CN101590421A - The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof - Google Patents
The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof Download PDFInfo
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- CN101590421A CN101590421A CNA2008101133772A CN200810113377A CN101590421A CN 101590421 A CN101590421 A CN 101590421A CN A2008101133772 A CNA2008101133772 A CN A2008101133772A CN 200810113377 A CN200810113377 A CN 200810113377A CN 101590421 A CN101590421 A CN 101590421A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 46
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 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 75
- 239000002808 molecular sieve Substances 0.000 claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 9
- 239000013081 microcrystal Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 39
- 239000000843 powder Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 206010013786 Dry skin Diseases 0.000 description 22
- 238000001035 drying Methods 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 13
- -1 polypropylene Polymers 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000007233 catalytic pyrolysis Methods 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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)
Abstract
The invention provides the catalyst and the using method thereof of a kind of novel olefin catalytic cracking to produce propylene and ethene.Catalyst of the present invention is by silica alumina ratio SiO
2/ Al
2O
3Be 10-300, size of microcrystal is that the ZSM-5 molecular sieve of 10-800 nanometer is formed with the P elements and the thulium that carry thereon.It is raw material that catalyst of the present invention is applied to carbon four-carbon laurylene hydrocarbon, is 450-650 ℃ in reaction temperature, and reaction pressure is 0-0.3MPa, and the alkene weight space velocity is 1-14 hour
-1, water/alkene weight ratio is under the condition of 0.1-10, raw material carries out the olefins by catalytic cracking reaction by beds and generates propylene and ethene.Utilize catalyst provided by the invention, can when keeping high propylene, yield of ethene, have long the reaction duration of runs, can be used for suitability for industrialized production.
Description
Technical field
The present invention relates to the catalyst and the application thereof of a kind of catalytic cracking for producing propylene using, ethene, particularly a kind of catalyst and application thereof that is used for carbon four～carbon laurylene hydrocarbon catalytic cracking for producing propylene using, ethene.
Background technology
According to statistics, nineteen ninety-five world Ethylene production capacity be 7,932 ten thousand tons/year, estimate to 2010 then to be 11,038 ten thousand tons/year.Increase along with ethylene yield, the output of the by-product carbon four of steam cracking and carbon four above alkene constantly increases, be subjected to the influence of factors such as the variation in chemical products market and cost of transportation, it is a kind of approach that utilizes preferably that these low value-added materials are carried out deep processing on the spot.Simultaneously, be subjected to the influence of polypropylene and alkyl aromatic compound demand growth, the propylene demand growth is vigorous, will reach 7,800 ten thousand tons to propylene demand in 2008.The analyst points out, if do not manage to increase propone output, will reach 5,000,000 tons/year to the breach of 2010 propylene, and therefore, in one period from now on, propylene is considered to have the product of very big market potentiality.At above-mentioned situation, many in the world petro-chemical corporations drop into technology and the catalyst that strength develops carbon four and carbon four above low value alkene production propylene one after another.
CN1284109A discloses a kind of technology that is used for carbon four above olefin cracking system propylene, ethene, does not add water in the reaction system, and reaction velocity is 10-30 hour
-1, its used catalyst is a kind of silica alumina ratio greater than 200 hydrothermal modification ZSM-5 molecular sieve, and etherificate carbon four cracking conversion ratios are 54% in the embodiment 3, and propene yield only is 29%, and operation 160 hour datas are only arranged.
EPA0109059 discloses a kind of method with carbon four above olefin cracking system propylene, ethene, is catalyst with silica alumina ratio less than 360 ZSM-5 or ZSM-11 molecular sieve, does not add water in the reaction system, and reaction must be at 50 hours
-1High weight space velocity under carry out, could obtain higher propene yield, and the embodiment that provides also only is the result of several hrs, can not satisfy the requirement of explained hereafter hundreds of hour.
