CN108435245A - Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application - Google Patents
Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application Download PDFInfo
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- CN108435245A CN108435245A CN201810357940.4A CN201810357940A CN108435245A CN 108435245 A CN108435245 A CN 108435245A CN 201810357940 A CN201810357940 A CN 201810357940A CN 108435245 A CN108435245 A CN 108435245A
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- kaolin
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- 239000004005 microsphere Substances 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 65
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 65
- 229910001868 water Inorganic materials 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 claims abstract description 47
- 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 47
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000376 reactant Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- -1 dimethyl stearyl Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 150000001768 cations Chemical group 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 241000269350 Anura Species 0.000 abstract 6
- 239000000047 product Substances 0.000 description 57
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 23
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 18
- 238000011065 in-situ storage Methods 0.000 description 17
- 238000011066 ex-situ storage Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002689 soil Substances 0.000 description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000012216 screening Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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)
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of 34@kaolin microspheres catalyst of little crystal grain grade hole SAPO and its preparations and application.The preparation method includes the following steps：Kaolin microsphere, the kaolin microsphere activated after fired is prepared；It is mixed with the alukalin microballoon, water, phosphorus source, micropore template agent and mesoporous template to obtain reactant gel；Crystallizing treatment is carried out to the reactant gel, centrifuges, obtains 34@kaolin microsphere composite materials of little crystal grain grade hole SAPO；Calcination process is carried out to 34@kaolin microsphere composite materials of little crystal grain grade hole SAPO, obtains 34@kaolin microsphere catalyst of little crystal grain grade hole SAPO.34 molecular sieve contents of SAPO height, crystal grain are small in the 34@kaolin microsphere catalyst of SAPO, and have grade hole；Compared with the product being not added with obtained by mesoporous template, the yield with higher situ product.
Description
Technical field
The present invention relates to chemical technology fields, and specifically, the present invention relates to a kind of little crystal grain grade hole SAPO-34@high
Ridge soil microspherical catalyst and its preparation and application.
Background technology
Ethylene and propylene are the most important basic organic chemical raw materials of chemical industry, and act is played in modern petrochemical field
The effect of sufficient weight.In recent years, gradually decreasing with oil amount of storage, oil supply amount is increasingly deficient, is original with naphtha
Material production ethylene and the route of propylene will face a severe test, and therefore, seeking to substitute petroleum path, to prepare ethylene and propylene etc. low
The process route of carbon olefin becomes inevitable.By the research for many years of researcher, using coal or natural gas as raw material, through methanol or
Person's dimethyl ether is the process route for being most hopeful to substitute naphtha route for the route of low-carbon alkene.First industrially at present
The catalyst of alcohol alkene (MTO) is the catalyst using SAPO-34 as active component, and building-up process summary is：Chemical reagent closes
At micropore SAPO-34 molecular screen primary powders, then by it with matrix (generally kaolin), binder, pore creating material and water etc. mix,
Stir, be beaten, being spray dried to 80-100 μm or so of bead, as MTO catalyst.This method is referred to as " semi-synthetic " side
Method, there are following two disadvantages for MTO catalyst prepared by this " semi-synthetic " method：First, synthesized SAPO-34 molecular sieves
Usually micro porous molecular sieve, molecular sieve bore diameter is smaller, is unfavorable for the diffusion of reactants and products, easily coking and deactivation；Second, it adopts
It being unevenly distributed with the catalyst activity component prepared by " semi-synthetic ", binder blocks duct, catalyst duct not unicom,
Easily cause catalyst inactivation.
Some researches show that in MTO reactions, reduce the crystallite dimension of SAPO-34 molecular sieves, be conducive to reactants and products
Diffusion；On the other hand, mesoporous, SAPO-34 molecular sieve of the synthesis with grade pore passage structure is introduced in micro porous molecular sieve,
The diffusion that reactants and products can be improved, to improve catalyst service life and diene (ethylene+propylene) selectivity, simultaneously
Reaction depth can effectively be inhibited, carbon deposition rate is reduced and increase and hold carbon ability；Third, using in-situ crystallization method, in matrix
Upper growth in situ molecular sieve crystal, catalyst can be prepared to avoid " semi-synthetic " method to be caused Active components distribution unevenness, bonds
Agent blocks the problem of duct.
