US20130123557A1 - Process for producing phosphorus modified zeolite catalysts - Google Patents
Process for producing phosphorus modified zeolite catalysts Download PDFInfo
- Publication number
- US20130123557A1 US20130123557A1 US13/652,660 US201213652660A US2013123557A1 US 20130123557 A1 US20130123557 A1 US 20130123557A1 US 201213652660 A US201213652660 A US 201213652660A US 2013123557 A1 US2013123557 A1 US 2013123557A1
- Authority
- US
- United States
- Prior art keywords
- zeolite
- phosphorus
- catalyst
- catalyst body
- zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 56
- 239000011574 phosphorus Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- -1 phosphorus modified zeolite Chemical class 0.000 title claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000010457 zeolite Substances 0.000 claims abstract description 68
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 66
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007069 methylation reaction Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000011987 methylation Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000005336 cracking Methods 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
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- 150000003613 toluenes Chemical class 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C07C41/01—Preparation of ethers
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- C10G2400/04—Diesel oil
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- 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
- Y02P20/10—Process efficiency
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- This disclosure relates to a process for producing phosphorus modified zeolite catalysts.
- Phosphorus modification is a known method of improving the performance of zeolite catalysts for a variety of chemical processes including, for example, the conversion of methanol to hydrocarbons and the methylation of toluene to produce xylenes.
- U.S. Pat. Nos. 4,590,321 and 4,665,251 disclose a process for producing aromatic hydrocarbons by contacting one or more non-aromatic compounds, such as propane, propylene, or methanol, with a catalyst containing a zeolite, such as ZSM-5, composited with an inorganic oxide binder.
- the catalyst is modified with phosphorus by impregnation with a source of phosphate ions, such as an aqueous solution of an ammonium phosphate, followed by calcination to produce phosphorus oxide in an amount of about 0.05% to 50%, preferably from about 0.7% to about 15%, by weight of the catalyst composite.
- a source of phosphate ions such as an aqueous solution of an ammonium phosphate
- U.S. Pat. No. 7,662,737 discloses a process for producing a bound phosphorus-modified zeolite catalyst, in which a zeolite, such as ZSM-5, which may be in the NH 4 + or the H + form, is slurried with an aqueous solution of a phosphorus compound and then water is removed from the slurry to form a phosphorus-modified zeolite.
- the phosphorus-modified, pre-calcined zeolite is then mixed with an acid-treated inorganic oxide binder material selected from alumina, clay, aluminum phosphate and/or silica-alumina.
- the zeolite-binder mixture is heated at a temperature of about 400° C. or higher to form a bound zeolite catalyst, typically from 0.01 to about 0.15 gram of phosphorus per gram of zeolite.
- the catalyst is particularly intended for use in the alkylation of toluene with methanol to produce xylenes, but is also said to be useful in MTG processes. Similar processes of producing phosphorus-modified toluene methylation catalysts are disclosed in U.S. Pat. Nos. 7,368,410 and 7,507,685, and in U.S. Patent Application Publication Nos. 2007/0149384, 2008/0275280, and 2009/0036723.
- U.S. Pat. No. 7,285,511 discloses a process of modifying a zeolite catalyst to increase its para-xylene selectivity in toluene methylation reactions, wherein the method comprises forming a slurry consisting essentially of a binder-free ZSM-5-type zeolite having a SiO 2 /Al 2 O 3 mole ratio of from about 250 to about 1000 and an aqueous solution of a phosphorus-containing compound; and removing water from the slurry to provide a non-steamed, phosphorus treated ZSM-5 zeolite having a phosphorus content of from 0.04 g P/g zeolite or more and a pore volume of from 0.2 ml/g or less.
- the resultant phosphorus treated ZSM-5 can be used as a toluene methylation catalyst either in unbound form or may be composited with a binder, such as alumina, clay or silica.
- a binder such as alumina, clay or silica.
- U.S. Pat. No 6,504,072 discloses selective production of para-xylene by the reaction of toluene with methanol over a severely steamed ZSM-5 catalyst combined with oxide modifier, preferably an oxide of phosphorus, to control the reduction of the micropore volume of the catalyst during the steaming step.
- oxide modifier preferably an oxide of phosphorus
- Incorporation of phosphorus in the catalyst is conveniently accomplished by contacting the ZSM-5, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to an oxide form.
- One desirable result of modifying a zeolite catalyst by the addition of phosphorus can be that the tendency for the zeolite to lose its catalytic activity when exposed to high temperature steam can be reduced. There is, however, significant interest in the development of phosphorus-modified zeolite catalysts in which the steam stabilization resulting from the phosphorus addition can be improved/maximized.
- a zeolite catalyst with improved steam stability can be produced by phosphorus treatment of a zeolite catalyst which is self-bound or is combined with a binder that is substantially free of aluminum.
- the invention resides in a process for producing a phosphorus-modified zeolite catalyst, said process comprising: (a) forming as-synthesized zeolite crystals into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder which is substantially free of aluminum; (b) converting the zeolite crystals to the hydrogen form; (c) removing any organic directing agent employed in the synthesis of the zeolite crystals; (d) treating the shaped catalyst body with an aqueous solution of a phosphorus compound; and (e) heating the treated catalyst body to remove water and convert the phosphorus compound to an oxide form.
- the zeolite crystals can be formed into a shaped catalyst body in the presence of a separate inorganic oxide binder containing less than 5 wt %, for example less than 3 wt %, of aluminum.
- the forming (a) can be accomplished by extrusion.
- the zeolite crystals can be mixed with a silica binder prior to the forming (a).
- the converting (b) can be accomplished before the forming (a).
- the removing (c) can be accomplished before the forming (a).
- the treating (d) can be accomplished by impregnation, such as with an aqueous solution of a phosphorus oxyacid.
- the catalyst body can comprise from about 0.1 wt % to about 3 wt % of elemental phosphorus present as an oxide of phosphorus.
- the heating in (e) can be conducted at a temperature from about 350° C. to about 650° C. for a time from about 0.2 hours to about 5.0 hours.
- the zeolite can have a molar ratio of silica to alumina from about 20 to about 200, e.g., from about 20 to about 150.
- the zeolite can comprise, consist essentially of, or be ZSM-5.
- the invention can reside in a phosphorus-modified zeolite catalyst produced by the process described herein, and/or in use of the catalyst in organic conversion reactions, especially in a process for conversion of methanol to hydrocarbons.
- Described herein is a process for producing a phosphorus-modified zeolite catalyst.
- the phosphorus incorporation can be accomplished after the zeolite has been formed into a shaped catalyst body, either in the absence of a separate inorganic oxide binder (self-bound) or in the presence of a separate inorganic oxide binder which can advantageously be substantially free of aluminum.
- a separate inorganic oxide binder self-bound
- a separate inorganic oxide binder which can advantageously be substantially free of aluminum.
- the present process can be employed to produce a phosphorus-modified zeolite catalyst containing any known zeolite or mixture of zeolites.
- the catalyst described herein can comprise, consist essentially of, or be at least one medium pore zeolite having a Constraint Index of 2-12 (as defined in U.S. Pat. No. 4,016,218), Suitable medium pore molecular sieves can include, but are not limited to, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and the like, and combinations thereof.
- ZSM-5 is described in detail in U.S. Pat. Nos. 3,702,886 and RE 29,948.
- ZSM-11 is described in detail in U.S. Pat. No. 3,709,979.
- ZSM-12 is described in U.S. Pat. No. 3,832,449.
- ZSM-22 is described in U.S. Pat. No. 4,556,477.
- ZSM-23 is described in U.S. Pat. No. 4,076,842.
- ZSM-35 is described in U.S. Pat. No, 4,016,245.
- ZSM-48 is more particularly described in U.S. Pat. No. 4,234,231.
- the catalyst described herein can comprise one or more large pore zeolites having a Constraint Index less than 2.
- Suitable large pore molecular sieves can include, but are not limited to, zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, and the like, and combinations thereof.
- ZSM-14 is described in U.S. Pat. No. 3,923,636.
- ZSM-20 is described in U.S. Pat. No. 3,972,983.
- Zeolite beta is described in U.S. Pat. Nos. 3,308,069, and RE 28,341.
- Low sodium Ultrastable Y molecular sieve USY
- U.S. Pat. Nos. 3,293,192 and 3,449,070 Deluminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Pat. No. 3,442,795.
- Zeolite UHP-Y is described in U.S. Pat. No. 4,401,556.
- Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetically prepared from a reaction mixture comprising a tetraethylammonium directing agent), which is disclosed in U.S. Pat. Nos. 3,766,093 and 3,894,104.
