CN103785473A - High-activity catalyst for alkene production by catalytic cracking and preparation method and application thereof - Google Patents
High-activity catalyst for alkene production by catalytic cracking and preparation method and application thereof Download PDFInfo
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- CN103785473A CN103785473A CN201210427703.3A CN201210427703A CN103785473A CN 103785473 A CN103785473 A CN 103785473A CN 201210427703 A CN201210427703 A CN 201210427703A CN 103785473 A CN103785473 A CN 103785473A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 230000000694 effects Effects 0.000 title description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- 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 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 25
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 14
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 32
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012686 silicon precursor Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- -1 propylene, butylene Chemical group 0.000 description 12
- 238000011084 recovery Methods 0.000 description 10
- 238000005336 cracking Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012962 cracking technique Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for alkene production by catalytic cracking. The catalyst comprises, by weight, 0.1%-3% of heteropoly acid, 5-30% of an MFI-type molecular sieve and the balance of SiO2, and preferably comprises 0.5-2.5% of heteropoly acid and 15-25% of an MFI-type molecular sieve. The heteropoly acid is one or more selected from phosphotungstic acid, silicotungstic acid, arsenowolframic acid, germanotungtic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanomolybdic acid, and preferably phosphotungstic acid and / or phosphomolybdic acid, and more preferably phosphotungstic acid. The catalyst can solve the problems of low yield, high reaction temperature and easy deactivation of catalyst in the ethylene propylene production by naphtha catalytic cracking.
Description
Technical field
The present invention relates to a kind of catalyst for preparing olefin by catalytic cracking and its preparation method and application, particularly the Catalysts and its preparation method of naphtha catalytic pyrolysis preparing ethylene and propylene and application.
Background technology
Since entering the new century, world's petrochemical material and petroleum chemicals demand will sustainable growths, to continue to increase as the demand of petrochemical industry basic material ethene, propylene, and conventional steam heat cracking technique production capacity can not meet the propylene demand of rapid growth, and the cracking of conventional tubular stove steam heat is the process that consumes in a large number the energy, process conditions harshness.Naphtha catalytic cracking is compared with steam heat cracking, and this process reaction temperature is than the approximately low 50-200 ℃ of standard cracking reaction, and therefore, than common steam thermal cracking less energy consumption, cracking furnace pipe inwall coking rate reduces, thereby can prolong operation cycle, increases the boiler tube life-span.Carbon monoxide emission also can reduce, and can adjust the product mix flexibly.Compared with traditional steam heat cracking technique, this new technology can increase the total recovery of ethene and propylene, produces equal number ethene feed naphtha used and can reduce, and production cost of ethylene significantly reduces.
It is catalyst that USP3767567 adopts any one oxide (>20wt%) and aluminium oxide in CaO, BeO, SrO, take boiling point at the naphtha of 70-180 ℃ as raw material, reaction temperature 650-900 ℃, water-oil factor 0.5-10, wherein CaO-Al
2o
3type catalyst is best, and in product, the highest yield of ethene is large 52.5%, propene yield 16.3%.Apply this quasi-metal oxides or its mixture as catalyst, reaction temperature requires very high, although the productive rate that can improve ethene is with selective, generates a large amount of dry gas, CO and CO in course of reaction
2, reclaim and bring many difficulties to product.
US4620051 and US4705769 have adopted take manganese oxide or iron oxide as active component, have added rare-earth elements La, and the oxide catalyst of alkaline-earth metal Mg, cracking C3, C4 raw material.With Mn, Mg/Al
2o
3for catalyst, employing iso-butane is raw material, 700 ℃ of reaction temperatures, fixed bed reactors evaluation, butanes conversion is 80%, ethene and propylene be selectively respectively 34% and 20%.And claim that catalyst can be used for naphtha and fluidized-bed reactor.
Adopt containing the catalyst of molecular sieve and carry out catalytic cracking reaction, not only can obtain relatively large ethene, can also produce more propylene, butylene.CN101279285A adopts on ZSM-5/ mercerization zeolite symbiosis molecular screen, ZSM-5/ beta zeolite coexisting molecular sieve or ZSM-5/Y zeolite coexisting molecular sieve the catalyst of at least one element in IVB family element or VB family element in the load periodic table of elements or its oxide composition for naphtha catalytic pyrolysis preparing ethylene propylene.In fixed bed reactors, reaction temperature 600-700 ℃, naphtha catalytic cracking obtains ethylene, propylene total recovery can reach 54%.
