CN106082253A - The preparation method of a kind of SAPO 34 microsphere zeolite catalyst and the application of catalyst - Google Patents
The preparation method of a kind of SAPO 34 microsphere zeolite catalyst and the application of catalyst Download PDFInfo
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- CN106082253A CN106082253A CN201610399559.5A CN201610399559A CN106082253A CN 106082253 A CN106082253 A CN 106082253A CN 201610399559 A CN201610399559 A CN 201610399559A CN 106082253 A CN106082253 A CN 106082253A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000010457 zeolite Substances 0.000 title claims abstract description 23
- 239000004005 microsphere Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 241000269350 Anura Species 0.000 title abstract 2
- 238000002425 crystallisation Methods 0.000 claims abstract description 35
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010413 mother solution Substances 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 9
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 8
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 91
- 239000007921 spray Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 23
- 238000001694 spray drying Methods 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000007493 shaping process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 70
- 238000001354 calcination Methods 0.000 description 17
- 239000002002 slurry Substances 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001033 granulometry Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- -1 carbinol alkene Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 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
- 239000005977 Ethylene Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011148 porous material Substances 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
- 238000010926 purge Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The preparation method of a kind of SAPO 34 microsphere zeolite catalyst is to be stirred at room temperature under state to join in deionized water by aluminum source, add phosphorus source to stir, it is then slowly added into silicon source to continue to stir, it is eventually adding tetraethyl ammonium hydroxide solution to be mixed uniformly, continuously add 2-aminopropane., in diethylamine, triethylamine one with or several after become homogeneous gel, again through crystallization, after crystallization completes, synthetic product mother solution is drawn off from autoclave, it is spray-dried, roasting 1.5 2.5 hours, obtains catalyst.It is high that the present invention has synthesis yield, it is not necessary to Zeolite synthesis product is separated, washed, it is achieved the advantage of disposable shaping of catalyst pelletize.
Description
Technical field
The invention belongs to the preparation method of a kind of molecular sieve catalyst, be specifically related to a kind of SAPO-34 molecular sieve microsphere and urge
The preparation method of agent and the application of catalyst.
Background technology
SAPO-34 be once 1984 U.S. combinating carbide company (UCC) invent to have chabazite structure (CHA) novel
Sial phosphorus molecular sieve.SAPO-34 molecular sieve has the acid site of moderate strength, unique wicket pore passage structure, bigger surpassing
The advantages such as cage, abundant micropore, bigger specific surface area so that it is at methanol-to-olefins (MTO), the low-carbon (LC) such as chloromethanes, ethanol contains
Oxygen compound converts alkene processed, catalytic field, purifying vehicle exhaust field, the film such as High-carbon alkane or olefin cracking producing light olefins
Separation field and functional material field obtain a wide range of applications.
SAPO-34 molecular sieve is by PO2 +、AlO2 -、SiO2Three kinds of tetrahedrons share the ellipsoid that oxygen atom is connected with each other
Shape cage, circular or wrinkling shape structure, orifice diameter is maintained between 0.36-0.42nm.This molecular sieve pores is for exceeding
0.25cm3/ g, space symmetr group R3m, belong to trigonal system, there is the structure that chabasie is similar.The synthesis that SAPO-34 is the most frequently used
Method is to use organic ammonium, the Hydrothermal Synthesis of amine template.The mould that can synthesize SAPO-34 molecular sieve of document report at present
Plate agent has triethylamine, tetraethyl ammonium hydroxide, morpholine, diethylamine etc., 2-aminopropane. and mixture thereof.What prior art existed asks
Topic is that synthesis yield is low, or synthesized gel rubber is admittedly containing low, causes overall Autoclaves for synthesis unit volume output low and follow-up
It is serious that crystallized product reclaims washing loss.
Summary of the invention
It is an object of the invention to provide a kind of synthesis yield high, it is not necessary to Zeolite synthesis product is separated, washed,
Realize the preparation of the SAPO-34 microsphere zeolite catalyst of disposable shaping of catalyst pelletize and at methanol-to-olefins
(MTO), the application of particularly coal base crude carbinol alkene (CTO) catalyst.