- the catalyst described herein can comprise at least one molecular sieve of the MCM-22 family.
- the term “molecular sieve of the MCM-22 family” includes one or more of:
- Molecular sieves of the MCM-22 family can include those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstroms.
- the X-ray diffraction data used to characterize the material can be obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
- Materials of the MCM-22 family can additionally or alternately include, but are not limited to, MCM-22 (described in U.S. Pat. No. 4,954,325), PSF-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERR-1 (described in European Patent No. 0293032).
- ITQ-1 (described in U.S. Pat. No. 6,077,498)
- ITQ-2 (described in International Patent Publication No. WO97/17290)
- MCM-36 described in U.S. Pat. No. 5,250,277)
- MCM-49 described in U.S. Pat. No. 5,236,575
- MCM-56 described in U.S. Pat. No. 5,362,697
- UZM-8 described in U.S. Pat. No. 6,756,030
- the catalyst described herein can comprise or be ZSM-5. Additionally or alternately, the catalyst described herein can comprise or be a zeolite having a silica to alumina molar ratio from about 20 to about 200, for example from about 20 to about 150.
- the catalyst employed in the present process may contain a separate inorganic oxide binder that is substantially free of aluminum.
- substantially free is meant the separate inorganic oxide binder should contain less than 5 wt % of aluminum, for example less than 3 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.3 wt %, less than 0.1 wt %, less than 0.05 wt %, or completely free of measurable aluminum.
- suitable inorganic oxide binders can include, but are not necessarily limited to, silica, titanic, zirconia, and the like, and mixtures thereof with each other and other metal oxides (again typically not including alumina).
- the inorganic oxide binder can be present in an amount from about 5 wt % to about 65 wt %, for example from about 10 wt % to about 35 wt %, of the total catalyst.
- the present zeolite catalyst may be formed into a shaped catalyst body without the aid of a separate binder, i.e., the catalyst may be self-bound.
- as-synthesized crystals of the target zeolite can be formed into a slurry with a solvent, generally water, and, where applicable, a substantially aluminum-free inorganic oxide binder.
- the resultant slurry can then formed into a shaped catalyst body, generally by extrusion, and the catalyst body can then be treated with an aqueous solution of a phosphorus compound, such as a phosphorus oxyacid.
- Phosphorus treatment can conveniently be accomplished by impregnation. After phosphorus treatment, the treated catalyst body can be heated to remove the water and to convert the phosphorus compound to an oxide form.
- Heating can be conducted, advantageously in an oxidizing environment such as in air, at a temperature from about 350° C. to about 650° C. for an appropriate time, e.g., from about 0.2 hours to about 5.0 hours.
- the final catalyst can comprise from about 0.1 wt % to about 3 wt % of elemental phosphorus, present as an oxide of phosphorus.
- the as-synthesized zeolite crystals used to produce the desired catalyst can contain an organic directing agent used in the synthesis of the zeolite.
- Such directing agents can frequently block the pores of the zeolite and so should generally be removed before the zeolite is used catalytically.
- the directing agent can be removed prior to formation of the shaped catalyst body, in some preferred embodiments, the directing agent can be removed by heating the shaped catalyst body in an oxidizing or non-oxidizing environment (e.g., in air) at a temperature from about 400° C. to about 820° C. for an appropriate time, e.g., from about 0.3 hours to about 3 hours.
- heating to remove the organic directing agent can be conducted before phosphorus treatment of the shaped catalyst body.
- zeolite synthesis processes can be conducted under alkaline conditions in the presence of alkali metal ions, especially sodium ions.
- the as-synthesized zeolite crystals can often be in the sodium form and so should be converted to the catalytically active hydrogen form before use.
- Such conversion can typically be achieved by ion exchange with ammonium cations and heating to drive off the ammonia, thus leaving the H + form of the zeolite.
- ammonium exchange and subsequent conversion to the hydrogen form can be conducted on the shaped catalyst body.
- conversion of the zeolite to the hydrogen form can be conducted before phosphorus treatment of the shaped catalyst body, but after removal of the organic directing agent employed in the synthesis of the zeolite.
- the phosphorus-modified ZSM-5 catalyst produced by the present process can be particularly useful in any organic conversion process where the hydrothermal stability of the catalyst is important.
- examples of such processes can include, but are not necessarily limited to, fluid catalytic cracking of heavy hydrocarbons to gasoline and diesel boiling range hydrocarbons, methylation and disproportionation of toluene to produce xylenes, n-paraffin (e.g., C 6 and higher) cyclization, conversion of methanol to gasoline and diesel boiling range hydrocarbons, and the like, and combinations and/or integrations thereof.
- the invention can additionally or alternately include one or more of the following embodiments.
- EMBODIMENT 1 A process for producing a phosphorus-modified zeolite catalyst, said process comprising: (a) forming zeolite crystals into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder which is substantially free of aluminum; (b) converting the zeolite crystals to the hydrogen form; (c) removing any organic directing agent employed in the synthesis of the zeolite crystals; (d) treating the shaped catalyst body with an aqueous solution of a phosphorus compound; and (e) heating the treated catalyst body to remove the water and convert the phosphorus compound to an oxide form.
- EMBODIMENT 2 The process of embodiment 1, wherein the zeolite crystals are formed into a shaped catalyst body in the presence of a separate inorganic oxide hinder which contains less than 5 wt % of aluminum.
- EMBODIMENT 3 The process of any one of the previous embodiments, wherein the zeolite crystals are mixed with a silica binder prior to the forming (a).
- EMBODIMENT 4 The process of any one of the previous embodiments, wherein the forming (a) is accomplished by extrusion.
- EMBODIMENT 5 The process of any one of the previous embodiments, wherein the converting (b) is accomplished before the forming (a).
- EMBODIMENT 6 The process of embodiment 5, wherein the removing (c) is accomplished before the forming (a).
- EMBODIMENT 7 The process of any one of the previous embodiments, wherein the treating (d) is accomplished by impregnation, e.g., with an aqueous solution of a phosphorus oxyacid.
- EMBODIMENT 8 The process of any one of the previous embodiments, wherein the heating in (e) is conducted at a temperature from about 350° C. to about 650° C. for a time of about 0.2 hours to about 5.0 hours.
- EMBODIMENT 9 The process of any one of the previous embodiments, wherein the zeolite has a molar ratio of silica to alumina from about 20 to about 200, e.g., from about 20 to about 150.
- EMBODIMENT 10 The process of any one of the previous embodiments, wherein the zeolite comprises ZSM-5.
- EMBODIMENT 11 A phosphorus-modified zeolite catalyst produced by the process of any one of the previous embodiments,
- EMBODIMENT 12 A process for organic compound conversion employing contacting a feedstock with the phosphorus-modified zeolite catalyst of embodiment 11 under organic compound conversion conditions.
- EMBODIMENT 13 The process of embodiment 12, wherein said organic compound conversion comprises the conversion of methanol to hydrocarbons boiling in the gasoline boiling range.
- the ZSM-5 crystal employed was an as-synthesized sodium form ZSM-5 having a silica to alumina molar ratio of about 50, produced using tetrapropylammonium bromide as a structure directing agent.
- alpha values are used to provide an indication of the catalytic cracking activity of a catalyst, compared to a standard catalyst, and to help assess the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time).
- the alpha value is based on the activity of a silica-alumina cracking catalyst taken as an alpha of 1 (Rate Constant ⁇ 0.016 sec ⁇ 1 ).
- the Alpha Test is described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis, 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), each incorporated herein by reference as to that description.
- the experimental conditions of the test used herein include ⁇ 100 torr ( ⁇ 13 kPa) hexane vapor pressure in He carrier gas flowing through a reactor held at ⁇ 1000° F. ( ⁇ 538° C.).
- Alumina ⁇ 200 grams on solids basis was first added to a mixer and dry Deionized water ( ⁇ 100 grams) was then added to moisten the alumina, followed by addition of an amount of phosphoric acid ( ⁇ 0, ⁇ 61, ⁇ 122, or ⁇ 183.2 grams, respectively, on solids basis) to achieve targeted phosphorus levels.
- Na-ZSM-5 crystals ⁇ 800 grams on solids basis
- additional deionized water were then added, and the mixtures were mulled for ⁇ 10-30 minutes to achieve the desired consistency for extrusion, Mixtures with four different phosphorus levels ( ⁇ 0, ⁇ 1.7, ⁇ 3.4, and ⁇ 4.2 wt %, respectively) were thereby prepared.
- each mixture was then extruded into ⁇ 1/16′′ cylinders.