Research about little crystal grain and grade hole SAPO-34 molecular sieves has very much, such as：Liu Hongxing has applied for a series of passes
In how the patent of the method for synthesizing small-grain SAPO-34 molecular sieves：CN104445266A, CN103420391A and
CN102464338A.Wherein, the method for CN104445266A reports is first to obtain the initial crystallization 1-10h of SAPO-34 defective
SAPO-34 crystal seeds, then this defective crystal seed is added in the initial crystallization liquid of SAPO-34, at 140-170 DEG C
Hydro-thermal process 0.1-4h dissolves defect crystal seed, then continues the SAPO-34 molecular sieves that heating crystallization obtains little crystal grain；CN
The method of 103420391 A reports is to prepare fine grain SAPO-34 by the method for being segmented crystallization, and concrete operations are first in 180-
250 DEG C of crystallization 1-20h, then program be cooled to -160 DEG C of room temperature, at least keep 0.1h, be finally continuously heating to 180-250 DEG C
Crystallization 2-24h, obtains fine grain SAPO-34；The method of 102464338 A of CN is similar with 104445266 A of CN, only raw material
In add HF solution.
Preparation report about grade hole SAPO-34 is few.106608632 A of CN describe a kind of hierarchical porous structure
The preparation method of SAPO-34 molecular sieves is mainly obtained by the method that nano carbon black hard mould agent is added in synthesized gel rubber
Multi-stage porous；105858684 A of CN 104525250 A and CN reports the crystal seed by introducing broken crystal seed and Nano lamellite
The method for preparing multi-stage porous SAPO-34 molecular sieves；104973608 A of patent CN report poly- by being added in synthesized gel rubber
The method of ethylene glycol prepares the SAPO-34 molecular sieves of multi-stage porous；It is more that 107285342 A of CN report a kind of post-processing preparation
SAPO-34 molecular sieves and solid acid, i.e., be pulverized and mixed uniformly by the method for grade hole SAPO-34 molecular sieves, anti-at 20-120 DEG C
The regular hour is answered to obtain multi-stage porous SAPO-34 molecular sieves；The little crystal grain or more that above-mentioned a series of preparation method obtains
Grade hole SAPO-34 molecular sieves all have good reactivity worth, however the synthetic method that gained has been reported for work is entirely that ex situ is closed
At using the deficiency for equally existing " semi-synthetic " catalyst.
In conclusion existing literature report changes building-up process and synthesis condition comes mainly by the method for ex situ
It prepares little crystal grain or multi-stage porous SAPO-34 molecular sieves, the molecular sieve of gained is required to be prepared into MTO using " semi-synthetic " method
Catalyst, therefore, using in-situ synthetic method, exploitation diffusion is good, the high fabricated in situ little crystal grain grade of catalytic performance
Hole SAPO-34 molecular sieve catalytic materials and catalyst have great importance.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of little crystal grain grade hole SAPO-34@kaolin
The preparation method of microspherical catalyst.Whole sial of SAPO-34 Zeolite synthesis are provided by using kaolin microsphere for raw material
Source, and as the matrix of molecular sieve growth, phosphorus source is supplemented, and specific mesoporous template is added in the synthesis process, it is in situ brilliant
Change and realizes.
Another object of the present invention is to provide a kind of high yield SAPO-34@kaolin microsphere catalyst.
Another object of the present invention is to provide a kind of methods of methanol-to-olefins.
In order to achieve the above objectives, the present invention provides a kind of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst
Preparation method, wherein this method comprises the following steps：
(1) kaolin microsphere, the kaolin microsphere activated after fired is prepared；
(2) kaolin microsphere, water of the activation for obtaining step (1), phosphorus source, micropore template agent and the mixing of mesoporous template
Reactant gel is prepared, each component molar ratio meets following condition：
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2
+R3):(100-300)H2O, wherein R1 is micropore template agent, and R2 and R3 are mesoporous template, and silicon source and silicon source are all from kaolinite
Native microballoon；
(3) Crystallizing treatment is carried out to the reactant gel that step (2) obtains, is then centrifuged for detaching, obtains little crystal grain grade
Hole SAPO-34@kaolin microsphere composite materials；
(4) calcination process is carried out to the composite material that step (3) obtains, obtains little crystal grain grade hole SAPO-34@high
Ridge soil microspherical catalyst.
