AU2001249363B2 - Metallo aluminophosphate molecular sieve with cubic crystal morphology and methanol to olefin process using the sieve - Google Patents
Metallo aluminophosphate molecular sieve with cubic crystal morphology and methanol to olefin process using the sieve Download PDFInfo
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- AU2001249363B2 AU2001249363B2 AU2001249363A AU2001249363A AU2001249363B2 AU 2001249363 B2 AU2001249363 B2 AU 2001249363B2 AU 2001249363 A AU2001249363 A AU 2001249363A AU 2001249363 A AU2001249363 A AU 2001249363A AU 2001249363 B2 AU2001249363 B2 AU 2001249363B2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 93
- 239000002808 molecular sieve Substances 0.000 title claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 30
- 239000013078 crystal Substances 0.000 title claims description 29
- 150000001336 alkenes Chemical class 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 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 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- 241000269350 Anura Species 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- -1 C 4 olefins Chemical class 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 101100501247 Caenorhabditis elegans elo-2 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101000916532 Rattus norvegicus Zinc finger and BTB domain-containing protein 38 Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940009859 aluminum phosphate Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
-
- 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
-
- 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
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
WO 02/076612 PCT/US01/09263 "METALLO ALUMINOPHOSPHATE MOLECULAR SIEVE WITH CUBIC CRYSTAL MORPHOLOGY AND METHANOL TO OLEFIN PROCESS USING THE SIEVE" BACKGROUND OF THE INVENTION The limited supply and increasing cost of crude oil has prompted the search for alternative processes for producing hydrocarbon products. One such process is the conversion of methanol to hydrocarbons and especially light olefins (by light olefins is meant C 2 to C 4 olefins). The interest in the methanol to olefin (MTO) process is based on the fact that methanol can be obtained from coal or natural gas by the production of synthesis gas which is then processed to produce methanol.
Processes for converting methanol to light olefins are well known in the art.
Initially aluminosilicates or zeolites were used as the catalysts necessary to carry out the conversion. For example, see US-A-4,238,631; US-A-4,328,384, US-A-4,423,274.
These patents further disclose the deposition of coke onto the zeolites in order to increase selectivity to light olefins and minimize the formation of Cs+ byproducts. The effect of the coke is to reduce the pore diameter of the zeolite.
The prior art also discloses that silico aluminophosphates (SAPOs) can be used to catalyze the methanol to olefin process. Thus, US-A-4,499,327 discloses that many of the SAPO family of molecular sieves can be used to convert methanol to olefins.
The '327 patent also discloses that preferred SAPOs are those that have pores large enough to adsorb xenon (kinetic diameter of 4.0 A) but small enough to exclude isobutane (kinetic diameter of 5.0 A particularly preferred SAPO is SAPO-34.
US-A-4,752,651 discloses the use of nonzeolitic molecular sieves (NZMS) including ELAPOs and MeAPO molecular sieves to catalyze the methanol to olefin reaction.
The effect of the particle size of the molecular sieve on activity has also been documented in US-A-5,126,308. In the '308 patent it is disclosed that molecular sieves in which 50% of the molecular sieve particles have a particle size less than 1.0 pm and no more than 10% of the particles have a particle size greater than 2.0 pm have increased activity and/or durability. The '308 patent also discloses that restricting the silicon content to about 0.005 to about 0.05 mole fraction also improves catalytic performance.
WO 02/076612 PCT/US01/09263 In contrast to this art, applicants have found that molecular sieves having the empirical formula (ELAlyPz)O 2 (hereinafter ELAPO) where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof and x, y and z are the mole fractions of EL, Al and P respectively and having a predominantly plate crystal morphology wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect ratio of less than or equal to 5. These molecular sieves produce a higher amount of ethylene versus propylene. This increased selectivity is a very desirable feature of a MTO catalyst. This morphology is obtained by controlling the metal (EL) content of the molecular sieve and lo the crystallization time during synthesis of the molecular sieve.
