CN103623859A - Methanol to propylene catalyst with high propylene/ethylene ratio obtained at high airspeed and preparation method of methanol to propylene catalyst - Google Patents
Methanol to propylene catalyst with high propylene/ethylene ratio obtained at high airspeed and preparation method of methanol to propylene catalyst Download PDFInfo
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- CN103623859A CN103623859A CN201310660584.0A CN201310660584A CN103623859A CN 103623859 A CN103623859 A CN 103623859A CN 201310660584 A CN201310660584 A CN 201310660584A CN 103623859 A CN103623859 A CN 103623859A
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- catalyst
- methanol
- propylene
- molecular sieve
- ratio
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000005977 Ethylene Substances 0.000 title abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 89
- 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 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002270 dispersing agent Substances 0.000 claims abstract description 29
- 238000007598 dipping method Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000011863 silicon-based powder Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 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 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000012216 screening Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001908 cumenes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000002309 gasification Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052725 zinc 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
-
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a methanol to propylene catalyst with a high propylene/ethylene ratio obtained at a high airspeed and a preparation method of the methanol to propylene catalyst. The propylene catalyst comprises the following components by mass percentage: 20-86% of ZSN-5 molecular sieve, 14-80% of dispersing agent, 0-5% of P2O5, and 0-5% of La2O3 or Ce2O3. The preparation method of the catalyst comprises the steps of effectively dispersing and forming molecular sieve raw powder with the dispersing agent, and modifying the dispersed and formed molecular sieve by an isovolumetric dipping method with one or more saline solutions of nonmetal and rare earth metal. The dispersing agent is cheap and easy to obtain; the preparation method of the catalyst is simple; the catalyst is used for methanol to propylene reaction; the reaction temperature is 500 DEG C; when the mass airspeed of methanol is high (15h<-1>), the methanol conversion rate is greater than 99%; the propylene selectivity in a product reaches 45.25%; and the propylene to ethylene ratio can reach 8.17.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of propylene catalyst and preparation method thereof, under especially a kind of high-speed, obtain catalyst for producing propylene with methanol of high the third second ratio and preparation method thereof.
Background technology
Propylene is one of important organic chemical industry's basic material being only second to by ethene, mainly for the production of organic matters such as polypropylene, acrylonitrile, acrylic acid, expoxy propane, isopropyl alcohol, glycerine and cumenes.Recent two decades comes, and the application of propylene constantly expands, and replaces the extensive use of the synthetic resin of the nonplastic materials such as paper, steel, timber and costliness by propylene downstream product, makes the growth rate of World Propylene demand faster than ethene.
Propylene is mainly obtained through steam cracking or catalytic cracking by petroleum at present, and 57% propylene is produced by steam cracking device, and 35% propylene is from the catalytic cracking unit accessory substance of oil plant.Continuous decrease along with petroleum resources reserves, oil price constantly increases, and makes the cost of material of production of propylene continue to rise, and therefore each state is all improving original petroleum path technique in the world, the Non oil-based route of active research exploitation is simultaneously produced propylene technology, to reduce production of propylene cost.Non oil-based route technology is mainly utilized the synthesis gas through methanol of coal, natural gas or gasification of biomass system or dimethyl ether synthesizing propylene again.Current domestic coal methyl alcohol production capacity processed is seriously superfluous, methanol device utilization of capacity less than 50%, and therefore exploitation has high added value preparing propylene from methanol (MTP) technique and can be superfluous methyl alcohol production capacity good outlet is provided.
MTP reaction is a kind of gas-solid heterogeneous catalytic reaction, conventionally adopt acid molecular sieve catalyst, the eighties in 20th century, U.S. Mobil company was when research preparing gasoline by methanol Catalytic processes, discovery is by the change of process conditions, the ZSM-5 molecular sieve of take after modifying as catalyst can be low-carbon alkene by methanol conversion.Take the lead in having carried out with the ZSM-5 molecular sieve research of preparing propylene by methanol transformation industrialization technology of Germany LURGI, they adopt fixed bed reactors to take high-silicon small grain ZSM-5 molecular sieve as catalyst, by Cd and Zn modification, prepare ZSM-5 catalyst series, propylene one way is selectively 35～40% left and right, heavy component circulation Returning reactor, can make propene yield reach 71.2%.But this technique still exists, and propylene once through yield is low, propylene/ethylene is than low, a large amount of ethene needs the problem (patent No.s: CN103263944A) such as freshening and energy consumption height.
