CN106607089A - Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application - Google Patents
Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application Download PDFInfo
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- CN106607089A CN106607089A CN201510686404.5A CN201510686404A CN106607089A CN 106607089 A CN106607089 A CN 106607089A CN 201510686404 A CN201510686404 A CN 201510686404A CN 106607089 A CN106607089 A CN 106607089A
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- methanol
- petroleum
- catalyst
- coupling
- cracking
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 230000008878 coupling Effects 0.000 title claims abstract description 24
- 238000010168 coupling process Methods 0.000 title claims abstract description 24
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000007233 catalytic pyrolysis Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005977 Ethylene Substances 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 239000003208 petroleum Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000005336 cracking Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000003209 petroleum derivative Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- -1 ethylene, propylene Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 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
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
- B01J29/48—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 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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)
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
-
- 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
Abstract
The invention relates to a catalyst for coupling catalytic pyrolysis of methanol and naphtha, a preparation method and an application, to mainly solve the technical problem that the ethylene and propylene yield is low in a method for catalytic pyrolysis of methanol and naphtha to prepare ethylene and propylene in the prior art. The technical scheme that methanol and naphtha are adopted and contact a fluidized bed catalyst to prepare a material fluid containing ethylene and propylene in a situation of certain temperature, pressure, the weight ratio of methanol to naphtha, and the weight space velocity of methanol to naphtha. The fluidized bed catalyst contains a ZSM-5 composite molecular sieve modified by SAPO-34 and oxide of P, La or Mn is adopted, so that the problem above is well solved. The catalyst can be used for industrial production of ethylene and propylene prepared through catalytic pyrolysis of methanol and naphtha.
Description
Technical field
The present invention relates to a kind of methanol and Petroleum coupling and catalyzing cracking ethylene preparation and the method for propylene, specifically
ZSM-5 or ZSM-11 are adopted with SAPO-34 composite molecular screen urging for catalyst activity component with regard to a kind of
Change producing ethylene by cracking cyclopropene method.
Background technology
Ethylene and propylene are most important two kinds of basic organic chemical industry raw materials.At present, global ethylene is main with propylene
It is to be produced by steam-cracking process.Steam-cracking process has reaction temperature height (820～1000 DEG C), process energy
Consumption is high, and ethylene is low with productivity of propylene and ethylene/propene is than series of malpractice such as relatively low (0.5～0.7).Catalysis
Cracking is the process for carrying out producing low-carbon olefins by cracking using catalyst to Petroleum.Compared with steam cracking, urge
Change cracking with reaction temperature low (600-780 DEG C), energy consumption is significantly reduced and product propylene/ethylene ratio
The advantage of high (0.6～1.3).This technology occurs, and is the leather that traditional steam cracking produces ethylene, propylene process
Hope is brought newly.
From the point of view of current document report, the reaction temperature of light naphthar catalytic pyrolysiss at 630～700 DEG C or so, together
When need to introduce a certain amount of water vapour, play a part of dilution, carbon distribution suppress.The activearm of used catalyst
Divide the molecular sieve of predominantly sial class.Catalytic pyrolysiss are a strong endothermic reactions, therefore, catalytic pyrolysis process
Realize needing outside heat supply.To alleviate the dependence rate to oil.Methanol oxidation cracks alkene processed by-product simultaneously
56.3% water, therefore consider methanol is introduced in light naphthar catalytic pyrolysiss to be coupled, reacted by methanol
Necessary " water vapour " and heat are provided for light naphthar catalytic pyrolysiss, but also expands ethylene, production of propylene
Raw material sources, it should with preferable prospects for commercial application.
Chinese patent 102531821A provides one kind and adopts phosphorus or lanthanum-oxides ZSM-5 Type Zeolites
Agent, by methanol and Petroleum catalysis methanol coupling naphtha catalytic cracking reaction, with produce low-carbon alkene and/or
The method of aromatic hydrocarbons.The ZSM-5 Type Zeolites agent includes 25-80wt%'s by weight percentage
The binding agent of ZSM-5 molecular sieve, 15-70wt%, and the 2.2-6.0wt% being loaded on the ZSM-5 molecular sieve
Lanthanum and 1.0-2.8wt% phosphorus.
Chinese patent 102276391A report by adopt it is a kind of include methanol conversion, regenerator,
Petroleum conversion reactor, auxiliary sedimentation stripper, gas-solid cyclone separator, the reaction of catalyst recycle line
Device, by two kinds of technique organic coupling catalytic production low-carbon (LC) alkene of methanol-to-olefins and producing olefin hydrocarbon by catalytic pyrolysis of naphtha
Hydrocarbon.
