CN101157051B - Recovery method of microspherical catalyst of fluid bed - Google Patents
Recovery method of microspherical catalyst of fluid bed Download PDFInfo
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- CN101157051B CN101157051B CN2007100636939A CN200710063693A CN101157051B CN 101157051 B CN101157051 B CN 101157051B CN 2007100636939 A CN2007100636939 A CN 2007100636939A CN 200710063693 A CN200710063693 A CN 200710063693A CN 101157051 B CN101157051 B CN 101157051B
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- dry basis
- microspherical catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims abstract description 10
- 239000012530 fluid Substances 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001694 spray drying Methods 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- 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 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000005299 abrasion Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003292 glue Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 241000269350 Anura Species 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000009434 installation Methods 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000003801 milling Methods 0.000 abstract 2
- 150000002927 oxygen compounds Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- -1 phosphorus-silicon-aluminum Chemical compound 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000261422 Lysimachia clethroides Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a recovery method of microspherical catalyst for a fluidized bed. The invention provides the method that catalyst to be recovered is mixed with each raw material preparing the fresh microspherical catalyst in certain proportion, the spray drying and the high temperature roasting are performed after the colloid milling of feed pulp, and the microspherical catalyst having the low abrasion index and the suitable particle size distribution can be obtained. The invention has the preparation processes that: firstly, according to the stoichiometric ratio of oxide dry basis, the catalyst to be recovered, molecular sieve initial powder, binding agent, auxiliary agent, pore forming agent, and deionized water are mixed and pulped, and the weight content of the oxide dry basis of recovered catalyst is not more than 80 percent in total blending; secondly, the colloid milling of the feed pulp through a colloid mill is performed, thereby the solid particle diameter contained in the feed pulp is smaller than 20 micron, 90 percent of the particle diameter is small than 10 micron, and 70 percent of the particle diameter is small than 5 micron; thirdly, the spray drying is performed, thereby producing a microspherical sample; fourthly, the microspherical sample is roasted in oxygen-containing atmosphere at 500 to 800 DEG C, thereby obtaining the microspherical catalyst for the fluidized bed. The recovered and prepared microspherical catalyst can be used for the reaction of producing alkene by converting an oxygen compound.
Description
Technical field
The catalytic applications of the catalyst that the present invention relates to a kind of recovery method of microspherical catalyst of fluid bed and reclaimed in the oxygen-containing compound conversion to produce olefine reaction.
Background technology
Ethene and propylene are important basic chemical industry raw materials, and China mainly adopts the preparation of light oil cracking method at present.Along with the in short supply and rise in price of petroleum resources, it is urgent day by day that non-petroleum path is produced the technology of low-carbon alkene.The research and development of ethene, propylene has become the focus of domestic and international research institution and international each major company's technology input.The technology of single series, heavy industrialization that natural gas or coal are produced methyl alcohol is very ripe, so the research of producing alkene (MTO) by methyl alcohol becomes the key technology that non-petroleum path is produced low-carbon alkene.
Pinhole phosphorus-silicon-aluminum molecular sieve has MTO catalytic performance preferably, but has the characteristic of quick carbon distribution in the fixed bed reaction process, thereby causes the rapid deactivation of catalyst and selectivity to reduce, and can not satisfy the industrial continuous production requirement.Fluid bed is a kind of common reactant device form that is applied to chemical industry, adopts the MTO process of the fluidized-bed reactor of successive reaction-regeneration can avoid above problem.The catalyst that is applicable to fluidized-bed reactor should be microspheroidal, and have proper intensity and size distribution under the prerequisite that keeps the greater catalytic performance.
At present, microspherical catalyst of fluid bed adopts the spray drying process preparation.In general, microspherical catalyst is made of active component such as molecular sieve and binding agent, and binding agent plays the dispersed activity component, improves catalyst strength.In addition, the existence of non-active ingredient can also be played the diluent molecules sieve in the catalyst, thereby reaches the effect that reduces reaction heat effect.Reported a kind of preparation of high strength Cracking catalyst as USP5126298, with two kinds of different clays, zeolite molecular sieve and phosphorus-containing compound are made the slurry of pH＜3, and spray-drying makes; USP5248647 has reported the molecular sieve with SAPO-34, the spray-dired method of the slurry that kaolin and Ludox are made; USP6153552 has reported a kind of microspherical catalyst preparation method of the SAPO of containing molecular sieve, and it is with the SAPO molecular sieve, inorganic oxide sol, and phosphorus-containing compound mixing, and spray-drying makes; USP6787501 has reported the spray-dried methanol conversion catalyst of making of SAPO-34 molecular sieve, binding agent and host material; CN01132533A has reported the wear-resistant index Preparation of Catalyst that is used for methanol conversion, and it is to play the effect that improves the catalyst abrasion index by the mass content that reduces molecular sieve in the catalyst.
