CN1182034C - Method for preparing aluminium silicophosphate molecular sieve - Google Patents
Method for preparing aluminium silicophosphate molecular sieve Download PDFInfo
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- CN1182034C CN1182034C CNB021124434A CN02112443A CN1182034C CN 1182034 C CN1182034 C CN 1182034C CN B021124434 A CNB021124434 A CN B021124434A CN 02112443 A CN02112443 A CN 02112443A CN 1182034 C CN1182034 C CN 1182034C
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- molecular sieve
- sapo
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- triethylamine
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000004411 aluminium Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- -1 carbon olefin Chemical class 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000004939 coking Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009416 shuttering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing an aluminium silicophosphate molecular sieve. The problem that an SAPO-34 molecular sieve has high synthesis cost or a molecular sieve obtained by synthesis has large crystal grain, low relative crystallization degree and rapid coking speed when used for preparing low carbon olefin by converting methanol is mainly solved. In the present invention, the problem is well solved by the technical scheme that triethylamine and fluoride are used as compound template agents to prepare the SAPO-34 molecular sieve. The present invention can be used for the industrial production of low carbon olefin preparation by converting the methanol.
Description
Technical field
The present invention relates to the preparation method of aluminium silicophosphate molecular sieve, particularly about the preparation method of aluminium silicophosphate molecular sieve SAPO-34.
Background technology
Synthesized silicon phosphor aluminum molecular sieve SAPO-34 is a kind of molecular sieve of being made up of silicon, aluminium, phosphorus, oxygen with class chabazite structure.Its structural unit is by PO
2 +, AlO
2 -And SiO
2Tetrahedron constitutes.Anhydrous chemical constitution can be expressed as: mR (Si
xAl
yP
z) O
2, R is the template in existence and the molecular sieve crystal micropore in the following formula, and m is the mole number of R, and x, y, z are respectively the molar fraction of Si, Al, P, and satisfy x+y+z=1.European patent EP 0103117 discloses a kind of hydrothermal synthesis method of SAPO-34 molecular sieve.One of its technical characterstic is to have used tetraethyl ammonium hydroxide in the building-up process, Isopropylamine or be template with the mixture of tetraethyl ammonium hydroxide and di-n-propylamine.On this basis, U.S. Pat 4440871 has reported that again relevant SAPO-34 molecular sieve synthetic improves one's methods.It also adopts identical template, and the difficulty but these template cost an arm and a leg and originate is difficult in the industrial production and adopts.
Disclosing a kind of among the document CN1037334C is the preparation method of the synthesized silicon phosphor aluminum molecular sieve of template with the triethylamine.Form template with triethylamine or based on the organic compounds containing nitrogen of triethylamine in the document, under 100～225 ℃ of conditions, after the crystallization time is no less than 0.5 hour, after filtration, washing, dry SAPO-34 molecular sieve.This method is owing to use cheap triethylamine to be template, reduced the cost of synthetic SAPO-34 molecular sieve significantly, but the crystallographic grain diameter that this method obtains is more greatly greater than 10 μ m, and confirm through test, its molecular sieve relative crystallinity is lower, and coking rate is very fast when being used for methanol-to-olefins reaction.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist the high or synthetic zeolite crystal that obtains of the synthetic cost of SAPO-34 molecular sieve bigger in the document, relative crystallinity is lower, the fast problem of coking rate when being used for methanol-to-olefins reaction provides a kind of preparation method of new aluminium silicophosphate molecular sieve.It is little that this method has a SAPO-34 zeolite crystal diameter that makes, relative crystallinity height, the slow characteristics of coking rate when being used for methanol-to-olefins reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of a kind of aluminium silicophosphate molecular sieve SAPO-34, raw material comprises silicon source, phosphorus source, aluminium source and water, is composite mould plate agent by triethylamine and fluorochemical, and the feed molar of reaction system consists of: mRnF (Si
aAl
bP
c) O
2, wherein R is a triethylamine, m is the mole number of triethylamine, F is a fluorion, and n is the mole number of fluorion, m=0.03～0.6, n=0.03～0.6, a=0.01～0.98, b=0.01～0.60, c=0.01～0.60, and satisfy the condition of a+b+c=1, reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, and the crystallization time is 40～90 hours, gained solid after filtration after the crystallization, again through washing, be drying to obtain molecular sieve.