SUMMARY OF THE INVENTION As stated, this invention relates to an ELAPO containing catalyst and a process for converting methanol to light olefins using the catalyst. Accordingly, one embodiment of the invention is a process for converting methanol to light olefins comprising contacting the methanol with a catalyst at conversion conditions, the catalyst comprising a crystalline metal aluminophosphate molecular sieve having a chemical composition on an anhydrous basis expressed by an empirical formula of: (ELAlyPI)O 2 where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, is the mole fraction of EL and has a value of at least 0.005, is the mole fraction of Al and has a value of at least 0.01, is the mole fraction of P and has a value of at least 0.01 and x y z 1, the molecular sieve characterized in that it has predominantly a plate crystal morphology, wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect of less than or equal to Another embodiment of the invention is a catalyst for converting methanol to light olefins comprising a crystalline metallo aluminophosphate molecular sieve having an empirical chemical composition on an anhydrous basis expressed by the formula: (ELxAlyP,)O 2 where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, is the mole fraction WO 02/076612 PCT/US01/09263 of EL and has a value of at least 0.005, is the mole fraction of Al and has a value of at least 0.01, is the mole fraction of P and has a value of at least 0.01 and x y z 1, the molecular sieve characterized in that it has a crystal morphology wherein the average smallest crystal dimension is at least 0.1 micron.
These and other objects and embodiments of the invention will become more apparent after the detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION An essential feature of the process of the instant invention is an ELAPO molecular sieve. ELAPOs are molecular sieves which have a three-dimensional to microporous framework structure of A10 2 P0 2 and ELO 2 tetrahedral units. Generally the ELAPOs have the empirical formula (ELxAlyP,)O 2 where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, is the mole fraction of EL and has a value of at least 0.005, is the mole fraction of Al and has a value of at least 0.01, is the mole fraction of P and has a value of at least 0.01 and x y z 1. When EL is a mixture of metals, represents the total amount of the metal mixture present. Preferred metals (EL) are silicon, magnesium and cobalt with silicon being especially preferred.
The preparation of various ELAPOs are well known in the art and may be found in US-A-: 4,554,143 (FeAPO); 4,440,871 (SAPO); 4,853,197 (MAPO, MnAPO, ZnAPO, CoAPO); 4,793,984 (CAPO), 4,752,651 and 4,310,440. Generally, the ELAPO molecular sieves are synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of EL, aluminum, phosphorus and a templating agent. Reactive sources of EL are the metal salts such as the chloride and nitrate salts.
When EL is silicon a preferred source is fumed, colloidal or precipitated silica.
Preferred reactive sources of aluminum and phosphorus are pseudo-boehmite alumina and phosphoric acid. Preferred templating agents are amines and quaternary ammonium compounds. An especially preferred templating agent is tetraethylammonium hydroxide (TEAOH).
The reaction mixture is placed in a sealed pressure vessel, optionally lined with WO 02/076612 PCT/US01/09263 an inert plastic material such as polytetrafluoroethylene and heated preferably under autogenous pressure at a temperature between 500C and 2500C and preferably between 1000C and 2000C for a time sufficient to produce crystals of the ELAPO molecular sieve. Typically the time varies from 1 hour to 120 hours and preferably from 24 hours to 48 hours. The desired product is recovered by any convenient method such as centrifugation or filtration.
The ELAPO molecular sieves of this invention have predominantly a plate crystal morphology. By predominantly is meant greater than 50% of the crystals. Preferably at least 70% of the crystals have a plate morphology and most preferably at least 90% of the crystals have a plate morphology. Especially good selectivity (C2 versus C3=) is obtained when at least 95% of the crystals have a plate morphology By plate morphology is meant that the crystals have the appearance of rectangular slabs. More importantly, the aspect ratio is less than or equal to 5. The aspect ratio is defined as the ratio of the largest crystalline dimension divided by the smallest crystalline dimension. A preferred morphology which is encompassed within the definition of plate is cubic morphology. By cubic is meant not only crystals in which all the dimensions are the same, but also those in which the aspect ratio is less than or equal to 2. It is also necessary that the average smallest crystal dimension be at least 0.1 microns and preferably at lest 0.2 microns.
As is shown in the examples, the morphology of the crystals and the average smallest crystal dimension is determined by examining the ELAPO molecular sieve using Scanning Electron Microscopy (SEM) and measuring the crystals in order to obtain an average value for the smallest dimension.