Preparation method provided by the present invention using in kaolin silicon, aluminium species are as synthesis SAPO-34 molecular sieves
One of raw material supplements phosphorus source, and using specific template is introduced, induces the SAPO-34@kaolin in synthesizing small-grain grade hole
Microspherical catalyst.Method using the present invention is using the sial component in kaolin as the raw material of synthesis SAPO-34 molecular sieves, energy
It is enough largely to reduce synthesis cost, synthesized SAPO-34 small, step hole feature structures with crystal grain, and have
Very high yield, while being conducive to the raising of MTO reactivity worth.
In the present invention, silicon, the aluminium species (i.e. silicon source, silicon source) of kaolin offer refer in kaolin microsphere by roasting
After processing, it can be extracted by hydrochloric acid or sodium hydroxide solution, into reactant gel, the sial object as Zeolite synthesis
Kind.
In the preparation process in accordance with the present invention, the kaolin microsphere of step (1) can be carried out according to prior art conventional method
It prepares, step (1) can be that it is micro- to prepare kaolin using the method for spray drying after mixing kaolin with water and binder
Ball.Specifically, first kaolin can be crushed, screening, is then mixed again with water and binder.
In the preparation process in accordance with the present invention, in step (1), the mass ratio of kaolin and binder is preferably 2.5-3:1.
In the preparation process in accordance with the present invention, in step (1), binder is preferably in waterglass, Aluminum sol and Ludox
One or more mixtures.
In the preparation process in accordance with the present invention, it is preferable that in step (1), the temperature of roasting is 700-900 DEG C, more preferably
It is 800 DEG C；The time of roasting is 1-6h, more preferably 3-4h.
In the preparation process in accordance with the present invention, in step (1), kaolin microsphere can be according to prior art conventional kaolin
Prepared by Microsphere Size, it is preferable that the grain size of kaolin microsphere is 80-110 μm.
In the preparation process in accordance with the present invention, the charging sequence in step (2) can be：Water-phosphoric acid-micropore template agent-height
The aqueous solution of the mesoporous template R3 of ridge soil microballoon-mesoporous template R2-.Mesoporous template is first added when mesoporous template is added
Mesoporous template R3 is added in R2 afterwards.Mesoporous template R3 needs thoroughly to be dissolved with a certain amount of deionized water before addition.
In the preparation process in accordance with the present invention, it is preferable that step (2) includes：First mesoporous template R3 is mixed with part water,
It is stirred overnight, so that mesoporous template R3 is fully dissolved, obtain solution A；Phosphorus source is uniformly mixed with part water, micropore is then added
Template R1 is added the kaolin microsphere for the activation that step (1) obtains, mesoporous template R2 is then added, stirs after mixing
It mixes after so that it is sufficiently mixed, the solution A is added.
In the preparation process in accordance with the present invention, it is preferable that in step (2), the molar ratio of each component preferably satisfies following item
Part：(0.2-0.27)SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9)R1:(0.13-0.61)(R2+R3):
(114-300)H2O。
In the preparation process in accordance with the present invention, it is preferable that in step (2), mesoporous template R2 is added and carries out aging later
Processing, the temperature of the burin-in process may be controlled to 40-90 DEG C, preferably 70 DEG C.
In the preparation process in accordance with the present invention, it is preferable that in step (2), the solution A containing mesoporous template R3 is to add
It is added after entering mesoporous template R2 and aging 0-5h；It is added after preferably burin-in process 3.5h.
In the preparation process in accordance with the present invention, it is preferable that the micropore template agent is triethylamine.
In the preparation process in accordance with the present invention, it is preferable that phosphorus source is orthophosphoric acid.
In the preparation process in accordance with the present invention, it is preferable that the mesoporous template R2 is selected from cationic surfactant 16
One kind in alkyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide and dodecyl trimethyl ammonium bromide etc..
In the preparation process in accordance with the present invention, it is preferable that the mesoporous template R3 is selected from organosilan dimethyl hexadecyl
One kind in base [3- trimethoxy silicon propyl] ammonium chloride and dimethyl stearyl [3- trimethoxy silicon propyl] ammonium chloride etc..
In the preparation process in accordance with the present invention, it is preferable that in step (3), the temperature of Crystallizing treatment is 180-220 DEG C, excellent
It is selected as 200 DEG C；The time of Crystallizing treatment is 24-72h, preferably 48h.