- the extrudates were dried overnight ( ⁇ 8-16 hours) at ⁇ 250° F. ( ⁇ 121° C.) and then precalcined in nitrogen for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- Each extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate.
- the resultant exchanged catalyst was dried overnight at ⁇ 250° F. ( ⁇ 121° C.) and then calcined in air for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- ZSM-5 ⁇ 800 grams on solids basis
- VersalTM 300 alumina ⁇ 200 grams on solids basis
- ⁇ 492 grams of deionized water were added to achieve the desired consistency for extrusion.
- the mixture was then extruded into ⁇ 1/16′′ cylinders, The extrudates were dried overnight ( ⁇ 8-16 hours) at ⁇ 250° F. ( ⁇ 121° C.) and then precalcined in nitrogen for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- the extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate.
- the exchanged catalyst was dried overnight at ⁇ 250° F.
- ZSM-5 ⁇ 800 grams on solids basis
- UltrasilTM VN3SP silica ⁇ 100 grams on solids basis
- LudoxTM-40 silica ⁇ 100 grams was then added to the mixture followed by the addition of ⁇ 60 grams of ⁇ 50 wt % caustic (NaOH) solution. While mulling, ⁇ 85 grams of deionized water were added to achieve the desired consistency for extrusion.
- the mixture was then extruded into ⁇ 1/16′′ cylinders. The extrudates were dried overnight ( ⁇ 8-16 hours) at ⁇ 250° F. ( ⁇ 121° C.) and then precalcined in nitrogen for ⁇ 3 hours at ⁇ 1000° F.
- the extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate.
- the exchanged catalyst was dried overnight at ⁇ 250° F. ( ⁇ 121° C.) and then calcined in air for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- the extrudate was then impregnated via incipient wetness with targeted levels of ⁇ 2, ⁇ 4, or ⁇ 6 wt % phosphorus (actual levels as indicated in Table 1 below) using an aqueous solution of phosphoric acid.
- the impregnated crystal was then dried at ⁇ 250° F. ( ⁇ 121° C.) overnight and then calcined in air for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- ZSM-5 crystal ( ⁇ 1,4 kg on solids basis) was added to a mixer and dry mulled. Approximately 190 grams of deionized water was then added during mulling. After about 10 minutes, ⁇ 28 grams of ⁇ 50 wt % caustic (NaOH) solution mixed with approximately 450 grams of water were added to the mixture and mulled for an additional ⁇ 5 minutes. The mixture was then extruded into ⁇ 1/10′′ quadralobes. The extrudates were dried overnight ( ⁇ 8-16 hours) at ⁇ 250° F. ( ⁇ 121° C.) and then precalcined in nitrogen for ⁇ 3 hours at ⁇ 1000° F. ( ⁇ 538° C.).
- the extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate.
- the exchanged catalyst was dried overnight at ⁇ 250° F. ( ⁇ 121° C.) and then calcined in air for ⁇ 3 hours at ⁇ 4000° F. ( ⁇ 538° C.).
- the extrudate was then impregnated via incipient wetness with targeted levels of ⁇ 2, ⁇ 4, or ⁇ 6 wt % phosphorus (actual levels as indicated in Table 1 below) using an aqueous solution of phosphoric acid.
- the impregnated crystal was then dried at ⁇ 250° F. ( ⁇ 121° C.) overnight and then calcined in air for ⁇ 3 hours at ⁇ 1000° F.
- the ZSM-5 containing extrudates of Examples 1-4 were analyzed for phosphorus content and steamed for ⁇ 96 hours at ⁇ 1000° F. ( ⁇ 538° C.) and ⁇ 14.7 psia steam partial pressure.
- the as-prepared and steamed catalysts were then screened for acidic activity with hexane cracking measurements in a routine Alpha test.
- the Alpha values and phosphorus levels of the extrudates from Examples 1-4 are shown in Table 1 below.
- the results show that the alumina-containing catalysts from Examples 1 and 2 have much lower alpha activity than the silica and self-bound catalysts from Examples 3 and 4 after steaming. Both silica and self-bound catalysts with approximately 0.8 wt % P retain ⁇ 110 alpha value after steaming as compared to the same catalysts with no P that retain ⁇ 14 and ⁇ 11 alpha value after steaming.
- Example 1a 0.0 ⁇ 300 ⁇ 13
- Example 1b ⁇ 1.7 ⁇ 270 ⁇ 5.3
- Example 1c ⁇ 3.4 ⁇ 250 ⁇ 12
- Example 1d ⁇ 4.2 ⁇ 240 ⁇ 19
- Example 2a 0.0 ⁇ 320 ⁇ 13
- Example 2b ⁇ 2.7 ⁇ 340 ⁇ 22
- Example 2c ⁇ 4.2 ⁇ 210 ⁇ 38
- Example 2d ⁇ 5.3 ⁇ 160 ⁇ 79
- Example 3b ⁇ 0.8 ⁇ 240 ⁇ 110
- Example 3c ⁇ 1.6 ⁇ 170 ⁇ 96
- Example 3d ⁇ 2.4 ⁇ 99 ⁇ 26
- Example 4a 0.0 ⁇ 540 ⁇ 11
- Example 4b ⁇ 0.84 ⁇ 290 ⁇ 110
- Example 4c ⁇ 1.67 ⁇ 160, ⁇ 210 ⁇ 85
- Example 4d ⁇ 2.47 ⁇ 70 ⁇ 47, ⁇ 29
Abstract
In a process for producing a phosphorus-modified zeolite catalyst, zeolite crystals can be formed into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder that is substantially free of aluminum. After converting the zeolite crystals to the hydrogen form and removing any organic directing agent employed in the synthesis of the zeolite crystals, the shaped catalyst body can be treated with an aqueous solution of a phosphorus compound, and the treated catalyst body can be heated to remove the water and to convert the phosphorus compound to an oxide form.
Description
- This application claims the benefit of U.S. Provisional Application No. 61/548,038, filed on Oct. 17, 2011, the entire contents of which are hereby incorporated by reference herein.
- This application also claims the benefit of related U.S. Provisional Application Nos. 61/548,015, 61/548,044, 61/548,052, 61/548,057, and 61/548,064, each filed on Oct. 17, 2011, the entire contents of each of which are hereby also incorporated by reference herein. This application is also related to five other co-pending U.S. utility applications, each filed on even date herewith and claiming the benefit to the aforementioned provisional patent applications, and which are entitled “Process for Producing Phosphorus Modified Zeolite Catalysts”, “Phosphorus Modified Zeolite Catalysts”, “Phosphorus Modified Zeolite Catalysts”, “Phosphorus Modified Zeolite Catalysts”, and “Selective Dehydration of Alcohols to Dialkyl Ethers”, respectively, the entire contents of each of which utility patents are hereby further incorporated by reference herein.
- This disclosure relates to a process for producing phosphorus modified zeolite catalysts.
- Phosphorus modification is a known method of improving the performance of zeolite catalysts for a variety of chemical processes including, for example, the conversion of methanol to hydrocarbons and the methylation of toluene to produce xylenes. For example, U.S. Pat. Nos. 4,590,321 and 4,665,251 disclose a process for producing aromatic hydrocarbons by contacting one or more non-aromatic compounds, such as propane, propylene, or methanol, with a catalyst containing a zeolite, such as ZSM-5, composited with an inorganic oxide binder. The catalyst is modified with phosphorus by impregnation with a source of phosphate ions, such as an aqueous solution of an ammonium phosphate, followed by calcination to produce phosphorus oxide in an amount of about 0.05% to 50%, preferably from about 0.7% to about 15%, by weight of the catalyst composite.
- In addition, U.S. Pat. No. 7,662,737 discloses a process for producing a bound phosphorus-modified zeolite catalyst, in which a zeolite, such as ZSM-5, which may be in the NH4 + or the H+ form, is slurried with an aqueous solution of a phosphorus compound and then water is removed from the slurry to form a phosphorus-modified zeolite. The phosphorus-modified, pre-calcined zeolite is then mixed with an acid-treated inorganic oxide binder material selected from alumina, clay, aluminum phosphate and/or silica-alumina. After optional extrusion, the zeolite-binder mixture is heated at a temperature of about 400° C. or higher to form a bound zeolite catalyst, typically from 0.01 to about 0.15 gram of phosphorus per gram of zeolite. The catalyst is particularly intended for use in the alkylation of toluene with methanol to produce xylenes, but is also said to be useful in MTG processes. Similar processes of producing phosphorus-modified toluene methylation catalysts are disclosed in U.S. Pat. Nos. 7,368,410 and 7,507,685, and in U.S. Patent Application Publication Nos. 2007/0149384, 2008/0275280, and 2009/0036723.