The method that CN1504542 provides a kind of petroleum hydrocarbon catalytic pyrolysiss preparing low-carbon olefins of coupling, with stone
Petroleum hydrocarbon class is raw material with organic oxygen-containing compound, using fluidized-bed reactor, in solid acid catalyst and high-temperature water
In the presence of steam, by the catalytic pyrolysis process preparing low-carbon olefins for coupling.The sial of Si-Al molecular sieve used
Than for 25～100.Reaction condition is：Temperature 500-720 DEG C, the weight of catalyst and petroleum hydrocarbon is than 5-40: 1,
The weight of organic oxygen-containing compound and petroleum hydrocarbon is than 0-2: 1, the weight of vapor and petroleum hydrocarbon is than 0-1: 1.
Petroleum hydrocarbon include low-carbon (LC) class hydro carbons, the gasoline of different boiling ranges, diesel oil, vacuum gas oil (VGO), crude oil or residual oil and
Its mixture, is especially suitable for various heavy hydrocarbons.
CN101381271 be related to it is a kind of with methanol and carbon four and above alkene as raw material copyrolysis prepare ethylene and
The method of propylene.Its method is by the first material benzenemethanol, dimethyl ether and second material carbon four and above alkene
Hydrocarbon, adds same conversion zone, the method for carrying out being cracked to form ethylene and propylene under catalyst for cracking effect.
Methanol is currently used for the Petroleum method that catalytic pyrolysiss produce ethylene and propylene altogether, wherein used catalyst
Mainly based on the molecular sieve of sial class.The molecular sieve of sial class compared with the molecular sieve SAPO-34 of non-sial,
It is acid relatively strong, and aperture is also big, thus cause ethylene in common catalytic pyrolysiss product and propylene product concentration compared with
It is low, and ethylene is relatively low with the selectivity of propylene, which limits the futurity industry application prospect of the technology.
The content of the invention
To be solved by this invention is catalytic pyrolysis preparing ethylene and propylene process prepared by prior art, there is ethylene
The low technical problem of+propene yield.One of unresolved technical problem, the present invention provide a kind of by adopting
SAPO-34 and the fluid catalyst that ZSM-5 or ZSM-11 molecular sieves composite molecular screen is active component,
The catalyst is applied in catalytic pyrolysis process, has the advantages that ethylene+propene yield is high.For solve problem it
Two, the present invention provides a kind of methanol corresponding with one of solve problem and Petroleum coupling and catalyzing cracking and catalyzing
Agent.For the three of solve problem, the present invention provides a kind of corresponding methanol of two-phase and stone therewith one of with solve problem
The method of cerebrol coupling and catalyzing cracking.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of methanol and Petroleum
Coupling and catalyzing catalyst for cracking, comprising following components in terms of parts by weight：A) P, La or Mn of 0.5-20 parts
At least one of oxide oxide；B) 80～99.5 parts containing SAPO-34 and ZSM-5 or ZSM-11 point
The composite molecular screen microsphere of at least one composition in son sieve.
In above-mentioned technical proposal, it is preferred that composite molecular screen microsphere adopts in-situ synthesis；SAPO-34 point
Relative crystallinity of the son sieve in composite molecular screen microsphere is 5～30%；Silicon oxide/the oxygen of SAPO-34 molecular sieves
The mol ratio for changing aluminum is 0.01～0.6；The silicon oxide of ZSM-5 or ZSM-11 molecular sieves and the mol ratio of aluminium oxide
For 20～200；It it is 0.5～12 part selected from the consumption of P, La or Mn oxide；It is preferred that a) for P and La's
Hopcalite, in terms of the parts by weight of catalyst, 0.5～8 part of the consumption of the oxide of P, La's
0.2～7 part of consumption.
To solve the two of above-mentioned technical problem, the present invention provide a kind of methanol corresponding with one of solve problem and
The preparation method of Petroleum coupling and catalyzing catalyst for cracking, comprises the steps：
1) weigh the desired amount of solution selected from least one of P, La or Mn oxide oxide precursor
At least one molecular sieve of the dipping in ZSM-5 or ZSM-11 molecular sieves, ageing 2～24 is little at room temperature
When, 2-24 hours are dried at 100～140 DEG C, roasting 2-12 hours at 500～750 DEG C；
2) weigh the desired amount of SAPO-34 and previous step obtain modified molecular screen, Kaolin, selected from aluminium oxide
Mix homogeneously with least one and water in alumina material and be made into serosity Jing that solid content is 20～50% spraying
Prepared particle diameter is 10～200 μm of microsphere, and 900～1200 DEG C of Jing roastings 4 hours obtain the catalysis of fluid bed microsphere
Agent.
