CN104828842B - A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO - Google Patents
A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO Download PDFInfo
- Publication number
- CN104828842B CN104828842B CN201510153532.3A CN201510153532A CN104828842B CN 104828842 B CN104828842 B CN 104828842B CN 201510153532 A CN201510153532 A CN 201510153532A CN 104828842 B CN104828842 B CN 104828842B
- Authority
- CN
- China
- Prior art keywords
- sapo
- silicon source
- molecular screen
- source
- composite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 241000269350 Anura Species 0.000 title abstract 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 74
- 239000010703 silicon Substances 0.000 claims abstract description 74
- 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
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 24
- 230000008025 crystallization Effects 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000002734 clay mineral Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910001868 water Inorganic materials 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000007812 deficiency Effects 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- -1 pseudobochmite Chemical compound 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017119 AlPO Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of preparation method of 34 composite molecular screen of SAPO 5/SAPO, wherein, using Hydrothermal Synthesiss crystallization steps, obtains the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO, wherein, using SiO2/Al2O3Naturally occurring or synthetic clay minerals matter or their arbitrary mixture of the molar ratio range between 0.05 1.5 are used as silicon source and the complex of silicon source.In 5 molecular sieve of SAPO, more macropore and mesoporous quantity effectively compensate for the deficiency of macropore and mesoporous quantity in 34 molecular sieve of SAPO, so that the composite molecular screen is when for being catalyzed organic oxygen-containing compound reaction for preparing light olefins, the yield of propylene and butylene is improved.
Description
Technical field
The present invention relates to a kind of preparation by SAPO-5 molecular sieve and the composite molecular screen of SAPO-34 molecular sieve symbiosis
Method.
Background technology
The catalysis material used by methanol to olefins reaction is mainly the acid zeolite of aperture and mesopore.Nineteen eighty-two, the U.S.
Union carbide corporation (UCC) scientist Wilson S T and Flanigen E M are closed with organic amine as template first in hydrothermal system
Become new aluminophosphate molecular sieve, subsequently, AlPO with aperture, mesoporous and macropore4- n series of micropores molecular sieve goes out in succession
Existing.1984, Si was introduced AlPO by Lok et al. first4In Series Molecules sieve, synthesize the new silicoaluminophosphate of a class (SAPO-n)
Molecular sieve, this molecular sieve analog include 13 kinds of three dimensional skeletal structure being made up of tetrahedron, with from hexatomic ring to twelve-ring
Pore passage structure, aperture is between 0.3～0.8nm.Silicoaluminophosphamolecular molecular sieve (SAPO-n) be by [SiO4]、[AlO4]-With
[PO4]+The microporous crystal with aperture, mesopore or macropore that three kinds of tetrahedron elements are constituted, wherein, n represents different crystal knots
Structure.
SAPO-34 micro porous molecular sieve has three dimensional intersection duct, and average pore size is about 0.38-0.43nm.SAPO-34 has
Less aperture, its as methanol to olefins reaction catalyst when, reaction easily generates ethene and the propylene of small molecule.Due to
SAPO-34 molecular sieve has suitable Bronsted acidity and pore passage structure, larger specific surface area, preferable absorption property and good
Good hydrothermal stability, which presents preferable catalysis activity and selectivity to methanol to olefins reaction, the choosing to low-carbon alkene
Selecting property can be usually reached or be close to 90%, and at present, SAPO-34 molecular sieve is the optimal catalyst for promoting methanol to olefins reaction.
But, in reaction for preparing light olefins from methanol, though SAPO-34 is shown to ethene and propylene as micro porous molecular sieve
The excellent product selectivity of comparison, but easily quickly form carbon distribution during the course of the reaction and make rapid catalyst deactivation.
Generally, micro porous molecular sieve has a regular microcellular structure, suitable acidity, good hydrothermal stability, but micropore
Molecular sieve can also generate bigger molecule in reaction process, and narrow duct easily causes reactant and product mass transfer diffusional resistance
Excessive, reactant extremely difficult entrance is reacted inside crystal duct, and product is out also more difficult from duct diffusion inside, from
And, the coking of molecular sieve catalyst duct is exacerbated, and causes catalyst to inactivate.