The fluorochemical preferred version is a hydrofluoric acid in the technique scheme, and the crystallization temperature preferable range is 150～225 ℃.The phosphorus source is an ortho-phosphoric acid, and the silicon source is silicon sol, active silica or tetraethoxy, and the aluminium source is activated alumina, false vigorous relation by marriage stone, pseudo-boehmite or aluminum alkoxide.The order of addition(of ingredients) preferred version of phosphorus source and fluorochemical is for joining in the reaction system simultaneously.The consumption of water is in mole number in the proportioning raw materials of reaction system, when m=0.03～0.6, and water H
2The mole number of O is 2～500.
Concrete molecular sieve preparation method carries out according to the following steps:
1,, takes by weighing a certain amount of silicon source, phosphorus source, aluminium source, water, fluorochemical according to the proportioning in the said structure formula.
2, according to a definite sequence with the mixing of materials that weighs up, and stir the formation gel fully.
3, with 2 resulting gels again 100～250 ℃ of following crystallization, the reaction times is greater than 0.5 hour, the solid that the product behind the crystallization filters and centrifugation obtains, through wash, drying can obtain the SAPO-34 molecular screen primary powder.Its drying can seasoning or is carried out under 80～150 ℃.
The molecular sieve that utilizes the present invention to prepare can be used for methyl alcohol or dme producing light olefins catalyzed reaction, and this molecular sieve catalyst has low-carbon alkene yield height, and coking speed waits characteristics slowly.The treating processes of SAPO-34 molecular screen primary powder is undertaken by following step:
1, will utilize the inventive method preparation is that SAPO-34 molecular screen primary powder that composite shuttering makes carries out roasting and removes template under 300～700 ℃ in air with fluorochemical-triethylamine promptly.
2, the SAPO-34 molecular sieve of calcination process being crossed adds binding agent, for example SiO
2, Al
2O
3, MgO, TiO
2Deng mixing, moulding, drying is carried out roasting again and is made catalyzer in 300～700 ℃ of temperature ranges.
Through above-mentioned 1, or 1 and 2 SAPO-34 molecular sieve catalysts after handling when being used for methyl alcohol or dimethyl ether conversion producing light olefins, temperature of reaction is 300～500 ℃, reaction pressure is a normal pressure, preferable temperature of reaction is 400～500 ℃, and the weight space velocity of methyl alcohol or dme was at 1.0～5.0 o'clock
-1, conversion of raw material can reach 100%, and the yield of low-carbon alkene is higher than the sieve sample of simple employing triethylamine.
The present invention greatly reduces the cost of preparation SAPO-34 molecular sieve owing to adopt triethylamine to make template.Use the composite mould plate agent of triethylamine and fluorochemical, improved the relative crystallinity of molecular sieve SAPO-34, make relative crystallinity reach 100%, the SAPO-34 molecular sieve particle diameter that makes simultaneously is even, particle diameter is little, approximately less than 3 μ m, has increased the specific surface area and the pore volume of SAPO-34 molecular sieve.Fluorochemical and phosphorus source are joined in the reaction system simultaneously, and the amount that makes the silicon source enter framework of molecular sieve has obtained effective control, helps the acidity control of molecular sieve, has improved the catalytic performance that makes catalyzer, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[comparative example 1]
The SAPO-34 molecular sieve prepared for 1 (not adding fluorochemical)
12.2 gram γ-Al
2O
3Mix formation solution a with 30.0 gram deionized waters; 23.5 gram ortho-phosphoric acid (85% weight) and 37.5 gram deionized waters mix and form solution b; At room temperature stir after a and b mix and form homogeneous jelly c after 3.0 hours.Keep whipped state, in c, add silicon sol 9.0 grams successively, 18.0 gram triethylamines and 24.4 gram deionized waters.Fully stir the back and form crystallization mixture d.200 ℃ of following crystallization 48 hours, product obtained solid phase prod after centrifugation with d liquid.Solid phase prod 110 ℃ of oven dry in baking oven are spent the night, test shows, products obtained therefrom is the SAPO-34 molecular sieve, and relative crystallinity is 70%, and crystal particle diameter is 10.5 μ m, and specific surface area is 368.2 meters
2/ gram, pore volume is 0.18 centimetre
3/ gram.