CN1955255A provides a kind of petroleum hydrocarbon catalytic pyrolysis catalyst and application thereof.The component of its petroleum hydrocarbon catalytic pyrolysis catalyst comprises 1) rare earth element, 2) phosphorus or boron, 3) alkali metal, alkaline-earth metal and transition metal, 4) carrier.This catalyst is produced low-carbon alkene for the heavy hydrocarbon such as cracking naphtha, diesel oil and decompression diesel oil, and raw material do not need nitrogen dilution, can improve ethene, propylene, butylene and butadiene yield more than 5%.
Above-mentioned catalyst ubiquity one or more deficiencies such as cost is high, olefin yields is low, reaction temperature is higher, catalysqt deactivation is too fast, less stable.
Summary of the invention
, the deficiency such as reaction temperature high, catalyst easy inactivation low for existing naphtha catalytic pyrolysis preparing ethylene propylene yield, the invention provides a kind of Catalysts and its preparation method for naphtha catalytic pyrolysis preparing ethylene propylene and application.
A kind of catalyst for preparing olefin by catalytic cracking, by the weight content of catalyst, contains 0.1% ~ 3% heteropoly acid, 5～30% MFI type molecular sieve, and surplus is SiO
2.Preferably contain 0.5% ~ 2.5% heteropoly acid, 15～25% MFI type molecular sieve.
Heteropoly acid described in the present invention is one or more in phosphotungstic acid, silico-tungstic acid, arsenowolframic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid, preferably phosphotungstic acid and/or phosphomolybdic acid, more preferably phosphotungstic acid.
MFI type molecular sieve of the present invention is Hydrogen ZSM-5 molecular sieve.
A preparation method for catalyst for preparing olefin by catalytic cracking, comprises following content:
(1) get appropriate heteropoly acid water-soluble, and stir;
(2) in step (1) solution, add appropriate alcoholic solvent and contain silicon precursor, after solution is stirred, regulator solution pH value is 2-5;
(3) in step (2) solution, add MFI type molecular sieve, constant temperature is stirred to solution and is converted into colloidal sol, and then aged at room temperature obtains gel;
(4) by the gel drying obtaining in step (3) to constant weight, grinding, obtain final catalytic cracking catalyst.
Heteropoly acid described in the inventive method step (1) is one or more in phosphotungstic acid, silico-tungstic acid, arsenowolframic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid, preferably phosphotungstic acid and/or phosphomolybdic acid, more preferably phosphotungstic acid.The addition of heteropoly acid is weight content 0.1% ~ 3% in final catalyst by it, preferably by 0.5% ~ 2.5%.
Alcoholic solvent described in the inventive method step (2) is one or more in absolute ethyl alcohol, n-butanol, isopropyl alcohol, preferably n-butanol.Described is ethyl orthosilicate containing silicon precursor.In solution, water is 1～20 with the mol ratio of the ethyl orthosilicate that adds, preferably 5～15; N-butanol and ethyl orthosilicate mol ratio are 0.1～5, preferably 0.5～3.
MFI molecular sieve described in the inventive method step (3) is Hydrogen ZSM-5 molecular sieve, and the addition of Hydrogen ZSM-5 molecular sieve is weight content 5～30% in final catalyst by it, preferably by 15～25%.Thermostat temperature is 60～120 ℃, is preferably 70～100 ℃, and constant temperature time is 1～5h, preferably 2～4h; Ageing time is 1～10h, is preferably 2～8h.
Baking temperature described in the inventive method step (4) is 60～150 ℃, and preferably 70～130 ℃, be 6～28h drying time, is preferably 8～15h.
The application of above-mentioned catalyst for preparing olefin by catalytic cracking in naphtha catalytic pyrolysis preparing ethylene and propylene, with C
5～C
10naphtha is raw material, and nitrogen is carrier gas, and reaction temperature is 500～700 ℃, and in gauge pressure reaction pressure 0.01～0.5MPa, naphtha weight space velocity is 0.5～4h
-1, water oil volume is than under 0.5～3 condition.
What the present invention adopted prepared by sol-gal process contains active component heteropoly acid and ZSM-5 and carrier S iO
2catalyst for preparing olefin by catalytic cracking, have suitable duct and acid distribute, active component is uniformly dispersed, and can improve the activity stability of catalyst and reduce reaction temperature.
the specific embodiment
Further illustrate effect of the present invention and effect below in conjunction with embodiment.
Example 1
(1) get 0.5g phosphotungstic acid, be dissolved in 20ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 0.6; In solution, water is 6 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 3;
(3) in step (2) solution, add 13g Hydrogen ZSM-5 molecular sieve, 70 ℃ of constant temperature stir 3.5h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 6h.
(4) by the gel obtaining in step (3) dry 14h at 70 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 0.6% heteropoly acid by weight, 16% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, take naphtha as raw material, nitrogen is as carrier gas, 2 grams of catalyst qualities, and water oil volume is than 1, and in gauge pressure reaction pressure 0.02MPa, naphtha weight space velocity is 2 hours
-1, 550 ℃ of reaction temperatures, ethylene, propylene total recovery reaches 53.41%.