In the preparation process in accordance with the present invention, it is preferable that step (3), by standing sedimentation, is centrifuged, washed after crystallization
It washs and obtains little crystal grain grade hole SAPO-34@kaolin microsphere composite materials with drying and other steps.The standing sedimentation time can control
For 2-15min.Dry temperature may be controlled to 100-120 DEG C, be carried out in air atmosphere, and drying time can be 4-12h.
In the preparation process in accordance with the present invention, it is preferable that in step (4), the temperature of the roasting is 500-650 DEG C, institute
The time for stating roasting is 3-6h.
It is excellent the present invention also provides the little crystal grain grade hole SAPO-34@kaolin microspheres that above-mentioned preparation method is prepared
Selection of land, in terms of relative crystallinity, the relative amount of SAPO-34 molecular sieves is 15-35wt.%.
Specific embodiment according to the present invention, yield in situ=(situ product quality after roasting)/(feed intake middle kaolin
The quality of the corresponding phosphorus pentoxide of microballoon+phosphoric acid), little crystal grain grade hole SAPO-34@kaolin microspheres prepared by the present invention are urged
The yield of agent is 55-70wt.%.
The present invention also provides a kind of methods of methanol-to-olefins, wherein this method is with the methanol of a concentration of 95wt.%
Aqueous solution is raw material, using above-mentioned little crystal grain grade hole SAPO-34 kaolin microspheres as catalyst, in normal pressure, reaction temperature 450
DEG C, mass space velocity 2.5h-1Under conditions of prepare alkene.
Technical scheme of the present invention has the following advantages that：
The present invention, simultaneously as matrix and part material, provides synthesis SAPO-34 molecular sieves institute using kaolin microsphere
Whole silicon and aluminum sources needed, and specific mesoporous template is added in the synthesis process, obtained SAPO-34 molecular sieve contents it is high,
The small SAPO-34@kaolin microsphere catalyst with grade hole of crystal grain；Compared with the product being not added with obtained by mesoporous template,
Yield with higher situ product.
The little crystal grain grade hole SAPO-34@kaolin microspheres catalyst can be reacted directly as MTO catalyst for MTO
Device, this can not only greatly shorten the preparation path of catalyst, reduce catalyst preparation cost, and can be closed by modulation
Come the grain size of modulation SAPO-34 and mesoporous content, and then the architectural characteristic of modulation composite material at condition, avoids " semi-synthetic " side
The drawbacks of method matrix or binder block molecular sieve pore passage, can also avoid the generation of a large amount of ex situ products, play small crystalline substance
The synergistic effect of grain and grade pore structure, to improve MTO reaction service life and diene (ethylene+propylene) selectivity.
Description of the drawings
Fig. 1 is the XRD spectra of 1 obtained catalyst of embodiment.
Fig. 2 a and Fig. 2 b are the Flied emission scanning that 1 obtained composite material of embodiment amplifies 400 times and 10000 times respectively
Electronic Speculum (FESEM) photo.
Fig. 3 is the XRD spectra of 2 obtained catalyst of embodiment.
Fig. 4 a and Fig. 4 b are the FESEM photos that 2 obtained composite material of embodiment amplifies 800 times and 10000 times respectively.
Fig. 5 is the XRD spectra of 3 obtained catalyst of embodiment.
Fig. 6 a and Fig. 6 b are the FESEM photos that 3 obtained composite material of embodiment amplifies 500 times and 10000 times respectively.
Fig. 7 is the XRD spectra of 4 obtained catalyst of embodiment.
Fig. 8 a and Fig. 8 b are the FESEM photographs that 4 obtained composite material of embodiment amplifies 2000 times and 10000 times respectively
Piece.
Fig. 9 is the XRD spectra of 5 obtained catalyst of embodiment.
Figure 10 a and Figure 10 b are the FESEM photographs that 5 obtained composite material of embodiment amplifies 500 times and 20000 times respectively
Piece.
Figure 11 is the XRD spectra of 6 obtained catalyst of embodiment.
Figure 12 a and Figure 12 b are the FESEM photographs that 6 obtained composite material of embodiment amplifies 2000 times and 20000 times respectively
Piece.
Figure 13 is the XRD spectra of 7 obtained catalyst of embodiment.