[embodiment 1]
SAPO-34 molecular sieve preparation 1 (adding fluorochemical)
12.2 gram γ-Al
2O
3Mix formation solution a with 30.0 gram deionized waters; 23.5 gram ortho-phosphoric acid (85% weight), 1.82 gram hydrofluoric acid (40% weight) and 37.5 gram deionized waters mix and form solution b; At room temperature stir after a and b mix and form homogeneous jelly c after 3.0 hours.Keep whipped state, in c, add silicon sol 9.0 grams successively, 18.0 gram triethylamines and 23.2 gram deionized waters.Fully stir the back and form crystallization mixture d.200 ℃ of following crystallization 48 hours, product obtained solid phase prod after centrifugation, it 110 ℃ of oven dry in baking oven is spent the night with d liquid, test shows, products obtained therefrom are the SAPO-34 molecular sieve, and relative crystallinity is 100%, crystal particle diameter is 2.3 μ m, and specific surface area is 535.9 meters
2/ gram, pore volume is 0.28 centimetre
3/ gram.
[embodiment 2]
According to each Step By Condition of embodiment 1, just changing crystallization temperature is 150 ℃, and the crystallization time is 90 hours, and the test shows products obtained therefrom is the SAPO-34 molecular sieve, and relative crystallinity is 98%, and crystal particle diameter is 2.5 μ m, and specific surface area is 527.2 meters
2/ gram, pore volume is 0.26 centimetre
3/ gram.
[embodiment 3]
According to each Step By Condition of embodiment 1, just changing crystallization temperature is 225 ℃, and the crystallization time is 40 hours, and the test shows products obtained therefrom is the SAPO-34 molecular sieve, and relative crystallinity is 97%, and crystal particle diameter is 2.9 μ m, and specific surface area is 523.5 meters
2/ gram, pore volume is 0.25 centimetre
3/ gram.
[embodiment 4]
The preparation of SAPO-34 molecular sieve catalyst
The former powder that makes among comparative example 1 and the embodiment 1 was removed template in 3.0 hours 600 ℃ of following roastings, carry out compressing tablet respectively, broken back sieve is got 20～40 purpose granularity parts, is numbered S-01 and S-02 catalyzer, wait to check and rate; The pore volume test shows, the pore volume of S-02 is apparently higher than S-01.
[embodiment 5]
Catalyzer examination experiment
Adopt fixed-bed catalytic reactor, embodiment 4 resulting S-01, S-02 are carried out catalyzer examination experiment respectively.Experiment condition is: the catalyzer loading capacity is 2.7 grams, and temperature of reaction is 450 ℃, and reaction pressure is a normal pressure, and the weight space velocity of first alcohol and water is respectively 1.25 and 3.75, and the flow of nitrogen is 100 ml/min.The results are shown in Table 1.
The result of table 1 S-01, S-02 methanol-to-olefins reaction
| Sample | Methanol conversion (weight %) | Reaction times *(hour) | Hydrocarbon product distributes | ||||||||
| CH 4 | C 2H 6 | C 2H 4 | C 3H 8 | C 3H 6 | C 4H 10 | C 4H 8 | C 5+ | C 2 ＝～C 4 ＝ | |||
| S-01 | 100％ | 2.0 | 1.01 | 0.57 | 48.74 | 1.52 | 35.73 | 0.16 | 9.42 | 1.92 | 93.89 |
| S-02 | 100％ | 6.0 | 2.57 | 0.63 | 51.06 | 1.31 | 34.83 | 0 | 8.48 | 1.12 | 94.37 |
Reaction times
*Be defined as before the dme appearance, the oxygenate rate is 100% time.