CN1274342A discloses a kind of method of producing ethene and propylene with carbon four to carbon laurylene hydrocarbon.Not adding water in the reaction system, is 16.3 hours when being reflected at 600 ℃, weight space velocity
-1Condition under when carrying out, the propylene selectivity is 45.7%, propene yield is 34.0%.The catalyst that uses in this method is the ZSM-5 molecular sieve, by ion-exchange, impregnating means catalyst is carried out modification with Alkali-Metal Na, K and the metal Cu of IB family, Ag etc., prepares the ZSM-5 molecular sieve catalyst that does not contain proton substantially.
US5981819 discloses a kind of technology that carbon four is turned to propylene and butylene to carbon seven alkene.Add water vapour in the reaction system, it is said to add the carbon distribution that steam can slow down catalyst, improved the stability of catalyst.The catalyst that uses is the Pentasil type molecular sieve catalyst of silica alumina ratio as 10-200, and its BET specific surface is a 300-600 rice
2/ gram, particle diameter is the 0.1-0.9 micron.Do not handle because the ZSM-5 molecular sieve catalyst that uses in this patent carries out modification, so the yield of purpose product propylene is not high, at 462 ℃, the carrying capacity of catalyst is under the condition of 2 kilograms of catalyst of per kilogram raw material, and interior alkene yield only is 28.5%.
Chinese patent CN1490287A discloses a kind of method for preparing ethene and propylene, this method comprises that the hydrocarbon mixture with carbon containing four or C 5 monoolefin is a raw material, in fixed bed reactors, contact with zeolite containing catalyst, and at 350-500 ℃ temperature, pressure and the 1-10h of 0.6-1.0MPa
-1The condition of weight hourly space velocity under react, generate the reactant mixture that contains ethene and propylene, described catalyst comprises Al
2O
3Or SiO
2Be 20-45%, silica-rich zeolite (the preferred 200-300 of its silica alumina ratio) is 40-70%, and modified component is 8-20%; Described modified component is selected from least a in oxide, alkaline earth oxide and the rare-earth oxide of molybdenum oxide, tungsten oxide, phosphorus.
Chinese patent CN 1676499A discloses the method that a kind of catalytic pyrolysis prepares olefine in low carbon number, this method is a raw material with carbon four or carbon five hydrocarbon mixtures that do not contain diolefin, with raw material with after water mixes, in fixed bed reactors with under zeolite containing catalyst contacts, react, generation contains the reactant mixture of propylene and ethene, after refrigerated separation, obtain ethene and propylene, wherein said zeolite containing catalyst is obtained by following component: with the total restatement of raw material, silica-rich zeolite (the preferred 180-300 of its silica alumina ratio) 20-65%, silica 20-65%, inorganic oxide 0-20%.Described inorganic oxide is selected from least a in oxide, alkaline earth oxide and the rare-earth oxide of zirconia, phosphorus.
The method of a kind of carbon four and above olefin catalytic cracking to produce propylene thereof is disclosed among the CN1506342A.Do not add steam in the reaction system, reaction raw materials carbon four and above alkene thereof are 400-600 ℃ in reaction temperature, and reaction pressure is 0-0.15MPa, and the liquid phase air speed is 10-50 hour
-1Cracking reaction takes place under the condition produce propylene.The catalyst that is used for this process is an alkaline-earth metal, and loading is the ZSM-5 molecular sieve that 0.3-3%, silica alumina ratio example are preferably 80-300.
A kind of method that relates to carbon four and above olefin catalytic cracking to produce propylene thereof is disclosed among the CN1611471A.Do not add water vapour in the reaction system, reaction raw materials carbon four and above alkene thereof are 400-600 ℃ in reaction temperature, and reaction pressure is 0-0.15MPa, and the liquid phase air speed is 2-30 hour
-1Cracking reaction takes place under the condition produce propylene.The catalyst that is used for this process is a phosphorus, and loading is that 0.6-2.4%, silica alumina ratio are the ZSM-5 molecular sieve of 20-100.
