CN103623859B - Catalyst for producing propylene with methanol of high third second ratio and preparation method thereof is obtained under high-speed - Google Patents
Catalyst for producing propylene with methanol of high third second ratio and preparation method thereof is obtained under high-speed Download PDFInfo
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- CN103623859B CN103623859B CN201310660584.0A CN201310660584A CN103623859B CN 103623859 B CN103623859 B CN 103623859B CN 201310660584 A CN201310660584 A CN 201310660584A CN 103623859 B CN103623859 B CN 103623859B
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- molecular sieve
- methanol
- propylene
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 88
- 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 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000002270 dispersing agent Substances 0.000 claims abstract description 29
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 206010013786 Dry skin Diseases 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 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
- 238000007598 dipping method Methods 0.000 claims description 11
- 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
- 238000002156 mixing Methods 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- 238000006424 Flood reaction Methods 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011863 silicon-based powder Substances 0.000 claims description 8
- 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
- 238000000034 method Methods 0.000 abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 238000009938 salting Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 4
- 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
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002994 raw material Substances 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
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect 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
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 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
- 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
Abstract
Obtain catalyst for producing propylene with methanol of high third second ratio and preparation method thereof under the present invention relates to a kind of high-speed, this propylene catalyst comprises in mass percentage: the ZSM-5 molecular sieve of 20 ~ 86%; The dispersant of 14 ~ 80%; The P of 0 ~ 5%
2o
5; The La of 0 ~ 5%
2o
3or Ce
2o
3.Its preparation method is that to adopt dispersant to carry out effective dispersion to molecular screen primary powder shaping, then with one or more salting liquids in nonmetal, rare earth metal, carries out modification by the method for incipient impregnation to the shaping molecular sieve of dispersion.The dispersant that the present invention relates to is cheap and easy to get, method for preparing catalyst is simple; For preparing propylene from methanol reaction, reaction temperature 500 DEG C, the mass space velocity of methyl alcohol is 15h
-1high-speed under, methanol conversion is greater than 99%, and in product, Propylene Selectivity reaches 45.25%, and propylene/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 third second ratio and preparation method thereof.
Background technology
Propylene is one of important organic chemical industry's basic material being only second to 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, make the growth rate of World Propylene demand faster than ethene by propylene downstream product.
Current propylene obtains through steam cracking or catalytic cracking primarily of petroleum, and the propylene of 57% is produced by steam cracking device, and the propylene of 35% is from the catalytic cracking unit accessory substance of oil plant.Along with the continuous decrease of petroleum resources reserves, oil price constantly increases, and make the cost of material of production of propylene continue to rise, therefore each state is all improving original petroleum path technique in the world, the Non oil-based route of active research exploitation simultaneously produces propylene technology, to reduce production of propylene cost.Non oil-based route technology mainly utilizes synthesis gas through methanol or the dimethyl ether synthesizing propylene again of coal, natural gas or gasification of biomass.Current domestic ammonia from coal production capacity is seriously superfluous, and the methanol device utilization of capacity is less than 50%, and therefore exploitation has high added value preparing propylene from methanol (MTP) technique and can be superfluous methyl alcohol production capacity and provide good outlet.
MTP reaction is a kind of gas-solid heterogeneous catalytic reaction, usual employing acid molecular sieve catalyst, the eighties in 20th century, U.S. Mobil company was when studying preparing gasoline by methanol Catalytic processes, find by the change of process conditions, with the ZSM-5 molecular sieve after modifying for catalyst can by methanol conversion for low-carbon alkene.LURGI of Germany takes the lead in having carried out with ZSM-5 molecular sieve the research of preparing propylene by methanol transformation industrialization technology, they adopt fixed bed reactors with high-silicon small grain ZSM-5 molecular sieve for catalyst, ZSM-5 catalyst series is prepared by Cd and Zn modification, propylene one way is selective is about 35 ~ 40%, 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 than low, a large amount of ethene needs the problems (patent No.: CN103263944A) such as freshening and energy consumption are high.