When adopting spray drying process to produce catalyst, can obtain the product that two kinds of different grain sizes of meal and fine powder distribute simultaneously.It is to have certain requirements that the catalyst grain size that really is used for fluid bed distributes, generally be with meal and fine powder in proportion mixing preparation form.If the ratio of meal and fine powder is different in the modulation ratio of catalyst and the production process, will some catalyst residue.Remaining catalyst is not recycled not only and can be caused damage to production, and can increase production cost.In addition, catalyst can wear and tear in circulating fluidized bed device, and wherein the catalyst of most of efflorescence can reclaim by Cyclonic separating apparatus.If these efflorescence catalyst still keep original good reactivity worth, its recycling also will reduce catalyst production cost, has certain economic and is worth.
Patent CN1615177A has reported a kind of method that contains molecular sieve catalyst of utilizing again, being about to contain microsphere zeolite catalyst mixes with a large amount of deionized water, the glue mill is to reduce the granularity of particle in the slip, again spray-drying then, preparation has the catalyst of low abrasion index and suitable size distribution.But it is pointed out that the catalyst that is used to reclaim must be fresh not roasting sample, promptly contains organic formwork agent in the molecular sieve.Reclaim huge profit and yet there are no bibliographical information so far with the method that post catalyst reaction (sample after carbon containing sample or the roasting) prepares microspherical catalyst of fluid bed.
Summary of the invention
The inventor's research work shows can be with any catalyst (abrasion index and pattern can not meet the demands) that can not be directly used in fluidized-bed reactor, be the catalyst of fresh not calcined catalyst, fresh roasting rear catalyst, reaction back carbon-contained catalyst and reaction back and roasting de-carbon, recycle again and be prepared into microspherical catalyst of fluid bed with low abrasion index and suitable abrasion index.Detailed preparation method about the fresh microspherical catalyst that is used for oxygen-containing compound conversion to produce olefine reaction of indication in this patent asks for an interview the patent (application number 200610089171.1) of our application.
One of purpose of the present invention is to provide a kind of recovery method of microspherical catalyst of fluid bed.This method is that the catalyst that desire reclaims is mixed slip glue mill back spray-drying and high-temperature roasting, the microspherical catalyst that can obtain to have low abrasion index and suitable size distribution with each raw material of preparation fresh microspherical catalyst by a certain percentage.
The microspherical catalyst that the characteristics of the above-mentioned recovery method of the present invention are indication, is added binding agent, auxiliary agent and pore creating material and is prepared from as active component by SAPO or MeAPSO molecular sieve.To form (mass content) be silica 2～60%, phosphorous oxide 8-50%, aluminium oxide 20-70%, alkaline earth oxide 0-10% to element in the catalyst, transition metal oxide 0-20%, and to satisfy gross mass content sum be 100%.Wherein, the SAPO of indication or MeAPSO molecular sieve are its former powder form, promptly contain the organic formwork agent of introducing in the building-up process in the molecular sieve, and the aperture is less than 0.5nm; Institute's containing metal is a kind of of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium etc. or any several mixture in the MeAPSO molecular sieve; Binding agent is one or more the mixture in kaolin, bentonite, imvite, aluminium colloidal sol, Ludox and the aluminium oxide etc.; Auxiliary agent is one or more the mixture in oxide, inorganic salts or the organic salt of calcium, strontium, barium and zirconium; The auxiliary agent of indication can also be a phosphoric acid, diammonium hydrogen phosphate, the mixture of one or more in the ammonium hydrogen phosphate; Pore creating material is an organic compound, preferred natural products such as sesbania powder.