Without wishing to be bound by any one particular theory, it appears that a minimum thickness is required so that the diffusion path for the desorption of ethylene and propylene is sufficiently long to allow differentiation of the two molecules. Since ethylene is a more valuable product, by controlling the crystal dimensions one can maximize the formation of ethylene. As will be shown in the examples, when the smallest dimension is less than 0.1, the ratio of ethylene to propylene (C2=/C3 is about 1.2, whereas when the smallest dimension is greater than 0.1 microns, the ratio of C2/C3 is 1.4. This provides a greater production of ethylene.
The ELAPOs which are synthesized using the process described above will usually contain some of the organic templating agent in its pores. In order for the WO 02/076612 PCT/US01/09263 ELAPOs to be active catalysts, the templating agent in the pores must be removed by heating the ELAPO powder in an oxygen containing atmosphere at a temperature of about 2000 to about 7000C until the template is removed, usually a few hours.
A preferred embodiment of the invention is one in which the metal (EL) content varies from 0.005 to 0.05 mole fraction. If EL is more than one metal then the total concentration of all the metals is between 0.005 and 0.05 mole fraction. An especially preferred embodiment is one in which EL is silicon (usually referred to as SAPO). The SAPOs which can be used in the instant invention are any of those described in U.S.
Patent 4,440,871. Of the specific crystallographic structures described in the '871 patent, the SAPO-34, structure type 34, is preferred. The SAPO-34 structure is characterized in that it adsorbs zenon but does not adsorb isobutane, indicating that it has a pore opening of about 4.2 A.
The ELAPO molecular sieve of this invention may be used alone or they may be mixed with a binder and formed into shapes such as extrudates, pills, spheres, etc. Any inorganic oxide well known in the art may be used as a binder. Examples of the binders which can be used include alumina, silica, aluminum-phosphate, silica-alumina, etc.
When a binder is used, the amount of ELAPO which is contained in the final product ranges from 10 to 90 weight percent and preferably from 30 to 70 weight percent.
The conversion of methanol to light olefins is effected by contacting the methanol with the ELAPO catalyst at conversion conditions, thereby forming the desired light olefins. The methanol can be in the liquid or vapor phase with the vapor phase being preferred. Contacting the methanol with the ELAPO catalyst can be done in a continuous mode or a batch mode with a continuous mode being preferred. The amount of time that the methanol is in contact with the ELAPO catalyst must be sufficient to convert the methanol to the desired light olefin products. When the process is carried out in a batch process, the contact time varies from about 0.001 hr. to about 1 hr. and preferably from about 0.01 hr. to about 1.0 hr. The longer contact times are used at lower temperatures while shorter times are used at higher temperatures.
Further, when the process is carried out in a continuous mode, the Weight Hourly Space Velocity (WHSV) based on methanol can vary from about 1 hr 1 to about 1000 hr 1 and preferably from about 1 hr 1 to about 100 hr'.
Generally, the process must be carried out at elevated temperatures in order to form light olefins at a fast enough rate. Thus, the process should be carried out at a WO 02/076612 PCT/US01/09263 temperature of 3000°C to 600°C, preferably from 400°C to 550°C and most preferably from 450°C to 525°C. The process may be carried out over a wide range of pressure including autogenous pressure. Thus, the pressure can vary from about 0 kPa to 1724 kPa and preferably from 34 kPa to 345 kPa.
Optionally, the methanol feedstock may be diluted with an inert diluent in order to more efficiently convert the methanol to olefins. Examples of the diluents which may be used are helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, methane, aromatic hydrocarbons, benzene, toluene and mixtures thereof. The amount of diluent used can vary considerably and is usually io from 5 to 90 mole percent of the feedstock and preferably from 25 to 75 mole percent.
The actual configuration of the reaction zone may be any well known catalyst reaction apparatus known in the art. Thus, a single reaction zone or a number of zones arranged in series or parallel may be used. In such reaction zones the methanol feedstock is flowed through a bed containing the ELAPO catalyst. When multiple reaction zones are used, one or more ELAPO catalyst may be used in series to produce the desired product mixture. Instead of a fixed bed, a dynamic bed system, fluidized or moving, may be used. Such a dynamic system would facilitate any regeneration of the ELAPO catalyst that may be required. If regeneration is required, the ELAPO catalyst can be continuously introduced as a moving bed to a regeneration zone where it can be regenerated by means such as oxidation in an oxygen containing atmosphere to remove carbonaceous materials.