A kind of method that is used for olefin catalytic cracking to produce propylene, ethene is disclosed among the CN1704389A.By adopting with carbon four-carbon eight alkene is raw material, with the rare earth metal loading is that the ZSM-5 molecular sieve that 0.1-2%, silica alumina ratio example are preferably 80-400 is a catalyst, in reaction temperature is 450-650 ℃, reaction pressure is 0-0.2MPa, water/alkene weight ratio is 0.5-5, and the alkene weight space velocity is 0.5-15 hour
-1Produce propylene and ethene under the condition.
Therefore alkene prepares the process of propylene, ethene through catalytic pyrolysis, can take to add water and not add two kinds of technologies of water, and the key component of catalyst is to have more highly acid molecular sieve.Because the acidity of molecular sieve, carrying out also existing state of conflict and back ideotype side reactions such as alkene oligomerization chain growth, hydrogen migration and aromatisation when olefins by catalytic cracking prepares propylene, ethene, on the one hand reduced the yield of ethene, propylene, these side reactions may cause coking in the molecular sieve catalyst duct on the one hand, cover chain carrier, make rapid catalyst deactivation.In the technical process that does not add water,, generally be (generally will be at 10 hours by the charging air speed that increases alkene for obtaining higher ethene, propene yield
-1More than) suppress the generation of other side reactions, but catalyst is because of the fast inactivation rapidly of carbon distribution speed.In adding the water conservancy project skill, to reduce carbon distribution etc. very favourable for suppressing side reaction as heat carrier and diluent in the adding of water, but the existence of water can cause the framework dealumination of molecular sieve catalyst, thereby catalyst acid density is descended rapidly, and the long-term use of catalyst is also had certain influence.As seen, add water and do not add two kinds of technical process of water and respectively have superiority.From catalyst research, though the main active component of catalyst is ZSM-5, ZSM-11 or SAPO equimolecular sieve, but in order to reach certain catalytic effect, to select the ZSM-5 molecular sieve (from embodiment, the silica alumina ratio of the ZSM-5 molecular sieve that most of effect preferred catalysts is used is greater than 150) of suitable silica alumina ratio on the one hand; Will add suitable modifying element on the one hand, modifying element can be independent thulium or alkali earth metal, can be the common interpolation of alkali metal and IB family metallic element, also can be P elements.
But, the olefins by catalytic cracking catalyst that exists in the prior art can not be when guaranteeing high propylene, ethylene yield long-term operation, therefore, for addressing the above problem, it is extremely necessary that a kind of novel catalyst that is used for olefin catalytic cracking to produce propylene, ethene and using method thereof are provided.
Summary of the invention
The catalyst and the using method thereof that the purpose of this invention is to provide a kind of novel olefin catalytic cracking to produce propylene, ethene.This catalyst has can make olefins by catalytic cracking be reflected at the characteristics that have when keeping high propylene, yield of ethene than the long running cycle.
For realizing purpose of the present invention, the concrete technical scheme that adopts is as follows:
The catalyst that is used for olefin catalytic cracking to produce propylene, ethene of the present invention, composed of the following components:
A) 40-75% silica alumina ratio SiO
2/ Al
2O
3Be 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer; With carry thereon
B) P elements of 0.01-10%;
C) thulium of 0.01-10%;
D) binding agent of 5-60%.
Wherein said percentage composition is weight percentage, and with the total restatement of catalyst.
The silica alumina ratio of the type ZSM 5 molecular sieve that uses in the preferred catalyst of the present invention for more than or equal to 20 to smaller or equal to 200; More preferably the silica alumina ratio of type ZSM 5 molecular sieve is 20-180.
The size of microcrystal of the type ZSM 5 molecular sieve described in the preferred catalyst of the present invention is the 10-500 nanometer.
In a preferred embodiment of the invention, the silica alumina ratio of described type ZSM 5 molecular sieve is 20-180; Size of microcrystal is the 10-500 nanometer.
The weight content of preferred described ZSM-5 molecular sieve is 50-70%
The weight content of the rare earth metal described in the preferred catalyst of the present invention is 0.1-8%; More preferably 0.5-8%; Further preferred 3-7%.