For methanol to olefins reaction, molecular sieve inside diffusional resistance have impact on the diffusion rate of reactant and product；
After target product-alkene being generated in the cage of molecular sieve, alkene to external diffusion during, is understanding the acidic site in molecular sieve
There is hydrogen transfer reaction on point further, generate accessory substance alkane or occur polymerisation that Jiao is generated, this reduces purpose product
The selectivity of thing-alkene, and cause catalyst coking and deactivation.
Above-mentioned it may be the case that cause the one of the main reasons of SAPO-34 molecular sieve catalyst fast deactivation, therefore,
The appropriate molecular sieve with macropore and/or meso-hole structure is introduced in SAPO-34 molecular sieve, it will effectively alleviate reactant and product
Mass transfer diffusional resistance of the thing in molecular sieve pore passage, and then, reduce the carbon deposition rate of SAPO-34 molecular sieve, extend SAPO-34 and divide
Son sieve and its service life of catalyst, or even the selectivity for increasing low-carbon alkene, such as propylene and butylene.
CN102049294B discloses a kind of molecular sieve of composite construction and its preparation method and application, in fact, being one
AlPO-5/SAPO-34 composite molecular screen is planted, in the preparation process of the composite molecular screen, SAPO-34 molecular sieve is incorporated into system
In the raw material of standby AlPO-5 molecular sieve, the composite molecular screen synthesized by AlPO-5 and SAPO-34 is ultimately formed.When this compound point
When son is sieved for organic oxygen-containing compound reaction for preparing light olefins, as AlPO-5 has a number of macropore and/or mesoporous
Structure so that the service life of molecular sieve catalyst has extended, and increased the selectivity of propylene.But above-mentioned AlPO-5/
In SAPO-34 composite molecular screen, AlPO-5 and SAPO-34 is clearly not symbiosis.
CN103011195A discloses the multistage porous molecular sieve that an a kind of step prepares SAPO-5 the and SAPO-34 symbiosis of Hydrogen
Method.Wherein, in addition to using a kind of template, a kind of surfactant is also used, the silicon source for using is positive silicic acid second
Ester, Ludox, waterglass, white carbon or their arbitrary mixtures；The silicon source for using is boehmite, pseudobochmite, aluminium
Colloidal sol, aluminium isopropoxide, aluminate, activated alumina or their arbitrary mixtures, these are expensive as the material of raw material,
So that the production cost of composite molecular screen is higher.
CN102372290A discloses a kind of synthetic method of SAPO-5 and SAPO-34 coexisting molecular sieve.Wherein, use
Silicon source is also tetraethyl orthosilicate, Ludox, waterglass, white carbon or their arbitrary mixtures, and the silicon source for using is also that plan is thin
Diaspore, pseudobochmite, Alumina gel, aluminium isopropoxide, aluminate, activated alumina or their arbitrary mixtures.The synthesis side
Method there is also the higher problem of expensive raw material price, composite molecular screen production cost.
This invention address that overcome the defect of existing SAPO-34 molecular sieve, and strive developing a kind of by SAPO-5 and
The preparation method of the composite molecular screen of SAPO-34 symbiosis, wherein, using wide material sources and cheap silicon source and silicon source
Complex replace silicon source costly and silicon source, to reduce the purpose of composite molecular screen production cost, meanwhile, by this
The composite molecular screen of SAPO-5 and SAPO-34 symbiosis prepared by inventive method is to organic oxygen-containing compound producing light olefins
Reaction shows the selective and excellent service life of good catalysis activity, higher propylene and/or butylene.