ZSM-5 molecular sieve has larger orifice diameter, is conducive to the formation of propylene and diffusion.Large quantifier elimination shows, along with weakening of acidic site concentration and intensity, in product, low-carbon alkene (ethene, propylene and butylene) is selective will rise thereupon, but propylene and the selective of ethene rise (patent No.: CN100593434C, CN102218336B, CN103028435A) simultaneously often; Or the complex manufacturing technology of catalyst, cost higher (patent No.: CN101172246B).Therefore, under the prerequisite ensureing high methanol conversion ratio, how by catalyst performance modulation, obtaining high Propylene Selectivity and propylene/ethylene ratio, reduce 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 the shortcoming overcoming above-mentioned prior art, catalyst for producing propylene with methanol of high third second ratio and preparation method thereof is obtained under a kind of high-speed is provided, when this catalyst is used for MTP reaction, under the condition of high methanol mass space velocity, there is methanol conversion and the high advantage of product propylene/ethylene ratio.The preparation method of two of technical problem to be solved by this invention catalyst for producing propylene with methanol of high propylene/ethylene ratio under being to provide a kind of high-speed corresponding with technical solution problem one, 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:
Obtain the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise in mass percentage: the ZSM-5 molecular sieve of 20 ~ 86%; The dispersant of 14 ~ 80%; The P of 0 ~ 5%
2o
5; The La of 0 ~ 5%
2o
3or Ce
2o
3; Described dispersant is selected from one in kaolin, boehmite, pure silicon powder, Ludox or its several mixing.
Further, above ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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 one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid or its several mixing.
Above-mentioned La
2o
3and Ce
2o
3precursor be selected from the salt of solubility respectively.
Above-mentioned La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
The present invention obtains the preparation method of the catalyst for producing propylene with methanol of high third second ratio under also proposing a kind of above-mentioned high-speed, specifically comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 20 ~ 86% and the dispersant of 14 ~ 80%, shaping, then 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and 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, the temperature of above step b) and c) middle dipping is room temperature ~ 100 DEG C, and the time of dipping is 1 ~ 24 hour; In step c), drying is: 100 ~ 250 DEG C of dryings 1 ~ 24 hour.
Further, above step a), b) and c) in sintering temperature be 350 ~ 650 DEG C, roasting time is 3 ~ 24 hours.
Further, it is 5 ~ 21h that the propylene catalyst prepared by the present invention is applicable to methanol quality air speed
-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 the adding of dispersant, and effectively can disperse, add the touch opportunity of material benzenemethanol and strong acidic activity position to strong acidic site on catalyst; Oxide through dipping then can enter into the intracrystalline duct of molecular sieve, causes channel surfaces dealuminzation, thus occurs duct defect, makes aperture become large, increases the diffusion rate of product, reduce the generation of side reaction.Thus, the present invention, by controlling amount and the combination of dispersant and modifier in catalyst, effectively can modulate the product distribution 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 DEG C, and reaction pressure is normal pressure, and the mass ratio of methanol/water is 6 ~ 1:1, is 5 ~ 21h to the mass space velocity of methyl alcohol
-1, the conversion ratio of material benzenemethanol is greater than 99%, and Propylene Selectivity can reach 42 ~ 45.5%, and propylene/ethylene ratio can reach 5 ~ 8.5.Achieve good technique effect.
Detailed description of the invention
The present invention obtains the catalyst for producing propylene with methanol of high third second ratio under first proposing a kind of high-speed, this propylene catalyst comprises in mass percentage: the ZSM-5 molecular sieve of 20 ~ 86%; The dispersant of 14 ~ 80%; The P of 0 ~ 5%
2o
5; The La of 0 ~ 5%
2o
3or Ce
2o
3.Wherein said dispersant is selected from one in kaolin, boehmite, pure silicon powder, Ludox or its several mixing.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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 one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid or its several mixing.Described La
2o
3and Ce
2o
3precursor be selected from the salt of solubility respectively, be wherein preferably: La
2o
3precursor select lanthanum nitrate hexahydrate; Ce
2o
3precursor select six nitric hydrate ceriums.