Claims (5)
1, the preparation method of a kind of aluminium silicophosphate molecular sieve SAPO-34, raw material comprises silicon source, phosphorus source, aluminium source and water, is composite mould plate agent by triethylamine and fluorochemical, the feed molar of reaction system consists of: mRnF (Si
aAl
bP
c) O
2, wherein R is a triethylamine, m is the mole number of triethylamine, F is a fluorion, and n is the mole number of fluorion, m=0.03～0.6, n=0.03～0.6, a=0.01～0.98, b=0.01～0.60, c=0.01～0.60, and satisfy the condition of a+b+c=1, reaction raw materials is to make the gel crystallization under 100～250 ℃ of conditions at crystallization temperature, and the crystallization time is 40～90 hours, gained solid after filtration after the crystallization, again through washing, be drying to obtain molecular sieve.
2,, it is characterized in that fluorochemical is a hydrofluoric acid according to the preparation method of the described aluminium silicophosphate molecular sieve SAPO-34 of claim 1.
3,, it is characterized in that crystallization temperature is 150～225 ℃ according to the preparation method of the described aluminium silicophosphate molecular sieve SAPO-34 of claim 1.
4, according to the preparation method of the described aluminium silicophosphate molecular sieve SAPO-34 of claim 1, it is characterized in that the phosphorus source is an ortho-phosphoric acid, the silicon source is silicon sol, active silica or tetraethoxy, and the aluminium source is activated alumina, false vigorous relation by marriage stone, pseudo-boehmite or aluminum alkoxide.
5,, it is characterized in that phosphorus source and fluorochemical are to join in the reaction system simultaneously according to the preparation method of the described aluminium silicophosphate molecular sieve SAPO-34 of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021124434A CN1182034C (en) | 2002-07-10 | 2002-07-10 | Method for preparing aluminium silicophosphate molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021124434A CN1182034C (en) | 2002-07-10 | 2002-07-10 | Method for preparing aluminium silicophosphate molecular sieve |
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| CN1467155A CN1467155A (en) | 2004-01-14 |
| CN1182034C true CN1182034C (en) | 2004-12-29 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368086C (en) * | 2004-04-16 | 2008-02-13 | 中国石油化工股份有限公司 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
| JP4990145B2 (en) * | 2004-10-01 | 2012-08-01 | エクソンモービル・ケミカル・パテンツ・インク | Aluminophosphate molecular sieve, its synthesis and use |
| CN1332761C (en) * | 2005-07-13 | 2007-08-22 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
| CN101121528A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Synthesis method of SAPO-34 molecular sieve with framework rich in Si(4Al) structure |
| CN101121148B (en) * | 2006-08-08 | 2010-05-12 | 中国科学院大连化学物理研究所 | A direct molding method of fluidized reaction catalyst containing molecular sieve |
| CN101284673B (en) * | 2008-04-24 | 2011-11-30 | 中国石油化工股份有限公司 | Process for preparing SAPO molecular sieve |
| CN101767800B (en) * | 2009-01-06 | 2011-11-23 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve |
| CN102372288B (en) * | 2010-08-23 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
| CN102451749A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing olefin by converting methanol and preparation and application thereof |
| CN102173437B (en) * | 2011-02-01 | 2013-01-09 | 吉林大学 | Preparation method of controllable metal-doped aluminum phosphate molecular sieve |
| CN105728032B (en) * | 2014-12-10 | 2019-06-18 | 国家能源投资集团有限责任公司 | Preparation method of composite molecular sieve and composite molecular sieve obtained and application thereof |
| CN110817898B (en) * | 2018-08-13 | 2021-09-03 | 中国科学院大连化学物理研究所 | Silicon-aluminum phosphate molecular sieve with ATS framework structure and preparation method and application thereof |
| CN111082012A (en) * | 2019-12-17 | 2020-04-28 | 桑顿新能源科技有限公司 | Silicon-aluminum-sulfur phosphate composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
-
2002
- 2002-07-10 CN CNB021124434A patent/CN1182034C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1467155A (en) | 2004-01-14 |
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