 3 or 4 wherein said conversion process is disproportionation of alkylbenzenes to produce benzene and dialkylbenzenes in which the proportion of 1,4-dialkylbenzene isomer is in excess of its normal equilibrium concentration.
9.The process of claim 1, 3 or 4 wherein said zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48.
10. A catalyst composition comprising a crystalline zeolite having a constraint index of 1 to 12 and a silica to alumina mole ratio of at least 12 and further comprising at least 0.25 weight percent of cadmium, said cadmium being present in said catalyst in the form of cadmium oxide.
11. The composition of claim 10 wherein said cadmium comprises between 2 and 35 weight percent of said composition.
12. The composition of claim 10 which also comprises at least 0.25 weight percent of phosphorus, said phosphorus also being present in said catalyst in the form of an oxide of phosphorus.
13. The composition of claim 10, 11 or 12 wherein said zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48.
14. The composition of claim 10, 11 or 12 wherein said zeolite is admixed with a binder therefor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000371534A CA1180309A (en) | 1981-02-23 | 1981-02-23 | Shape selective reactions with cadmium-modified zeolite catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000371534A CA1180309A (en) | 1981-02-23 | 1981-02-23 | Shape selective reactions with cadmium-modified zeolite catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1180309A true CA1180309A (en) | 1985-01-02 |
Family
ID=4119273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000371534A Expired CA1180309A (en) | 1981-02-23 | 1981-02-23 | Shape selective reactions with cadmium-modified zeolite catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1180309A (en) |
-
1981
- 1981-02-23 CA CA000371534A patent/CA1180309A/en not_active Expired
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