CN104923284A - Molded molecular sieve catalyst and preparation method and application thereof - Google Patents
Molded molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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- CN104923284A CN104923284A CN201410100278.6A CN201410100278A CN104923284A CN 104923284 A CN104923284 A CN 104923284A CN 201410100278 A CN201410100278 A CN 201410100278A CN 104923284 A CN104923284 A CN 104923284A
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- molecular sieve
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- roasting
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- binding agent
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 151
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 51
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910001593 boehmite Inorganic materials 0.000 claims description 28
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 24
- 238000007493 shaping process Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 235000019270 ammonium chloride 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 241000219782 Sesbania Species 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a molded molecular sieve catalyst and a preparation method and an application thereof; the method includes the following steps: (1) filtering, washing and separating a molecular sieve solution after crystallization in molecular sieve synthesis, to obtain a molecular sieve slurry; preferably, washing and separating the molecular sieve with membrane separation; (2) mixing the molecular sieve slurry obtained in the step (1) with a binder, adding an extrusion aid and an adhesive solvent, and processing and molding to obtained a molded catalyst; and (3) drying, carrying out ion exchange and roasting the molded catalyst obtained in the step (2), to obtain the molded molecular sieve catalyst, wherein preferably, the drying temperature is 50-120 DEG C, more preferably 100 DEG C; and preferably, the roasting is carried out for 5-7 h at the temperature of 550-650 DEG C, more preferably the roasting is carried out for 6 h at the temperature of 600 DEG C. The catalyst prepared by the method has the characteristic of high dispersion of an active phase, the performance of the catalyst is greatly improved, and the activity in methanol conversion preparation of propylene is more excellent.
Description
Technical field
The present invention relates to molecular sieve field, specifically, relate to a kind of molded molecular sieve catalyst and its preparation method and application.
Background technology
Propylene is as a kind of important basic chemical raw materials, and its traditional mode of production depends on petroleum refining process, and the shortage of petroleum resources facilitates the development of Non oil-based route propylene production technology.In recent years, be that raw material is subject to growing interest through solid acid catalyst preparing propylene transformed (MTP) technique by coal-based methanol/or dimethyl ether.As production of propylene new technology, MTP technique has that raw material sources are extensive, propene yield is high, easily realize the advantage such as polypropylene or other acryloyl derivative coproduction, especially the many coals of China, weak breath, oil-poor energy resource structure is applicable to, there is important using value, be the important supplement in following China propylene source, even likely become the main source of China's propylene.
ZSM-5 molecular sieve has the intersection ten-ring duct composition that the sinusoidal duct (0.51nm*0.54nm) of ten-ring straight hole road (0.54nm*0.56nm) and ten-ring is formed, and is widely used in the fields such as petroleum refining, fine chemistry industry and environmental protection.Due to the pore passage structure of its uniqueness, high heat endurance and hydrothermal stability, especially its framework si-al ratio can regulate and control in a big way, is considered to first-selected catalyst activity component at present in MTP reaction.At present, the emphasis of people's research mostly concentrates on high silica alumina ratio nano-ZSM-5 molecular sieve, and the preparation about ZSM-5 molecular sieve with small crystal grains has a large amount of documents and patent report.Such as, CN101269340A discloses the preparation method that silica alumina ratio is greater than the ZSM-5 zeolite crystal of the submicron grain size of 1000; CN101624192A discloses the preparation method of crystallite dimension at the ZSM-5 zeolite of 25 ~ 250 nanometers of silica alumina ratio 250 ~ 1150.But because the average grain diameter of powder is less, separation difficulty, is easy to reunite, cannot be directly used in commercial fixed bed reactor, must be made by processing and forming and there is suitable shape, good mechanical strength and have greater activity and optionally catalyst.So shaping of catalyst problem becomes an important subject of commercial fixed bed reaction technology, be also the technology secret of each large patent business UOP, Mobil etc. simultaneously, in disclosed document, do not reveal any report.
