CN102372289B - Synthetic method of SAPO (Silicoaluminophosphate)-11 molecular sieve - Google Patents
Synthetic method of SAPO (Silicoaluminophosphate)-11 molecular sieve Download PDFInfo
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- CN102372289B CN102372289B CN201010261904.1A CN201010261904A CN102372289B CN 102372289 B CN102372289 B CN 102372289B CN 201010261904 A CN201010261904 A CN 201010261904A CN 102372289 B CN102372289 B CN 102372289B
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- molecular sieve
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Abstract
The invention relates to a synthetic method of an SAPO (Silicoaluminophosphate)-11 molecular sieve and mainly aims at solving the problems of relatively-low crystallinity, larger molecular sieve crystal grains and higher synthetic cost of the SAPO-11 molecular sieve in the prior art. The technical scheme that the SAPO-11 molecular sieve is produced by adding a low-price composite template agent of diethylamine and fluoride is adopted in the invention, so that the problem can be better solved; and the invention can be used for alkanes isomerization industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of aluminium silicophosphate molecular sieve, particularly a kind of use diethylamine and hydrofluoric acid are mixed templates, synthesize the preparation method of the little grain SAPO-11 molecular sieve with AEL structure.
Background technology
Silicon aluminium phosphate type (SAPO) molecular sieve is the novel non-zeolitic molecular sieves of a class that U.S. combinating carbide company releases for 1984.SAPO-n replaces AlPO by Si atom
4after P in skeleton or Al atom, form by AlO
4, PO
4and SiO
4the non-neutral framework of molecular sieve that tetrahedron forms, therefore has tradable positively charged ion, and has proton acidity; The aperture of SAPO-n molecular sieve is 0.3～0.8nm simultaneously, almost comprises whole pore diameter ranges of zeolite molecular sieve; Pore volume (the H of SAPO-n type molecular sieve
2o) be 0.18～0.48cm
3/ g.As generation novel molecular sieve, SAPO-n type molecular sieve is in widespread attention in catalytic field.SAPO-11 molecular sieve, as a member in SAPO-n type molecular sieve family, belongs to mesoporous molecular sieve, has 10 ring ellipse ducts of three-dimensional non-intersection, and aperture is 0.39 × 0.64nm.
In recent years, SAPO-11 molecular sieve, with its unique pore passage structure and acidity that can modulation, shows higher activity and selectivity in the isomerization reaction of normal paraffin.Thereby can be applied to isomerization of paraffins and react to improve the octane value of gasoline, improve the low-temperature performance of diesel oil and lubricating oil, especially in the isomerization dewaxing reaction of lubricating oil distillate and intermediate oil, there is good application prospect, caused the great interest of people.In addition, SAPO-11 also shows good catalytic performance in the reactions such as hydrocracking, other isomerization.
Synthetic general employing Diisopropylamine or the di-n-propylamine of SAPO-11 molecular sieve are template, and employing diethylamine is that the research of the synthetic SAPO-11 molecular sieve of template is little, is that the synthetic SAPO-11 molecular sieve of mixed templates has no report and adopt diethylamine and hydrofluoric acid.CNP 1380251 has reported that diethylamine is the research of the synthetic SAPO-11 of template, but crystallization temperature will, higher than the temperature of conventional synthesis of molecular sieve, be 250～350 ℃, is unfavorable for normal operations; Hu Yunfeng etc. have studied different templates agent impact (the Reation Kinetics and Catalysis Letters synthetic on SAPO-11,2005,86,45～50), result shows that diethylamine can synthesize SAPO-11 as template, but in initial gel, silicone content can not be too low, and crystallization time is longer simultaneously, is 96 hours.CN1356264A by adding the method for alcohol type organic (as Virahol) can obtain a kind of small particle size SAPO-11 molecular sieve in alternatively mixing compound, but the method adds because alcohols is organic, and in building-up process, need through a colloid weathering process, and the template adopting is Diisopropylamine and di-n-propylamine, make system and operation more complicated, and increased cost.
The particle diameter that reduces molecular sieve is conducive to improve the catalytic performance of molecular sieve catalyst, adopts the simple mode synthesizing small-grain of a kind of cheapness SAPO-11 molecular sieve to our research from now on and applies extremely important.