Content of the invention
According to the first aspect of the invention, a kind of preparation side of the composite molecular screen of SAPO-5 and SAPO-34 symbiosis is provided
Method, its are comprised the following steps successively：
(1) in proportion phosphorus source and water, silicon source and silicon source complex and water, template and water are mixed at a temperature of 5 DEG C -90 DEG C
Close uniformly, obtain including the mixed solution of phosphorus source, silicon source and silicon source complex, water and template, in above-mentioned mixed solution,
P2O5:SiO2:Al2O3:H2O:The mol ratio of template is (0.5-1.5):(0.05-1.5)：1:(30-100):(1-5)；
(2) stir above-mentioned mixed solution to be uniformly dispersed up to each component, subsequently, the mixed solution 2-24 is little for ageing standing
When, so as to form mixed gel；
(3) mixed gel is made to carry out Hydrothermal Synthesiss crystallization 24-96 hour at 180 DEG C -220 DEG C, so as to shape
Become crystallization liquid；
(4) the solid crystal thing formed by crystallization is separated from the crystallization liquid, then dry at 80 DEG C -120 DEG C described
Solid crystal thing 2-12 hour, obtains the composite molecular screen original powder of SAPO-5 and SAPO-34 symbiosis；
(5) the above-mentioned composite molecular screen original powder 4-10 hour of roasting at 450-650 DEG C, to remove template therein, from
And, obtain by SAPO-5 molecular sieve and the composite molecular screen of SAPO-34 molecular sieve symbiosis.
Generally, in above-mentioned preparation method, the template is tetraethyl ammonium hydroxide, etamon chloride, tetraethyl
Ammonium bromide, triethylamine, diethylamine, ammoniacal liquor, n-butylamine, morpholine or their arbitrary mixtures；The silicon source and silicon source complex
It is SiO2/Al2O3Naturally occurring or synthetic clay minerals matter of the molar ratio range between 0.05-1.5 or they arbitrarily mix
Compound；Phosphorus source is phosphoric acid, phosphorous acid, phosphate and/or phosphorous oxides；The water is deionized water.
Generally, in above-mentioned preparation method, in step (4), the solid crystal thing formed by separation crystallization is referred to：Centrifugation
Formed solid crystal thing is filtered, so that the crystal mother liquor produced by Hydrothermal Synthesiss crystallization is removed, is washed with deionized institute
State solid crystal thing at least one times, then solid crystal thing described in centrifugal filtration is at least one times.
Preferably, in above-mentioned preparation method, by controlling the phase of phosphorus source, silicon source and silicon source complex, template and water
To consumption, hybrid mode and/or feeding sequence, and then control pore passage structure and the acidity of the composite molecular screen.
Preferably, in above-mentioned preparation method, the mixed solution is prepared as follows：
(1) silicon source and silicon source complex and phosphorus source are mixed with water respectively, forms silicon source and silicon source complex solution and phosphorus
Source solution；
(2) lentamente phosphorus source solution is added drop-wise in silicon source and silicon source complex solution or by silicon source and silicon source complex
Solution is added drop-wise in phosphorus source solution, forms the mixed solution of phosphorus source, silicon source and silicon source complex；
(3) template is added in the mixed solution of phosphorus source, silicon source and silicon source complex again, so as to be formed
Mixed solution including phosphorus source, silicon source, silicon source, water and template.
Preferably, in above-mentioned preparation method, the silicon source and silicon source complex are kaolin, diatomite, cover support soil, slide
One of stone, bentonite, aluminium vanadine or their arbitrary mixtures, affiliated silicon source and silicon source complex require to reach SiO2/Al2O3
Molar ratio range between 0.05-1.5, or with specific SiO2/Al2O3Mol ratio, such as SiO2/Al2O3Molar ratio range
SiO between 0.05-1.52And Al2O3Artificial synthesized compound.
According to the second aspect of the invention, a kind of catalyst of organic oxygen-containing compound producing light olefins is provided, described urged
The catalytic active component of agent is the composite molecular screen of the SAPO-5 and SAPO-34 symbiosis prepared by said method.
Preferably, the organic oxygen-containing compound is methyl alcohol and/or dimethyl ether；The low-carbon alkene be ethene, propylene and/
Or butylene.
Description of the drawings
Fig. 1 is the X-ray diffracting spectrum of SAPO-5/SAPO-34 composite molecular screen of the present invention.