Rare earth metal described in the preferred catalyst of the present invention is selected from least a in lanthanum, cerium, praseodymium and the neodymium.
The weight content of the P elements described in the preferred catalyst of the present invention is 0.1-8%; More preferably 0.5-8%.
Binding agent described in the catalyst of the present invention can be some binding agents commonly used in the prior art such as silica, aluminium oxide, kaolin, clay etc., preferred silica, aluminium oxide or their mixture.
In a specific embodiments of the present invention, described olefins by catalytic cracking catalyst comprises
A) the silica alumina ratio SiO of 40-75%
2/ Al
2O
3For 10-200, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer; With carry thereon
B) P elements of 0.5-8%;
C) thulium of 0.5-8%;
D) binding agent of 5-60%;
Wherein said percentage composition is weight percentage, and with the total restatement of catalyst.
In olefins by catalytic cracking catalyst of the present invention, described rare earth metal can exist with the metallic element form, also can exist with its oxide form.
Olefins by catalytic cracking catalyst of the present invention not only can be made into various difform fixed bde catalysts, equally also can be configured as microspherical catalyst by spraying and be applicable to fluidized bed process technology.
Another object of the present invention provides a kind of method of using catalyst of the present invention.
Concrete, the method that is used for olefin catalytic cracking to produce propylene, ethene of the present invention comprises:
With carbon four-carbon laurylene hydrocarbon is raw material, is 450-650 ℃ in reaction temperature, and reaction pressure is 0-0.3MPa, and the alkene weight space velocity is 1-14 hour
-1, water/alkene weight ratio is under the condition of 0.1-10, and hydrocarbon raw material carries out the olefin cracking reaction by beds and generates propylene and ethene, and wherein used catalyst is a catalyst of the present invention, with the total restatement of catalyst, comprises following component:
A) 40-75% silica alumina ratio SiO
2/ Al
2O
3Be 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer; With carry thereon
B) P elements of 0.01-10%;
C) thulium of 0.01-10%;
D) binding agent of 5-60%.
In the method for the invention, the reaction temperature preferable range is 475-625 ℃, and hydrocarbon raw material weight space velocity preferable range is 1-10 hour
-1, water/hydrocarbon raw material weight ratio is preferably 0.1-3.
In the described in the method for the invention catalyst, the weight content of described ZSM-5 molecular sieve is preferably 50-70%, and phosphorus element content is preferably 0.1-8%, and rare earth metal content is preferably 0.1-8%.The silica alumina ratio SiO of described ZSM-5 molecular sieve
2/ Al
2O
3Be preferably 20-200, the size of microcrystal of ZSM-5 molecular sieve is preferably the 10-500 nanometer, and described binding agent is preferably silica.
Catalyst of the present invention can be prepared according to method molecular sieve modified in the prior art, and preferably according to following method preparation, selecting silica for use with binding agent is that example is described:
1, moulding: with silica alumina ratio, grain size in institute of the present invention claimed range the HZSM-5 molecular sieve and an amount of sesbania powder, silicon oxide powder mix, use an amount of rare nitric acid furnishing pastel again, be extruded into the cylinder that diameter is 3 millimeter then; Through 100-120 ℃ of dry 2-10 hour, 400-800 ℃ roasting 2-20 hour and the bar of certain-length.Usually, the consumption of sesbania powder is that the 2-5% of the gross weight of molecular sieve, silica gets final product; The consumption of described rare nitric acid does not have special requirement, and the requirement that is fit to extrusion with the pastel of furnishing is advisable.
2, the interpolation of P elements: the bar that above-mentioned steps is obtained is with the aqueous solution vacuum impregnation at room temperature of the solable matter (as phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate etc.) that P elements can be provided, after dipping back bar is finished liquid-solid separation, at 90-120 ℃ of dry 1-10 hour, bar at 400-800 ℃ of roasting 2-20 hour and after must flooding P elements.