For fixed bed reactors, because extrusion molding production capacity is large, shaping expense is low, and be easy to form production line, can produce the catalyst of various diameter and different section shape by changing orifice plate, therefore this forming method is adopted in a large number.CN103041852A provides a kind of extruded moulding method of TS-1 titanium-silicon molecular sieve catalyst, former for TS-1 powder, Ludox, extrusion aid and NACF is it is characterized in that to mix, extruded moulding, the NACF that this patent adopts plays good pore-creating effect, effectively improves the activity of catalyst.But there is molecular sieve and mix inequality with binding agent in this traditional former powder straight forming method, causes particle aggregation, the shortcoming of active component bad dispersibility.(the ChemCatChem2013 such as PedroCastano, 5,2827 – 2831) research in point out, molecular sieve avtive spot distribution more even, it is lower fewer with carbon deposition quantity at the carbon distribution generating rate of the reaction of Methanol hydrocarbon (MTH), thus demonstrates better activity.CN101940944A provide a kind of utilize Crystallization of Zeolite after slurries prepare the method for molded molecular sieve catalyst, zeolite product and crystallization slurries are isolated from the slurries of crystallization molecular sieve, and both mixed with binding agent and obtain catalyst pulp, then sizing material forming is obtained catalyst.This method is by recycling crystallization slurries, save investment, decrease environmental pollution, but what adopt due to this patent is that spraying dry prepares fluidized catalyst, the mechanical performance of gained catalyst is applicable to fluidized-bed process and is not suitable for fixed-bed process catalyst.Based on the ZSM-5 MTP catalyst that is active component the technological process that is suitable for be fixed-bed process.So need to develop a kind of forming method that molecular sieve can be made to mix with binding agent, and complete under the condition of extruded moulding technique.
Summary of the invention
One object of the present invention is the preparation method providing a kind of molded molecular sieve catalyst;
Another object of the present invention is to the molded molecular sieve catalyst providing described method to prepare;
Another object of the present invention is to provide the application of molded molecular sieve catalyst of the present invention in methanol/dimethyl ether conversion propylene;
Another object of the present invention is to provide application molded molecular sieve catalyst of the present invention to take methanol/dimethyl ether as the method that propylene prepared by raw material.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of molded molecular sieve catalyst, described method comprises the steps:
(1) filtration washing separation is carried out to the molecular sieve solution after crystallization in Zeolite synthesis, obtain molecular sieve pulp;
(2) mixed with binding agent by the molecular sieve pulp that step (1) obtains, add extrusion aid and peptizing agent, machine-shaping obtains shaping catalyst;
(3), after the shaping catalyst that step (2) obtains being carried out drying, ion-exchange and roasting, described molded molecular sieve catalyst is obtained;
According to method of the present invention, the silica alumina ratio of molecular sieve crystal contained in the preferred described molecular sieve pulp of the present invention is 50-1000;
Wherein the mol ratio of the further preferred described molecular sieve crystal of the present invention is 100-500, and grain size is at 50 ~ 500nm;
Wherein the present invention more preferably described molecular sieve crystal be ZSM-5 molecular sieve.
According to method of the present invention, the preferred described binding agent of the present invention is selected from activated alumina (i.e. γ-Al
2o
3), one in boehmite and kaolin.
Wherein said activated alumina, boehmite and kaolin are existing conventional products, and namely existing commercially available prod can be used for the present invention.
According to method of the present invention, the preferred described extrusion aid of the present invention is selected from the one in sesbania powder, graphite powder and glycerine.
According to method of the present invention, the preferred described peptizing agent of the present invention is selected from the one in nitric acid, hydrochloric acid, phosphoric acid, oxalic acid and citric acid.