Specific embodiment
The present invention is further explained in detail by the description below with reference to embodiment and accompanying drawing, but following description is only used for making
General technical staff of the technical field of the invention can be more clearly understood from the principle of the present invention and marrow, be not intended to
Carries out any type of restriction to the present invention.
Preferably, the present invention is by SAPO-5 molecular sieve and the preparation side of the composite molecular screen of SAPO-34 molecular sieve symbiosis
Method, is comprised the following steps successively：
(1) in proportion phosphorus source and water, silicon source and silicon source complex and water, template and water are mixed at a temperature of 5 DEG C -90 DEG C
Close uniformly, obtain including the mixed solution of phosphorus source, silicon source and silicon source complex, water and template, in above-mentioned mixed solution,
P2O5:SiO2:Al2O3:H2O:The mol ratio of template is (0.5-1.5):(0.05-1.5)：1:(30-100):(1-5)；
(2) stir above-mentioned mixed solution to be uniformly dispersed up to each component, subsequently, the mixed solution 2-24 is little for ageing standing
When, so as to form mixed gel；
(3) mixed gel is made to carry out Hydrothermal Synthesiss crystallization 24-96 hour at 180 DEG C -220 DEG C, so as to shape
Become crystallization liquid；
(4) the solid crystal thing formed by crystallization is separated from the crystallization liquid, then dry at 80 DEG C -120 DEG C described
Solid crystal thing 2-12 hour, obtains the composite molecular screen original powder of SAPO-5 and SAPO-34 symbiosis；
(5) the above-mentioned composite molecular screen original powder 4-10 hour of roasting at 450-650 DEG C, to remove template therein, from
And, obtain by SAPO-5 molecular sieve and the composite molecular screen of SAPO-34 molecular sieve symbiosis.
The composite molecular screen of the SAPO-5 and SAPO-34 symbiosis prepared by above-mentioned preparation method can be used as organic oxygen-containing chemical combination
The catalytic active component of the catalyst of thing producing light olefins.
The SAPO-5 prepared by the inventive method and the composite molecular screen of SAPO-34 and its preferred condition of work of catalyst
As follows：Reaction temperature：300-500 DEG C, preferably 400-500 DEG C；Reaction pressure：0-0.5MPa；Methanol quality air speed：1.0-5.0/
Hour；Under the condition of work, methanol conversion is close to 100%；Ethene+propylene+butylene yield ＞ 75%；Propylene+butylene is received
Rate ＞ 52%；SAPO-5/SAPO-34 composite molecular screen service life more than 200 minutes, SAPO-5/SAPO-34 composite molecular screen
Catalyst service life was more than 2 hours.
Embodiment
Embodiment 1：Prepare the SAPO-5/SAPO-34 composite molecular screen of symbiosis
Choose purchased from German Sa Suo factory amorphous silicon aluminium powder as silicon source and the complex of silicon source, its trade name is
SIRAL40, SiO2/Al2O3Weight ratio is 2:3, its mol ratio is 1.13, and specific surface area is 500m2/g.
By 12 grams above-mentioned amorphous silicon aluminium powder (SIRAL40) and 64.5 grams of deionized water mix and blends, silicon source and aluminium is formed
The slurries of source complex, then it is slowly added dropwise the phosphoric acid that 20 grams of concentration is 85 weight % thereto, uniform stirring 1.5 hours, formed
Silicon source and the mixed serum of silicon source complex and phosphorus source.
Then, 14.5 grams of triethylamines (template) are added in above-mentioned mixed serum, are aged 2 hours under stirring,
So as to form mixed gel.
In above-mentioned mixed serum, P2O5:SiO2:Al2O3:H2O:The mol ratio of template is 1.24:1.13：1:51.4:
2.
Above-mentioned mixed gel is loaded in stainless steel cauldron of the inner bag for polytetrafluoroethylene (PTFE) (teflon), at 200 DEG C
Carry out Hydrothermal Synthesiss crystallization 48 hours, form crystallization liquid.