Characteristics of the present invention are that catalyst that desire reclaims can be fresh microspherical catalyst (roasting or not roasting sample), also can be reacted catalyst (carbon containing or roasting de-carbon sample), can also be that the cyclone separator by fluid bed reclaims the catalyst fines (carbon containing or roasting de-carbon sample) that obtains.Wherein, the content and the fresh catalyst of molecular sieve is close in the catalyst of cyclonic separation acquisition.
Specifically, the present invention is as follows as the preparation process of the microspherical catalyst recovery method of active component by molecular sieve:
1) by certain oxide dry basis metering ratio, the catalyst that desire is reclaimed adds molecular screen primary powder, binding agent, auxiliary agent, pore creating material and deionized water mixing, making beating, and optionally add auxiliary agent and pore creating material;
2) slip is crossed colloid mill glue mill, makes wherein contained solid particle diameter less than 20 μ m, and 90% particle diameter is less than 10 μ m, and 70% particle diameter is less than 5 μ m;
3) adopt press spray drying device or centrifugal spray-drying installation spray-drying, make the microballoon sample.The size distribution of catalyst microsphere particle can change the rotation speed change (25-40Hz) of atomizer in (0.5-2.5MPa) or the centrifugal spray drying device by the pressure of nozzle in the press spray drying equipment and carry out modulation.300-500 ℃ of spray drying device inlet temperature, outlet temperature are not less than 100 ℃.
4) roasting in 500-800 ℃ of oxygen-containing atmosphere of microballoon sample is promptly obtained microspherical catalyst of fluid bed.
Wherein, the oxide dry basis content of the catalyst of recovery in total batching is no more than 80%, and preferred range is 10-80%; Catalyst that is reclaimed and molecular screen primary powder are that SAPO or MeAPSO molecular sieve and the oxide dry basis content in total batching are 20-50%; The oxide dry basis content of binding agent in total batching is 10-75%; The oxide dry basis content of auxiliary agent in total batching is 0-30%; The oxide dry basis content of sesbania powder in total batching is 0-2%.
Characteristics of the present invention are that the abrasion index of microspherical catalyst is less than 2.
Another object of the present invention is the recirculating fluidized bed that above-mentioned microspheres prepared catalyst is directly applied to the oxygen-containing compound conversion to produce olefine reaction, as the catalyst with suitable size distribution, abrasion index and higher catalytic activity.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
By oxide dry basis solid content in the feed liquid is that 30wt% calculates, Ludox (content 30wt%), aluminium colloidal sol (content 20%) with metering, calcium nitrate (content 23%), kaolin (content 85wt%) and SAPO-34 molecular screen primary powder join in a certain amount of deionized water in turn, (the oxide dry basis mass content of each raw material is respectively 25% in turn to stir 30min, 10%, 5%, 30%, 30%), add the sesbania powder (soaking into) that is equivalent to total oxide butt quality 0.5% at last, stir 30min with small amount of ethanol.Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 5 μ m in the last gained slurry.The slurry room temperature is carried out centrifugal spray drying after placing 2h, atomizer rotating speed 30Hz, and 400 ℃ of inlet temperatures, outlet temperature are not less than 120 ℃.The spray dried products that obtains is designated as M, and product roasting 4h in 650 ℃ of air promptly obtains the oxygen-containing compound conversion to produce olefine catalyst, is designated as MC.
Embodiment 2
The MC sample that embodiment 1 is obtained is used for the recirculating fluidized bed (4 tons of catalyst loading amounts, 50 tons/day of methyl alcohol treating capacities) of type approval test, carries out methanol conversion system olefine reaction.Device is flat
Steady operation was taken out the catalyst fines of collecting after 30 days from the cyclone separator sample tap, be designated as XM.From the sample tap of reactor, take out the little amount of catalyst sample, be designated as FM.
Embodiment 3
Get part XM and FM sample, remove wherein contained moisture and reaction carbon residue at air in 650 ℃ of roastings, the sample that obtains is designated as XMC and FMC respectively.