Summary of the invention
Technical problem to be solved by this invention is to overcome in previous literature to exist the synthetic cost of SAPO-11 molecular sieve high, synthetic zeolite crystal is larger, the problem that degree of crystallinity is lower, provide a kind of take diethylamine and fluorochemical as composite mould plate agent the method for synthetic SAPO-11 molecular sieve.It is low that the synthetic method of this molecular sieve has cost, and zeolite crystal is little, the advantage that relative crystallinity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the synthetic method of a kind of aluminium silicophosphate molecular sieve SAPO-11, with water, phosphorus source, aluminium source, silicon source, template is the synthetic SAPO-11 molecular sieve of raw material, comprise formation, the colloid admixture crystallization steps of colloid admixture, in colloid admixture forming process, add template, it is characterized in that mixture has following mole of composition: AlO
3: P
2o
5: SiO
2: R: H
2o=1: 0.5～2.0: 0.1～1.0: 0.6～3.0: 20～80, R is the mixed templates of diethylamine and fluorochemical.
In technique scheme, in mixed templates, fluorochemical preferred version is hydrofluoric acid, and the consumption of fluorochemical accounts for 9%～60% of mixed templates consumption by mole% meter.The temperature preferable range of hydrothermal crystallizing is 150～220 ℃, and crystallization time preferable range is 12～72 hours, and crystallization pressure is himself pressure, and the feature of its Zeolite synthesis is in building-up process without through overaging or other processes.Phosphorus of the present invention source is selected from least one in ortho-phosphoric acid, phosphoric acid salt or phosphorous oxides; Described silicon source is selected from least one in silicon sol, water glass, active silica or positive silicon ester; Described aluminium source is selected from least one in aluminium salt, aluminate, activated alumina, pseudobochmite or pseudo-boehmite.The addition sequence of phosphorus source described in technical scheme of the present invention, aluminium source, silicon source, water and template preferably adds according to the sequencing of water, phosphorus source, aluminium source, silicon source, template.
Method provided by the present invention, adopt diethylamine as template, compared with di-n-propylamine in the past used or the conventional template of Diisopropylamine, greatly reduce the cost of preparation SAPO-11 molecular sieve, and in diethylamine, add again the method for fluorochemical as composite mould plate agent, greatly improve the relative crystallinity of molecular sieve SAPO-11, relative crystallinity can reach 100%, this is the positive charge in template that had balance due to fluorion, thereby reduce the defect of molecular sieve crystal, be conducive to form high-quality molecular sieve crystal; And in system during without fluorion, the negative charge that the positive charge of template is caused by framework of molecular sieve defect mostly carrys out balance, the molecular sieve therefore obtaining often defect is more, causes degree of crystallinity to decline.In addition, the HF adding in system and diethylamine can interact, and formation composite mould plate agent enters into the skeleton of micro porous molecular sieve, except playing the effect of mineralizer, also the formation of SAPO-11 molecular sieve is played to structure-directing effect.Application the method for the invention, the SAPO-11 molecular sieve cost making is low, and particle diameter is even, and particle diameter I reaches 1.8 μ m, and relative crystallinity Gao Keda 100% has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[comparative example 1]
SAPO-11 molecular sieve (not adding fluorochemical)
After raw material pseudo-boehmite 10.2g is mixed with 77.1g deionized water, stir, under agitation add phosphoric acid (85% aqueous solution) 16.4g, after stirring and then add silicon sol (containing SiO
225%), after stirring reaction plastic, finally again 5.2g diethylamine solution is slowly joined in above-mentioned gel, continue to stir and make gel reaction mixture.Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 24 hours under 180 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 75%, and crystal particle diameter is 12.5 μ m.
[embodiment 1]
SAPO-11 molecular sieve (adding fluorochemical)
After raw material phosphoric acid (85% aqueous solution) 16.4g is mixed with 77.1g deionized water, stir, under agitation add pseudo-boehmite 10.2g, after stirring and then add silicon sol (containing SiO
225%) 5.1g, after stirring reaction plastic, finally slowly joins 5.2g diethylamine solution and 1.8g hydrofluoric acid solution in above-mentioned gel again, continues to stir and makes gel reaction mixture.Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 24 hours under 180 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 100%, and crystal particle diameter is 2.2 μ m.
[embodiment 2]
Identical with operation steps and the experiment condition of embodiment 1, the add-on that just changes hydrofluoric acid is 3.6g, and products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, and relative crystallinity is 100%, and crystal particle diameter is 1.8 μ m.
[embodiment 3]
Identical with operation steps and the experiment condition of embodiment 1, just changing crystallization temperature is 160 ℃, and crystallization time is 48 hours, and products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, and relative crystallinity is 98%, and crystal particle diameter is 2.5 μ m.
[embodiment 4]
After raw material phosphoric acid (85% aqueous solution) 12.8g is mixed with 50g deionized water, stir, under agitation add pseudo-boehmite 7.9g, after stirring and then add silicon sol (containing SiO
225%) 8.0g, after stirring reaction plastic, finally slowly joins 2.4g diethylamine solution and 0.9g hydrofluoric acid solution in above-mentioned gel again, continues to stir and makes gel reaction mixture.Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 24 hours under 180 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 100%, and crystal particle diameter is 2.0 μ m.
[embodiment 5]
After being mixed with 45g deionized water, raw material phosphoric acid (85% aqueous solution) 13.9g stirs, under agitation add aluminum oxide powder 7.1g, after stirring and then add tetraethoxy 6.3g, after stirring reaction plastic, finally again 4.4g diethylamine solution and 1.5g hydrofluoric acid solution are slowly joined in above-mentioned gel, continue to stir and make gel reaction mixture.Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 24 hours under 180 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 100%, and crystal particle diameter is 1.9 μ m.
[embodiment 6]
After raw material Vanadium Pentoxide in FLAKES 7.3g is mixed with 50g deionized water, stir, under agitation add pseudobochmite 7.2g, after stirring and then add silicon sol (containing SiO
225%) 6.3g, after stirring reaction plastic, finally slowly joins 4.4g diethylamine solution and 1.5g hydrofluoric acid solution in above-mentioned gel again, continues to stir and makes gel reaction mixture.Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 24 hours under 180 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 100%, and crystal particle diameter is 1.8 μ m.
Claims (1)
1. a synthetic method of aluminium silicophosphate molecular sieve SAPO-11, stirs after the raw material phosphoric acid 16.4g of 85% aqueous solution is mixed with 77.1g deionized water, under agitation adds pseudo-boehmite 10.2g, after stirring, adds containing SiO again
2be 25% silicon sol 5.1g, after stirring reaction plastic, finally again 5.2g diethylamine solution and 1.8g hydrofluoric acid solution slowly joined in above-mentioned gel, continue to stir and make gel reaction mixture; Above-mentioned reaction mixture is packed in the crystallizing kettle with polytetrafluoroethylene bushing, crystallization 48 hours under 160 ℃ of autogenous pressures, finally by deionized water wash, filtration for crystallization product, in 100 ℃ of air, dry, products obtained therefrom is SAPO-11 molecular sieve through XRD diffraction analysis, relative crystallinity is 98%, and crystal particle diameter is 2.5 μ m.
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| CN102815720B (en) * | 2012-07-24 | 2014-12-03 | 黑龙江大学 | Synthetic method for SAPO-11 molecular sieve |
| CN104226364B (en) * | 2013-06-17 | 2016-08-24 | 中国石油化工股份有限公司 | The method preparing molecular sieve fluid bed catalyst |
| CN105217652A (en) * | 2014-06-30 | 2016-01-06 | 中国石油天然气集团公司 | A kind of SAPO-11 molecular sieve and synthetic method thereof and application |
| CN108745411A (en) * | 2018-05-23 | 2018-11-06 | 中国中化股份有限公司 | A kind of long-chain normal paraffin catalyst for hydroisomerizing and preparation method thereof |
Citations (3)
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| CN1488579A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Aluminosilicophosphate molecular sieve and preparing method thereof |
| CN1982215A (en) * | 2005-12-16 | 2007-06-20 | 中国石油化工股份有限公司 | Core-shell structured molecular sieve, its production and use |
| EP1350763B1 (en) * | 2001-01-05 | 2008-07-30 | China Petroleum & Chemical Corporation | Sapo-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1350763B1 (en) * | 2001-01-05 | 2008-07-30 | China Petroleum & Chemical Corporation | Sapo-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve |
| CN1488579A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Aluminosilicophosphate molecular sieve and preparing method thereof |
| CN1982215A (en) * | 2005-12-16 | 2007-06-20 | 中国石油化工股份有限公司 | Core-shell structured molecular sieve, its production and use |
Non-Patent Citations (4)
| Title |
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| SAPO-11型分子筛水热合成改进工艺研究;余秋惠等;《武汉工程大学学报》;20100115;第32卷(第1期);第46页第二栏第11-18行，第47页第1-2行，表1 * |
| 余秋惠等.SAPO-11型分子筛水热合成改进工艺研究.《武汉工程大学学报》.2010,第32卷(第1期), |
| 含HF体系中SAPO-11分子筛的合成与表征;张胜振等;《催化学报》;20061030;第27卷(第10期);第869页第一栏7-19行 * |
| 张胜振等.含HF体系中SAPO-11分子筛的合成与表征.《催化学报》.2006,第27卷(第10期), |
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