After the cooling of crystallization kettle, from crystallization liquid, solid crystallized product is separated, solid crystallized product is again through deionization
Water washing and centrifugal filtration, until then body crystallized product is done at 120 DEG C by the electrical conductivity of cleaning fluid in below 200 μ S/cm
Dry 8 hours, so as to obtain the composite molecular screen original powder of SAPO-5 and SAPO-34 symbiosis.
Subsequently, the above-mentioned SAPO-5 and SAPO-34 composite molecular screen original powder of roasting 5 hours in air atmosphere and at 650 DEG C,
Obtain SAPO-5 and SAPO-34 composite molecular screen.
Comparative example 1：Prepare the SAPO-5/SAPO-34 composite molecular screen of symbiosis
Except 12 grams above-mentioned amorphous silicon aluminium powder (SIRAL40) with the Ludox (silicon source) of equimolar amounts and are intended thin water aluminium
Stone (silicon source) replaces outer, the process of repetition embodiment 1, obtains SAPO-5 and SAPO-34 composite molecular screen.
Embodiment 2：Prepare the SAPO-5/SAPO-34 composite molecular screen of symbiosis
SiO is configured to using the kaolin and aluminium vanadine that commercially available purity is more than 99%2/Al2O3Mol ratio is 43%
Used as silicon source and the complex of silicon source, its specific surface area is 550m to the mixed powder of kaolin and aluminium vanadine2/g.
By the mixed powder and 85 grams of deionized water mix and blends of 15 grams of above-mentioned kaolin and aluminium vanadine, silicon source and aluminium is formed
The slurries of source complex, then it is slowly added dropwise the phosphoric acid that 25 grams of concentration is 85 weight % thereto, uniform stirring 1.5 hours, formed
Silicon source and the mixed serum of silicon source complex and phosphorus source.
Then, 16.5 grams of triethylamines (template) are added in above-mentioned mixed solution, are aged 2 hours under stirring,
So as to form mixed gel.
In above-mentioned mixed solution, P2O5:SiO2:Al2O3:H2O:The mol ratio of template is 0.61:0.43：1:33.7:
1.16.
Above-mentioned mixed gel is loaded in stainless steel cauldron of the inner bag for polytetrafluoroethylene (PTFE) (teflon), at 200 DEG C
Carry out Hydrothermal Synthesiss crystallization 48 hours, form crystallization liquid.
After the cooling of crystallization kettle, from crystallization liquid, solid crystallized product is separated, solid crystallized product is again through deionization
Water washing and centrifugal filtration, until then body crystallized product is done at 120 DEG C by the electrical conductivity of cleaning fluid in below 200 μ S/cm
Dry 8 hours, so as to obtain the composite molecular screen original powder of SAPO-5 and SAPO-34 symbiosis.
Subsequently, the above-mentioned SAPO-5 and SAPO-34 composite molecular screen original powder of roasting 6 hours in air atmosphere and at 600 DEG C,
Obtain SAPO-5 and SAPO-34 composite molecular screen.
Test case
Test case 1：X-ray diffraction (XRD) analysis of SAPO-5 and SAPO-34 composite molecular screen
SAPO-5 and SAPO-34 composite molecular screen to obtaining in embodiment 1 carries out X-ray diffraction (XRD) analysis, obtains
To Fig. 1, it can be found that from Fig. 1：In the XRD spectra of the SAPO-5/SAPO-34 composite molecular screen obtained in embodiment 1 while
The XRD characteristic diffraction peak of SAPO-5 and SAPO-34 molecular sieve is occurred in that, illustrates to define the chemically composited knot of two kinds of molecular sieves
Structure.
Test case 2：The catalysis activity assessment of SAPO-5 and SAPO-34 composite molecular screen
Using fixed bed catalyst evaluating apparatus, the molecular sieve to obtaining in embodiment 1-2 and comparative example 1 is carried out
The test of catalysis activity, selectivity of product and service life.
After above-mentioned molecular sieve is carried out compressing tablet and crushes, sieve takes the part that granularity is 20-40 mesh and treats as sieve sample
With.
