CN1176848C - SAPO-11 molecular sieve catalyst and its preparation method - Google Patents
SAPO-11 molecular sieve catalyst and its preparation methodInfo
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- CN1176848C CN1176848C CNB021118701A CN02111870A CN1176848C CN 1176848 C CN1176848 C CN 1176848C CN B021118701 A CNB021118701 A CN B021118701A CN 02111870 A CN02111870 A CN 02111870A CN 1176848 C CN1176848 C CN 1176848C
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- sapo
- molecular sieve
- sieve catalyst
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- roasting
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Abstract
The present invention relates to a method for synthesizing an SAPO-11 molecular sieve catalyzer. Dipropylamine is adopted as a template agent in the prior art, but synthetic product is unstable and easy to form many silicon zones so that the catalytic property is reduced. The present invention adopts cheap diethylamine as the template agent, and the SAPO-11 molecular sieves are synthesized at a higher crystallization temperature and a shorter crystallization time. The molecular sieve has more SAPO zones and higher ratio of medium strong acids to weak acids. After molecular sieves are loaded with precious metals, the selectivity and the yield rate of alkane hydroisomerization reaction are greatly raised with molecular sieves.
Description
Technical field:
The present invention relates to a kind of SAPO-11 molecular sieve catalyst and preparation method thereof.
Background technology:
Normal paraffin in the hydrocarbon ils mainly is a long-chain n-praaffin, must reduce its content for improving oil property.For example, can significantly improve low-temperature performance by removing normal paraffin to diesel oil or lubricating oil to reduce condensation point or pour point; Also can select the purpose that the shape isomery reaches boosting of octane rating to gasoline fraction.The SAPO-11 molecular sieve is because of it has special structure and acid matter, supports to have excellent hydroisomerization performance behind the precious metal and receive much attention.
The SAPO-11 molecular sieve belongs to the AEL structure, spacer Ima2, and oval duct size is 0.39 * 0.63nm.The catalytic performance of SAPO-11 molecular sieve depends primarily on position and the environment that Si enters skeleton.If two Si P of replacement and an Al enter skeleton, then form the Si district, do not generate active sites; If a Si replaces a P and enters skeleton, then form SAPO district Si (4Al), obtain a Br nsted acid activity position.SAPO district and Si district intersection form more and the corresponding stronger acid site of Si (nAl, n=1,2,3).Therefore, control Si enters the mechanism of skeleton, the amount at the strong active acid center of raising, is the key of the more excellent SAPO-11 molecular sieve of synthetic performance.
Synthesizing of existing AEL molecular sieve comprises U.S Pat 4,440,871, U.S Pat 4,701,485 and U.S Pat 5,208,005, and U.S Pat No 4,943,424, all adopting dipropyl amine is template.Conventional SAPO-11 synthesis condition is: dipropyl amine is a template, and false boehmite is the aluminium source, and phosphoric acid is the phosphorus source, and tetraethyl silicate or silicon sol are the silicon source, crystallization temperature 473K, crystallization time 24 hours.Many researchs all are devoted to improve colloidal sol composition and crystallization condition, make and form more SAPO district in the SAPO-11 skeleton.With the synthetic method of routine, the SAPO-11 that often obtains synthesizes the result and is difficult for repeating, or easily forms more Si district and the reduction catalytic performance, is unfavorable for that all the industrialization of SAPO-11 is amplified and production.
Summary of the invention:
The objective of the invention is SAPO-11 molecular sieve catalyst of studying a kind of high silicon and preparation method thereof.
The objective of the invention is to study a kind of SAPO-11 molecular sieve catalyst that improves the active acid center and preparation method thereof.
The present invention is by theoretical modeling, proved diethylamine and does template more helps the SAPO-11 framework of molecular sieve of high silicon content than dipropyl amine generation with learning the result.But because diethylamine is done template under conventional synthesis condition, easily generate CHA or AFI structure, maybe can only obtain containing the SAPO-11 crystal of more stray crystal, the present invention has improved conventional synthetic method, the employing diethylamine is a template, improve crystallization temperature, shortened crystallization time, had the catalytic performance of good n-dodecane hydroisomerization after can obtaining the more high silicon SAPO-11 molecular sieve crystal in SAPO district and making dual-function catalyst.
Mole before the catalyzer roasting removed template method of the present invention is xR when forming with the anhydrous chemical formulation of oxide form: Al
2O
3: yP
2O
5: zSiO
2, wherein R is the diethylamine template in the molecular sieve crystal duct, and the value of x is 0.05～0.5, and y is 0.60～1.20, and z is 0.05～1.3.
