CN100390056C - Method for changing crystal structure of molecular sieve - Google Patents
Method for changing crystal structure of molecular sieve Download PDFInfo
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- CN100390056C CN100390056C CNB2005100669736A CN200510066973A CN100390056C CN 100390056 C CN100390056 C CN 100390056C CN B2005100669736 A CNB2005100669736 A CN B2005100669736A CN 200510066973 A CN200510066973 A CN 200510066973A CN 100390056 C CN100390056 C CN 100390056C
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- molecular sieve
- alkaline compound
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Abstract
The present invention relates to a processing method for changing crystal structures of molecular sieves. After SAPO-11 molecular sieves are processed by an alkaline solution, the crystal structures of the molecular sieves are changed. The present invention is characterized in that the unmodified SAPO-11 molecular sieves have the crystal structures of Pna2<1> space group, and the modified SAPO-11 molecular sieves have the crystal structures of Ima2 space groups.
Description
Technical field
The invention discloses a kind of treatment process that changes crystal structure of molecular sieve, specifically the SAPO-11 molecular sieve is handled with basic solution, the crystalline structure of molecular sieve is changed.
Background technology
In current commercial catalysts, molecular sieve can be described as a class catalyzer the most widely of application.Because they generally have distinctive pore passage structure, acidity and absorption property, a lot of commercial runs have all been used the catalyzer that contains molecular sieve, and the scientific research personnel has also carried out a large amount of research at its characteristics and corresponding catalytic performance.People find that can change with a kind of unit cell parameters and skeleton symmetry of molecular sieve, typical example is the ZSM-5 molecular sieve when the crystalline structure of research molecular sieve.ZSM-5 is a kind of representative type with high-silica zeolite of important use, the ZSM-5 skeleton structure of common not removed template method is a rhombic system, spacer is Pnma, and by some post-treating method (changing silica alumina ratio and ammonium exchange etc.), above-mentioned skeleton structure can change, show as by rhombic system and change oblique system into, spacer is changed to P2
1/ n, variation has also taken place in unit cell parameters.Also have the molecular sieve of number of different types also to have same transformable unit cell parameters and skeleton symmetry, for example the unit cell parameters of faujusite (faujasite) molecular sieve can change along with the variation of aluminium content, the skeleton of chabazite (chabazite) can be destroyed because of suction, and belongs to the ALPO of AEL topological framework together with SAPO-11
4-11 molecular sieves also are found has variable structural symmetry.
SAPO series molecular sieve is introduced silicon formation in the aluminium phosphate molecular sieve skeleton, appear at U.S.Pat.NO.4 the earliest, and in 440,871, its framework of molecular sieve is made up of phosphorus oxygen tetrahedron, silicon-oxy tetrahedron and aluminum-oxygen tetrahedron.Wherein the structure of SAPO-11 molecular sieve can change before and after the roasting removed template method, according to U.S.Pat.NO.4,440,871 results reported, the crystalline structure that does not have the SAPO-11 molecular sieve of removed template method is the Ima2 spacer, and adopting different raw material synthetic SAPO-11 molecular sieves behind the roasting removed template method, its XRD spectra data are different.With phosphoric acid, aluminum isopropylate, when be fuming silica gel and di-n-propylamine are raw material, the synthetic molecular sieve is behind the roasting removed template method, and the XRD spectra data part take place change, and some new diffraction peaks occurred, and the crystalline structure of this moment is Ima2 spacer and Pna2
1The mixed state of spacer; When being raw material with phosphoric acid, aluminum isopropylate, silicon sol and di-n-propylamine, the XRD spectra data generation noticeable change of molecular sieve behind the roasting removed template method of synthetic gained, in the new diffraction peak of same appearance, some original diffraction peak completely dissolves, crystalline structure is Pna2
1Spacer.
It is the catalyst for hydroisomerizing of carrier with the SAPO-11 molecular sieve with good structural stability that Zhang Fengmei etc. (CN 1283668A) disclose a kind of.By selecting different synthesis conditions for use, both can obtain the SAPO-11 molecular sieve that its crystalline structure of roasting removed template method front and back does not change, promptly still be the Ima2 spacer, can obtain the SAPO-11 molecular sieve (Pna2 that its crystalline structure of roasting removed template method front and back changes again
1Spacer).And the molecular sieve that crystalline structure does not change before and after preceding a kind of removed template method can improve the isomerization selectivity and the isomerization product yield of reaction when being used as the carrier of catalyst for hydroisomerizing.