Weigh 1.0 grams of above-mentioned sieve samples respectively, and respectively they are put in reactor, in 500 DEG C of downhill reactions
Nitrogen being passed through in device, activating above-mentioned molecular sieve 1 hour, then, temperature of reactor is down to 450 DEG C, methanol solution is used as raw material
After flow measurement pump, mix with carrier gas, and enter under nitrogen-carrier gas is carried in preheating furnace, methyl alcohol quilt in preheating furnace
Gas is vaporized into, and then, enters in reactor, reaction for preparing light olefins from methanol is carried out under the catalytic action of above-mentioned molecular sieve.
In above process, nitrogen flow rate：150 ml/min, methanol weight air speed：3.0/ hour, product are adopted
Offline gas-chromatography carries out constituent analysis, wherein, when alcohol and ether occurs in gas-chromatography in figure, illustrates methanol conversion not
It is 100%, now, stops test, started to the time now as molecular sieve service life using reacting.
The product composition that measurement is tested every time, and calculate each product selectivity, and ethene, propylene and butylene
Conversion ratio, by they represent in the following Table 1.
Table 1
As can be seen from Table 1：Compared with existing SAPO-34 molecular sieve (comparative example 1), prepared by the inventive method is total to
Raw SAPO-5/SAPO-34 composite molecular screen (embodiment 1) equally also has excellent catalysis activity, and in methanol-to-olefins
Good propylene and butylene selectivity is shown in reaction.Particularly, with symbiosis prepared by the carrying out of reaction, the inventive method
SAPO-5/SAPO-34 composite molecular screen there is the overall selectivity of higher and higher butylene selective and propylene and butylene
It is gradually increased.
Term and form of presentation used by this specification is merely used as descriptive and nonrestrictive term and statement side
Formula, is not intended to any equivalent of feature or its part for having been represented and having described when using these terms and form of presentation
Exclusion.
Several embodiments of the invention is although show and described, but the present invention has been not limited to described enforcement
Mode.Conversely, those skilled in the art are it should be recognized that in the feelings without departing from principle of the present invention and spirit
These embodiments can be carried out any flexible under condition and improve, protection scope of the present invention by appended claim and its is waited
Jljl is determined.
Claims (7)
1. a kind of preparation method of the composite molecular screen of SAPO-5 and SAPO-34 symbiosis, which comprises the following steps successively：
(1) in proportion phosphorus source and water, silicon source and silicon source complex and water, template and water are mixed all at a temperature of 5 DEG C -90 DEG C
Even, obtain including the mixed solution of phosphorus source, silicon source and silicon source complex, water and template, in above-mentioned mixed solution, P2O5:
SiO2:Al2O3:H2O:The mol ratio of template is (0.5-1.5):(0.05-1.5)：1:(30-100):(1-5)；
(2) stir above-mentioned mixed solution to be uniformly dispersed up to each component, subsequently, the ageing standing mixed solution 2-24 hour,
So as to form mixed gel；
(3) mixed gel is made to carry out Hydrothermal Synthesiss crystallization 24-96 hour at 180 DEG C -220 DEG C, so as to be formed brilliant
Change liquid；
(4) the solid crystal thing formed by crystallization is separated from the crystallization liquid, then the drying solid at 80 DEG C -120 DEG C
Crystal 2-12 hour, obtains the composite molecular screen original powder of SAPO-5 and SAPO-34 symbiosis；
(5) the above-mentioned composite molecular screen original powder 4-10 hour of roasting at 450-650 DEG C, to remove template therein, so as to obtain
Arrive by SAPO-5 molecular sieve and the composite molecular screen of SAPO-34 molecular sieve symbiosis,
Wherein, the silicon source and silicon source complex are SiO2/Al2O3Molar ratio range is naturally occurring or synthetic between 0.05-1.5
Clay minerals matter or their arbitrary mixtures, the naturally occurring or synthetic clay minerals matter is kaolin, diatom
One of soil, illiteracy support soil, talcum, bentonite, aluminium vanadine or their arbitrary mixtures or SiO2/Al2O3Molar ratio range exists
SiO between 0.05-1.52And Al2O3Artificial synthesized compound.