The following examples are presented in illustration of this invention and are not intended as undue limitations on the generally broad scope of the invention as set out in the appended claims EXAMPLE 1 A series of molecular sieves (SAPOs) were prepared by the following procedure.
In a container orthophosphoric acid was combined with water. To this there was added a silica sol and a 35 wt.% aqueous solution of tetraethylammonium hydroxide (TEAOH). Finally, alumina in the form of pseudo-boehmite along with water and SAPO-34 seed material were added and blended in. The resulting mixtures had compositions in molar oxide ratios as set forth in Table 1 below.
WO 02/076612 PCT/US01/09263 TABLE 1 Reaction Mixture Compositions For SAPOs Reaction Sample Time TEAOH SiOz A1 2 0 3
P
2 0 5
H
2 0
I.D.
A 48 1.0 0.10 1.0 1.0 B 48 1.0 0.10 1.0 1.0 C 48 1.0 0.10 1.0 1.0 D 24 1.0 0.10 1.0 1.0 E 36 1.0 0.15 1.0 1.0 F 48 1.0 0.20 1.0 1.0 The mixture was now placed in a steel pressure reactor equipped with a turbine stirrer.
The mixture was now stirred and heated to 100°C over a 6 hour period, held at 100°C for 6 hours, then heated to 175°C over a period of 3 hours and held there for the reaction time of 24, 36 or 48 hours. Finally, the reaction mixture was cooled to ambient temperature and the solid product recovered by centrifugation and washed with water.
All the products were analyzed and found to be SAPO-34 molecular sieves.
EXAMPLE 2 The catalysts prepared in Example 1 were evaluated for the conversion of to methanol to light olefins in a fixed bed pilot plant. A 4 gram sample in the form of 20-40 mesh agglomerates was used for the testing. Before testing, each sample was calcined in air in a muffle oven at 650°C for 2 hours and then pre-treated in situ by heating to 400°C for 1 hour under nitrogen. The pretreated sample was now contacted with a feed consisting of methanol and H 2 0 in a 1/0.44 molar ratio at 435°C, 5 psig and 2.5 hr 1 MeOH WHSV. The composition of the effluent was measured by an on-line GC after minutes on stream to determine initial conversion and selectivities. Complete conversion was obtained initially with all catalysts but it fell with time on stream as the catalysts deactivated. Table 2 presents the selectivity to ethylene and propylene and the ethylene/propylene product ratio at the point where conversion was 99% for each catalyst.
TAB8LE 2 Efect of Crytal Dimension on Ethvlene/Proovlene Production Average Smallest 2C7 Catalyst Dimension (Microns) Crystal Morphology Selectivity 0,7/C?7 A 0.07 Thin plates 82.4 1.17 B 0.08 Plates 79.2 1.18 C 0.09 Thin Plates 82.2 1.25 D 0.13 Plates 80.8 1.40 E 0.17 Plates 81.2 1.41 F 0.58 Cubic 78.7 1.48 The average smallest crystallite dimension was determined by measuring representative crystallites in one or more micrographs obtained using a Scanning s Electron Microscope at 30,000x magnification. The data indicate that when the smallest crystal dimension is greater than 0.1 mnicron and the crystal morphology is plates, a greater amount of ethylene is produced. It is also observed that when the crystal morphology is cubic and the smallest dimension is greater than 0.2 microns, one obtains the highest production of ethylene. Note that when the smallest dimension is less than 0.1, one obtains poor results (greater propylene production) even though the crystal morphology is plates.
Where the terms oomnpuise", "compuises", ffcompiised" or "comprisingu are Used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.