Figure 14 a and Figure 14 b are that 7 obtained composite material of embodiment amplifies 700 times and 50000 times of FESEM photos respectively.
Figure 15 is the XRD spectra of 1 obtained catalyst of comparative example.
Figure 16 a and Figure 16 b are the FESEM photographs that 1 obtained composite material of comparative example amplifies 1500 times and 20000 times respectively
Piece.
Figure 17 is the XRD spectra of 2 obtained catalyst of comparative example.
Figure 18 a and Figure 18 b are the FESEM photographs that 2 obtained composite material of comparative example amplifies 1500 times and 20000 times respectively
Piece.
Figure 19 is the XRD spectra of 3 obtained catalyst of comparative example.
Figure 20 a and Figure 20 b are the FESEM photographs that 3 obtained composite material of comparative example amplifies 2400 times and 20000 times respectively
Piece.
The N of sample in Figure 212Adsorption/desorption curve.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
The present invention uses the crystal phase structure of XRD determining sample；Using the crystalline form crystalline substance looks of FESEM determination samples；It is inhaled using N2-
The texture property of attached desorption determination sample.
The content of SAPO-34 molecular sieves in the SAPO-34@kaolin microsphere catalyst of little crystal grain step provided by the invention hole
Calculated with relative crystallinity data.Relative crystallinity refers to that the characteristic peak of each molecular sieve in in-situ crystallization product is corresponding
The area of the characteristic peak of molecular sieve standard specimen and the ratio between, the characteristic peaks of SAPO-34 molecular sieves be 2 θ=9.5 °, 16.0 °, 20.5 °,
Peak at 31 °.Standard specimen molecular sieve is the conventional micropore SAPO-34 molecular sieves of Nankai's catalyst plant production, by its crystallinity
It is set to 100%.
Original position yield and ex situ relative productivity provided by the invention are calculated by following equation：Yield=roasting in situ
The quality of SAPO-34@kaolin microsphere catalyst after burning Template removal/(quality for the kaolin microsphere that feeds intake+feed intake phosphoric acid correspondence
Phosphorus pentoxide quality), ex situ relative productivity=ex situ product quality/SAPO-34@kaolin microsphere catalyst
Quality.
Embodiment 1
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 700 DEG C by ridge soil microballoon, spare.
0.5g dimethyl stearyls [3- trimethoxy silicon propyl] ammonium chloride (TPOAC) is weighed to pour into equipped with 15g water
In beaker, 12h is stirred, so that it is fully dissolved, obtains solution A.
It weighs 4g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.1g cetyl trimethylammonium bromides (CTAB) is added, and 70 DEG C of water-baths stand 1h, add
Enter solution A, obtain reactant gel, each component molar ratio meets in the gel of preparation：0.20SiO2:1Al2O3:1.7P2O5:
3.9R1:0.13(R2+R3):170H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 40h in baking oven is rotated at 180 DEG C.
Product is taken out, standing sedimentation 2min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 4h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 15% in product, and situ product yield is
55%, the XRD diffraction patterns of microspherical catalyst are as shown in Figure 1, FESEM photos are as shown in Figure 2 a and 2 b, SAPO-34 grain sizes
About 380nm.
Embodiment 2
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Ludox 35g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 0.7g TPOAC to pour into the beaker equipped with 10g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 4g phosphoric acid to mix with 10g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.3g CTAB is added, and 75 DEG C of water-baths stand 2h, solution A is added, and it is solidifying to obtain reactant
Glue, each component molar ratio meets in the gel of preparation：0.25SiO2:1.17Al2O3:1.7P2O5:3.9R1:0.22(R2+R3):
114H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 5min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 6h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 20% in product, and yield in situ is 57%, micro-
The XRD diffraction patterns of sphere catalyst as shown in figure 3, FESEM photos as shown in figures 4 a and 4b, SAPO-34 grain sizes are about
360nm。
Embodiment 3
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 850 DEG C by ridge soil microballoon, spare.
0.17g dimethyl hexadecyls base [3- trimethoxy silicon propyl] ammonium chloride (TPHAC) is weighed to pour into equipped with 10g water
In beaker, 12h is stirred, so that it is fully dissolved, obtains solution A.