To solve the three of above-mentioned technical problem, the present invention provides a kind of methanol and cracks alkene processed with Petroleum coupling and catalyzing
The method of hydrocarbon, is 610～760 DEG C in reaction temperature, and the weight space velocity of light naphthar is 0.1～10h-1, reaction pressure
Power is 0～2.0MPa, and the weight ratio of water and light naphthar is 0～10 and Petroleum with the weight ratio of methanol is
Under 0.1～10 reaction condition, methanol, Petroleum and above-mentioned methanol and Petroleum coupling and catalyzing catalyst for cracking phase
Haptoreaction obtains the logistics containing ethylene Yu propylene.
In above-mentioned technical proposal, the preferred scope of reaction temperature is 630～710 DEG C；The weight space velocity of light naphthar
Preferred scope is 0.5～4h-1；The preferred scope of reaction pressure is 0～0.8MPa；Water and light naphthar and weight
Amount is 0～4 than preferred scope.
Wherein the presoma of metallic element can be nitrate, sulfate, chloride or acetate.P elements
Presoma can be originated as the mixed of phosphoric acid, ammonium di-hydrogen phosphate, DAP, ammonium phosphate or phosphoric acid and ammonia
At least one in compound.
Compared with fluid catalyst in prior art, the present invention by using SAPO-34 and ZSM-5 or
ZSM-11 molecular sieves composite molecular screen is used for naphtha catalytic cracking second for the fluid catalyst of active component
The method of allyl alkene process, meanwhile, by the introducing of La, P or Mn metal-oxide, can be to catalyst
Acid centre is modified, and adjusts the density and acid strength of the acid centre of catalyst, suppresses hydrogen to turn so as to reach
The side reaction such as shifting and carbon distribution occurs, and improves the stability and diene yield of catalyst.
The present invention is adopted by adopting SAPO-34 with ZSM-5 or ZSM-11 molecular sieves composite molecular screen to live
Property component fluid catalyst, in 600～700 DEG C of temperature, 0～0.2MPa of pressure, methanol and Petroleum weight
Than being 0.5～8.0, contacted amount the logistics obtained containing ethylene Yu propylene with fluid catalyst.Comment in identical
Under the conditions of valency, with methanol and Petroleum as raw material, the yield of ethylene+propylene is received than prior art ethylene+propylene
Rate is significantly improved, and achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.But these embodiments are not to the present invention
Scope is limited.
Specific embodiment
【Embodiment 1】
Weigh solution 240 grams of dippings, the 200 grams of Hydrogen ZSM-5 molecular sieve (SiO containing 30.7 grams of phosphoric acid2With Al2O3
Silica alumina ratio for 20), be aged 2～24 hours at room temperature, in 100～140 DEG C of dryings 12 hours, at 550 DEG C
Roasting 6 hours.Weigh previous step and obtain 100.0 grams of modified zsm-5 zeolite, 10.0 grams of SAPO-34 divide
Son sieve (SiO2With Al2O3Silica alumina ratio for 0.01), 40.0 grams of Kaolin, 238.1 grams of Alumina gels
(21.0%Al2O3) and 212.0 water mix homogeneously be made into serosity Jing spraying be obtained particle diameter be 10～200 μm
Microsphere, 600 DEG C of Jing roastings 4 hours obtain fluidized bed microspherical catalyst, and specific catalyst composition can be shown in Table 2.
It it is 650 DEG C in reaction temperature, Petroleum air speed is 0.7h-1, methanol is 1.0 with the weight ratio of Petroleum,
Condition of the pressure for normal pressure, carries out catalyst Petroleum and methanol performance evaluation, and reaction evaluating the results are shown in Table 3.
The composition of Petroleum is shown in Table 1.
【Embodiment 2-6】
Prepare according to identical preparation method and evaluate catalyst b-f, composition and the evaluation result of catalyst can be shown in Table 3.
【Comparative example 1】
According to the composition similar to embodiment 5, Kaolin, aluminium oxide, P are kept2O5And La2O3Content
It is constant, simply will wherein ZSM-5 (SiO2With Al2O3Silica alumina ratio be changed to 56 for parts by weight 100),
Preparation method is same as Example 5 with evaluation methodology.
【Comparative example 2】
According to the composition similar to embodiment 6, Kaolin, aluminium oxide and P are kept2O5Content it is constant, only
It is by wherein ZSM-5 (SiO2With Al2O3Silica alumina ratio be changed to 30.5 for parts by weight 200), preparation side
Method is same as Example 6 with evaluation methodology.