ZSM-5 molecular sieve has larger orifice diameter, is conducive to formation and the diffusion of propylene.A large amount of researchs show, along with weakening of acidic site concentration and intensity, low-carbon alkene in product (ethene, propylene and butylene) selectively will rise thereupon, but selectively simultaneously rise (patent No.: CN100593434C, CN102218336B, the CN103028435A) of propylene and ethene often; Or the complex manufacturing technology of catalyst, the higher (patent No.: CN101172246B) of cost.Therefore, guaranteeing under the prerequisite of high methanol conversion ratio, how by catalyst performance modulation, obtaining high Propylene Selectivity and propylene/ethylene ratio, reducing catalyst low cost of manufacture simultaneously, is the emphasis of propylene catalyst from methanol conversion research.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, catalyst for producing propylene with methanol obtaining under a kind of high-speed high the third second ratio and preparation method thereof is provided, when this catalyst reacts for MTP, under the condition of high methanol mass space velocity, there is methanol conversion and product propylene/ethylene than high.Two of technical problem to be solved by this invention is to provide the preparation method of the catalyst for producing propylene with methanol of high propylene/ethylene ratio under a kind of high-speed corresponding with technical solution problem one, and it is cheap and easy to get that the method has raw material, the simple advantage of preparation technology.
The object of the invention is to be achieved through the following technical solutions:
The catalyst for producing propylene with methanol that obtains high the third second ratio under this high-speed, comprises in quality percentage composition: 20～86% ZSM-5 molecular sieve; 14～80% dispersant; 0～5% P
2o
5; 0～5% La
2o
3or Ce
2o
3; Described dispersant is selected from a kind of or its several mixing in kaolin, boehmite, pure silicon powder, Ludox.
Further, above ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.
Above-mentioned P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid.
Above-mentioned La
2o
3and Ce
2o
3precursor be selected from respectively the salt of solubility.
Above-mentioned La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
The present invention also proposes to obtain under a kind of above-mentioned high-speed the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, specifically comprises the following steps:
A) ZSM-5 molecular sieve that is 20～86% by quality percentage composition and 14～80% dispersant, moulding, then 100～250 ℃ are dried 1～24 hour, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 100～250 ℃, be dried 1～24 hour, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Further, in above step a), hybrid mode is: use colloid mill to carry out sufficient homogeneous, premix to material.
Further, above step b) and c) in the temperature of dipping be room temperature～100 ℃, the time of dipping is 1～24 hour; In step c), be dried and be: 100～250 ℃ are dried 1～24 hour.
Further, above step a), b) and c) in sintering temperature be 350～650 ℃, roasting time is 3～24 hours.
Further, to be applicable to methanol quality air speed be 5～21h to the prepared propylene catalyst of the present invention
-1high-speed under preparing propylene from methanol reaction.
The present invention has following beneficial effect:
The present invention adopts ZSM-5 molecular sieve, and wherein the strong acidic site of Hydrogen ZSM-5 is preparing propylene from methanol main reaction active sites, in addition adding of dispersant, can effectively disperse strong acidic site on catalyst, has increased the touch opportunity of material benzenemethanol and strong acid active sites; Through the oxide of dipping, can enter into the intracrystalline duct of molecular sieve, cause surface, duct dealuminzation, thereby occur duct defect, make aperture become large, increase the diffusion rate of product, reduce the generation of side reaction.Thereby the present invention, by amount and the combination of dispersant and modifier in control catalyst, can distribute and effectively modulate the product of preparing propylene from methanol reaction.
Propylene catalyst of the present invention is evaluated by fixed-bed micro-reactor, take methyl alcohol as raw material, and water is diluent, and reaction temperature is 480～520 ℃, and reaction pressure is normal pressure, and the mass ratio of methanol/water is 6～1:1, to the mass space velocity of methyl alcohol, is 5～21h
-1, the conversion ratio of material benzenemethanol is greater than 99%, and Propylene Selectivity can reach 42～45.5%, and propylene/ethylene specific energy reaches 5～8.5.Obtained good technique effect.
The specific embodiment
First the present invention proposes to obtain under a kind of high-speed the catalyst for producing propylene with methanol of high the third second ratio, and this propylene catalyst comprises in quality percentage composition: 20～86% ZSM-5 molecular sieve; 14～80% dispersant; 0～5% P
2o
5; 0～5% La
2o
3or Ce
2o
3.Wherein said dispersant is selected from a kind of or its several mixing in kaolin, boehmite, pure silicon powder, Ludox.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.Described P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid.Described La
2o
3and Ce
2o
3precursor be selected from respectively the salt of solubility, be wherein preferably: La
2o
3precursor select lanthanum nitrate hexahydrate; Ce
2o
3precursor select six nitric hydrate ceriums.