Example 2
(1) get 1.2g phosphotungstic acid, be dissolved in 20ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 1.5; In solution, water is 10 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 4;
(3) in step (2) solution, add 17g Hydrogen ZSM-5 molecular sieve, 80 ℃ of constant temperature stir 3h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 4h.
(4) by the gel obtaining in step (3) dry 12h at 100 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 1.8% heteropoly acid by weight, 25% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, 1.5 grams of catalyst qualities, water oil volume is than 0.9, mass space velocity 3 hours
-1, 500 ℃ of reaction temperatures, in gauge pressure reaction pressure 0.1MPa, naphtha is raw material, nitrogen reaches 50.32% as carrier gas ethylene, propylene total recovery.
Example 3
(1) get 0.3g phosphotungstic acid, be dissolved in 11ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 2.7; In solution, water is 13 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 4;
(3) in step (2) solution, add 7g Hydrogen ZSM-5 molecular sieve, 95 ℃ of constant temperature stir 2h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 4h.
(4) by the gel obtaining in step (3) dry 8h at 125 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 2.2% heteropoly acid by weight, 19% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, 3 grams of catalyst qualities, water oil volume is than 1.5, mass space velocity 2 hours
-1, 650 ℃ of reaction temperatures, in gauge pressure reaction pressure 0.3MPa, naphtha is raw material, and nitrogen is as carrier gas, and ethylene, propylene total recovery reaches 54.56%.
Example 4
(1) get 0.7g phosphotungstic acid, be dissolved in 24ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 0.9; In solution, water is 9 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 5;
(3) in step (2) solution, add 17g Hydrogen ZSM-5 molecular sieve, 75 ℃ of constant temperature stir 3h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 6h.
(4) by the gel obtaining in step (3) dry 9h at 90 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 0.9% heteropoly acid by weight, 21% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, 3 grams of catalyst qualities, water oil volume is than 4.7, mass space velocity 3.5 hours
-1, 630 ℃ of reaction temperatures, in gauge pressure reaction pressure 0.5MPa, naphtha is raw material, and nitrogen is as carrier gas, and ethylene, propylene total recovery reaches 52.78%.
Example 5
(1) get 1.0g phosphotungstic acid, be dissolved in 18ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 2.0; In solution, water is 12 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 5;
(3) in step (2) solution, add 16g Hydrogen ZSM-5 molecular sieve, 85 ℃ of constant temperature stir 4h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 8h.
(4) by the gel obtaining in step (3) dry 9h at 80 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 1.4% heteropoly acid by weight, 23% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, 2.5 grams of catalyst qualities, water oil volume is than 3.5, mass space velocity 0.6 hour
-1, 580 ℃ of reaction temperatures, in gauge pressure reaction pressure 0.01MPa, naphtha is raw material, and nitrogen is as carrier gas, and ethylene, propylene total recovery reaches 51.63%.
Example 6
(1) get 1.1g phosphotungstic acid, be dissolved in 18ml distilled water, uniform stirring to phosphotungstic acid dissolves completely;
(2) in step (1) solution, add n-butanol and ethyl orthosilicate, the n-butanol adding and ethyl orthosilicate mol ratio are 2.4; In solution, water is 14 with the mol ratio of the ethyl orthosilicate adding, and continues to stir, and in solution, splashes into hydrochloric acid, and the pH value of regulator solution is 5;
(3) in step (2) solution, add 11g Hydrogen ZSM-5 molecular sieve, 90 ℃ of constant temperature stir 3h and are converted into colloidal sol to solution, and then aged at room temperature obtains gel, and ageing time is 4h.
(4) by the gel obtaining in step (3) dry 11h at 110 ℃ of temperature, grind, obtain final catalytic cracking catalyst.In prepared catalyst, content meter contains 2.0% heteropoly acid by weight, 20% hydrogen ZSM-5 molecular sieve, and surplus is SiO
2.
Adopt fixed bed reactors to carry out evaluating catalyst, 2 grams of catalyst qualities, water oil volume is than 2.6, mass space velocity 1.6 hours
-1, 690 ℃ of reaction temperatures, in gauge pressure reaction pressure 0.25MPa, naphtha is raw material, and nitrogen is as carrier gas, and ethylene, propylene total recovery reaches 51.07%.
Comparative example 1
Carried heteropoly acid on hydrogen ZSM-5 molecular sieve molecular sieve.In catalyst, content meter contains 2.0% heteropoly acid by weight.Appreciation condition is with embodiment 6, and ethylene, propylene total recovery reaches 46.5%.