It is an object of the invention to be achieved through the following technical solutions:
(1) prepared by gel: is first stirred at room temperature under state and joins in deionized water by aluminum source, adds phosphorus source stirring
Uniformly, it is then slowly added into silicon source and continues to stir, be eventually adding tetraethyl ammonium hydroxide solution to be mixed uniformly, continue to add
Enter 2-aminopropane., in diethylamine, triethylamine one and or several, mixing speed is 200-660 rev/min, stirs 4-14 hour, makes
System becomes homogeneous gel；
(2) crystallization: transferred to by gel in autoclave, under stirring, with the intensification speed of 0.5-5 DEG C/h
Rate rise to 160-190 DEG C at crystallization 36-84 hour；
(3) crystallization mother liquor: after crystallization completes, to reacting kettle jacketing logical cooling oil cooling rapidly, treats that system temperature is less than
65 DEG C, this SAPO-34 Zeolite synthesis product mother solution is drawn off from autoclave；
(4) it is spray-dried: step (3) gained synthetic product mother solution is spray-dried, it is thus achieved that Spray dried products；
(5) by (4) gained Spray dried products in 540-560 DEG C of roasting 1.5-2.5 hour, SAPO-34 molecular sieve is obtained
Microspherical catalyst；
Source of aluminium is with Al2O3Meter, phosphorus source is with P2O5Meter, silicon source is with SiO2Meter, solvent is with H2O counts, template tetraethyl hydrogen
Amine-oxides is with R1Meter, template 2-aminopropane. is with R2Meter, template diethylamine is with R3Meter, template triethylamine is with R4Meter, molecular sieve closes
The mol ratio of one-tenth reaction mass is:
1.0Al2O3:1.0-1.4P2O5:0.05-0.25SiO2:0.5-1.8(R1+R2+R3+R4):25-95H2O, wherein R2/
R1=0-0.55；R3/R1=0-0.3；R4/R1=0-0.25, and R2, R3, R4Can not be 0 simultaneously.
Source of aluminium is boehmite, and phosphorus source is orthophosphoric acid, and silicon source is neutral Ludox.
Described spray drying is twin, and spray drying temperature is 250-435 DEG C, and atomizing pressure is 120kPa-
800kPa, atomization gas is the mixture of noble gas or noble gas and air, atomization gas flow rate be 1-20 cubic meter/
Minute, spray drying exit temperature is 85-155 DEG C.
The present invention increases substantially the molecular sieve simultaneously synthesizing product of unit volume yield without carrying out being recovered by filtration of crystal
And directly carry out spray drying forming pelletize.It is 25-275 that the present invention uses spray drying method molding, granulating to obtain average particle size
Micron.
Catalyst of the present invention is used for methanol-to-olefins (MTO) catalytic conversion process, and application comprises the steps: to urge activation
Agent is the methanol aqueous solution of 35-95wt% with methanol or methanol content, is 400-550 DEG C in reaction temperature；Reaction pressure
For 1-300kPa；Reaction mass space velocity be 1.2-30.5 gram of methanol/gram catalyst/hour under the conditions of carry out haptoreaction.
Advantages of the present invention and good effect be:
The method have the characteristics that the mother solution to Zeolite synthesis product directly carries out being spray-dried preparation SAPO-34 molecule
Sieve microspherical catalyst, (1) yield is high, and (2) are not required to SAPO-34 molecular sieve crystal is separated and washed, and (3) need not add
Binding agent, (4) need not add any auxiliary agent can realize efficient molecular sieve based catalyst forming pelletize.Spray drying yield is high
Reaching nearly 90%, catalyst granules specific surface area is more than 231m2/g。
The present invention can be greatly lowered fixed-end forces cost, it is to avoid uses binding agent and other catalytic preparation process institutes
Required promoter additive, hence it is evident that reduce catalyst cost.And present invention can apply to methanol to olefins reaction, high anti-
Answer under air speed, there is the advantages such as methanol conversion is higher, diene selective is higher, catalyst life length.
Accompanying drawing explanation
Fig. 1 is embodiment 1 Spray dried products SD-493 (left) and the optics of calcination process product SD-493-C1 (right) thereof
The optical microscope microphotograph of microgram, product is the spherical particle of 35-255 micron, transparent shape.
Fig. 2 is embodiment 2 Spray dried products SD-501 (left) and the optics of calcination process product SD-501-C1 (right) thereof
Micrograph, product is the spherical particle of 35-285 micron, transparent shape.
Fig. 3 is embodiment 3 Spray dried products SD-506 (left) and the optics of calcination process product SD-506-C1 (right) thereof
Micrograph, product is the spherical particle of 40-250 micron, shape white, opaque.
The laser granulometry distribution results of Fig. 4 embodiment 3 sieve sample SAPO-34 (SMT-LU-6) zeolite crystal.
The XRD spectra that Fig. 5 embodiment 1 spray dried products SD-493 roasting is forward and backward, belongs to typical SAPO-34 molecular sieve
Structure.
The scanning electron microscope displaing micro picture of Fig. 6 embodiment 1 spray dried products SD-493 microsphere particle: surface topography display crystalline substance
Intergranular is the most tightly packed, is evenly distributed.
The scanning electron microscope displaing micro picture of Fig. 7 embodiment 3 spray dried products SD-506 microsphere particle: surface topography display crystalline substance
Intergranular is mutually piled up compactness difference and has hole, and intercrystalline bonding is inadequate.