According to method of the present invention, in step (1), described filtration washing is separated into this area routine operation, conventional filter method for example can be used to be separated, wash away the compositions such as template in water and alkali lye), and retain remaining molecular sieve pulp (mixed solution of molecular sieve crystal and water);
For example the present invention preferably uses membrane filtration to carry out filtration washing separation to molecular sieve again; It can be for example more specifically the film of aperture 20-200.
It is other compositions in order to remove in molecular sieve solution except molecular sieve crystal that the present invention carries out that filtration washing is separated, such as remaining template and alkali lye.
Wherein the present invention preferably just can stop washing when the molecular sieve pulp obtained (filtrate) pH is between 7-8.
Wherein the present invention also preferred water carry out filtration washing separation, be more preferably deionized water.
The weight percent content wherein obtaining water in molecular sieve pulp after preferable separate of the present invention be 10%-60%(in molecular sieve pulp gross weight for 100%).
It can be join in membrane separation device by the molecular sieve solution obtained after crystallization that wherein said filtration washing is separated, and finally can complete filtration washing step when the molecular sieve pulp pH on film is 7-8;
Also can be join in centrifuge by the molecular sieve solution obtained after crystallization, filtration washing, can complete filtration washing step when molecular sieve pulp pH is 7-8;
Even also can be obtain molecular sieve crystal by after molecular sieve solution filtration washing, then add water and be mixed with molecular sieve pulp.
According to method of the present invention, in step (1), described machine-shaping is this area routine operation, such as can be kneaded and formed, and is shaped to any conventional shape, such as is shaped to bar shaped, granulated etc.; More specifically for example molecular sieve pulp is mixed with binding agent, mediate after adding extrusion aid and peptizing agent, kneaded wet feed group is put into banded extruder extruded moulding.
Wherein the present invention preferably mediates 30-50min further.
According to method of the present invention, in preferred steps of the present invention (2), with parts by weight, molecular sieve butt in molecular sieve pulp is 30-80 part, binding agent is 20-70 part, the addition of extrusion aid is the 1-5% of molecular sieve butt and binding agent gross mass, and in peptizing agent and molecular sieve pulp, the gross mass of water and molecular sieve butt and binding agent total mass ratio are 0.3 ~ 0.6.
According to method of the present invention, the molecular sieve butt wherein in further preferred molecular sieve slurries is 60-80 part, and binding agent is 20-40 part.
According to method of the present invention, step (3) described drying is this area routine operation, and the temperature that the present invention is preferably dry is 50-120 DEG C;
Wherein the temperature of more preferably described drying is 100 DEG C;
According to method of the present invention, also preferred steps (3) described roasting is roasting 5-7h at 550-650 DEG C;
Wherein be more preferably roasting 6h at 600 DEG C.
According to method of the present invention, the ion-exchange of preferred steps of the present invention (3) is for carry out ion-exchange with aqueous ammonium chloride solution;
Wherein preferably at 90 DEG C, exchange 2h;
Wherein more preferably the molar concentration of ammonium chloride is 1mol/L in described aqueous ammonium chloride solution.
On the other hand, present invention also offers the molded molecular sieve catalyst that any described method of the present invention prepares.
Binding agent on the one hand, present invention also offers the application of molded molecular sieve catalyst of the present invention in methanol/dimethyl ether conversion propylene again;
According to application of the present invention, the Propylene Selectivity in wherein particular methanol/dimethyl ether conversion propylene is 35-40%, ethene and propylene overall selectivity are 48-52%.
Another aspect, present invention also offers application molded molecular sieve catalyst of the present invention take methanol/dimethyl ether as the method that propylene prepared by raw material, and described method comprises following reaction condition: temperature 470 DEG C, normal pressure, methanol feeding mass space velocity 3h
-1;
According to method of the present invention, wherein particular methanol/dimethyl ether is the raw material Propylene Selectivity prepared in propylene be 35-40%, ethene and propylene overall selectivity is 48-52%.
For contributing to understanding the present invention, below define some terms.These terms defined have the implication that those of ordinary skill in the related art of the present invention understand usually.