- U.S. Pat. No. 7,285,511 discloses a process of modifying a zeolite catalyst to increase its para-xylene selectivity in toluene methylation reactions, wherein the method comprises forming a slurry consisting essentially of a binder-free ZSM-5-type zeolite having a SiO2/Al2O3 mole ratio of from about 250 to about 1000 and an aqueous solution of a phosphorus-containing compound; and removing water from the slurry to provide a non-steamed, phosphorus treated ZSM-5 zeolite having a phosphorus content of from 0.04 g P/g zeolite or more and a pore volume of from 0.2 ml/g or less. The resultant phosphorus treated ZSM-5 can be used as a toluene methylation catalyst either in unbound form or may be composited with a binder, such as alumina, clay or silica. A similar process of producing a phosphorus-modified toluene methylation catalyst is disclosed in U.S. Pat. No. 7,399,727.
- U.S. Pat. No 6,504,072 discloses selective production of para-xylene by the reaction of toluene with methanol over a severely steamed ZSM-5 catalyst combined with oxide modifier, preferably an oxide of phosphorus, to control the reduction of the micropore volume of the catalyst during the steaming step. Incorporation of phosphorus in the catalyst is conveniently accomplished by contacting the ZSM-5, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to an oxide form.
- One desirable result of modifying a zeolite catalyst by the addition of phosphorus can be that the tendency for the zeolite to lose its catalytic activity when exposed to high temperature steam can be reduced. There is, however, significant interest in the development of phosphorus-modified zeolite catalysts in which the steam stabilization resulting from the phosphorus addition can be improved/maximized.
- According to the present invention, it has now been found that a zeolite catalyst with improved steam stability can be produced by phosphorus treatment of a zeolite catalyst which is self-bound or is combined with a binder that is substantially free of aluminum.
- In one aspect, the invention resides in a process for producing a phosphorus-modified zeolite catalyst, said process comprising: (a) forming as-synthesized zeolite crystals into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder which is substantially free of aluminum; (b) converting the zeolite crystals to the hydrogen form; (c) removing any organic directing agent employed in the synthesis of the zeolite crystals; (d) treating the shaped catalyst body with an aqueous solution of a phosphorus compound; and (e) heating the treated catalyst body to remove water and convert the phosphorus compound to an oxide form.
- Conveniently, the zeolite crystals can be formed into a shaped catalyst body in the presence of a separate inorganic oxide binder containing less than 5 wt %, for example less than 3 wt %, of aluminum.
- Conveniently, the forming (a) can be accomplished by extrusion.
- In some embodiments, the zeolite crystals can be mixed with a silica binder prior to the forming (a).
- Additionally or alternately in some embodiments, the converting (b) can be accomplished before the forming (a).
- Additionally or alternately in some embodiments, the removing (c) can be accomplished before the forming (a).
- Conveniently, the treating (d) can be accomplished by impregnation, such as with an aqueous solution of a phosphorus oxyacid.
- Conveniently, the catalyst body can comprise from about 0.1 wt % to about 3 wt % of elemental phosphorus present as an oxide of phosphorus.
- Conveniently, the heating in (e) can be conducted at a temperature from about 350° C. to about 650° C. for a time from about 0.2 hours to about 5.0 hours.
- Conveniently, the zeolite can have a molar ratio of silica to alumina from about 20 to about 200, e.g., from about 20 to about 150.
- Conveniently, the zeolite can comprise, consist essentially of, or be ZSM-5.
- In further aspects, the invention can reside in a phosphorus-modified zeolite catalyst produced by the process described herein, and/or in use of the catalyst in organic conversion reactions, especially in a process for conversion of methanol to hydrocarbons.
- Described herein is a process for producing a phosphorus-modified zeolite catalyst. In the present process, the phosphorus incorporation can be accomplished after the zeolite has been formed into a shaped catalyst body, either in the absence of a separate inorganic oxide binder (self-bound) or in the presence of a separate inorganic oxide binder which can advantageously be substantially free of aluminum. In particular, it has been found that, by omitting the binder or by employing a binder that is substantially aluminum-free, the thermal stability of the catalyst can be significantly improved, as compared with a conventional alumina-bound catalyst containing the same amount of phosphorus.
- The present process can be employed to produce a phosphorus-modified zeolite catalyst containing any known zeolite or mixture of zeolites. In one embodiment, the catalyst described herein can comprise, consist essentially of, or be at least one medium pore zeolite having a Constraint Index of 2-12 (as defined in U.S. Pat. No. 4,016,218), Suitable medium pore molecular sieves can include, but are not limited to, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, and the like, and combinations thereof. ZSM-5 is described in detail in U.S. Pat. Nos. 3,702,886 and RE 29,948. ZSM-11 is described in detail in U.S. Pat. No. 3,709,979. ZSM-12 is described in U.S. Pat. No. 3,832,449. ZSM-22 is described in U.S. Pat. No. 4,556,477. ZSM-23 is described in U.S. Pat. No. 4,076,842. ZSM-35 is described in U.S. Pat. No, 4,016,245. ZSM-48 is more particularly described in U.S. Pat. No. 4,234,231.
- Additionally or alternately, the catalyst described herein can comprise one or more large pore zeolites having a Constraint Index less than 2. Suitable large pore molecular sieves can include, but are not limited to, zeolite beta, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, and the like, and combinations thereof. ZSM-14 is described in U.S. Pat. No. 3,923,636. ZSM-20 is described in U.S. Pat. No. 3,972,983. Zeolite beta is described in U.S. Pat. Nos. 3,308,069, and RE 28,341. Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Pat. Nos. 3,293,192 and 3,449,070. Deluminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Pat. No. 3,442,795. Zeolite UHP-Y is described in U.S. Pat. No. 4,401,556. Mordenite is a naturally occurring material but is also available in synthetic forms, such as TEA-mordenite (i.e., synthetically prepared from a reaction mixture comprising a tetraethylammonium directing agent), which is disclosed in U.S. Pat. Nos. 3,766,093 and 3,894,104.
- Further additionally or alternately, the catalyst described herein can comprise at least one molecular sieve of the MCM-22 family. As used herein, the term “molecular sieve of the MCM-22 family” (or “material of the MCM-22 family” or “MCM-22 family material” or “MCM-22 family zeolite”) includes one or more of:
-
- molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the MWW framework topology. (A unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the “Atlas of Zeolite Framework Types”, Fifth Edition, 2001, the entire contents of which are incorporated by reference herein);
- molecular sieves made from a common second degree building block, being a 2-dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
- molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness can be made from stacking, packing, or binding at least two monolayers of one unit cell thickness. The stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and
- molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
- Molecular sieves of the MCM-22 family can include those molecular sieves having an X-ray diffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms. The X-ray diffraction data used to characterize the material can be obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
- Materials of the MCM-22 family can additionally or alternately include, but are not limited to, MCM-22 (described in U.S. Pat. No. 4,954,325), PSF-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERR-1 (described in European Patent No. 0293032). ITQ-1 (described in U.S. Pat. No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/17290), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat. No. 5,362,697), UZM-8 (described in U.S. Pat. No. 6,756,030), and mixtures thereof.
- In certain preferred embodiments, the catalyst described herein can comprise or be ZSM-5. Additionally or alternately, the catalyst described herein can comprise or be a zeolite having a silica to alumina molar ratio from about 20 to about 200, for example from about 20 to about 150.
- In addition to the zeolite, the catalyst employed in the present process may contain a separate inorganic oxide binder that is substantially free of aluminum. By “substantially free” is meant the separate inorganic oxide binder should contain less than 5 wt % of aluminum, for example less than 3 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.3 wt %, less than 0.1 wt %, less than 0.05 wt %, or completely free of measurable aluminum. Examples of suitable inorganic oxide binders can include, but are not necessarily limited to, silica, titanic, zirconia, and the like, and mixtures thereof with each other and other metal oxides (again typically not including alumina). The inorganic oxide binder can be present in an amount from about 5 wt % to about 65 wt %, for example from about 10 wt % to about 35 wt %, of the total catalyst. Alternatively, the present zeolite catalyst may be formed into a shaped catalyst body without the aid of a separate binder, i.e., the catalyst may be self-bound. For more information on the production of silica-rich catalysts, reference is directed to U.S. Pat. No. 4,582 815, the entire contents of which are incorporated herein by reference.