It weighs 5g phosphoric acid to mix with 10g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.5g dodecyl trimethyl ammonium bromide (DTAB) is added, and 70 DEG C of water-baths stand 2.5h,
Solution A is added, obtains reactant gel, each component molar ratio meets in the gel of preparation：0.26SiO2:1.20Al2O3:
2.16P2O5:5.0R1:0.196(R2+R3):115H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 6min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 8h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 22% in product, and yield in situ is 65%, micro-
The XRD diffraction patterns of sphere catalyst as shown in figure 5, FESEM photos as shown in figures 6 a and 6b, SAPO-34 grain sizes are about
350nm。
Embodiment 4
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and waterglass 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 3h at 900 DEG C by ridge soil microballoon, spare.
It weighs 0.8g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.8g tetradecyltrimethylammonium bromide (TTAB) is added, and 70 DEG C of water-baths stand 3h, add
Enter solution A, obtain reactant gel, each component molar ratio meets in the gel of preparation：0.27SiO2:1.25Al2O3:
2.16P2O5:5.0R1:0.40(R2+R3):292H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 8min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 10h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 25% in product, and yield in situ is 56%, micro-
The XRD diffraction patterns of sphere catalyst as shown in fig. 7, FESEM photos as figures 8 a and 8 b show, SAPO-34 grain sizes are about
470nm。
Embodiment 5
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 4g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, obtains reactant
Gel, each component molar ratio meets in the gel of preparation：0.25SiO2:1.17Al2O3:1.73P2O5:3.9R1:0.42(R2+
R3):170H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 34% in product, and yield in situ is 68%, micro-
The XRD diffraction patterns of sphere catalyst as shown in figure 9, FESEM photos as as-shown-in figures 10 a and 10b, SAPO-34 grain sizes are about
600nm。
Embodiment 6
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.7g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 6g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 6g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 1g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, and it is solidifying to obtain reactant
Glue, each component molar ratio meets in the gel of preparation：0.25SiO2:1.17Al2O3:2.6P2O5:5.9R1:0.61(R2+R3):
300H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 30% in product, and yield in situ is 62%.It is micro-
The XRD diffraction patterns of sphere catalyst are as shown in figure 11, and as depicted in figs. 12 a and 12b, SAPO-34 grain sizes are about FESEM photos
550nm。
Embodiment 7
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped
Include following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, obtains reactant
Gel, each component molar ratio meets in the gel of preparation：0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.42(R2+
R3):292H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h
Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 35% in product, and yield in situ is 70%, micro-
The XRD diffraction patterns of sphere catalyst are as shown in figure 13, and as shown in Figure 14 a and Figure 14 b, SAPO-34 grain sizes are about FESEM photos
260nm。
Comparative example 1
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition
Amine continues to stir, and 5g kaolin microspheres are added, and 70 DEG C of water-baths stand 3.5h；Solution A is added, in the gel of preparation respectively at centimorgan
You are than meeting：0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.20R3:292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 19% in product, and yield in situ is 70.2%,
The XRD diffraction patterns of microspherical catalyst are as shown in figure 15, and as shown in fig 16 a and fig 16b, SAPO-34 grain sizes are about for FESEM photos
It is 1 μm.
Comparative example 2
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
Weigh 5g phosphoric acid to mix with 15g water phases, stir 30min under 40 DEG C of water bath conditions, be added under stirring condition 15g water and
5g triethylamines continue to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h；It is each in the gel of preparation
Component molar ratio meets：0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.22R2:292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 33% in product, and yield in situ is 64.9%,
The XRD diffraction patterns of microspherical catalyst are as shown in figure 17, and FESEM photos are as shown in Figure 18 a and Figure 18 b, and SAPO-34 grain sizes are about
For 800nm.
Comparative example 3
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps：
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height
Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
Weigh 5g phosphoric acid to mix with 15g water phases, stir 30min under 40 DEG C of water bath conditions, be added under stirring condition 15g water and
5g triethylamines continue to stir, and 5g kaolin microspheres are added, and 70 DEG C of water-baths stand 3.5h；Each component molar ratio in the gel of preparation
Meet：0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0(R2+R3):292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point
From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 11.2% in product, and yield in situ is
54.2%, the XRD diffraction patterns of microspherical catalyst are as shown in figure 19, and for FESEM photos as shown in Figure 20 a and Figure 20 b, SAPO-34 is brilliant
Grain size is about 2 μm.