Fig. 8 is the MTO catalytic effect evaluation result of embodiment 1 mother solution SAPO-34 molecular sieve.
Detailed description of the invention
The present invention is further illustrated below in conjunction with specific embodiment；It is emphasized that: for ordinary skill
For personnel, can be improved according to the above description or be converted, and all these modifications and variations all should be belonged to institute of the present invention
Attached scope of the claims.Various technical specifications employing mode calculated as below:
(1) MTO conversion ratio is converted into all carbonaceous products after deduction dimethyl ether with sample introduction methanol；(2) diene selective
For ethylene and propylene at hydrocarbon products accretion carbon mass percent；(3) catalyst life is defined as every gram of catalyst during MTO
Methanol conversion converts the amount (in grams) of methanol when being brought down below 20%；(4) second third is than being then defined as MTO conversion process
The middle ethylene weight ratio to propylene；(5) coking amount that coking selectivity is total during being then MTO account for methanol be converted into dimethyl ether with
The mass percent of outer Hydrocarbon.
Embodiment 1
(1) prepared by gel: first join in autoclave by 215.13 kilograms of distilled water, mixing speed 100 revs/min
Clock, be slowly added to 43.4 kilograms solid containing the boehmite for 70wt%, 40 DEG C of oil baths, be then slowly added into 89.93 kilograms dense
Degree is the phosphoric acid of 85wt%, stirs, and is slow added into the Ludox that 6.76 kilograms of concentration is 40wt% and stirs, then adds
Enter the tetraethyl ammonium hydroxide aqueous solution that 176.76 kilograms of concentration is 25wt%, add 6.07 kilograms of triethylamines, strengthen stirring
Speed stirs 5 hours to 300 revs/min, makes system become homogeneous gel；By homogeneous gel on homogenizer 10000 revs/min cut
Cut 30 minutes.Aged at room temperature 16 hours.
(2) crystallization: with the heating rate of 5 DEG C/h, is warming up to crystallization temperature 160 DEG C, and crystallization time is 84 hours, stirs
Mixing speed is 300 revs/min, after crystallization is complete, cools down rapidly to reacting kettle jacketing logical cooling oil.
(3) crystallization mother liquor: treat that system temperature is less than 65 DEG C, by this SAPO-34 Zeolite synthesis product mother solution from autoclave
Drawing off the spray drying for the present invention to be used, this sample is SMT-LU-3；
(4) it is spray-dried: the 65 kilograms of synthetic product mother solutions obtained in this case step (3) are spray-dried.Spray
Mist hothouse temperature stabilization is at 407 DEG C, and water slurry processing speed is 11.5 kgs/hr.Spray dried products is from cyclone separator
Draw off with being spray-dried tower bottom, named SD-493.Being regular spheroid through Olympus observation by light microscope, spheroid is big
Little between 35-230 micron, microphotograph is shown in Fig. 1 (left).
(5) by SD-493 2 hours available target products of 550 DEG C of roastings, named SD-493-C1 in Muffle furnace.Its
Bulk density is 0.68 gram/cm3.Its light micrograph is shown in Fig. 1 (right).SD-493-C1 obtains mill through jet cup abrasion test instrument
Consumption index is 0.65%/hour.The average particle size using Malvern MasterSizer laser granulometry instrument to obtain is
118.2 micron.Analyze through Micromeritics ASAP-2020 specific surface area measuring instrument BET, the specific surface area of products therefrom
For 213.3m2/g。
(6) catalyst SD-493-C1 good for calcination activation is carried out methanol-to-olefins catalytic performance test, in reaction raw materials
Methanol content 95wt.%, water 5wt.%, reaction temperature 440 DEG C, methanol quality air speed 20h-1, reaction pressure 4kPa, obtain this sample
The MTO catalytic performance of product the results are shown in Table 2.
Embodiment 2
(1) prepared by gel: first add 235.88 kilograms of distilled water to autoclave, 20 DEG C of oil baths, mixing speed
200 revs/min, it is slowly added to 27.2 kilograms afterwards and consolidates containing the boehmite being 75%, be then slowly added into 46.12 kilograms
The phosphoric acid of 85wt%, stirs, and is slow added into the Ludox of 1.50 kilograms of 40wt%, continues to stir；Add
The tetraethyl ammonium hydroxide aqueous solution of 176.76 kilograms of 25wt%, adds the 2-aminopropane. of 7.09 kilograms.Strengthen mixing speed extremely
400 revs/min are stirred 2 hours；Solution within 150 minutes, is made to become homogeneous solidifying the 4000 revs/min of shearings on homogenizer of homogeneous gel
Glue.Aged at room temperature 6 hours.
(2) crystallization: with the heating rate of 50 DEG C/h, is warming up to crystallization temperature 190 DEG C, and crystallization time is 36h, stirring
Speed 200 revs/min, after crystallization is complete, cools down rapidly to reacting kettle jacketing logical cooling oil.