The research of being reported in the prior art that changes about the SAPO-11 crystal structure of molecular sieve at all be the molecular sieve synthesis phase, that is to say the SAPO-11 molecular sieve that obtains the different crystal structure by the control synthesis condition, still can not realize the transformation of the molecular sieve of different crystal structure.
Summary of the invention
The object of the present invention is to provide a kind of method that changes crystal structure of molecular sieve, with the crystalline structure of the SAPO-11 molecular sieve of roasting removed template method by Pna2
1Spacer changes the Ima2 spacer into.
The present invention carries out corresponding aftertreatment by the SAPO-11 molecular sieve to the roasting removed template method, just can change the crystalline structure of SAPO-11 molecular sieve, the Pna2 after making it by roasting
1Spacer changes the Ima2 spacer into.
Specifically, the method for change crystal structure of molecular sieve provided by the invention, its step is as follows:
A) mass ratio of alkaline compound solution and molecular sieve is 50-500: 1, and 15-90 ℃ is mixed stirring 1-35 minute;
B) mixed solution with step a filters, solid substance is washed to neutrality, and 100-150 ℃ of air drying calcined 6-12 hour for 300-550 ℃, obtaining crystalline structure is the SAPO-11 molecular sieve of Ima2 spacer, and its chemical constitution is expressed as with sial phosphorous oxides mol ratio: Al
2O
3: (0.40～1.0) P
2O
5: (0.1～0.8) SiO
2, and have following X-ray powder diffraction data at least:
2θ/° d/nm
8.15-8.25 10.95-10.70
9.50-9.740 9.25-9.05
13.15-13.25 6.76-6.70
15.80-15.95 5.60-5.50
20.35-20.45 4.38-4.31
21.15-21.40 4.20-4.11
22.30-22.45 4.00-3.91
23.10-23.33 3.90-3.81
23.45-23.60 3.82-3.75；
Molecular sieve described in the step a is to have an AEL topological framework, and through the SAPO-11 molecular sieve of at least 300 ℃ of roasting removed template methods, its crystalline structure is Pna2
1Spacer;
Alkaline compound solution described in the step a is the aqueous solution of inorganic alkaline compound or organic basic compound.
In the described method, the mass ratio of alkaline compound solution and molecular sieve is 100～300: 1.
In the described method, the mass ratio of alkaline compound solution and molecular sieve is 200～250: 1.
In the described method, the pH of alkaline compound solution is 12-14.
In the described method, inorganic alkaline compound is potassium hydroxide, sodium hydroxide, yellow soda ash or salt of wormwood, and organic basic compound is aliphatic amide, hydramine or quaternary ammonium hydroxide compounds.
In the described method, alkaline compound solution is the aqueous solution of inorganic alkaline compound.
In the described method, mixing the temperature that stirs among the step a is 15-50 ℃.
In the described method, mixing the temperature that stirs among the step a is 30-40 ℃.
In method provided by the invention, the SAPO-11 molecular sieve that step a adopts can be synthetic by existing technology, and required raw silicon source, aluminium source, phosphorus source and organic formwork agent are the raw material that generally adopts in the prior art.These raw materials can be: the silicon source comprises solid silicone, silicon sol or white carbon black; The aluminium source comprises aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate, aluminum phosphate or pseudo-boehmite; The phosphorus source comprises phosphoric acid or aluminum phosphate; Organic formwork agent di-n-propylamine or Diisopropylamine.
In method provided by the invention, among the step a to having the AEL topological framework, and the roasting method through the SAPO-11 molecular sieve of at least 300 ℃ of roasting removed template methods is a known technology, specific as follows: under oxygen-containing atmosphere, temperature rise rate with 0.5-10 ℃/minute, rise to 500-600 ℃ from room temperature, then at 500-600 ℃ of roasting 30-50 hour.Preferable methods is: under air atmosphere, with 1-5 ℃/minute temperature rise rate, rise to 550-580 ℃ from room temperature, then at 550-580 ℃ of roasting 40-45 hour.
Embodiment
Following embodiment will the present invention is described further, but the present invention is not limited among the following embodiment.Wherein Comparative Examples is the sample that non-modified is handled, and its roasting removes the data that X-ray diffraction result after the masterplate agent meets table 1.
Comparative Examples
This Comparative Examples is the method synthetic SAPO-11 molecular sieve with reference to relevant document.Get 80 gram aluminum isopropylates and mix, add 150 gram phosphoric acid then with 300 gram deionized waters, be stirred to evenly after, add the positive dipropyl amine of 82 grams successively, 73 gram silicon sol and 120 gram deionized waters and abundant stirring obtain gel.