The present invention obtains the preparation method of the catalyst for producing propylene with methanol of high third second ratio under also proposing a kind of above-mentioned high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 20 ~ 86% and the dispersant of 14 ~ 80%, shaping, then 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then obtain molecular sieve catalyst A with 350 ~ 650 DEG C of roastings after 3 ~ 24 hours.In this step, concrete hybrid mode is: use colloid mill to carry out sufficient homogeneous, premix to material.
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of the aqueous solution of phosphorous presoma, dipping temperature is room temperature ~ 100 DEG C, the time of dipping is 1 ~ 24 hour, then with 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then within 3 ~ 24 hours, molecular sieve catalyst B is obtained with 350 ~ 650 DEG C of roastings;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, dipping temperature is room temperature ~ 100 DEG C, the time of dipping is 1 ~ 24 hour, with 100 ~ 250 DEG C of dryings 1 ~ 24 hour, within 3 ~ 24 hours, obtains propylene catalyst of the present invention with 350 ~ 650 DEG C of roastings 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, add water with 320g boehmite and fully mix, after filtration in 150 DEG C of baking ovens dry 2 hours, Muffle furnace 600 DEG C of roastings 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 are than being 2:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 5h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 2:
Take 200g silica alumina ratio SiO
2/al
2o
3be 100, crystal grain is the HZSM-5 molecular screen primary powder of 2500nm, and adding water with 800g pure silicon powder fully mixes, after filtration in 100 DEG C of baking ovens dry 15 hours, Muffle furnace 350 DEG C of roastings 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 are than being 6:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 11h
-1, reaction temperature 520 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 3:
Take 200g silica alumina ratio SiO
2/al
2o
3be 60, crystal grain is the HZSM-5 molecular screen primary powder of 800nm, and adding water with 160g boehmite fully mixes, after filtration in 180 DEG C of baking ovens dry 5 hours, Muffle furnace 500 DEG C of roastings 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 are than being 1:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 19h
-1, reaction temperature 480 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 4:
Take 200g silica alumina ratio SiO
2/al
2o
3be 200, crystal grain is the HZSM-5 molecular screen primary powder of 5000nm, and adding water with 440g pure silicon powder fully mixes, after filtration in 240 DEG C of baking ovens dry 24 hours, Muffle furnace 350 DEG C of roastings 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 are than being 4:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 21h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 5:
Take 2000g silica alumina ratio SiO
2/al
2o
3be 100, crystal grain be 2500nm HZSM-5 molecular sieve, with the Ludox of 800g and the boehmite of 1000g, add water and fully mix dispersion, through spray ball forming, 600 DEG C of roastings obtain molecular sieve catalyst in 24 hours, and screening is chosen 40 ~ 80 orders and evaluates in fixed bed reactors.Examination reaction condition is: methyl alcohol and water quality are than being 3:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 19h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 6:
The catalyst 200g obtained in Example 2, with equi-volume impregnating, 70 DEG C of dippings 24 hours in the aqueous solution that 10g diammonium hydrogen phosphate is made into, 180 DEG C of dryings are 600 DEG C 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 are than being 4:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 15h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 7:
The catalyst 100g obtained in Example 6, with equi-volume impregnating, in the aqueous solution that 16g six nitric hydrate cerium is made into, 90 DEG C flood 16 hours, and other conditions are with embodiment 6, and methanol conversion and product distribution are in table 1.
Embodiment 8:
The catalyst 200g obtained in Example 4, with equi-volume impregnating, floods 24 hours under room temperature in the aqueous solution that 16.8g phosphoric acid dihydro amine is made into, and 150 DEG C of dryings are 600 DEG C 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 are than being 2:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 5h
-1, reaction temperature 520 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 9:
The catalyst 100g obtained in Example 8, with equi-volume impregnating, in the aqueous solution that 3g lanthanum nitrate hexahydrate is made into, 90 DEG C flood 16 hours, and other conditions are with embodiment 6, and methanol conversion and product distribution are in table 1.