2. preparation method according to claim 1, wherein, the template is tetraethyl ammonium hydroxide, tetraethyl chlorination
Ammonium, tetraethylammonium bromide, triethylamine, diethylamine, ammoniacal liquor, n-butylamine, morpholine or their arbitrary mixtures；Phosphorus source is phosphorus
Acid, phosphorous acid, phosphate and/or phosphorous oxides；The water is deionized water.
3. preparation method according to claim 1, wherein, in step (4), separates the solid crystal thing formed by crystallization
Refer to：The solid crystal thing formed by centrifugal filtration, to remove the crystal mother liquor produced by Hydrothermal Synthesiss crystallization, uses deionization
At least one times, then solid crystal thing described in centrifugal filtration is at least one times for solid crystal thing described in water washing.
4. preparation method according to claim 1, wherein, by control phosphorus source, silicon source and silicon source complex, template and
The relative usage of water, hybrid mode and/or feeding sequence, and then control pore passage structure and the acidity of the composite molecular screen.
5. preparation method according to claim 1, wherein, the mixed solution is prepared as follows：
(1) silicon source and silicon source complex and phosphorus source are mixed with water respectively, forms silicon source and silicon source complex solution and phosphorus source is molten
Liquid；
(2) lentamente phosphorus source solution is added drop-wise in silicon source and silicon source complex solution or by silicon source and silicon source complex solution
It is added drop-wise in phosphorus source solution, forms the mixed solution of phosphorus source, silicon source and silicon source complex；
(3) template is added in the mixed solution of phosphorus source, silicon source and silicon source complex again, so as to formation includes
The mixed solution of phosphorus source, silicon source, silicon source, water and template.
6. a kind of catalyst of organic oxygen-containing compound producing light olefins, the active component of the catalyst be by will according to right
The composite molecular screen of SAPO-5 and SAPO-34 symbiosis prepared by the method described in one of asking 1-5 any.
7. catalyst according to claim 6, wherein, the organic oxygen-containing compound is methyl alcohol and/or dimethyl ether；Described
Low-carbon alkene is ethene, propylene and/or butylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510153532.3A CN104828842B (en) | 2014-12-18 | 2015-04-02 | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410799505 | 2014-12-18 | ||
| CN2014107995059 | 2014-12-18 | ||
| CN201510153532.3A CN104828842B (en) | 2014-12-18 | 2015-04-02 | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104828842A CN104828842A (en) | 2015-08-12 |
| CN104828842B true CN104828842B (en) | 2017-03-08 |
Family
ID=53807104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510153532.3A Active CN104828842B (en) | 2014-12-18 | 2015-04-02 | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104828842B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563496B (en) * | 2015-10-10 | 2019-04-09 | 神华集团有限责任公司 | A kind of SAPO-34/AlPO4- 5 composite molecular screens and its preparation method and application |
| CN106115735B (en) * | 2016-06-15 | 2018-08-07 | 南开大学 | AlPO4- 34 with SAPO-34 composite molecular sieves and its synthetic method |
| CN107601523B (en) * | 2017-09-27 | 2020-06-05 | 西安元创化工科技股份有限公司 | Preparation method of SAPO-34/SAPO-5 composite molecular sieve |
| CN108128782B (en) * | 2017-12-20 | 2019-08-02 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of low silicon SAPO-34 molecular sieve |
| CN109133094A (en) * | 2018-08-15 | 2019-01-04 | 潍坊天晟新材料有限公司 | A kind of preparation method of mesoporous SAPO-34 molecular sieve |
| CN108609633B (en) * | 2018-08-16 | 2021-11-30 | 于向真 | Method for synthesizing efficient and clean NaY molecular sieve |
| CN110227540B (en) * | 2019-05-10 | 2020-09-08 | 四川大学 | AFI-CHA mixed crystal molecular sieve and NH using same as carrier3-SCR catalysts and process for their preparation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481122B (en) * | 2009-02-16 | 2011-03-02 | 上海化工研究院 | Process for producing composite silicophosphoaluminate molecular sieve by in situ synthesis |