Unless otherwise indicated, herein " shaping " to refer to the raw material of definite composition by compressing, extrude, the method such as rotation, be processed into operation or the step of the beaded catalyst with definite shape, size and mechanical strength.
Unless otherwise indicated, " binding agent " refers to the viscosity that can to increase in the preparation of catalyst in molecular sieve molded process herein, and improves the material of shaping rear catalyst intensity.
Unless otherwise indicated, herein " extrusion aid " refers to and contribute to catalyst raw material by the raw material required for forming operation in catalyst preparing.
Unless otherwise indicated, " peptizing agent " refers to and can be partly dissolved aluminium oxide in catalyst preparing herein, the raw material of intensity when simultaneously can improve shaping.
Unless otherwise indicated, herein the solid that " butt " is remaining after referring to the water contained by molecular sieve pulp deduction synthesized.
Unless otherwise indicated, herein " molecular sieve pulp " refers to that the molecular sieve solution after to crystallization carries out the mixed serum of molecular sieve crystal that membrane filtration obtains and water.Wherein be understandable that, " methanol/dimethyl ether " in the present invention in methanol/dimethyl ether conversion propylene represents with methyl alcohol and/or dimethyl ether for raw material prepares propylene by conversion.
Slurries after crystallization during the synthesis of molecular sieve that the present invention utilizes can be the slurries obtained after the synthesis of molecular sieve crystallization of any routine of prior art, are the slurries that synthesis ZSM-5 molecular sieve obtains after crystallization by it; Can be for example specifically following Zeolite synthesis:
At ambient temperature, add NaOH, sodium metaaluminate, 4-propyl bromide and silochrom successively in deionized water, stir in after gel state, be encased in polytetrafluoro reactor and carry out crystallization to prepare molecular sieve.
In sum, the invention provides a kind of molded molecular sieve catalyst and Synthesis and applications thereof.Molded molecular sieve catalyst tool of the present invention has the following advantages:
The uniformity that the present invention is based on active Entropy density deviation in catalyst directly has influence on the key issues such as its life-span at the activity of preparing propylene from methanol reaction, the selective and catalyst of primary product, pretreatment slurry and binding agent straight forming is adopted to prepare highly active catalyst for producing propylene with methanol, not only simplify operation sequence, and the catalyst prepared of the method has the feature of active phase high dispersive, substantially increases the performance of catalyst.
In the present invention, compare traditional molding methods, binding agent evenly be distributed in molecular sieve surface, thus make catalyst have higher Propylene Selectivity, and improve its anticoking capability, the activity in preparing propylene by methanol transformation is more excellent.
Accompanying drawing explanation
Fig. 1 is the SEM spectrogram of the catalyst that comparative example (Z1) molds.
Fig. 2 is embodiment 2(HZ2) the SEM spectrogram of catalyst that molds.
Detailed description of the invention
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Embodiment HZ1-HZ4
Choosing silica alumina ratio is 200, the molecular sieve solution newly going out still after crystallization that grain size is about 150nm carries out membrane filtration, and filtrate PH between 7-8 after, obtaining water content is respectively 10%, 25%, 35%, the molecular sieve pulp of 50%, by these slurries and boehmite, salpeter solution and sesbania powder are by following mass ratio mixing, molecular sieve butt and boehmite mass ratio get 7:3, salpeter solution (water containing in molecular sieve solution) quality is 50% of molecular sieve butt and boehmite gross mass, sesbania opaque amount is 1% of molecular sieve butt and boehmite gross mass, extruded moulding is carried out after stirring, roasting 6 hours at 600 DEG C after drying at 100 DEG C.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ1-HZ4.Wherein the SEM spectrogram of HZ2 as shown in Figure 2.