(3) crystallization mother liquor: treat that system temperature is less than 65 DEG C, by this SAPO-34 Zeolite synthesis product mother solution from autoclave
Drawing off the spray drying for the present invention to be used, this sample is SMT-LU-4.
(4) it is spray-dried: this example (3) step 107 kilogram synthetic product mother solution is spray-dried.Spray drying chamber
Temperature stabilization is at 400 DEG C, and water slurry sample introduction speed is 10.3 kgs/hr.Spray dried products is from cyclone separator and spray dried
Drawing off bottom dry instrument, collecting spray dried products is 21.86 kilograms (butts), i.e. spray dried products yield is 84.2%.
By named for this spray dried products SD-501.Being regular spheroid through Olympus observation by light microscope, spheroid size exists
Between 35-230 micron, microphotograph is shown in Fig. 2 (left).
(5) by SD-501 2 hours available target products of 550 DEG C of roastings, named SD-501-C1 in Muffle furnace.Its
Bulk density is 0.60 gram/cm3.Its light micrograph is shown in Fig. 2 (right).SD-501-C1 obtains mill through jet cup abrasion test instrument
Consumption index is 0.67%/hour.The average particle size using Malvern MasterSizer laser granulometry instrument to obtain is
156.3 micron.Analyze through Micromeritics ASAP-2020 specific surface area measuring instrument BET, the specific surface area of products therefrom
For 328.5m2/g。
(6) catalyst good for calcination activation is carried out methanol-to-olefins catalytic performance test, reaction raw materials methanol aqueous solution
Consist of 80wt.% methanol, 20wt.% water, reaction temperature 470 DEG C, methanol quality air speed 10h-1, reaction pressure 50kPa, obtains
The MTO catalytic performance obtaining this sample the results are shown in Table 2.
Embodiment 3
(1) prepared by gel: first join in autoclave by 103.26 kilograms of distilled water, 30 DEG C of oil baths, stirring speed
Spend 630 revs/min, be slowly added to 62.77 kilograms afterwards and consolidate containing the boehmite being 65%, be then slowly added into 138.35 thousand
The phosphoric acid of gram 85wt%, stirs, is slow added into the Ludox of 15.03 kilograms of 40wt%, continue to stir, add
The tetraethyl ammonium hydroxide aqueous solution of 117.84 kilograms of 25wt%, adds the diethylamine of 2.13 kilograms.Strengthen mixing speed extremely
500 revs/min are stirred 4 hours；The 7000 revs/min of shearings on homogenizer of homogeneous gel are made homogeneous gel in 90 minutes.Room
Under temperature aging 24 hours.
(2) crystallization: with the heating rate of 30 DEG C/h, is warming up to crystallization temperature 175 DEG C, and crystallization time is 60h, stirring
Speed 100 revs/min, after crystallization is complete, cools down rapidly to reacting kettle jacketing logical cooling oil.
(3) crystallization mother liquor: treat that system temperature is less than 65 DEG C, by this SAPO-34 Zeolite synthesis product mother solution from autoclave
Drawing off the spray drying for the present invention to be used, this sample is SMT-LU-6.
(4) it is spray-dried: this example (3) step 218.53 kilogram synthetic product mother solution is spray-dried.Treat Niro
Spray drying instrument spray drying chamber temperature stabilization, between 350 DEG C to 450 DEG C, introduces molecular sieve mother solution, is spray-dried, spray
Mist baking temperature is 271 DEG C, and spray gun is Niro two-fluid spray nozzle, and atomization pressure is 140kPa.Water slurry is made a gift to someone through screw pump
Spray gun, is atomized with upper-spraying type.Water slurry sample introduction speed maintains 110-140 DEG C with spray dryer outlet temperature and is advisable, water
Slurry sample introduction speed is 7.3 kgs/hr.Spray dried products draws off bottom cyclone separator and spray drying instrument, spray dried
Dry product yield is collected product and is spray-dried the theory that the partially recycled summation of the viscous wall in indoor contains admittedly relative to mother solution at two
Yield percent.Collecting spray dried products is 34.95 kilograms (butts), i.e. spray dried products yield is 87.2%.Will
The named SD-506 of this spray dried products.Being regular spheroid through Olympus observation by light microscope, spheroid size is at 25-
Between 310 microns, microphotograph is shown in Fig. 3 (left).