Experimental example：The texture property and catalytic performance of fine grain SAPO-34@kaolin microsphere catalyst
Texture property is tested using the full-automatic specific surfaces of Kang Ta and Porosimetry (Autosorb-iQ3-XR), is inhaled
Attached gas is nitrogen, (is denoted as S@to the little crystal grain grade hole SAPO-34@kaolin microspheres catalyst prepared by embodiment 7 respectively
KCT), the SAPO-34@kaolin microspheres catalyst (being denoted as S@KT) prepared by comparative example 1, the SAPO- prepared by comparative example 2
SAPO-34@kaolin microspheres catalyst prepared by 34@kaolin microspheres catalyst (being denoted as S@KC) and comparative example 3 (is denoted as S@
K N) is carried out2Adsorption/desorption characterizes, N2Adsorption/desorption curve is as shown in figure 21, and texture property is as shown in table 1.As shown in Table 1, single
The mesoporous template R2, that is, cetyl trimethylammonium bromide of pure introducing, the mesoporous influence on product are not very big, but from it
FESEM photos can see, kaolin microsphere surface distribution little crystal grain SAPO-34 molecular sieves, illustrate, the introducing of CTAB
Contribute to the generation of little crystal grain；Occurs a large amount of mesoporous knot if the mesoporous template R3, that is, TPOAC of simple introducing, in product
Structure, mesoporous and micropore volume ratio be up to 3.2, however from its FESEM photo it is found that the SAPO-34 on kaolin microsphere surface
Grain diameter is larger.And if CTAB and TPOAC is added simultaneously, what can be will be apparent that sees, synthetic product has had both simple introducing
Advantage when two kinds of mesoporous templates, i.e., existing a large amount of mesoporous generation, and there is the SAPO-34 of little crystal grain to generate, to success
Obtain little crystal grain grade hole SAPO-34@kaolin microsphere catalyst.
The texture property of 1 sample of table
MTO is carried out to aforementioned four catalyst S@K, S@KC, S@KT and S@KCT and is catalyzed reaction evaluating, wherein evaluation raw material
For the methanol aqueous solution of 95wt.%, evaluation condition is：450 DEG C of reaction temperature, mass space velocity 2.5h-1, flow rate of carrier gas 20ml/
min.Product after reaction is analyzed using offline gas-chromatography, divides 3420A gas chromatographs using north, HP PLOT-Q columns,
Fid detector is detected.When methanol conversion is less than 98wt.%, you can think that catalyst has inactivated, stop at this time real
It tests, and using the time point as catalyst life.Selectivity of product result takes in methanol-to-olefins reaction process in sample point
Maximum value.Evaluation result is as shown in table 2.
The data provided from table 2 are prepared into merely little crystal grain it is found that for simple introducing meso-hole structure
SAPO-34@kaolin microspheres have more preferably MTO reactivity worth, wherein compared with the catalyst S@K for being not added with mesoporous template,
Fine grain SAPO-34@kaolin microsphere catalyst S@KC have relatively high diene selective and react the service life, and grade hole
The diene selective of SAPO-34@kaolin microsphere catalyst S@KT is suitable with S@K, but its catalytic life slightly extends.And lead to
The double mesoporous templates of addition are crossed, obtained little crystal grain grade hole SAPO-34@kaolin microsphere catalyst has optimal MTO anti-
Performance is answered, not only catalytic life greatly extends, and close to 200min, while diene selective is also up to 81%, illustrates little crystal grain
The effect of collaboration has been played with step hole.
2 methanol-to-olefins catalytic performance test result of table
It is above-mentioned the experimental results showed that, method through the invention can be prepared that zeolite crystal is small, molecular sieve content
High, situ product yield height and the fine grain SAPO-34@kaolin microsphere catalyst with grade pore structure；Meanwhile Ke Yitong
Cross modulation synthesis condition, the grain size of modulation SAPO-34 and mesoporous content；And it is prepared compared to mesoporous template is not added with
SAPO-34@kaolin microsphere catalyst, the obtained product of the present invention has better activity stability, catalyst life
Long, about 200min, diene selective is up to 81%, has good prospects for commercial application.