The value of x was 0.10～0.30 when the mole before the catalyzer roasting removed template method of the present invention was formed with the anhydrous chemical formulation of oxide form, and y is 0.60～1.20, and z is 0.10～1.10.
The synthetic method of said SAPO-11 molecular sieve comprises in the catalyzer provided by the present invention: distilled water, aluminium source, silicon source, phosphorus source and organic formwork agent are mixed, make mole and consist of aR: Al
2O
3: bP
2O
5: cSiO
2: dH
2The reaction mixture of O progressively heats up then with the mixture hydrothermal crystallizing, and with the filtration of crystallization mixture, washing, drying; Wherein said raw material mixing temperature is 15～60 ℃; Said crystallization condition is a hydrothermal crystallizing 0.5～15 hour under 250～350 ℃ temperature and autogenous pressure; Wherein the value of a is 0.2～2.0, and the value of b is 0.6～1.4, and the value of c is 0.05～1.5, and the value of d is 15～150.
Said aluminium source, silicon source, phosphorus source are the corresponding raw material that generally adopts in the prior art, and the present invention has no particular limits.Organic formwork agent is a diethylamine.These raw materials can be: said aluminium source comprises aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, and said silicon source comprises white carbon black, solid silicone or silicon sol, and said phosphorus source comprises phosphoric acid or aluminum phosphate, and said organic formwork agent is a diethylamine.
Above-mentioned synthetic method good conditions is: the raw material mixing temperature is 20～40 ℃, and 260～330 ℃ of following hydrothermal crystallizings 1～12 hour, and a was 0.3～1.5 in the mixture during crystallization, and b is 0.75～1.2, and c is 0.1～1.1, and d is 15～150.
Above-mentioned synthetic method better condition is: the reaction mixing temperature is 25～35 ℃, and crystallization is that a was 0.5～1.0 in the mixture 280～310 ℃ of following hydrothermal crystallizings 1.5～6 hours, and d is 50～100, and b, c are as hereinbefore.
The preparation method of catalyst loading precious metal provided by the present invention carries out according to existing dipping method.This method can be: with kneading and compactings such as the precursor of SAPO-11 molecular sieve powder and aluminum oxide after the roasting and nitric acid, deionized waters, then through super-dry, roasting; With compound or the mixture of gained forming composition, after super-dry and roasting, promptly obtain catalyzer of the present invention more again with pickling process load P d or Pt; Wherein the precursor of said aluminum oxide can be generally adopt in the prior art after roasting, form γ-Al
2O
3Compound aluminium; These precursor can be to be selected from amorphous hydroted alumina, pseudo-boehmite, gibbsite or the Bayer aluminium stone one or more, wherein pseudo-boehmite preferably.Said aluminum oxide is above-mentioned aluminum oxide precursor through 400 ℃～700 ℃ roastings resulting aluminum oxide after 1～5 hour in the catalyzer of the present invention.
The molecular sieve supported precious metals pd of above-mentioned SAPO-11, Pt or their mixture.After supporting precious metals pd, Pt, long chain alkane hydroisomerization selectivity and activity there is very good effect.
Also available diethylamine of the present invention and dipropyl amine are made mixed templates, and its effect is also very good.
The roasting condition of SAPO-11 molecular sieve removed template method of the present invention can be the condition that generally adopts in the prior art, but condition of the present invention is roasting 2～24 hours under 500～650 ℃ of air atmospheres; Also can be earlier at N with molecular sieve
2500～650 ℃ of roastings are 2～24 hours under the atmosphere, and then roasting 2～24 hours under 500～650 ℃ of air atmospheres.
Molecular sieve provided by the invention can use by the catalyst for hydroisomerizing as normal paraffin behind carried noble metal, and the catalyzer that also can be used as aromatizing low-carbon paraffin uses.For molecular sieve being prepared into have the dual-function catalyst in metal and acid site, molecular sieve elder generation roasting removed template method can be flooded precious metal again, also can earlier molecular sieve be flooded behind the precious metal roasting removed template method again.
The present invention is template with the diethylamine, adopts new system synthesizing high-silicon SAPO-11 molecular sieve crystal.This molecular sieve catalyst has compared with prior art obviously enlarged the SAPO district in the AEL molecular sieve, and stronger middle strong acid/weak acid ratio is arranged; Under the high temperature based on Br nsted acid site; This molecular sieve crystal is after supporting precious metal, and compared with prior art, its isomerization selectivity and isomerization yield obviously improve.