3, the interpolation of thulium: the bar that above-mentioned steps is obtained is with the rare earth metal salt solutions dipping of requirement, then at 90-120 ℃ of dry 1-10 hour, bar at 400-800 ℃ of roasting 2-20 hour and after must flooding thulium.
4, hydrothermal aging is handled: the bar behind the dipping rare earth metal class modifying element under 300-800 ℃ temperature steam treatment 2-20 hour.
5, organic acid is handled: the gained bar with solution-treated certain hours such as organic acid such as formic acid, acetate and oxalic acid, citric acids, carried out liquid-solid separation then after hydrothermal aging was handled under the uniform temperature condition.
6, catalyst roasting: got required catalyst at 400-800 ℃ of roasting 2-20 hour handle the back bar through organic acid.
In Preparation of catalysts process of the present invention, employed raw material is: the molecular sieve raw material is the molecular sieve with MEI structure, as ZSM-5 or ZSM-11, but unlike the prior art, the silica alumina ratio SiO of employed ZSM-5 molecular sieve in the catalyst of the present invention
2/ Al
2O
3Be preferably 20-200, and the grain size preferable range of molecular sieve is the 10-500 nanometer.The raw material of described modifying element phosphorus is the solable matter that P elements can be provided, such as phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate etc.The raw material of described modified metal is the soluble-salt of thulium, as nitrate, and chloride etc.Described binding agent raw material is preferably silicon oxide powder.
Catalyst of the present invention and using method have following beneficial effect:
1, because in the catalyst of the present invention, the silica alumina ratio of the molecular sieve that uses is lower, crystal grain is little, acid density height, be very beneficial for state of conflict and the generations of ideotype side reaction afterwards such as alkene oligomerization chain growth, hydrogen migration and aromatisation, therefore phosphorus and the rare earth metal method of modification together must be taked, higher ethene, propene yield could be obtained.
2, catalyst of the present invention, when obtaining higher ethene, propene yield, service life is also longer, can satisfy need of industrial production.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
The preparation method of H type ZSM-5 molecular sieve:
After the template agent is removed in 550 ℃ of following roastings, is 1: 10 ratio in molecular sieve (g) and exchange liquid (ml) with the ZSM-5 molecular screen primary powder of required silica alumina ratio and particle diameter, uses NH
4NO
3Solution (0.8mol/L) exchanges 5h in 90 ℃ of water-baths, filter; Filter cake is used with the exchange liquid of equivalent last time and is exchanged twice repeatedly again, filters, and is washed with distilled water to and does not have NO in the filtrate
3 -Exist, 110 ℃ of dryings, 550 ℃ of roastings promptly obtain the HZSM-5 molecular sieve.
Comparative Examples 1
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 250, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to above-mentioned preparation method's processing.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, use this particle of solution impregnation that contains phosphoric acid under the room temperature, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, the column type particle was through 450 ℃ of steam treatment 4 hours after the roasting, handling 5h in 80 ℃ of water-baths of 0.3mol/L acetic acid solution, after the Separation of Solid and Liquid 600 ℃ of roastings 4 hours and required catalyst A.
Comparative Examples 2
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 350, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 110 ℃ of dryings and in 520 ℃ of roastings, the column type particle was through 500 ℃ of steam treatment 5 hours behind dipping P, the Ce, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the Separation of Solid and Liquid 600 ℃ of roastings 4 hours and required catalyst B.
Comparative Examples 3
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 150, and particle diameter is 900nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, handle according to Comparative Examples 1 identical condition, required catalyst C.
Comparative Examples 4
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 180, and particle diameter is 400nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings, the column type particle was through 500 ℃ of steam treatment 5 hours behind the dipping Ce, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the Separation of Solid and Liquid 600 ℃ of roastings 4 hours and required catalyst D.