- To produce the desired phosphorus-modified catalyst, as-synthesized crystals of the target zeolite can be formed into a slurry with a solvent, generally water, and, where applicable, a substantially aluminum-free inorganic oxide binder. The resultant slurry can then formed into a shaped catalyst body, generally by extrusion, and the catalyst body can then be treated with an aqueous solution of a phosphorus compound, such as a phosphorus oxyacid. Phosphorus treatment can conveniently be accomplished by impregnation. After phosphorus treatment, the treated catalyst body can be heated to remove the water and to convert the phosphorus compound to an oxide form. Heating can be conducted, advantageously in an oxidizing environment such as in air, at a temperature from about 350° C. to about 650° C. for an appropriate time, e.g., from about 0.2 hours to about 5.0 hours. Typically, the final catalyst can comprise from about 0.1 wt % to about 3 wt % of elemental phosphorus, present as an oxide of phosphorus.
- Generally, but not always, the as-synthesized zeolite crystals used to produce the desired catalyst can contain an organic directing agent used in the synthesis of the zeolite. Such directing agents can frequently block the pores of the zeolite and so should generally be removed before the zeolite is used catalytically. In this case, although the directing agent can be removed prior to formation of the shaped catalyst body, in some preferred embodiments, the directing agent can be removed by heating the shaped catalyst body in an oxidizing or non-oxidizing environment (e.g., in air) at a temperature from about 400° C. to about 820° C. for an appropriate time, e.g., from about 0.3 hours to about 3 hours. Typically, heating to remove the organic directing agent can be conducted before phosphorus treatment of the shaped catalyst body.
- In addition, many zeolite synthesis processes can be conducted under alkaline conditions in the presence of alkali metal ions, especially sodium ions. In this case, the as-synthesized zeolite crystals can often be in the sodium form and so should be converted to the catalytically active hydrogen form before use. Such conversion can typically be achieved by ion exchange with ammonium cations and heating to drive off the ammonia, thus leaving the H+ form of the zeolite. Again, although these steps can be conducted on the as-synthesized zeolite crystals before catalyst formation, in some preferred embodiments, ammonium exchange and subsequent conversion to the hydrogen form can be conducted on the shaped catalyst body. Typically, conversion of the zeolite to the hydrogen form can be conducted before phosphorus treatment of the shaped catalyst body, but after removal of the organic directing agent employed in the synthesis of the zeolite.
- The phosphorus-modified ZSM-5 catalyst produced by the present process can be particularly useful in any organic conversion process where the hydrothermal stability of the catalyst is important. Examples of such processes can include, but are not necessarily limited to, fluid catalytic cracking of heavy hydrocarbons to gasoline and diesel boiling range hydrocarbons, methylation and disproportionation of toluene to produce xylenes, n-paraffin (e.g., C6 and higher) cyclization, conversion of methanol to gasoline and diesel boiling range hydrocarbons, and the like, and combinations and/or integrations thereof.
- The invention can additionally or alternately include one or more of the following embodiments.
- EMBODIMENT 1. A process for producing a phosphorus-modified zeolite catalyst, said process comprising: (a) forming zeolite crystals into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder which is substantially free of aluminum; (b) converting the zeolite crystals to the hydrogen form; (c) removing any organic directing agent employed in the synthesis of the zeolite crystals; (d) treating the shaped catalyst body with an aqueous solution of a phosphorus compound; and (e) heating the treated catalyst body to remove the water and convert the phosphorus compound to an oxide form.
- EMBODIMENT 2. The process of embodiment 1, wherein the zeolite crystals are formed into a shaped catalyst body in the presence of a separate inorganic oxide hinder which contains less than 5 wt % of aluminum.
- EMBODIMENT 3. The process of any one of the previous embodiments, wherein the zeolite crystals are mixed with a silica binder prior to the forming (a).
- EMBODIMENT 4. The process of any one of the previous embodiments, wherein the forming (a) is accomplished by extrusion.
- EMBODIMENT 5. The process of any one of the previous embodiments, wherein the converting (b) is accomplished before the forming (a).
- EMBODIMENT 6. The process of embodiment 5, wherein the removing (c) is accomplished before the forming (a).
- EMBODIMENT 7. The process of any one of the previous embodiments, wherein the treating (d) is accomplished by impregnation, e.g., with an aqueous solution of a phosphorus oxyacid.
- EMBODIMENT 8. The process of any one of the previous embodiments, wherein the heating in (e) is conducted at a temperature from about 350° C. to about 650° C. for a time of about 0.2 hours to about 5.0 hours.
- EMBODIMENT 9. The process of any one of the previous embodiments, wherein the zeolite has a molar ratio of silica to alumina from about 20 to about 200, e.g., from about 20 to about 150.
- EMBODIMENT 10. The process of any one of the previous embodiments, wherein the zeolite comprises ZSM-5.
- EMBODIMENT 11. A phosphorus-modified zeolite catalyst produced by the process of any one of the previous embodiments,
- EMBODIMENT 12. A process for organic compound conversion employing contacting a feedstock with the phosphorus-modified zeolite catalyst of embodiment 11 under organic compound conversion conditions.
- EMBODIMENT 13. The process of embodiment 12, wherein said organic compound conversion comprises the conversion of methanol to hydrocarbons boiling in the gasoline boiling range.
- The invention will now be more particularly described with reference to the following non-limiting Examples and the accompanying drawings.
- In the Examples, the ZSM-5 crystal employed was an as-synthesized sodium form ZSM-5 having a silica to alumina molar ratio of about 50, produced using tetrapropylammonium bromide as a structure directing agent.
- In the Examples, alpha values are used to provide an indication of the catalytic cracking activity of a catalyst, compared to a standard catalyst, and to help assess the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). The alpha value is based on the activity of a silica-alumina cracking catalyst taken as an alpha of 1 (Rate Constant≈0.016 sec−1). The Alpha Test is described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis, 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), each incorporated herein by reference as to that description. The experimental conditions of the test used herein include ˜100 torr (˜13 kPa) hexane vapor pressure in He carrier gas flowing through a reactor held at ˜1000° F. (˜538° C.).
- Alumina (˜200 grams on solids basis) was first added to a mixer and dry Deionized water (˜100 grams) was then added to moisten the alumina, followed by addition of an amount of phosphoric acid (˜0, ˜61, ˜122, or ˜183.2 grams, respectively, on solids basis) to achieve targeted phosphorus levels. Na-ZSM-5 crystals (˜800 grams on solids basis) and additional deionized water were then added, and the mixtures were mulled for ˜10-30 minutes to achieve the desired consistency for extrusion, Mixtures with four different phosphorus levels (˜0, ˜1.7, ˜3.4, and ˜4.2 wt %, respectively) were thereby prepared. Each mixture was then extruded into ˜ 1/16″ cylinders. The extrudates were dried overnight (˜8-16 hours) at ˜250° F. (˜121° C.) and then precalcined in nitrogen for ˜3 hours at ˜1000° F. (˜538° C.). Each extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate. The resultant exchanged catalyst was dried overnight at ˜250° F. (˜121° C.) and then calcined in air for ˜3 hours at ˜1000° F. (˜538° C.).
- ZSM-5 (˜800 grams on solids basis) and Versal™ 300 alumina (˜200 grams on solids basis) were added to a mixer and dry mulled. While mulling, ˜492 grams of deionized water were added to achieve the desired consistency for extrusion. The mixture was then extruded into ˜ 1/16″ cylinders, The extrudates were dried overnight (˜8-16 hours) at ˜250° F. (˜121° C.) and then precalcined in nitrogen for ˜3 hours at ˜1000° F. (˜538° C.). The extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate. The exchanged catalyst was dried overnight at ˜250° F. (˜121° C.) and then calcined in air for ˜3 hours at ˜1000° F. (˜538° C.). The extrudate was then impregnated via incipient wetness with targeted levels of ˜2, ˜4, or ˜6 wt % phosphorus (actual levels as indicated in Table 1 below) using an aqueous solution of phosphoric acid. The impregnated crystal was then dried at ˜250° F. (˜121° C.) overnight and then calcined in air for ˜3 hours at ˜1000° F. (˜538° C.).