Claims (10)
1. a kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst, wherein this method includes as follows
Step：
(1) kaolin microsphere, the kaolin microsphere activated after fired is prepared；
(2) kaolin microsphere of the activation, water, phosphorus source, micropore template agent and mesoporous template are mixed with and are reacted
Object gel, each component molar ratio meet following condition：
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2+
R3):(100-300)H2O；Wherein, R1 is micropore template agent, and R2 and R3 are mesoporous template, and silicon source and silicon source are all from kaolinite
Native microballoon；
(3) Crystallizing treatment is carried out to the reactant gel, centrifuges, it is micro- obtains little crystal grain grade hole SAPO-34@kaolin
Ball composite material；
(4) calcination process is carried out to little crystal grain grade hole SAPO-34@kaolin microsphere composite materials, obtains the small crystalline substance
Grain grade hole SAPO-34@kaolin microsphere catalyst.
2. preparation method according to claim 1, wherein the step (1) includes following operation：By kaolin, bonding
Agent and water mixing, kaolin microsphere, the fired kaolin microsphere activated are prepared by spray drying；
Preferably, the mass ratio of the kaolin and binder is 2.5-3:1；
Preferably, the binder is one or more mixtures in waterglass, Aluminum sol and Ludox；
Preferably, the temperature of the roasting is 700-900 DEG C, and more preferably 800 DEG C, the time of the roasting is 1-6h, more excellent
It is selected as 3-4h；
Preferably, the grain size of the kaolin microsphere is 80-110 μm.
3. preparation method according to claim 1, wherein the step (2) includes：
Mesoporous template R3 is mixed with part water first, is stirred overnight, so that mesoporous template R3 is fully dissolved, obtains solution A；
Phosphorus source is uniformly mixed with part water, micropore template agent R1 is then added, the work that step (1) obtains is added after mixing
The kaolin microsphere of change is then added mesoporous template R2 and the solution A is added, is prepared after stirring makes it be sufficiently mixed
Reactant gel；
Preferably, each component molar ratio is (0.2-0.27) SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9)
R1:(0.13-0.61)(R2+R3):(114-300)H2O；
Preferably, mesoporous template R2 is added and carries out burin-in process later, it is highly preferred that the temperature of the burin-in process is 40-90
DEG C, further preferably 70 DEG C；
Preferably, the solution A is added after burin-in process 0-5h, is preferably added after burin-in process 3.5h.
4. preparation method according to claim 1 or 3, wherein the micropore template agent is triethylamine.
5. preparation method according to claim 1 or 3, wherein phosphorus source is orthophosphoric acid.
6. preparation method according to claim 1 or 3, wherein the mesoporous template R2 is selected from cation surface activating
One kind in agent cetyl trimethylammonium bromide, tetradecyltrimethylammonium bromide and dodecyl trimethyl ammonium bromide.
7. preparation method according to claim 1 or 3, wherein the mesoporous template R3 is selected from organosilan dimethyl
In cetyl [3- trimethoxy silicon propyl] ammonium chloride and dimethyl stearyl [3- trimethoxy silicon propyl] ammonium chloride
It is a kind of.
8. preparation method according to claim 1, wherein in step (3), the temperature of the Crystallizing treatment is 180-
220 DEG C, preferably 200 DEG C；The time of the Crystallizing treatment is 24-72h, preferably 48h；
In step (4), the temperature of the roasting is 500-650 DEG C, and the time of the roasting is 3-6h.
9. the little crystal grain grade hole SAPO-34@kaolin microspheres that claim 1-8 any one of them preparation methods are prepared
Catalyst, it is preferable that in terms of relative crystallinity, the relative amount of SAPO-34 molecular sieves is 15-35wt.%, situ product yield
For 55-70wt.%.
10. a kind of method of methanol-to-olefins, wherein this method be using the methanol aqueous solution of a concentration of 95wt.% as raw material, with
Little crystal grain grade hole SAPO-34@kaolin microsphere catalyst described in claim 9 is catalyst, in normal pressure, reaction temperature
450 DEG C, mass space velocity 2.5h-1Under conditions of prepare alkene.
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| CN106582804A (en) * | 2015-10-20 | 2017-04-26 | 中国石油大学(北京) | Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof |
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| Title |
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| HASSAN SHARIFI PAJAIE ET AL.: "Methanol conversion to light olefins over surfactant-modified nanosized SAPO-34", 《REAC KINET MECH CAT》 * |
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