Embodiment 1
The former powder of ZSM-5 molecular sieve (silica alumina ratio is 180, and particle diameter is 400nm) is obtained the HZSM-5 molecular sieve according to the processing of above-mentioned preparation side.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 110 ℃ of dryings and in 520 ℃ of roastings, the column type particle was through 500 ℃ of steam treatment 5 hours behind dipping Ca, the Ce, handling 3h in 90 ℃ of water-baths of 0.2mol/L citric acid solution, after the Separation of Solid and Liquid 600 ℃ of roastings 4 hours and required catalyst E.
Embodiment 2
(silica alumina ratio is 80 with the ZSM-5 molecular sieve, particle diameter is 200nm) former powder handles according to above-mentioned preparation side: the sintering temperature of molecular screen primary powder is become 450 ℃ for 550 ℃, change 3h by 5h swap time, filter cake sintering temperature after the exchange changes 650 ℃ into, other condition is constant, obtains the HZSM-5 molecular sieve.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing La (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 110 ℃ of dryings and in 520 ℃ of roastings, the column type particle was through 400 ℃ of steam treatment 5 hours after the roasting, handling 8h in 90 ℃ of water-baths of 0.2mol/L acetic acid solution, after the Separation of Solid and Liquid 600 ℃ of roastings 4 hours and required catalyst F.
Embodiment 3
(silica alumina ratio is 50 with the ZSM-5 molecular sieve, particle diameter is 300nm) former powder handles according to above-mentioned preparation side: the sintering temperature of molecular screen primary powder is become 500 ℃ for 550 ℃, change 8h by 5h swap time, filter cake sintering temperature after the exchange changes 600 ℃ into, other condition is constant, obtains the HZSM-5 molecular sieve.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 110 ℃ of dryings and in 520 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing La (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 620 ℃ of roastings, the column type particle was through 450 ℃ of steam treatment 6 hours after the roasting, handling 2h in 90 ℃ of water-baths of 0.2mol/L formic acid solution, after the Separation of Solid and Liquid 610 ℃ of roastings 4 hours and required catalyst G.
Embodiment 4
(silica alumina ratio is 25 with the ZSM-5 molecular sieve, particle diameter is 100nm) former powder handles according to above-mentioned preparation side: the sintering temperature of molecular screen primary powder is become 540 ℃ for 550 ℃, filter cake sintering temperature after the exchange changes 580 ℃ into, and other condition is constant, obtains the HZSM-5 molecular sieve.With this HZSM-5 molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of ZSM-5 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing this particle of solution impregnation of phosphoric acid, after the isolated by filtration, 110 ℃ of dryings and in 500 ℃ of roastings, under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 610 ℃ of roastings, the column type particle was through 570 ℃ of steam treatment 4 hours after the roasting, handling 6h in 70 ℃ of water-baths of 0.2mol/L citric acid solution, after the Separation of Solid and Liquid 590 ℃ of roastings 4 hours and required catalyst H.
By listing in table 1 respectively the forming of catalyst that Comparative Examples 1-4 and embodiment 1-4 obtain.
Embodiment 5
Being reflected in the small stationary bed bioreactor of C _ 4 alkene catalytic pyrolysis system propylene, ethene carried out.Reaction tube is that internal diameter is that 16mm, wall thickness are the stainless steel tube of 2mm, interior dress 25ml catalyst.Before reaction was carried out, catalyst activated 2 hours in 500 ℃ under nitrogen atmosphere.After activation finished, C 4 olefin raw material and water were 3h according to the alkene air speed
-1, water/alkene weight ratio is that 0.5 condition is squeezed into preheater and reactor by micro-plunger metering pump, the maintenance reaction pressure is 0.1MPa, reaction temperature is 520 ℃ and carries out C _ 4 alkene catalytic pyrolysis system propylene, ethylene reaction.Product is got gas phase respectively after refrigerated separation, liquid product is analyzed and carry out material balance calculating.The C 4 olefin conversion ratio is for transforming the mark that the C 4 olefin quality accounts for alkene quality in the initiation material, productivity of propylene is the mark that the propylene quality accounts for C 4 olefin quality in the raw material in the product, and ethylene yield is the mark that the ethene quality accounts for C 4 olefin quality in the raw material in the product.