Embodiment:
Example one .5.0g pseudo-boehmite (water content 30%, Wenzhou two magnificent groups) places 50mL distilled water vigorous stirring, slowly adds the white carbon black of 2.0g (99%, Wu Jing chemical plant, Shanghai), 15 ℃ of following vigorous stirring 30 minutes; Slowly add 3.7mL phosphoric acid (AR, 85%, Shanghai chemical reagent company), vigorous stirring 40 minutes; Slowly add the 18mL diethylamine, continue to stir 10 minutes, in the stainless steel cauldron of packing into, 300 ℃ of crystallization 2 hours, take out then, cooling is filtered, and 80 ℃ of oven dry slowly heat up, earlier at N
2The following 550 ℃ of roastings of atmosphere 20 hours, and then 550 ℃ of roastings 24 hours under air atmosphere promptly obtain the SAPO-11 sample after the roasting.The solid sample yield is not less than 90%.
Example two .5.0g pseudo-boehmites (water content 30%, the two magnificent groups in Wenzhou) place 86mL distilled water vigorous stirring; Slowly added 5.5mL phosphoric acid (AR, 85%, Shanghai chemical reagent company) vigorous stirring 40 minutes; Slowly add the 34mL diethylamine, continue to stir 2 hours, slowly add the white carbon black of 3.1g (99%, Wu Jing chemical plant, Shanghai), vigorous stirring 30 minutes; Pack in the stainless steel cauldron, 260 ℃ of crystallization 12 hours, take out then, cooling is filtered, and 80 ℃ of oven dry slowly heat up, and 550 ℃ of roastings are 24 hours under air atmosphere, promptly obtains the SAPO-11 sample after the roasting.The solid sample yield is not less than 75%.
Example three .5.0g pseudo-boehmites (water content 30%, the two magnificent groups in Wenzhou) place 8.7mL distilled water vigorous stirring; Slowly added 2.5mL phosphoric acid (AR, 85%, Shanghai chemical reagent company) vigorous stirring 40 minutes; Slowly add the 4.4mL diethylamine, continue to stir 2 hours, slowly add the white carbon black of 0.13g (99%, Wu Jing chemical plant, Shanghai), vigorous stirring 30 minutes; Pack in the stainless steel cauldron, 320 ℃ of crystallization 1.5 hours, take out then, cooling is filtered, and 80 ℃ of oven dry slowly heat up, and 550 ℃ of roastings are 24 hours under air atmosphere, promptly obtains the SAPO-11 sample after the roasting.The solid sample yield is not less than 80%.
Claims (10)
1. SAPO-11 molecular sieve catalyst is characterized in that when mole before its roasting removed template method is formed anhydrous chemical formulation with oxide form be xR: Al
2O
3: yP
2O
5: zSiO
2, wherein R is the diethylamine template in the molecular sieve crystal duct, and the value of x is 0.05～0.5, and y is 0.60～1.20, and z is 0.05～1.3.
2. SAPO-11 molecular sieve catalyst according to claim 1 is characterized in that the value of x was 0.10～0.30 when mole before its roasting removed template method was formed anhydrous chemical formulation with oxide form, and y is 0.60～1.20, and z is 0.10～1.10
3. the preparation method of SAPO-11 molecular sieve catalyst according to claim 1 and 2 is characterized in that synthetic method is: it is aR that diethylamine or diethylamine and dipropyl amine template and aluminium source, silicon source, phosphorus source, distilled water are made homogeneous reaction mixture: Al
2O
3: bP
2O
5: cSiO
2: dH
2O progressively heats up then, with the mixture hydrothermal crystallizing, and filtration, washing, drying, actual conditions is: (1) raw material mixing temperature is 15～60 ℃; (2) crystallization condition is 250～350 ℃ of following crystallization 0.5～15 hour; (3) a is 0.2～2.0 in the mixture, and b is 0.6～1.4, and c is 0.05～1.5, and d is 15～150.
4. the preparation method of SAPO-11 molecular sieve catalyst according to claim 3 is characterized in that synthesis condition is: (1) raw material mixing temperature is 20～40 ℃; (2) crystallization condition is 260～330 ℃ of following hydrothermal crystallizings 1～12 hour; (3) a is 0.3～1.5 in the mixture, and b is 0.75～1.2, and c is 0.1～1.1, and d is 15～150.