The present invention also proposes to obtain under a kind of above-mentioned high-speed the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, comprises the following steps:
A) ZSM-5 molecular sieve that is 20～86% by quality percentage composition and 14～80% dispersant, moulding, then 100～250 ℃ are dried 1～24 hour, then after 3～24 hours, obtain molecular sieve catalyst A with 350～650 ℃ of roastings.In this step, concrete hybrid mode is: use colloid mill to carry out sufficient homogeneous, premix to material.
B) the medium volume dipping of the aqueous solution at phosphorous presoma by the resulting molecular sieve catalyst A of step a), dipping temperature is room temperature～100 ℃, the time of dipping is 1～24 hour, then with 100～250 ℃, be dried 1～24 hour, then within 3～24 hours, obtain molecular sieve catalyst B with 350～650 ℃ of roastings;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, dipping temperature is room temperature～100 ℃, the time of dipping is 1～24 hour, with 100～250 ℃ dry 1～24 hour, with 350～650 ℃ of roastings, within 3～24 hours, obtain propylene catalyst of the present invention again.It is 5～21h that prepared propylene catalyst is applicable to methanol quality air speed
-1high-speed under preparing propylene from methanol reaction.
Below in conjunction with embodiment, the present invention is described in more detail:
Embodiment 1:
Take 200g silica alumina ratio SiO
2/al
2o
3be 25, crystal grain is the HZSM-5 molecular screen primary powder of 200nm, adding water with 320g boehmite fully mixes, after filtration, in 150 ℃ of baking ovens, be dried 2 hours, 600 ℃ of roastings of Muffle furnace 3 hours, 40～80 order catalyst were chosen in compressing tablet screening, and evaluate in fixed bed reactors, examination reaction condition is: methyl alcohol and water quality ratio are 2:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 5h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 2:
Take 200g silica alumina ratio SiO
2/al
2o
3be 100, the HZSM-5 molecular screen primary powder that crystal grain is 2500nm, adds water with 800g pure silicon powder and fully mixes, after filtration, in 100 ℃ of baking ovens, be dried 15 hours, 350 ℃ of roastings of Muffle furnace 6 hours, 40～80 order catalyst were chosen in compressing tablet screening, and evaluate in fixed bed reactors.Examination reaction condition is: methyl alcohol and water quality ratio are 6:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 11h
-1, 520 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 3:
Take 200g silica alumina ratio SiO
2/al
2o
3be 60, the HZSM-5 molecular screen primary powder that crystal grain is 800nm, adds water with 160g boehmite and fully mixes, after filtration, in 180 ℃ of baking ovens, be dried 5 hours, 500 ℃ of roastings of Muffle furnace 16 hours, 40～80 order catalyst were chosen in compressing tablet screening, and evaluate in fixed bed reactors.Examination reaction condition is: methyl alcohol and water quality ratio are 1:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 19h
-1, 480 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 4:
Take 200g silica alumina ratio SiO
2/al
2o
3be 200, the HZSM-5 molecular screen primary powder that crystal grain is 5000nm, adds water with 440g pure silicon powder and fully mixes, after filtration, in 240 ℃ of baking ovens, be dried 24 hours, 350 ℃ of roastings of Muffle furnace 24 hours, 40～80 order catalyst were chosen in compressing tablet screening, and evaluate in fixed bed reactors.Examination reaction condition is: methyl alcohol and water quality ratio are 4:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 21h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 5:
Take 2000g silica alumina ratio SiO
2/al
2o
3be 100, the HZSM-5 molecular sieve that crystal grain is 2500nm, with the Ludox of 800g and the boehmite of 1000g, add water and fully mix dispersion, through spray ball forming, 600 ℃ of roastings obtain molecular sieve catalyst for 24 hours, and screening is chosen 40～80 orders and evaluates in fixed bed reactors.Examination reaction condition is: methyl alcohol and water quality ratio are 3:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 19h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 6:
Get the catalyst 200g obtaining in embodiment 2, with equi-volume impregnating, in the aqueous solution being made at 10g diammonium hydrogen phosphate, 70 ℃ of dippings are 24 hours, and 180 ℃ of dry 600 ℃ of roastings 6 hours again after 15 hours, obtain molecular sieve catalyst; 40～80 order catalyst are chosen in screening, and evaluate in fixed bed reactors, and examination reaction condition is: methyl alcohol and water quality ratio are 4:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 15h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 7:
Get the catalyst 100g obtaining in embodiment 6, with equi-volume impregnating, in the aqueous solution being made at 16g six nitric hydrate ceriums, 90 ℃ flood 16 hours, and other conditions are with embodiment 6, and methanol conversion and product distribute in Table 1.
