GB2089366A - Hydrocarbon conversion - Google Patents
Hydrocarbon conversion Download PDFInfo
- Publication number
- GB2089366A GB2089366A GB8135402A GB8135402A GB2089366A GB 2089366 A GB2089366 A GB 2089366A GB 8135402 A GB8135402 A GB 8135402A GB 8135402 A GB8135402 A GB 8135402A GB 2089366 A GB2089366 A GB 2089366A
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- United Kingdom
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- zeolite
- diluent
- catalyst
- weight
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- 238000006243 chemical reaction Methods 0.000 title claims description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008096 xylene Substances 0.000 claims abstract description 11
- 150000003738 xylenes Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000006069 physical mixture Substances 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- -1 alkyl benzene hydrocarbons Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Chemical group 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The process comprises isomerisation, in the liquid or vapour phase, of a feed comprising a xylene or mixture of xylenes and optionally also containing up to 25% ethylbenzene using a catalyst comprising a novel crystalline aluminosilicate zeolite Nu-6(2).
Description
SPECIFICATION
Hydrocarbon conversion
This invention relates to a process for the isomerisation of alkyl benzene hydrocarbons using a catalyst comprising new zeolite materials. The new zeolite materials will be referred to hereinafter as "zeolite Nu 6(1)" and "zeolite Nu 6(2)" or simply as "Nu6(1)" and "Nu6(2)".
Zeolites Nu6(1) and Nu6(2) and their preparation are described in our co-pending UK patent application No. 8039685.
Zeolites Nu6(1) and Nu6(2) have a chemicai composition, in terms of mole ratios of oxides, expressed by the formula
0.5 to 1.5 R2O:Y203:at least 10 To2:0 to 2000 H2O wherein R is a monovalent cation or 1/n of a cation of valency n, X is silicon and/or germanium, Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, antimony, arsenic, manganese, gallium, or boron, and H2O is water of hydration additional to water notionally present when R is H. Zeolite Nu6(1) and Nu6(2) as prepared have X-ray patterns substantially as set out in Tables 1 and 2 (as determined by standard technique using copper K a radiation).
TABLE 1
Zeolite Nu-6(1)
dA 1001/lo 13.4 89 11.3 6 6.89 3 5.46 13 4.52 17 4.48 15 4.29 84 4.23 19 3.998 100 3.683 34 3.478 40 3.382 91 3.335 61 3.107 13 3.019 11 2.986 3 2.964 3 2.484 17 Within the above definition of chemical composition, the number of moles of XO2 is typically in the range 10 to 5000 and zeolites Nu-6( 1) and Nu-6(2) appear to be most readily formed in a state of high purity when the number of moles of X02 is in the range 20 to 1000.
This definition includes both freshly prepared Nu-6(1) and Nu-6(2) ("freshly prepared" means the product of synthesis and washing, with optional drying, as hereinafter described) and also forms of it resuiting from dehydration, and/or calcination, and/or ion exchange. In freshly prepared Nu6(1) and
Nu6(2), R may include an alkali metal cation especially sodium, and/or ammonium, and hydrogen and usually or when prepared from nitrogen compounds, including nitrogen-containing organic cations as described below or cationic degradation products thereof, or precursors thereof. These nitrogen containing cations are hereinafter referred to as Q.
The freshly prepared Nu-6(1) and Nu-6(2) may also contain nitrogen-containing compounds well in excess of the 1.5 moles set out in the aforesaid definition of the composition of Nu-6( 1) and Nu-6(2) typically in the range 0.1 to 20 moles per mole of Y203. Since Nu-6(1) and Nu-6(2) are zeolites, the nitrogen containing base must be physically trapped within the crystal lattice. It can be removed by thermal or oxidative degradation or by displacement by suitable small molecules. This physically trapped basic material does not constitute part of the composition for the purposes of the definition.
Thus Nu-6(1) and Nu-6(2) as made typically have the following molar composition: 0 to 1.8 M2O:1.0 to 400 Q:Y203:1 0 to 5000 To2:0 to 2000 H20 wherein M is an alkali metal and/or ammonium, and M20 + Q 2 1.0.
The H2O content of freshly prepared zeolite Nu-6(1) depends on the conditions in which it has been dried after synthesis. indeed, if dried at temperatures at or above 2000C it converts to zeolite Nu6(2).
In calcined forms of zeolite Nu6(2), R may be alkali metal but includes less or no nitrogencontaining organic compounds, since these are burnt out in the presence of air, leaving hydrogen as the other balancing cation, or otherwise displaced prior to calcination.