C 4 olefin conversion ratio and ethene, the productivity of propylene of different catalysts under the differential responses time listed in table 2.From the result of table 2 as can be seen, use catalyst of the present invention to carry out catalytic cracking reaction, the cycle of operation can obviously be longer than the catalyst of prior art.
Table one different catalysts compositing characteristic
Table two different catalysts exists C _ 4 alkene catalytic pyrolysis system ethene, propylene result down
Claims (10)
1, a kind of catalyst that is used for olefin catalytic cracking to produce propylene and ethene, it is composed of the following components:
A) the silica alumina ratio SiO of 40-75%
2/ Al
2O
3For 10-300, size of microcrystal is the ZSM-5 molecular sieve of 10-800 nanometer; With carry thereon
B) P elements of 0.01-10%;
C) thulium of 0.01-10%;
D) binding agent of 5-60%;
Wherein said percentage composition is weight percentage, and with the total restatement of catalyst.
2, catalyst according to claim 1 is characterized in that: the silica alumina ratio of described type ZSM 5 molecular sieve for more than or equal to 20 to smaller or equal to 200.
3, catalyst according to claim 2 is characterized in that: the silica alumina ratio of described type ZSM 5 molecular sieve is 20-180.
4, catalyst according to claim 1 is characterized in that: the size of microcrystal of described type ZSM 5 molecular sieve is the 10-500 nanometer.
5, catalyst according to claim 1 is characterized in that: the weight content of described P elements is 0.5-8%.
6, catalyst according to claim 1 is characterized in that: the weight content of described rare earth metal is 0.5-8%.
7, catalyst according to claim 1 is characterized in that: described rare earth metal is selected from least a in lanthanum, cerium, praseodymium and the neodymium.
8, catalyst according to claim 1 is characterized in that: described binding agent is selected from silica, aluminium oxide or their mixture.
9, a kind of method that is used for olefin catalytic cracking to produce propylene and ethene is a raw material with carbon four-carbon laurylene hydrocarbon, is 450-650 ℃ in reaction temperature, and reaction pressure is 0-0.3MPa, and the hydrocarbon raw material weight space velocity is 1-14 hour
-1, water/hydrocarbon raw material weight ratio is under the condition of 0.1-10, and hydrocarbon raw material carries out the olefin cracking reaction by beds and generates propylene and ethene, and wherein used catalyst is the described catalyst of one of claim 1-8.
10, method according to claim 9 is characterized in that: described reaction temperature is 475-625 ℃, and the weight space velocity of described hydrocarbon raw material is 1-10 hour
-1, the weight ratio of described water/hydrocarbon raw material is 0.1-3.
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| CN103058811A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for preparing olefin by utilizing fluidized bed in catalytic cracking manner |
| CN103785449A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, preparation method thereof and using method thereof |
| CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103058811A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for preparing olefin by utilizing fluidized bed in catalytic cracking manner |
| CN103058811B (en) * | 2011-10-24 | 2015-09-09 | 中国石油化工股份有限公司 | The method of fluid catalytic cracking alkene |
| CN103785449A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, preparation method thereof and using method thereof |
| CN103785449B (en) * | 2012-10-29 | 2015-10-21 | 中国石油化工股份有限公司 | Adhesiveless ZSM-5 molecular sieve catalyst and preparation and application thereof |
| CN104549436A (en) * | 2013-10-12 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogen type ZSM-5 molecular sieve catalyst as well as preparation method and application thereof |
| CN107570203A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | F- T synthesis naphtha reforming catalyst and preparation method thereof |
| CN107570203B (en) * | 2016-07-05 | 2020-05-19 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof |
| CN111068752A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | A kind of MFI structure molecular sieve rich in mesopores and preparation method thereof |
| CN111068758A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | A kind of mesoporous-rich phosphorus and rare earth-containing MFI structure molecular sieve and preparation method thereof |
| CN115974635A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | A catalytic conversion method and system for producing ethylene and propylene |
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