- ZSM-5 (˜800 grams on solids basis) and Ultrasil™ VN3SP silica (˜100 grams on solids basis) were added to a mixer and dry mulled. Ludox™-40 silica (˜100 grams) was then added to the mixture followed by the addition of ˜60 grams of ˜50 wt % caustic (NaOH) solution. While mulling, ˜85 grams of deionized water were added to achieve the desired consistency for extrusion. The mixture was then extruded into ˜ 1/16″ cylinders. The extrudates were dried overnight (˜8-16 hours) at ˜250° F. (˜121° C.) and then precalcined in nitrogen for ˜3 hours at ˜1000° F. (˜538° C.). The extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate. The exchanged catalyst was dried overnight at ˜250° F. (˜121° C.) and then calcined in air for ˜3 hours at ˜1000° F. (˜538° C.). The extrudate was then impregnated via incipient wetness with targeted levels of ˜2, ˜4, or ˜6 wt % phosphorus (actual levels as indicated in Table 1 below) using an aqueous solution of phosphoric acid. The impregnated crystal was then dried at ˜250° F. (˜121° C.) overnight and then calcined in air for ˜3 hours at ˜1000° F. (˜538° C.).
- ZSM-5 crystal (˜1,4 kg on solids basis) was added to a mixer and dry mulled. Approximately 190 grams of deionized water was then added during mulling. After about 10 minutes, ˜28 grams of ˜50 wt % caustic (NaOH) solution mixed with approximately 450 grams of water were added to the mixture and mulled for an additional ˜5 minutes. The mixture was then extruded into ˜ 1/10″ quadralobes. The extrudates were dried overnight (˜8-16 hours) at ˜250° F. (˜121° C.) and then precalcined in nitrogen for ˜3 hours at ˜1000° F. (˜538° C.). The extrudate was then exchanged twice with a 1N aqueous solution of ammonium nitrate. The exchanged catalyst was dried overnight at ˜250° F. (˜121° C.) and then calcined in air for ˜3 hours at ˜4000° F. (˜538° C.). The extrudate was then impregnated via incipient wetness with targeted levels of ˜2, ˜4, or ˜6 wt % phosphorus (actual levels as indicated in Table 1 below) using an aqueous solution of phosphoric acid. The impregnated crystal was then dried at ˜250° F. (˜121° C.) overnight and then calcined in air for ˜3 hours at ˜1000° F.
- The ZSM-5 containing extrudates of Examples 1-4 were analyzed for phosphorus content and steamed for ˜96 hours at ˜1000° F. (˜538° C.) and ˜14.7 psia steam partial pressure. The as-prepared and steamed catalysts were then screened for acidic activity with hexane cracking measurements in a routine Alpha test. The Alpha values and phosphorus levels of the extrudates from Examples 1-4 are shown in Table 1 below. The results show that the alumina-containing catalysts from Examples 1 and 2 have much lower alpha activity than the silica and self-bound catalysts from Examples 3 and 4 after steaming. Both silica and self-bound catalysts with approximately 0.8 wt % P retain ˜110 alpha value after steaming as compared to the same catalysts with no P that retain ˜14 and ˜11 alpha value after steaming.
-
TABLE 1 Phosphorus Alpha value Alpha value Catalyst wt % (as prepared) (as steamed) Example 1a 0.0 ~300 ~13 Example 1b ~1.7 ~270 ~5.3 Example 1c ~3.4 ~250 ~12 Example 1d ~4.2 ~240 ~19 Example 2a 0.0 ~320 ~13 Example 2b ~2.7 ~340 ~22 Example 2c ~4.2 ~210 ~38 Example 2d ~5.3 ~160 ~79 Example 3a 0.0 ~580 ~14 Example 3b ~0.8 ~240 ~110 Example 3c ~1.6 ~170 ~96 Example 3d ~2.4 ~99 ~26 Example 4a 0.0 ~540 ~11 Example 4b ~0.84 ~290 ~110 Example 4c ~1.67 ~160, ~210 ~85 Example 4d ~2.47 ~70 ~47, ~29 - While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
Claims (14)
1. A process for producing a phosphorus-modified zeolite catalyst, said process comprising:
(a) forming zeolite crystals into a shaped catalyst body either in the absence of a separate inorganic oxide binder or in the presence of a separate inorganic oxide binder which is substantially free of aluminum;
(b) converting the zeolite crystals to the hydrogen form;
(c) removing any organic directing agent employed in the synthesis of the zeolite crystals;
(d) treating the shaped catalyst body with an aqueous solution of a phosphorus compound; and
(e) heating the treated catalyst body to remove the water and convert the phosphorus compound to an oxide form.
2. The process of claim 1 , wherein the zeolite crystals are formed into a shaped catalyst body in the presence of a separate inorganic oxide binder which contains less than 5 wt % of aluminum.
3. The process of claim 1 , wherein the zeolite crystals are mixed with a silica binder prior to the forming (a).
4. The process of claim 1 , wherein the forming (a) is accomplished by extrusion.
5. The process of claim 1 , wherein the converting (b) is accomplished before the forming (a).
6. The process of claim 5 , wherein the removing (c) is accomplished before t forming (a).
7. The process of claim 1 , wherein the treating (d) is accomplished by impregnation with an aqueous solution of a phosphorus oxyacid.
8. The process of claim 1 , Wherein the heating in (e) is conducted at a temperature from about 350° C. to about 650° C. for a time of about 0.2 hours to about 5.0 hours.
9. The process of claim 1 , wherein the zeolite has a molar ratio of silica to alumina from about 20 to about 200.
10. The process of claim 1 , wherein the zeolite has a molar ratio of silica to alumina from about 20 to about 150.
11. The process of claim 1 , wherein the zeolite comprises ZSM-5.
12. A phosphorus-modified zeolite catalyst produced by the process of claim 11 .
13. A process for organic compound conversion employing contacting a feedstock with the phosphorus-modified zeolite catalyst of claim 12 under organic compound conversion conditions.
14. The process of claim 13 , wherein said organic compound conversion comprises the conversion of methanol to hydrocarbons boiling in the gasoline boiling range.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9783460B2 (en) | 2013-12-20 | 2017-10-10 | Exxonmobil Chemical Patents Inc. | Process for converting oxygenates to aromatic hydrocarbons |
US9895682B2 (en) | 2013-12-20 | 2018-02-20 | Exxonmobil Research And Engineering Company | Catalyst for selective conversion of oxygenates to aromatics |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015089256A1 (en) | 2013-12-13 | 2015-06-18 | Exxonmobil Research And Engineering Company | Enhanced methane formation in reforming catalysts |
CA2964307A1 (en) | 2014-12-22 | 2016-06-30 | Exxonmobil Research And Engineering Company | Conversion of oxygenates to aromatics |
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4197413A (en) * | 1978-12-14 | 1980-04-08 | Mobil Oil Corporation | Production of 3-methylphenol |
US4356338A (en) * | 1979-07-27 | 1982-10-26 | Mobil Oil Corporation | Extending catalyst life by treating with phosphorus and/or steam |
US4423266A (en) * | 1980-10-08 | 1983-12-27 | Mobil Oil Corporation | Extending isomerization catalyst life by treating with phosphorous and/or steam |
US4429176A (en) * | 1982-02-08 | 1984-01-31 | Mobil Oil Corporation | Active zeolite catalysts of improved stability |
US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
US5665325A (en) * | 1991-01-23 | 1997-09-09 | Exxon Chemical Patents Inc. | Process for producing substantially binder-free zeolite |
US6198013B1 (en) * | 1994-11-23 | 2001-03-06 | Exxon Chemical Patents Inc. | Toluene disproportionation process using a zeolite bound zeolite catalyst |
US6504072B1 (en) * | 1999-11-15 | 2003-01-07 | Exxonmobil Oil Corporation | Selective para-xylene production by toluene methylation |
US20030047487A1 (en) * | 1999-03-02 | 2003-03-13 | Ziebarth Michael S. | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
US7125818B2 (en) * | 2002-10-08 | 2006-10-24 | Exxonmobil Research & Engineering Co. | Catalyst for wax isomerate yield enhancement by oxygenate pretreatment |
US7285511B2 (en) * | 2004-04-23 | 2007-10-23 | Saudi Basic Industries Corporation | Method of modifying zeolite catalyst |