A very surprising characteristic of zeolite Nu-6(1) which makes it unique in high silica zeolites, is its behaviour on heating. Thus when.as made Nu-6(1) is heated at temperatures of from 200 to 7500C, it recrystallises to a novel crystalline phase designated zeolite Nu-6(2). Typical X-ray diffraction data for zeolite Nu-6(2) is given in Table 2.
TABLE 2
Zeolite Nu-6 (2)
dA 1001/lo do a 1001/lo 8.41 45 B- 3.94 2 B 6.67 42 3.76 11 B 6.09 15 B 3.65 15 B 4.61 27.5 3.44 27 B 4,33 100 1 3.33 76 ca 4.19 Shoulder t 3.17 15 B ca 4.10 J 3.05 9 All diffraction lines show some broadening, those marked B are the broadest Significant line broadening appears to be a characteristic of zeolite Nu-6(2).The degree of broadening depends upon the temperature as further discussed in our co-pending UK patent application No. 8039685.
According to the present invention a hydrocarbons conversion process comprises contacting a feed of an alkylbenzene or a mixture of alkylbenzenes under isomerisation conditions in the vapour or liquid phase with a catalyst comprising zeolite Nu6-(2).
The catalyst used in the process of this invention may be zeolite Nu6-(2) per sue but in a preferred embodiment of the process zeolite Nu6-(2) is used in the form of a physical mixture with a suitable diluent and/or binder, for example alumina, silica or a clay. Ammonia is particularly preferred as a diluent, the amount of alumina present in the catalyst being preferably in the range 5 to 95% by weight based on total catalyst weight. The catalyst is conveniently used in the form of pellets, extrudates or other aggregates well known to those skilled in this art.
In the vapour phase, suitable isomerisation conditions for the process of this invention include a temperature in the range 100 to 6000C, preferably 200 to 45O0C and a pressure in the range 0.5 to 50 preferably 1 to 5, Kg/cm2 absolute.
In the liquid phase embodiment of the process of this invention, suitable isomerisation conditions include a temperature in the range 0 to 3500 C, a pressure in the range 1 to 200, preferably 5 to 70,
Kg/cm2 absolute and, in a flow system, a space velocity in the range 0.1 to 100, preferably 0.5 to 30, w/w hour, the higher flow rates being used at the higher temperatures. Optionally a diluent is present, suitably one or more of those having a critical temperature higher than the isomerisation temperature being used and including toluene, trimethylbenzene, naphthenes and paraffins. Preferably, the diluent if present, amounts to 1 to 90% of the feed to the isomerisation reaction. In the above mentioned forms of the process of this invention the catalyst preferably contains no hydrogenation/dehydrogenation component.
Optionally the isomerisation reaction is conducted in the presence of hydrogen. A suitable mole ratio of hydrogen to alkylbenzene feed lies in the range 1:1 to 30:1. If hydrogen is used, it is preferred that the catalyst should comprise a metal of Group VIII of the Periodic Table together with the zeolite.
Preferably the metal of Group Vlil is platinum or nickel. The amount of metal used preferably lies in the range 0.1 to 2% by weight of metal based on the total weight of catalyst. If desired, the catalyst may contain one or more additional metals, for example rhenium, suitably in the range 0.1 to 2% by weight based on the total weight of catalyst.
Preferably the alkylbenzene is a xylene, for example m-xylene for conversion to p-xylene, or a mixture of xylenes, possibly with ethylbenzene. The amount of ethylbenzene present will depend to some extent on the source of the xylene mixture but will usually lie in the range 0 to 25% by weight of the feedstock. However, we believe that the process of this invention is very suitable for at least partial destruction of the ethylbenzene in feedstocks containing relatively large amounts of ethylbenzene, say in the range 6 to 25% by weight of the feedstock.
The invention is illustrated by the following Examples.
EXAMPLE 1
A sample of zeolite Nu-6(2) prepared as described in Example 3 of our co-pending UK Patent
Application No. 8039685 was formed into aggregates having diameters in the size range of 425 to 1000 Mm. The zeolite's empirical formula was 0.25 Na20:Ai203:77.4 SiO2 and it contained 0.20% by weight sodium, 0.95% by weight aluminium and 36.8% by weight silicon.
The sample was charged to a glass reactor and heated in a stream of air at 5000C for 1 6 hours. It was then cooled in a nitrogen stream to 4000C. A feedstock consisting mainly of C8 aromatic hydrocarbons was passed over the aggregated zeolite for 1 8 hours at a weight hourly space velocity of 13.8. Details of the composition of the feed and of the product obtained after 8 hours and 1 8, hours are given in Table 3. All percentages given are by weight.