(5) by SD-506 2 hours available target products of 550 DEG C of roastings, named SD-506-C1 in Muffle furnace.Its
Bulk density is 0.52 gram/cm3.Its light micrograph is shown in Fig. 3 (right).SD-506-C1 obtains mill through jet cup abrasion test instrument
Consumption index is 6.30% hour.The average particle size using Malvern MasterSizer laser granulometry instrument to obtain is 135.2
Micron.Analyzing through Micromeritics ASAP-2020 specific surface area measuring instrument BET, the specific surface area of products therefrom is
428.1m2/g。
(6) catalyst good for calcination activation is carried out methanol-to-olefins catalytic performance test, reaction raw materials methanol aqueous solution
Consist of 40wt.% methanol, 60wt.% water, reaction temperature 550 DEG C, methanol quality air speed 5h-1, reaction pressure 200kPa, obtains
The MTO catalytic performance obtaining this sample the results are shown in Table 2.
Embodiment 4
(1) prepared by gel: first join in autoclave by 215.13 kilograms of distilled water, mixing speed 330 revs/min
Clock, be slowly added to 43.4 kilograms solid containing the boehmite for 70wt%, 40 DEG C of oil baths, be then slowly added into 89.93 kilograms dense
Degree is the phosphoric acid of 85wt%, stirs, and is slow added into the Ludox that 6.76 kilograms of concentration is 40wt% and stirs, then adds
Enter the tetraethyl ammonium hydroxide aqueous solution that 176.76 kilograms of concentration is 25wt%, add 3.03 kilograms of diethylamine, add
3.04 kilograms of triethylamines, strengthen mixing speed and stir 5 hours to 630 revs/min, make system become homogeneous gel；By homogeneous gel
Shear 30 minutes for 10000 revs/min on homogenizer.Aged at room temperature 16 hours.
(2) crystallization: with the heating rate of 5 DEG C/h, is warming up to crystallization temperature 160 DEG C, and crystallization time is 84 hours, stirs
Mixing speed is 300 revs/min.
(3) crystallization mother liquor: after crystallization is complete, cools down rapidly to reacting kettle jacketing logical cooling oil, treats that system temperature is less than
65 DEG C, from autoclave, this SAPO-34 Zeolite synthesis product mother solution being drawn off the spray drying for the present invention and is used, this sample is
SMT-LU-3A；
(4) it is spray-dried: this example (3) step 53 kilogram synthetic product mother solution is spray-dried.Spray drying chamber
Temperature stabilization is at 401 DEG C, and water slurry sample introduction speed is 10.3 kgs/hr.Spray dried products is from cyclone separator and spray dried
Dry tower bottom draws off, and collecting spray dried products is 9.82 kilograms (butts), i.e. spray dried products yield is 82.3%.
By named for this spray dried products SD-496A.Being regular spheroid through Olympus observation by light microscope, spheroid size exists
Between 33-275 micron.
(5) by SD-496A 2 hours available target products of 550 DEG C of roastings, named SD-496A-C1 in Muffle furnace.
Its bulk density is 0.65 gram/cm3.SD-496A-C1 through jet cup abrasion test instrument obtain abrasion index be 0.71%/hour.Adopt
The average particle size obtained with Malvern MasterSizer laser granulometry instrument is 115.6 microns.Pass through
Micromeritics ASAP-2020 specific surface area measuring instrument BET analyzes, and the specific surface area of products therefrom is 253.3m2/g。
(6) catalyst good for calcination activation is carried out methanol-to-olefins catalytic performance test, methanol content in reaction raw materials
35wt.%, water 65wt.%, reaction temperature 500 DEG C, methanol quality air speed 1.2h-1, reaction pressure 300kPa, it is thus achieved that this sample
MTO catalytic performance the results are shown in Table 2.
Embodiment 5
(1) prepared by gel: first join in autoclave by 215.13 kilograms of distilled water, mixing speed 320 revs/min
Clock, be slowly added to 43.4 kilograms solid containing the boehmite for 70wt%, 40 DEG C of oil baths, be then slowly added into 89.93 kilograms dense
Degree is the phosphoric acid of 85wt%, stirs, and is slow added into the Ludox that 6.76 kilograms of concentration is 40wt% and stirs, then adds
Enter the tetraethyl ammonium hydroxide aqueous solution that 176.76 kilograms of concentration is 25wt%, add 3.03 kilograms of 2-aminopropane .s, add
3.04 kilograms of triethylamines, strengthen mixing speed and stir 5 hours to 460 revs/min, make system become homogeneous gel；By homogeneous gel
Shear 30 minutes for 10000 revs/min on homogenizer.Aged at room temperature 16 hours.