Embodiment 10:
The catalyst precursor 200g obtained in Example 5, with equi-volume impregnating, 70 DEG C of dippings 16 hours in the aqueous solution that 5.3g phosphoric acid is made into, 180 DEG C of dryings are 600 DEG C 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 are than being 4:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 15h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product process is with comparative example 1 ~ 2, and methanol conversion and product distribution are in table 1.
Embodiment 11:
The catalyst 100g obtained in Example 10, with equi-volume impregnating, in the aqueous solution that 22g lanthanum nitrate hexahydrate is made into, 90 DEG C flood 16 hours, and other conditions are with embodiment 10, and methanol conversion and product distribution are in table 1.
Embodiment 12:
22g lanthanum nitrate hexahydrate in embodiment 11 is changed to 4g six nitric hydrate cerium, other conditions are with embodiment 11.
Comparative example 1
With silica alumina ratio SiO
2/al
2o
3be 60 pure ZSM-5 molecular sieve make catalyst, choose 40 ~ 80 orders through compressing tablet screening, and to evaluate in fixed bed reactors.
Comparative example 2
With silica alumina ratio SiO
2/al
2o
3be 200, crystal grain is that the pure ZSM-5 molecular sieve of 800nm makees 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 are than being 4:1 mixed feeding, and loaded catalyst 1g, feed material feed rates is 15h
-1, reaction temperature 500 DEG C, reaction system normal pressure, product carries out on-line analysis through chromatogram, and FID passage and TCD are that analysis result is normalized by associations with methane, and methanol conversion and product distribution are 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 selective very low, thus do not list in the table.
Embodiment 13
The catalyst for producing propylene with methanol obtaining high third second ratio under the high-speed of the present embodiment comprises in mass percentage: the ZSM-5 molecular sieve of 20%; The dispersant of 80%; Described dispersant is selected from kaolin.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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.
Obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 20% and the dispersant of 80%, shaping, then 100 DEG C of dryings 24 hours, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 100 DEG C of dryings 1 hour, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 14
The catalyst for producing propylene with methanol obtaining high third second ratio under the high-speed of the present embodiment comprises in mass percentage: the ZSM-5 molecular sieve of 86%; The dispersant of 14%; Described dispersant is boehmite and pure silicon powder mixture.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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.
Obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 86% and the dispersant of 14%, shaping, then 250 DEG C of dryings 24 hours, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 250 DEG C of dryings 24 hours, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 15
The catalyst for producing propylene with methanol obtaining high third second ratio under the high-speed of the present embodiment comprises in mass percentage: the ZSM-5 molecular sieve of 50%; The dispersant of 40%; The P of 5%
2o
5; The La of 5%
2o
3or Ce
2o
3; Described dispersant selects Ludox.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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 the salt of solubility respectively.Described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
Obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 50% and the dispersant of 40%, shaping, then 200 DEG C of dryings 15 hours, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 200 DEG C of dryings 20 hours, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 16
The catalyst for producing propylene with methanol obtaining high third second ratio under the high-speed of the present embodiment comprises in mass percentage: the ZSM-5 molecular sieve of 30%; The dispersant of 65%; The P of 2%
2o
5; The La of 3%
2o
3or Ce
2o
3; Described dispersant is selected from one in kaolin, boehmite, pure silicon powder, Ludox or its several mixing.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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 one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid or its several mixing.Described La
2o
3and Ce
2o
3precursor be selected from the salt of solubility respectively.Best, La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
Obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 30% and the dispersant of 65%, shaping, then 150 DEG C of dryings 20 hours, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 150 DEG C of dryings 20 hours, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain catalyst for producing propylene with methanol.