Embodiment 4
By oxide dry basis solid content in the feed liquid is that 30wt% calculates, M sample with metering, Ludox (content 30wt%), aluminium colloidal sol (content 20%), calcium nitrate (content 23%), kaolin (content 85wt%) and ZnAPSO-34 molecular screen primary powder join in a certain amount of deionized water in turn, (the oxide dry basis content of each raw material is respectively 70% in turn to stir 30min, 7.5%, 3%, 1.5%, 9%, 9%).Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 5 μ m in the last gained slurry.Slurry carries out centrifugal spray drying, and the rotating speed of centrifugal type atomizer is 30Hz, and 400 ℃ of inlet temperatures, outlet temperature are not less than 120 ℃.The spray dried products that obtains roasting 3h in 650 ℃ of air promptly obtains microspherical catalyst, is designated as M-1S.
Embodiment 5
Press proportion scale and preparation method among the embodiment 4, respectively the M sample is substituted with MC, XM, XMC, FM, FMC sample, carry out Preparation of Catalyst.The spray dried products that obtains roasting 3h in 650 ℃ of air promptly obtains microspherical catalyst, is designated as MC-1S, XM-1S, XMC-1S, FM-1S, FMC-1S respectively.
Embodiment 6
By oxide dry basis solid content in the feed liquid is that 30wt% calculates, M sample with metering, Ludox (content 30wt%), kaolin (content 85wt%) and SAPO-34 molecular screen primary powder join in a certain amount of deionized water in turn, (the oxide dry basis content of each raw material is respectively 30% in turn to stir 30min, 14%, 21%, 35%).Feed liquid is crossed colloid mill and is carried out glue mill, makes that particle diameter 70% is less than 5 μ m in the last gained slurry.Slurry carries out centrifugal spray drying, and the rotating speed of centrifugal type atomizer is 30Hz, and 400 ℃ of inlet temperatures, outlet temperature are not less than 120 ℃.The spray dried products that obtains roasting 3h in 650 ℃ of air promptly obtains microspherical catalyst, is designated as M-2S.
Embodiment 7
Press proportion scale and preparation method among the embodiment 6, respectively the M sample is substituted with MC, XM, XMC, FM, FMC sample, carry out Preparation of Catalyst.The spray dried products that obtains roasting 3h in 650 ℃ of air promptly obtains microspherical catalyst, is designated as MC-2S, XM-2S, XMC-2S, FM-2S, FMC-2S respectively.
Embodiment 8
With embodiment 1,4, the catalyst sample that obtains in 5,6,7 carries out abrasion index to be measured, and the results are shown in table 1.The several catalytic agent all has lower abrasion index.
The abrasion index assay method: will about 7g catalyst sample be put in the gooseneck about internal diameter 2.5cm, humid air provides a fluidisation environment with the flow velocity of 20L/min by this pipe.The catalyst fines that blows out from catalyst is collected in the special filter bag, and 4h is carried out in test.Calculate abrasion index by the average per hour mass percent of loss of the first loading amount of catalyst.
The BT-9300 type laser particle size distribution instrument that the size distribution of catalyst adopts Baite Instrument Co., Ltd., Dandong to produce the results are shown in Table 2.
Embodiment 9
Resulting part catalyst in embodiment 1 and 5 is carried out methanol-to-olefins reaction (MTO) reaction evaluating.
Appreciation condition: take by weighing the 10g sample fixed fluidized-bed reactor of packing into, sample at first rises to 550 ℃ of activation half an hour under the nitrogen of 40ml/min, be cooled to 450 ℃ then and carry out chemical reaction.Stop logical nitrogen, use the micro pump charging, 40wt% methanol aqueous solution, weight space velocity WHSV are 2.0h
-1, product is analyzed by online gas-chromatography, the results are shown in Table 3.