Embodiment 8:
Get the catalyst 200g obtaining in embodiment 4, with equi-volume impregnating, in the aqueous solution being made into, flood 24 hours under room temperature at 16.8g phosphoric acid dihydro amine, 150 ℃ of dry 600 ℃ of roastings 3 hours again after 15 hours, obtain molecular sieve catalyst; 40～80 order catalyst are chosen in screening, and evaluate in fixed bed reactors, and examination reaction condition is: methyl alcohol and water quality ratio are 2:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 5h
-1, 520 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 9:
Get the catalyst 100g obtaining in embodiment 8, with equi-volume impregnating, in the aqueous solution being made at 3g lanthanum nitrate hexahydrate, 90 ℃ flood 16 hours, and other conditions are with embodiment 6, and methanol conversion and product distribute in Table 1.
Embodiment 10:
Get the catalyst precursor 200g obtaining in embodiment 5, with equi-volume impregnating, in the aqueous solution being made at 5.3g phosphoric acid, 70 ℃ of dippings are 16 hours, and 180 ℃ of dry 600 ℃ of roastings 6 hours again after 15 hours, obtain molecular sieve catalyst; 40～80 order catalyst are chosen in screening, and evaluate in fixed bed reactors, and examination reaction condition is: methyl alcohol and water quality ratio are 4:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 15h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product is processed with comparative example 1～2, and methanol conversion and product distribute in Table 1.
Embodiment 11:
Get the catalyst 100g obtaining in embodiment 10, with equi-volume impregnating, in the aqueous solution being made at 22g lanthanum nitrate hexahydrate, 90 ℃ flood 16 hours, and other conditions are with embodiment 10, and methanol conversion and product distribute in Table 1.
Embodiment 12:
22g lanthanum nitrate hexahydrate in embodiment 11 is changed to 4g six nitric hydrate ceriums, and other conditions are with embodiment 11.
Comparative example 1
With silica alumina ratio SiO
2/al
2o
3be that 60 pure ZSM-5 molecular sieve is made catalyst, through compressing tablet screening, choose 40～80 orders, and evaluate in fixed bed reactors.
Comparative example 2
With silica alumina ratio SiO
2/al
2o
3be 200, the pure ZSM-5 molecular sieve that crystal grain is 800nm is made catalyst, chooses 40～80 orders, and evaluate in fixed bed reactors through compressing tablet screening.
The evaluation response condition of comparative example is: methyl alcohol and water quality ratio are 4:1 mixed feeding, loaded catalyst 1g, and raw material charging rate is 15h
-1, 500 ℃ of reaction temperatures, reaction system normal pressure, product carries out on-line analysis through chromatogram, and FID passage and TCD be take methane and analysis result are normalized as associations, and methanol conversion and product distribute in Table 1.
The reaction result of the preparing propylene by methanol transformation of table 1 comparative example 1-2 and embodiment 1-12
Note: in table 1, the component of product distribution less than 100% is CO, CO
2and C
2h
6, due to selectively very low, thereby in form, do not list.
Embodiment 13
The catalyst for producing propylene with methanol that obtains high the third second ratio under the high-speed of the present embodiment comprises in quality percentage composition: 20% ZSM-5 molecular sieve; 80% dispersant; Described dispersant is selected from kaolin.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.
The preparation method who obtains the catalyst for producing propylene with methanol of high the third second ratio under this high-speed, comprises the following steps:
A) ZSM-5 molecular sieve that is 20% by quality percentage composition and 80% dispersant, moulding, then 100 ℃ are dried 24 hours, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 100 ℃, be dried 1 hour, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 14
The catalyst for producing propylene with methanol that obtains high the third second ratio under the high-speed of the present embodiment comprises in quality percentage composition: 86% ZSM-5 molecular sieve; 14% dispersant; Described dispersant is boehmite and pure silicon powder mixture.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.