Embodiment HZ5-HZ7
Choosing silica alumina ratio is 500, grain size is 50nm, water content is 10%, the molecular sieve pulp of PH between 7-8, by these slurries and kaolin, salpeter solution and sesbania powder are by following mass ratio mixing, molecular sieve butt and kaolin mass ratio get 8:2,7:3,6:4, salpeter solution (water containing in molecular sieve pulp) quality is 50% of molecular sieve butt and boehmite gross mass, sesbania opaque amount is 1% of molecular sieve butt and boehmite gross mass, extruded moulding is carried out, roasting 6 hours at 600 DEG C after drying at 100 DEG C after stirring.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ5-HZ7.
Embodiment HZ8-HZ9
Choosing silica alumina ratio is 100, grain size is 500nm, water content is 25%, the molecular sieve pulp of PH between 7-8 (, by these slurries respectively with activated alumina, kaolin, salpeter solution and sesbania powder are by following mass ratio mixing, molecular sieve butt and binding agent mass ratio get 7:3, salpeter solution (water containing in molecular sieve pulp) quality is 50% of molecular sieve butt and binding agent gross mass, sesbania opaque amount is 1% of molecular sieve butt and binding agent gross mass, extruded moulding is carried out, roasting 6 hours at 600 DEG C after drying at 100 DEG C after stirring.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ8-HZ9.
Embodiment HZ10-HZ13
Choosing silica alumina ratio is 300, grain size is 300nm, water content is 35%, the molecular sieve pulp of PH between 7-8, by these slurries and boehmite, salpeter solution and graphite powder are by following mass ratio mixing, molecular sieve butt and boehmite mass ratio get 7:3, salpeter solution (water containing in molecular sieve solution) quality is 30% of molecular sieve butt and boehmite gross mass, 38%, 45%, 60%, graphite powder quality is 1% of molecular sieve butt and boehmite gross mass, extruded moulding is carried out after stirring, roasting 6 hours at 600 DEG C after drying at 100 DEG C.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ10-HZ13.
Embodiment HZ14-HZ17
Choosing silica alumina ratio is 400, grain size is 400nm, water content is 50%, the molecular sieve pulp of PH between 7-8, by these slurries and boehmite, salpeter solution and glycerine are by following mass ratio mixing, molecular sieve butt and boehmite mass ratio get 7:3, hydrochloric acid, phosphoric acid, oxalic acid, citric acid solution (water containing in molecular sieve solution) quality is 50% of molecular sieve butt and boehmite gross mass, qualities of glycerin is 1% of molecular sieve butt and boehmite gross mass, extruded moulding is carried out after stirring, roasting 6 hours at 600 DEG C after drying at 100 DEG C.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ14-HZ17.
Embodiment HZ18-HZ21
Choosing silica alumina ratio is 100, grain size is 50nm, water content is 25%, the molecular sieve pulp of PH between 7-8, by these slurries and boehmite, phosphoric acid solution and sesbania powder are by following mass ratio mixing, molecular sieve butt and boehmite mass ratio get 7:3, phosphoric acid solution (water containing in molecular sieve solution) quality is 50% of molecular sieve butt and boehmite gross mass, sesbania opaque amount is 2% of molecular sieve butt and boehmite gross mass, 3%, 4%, 5%, extruded moulding is carried out after stirring, roasting 6 hours at 600 DEG C after drying at 100 DEG C.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst HZ18-HZ21.
Comparative example Z1
Choosing silica alumina ratio is 200, grain size is about the molecular screen primary powder of 150nm, by this molecular screen primary powder and boehmite, salpeter solution and sesbania powder are by following mass ratio mixing, molecular sieve powder and boehmite mass ratio get 7:3, and salpeter solution quality is 50% of molecular sieve powder and boehmite gross mass, and sesbania opaque amount is 1% of molecular sieve powder and boehmite gross mass, extruded moulding is carried out, roasting 6 hours at 600 DEG C after drying at 100 DEG C after stirring.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst Z1.