Comparative example 2
At SiO
2carried heteropoly acid on carrier.In catalyst, content meter contains 2.0% heteropoly acid by weight.Appreciation condition is with embodiment 6, and ethylene, propylene total recovery reaches 35.9%.
Claims (10)
1. a catalyst for preparing olefin by catalytic cracking, is characterized in that: by the weight content of catalyst, contain 0.1% ~ 3% heteropoly acid, and 5～30% MFI type molecular sieve, surplus is SiO
2.
2. catalyst according to claim 1, is characterized in that: by the weight content of catalyst, contain 0.5% ~ 2.5% heteropoly acid, 15～25% MFI type molecular sieve.
3. the preparation method of catalyst described in claim 1 or 2, is characterized in that: comprise following content:
(1) get appropriate heteropoly acid water-soluble, and stir;
(2) in step (1) solution, add appropriate alcoholic solvent and contain silicon precursor, after solution is stirred, regulator solution pH value is 2-5;
(3) in step (2) solution, add MFI type molecular sieve, constant temperature is stirred to solution and is converted into colloidal sol, and then aged at room temperature obtains gel;
(4) by the gel drying obtaining in step (3) to constant weight, grinding, obtain final catalytic cracking catalyst.
4. method according to claim 3, is characterized in that: the heteropoly acid described in step (1) is one or more in phosphotungstic acid, silico-tungstic acid, arsenowolframic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid.
5. method according to claim 4, is characterized in that: described heteropoly acid is phosphotungstic acid.
6. method according to claim 3, it is characterized in that: the alcoholic solvent described in step (2) is one or more in absolute ethyl alcohol, n-butanol, isopropyl alcohol, described is ethyl orthosilicate containing silicon precursor, and in solution, water is 1～20 with the mol ratio of the ethyl orthosilicate adding; N-butanol and ethyl orthosilicate mol ratio are 0.1～5.
7. method according to claim 3, is characterized in that: the MFI molecular sieve described in step (3) is Hydrogen ZSM-5 molecular sieve, and thermostat temperature is 60～120 ℃, and constant temperature time is 1～5h; Ageing time is 1～10h.
8. method according to claim 7, is characterized in that: thermostat temperature is 70～100 ℃, and constant temperature time is 2～4h; Ageing time is 2～8h.
9. method according to claim 8, is characterized in that: the baking temperature described in step (4) is 60～150 ℃, and be 6～28h drying time.
10. the application of catalyst in naphtha catalytic pyrolysis preparing ethylene and propylene described in claim 1 or 2, with C
5～C
10naphtha is raw material, and nitrogen is carrier gas, and reaction temperature is 500～700 ℃, and in gauge pressure reaction pressure 0.01～0.5MPa, naphtha weight space velocity is 0.5～4h
-1, water oil volume is than 0.5～3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552665A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking and its preparation method and application |
| CN110201716A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | Alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
| CN113318773A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60222428A (en) * | 1984-04-19 | 1985-11-07 | Res Assoc Util Of Light Oil | Catalytic conversion of hydrocarbon |
| CN1235873A (en) * | 1998-05-19 | 1999-11-24 | 中国石油化工总公司 | Silicon dioxide carried heteropoly acid catalyst, its preparation and use |
| CN1504540A (en) * | 2002-11-29 | 2004-06-16 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefins by cracking petroleum hydrocarbons |
| CN102463133A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking, preparation method and application |
-
2012
- 2012-11-01 CN CN201210427703.3A patent/CN103785473B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60222428A (en) * | 1984-04-19 | 1985-11-07 | Res Assoc Util Of Light Oil | Catalytic conversion of hydrocarbon |
| CN1235873A (en) * | 1998-05-19 | 1999-11-24 | 中国石油化工总公司 | Silicon dioxide carried heteropoly acid catalyst, its preparation and use |
| CN1504540A (en) * | 2002-11-29 | 2004-06-16 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefins by cracking petroleum hydrocarbons |
| CN102463133A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 赵新强等: "几种方法制备的H3PW12O40/SiO2催化剂的结构和催化性能", 《催化学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552665A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking and its preparation method and application |
| CN106552665B (en) * | 2015-09-30 | 2019-09-10 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking and its preparation method and application |
| CN110201716A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | Alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
| CN110201716B (en) * | 2019-05-21 | 2022-04-19 | 南京工业大学 | An ordered mesoporous C/SiO2 supported heteropolyacid catalyst modified by an alcoholamine group and its preparation method and application |
| CN113318773A (en) * | 2020-02-28 | 2021-08-31 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material as well as preparation method and application thereof |
| CN113318773B (en) * | 2020-02-28 | 2023-09-08 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material, preparation method and application thereof |
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