The preparation method who obtains the catalyst for producing propylene with methanol of high the third second ratio under this high-speed, comprises the following steps:
A) ZSM-5 molecular sieve that is 86% by quality percentage composition and 14% dispersant, moulding, then 250 ℃ are dried 24 hours, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 250 ℃, be dried 24 hours, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 15
The catalyst for producing propylene with methanol that obtains high the third second ratio under the high-speed of the present embodiment comprises in quality percentage composition: 50% ZSM-5 molecular sieve; 40% dispersant; 5% P
2o
5; 5% La
2o
3or Ce
2o
3; Described dispersant selects Ludox.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.Described P
2o
5precursor be selected from phosphoric acid.Described La
2o
3and Ce
2o
3precursor be selected from respectively the salt of solubility.Described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
The preparation method who obtains the catalyst for producing propylene with methanol of high the third second ratio under this high-speed, comprises the following steps:
A) ZSM-5 molecular sieve that is 50% by quality percentage composition and 40% dispersant, moulding, then 200 ℃ are dried 15 hours, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 200 ℃, be dried 20 hours, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 16
The catalyst for producing propylene with methanol that obtains high the third second ratio under the high-speed of the present embodiment comprises in quality percentage composition: 30% ZSM-5 molecular sieve; 65% dispersant; 2% P
2o
5; 3% La
2o
3or Ce
2o
3; Described dispersant is selected from a kind of or its several mixing in kaolin, boehmite, pure silicon powder, Ludox.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid.Described La
2o
3and Ce
2o
3precursor be selected from respectively the salt of solubility.Best, La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
The preparation method who obtains the catalyst for producing propylene with methanol of high the third second ratio under this high-speed, comprises the following steps:
A) ZSM-5 molecular sieve that is 30% by quality percentage composition and 65% dispersant, moulding, then 150 ℃ are dried 20 hours, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 150 ℃, be dried 20 hours, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 17
The catalyst for producing propylene with methanol that obtains high the third second ratio under the high-speed of the present embodiment comprises in quality percentage composition: 70% ZSM-5 molecular sieve; 25% dispersant; 1% P
2o
5; 4% La
2o
3or Ce
2o
3; Described dispersant is selected from a kind of or its several mixing in kaolin, boehmite, pure silicon powder, Ludox.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.Described P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid.Described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
The preparation method who obtains the catalyst for producing propylene with methanol of high the third second ratio under this high-speed, comprises the following steps:
A) ZSM-5 molecular sieve that is 70% by quality percentage composition and 25% dispersant, moulding, then 130 ℃ are dried 22 hours, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 130 ℃, be dried 22 hours, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
Claims (10)
1. a catalyst for producing propylene with methanol that obtains high the third second ratio under high-speed, is characterized in that, in quality percentage composition, comprises: 20～86% ZSM-5 molecular sieve; 14～80% dispersant; 0～5% P
2o
5; 0～5% La
2o
3or Ce
2o
3; Described dispersant is selected from a kind of or its several mixing in kaolin, boehmite, pure silicon powder, Ludox.
2. under high-speed according to claim 1, obtain the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that, described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o quality percentage composition is not higher than 0.1%; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 25～250, crystal grain is 20～5000nm.
3. under high-speed according to claim 1, obtain the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that described P
2o
5precursor be selected from a kind of or its several mixing in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid.
4. under high-speed according to claim 1, obtain the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that described La
2o
3and Ce
2o
3precursor be selected from respectively the salt of solubility.
5. under high-speed according to claim 4, obtain the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
6. described in claim 1-5 any one, under high-speed, obtain a preparation method for the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that, comprise the following steps:
A) ZSM-5 molecular sieve that is 20～86% by quality percentage composition and 14～80% dispersant, moulding, then 100～250 ℃ are dried 1～24 hour, then after roasting, obtain molecular sieve catalyst A;
B) the resulting molecular sieve catalyst A of step a) is flooded at the medium volume of phosphorous precursor water solution, then with 100～250 ℃, be dried 1～24 hour, then roasting obtains molecular sieve catalyst B;
C) the resulting molecular sieve catalyst B of step b) is flooded in the aqueous solution of the soluble-salt of required lanthanum or cerium, drying, roasting obtain catalyst for producing propylene with methanol.
7. under high-speed according to claim 6, obtain the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that, in step a), hybrid mode is: use colloid mill to carry out sufficient homogeneous, premix to material.
8. under high-speed according to claim 6, obtain the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that step b) and c) in dipping temperature be room temperature～100 ℃, the time of dipping is 1～24 hour; In step c), be dried and be: 100～250 ℃ are dried 1～24 hour.
9. under high-speed according to claim 6, obtain the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that step a), b) and c) in sintering temperature be 350～650 ℃, roasting time is 3～24 hours.
10. under high-speed according to claim 6, obtain the preparation method of the catalyst for producing propylene with methanol of high the third second ratio, it is characterized in that, it is 5～21h that prepared propylene catalyst is applicable to methanol quality air speed
-1high-speed under preparing propylene from methanol reaction.
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