(2) crystallization: with the heating rate of 5 DEG C/h, is warming up to crystallization temperature 160 DEG C, and crystallization time is 84 hours, stirs
Mixing speed is 300 revs/min,
(3) crystallization mother liquor: after crystallization is complete, cools down rapidly to reacting kettle jacketing logical cooling oil, treats that system temperature is less than
65 DEG C, from autoclave, this SAPO-34 Zeolite synthesis product mother solution being drawn off the spray drying for the present invention and is used, this sample is
SMT-LU-3B；
(4) it is spray-dried: (3) 67 kilograms of synthetic product mother solutions of this case step are spray-dried.Spray drying chamber
Temperature stabilization is at 401 DEG C, and water slurry sample introduction speed is 9.7 kgs/hr.Spray dried products is from cyclone separator and spray drying
Tower bottom draws off, and collecting spray dried products is 12.04 kilograms (butts), i.e. spray dried products yield is 81.7%.Will
The named SD-496B of this spray dried products.Being regular spheroid through Olympus observation by light microscope, spheroid size is at 23-
Between 290 microns.
(5) by SD-496B 2 hours available target products of 550 DEG C of roastings, named SD-496B-C1 in Muffle furnace.
Its bulk density is 0.63 gram/cm3.SD-496A-C1 through jet cup abrasion test instrument obtain abrasion index be 0.63%/hour.Adopt
The average particle size obtained with Malvern MasterSizer laser granulometry instrument is 108.6 microns.Pass through
Micromeritics ASAP-2020 specific surface area measuring instrument BET analyzes, and the specific surface area of products therefrom is 247.1m2/g。
(6) catalyst good for calcination activation is carried out methanol-to-olefins catalytic performance test, methanol content in reaction raw materials
95wt.%, water 5wt.%, reaction temperature 400 DEG C, methanol quality air speed 30h-1, reaction pressure 100kPa, it is thus achieved that this sample
MTO catalytic performance the results are shown in Table 2.
Comparative example 1
The molecular sieve mother solution double centner obtained in step (3) in embodiment 1 is carried out filter press filtration and filter wash.Plate
Frame filter pressing uses the XMQ320 filter press equipment that Yuzhou of Henan city great Zhang filter plant factory produces, and uses four pieces of filtrating-pressing plate frames,
Every piece of filter pressing area is 0.25 square metre, and filter cloth area is 1 square metre altogether；Molecular sieve mother solution sends into sheet frame through ARO membrane pump
Pressure filter, membrane pump outlet pressure is 550-700kPa.First carry out filter pressing filtrate to be reclaimed；Then deionized water is switched to carry out
Washing, treats less than 500 μ S, filtrate electrical conductivity i.e. thinks that molecular sieve washing is fully.Washed SAPO-34 molecular sieve filter cake is unloaded
Go out and within 4 hours, obtain SAPO-34-DW through 110 DEG C of oven dryings.
(1) it is stirred at room temperature under state 2000 grams of (butt) SAPO-34-DW molecular sieves are joined 7100 grams of deionized waters
In；
(2) water slurry of the present embodiment step (2) carries out Netzsch LMZ750 grinder medium milling process, it is thus achieved that all
Even water slurry；Water slurry molecular sieve content is 22%.
(3) the SAPO-34-DW water slurry of the present embodiment step (3) is spray-dried.Spray drying chamber's temperature stabilization exists
407 DEG C, slurry sample introduction speed is 11.5 kgs/hour.Spray dried products is from cyclone dust extractor and is spray-dried instrument bottom discharge
Outlet draws off, and treats that 8350 grams of SAPO-34-DW water slurrys are made a gift to someone spray drying, does not collects in cyclonic separation and spray drying tower location
It is attached to the inside of spray drying chamber to any spray dried products, only small part granule.Overall product yield is 4.7%.
This spray dried products is SD-517.Use Olympus optical microscope to collect sample carry out morphology observation be indefinite
The granule of type, almost can not see spheroid, and the spray-dried spheroid product that can not obtain of this sample, SAPO-34-DW molecular sieve are described
The bonding microsphere that can not be effectively formed and gather state is lacked between granule.
(4) the fibrage filter paper of 5 microns is used to carry out in buchner funnel SMT-LU-3 molecular sieve Sample Spray dry
Filtering and washing, makes cleaning mixture conductance be less than 500S, then by washed sample at 110 DEG C of oven for drying, the sample being dried the most at last
Product carry out calcination process at the micro-microwave Muffle furnace of CEM, and programming rate is 5 DEG C/min, to 550 DEG C, keep 150 points at a temperature of being somebody's turn to do
Clock, this catalyst is SD-493-DW-C1.
(5) catalyst good for calcination activation is carried out methanol-to-olefins catalytic performance test, methanol content in reaction raw materials
95wt.%, water 5wt.%, reaction temperature 460 DEG C, methanol quality air speed 20h-1, reaction pressure 4kPa, obtain the MTO of this sample
Catalytic performance the results are shown in Table 2.