TABLE 3
Hours on line Feedstock 8 hours 18 hours Benzene ( /O) 0.02 1.64 1.34 Toluene (%) 1.75 2.22 2.12 Ethylbenzene (O/o) 8.61 6.16 6.74 Paraxylene ( /0) 7.94 18.92 18.49 Metaxylene (O/o) 50.92 44.06 44.08 Orthoxylene (O/o) 25.54 20.90 21 .32 C, + aromatics (%) 3.86 4.88 4.49 Paraxylene approach to Paraxylene approach to equilibrium (O/o) Ethylbenzene loss (96) 28.4 21.72 Xylene loss ( /O) L 0.62 0.60 EXAMPLE 2
The sample of aggregated zeolite Nu-6(2) used in Example 1 was regenerated by heating in a stream of air at 5O00C for 1 6 hours. It was then cooled in a nitrogen stream to 4000 C. A feedstock consisting mainly of C8 aromatic hydrocarbons was passed over the aggregated zeolite for 6 hours at a weight hourly space velocity of 6.3.Details of the composition of the feed and of the product obtained after 6 hours are given in Table 4. All percentages are given by weight.
TABLE 4
Feedstock Product Benzene (%) 0.04 0.46 Toluene (%) 1.11 1.89 Ethylbenzene ( /0) 1.46 0.95 Paraxylene (%) 9.59 22.13 Metaxylene (O/o) 59.54 50.19 Orthoxylene (%) 27.46 22.84 C, + aromatics (O/o) 0.64 1.43 Paraxylene approach to equilibrium ( 98.71 Ethylbenzene loss (#) 34.93 Xylene loss (%) 1.48 From these results it can be seen that zeolite Nu-6(2) brings about the isomerisation of xylenes to close to equilibrium with very little loss of xylenes. Simultaneous loss of ethylbenzene is high.
Claims (15)
1. A hydrocarbon conversion process which comprises contacting a feed of an alkylbenzene or a mixture of alkylbenzenes under isomerisation conditions in the vapour or liquid phase with a catalyst comprising zeolite Nu6-(2).
2. A process as claimed in claim 1 in which zeolite Nu-6(2) is used in the form of a physical mixture with a diluent and/or binder.
3. A process as claimed in claim 1 or 2 in which zeolite Nu-6(2) is used with a diluent and/or binder comprising alumina, silica or a clay.
4. A process as claimed in claim 2 or 3 in which the diluent is alumina and the amount of alumina present in the catalyst is in the range 5 to 95% by weight based on total catalyst weight.
5. A process as claimed in any one of the preceding claims in which the process is carried out in the vapour phase under isomerisation conditions which include a temperature in the range 100 to 6000C and a pressure in the range 0.5 to 50 Kg/cm2 absolute.
6. A process as claimed in any one of claims 1 to 4 in which the process is carried out in the liquid phase under isomerisation conditions which include a temperature in the range 0 to 35000 and a pressure in the range 1 to 200 Kg/cm2.
7. A process as claimed in claim 6 in which a process diluent is present in an amount of 1 to 90% of the feed to the isomerisation reaction.
8. A process as claimed in claim 7 in which the diluent is seiected from toluene, trimethylbenzene, naphthalenes and paraffins.
9. A process as claimed in any one of the preceding claims in which the isomerisation reaction is carried out in the presence of hydrogen.
10. A process as claimed in claim 9 in which the mole ratio of hydrogen to alkylbenzene feed is in the range 1:1 to 30:1.
11. A process as claimed in claim 9 or 10 in which the catalyst comprises a metal of Group VIII of the Periodic Table together with zeolite Nu-6(2).
12. A process as claimed in claim 11 in which the amount of metal of Group VIII is in the range 0.1 to 2.0% by weight.
13. A process as claimed in any one of the preceding claims in which the alkylbenzene is a xylene or a mixture of xylene isomers.
14. A process as claimed in any one of the preceding claims in which the alkylbenzene feed contains up to 25% by weight of ethylbenzene.
1 5. A hydrocarbon conversion process substantially as hereinbefore described with reference to
Examples 1 and 2.
1 6. Xylene whenever produced by a process as claimed in any one of claims 1 to
1 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8135402A GB2089366B (en) | 1980-12-11 | 1981-11-24 | Hydrocarbon conversion |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8039686 | 1980-12-11 | ||
| GB8135402A GB2089366B (en) | 1980-12-11 | 1981-11-24 | Hydrocarbon conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2089366A true GB2089366A (en) | 1982-06-23 |
| GB2089366B GB2089366B (en) | 1984-04-26 |
Family
ID=26277801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8135402A Expired GB2089366B (en) | 1980-12-11 | 1981-11-24 | Hydrocarbon conversion |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2089366B (en) |
-
1981
- 1981-11-24 GB GB8135402A patent/GB2089366B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2089366B (en) | 1984-04-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |