CN1467155A - Method for preparing aluminium silicophosphate molecular sieve - Google Patents
Method for preparing aluminium silicophosphate molecular sieve Download PDFInfo
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- CN1467155A CN1467155A CNA021124434A CN02112443A CN1467155A CN 1467155 A CN1467155 A CN 1467155A CN A021124434 A CNA021124434 A CN A021124434A CN 02112443 A CN02112443 A CN 02112443A CN 1467155 A CN1467155 A CN 1467155A
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- molecular sieve
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Abstract
A process for preparing Si-P-Al molecular sieve SAPO-34 used to prepare low-carbon olefine from methanol features that the triethylamine and fluoride are used as composite template agent. Its advantages are low cost and fine crystal grains of molecular sieve.
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 for being no less than 0.5 hour, 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 ℃, and crystallization time preferable range is 40～90 hours.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
Reaction times
*Be defined as before the dme appearance, the oxygenate rate is 100% time.
| 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??? |
Claims (6)
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 for being no less than 0.5 hour, 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,, it is characterized in that the crystallization time is 40～90 hours according to the preparation method of the described aluminium silicophosphate molecular sieve SAPO-34 of claim 1.
5, 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.
6,, 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.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332761C (en) * | 2005-07-13 | 2007-08-22 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
| 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 |
| WO2008019583A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | A PROCESS FOR SYNTHESIZING SAPO-34 MOLECULAR SIEVE ENRICHED WITH A Si(4Al) STRUCTURE IN THE SKELETON |
| WO2008019591A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A directly shaping method of a fluid reaction catalyst containing molecular sieve |
| CN101031511B (en) * | 2004-10-01 | 2010-06-30 | 埃克森美孚化学专利公司 | Aluminophosphate molecular sieve, its synthesis and use |
| CN102173437A (en) * | 2011-02-01 | 2011-09-07 | 吉林大学 | Preparation method of controllable metal-doped aluminum phosphate 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 |
| 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 |
| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 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 conversion of methanol as well as preparation and application thereof |
| CN105728032A (en) * | 2014-12-10 | 2016-07-06 | 神华集团有限责任公司 | Preparation method of composite molecular sieve, and prepared composite molecular sieve and application thereof |
| CN110817898A (en) * | 2018-08-13 | 2020-02-21 | 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
Cited By (17)
| 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 |
| CN101031511B (en) * | 2004-10-01 | 2010-06-30 | 埃克森美孚化学专利公司 | 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 |
| WO2008019583A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | A PROCESS FOR SYNTHESIZING SAPO-34 MOLECULAR SIEVE ENRICHED WITH A Si(4Al) STRUCTURE IN THE SKELETON |
| WO2008019591A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A directly shaping method of a fluid 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 |
| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | 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 conversion of methanol as well as preparation and application thereof |
| CN102173437A (en) * | 2011-02-01 | 2011-09-07 | 吉林大学 | Preparation method of controllable metal-doped aluminum phosphate molecular sieve |
| CN102173437B (en) * | 2011-02-01 | 2013-01-09 | 吉林大学 | Preparation method of controllable metal-doped aluminum phosphate molecular sieve |
| CN105728032A (en) * | 2014-12-10 | 2016-07-06 | 神华集团有限责任公司 | Preparation method of composite molecular sieve, and prepared composite molecular sieve and application thereof |
| CN105728032B (en) * | 2014-12-10 | 2019-06-18 | 国家能源投资集团有限责任公司 | The preparation method of composite molecular screen and composite molecular screen obtained and its application |
| CN110817898A (en) * | 2018-08-13 | 2020-02-21 | 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 |
| 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 |
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