US20100113850A1 (en) * | 2008-11-03 | 2010-05-06 | Ashim Kumar Ghosh | Stable Shape-Selective Catalyst for Aromatic Alkylation and Methods of Using and Preparing |
US20110082025A1 (en) * | 2009-10-05 | 2011-04-07 | Ashim Kumar Ghosh | Phosphorus-Containing Zeolite Catalysts and Their Method of Preparation |
Family Cites Families (90)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6503410A (en) | 1963-02-21 | 1965-09-20 | ||
US3442795A (en) | 1963-02-27 | 1969-05-06 | Mobil Oil Corp | Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom |
US3308069A (en) | 1964-05-01 | 1967-03-07 | Mobil Oil Corp | Catalytic composition of a crystalline zeolite |
USRE28341E (en) | 1964-05-01 | 1975-02-18 | Marshall dann | |
US3354078A (en) | 1965-02-04 | 1967-11-21 | Mobil Oil Corp | Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide |
US3293192A (en) | 1965-08-23 | 1966-12-20 | Grace W R & Co | Zeolite z-14us and method of preparation thereof |
US3702886A (en) | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
US3709979A (en) * | 1970-04-23 | 1973-01-09 | Mobil Oil Corp | Crystalline zeolite zsm-11 |
US3832449A (en) | 1971-03-18 | 1974-08-27 | Mobil Oil Corp | Crystalline zeolite zsm{14 12 |
US3766093A (en) | 1972-01-07 | 1973-10-16 | Mobil Oil Corp | Treatment of organic cationcontaining zeolites |
US3894104A (en) | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Aromatization of hetero-atom substituted hydrocarbons |
US4016245A (en) | 1973-09-04 | 1977-04-05 | Mobil Oil Corporation | Crystalline zeolite and method of preparing same |
CA1040187A (en) | 1973-09-07 | 1978-10-10 | Mobil Oil Corporation | Method of preparing a crystalline aluminosilicate zeolite |
US3941871A (en) | 1973-11-02 | 1976-03-02 | Mobil Oil Corporation | Crystalline silicates and method of preparing the same |
US3923636A (en) | 1974-06-03 | 1975-12-02 | Texaco Inc | Production of lubricating oils |
US3972832A (en) | 1974-09-23 | 1976-08-03 | Mobil Oil Corporation | Phosphorus-containing zeolite catalyst |
NZ178543A (en) * | 1974-09-23 | 1978-04-03 | Mobil Oil Corp | Conversion catalyst, crystalline alumin osilicate zeolite containing phosphorus |
US3906054A (en) * | 1974-09-23 | 1975-09-16 | Mobil Oil Corp | Alkylation of olefins |
US3931349A (en) * | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
US4044065A (en) * | 1974-09-23 | 1977-08-23 | Mobile Oil Corporation | Conversion utilizing a phosphorus-containing zeolite catalyst |
US3972983A (en) | 1974-11-25 | 1976-08-03 | Mobil Oil Corporation | Crystalline zeolite ZSM-20 and method of preparing same |
US4016218A (en) | 1975-05-29 | 1977-04-05 | Mobil Oil Corporation | Alkylation in presence of thermally modified crystalline aluminosilicate catalyst |
CA1064890A (en) | 1975-06-10 | 1979-10-23 | Mae K. Rubin | Crystalline zeolite, synthesis and use thereof |
US4143084A (en) * | 1976-07-19 | 1979-03-06 | Mobil Oil Corporation | Di-alkylbenzene isomer mixtures |
PL199748A1 (en) * | 1976-07-19 | 1978-04-24 | Mobil Oil Corp | METHOD OF SELECTIVELY MANUFACTURING P-DUALKILOBENZENOW |
US4035430A (en) * | 1976-07-26 | 1977-07-12 | Mobil Oil Corporation | Conversion of methanol to gasoline product |
EP0007126A1 (en) * | 1978-07-06 | 1980-01-23 | Union Carbide Corporation | Cumene synthesis process |
US4234231A (en) | 1978-12-06 | 1980-11-18 | Mobil Oil Corporation | Method for restoring a leached formation |
US4401556A (en) | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
US4400571A (en) * | 1981-04-27 | 1983-08-23 | Uop Inc. | Hydrocarbon isomerization process |
DE3117135A1 (en) | 1981-04-30 | 1982-11-18 | Bayer Ag, 5090 Leverkusen | CRYSTALLINE ALUMOSILICATE, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR CATALYTICALLY CONVERTING METHANOL AND / OR DIMETHYL ETHER IN HYDROCARBONS |
US4409132A (en) * | 1982-03-18 | 1983-10-11 | Mobil Oil Corporation | Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion |
US4404414A (en) * | 1982-09-28 | 1983-09-13 | Mobil Oil Corporation | Conversion of methanol to gasoline |
EP0111748B1 (en) * | 1982-11-16 | 1987-03-25 | Hoechst Aktiengesellschaft | Aluminium silicates with a zeolite structure and process for their preparation |
DK149326C (en) | 1984-01-10 | 1986-09-15 | Haldor Topsoe As | PROCEDURE FOR THE PREPARATION OF CATALYSTS FOR ETHERSYNTHESIS |
US4556477A (en) | 1984-03-07 | 1985-12-03 | Mobil Oil Corporation | Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks |
JPS6115848A (en) * | 1984-06-30 | 1986-01-23 | Agency Of Ind Science & Technol | Production of lower olefin using zeolite catalyst modified with calcium phosphate |
US4582815A (en) * | 1984-07-06 | 1986-04-15 | Mobil Oil Corporation | Extrusion of silica-rich solids |
US4560542A (en) * | 1984-12-06 | 1985-12-24 | Exxon Research And Engineering Co. | Method for the preparation of zeolites using a low water low alkali metal content gel |
US4665249A (en) * | 1984-12-19 | 1987-05-12 | Mobil Oil Corporation | Method for feeding an MTG conversion reactor |
US4590321A (en) * | 1985-06-12 | 1986-05-20 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
US4665251A (en) | 1985-06-12 | 1987-05-12 | Mobil Oil Corporation | Aromatization reactions with zeolites containing phosphorus oxide |
US4826667A (en) | 1986-01-29 | 1989-05-02 | Chevron Research Company | Zeolite SSZ-25 |
US4954325A (en) | 1986-07-29 | 1990-09-04 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis and use |
IT1205681B (en) | 1987-05-26 | 1989-03-31 | Eniricerche Spa | SYNTHETIC POROUS CRYSTALLINE MATERIAL CONTAINING SILICON AND BORON OXIDES |
US5250277A (en) | 1991-01-11 | 1993-10-05 | Mobil Oil Corp. | Crystalline oxide material |
AU652222B2 (en) * | 1991-03-12 | 1994-08-18 | Mobil Oil Corporation | Preparation of cracking catalysts, and cracking process using them |
US5110776A (en) * | 1991-03-12 | 1992-05-05 | Mobil Oil Corp. | Cracking catalysts containing phosphate treated zeolites, and method of preparing the same |
JPH04371231A (en) * | 1991-06-18 | 1992-12-24 | N E Chemcat Corp | Catalyst for purification of exhaust gas |
US5236575A (en) | 1991-06-19 | 1993-08-17 | Mobil Oil Corp. | Synthetic porous crystalline mcm-49, its synthesis and use |
EP0568913A3 (en) * | 1992-05-03 | 1995-03-22 | Dalian Chemical Physics Inst | Process for the conversion of methanol to light olefins and catalyst used for such process. |
CN1039392C (en) * | 1992-09-22 | 1998-08-05 | 中国科学院大连化学物理研究所 | Catalyst for converting methanol into light olefines and its reaction process |
US5427753A (en) * | 1992-12-24 | 1995-06-27 | Tosoh Corporation | Process for removing nitrogen oxides from oxygen rich exhaust gas |
JPH06238131A (en) * | 1992-12-24 | 1994-08-30 | Tosoh Corp | Removing method for nitrogen oxide |
US5362697A (en) | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
US5457078A (en) | 1993-11-29 | 1995-10-10 | Mobil Oil Corporation | Manufacture of improved zeolite Beta catalyst |
CN1049406C (en) * | 1995-10-06 | 2000-02-16 | 中国石油化工总公司 | Phosphorus and RE containing molecular sieve with MFI structure |
ES2124154B1 (en) | 1995-11-08 | 1999-12-01 | Univ Politecnica De Valencia C | PREPARATION METHOD AND CATALYTIC PROPERTIES OF A MICROPOROUS SOLID WITH HIGH EXTERNAL SURFACE. |
ES2105982B1 (en) | 1995-11-23 | 1998-07-01 | Consejo Superior Investigacion | ZEOLITE ITQ-1 |
KR0165014B1 (en) * | 1996-03-11 | 1999-01-15 | 선우현범 | Fiber zeolite zsm-5 and its manufacturing method |
US6417421B1 (en) | 1998-03-03 | 2002-07-09 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and process therefor and therewith |
US6187983B1 (en) * | 1998-04-29 | 2001-02-13 | Exxon Chemical Patents Inc | Converting oxygenates to olefins in the presence of electromagnetic energy |
US6835863B2 (en) * | 1999-07-12 | 2004-12-28 | Exxonmobil Oil Corporation | Catalytic production of light olefins from naphtha feed |
EP1116519A1 (en) | 2000-01-12 | 2001-07-18 | Akzo Nobel N.V. | Solid-state phosphorous activation of crystalline porous silicates |