Claims (8)
1. A catalyst for converting methanol to light olefins comprising a crystalline metallo aluminophosphate molecular sieve having an empirical chemical composition on an anhydrous basis expressed by the formula: (ELAlyPz)O 2 where EL is a metal selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and mixtures thereof, is the mole fraction of EL and has a value of at least 0.005, is the mole fraction of Al and has a value of at least 0.01, is the mole fraction of P and has a value of at least 0.01 and x y z 1, the molecular sieve characterized in that it has predominantly a plate crystal morphology, wherein the average smallest crystal dimension is at least 0.1 micron and has an aspect ratio no greater than
2. The catalyst of Claim 1 where the EL metal is selected from the group consisting of silicon, magnesium, cobalt and mixtures thereof.
3. The catalyst of Claim 2 where the EL metal is silicon and the molecular sieve has the crystal structure of SAPO-34.
4. The catalyst of any one of claims 1 to 3 where catalyst comprises a metal aluminophosphate molecular sieve and an inorganic oxide binder selected from the group consisting of alumina, silica, aluminum phosphate, silica- alumina and mixtures thereof. The catalyst of any one of claims 1 to 4 where the molecular sieve is present in an amount from about 10 to about 90 weight percent of the catalyst.
6. The catalyst of any one of claims 1 to 5 where the aluminophosphate has a metal (EL) content from about 0.005 to about 0.05 mole fraction.
7. A process for converting methanol to light olefin comprising contacting the methanol with the catalyst of any one of claims 1 to 6 at conversion conditions. 14/07 2006 FRI 17:20 FAX 613 98516004 HOULIHAN 2 MELB AUST iii Patent Office 2006/015 Va 0 S8. The process of claim 7 where the conversion conditions are a temperature of about 300 0 C to about 600 0 C, a pressure of about 0 kPa to about 17224 kPa Z and a weight hourly space velocity of about 1 to about 1Ohr 1
9. A catalyst for converting methanol to light olefins according to anyone of Sclaims 1 to 6 substantially as hereinbefore described with reference to the N accompanying Examples. C 10. A process according to claim 7 or claim 8, substantially as hereinbefore S 10 described with reference to the accompanying Examples. 0
11. Use of the process of claim 7 or claim 8, substantially as hereinbefore described. DATED this 13th day of July, 2006 UOP LLC By their Patent Attorneys: Houlihan 2 COMS ID No: SBMI-04170789 Received by IP Australia: Time 17:18 Date 2006-07-14
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US7009086B2 (en) | 2002-10-29 | 2006-03-07 | Exxonmobil Chemical Patents Inc. | Use of molecular sieves for the conversion of oxygenates to olefins |
US7547812B2 (en) | 2005-06-30 | 2009-06-16 | Uop Llc | Enhancement of molecular sieve performance |
KR100991012B1 (en) | 2008-07-14 | 2010-10-29 | 한국화학연구원 | Catalyst for synthesizing filamentous carbons at low temperature and preparation methods thereof |
KR100996976B1 (en) | 2008-08-27 | 2010-11-29 | 현대엔지니어링 주식회사 | Long-time catalyst for ??? reaction and Preparing method thereof |
CN105585022B (en) * | 2014-10-20 | 2017-12-05 | 中国科学院大连化学物理研究所 | A kind of synthetic method of the molecular sieves of flake nano SAPO 34 |
CN106315616B (en) * | 2015-07-10 | 2018-08-14 | 中国石油天然气股份有限公司 | Method for synthesizing sheet SAPO-34 molecular sieve |
RU2694829C2 (en) * | 2016-09-06 | 2019-07-17 | Общество с ограниченной ответственностью ОКСО | Method for catalytic oxidation of n-hexane |
WO2019089206A1 (en) * | 2017-10-30 | 2019-05-09 | Dow Global Technologies Llc | Hybrid catalyst for selective and stable olefin production |
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WO2002076612A1 (en) | 2002-10-03 |
KR100793508B1 (en) | 2008-01-14 |
CA2442399A1 (en) | 2002-10-03 |
EA200301043A1 (en) | 2004-04-29 |
NO20034173L (en) | 2003-09-19 |
BR0116944A (en) | 2004-03-09 |
KR20040011481A (en) | 2004-02-05 |
EA004900B1 (en) | 2004-08-26 |
MXPA03008541A (en) | 2003-12-08 |
BR0116944B1 (en) | 2011-11-16 |
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