Embodiment 17
The catalyst for producing propylene with methanol obtaining high third second ratio under the high-speed of the present embodiment comprises in mass percentage: the ZSM-5 molecular sieve of 70%; The dispersant of 25%; The P of 1%
2o
5; The La of 4%
2o
3or Ce
2o
3; Described dispersant is selected from one in kaolin, boehmite, pure silicon powder, Ludox or its several mixing.Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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 one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid or its several mixing.Described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
Obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under this high-speed, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 70% and the dispersant of 25%, shaping, then 130 DEG C of dryings 22 hours, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 130 DEG C of dryings 22 hours, then roasting obtains molecular sieve catalyst B;
C) molecular sieve catalyst B step b) obtained floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain catalyst for producing propylene with methanol.
Claims (7)
1. obtain a catalyst for producing propylene with methanol for high third second ratio under high-speed, it is characterized in that, comprise in mass percentage: the ZSM-5 molecular sieve of 20 ~ 86%; The dispersant of 14 ~ 80%; The P of 0 ~ 5%
2o
5; The La of 0 ~ 5%
2o
3or Ce
2o
3; Described dispersant is selected from one in kaolin, boehmite, pure silicon powder, Ludox or its several mixing; Described ZSM-5 molecular sieve is Hydrogen ZSM-5 molecular sieve, wherein Na
2o mass percentage 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; It is 5 ~ 21h that prepared propylene catalyst is applicable to methanol quality air speed
-1high-speed under preparing propylene from methanol reaction; Described P
2o
5precursor be selected from one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid or its several mixing.
2. obtain the catalyst for producing propylene with methanol of high third second ratio under high-speed according to claim 1, it is characterized in that, described La
2o
3and Ce
2o
3precursor be selected from the salt of solubility respectively.
3. obtain the catalyst for producing propylene with methanol of high third second ratio under high-speed according to claim 2, it is characterized in that, described La
2o
3precursor select lanthanum nitrate hexahydrate; Described Ce
2o
3precursor select six nitric hydrate ceriums.
4. obtain a preparation method for the catalyst for producing propylene with methanol of high third second ratio under high-speed described in claim 1-3 any one, it is characterized in that, comprise the following steps:
A) by mass percentage be the ZSM-5 molecular sieve of 20 ~ 86% and the dispersant of 14 ~ 80%, shaping, then 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then after roasting, obtain molecular sieve catalyst A;
B) molecular sieve catalyst A step a) obtained is at the medium volume impregnation of phosphorous precursor water solution, and then with 100 ~ 250 DEG C of dryings 1 ~ 24 hour, then roasting obtains molecular sieve catalyst B;
C) by step b) the molecular sieve catalyst B that obtains floods in the aqueous solution of the soluble-salt of required lanthanum or cerium, and drying, roasting obtain propylene catalyst.
5. obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under high-speed according to claim 4, it is characterized in that, step a) middle hybrid mode is: use colloid mill to carry out sufficient homogeneous, premix to material.
6. obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under high-speed according to claim 4, it is characterized in that, step b) and c) in dipping temperature be room temperature ~ 100 DEG C, the time of dipping is 1 ~ 24 hour; Step c) in drying be: with 100 ~ 250 DEG C of dryings 1 ~ 24 hour.
7. obtain the preparation method of the catalyst for producing propylene with methanol of high third second ratio under high-speed according to claim 4, it is characterized in that, step a), b) and c) in sintering temperature be 350 ~ 650 DEG C, roasting time is 3 ~ 24 hours.
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| CN104107711A (en) * | 2014-07-18 | 2014-10-22 | 陕西煤化工技术工程中心有限公司 | Fluidized bed catalyst for preparing propylene from methanol and preparation method of fluidized bed catalyst |
| CN106608780B (en) * | 2015-10-21 | 2019-07-09 | 中国石油化工股份有限公司 | The method of oxygenatedchemicals propylene and aromatic hydrocarbons |
| CN110124731A (en) * | 2019-05-22 | 2019-08-16 | 陕西煤化工技术工程中心有限公司 | A kind of in-situ synthetic method of metal SAPO-34 molecular sieve and application |
| CN115025809B (en) * | 2022-07-14 | 2023-04-11 | 扬州晨化新材料股份有限公司 | Modified hzsm-5 molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof |
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