US6756030B1 (en) | 2003-03-21 | 2004-06-29 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-8 |
US7060864B2 (en) | 2003-09-30 | 2006-06-13 | Saudi Basic Industries Corporation | Toluene methylation process |
CN1257769C (en) | 2003-10-31 | 2006-05-31 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphor and metal component and its use |
US7399727B2 (en) | 2004-04-23 | 2008-07-15 | Saudi Basic Industries Corporation | Zeolite catalyst and method |
US7375048B2 (en) * | 2004-04-29 | 2008-05-20 | Basf Catalysts Llc | ZSM-5 additive |
KR100632563B1 (en) * | 2004-09-10 | 2006-10-09 | 에스케이 주식회사 | Solid acid catalyst for catalytic cracking and process for selectively preparing light olefins from full range naphtha |
US7304194B2 (en) | 2005-05-05 | 2007-12-04 | Saudi Basic Industries Corporation | Hydrothermal treatment of phosphorus-modified zeolite catalysts |
US7368410B2 (en) * | 2005-08-03 | 2008-05-06 | Saudi Basic Industries Corporation | Zeolite catalyst and method of preparing and use of zeolite catalyst |
CN100391610C (en) * | 2005-08-15 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
BRPI0505365A (en) | 2005-12-01 | 2007-09-25 | Petroleo Brasileiro Sa | process of obtaining more resistant zeolites to hydrothermal deactivation |
US7662737B2 (en) | 2005-12-22 | 2010-02-16 | Saudi Basic Industries Corporation | Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof |
CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
CN1915821A (en) * | 2006-09-06 | 2007-02-21 | 北京盛大京泰化学研究所 | Method for preparing phosphor modified ZSM-5 sieve |
EP2025402A1 (en) | 2007-07-31 | 2009-02-18 | Total Petrochemicals Research Feluy | Phosphorus modified molecular sieves, their use in conversion of organics to olefins |
US7563740B2 (en) * | 2006-12-19 | 2009-07-21 | Lyondell Chemical Technology, L.P. | Direct epoxidation process |
EP2036873A1 (en) * | 2007-09-12 | 2009-03-18 | Total Petrochemicals Research Feluy | Use of phosphorus modified molecular sieves in conversion of organics to olefins |
TW200918486A (en) | 2007-09-18 | 2009-05-01 | Asahi Kasei Chemicals Corp | Process for production of propylene |
JP5355910B2 (en) * | 2008-03-13 | 2013-11-27 | 旭化成ケミカルズ株式会社 | Silica molded body |
EP2082801A1 (en) | 2008-01-25 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for obtaining modified molecular sieves |
CN101723775B (en) * | 2008-11-04 | 2013-05-22 | 杭州林达化工技术工程有限公司 | Method and equipment for preparing hydrocarbon by methyl alcohol or/ and dimethyl ether |
CN101492349B (en) * | 2009-03-13 | 2011-11-09 | 清华大学 | Production process for energy-saving environment-friendly methanol dehydration joint production of combustion extractive dimethyl ether |
CN102438750A (en) | 2009-05-19 | 2012-05-02 | 国际壳牌研究有限公司 | Process for the manufacture of a formulated oxygenate conversion catalyst, formulated oxygenate conversion catalyst and process for the preparation of an olefinic product |
CN102049293B (en) | 2009-10-27 | 2012-11-14 | 中国石油化工股份有限公司 | ZSM-5/AlPO4-5 dual-structure molecular sieve as well as catalyst and method for preparing gasoline from methanol |
US8906224B2 (en) * | 2009-12-23 | 2014-12-09 | Exxonmobil Research And Engineering Company | Sweet or sour service catalytic dewaxing in block mode configuration |
TWI473651B (en) * | 2010-11-25 | 2015-02-21 | Asahi Kasei Chemicals Corp | Silica shaped body, method for producing the same, and production method of propylene using |
JP2012139640A (en) * | 2010-12-28 | 2012-07-26 | Jx Nippon Oil & Energy Corp | Catalyst for producing monocyclic aromatic hydrocarbon and method of producing the monocyclic aromatic hydrocarbon |
-
2012
- 2012-10-16 SG SG11201401258PA patent/SG11201401258PA/en unknown
- 2012-10-16 US US13/652,631 patent/US9821299B2/en active Active
- 2012-10-16 WO PCT/US2012/060372 patent/WO2013059164A2/en active Application Filing
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- 2012-10-16 EP EP12780368.2A patent/EP2768609A1/en not_active Withdrawn
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- 2012-10-16 CN CN201280061246.9A patent/CN103987457A/en active Pending
- 2012-10-16 CN CN201280051056.9A patent/CN103889574A/en active Pending
- 2012-10-16 CN CN201280062144.9A patent/CN103987454A/en active Pending
- 2012-10-16 CA CA2852667A patent/CA2852667A1/en not_active Abandoned
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- 2012-10-16 CA CA2852669A patent/CA2852669C/en not_active Expired - Fee Related
- 2012-10-16 US US13/652,681 patent/US20130102824A1/en not_active Abandoned
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- 2012-10-16 WO PCT/US2012/060367 patent/WO2013059161A1/en active Application Filing
- 2012-10-16 WO PCT/US2012/060369 patent/WO2013059162A1/en active Application Filing
- 2012-10-16 CN CN201280051031.9A patent/CN103945939A/en active Pending
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- 2012-10-16 SG SG11201401253XA patent/SG11201401253XA/en unknown
-
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- 2014-05-16 ZA ZA2014/03600A patent/ZA201403600B/en unknown
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4197413A (en) * | 1978-12-14 | 1980-04-08 | Mobil Oil Corporation | Production of 3-methylphenol |
US4356338A (en) * | 1979-07-27 | 1982-10-26 | Mobil Oil Corporation | Extending catalyst life by treating with phosphorus and/or steam |
US4423266A (en) * | 1980-10-08 | 1983-12-27 | Mobil Oil Corporation | Extending isomerization catalyst life by treating with phosphorous and/or steam |
US4429176A (en) * | 1982-02-08 | 1984-01-31 | Mobil Oil Corporation | Active zeolite catalysts of improved stability |
US5665325A (en) * | 1991-01-23 | 1997-09-09 | Exxon Chemical Patents Inc. | Process for producing substantially binder-free zeolite |
US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
US6198013B1 (en) * | 1994-11-23 | 2001-03-06 | Exxon Chemical Patents Inc. | Toluene disproportionation process using a zeolite bound zeolite catalyst |
US20030047487A1 (en) * | 1999-03-02 | 2003-03-13 | Ziebarth Michael S. | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
US6504072B1 (en) * | 1999-11-15 | 2003-01-07 | Exxonmobil Oil Corporation | Selective para-xylene production by toluene methylation |
US7125818B2 (en) * | 2002-10-08 | 2006-10-24 | Exxonmobil Research & Engineering Co. | Catalyst for wax isomerate yield enhancement by oxygenate pretreatment |
US7285511B2 (en) * | 2004-04-23 | 2007-10-23 | Saudi Basic Industries Corporation | Method of modifying zeolite catalyst |
US20100113850A1 (en) * | 2008-11-03 | 2010-05-06 | Ashim Kumar Ghosh | Stable Shape-Selective Catalyst for Aromatic Alkylation and Methods of Using and Preparing |
US20110082025A1 (en) * | 2009-10-05 | 2011-04-07 | Ashim Kumar Ghosh | Phosphorus-Containing Zeolite Catalysts and Their Method of Preparation |
Cited By (6)
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---|---|---|---|---|
US9783460B2 (en) | 2013-12-20 | 2017-10-10 | Exxonmobil Chemical Patents Inc. | Process for converting oxygenates to aromatic hydrocarbons |
US9790139B2 (en) | 2013-12-20 | 2017-10-17 | Exxonmobil Chemical Patents Inc. | Process for converting oxygenates to aromatic hydrocarbons |
US9895682B2 (en) | 2013-12-20 | 2018-02-20 | Exxonmobil Research And Engineering Company | Catalyst for selective conversion of oxygenates to aromatics |
US10099209B2 (en) | 2013-12-20 | 2018-10-16 | Exxonmobil Research And Engineering Company | Alumina bound catalyst for selective conversion of oxygenates to aromatics |
US10105690B2 (en) | 2013-12-20 | 2018-10-23 | Exxonmobil Research And Engineering Company | Bound catalyst for selective conversion of oxygenates to aromatics |
US10159963B2 (en) | 2013-12-20 | 2018-12-25 | Exxonmobil Research And Engineering Company | Catalyst for conversion of oxygenates to aromatics |
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