| CN102424399B (en) * | 2011-09-05 | 2014-04-02 | 中国科学院过程工程研究所 | Preparation process for aluminosilicophosphate molecular sieve |
| CN103447081B (en) * | 2013-09-09 | 2015-04-01 | 神华集团有限责任公司 | Low-silicon ALPO-5/low-silicon ALPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon alkene from organic oxygen-containing compound and preparation method of composite molecular sieve |
| CN103553073B (en) * | 2013-10-22 | 2015-06-10 | 神华集团有限责任公司 | SAPO-44 molecular sieve with rich Si(4Al) and multistage pore sizes, molecular sieve catalyst thereof and preparation methods thereof |
| CN103833047B (en) * | 2014-03-28 | 2015-06-24 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
-
2015
- 2015-04-02 CN CN201510153532.3A patent/CN104828842B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104828842A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104828842B (en) | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO | |
| CN101555022B (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
| CN102616810B (en) | Cubic or sheet-shaped nano SAPO-34 molecular sieve and application thereof | |
| CN101208149B (en) | Process for manufacture of silicoaluminophosphate molecular sieves | |
| RU2469792C2 (en) | Method of preparing silicoaluminophosphate (sapo) molecular sieves, catalysts, containing thereof, and methods of catalytic dehydration with application of said catalysts | |
| CN103787371B (en) | A kind of preparation method of submicron SAPO-18 molecular sieve | |
| US9499409B2 (en) | Metal silicoaluminophosphate molecular sieve with RHO framework structure, and method for preparing the same | |
| JP6006879B2 (en) | SAPO-34 molecular sieve and synthesis method thereof | |
| CN102633279B (en) | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof | |
| CN103495436B (en) | Method for manufacturing ALPO-5/SAPO-34 composite molecular sieve for preparing catalyst of low carbon olefin made of organic oxygenated chemicals | |
| CN103011195B (en) | One-step preparation method for hydrogen type multistage pore molecular sieve with SAPO-5 and SAPO-34 symbiosis | |
| CN107434252B (en) | Preparation method of low-silicon nano SAPO-34 molecular sieve | |
| CN106582804A (en) | Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof | |
| JP6076496B2 (en) | SAPO-34 molecular sieve using diglycolamine as template agent and synthesis method thereof | |
| CN105731484B (en) | A kind of synthetic method of the middle molecular sieves of micropore SAPO 34 | |
| CN108298550A (en) | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves | |
| CN103706394B (en) | Submicron SAPO-5/SAPO-18 composite molecular sieve and preparation method thereof | |
| CN104671256B (en) | Preparation method of SAPO-5/SAPO-34 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound | |
| CN105271302B (en) | A kind of 18 molecular sieves of SAPO and its synthetic method and a kind of method of methanol-to-olefins | |
| CN109796028B (en) | Method for preparing silicoaluminophosphate molecular sieve, silicoaluminophosphate molecular sieve and method for preparing olefin from methanol | |
| CN106542547B (en) | A kind of preparation method of the SAPO-34 molecular sieve of high activity low silicon content | |
| CN105439170A (en) | SAPO-35 molecular sieve and synthetic method thereof | |
| CN111056562B (en) | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol | |
| CN105347356B (en) | A kind of molecular sieves of SAPO 44 and its synthetic method | |
| CN105883850A (en) | Preparation method of empty-shell type SAPO-34 molecular sieves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 22, diazepam West Binhe Road, Dongcheng District, Beijing, Beijing Co-patentee after: National Institute of Clean and Low Carbon Energy Patentee after: National energy investment Refco Group Ltd Address before: 100011 Shenhua building 22, West Binhe Road, Dongcheng District, Beijing Co-patentee before: National Institute of Clean and Low Carbon Energy Patentee before: Shenhua Group LLC |
|
| CP03 | Change of name, title or address | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee before: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |
|
| CP01 | Change in the name or title of a patent holder |