Comparative example Z2
Choosing silica alumina ratio is 200, grain size is 150nm, water content is 25%, the molecular sieve pulp of PH between 7-8, by these slurries and activated alumina, hydrochloric acid solution is by following mass ratio mixing, molecular sieve butt and activated alumina mass ratio get 9:1, hydrochloric acid solution (water containing in molecular sieve solution) quality is 20% of molecular sieve butt and boehmite gross mass, carries out extruded moulding after stirring, roasting 6 hours at 600 DEG C after drying at 100 DEG C.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst Z2.
Comparative example Z3
Choosing silica alumina ratio is 200, grain size is 150nm, water content is 25%, the molecular sieve pulp of PH between 7-8, by these slurries and activated alumina, hydrochloric acid solution and graphite powder are by following mass ratio mixing, molecular sieve butt and activated alumina mass ratio get 5:5, hydrochloric acid solution (water containing in molecular sieve solution) quality is 70% of molecular sieve butt and boehmite gross mass, graphite powder quality is 10% of molecular sieve butt and boehmite gross mass, extruded moulding is carried out, roasting 6 hours at 600 DEG C after drying at 100 DEG C after stirring.The NH of gained sample 1mol/L
4cl exchanges 2 hours at 90 DEG C, with same condition drying and roasting.After carrying out twice exchange, finally obtain shaping molecular sieve catalyst Z3.
Fig. 2 shows, the SEM figure of HZ2 shows in forming method of the present invention, binding agent is dispersed to be attached on sieve particle, and Fig. 1 display, the SEM figure of comparative example Z1 then shows in tradition is shaping, because binding agent does not mix with molecular sieve powder, causes the distribution of molecular sieve powder and binding agent on catalyst also uneven, some places only have molecule powder, and both some places have.
The pore structure parameter of the sample that table 1 is prepared for different molding mode.Mesoporous micropore is than very large, and this should be define the secondary pore of more loose depos-its between binding agent and molecular sieve or intracrystalline pore causes.Compared with the sample that the shaping sample of the present invention is shaping with tradition, total pore volume and mesoporous pore volume are larger, and this should be being more evenly distributed due to binding agent and molecular sieve, the accumulation secondary pore of formation or intracrystalline pore more.
The evaluation of molecular sieve molded catalyst
Z1, Z2, Z3, HZ2, HZ5, HZ8, HZ11, HZ14, HZ17 preformed catalyst micro anti-evaluation device is evaluated.Reactant is the mixture of methyl alcohol and water, and water alcohol is than being mol ratio 1:1, and mass space velocity is 3h
-1.Reaction temperature 470 DEG C, pressure 0.1MPa, product gas chromatographic analysis forms.
Evaluation result is as follows:
Table 2 is MTP product distribution tables of initial reaction stage sample Z1, HZ2, when 0.5h is carried out in reaction, catalyst Propylene Selectivity prepared by molding mode of the present invention is far longer than catalyst sample (36.18%vs.32.01%) prepared by traditional molding mode, and low-carbon alkene (ethene+propylene) is selective also obviously larger (49.24%vs.46.79%) simultaneously.Type catalyst of the present invention presents good catalytic activity.
Table 3 is comparative example and embodiment of the present invention product reactivity worth comparison sheets at preparing propylene from methanol, and as can be seen from this table, embodiment of the present invention product has better selective and longer service life.
The pore structure parameter of sample prepared by the different molding mode of table 1
The MTP product distribution of table 2 initial reaction stage sample
Note:
arepresent the productive rate of methane, ethane, propane and butane in product.
brepresent the productive rate of C5 and higher carbon number species in product.
The preparation condition of table 3 catalyst and preparing propylene from methanol reactivity worth
akeep the reaction time of more than 95% methanol conversion.