The abrasion index of table 1 microspherical catalyst is measured
Table 2 microspherical catalyst size distribution
| Sample | Size distribution |
| MC | ＜20μm：3.0％?20μm-40μm：13.5％?40-80μm：43.5％ 80-120μm：23.2％?＞120μm：16.8％ |
| XM-1S | ＜20μm：0.5％?20μm-40μm：8.1％?40-80μm：48.3％ 80-120μm：25.7％?＞120μm：17.4％ |
| MC-2S | ＜20μm：3.1％ 20μm-40μm：14.3％?40-80μm：44.8％ 80-120μm：21.6％?＞120μm：16.2％ |
| XM-2S | ＜20μm：2.4％?20μm-40μm：15.8％?40-80μm：43.3％ 80-120μm：22.3％?＞120μm：16.2％ |
Table 3 methanol conversion system olefine reaction result
*
*Best reaction result when methyl alcohol 100% transforms
Claims (9)
1. the recovery method of a microspherical catalyst of fluid bed is that the catalyst that desire reclaims is mixed with each raw material of preparation fresh microspherical catalyst by a certain percentage, and slip glue mill back spray-drying and high-temperature roasting obtain microspherical catalyst; Its preparation process is as follows:
1) by certain oxide dry basis metering ratio, the catalyst selectivity ground that desire is reclaimed adds molecular screen primary powder, binding agent, auxiliary agent, pore creating material and deionized water mixing, making beating, what wherein select adding is auxiliary agent and pore creating material, and the weight content of the oxide dry basis of the catalyst that reclaims in total batching is no more than 80%, described recovery activity of such catalysts composition is SAPO or MeAPSO molecular sieve, and described molecular screen primary powder is SAPO or MeAPSO molecular sieve;
2) slip is crossed colloid mill glue mill, makes wherein contained solid particle diameter less than 20 μ m, and 90% particle diameter is less than 10 μ m, and 70% particle diameter is less than 5 μ m;
3) spray-drying makes the microballoon sample;
4) roasting in 500-800 ℃ of oxygen-containing atmosphere of microballoon sample is promptly obtained microspherical catalyst of fluid bed.
2. in accordance with the method for claim 1, it is characterized in that the oxide dry basis weight content of catalyst in total batching that reclaims in the step 1) is 10-80%.
3. in accordance with the method for claim 1, it is characterized in that the oxide dry basis content of binding agent described in the step 1) in total batching is 10-75%.
4. in accordance with the method for claim 1, it is characterized in that the oxide dry basis content of auxiliary agent described in the step 1) in total batching is 0-30%.
5. in accordance with the method for claim 1, it is characterized in that pore creating material described in the step 1) is that sesbania powder and the content in total batching are 0-2%.
6. in accordance with the method for claim 1, it is characterized in that adopting the press spray drying device in the step 3) or adopting centrifugal spray-drying installation.
7. in accordance with the method for claim 6, it is characterized in that 300-500 ℃ of the inlet temperature of spray-drying installation described in the step 3), outlet temperature is not less than 100 ℃.
8. according to the described method of claim 1, the abrasion index that it is characterized in that the microspherical catalyst for preparing is less than 2.
9. the direct application of microspherical catalyst in the oxygen-containing compound conversion to produce olefine reaction for preparing according to the described method of claim 1.
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| CN102085468B (en) * | 2009-12-04 | 2013-02-20 | 中国科学院大连化学物理研究所 | Pre-fluidizing agent for fluidized bed |
| CN102179251B (en) * | 2011-03-17 | 2013-01-30 | 清华大学 | Catalyst for synthesizing methanol by fluidized bed and preparation method thereof |
| CN103611581B (en) * | 2013-11-22 | 2015-09-23 | 中国天辰工程有限公司 | A kind of recovery of catalyst fines is used for the method for granulation again |
| CN106540744A (en) * | 2015-09-22 | 2017-03-29 | 正大能源材料(大连)有限公司 | A kind of reuse method of sial phosphorus molecular sieve catalyst |
| CN110038631A (en) * | 2019-05-22 | 2019-07-23 | 陕西煤化工技术工程中心有限公司 | A kind of reuse method of methanol-to-olefin catalyst fine powder |
| CN113797946A (en) * | 2020-06-15 | 2021-12-17 | 中国石油化工股份有限公司 | Aromatic hydrocarbon ammoxidation catalyst and preparation method thereof |
| CN112774726B (en) * | 2020-12-29 | 2022-09-13 | 上海华谊新材料有限公司 | Spherical titanium-silicon molecular sieve catalyst and preparation method thereof |
| CN114452662B (en) * | 2021-10-26 | 2023-09-19 | 中国石油化工股份有限公司 | Spray drying waste recycling device and application method |
| CN116371463A (en) * | 2023-03-13 | 2023-07-04 | 中触媒新材料股份有限公司 | Low-attrition rate SAPO-34 molecular sieve catalyst, and preparation method and application thereof |
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