【Embodiment 7-10】
Using catalyst c, change process conditions, the evaluation result for obtaining is listed in table 4
Table 1
| Project | Data |
| Density (20 DEG C) kg/m3 | 704.6 |
| The first boiling range DEG C of boiling range | 40 |
| Whole boiling range DEG C | 160 |
| Saturated vapor pressure (20 DEG C) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| N-alkane % (weight %) in alkane | >32.5 |
| Cycloalkane % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
Table 2
Table 3
Table 4
Claims (10)
1. a kind of methanol and Petroleum coupling and catalyzing catalyst for cracking, comprising following components in terms of parts by weight：
A) at least one of P, La or Mn oxide of 0.5-20 parts oxide；
B) 80～99.5 parts containing at least one composition in SAPO-34 and ZSM-5 or ZSM-11 molecular sieves
Composite molecular screen microsphere.
2. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, it is characterised in that
Composite molecular screen microsphere adopts in-situ synthesis.
3. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, it is characterised in that
Relative crystallinity of the SAPO-34 molecular sieves in composite molecular screen microsphere is 5～30%.
4. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, SAPO-34 point
The mol ratio of the silica/alumina of son sieve is 0.01～0.6.
5. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, it is characterised in that
The silicon oxide of ZSM-5 or ZSM-11 molecular sieves is 20～200 with the mol ratio of aluminium oxide.
6. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, it is characterised in that
It it is 0.5～12 part selected from the consumption of P, La or Mn oxide.
7. methanol according to claim 1 and Petroleum coupling and catalyzing catalyst for cracking, it is characterised in that a)
For the hopcalite of P and La, in terms of the parts by weight of catalyst, the consumption 0.5～8 of the oxide of P
Part, 0.2～7 part of the consumption of La.
8. the preparation side of the methanol described in any one of claim 1～7 and Petroleum coupling and catalyzing catalyst for cracking
Method, comprises the steps：
1) weigh the desired amount of solution selected from least one of P, La or Mn oxide oxide precursor
At least one molecular sieve of the dipping in ZSM-5 or ZSM-11 molecular sieves, ageing 2～24 is little at room temperature
When, 2-24 hours are dried at 100～140 DEG C, roasting 2-12 hours at 500～750 DEG C；
2) weigh the desired amount of SAPO-34 and previous step obtain modified molecular screen, Kaolin, selected from aluminium oxide
Mix homogeneously with least one and water in alumina material and be made into serosity Jing that solid content is 20～50% spraying
Prepared particle diameter is 10～200 μm of microsphere, and 900～1200 DEG C of Jing roastings 4 hours obtain the catalysis of fluid bed microsphere
Agent.
9. a kind of method that methanol cracks alkene processed with Petroleum coupling and catalyzing, in reaction temperature be
610～760 DEG C, the weight space velocity of light naphthar is 0.1～10h-1, reaction pressure is 0～2.0MPa, water and pumice
The weight ratio of cerebrol is 0～10 and the weight ratio of Petroleum and methanol is under 0.1～10 reaction condition, methanol,
Petroleum is contacted to react with catalyst described in any one of claim 1～7 and obtains the logistics containing ethylene Yu propylene.
10. the method that methanol according to claim 9 cracks alkene processed with Petroleum coupling and catalyzing, which is special
It is that reaction temperature is 630～710 DEG C to levy, and the weight space velocity of light naphthar is 0.5～4h-1, reaction pressure is
0～0.8MPa, water and light naphthar with weight ratio be 0～4.
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| CN110871107A (en) * | 2019-11-06 | 2020-03-10 | 厦门大学 | Catalyst for preparing low-carbon olefin by coupling catalytic cracking of low-carbon alcohol and naphtha as well as preparation method and application of catalyst |
| WO2020078437A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| CN114632544A (en) * | 2022-02-22 | 2022-06-17 | 中科合成油技术股份有限公司 | Catalyst for preparing olefin by coupling naphtha with low-carbon alcohol ether and preparation method and application thereof |
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| CN104557377A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from oxygen-containing compound and naphtha by coupled reaction |
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| WO2020078437A1 (en) * | 2018-10-18 | 2020-04-23 | 中国石油化工股份有限公司 | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof |
| RU2800708C2 (en) * | 2018-10-18 | 2023-07-26 | Чайна Петролеум Энд Кемикал Корпорейшн | Molecular sieve containing phosphorus and rare earth elements with mfi structure and high mesopore content, method for its production, catalyst containing it and its application |
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| CN110871107A (en) * | 2019-11-06 | 2020-03-10 | 厦门大学 | Catalyst for preparing low-carbon olefin by coupling catalytic cracking of low-carbon alcohol and naphtha as well as preparation method and application of catalyst |
| CN114632544A (en) * | 2022-02-22 | 2022-06-17 | 中科合成油技术股份有限公司 | Catalyst for preparing olefin by coupling naphtha with low-carbon alcohol ether and preparation method and application thereof |
| CN114887650A (en) * | 2022-04-26 | 2022-08-12 | 中科合成油技术股份有限公司 | In-situ crystallization catalyst for preparing olefin and preparation method and application thereof |
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