Claims (10)
1. a preparation method for molded molecular sieve catalyst, is characterized in that, described method comprises the steps:
(1) filtration washing separation is carried out to the molecular sieve solution after crystallization in Zeolite synthesis, obtain molecular sieve pulp; Preferred use UF membrane carries out washing to molecular sieve and is separated; More preferably described molecular sieve pulp pH is 7-8;
(2) mixed with binding agent by the molecular sieve pulp that step (1) obtains, add extrusion aid and peptizing agent, machine-shaping obtains shaping catalyst;
(3), after the shaping catalyst that step (2) obtains being carried out drying, ion-exchange and roasting, described molded molecular sieve catalyst is obtained; The temperature of preferred described drying is 50-120 DEG C; Be more preferably 100 DEG C; Also preferred described roasting is roasting 5-7h at 550-650 DEG C; Be more preferably roasting 6h at 600 DEG C.
2. method according to claim 1, is characterized in that, the silica alumina ratio of molecular sieve crystal contained in described molecular sieve pulp is 50-1000; The silica alumina ratio of preferred described molecular sieve crystal is 100-500, and grain size is at 50 ~ 500nm; More preferably described molecular sieve crystal is ZSM-5 molecular sieve.
3. method according to claim 1, is characterized in that, described binding agent is selected from the one in activated alumina, boehmite and kaolin.
4. method according to claim 1, is characterized in that, described extrusion aid is selected from the one in sesbania powder, graphite powder and glycerine.
5. method according to claim 1, is characterized in that, described peptizing agent is selected from the one in nitric acid, hydrochloric acid, phosphoric acid, oxalic acid and citric acid.
6. method according to claim 1, is characterized in that, in step (1), in the molecular sieve pulp obtained, the weight percent content of water is 10%-60%.
7. method according to claim 1, it is characterized in that, in step (2), with parts by weight, molecular sieve butt in molecular sieve pulp is 30-80 part, binding agent is 20-70 part, and the addition of extrusion aid is the 1-5% of molecular sieve butt and binding agent gross mass, and in peptizing agent and molecular sieve pulp, the gross mass of water and molecular sieve butt and binding agent total mass ratio are 0.3 ~ 0.6; Molecular sieve butt in preferred molecular sieve slurries is 60-80 part, binding agent is 20-40 part.
8. method according to claim 1, is characterized in that, the ion-exchange of step (3) is for carry out ion-exchange with aqueous ammonium chloride solution; Preferably at 90 DEG C, exchange 2h; More preferably in described aqueous ammonium chloride solution, the molar concentration of ammonium chloride is 1mol/L.
9. the molded molecular sieve catalyst that described in claim 1 ~ 8 any one, method prepares.
10. the application of molded molecular sieve catalyst according to claim 9 in methanol/dimethyl ether conversion propylene; It is characterized in that, described method comprises following reaction condition: temperature 470 DEG C, normal pressure, methanol feeding mass space velocity 3h
-1; Propylene initial selectivity in particular methanol/dimethyl ether conversion propylene is 35% ~ 40%, ethene and propylene overall selectivity are 48% ~ 52%.
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| CN111921553A (en) * | 2020-07-31 | 2020-11-13 | 江苏国瓷新材料科技股份有限公司 | Direct forming method of catalyst for preparing propylene from methanol |
| CN112250084A (en) * | 2020-09-25 | 2021-01-22 | 浙江浙能技术研究院有限公司 | Method for rapidly heat treating CHA molecular sieve slurry |
| CN113441174A (en) * | 2020-03-25 | 2021-09-28 | 中国石油化工股份有限公司 | Preparation method of catalyst, obtained catalyst and alkylation reaction method |
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| CN109748292A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve bar shaped agent and its extruded moulding methods and applications |
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| CN115845930A (en) * | 2022-11-03 | 2023-03-28 | 华侨大学 | Application of rice hull as molecular sieve catalyst forming template |
| CN115845930B (en) * | 2022-11-03 | 2024-03-29 | 华侨大学 | Application of rice husk as molecular sieve catalyst forming template |
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