The physical property characterization result of table 1 each embodiment catalyst
The methanol to olefins reaction Activity evaluation of table 2 embodiment 1 sieve sample
Material testing art
1, the material phase analysis synthesizing sieve sample, corresponding Sample Spray dry and calcination process catalyst sample leads to
Cross Brooker (Bruker) company X-ray powder instrument Discover D8 (HighStar GADDS two-dimensional detector) to measure, measure
Condition is: Cu K α target, graphite monocrystalline device, and pipe pressure 40kV, pipe flow 20mA, 12 °/min of scanning speed, 2theta are 5～80 °, survey
Test result Origin software processes.
2, the crystal morphology synthesizing sieve sample, corresponding Sample Spray dry and calcination process catalyst sample leads to
Crossing Hitachi (Hitachi) companies scan ultramicroscope TM-1000 to carry out, sample is the most gold-plated, and specimen holder coats conductive tape,
Then different regions is selected to carry out observing and imaging.
3, the specific surface area synthesizing sieve sample, corresponding Sample Spray dry and calcination process catalyst sample is led to
Crossing Merck & Co., Inc's Micromeritics ASAP-2020 ratio surface area instrument to be measured, sample needs to be de-gassed pre-place before measuring
Reason, use Micromeritics V60 de-aeration stage sweeping type degassing, degasification process in two stages: i.e. 30ml/ under room temperature condition
The nitrogen of min purges 30 minutes；After then heating to 350 DEG C, the nitrogen of 30ml/min purges 2 hours.
4, sieve sample, corresponding Sample Spray dry and the distribution of particle sizes of calcination process catalyst sample are synthesized
Measured by Britain's Malvern (Malvern) company laser granulometry instrument Mastersizer S, use wet method test sample, will treat
Test sample product join in certain dispersant (such as water), select the suitable refractive power factor, obscurity to measure.
5, the fired abrasion index processing Sample Spray dry catalyst sample measures with reference to U.S. ASTM test mark
The design of jet cup and test condition and method used by quasi-D5757.Abrasion index is average abrasion loss hourly.
6, sieve sample, corresponding Sample Spray dry and the methanol-to-olefins of calcination process catalyst sample are synthesized
Catalytic performance test product analysis uses Agilent instrument company gas chromatogram GC5890-II to carry out separating and quantitatively, measuring bar
Part: flame ionization ditector, 20 DEG C/min rises to 160 DEG C, quantified by external standard method.
It is spray-dried roasting sample bulk density to measure: 20.0 grams of calcined catalyst samples are put into 25 milliliters of graduated cylinders, with often
Minutes 30 times clash into laboratory table top, establishes the volume of this catalyst sample, and its bulk density (ABD) is catalyst weight
(gram) is divided by gained volume (milliliter).
7, the solid containing (wt%) of sieve sample, corresponding Sample Spray dry and calcination process catalyst sample is synthesized
Determine, MAS 7000 microwave Muffle furnace that the roasting of catalyst sample and activation processing use U.S. CE M instrument company to produce enters
Row heat treated.Sample is placed in quartz fibre container, in the case of a large amount of calcination atmospheres circulate (5 liters/min), with program
The form heated up is 5-10 DEG C/min from room temperature to 550 DEG C, programming rate.Constant temperature 150-200 minute at 550 DEG C, then with journey
The form of sequence cooling is down to 45 DEG C from 550 DEG C, after roasting sample taking out next step that carry out being correlated with from microwave Muffle furnace
Analyze.
Claims (7)
1. the preparation method of a SAPO-34 microsphere zeolite catalyst, it is characterised in that comprise the steps:
(1) prepared by gel: is first stirred at room temperature under state and joins in deionized water by aluminum source, adds phosphorus source stirring all
Even, it is then slowly added into silicon source and continues to stir, be eventually adding tetraethyl ammonium hydroxide solution to be mixed uniformly, continuously add
2-aminopropane., in diethylamine, triethylamine one and or several, mixing speed is 200-660 rev/min, stirs 4-14 hour, makes body
It is tied to form homogeneous gel；
(2) crystallization: transferred to by gel in autoclave, under stirring, with the heating rate liter of 0.5-5 DEG C/h
Crystallization 36-84 hour at 160-190 DEG C；
(3) crystallization mother liquor: after crystallization completes, to reacting kettle jacketing logical cooling oil cooling rapidly, treats that system temperature is less than 65 DEG C,
This SAPO-34 Zeolite synthesis product mother solution is drawn off from autoclave；
(4) it is spray-dried: step (3) gained synthetic product mother solution is spray-dried, it is thus achieved that Spray dried products；
(5) by (4) gained Spray dried products in 540-560 DEG C of roasting 1.5-2.5 hour, SAPO-34 molecular sieve microsphere is obtained
Catalyst；
Source of aluminium is with Al2O3Meter, phosphorus source is with P2O5Meter, silicon source is with SiO2Meter, solvent is with H2O counts, template tetraethyl hydroxide
Ammonium is with R1Meter, template 2-aminopropane. is with R2Meter, template diethylamine is with R3Meter, template triethylamine is with R4Meter, Zeolite synthesis is anti-
The mol ratio answering material is:
1.0Al2O3:1.0-1.4P2O5:0.05-0.25SiO2:0.5-1.8(R1+R2+R3+R4):25-95H2O, wherein R2/R1=
0-0.55；R3/R1=0-0.3；R4/R1=0-0.25, and R2, R3, R4Can not be 0 simultaneously.