5. the preparation method of SAPO-11 molecular sieve catalyst according to claim 4 is characterized in that synthesis condition is: (1) raw material mixing temperature is 25～35 ℃; (2) crystallization condition is 280～310 ℃ of following hydrothermal crystallizings 1.5～6 hours; (3) a is 0.5～1.0 in the mixture, and d is 50～100.
6. the preparation method of SAPO-11 molecular sieve catalyst according to claim 3, it is characterized in that will make the roasting of SAPO-11 molecular sieve remove after the template and the precursor of aluminum oxide and nitric acid, deionized water mixing moulding, drying, roasting, use pickling process load P d, Pt metallic compound or its mixture again.
7. the preparation method of SAPO-11 molecular sieve catalyst according to claim 6, the precious metal that it is characterized in that the pickling process load is Pd or Pt, or their mixture.
8. the preparation method of SAPO-11 molecular sieve catalyst according to claim 3 is characterized in that template is diethylamine and dipropyl amine mixed templates.
9. the preparation method of SAPO-11 molecular sieve catalyst according to claim 3, it is characterized in that the removed template method condition is: roasting is 2～24 hours under 500～650 ℃ of air atmospheres; Perhaps 500～650 ℃ of roastings 2～24 hours under nitrogen atmosphere, roasting 2～24 hours under 500～650 ℃ of air atmospheres again.
10. according to the application of claim 1 or 3 described SAPO-11 molecular sieve catalysts as the alkane hydroisomerization.
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|---|---|---|---|
| CNB021118701A CN1176848C (en) | 2002-05-30 | 2002-05-30 | SAPO-11 molecular sieve catalyst and its preparation method |
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| CNB021118701A CN1176848C (en) | 2002-05-30 | 2002-05-30 | SAPO-11 molecular sieve catalyst and its preparation method |
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| CN1176848C true CN1176848C (en) | 2004-11-24 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363260C (en) * | 2005-03-18 | 2008-01-23 | 中国科学院大连化学物理研究所 | Synthetic process of SAPO-11 Molecular sieve |
| CN101195492B (en) * | 2006-12-04 | 2010-09-29 | 中国科学院大连化学物理研究所 | Method for synthesizing SAPO-11 and SAPO-34 molecular sieve with diethylamine as template agent |
| CN101913623B (en) * | 2010-08-25 | 2011-12-07 | 中国石油大学(北京) | Multilevel pore channel SAPO-11 molecular sieve and synthetic method of hydrocarbon isomerization catalyst |
| CN103285915B (en) * | 2012-03-02 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier |
| CN104058424B (en) * | 2013-03-20 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of preparation method of state SAPO-11 molecular sieve of reuniting |
| CN106799257B (en) * | 2015-11-26 | 2020-02-07 | 中国科学院大连化学物理研究所 | Alkane isomerization catalyst and preparation method thereof |
| CN108114743A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院上海高等研究院 | A kind of solid phase synthesis process of hydroisomerization catalyst |
| CN107500306A (en) * | 2017-08-31 | 2017-12-22 | 江苏有容催化技术研究所有限公司 | A kind of molecular sieve catalysts of SAPO 11 and preparation method thereof |
| CN109465030B (en) * | 2017-09-07 | 2022-01-25 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst taking ATO type structure molecular sieve as carrier |
| CN109465031B (en) * | 2017-09-07 | 2021-07-20 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst taking AFO type structure molecular sieve as carrier |
| CN109465028B (en) * | 2017-09-07 | 2021-08-13 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with AEL-type structure molecular sieve as carrier |
| CN109465024B (en) * | 2017-09-07 | 2021-09-07 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst with MTW type structure molecular sieve as carrier |
| CN109465029B (en) * | 2017-09-07 | 2021-09-14 | 中国科学院大连化学物理研究所 | Preparation method of isomerization catalyst taking AFI type structure molecular sieve as carrier |
| CN107649175B (en) * | 2017-10-23 | 2020-11-03 | 上海歌通实业有限公司 | Preparation method of Ga-Ge-doped MnOx-SAPO molecular sieve catalyst |
| CN108816279B (en) * | 2018-05-23 | 2021-03-16 | 中国中化股份有限公司 | Preparation method of normal paraffin hydroisomerization catalyst |
| CN109939729B (en) * | 2019-04-16 | 2021-07-27 | 中国科学院上海高等研究院 | Preparation method and application of Pt/SAPO-11 bifunctional catalyst |
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