The preparation method of a kind of SAPO-34 microsphere zeolite catalyst the most as claimed in claim 1, it is characterised in that described aluminum
Source is boehmite.
The preparation method of a kind of SAPO-34 microsphere zeolite catalyst the most as claimed in claim 1, it is characterised in that described phosphorus
Source is orthophosphoric acid.
The preparation method of a kind of SAPO-34 microsphere zeolite catalyst the most as claimed in claim 1, it is characterised in that described silicon
Source is neutral Ludox.
The preparation method of a kind of SAPO-34 microsphere zeolite catalyst the most as claimed in claim 1, it is characterised in that described
Being spray-dried is twin, and spray drying temperature is 250-435 DEG C, and atomizing pressure is 120kPa-800kPa, atomization gas
For the mixture of noble gas or noble gas with air, atomization gas flow rate is 1-20 cubic meters per minute, is spray-dried out
Mouth temperature is 85-155 DEG C.
The preparation method of a kind of SAPO-34 microsphere zeolite catalyst the most as claimed in claim 1, it is characterised in that SAPO-
The average particle size of 34 microsphere zeolite catalysts is 25-275 micron.
7. method as described in any one of claim 1-6 prepares the application of catalyst, it is characterised in that catalyst is used for methanol system
Olefin catalytic conversion process, comprises the steps: water-soluble to catalyst and methanol or methanol that methanol content is 35-95wt%
Liquid, is 400-550 DEG C in reaction temperature；Reaction pressure is 1-300kPa；The mass space velocity of reaction is 1.2-30.5 gram of methanol/gram
Catalyst/hour under the conditions of carry out haptoreaction.
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| CN107399744A (en) * | 2017-08-29 | 2017-11-28 | 天津众智科技有限公司 | A kind of preparation method of molecular sieves of SAPO 34 and its application in preparing olefin by conversion of methanol |
| CN107572549A (en) * | 2017-08-29 | 2018-01-12 | 天津众智科技有限公司 | A kind of preparation method of molecular sieves of SAPO 34 and the application of the molecular sieves of SAPO 34 |
| CN107572549B (en) * | 2017-08-29 | 2021-01-26 | 天津众智科技有限公司 | Preparation method of SAPO-34 molecular sieve and application of SAPO-34 molecular sieve |
| CN111433157A (en) * | 2017-12-07 | 2020-07-17 | 赢创运营有限公司 | Preparation of powdery, porous crystalline metallosilicates by flame spray pyrolysis |
| CN111433157B (en) * | 2017-12-07 | 2023-09-29 | 赢创运营有限公司 | Preparation of powdery, porous crystalline metallosilicate by flame spray pyrolysis |
| CN110342533A (en) * | 2018-04-02 | 2019-10-18 | 国家能源投资集团有限责任公司 | Molecular sieve and its preparation method and application |
| CN110092390A (en) * | 2019-04-17 | 2019-08-06 | 汕头大学 | The loose porous spherical shape SAPO-34 molecular sieve of one kind and its preparation and application |
| CN110092390B (en) * | 2019-04-17 | 2022-03-22 | 汕头大学 | Loose porous spherical SAPO-34 molecular sieve and preparation and application thereof |
| CN112239218A (en) * | 2019-07-17 | 2021-01-19 | 国家能源投资集团有限责任公司 | Preparation method of MTO catalyst, MTO catalyst and application thereof |
| CN112239218B (en) * | 2019-07-17 | 2022-08-09 | 国家能源投资集团有限责任公司 | Preparation method of MTO catalyst, MTO catalyst and application thereof |
| CN111097511A (en) * | 2019-12-25 | 2020-05-05 | 山东江岳科技开发股份有限公司 | SAPO-34 molecular sieve catalyst production device |
| CN112062138A (en) * | 2020-09-08 | 2020-12-11 | 正大能源材料(大连)有限公司 | Catalyst for preparing olefin from methanol and preparation method and application thereof |
| CN112062138B (en) * | 2020-09-08 | 2022-04-15 | 正大能源材料(大连)有限公司 | Catalyst for preparing olefin from methanol and preparation method and application thereof |
| CN113562739A (en) * | 2021-08-06 | 2021-10-29 | 中海油天津化工研究设计院有限公司 | Method for fully crystallizing SAPO-34 molecular sieve balls by using aluminophosphate molecular sieve mother liquor |
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