Above-mentioned gel is packed in the autoclave of inner liner polytetrafluoroethylene, and in 190 ℃ of thermostatic crystallizations 24 hours, the solid product after the filtration was through washing, and then drying, do X-ray powder diffraction after at least 300 ℃ of roastings and measure, its result meets the data of table 1, illustrates that its spacer is Pna2
1
Embodiment 1
Get the SAPO-11 molecular sieve of Comparative Examples gained and concentration and be the 0.1mol/L sodium hydroxide solution according to molecular sieve (gram): the mixed of sodium hydroxide solution (gram)=1: 250, its pH=13.30 ℃ of following stir process 10 minutes, mixing speed was 150 rev/mins; Then solid substance is filtered, be washed till pH=7,120 ℃ of air dryings, 550 ℃ of roastings 6 hours with deionized water.Get this sieve sample of part and make X-ray powder diffraction mensuration, its result meets the data of table 2, illustrates that spacer becomes Ima2.
Embodiment 2
The SAPO-11 molecular sieve of getting the Comparative Examples gained is according to molecular sieve (gram): the mixed of sodium hydroxide solution (gram)=1: 50, and concentration of sodium hydroxide solution is 0.3mol/L, and its pH=13.5 stirred 15 minutes down at 30 ℃, and mixing speed is 150 rev/mins; Then solid substance is filtered, be washed till pH=7,120 ℃ of air dryings, 300 ℃ of roastings 6 hours with deionized water.Get this sieve sample of part and make X-ray powder diffraction mensuration, its result meets the data of table 2, illustrates that spacer becomes Ima2.
Embodiment 3
The SAPO-11 molecular sieve of getting the Comparative Examples gained is according to molecular sieve (gram): the mixed of sodium carbonate solution (gram)=1: 200, and sodium carbonate solution concentration is 2mol/L, and its pH=12.3 stirred 1 minute down at 40 ℃, and rotating speed is 150 rev/mins; Then solid substance is filtered, be washed till pH=7,120 ℃ of air dryings, 550 ℃ of roastings 8 hours with deionized water.Get this sieve sample of part and make X-ray powder diffraction mensuration, its result meets the data of table 2, illustrates that spacer becomes Ima2.
Embodiment 4
The SAPO-11 molecular sieve of getting the Comparative Examples gained is according to molecular sieve (gram): the mixed of sodium hydroxide solution (gram)=1: 150, and concentration of sodium hydroxide solution is 0.001mol/L, and its pH=11 stirred 35 minutes down at 90 ℃, and rotating speed is 150 rev/mins; Then solid substance is filtered, be washed till pH=7,120 ℃ of air dryings, 500 ℃ of roastings 12 hours with deionized water.Get this sieve sample of part and make X-ray powder diffraction mensuration, its result meets the data of table 2, illustrates that spacer becomes Ima2.
Embodiment 5
The SAPO-11 molecular sieve of getting the Comparative Examples gained is according to molecular sieve (gram): the ratio of sodium hydroxide solution (gram)=1: 500 at the uniform velocity stirs, and rotating speed is 150 rev/mins, and concentration of sodium hydroxide solution is 0.005mol/L, its pH=11.7.15 ℃ of down reactions 5 minutes, then solid substance is filtered, be washed till pH=7 with deionized water, 120 ℃ of air dryings, 550 ℃ of roastings 8 hours.Get this sieve sample of part and make X-ray powder diffraction mensuration, its result meets the data of table 2, illustrates that spacer becomes Ima2.
Table 1 Pna2
1Spacer structure SAPO-11 molecular sieve X-ray powder diffraction data
Table 2 Ima2 spacer structure SAPO-11 molecular sieve X-ray powder diffraction data
Claims (8)
1. method that changes crystal structure of molecular sieve, step is as follows:
A) mass ratio of alkaline compound solution and molecular sieve is 50-500: 1, and 15-90 ℃ is mixed stirring 1-35 minute;
B) mixed solution with step a filters, and solid substance is washed to neutrality, and 100-150 ℃ of air drying calcined 6-12 hour for 300-550 ℃, and obtaining crystalline structure is the SAPO-11 molecular sieve of Ima2 spacer, and has following X-ray powder diffraction data at least:
2θ/° d/nm
8.15-8.25 10.95-10.70
9.50-9.740 9.25-9.05
13.15-13.25 6.76-6.70
15.80-15.95 5.60-5.50
20.35-20.45 4.38-4.31
21.15-21.40 4.20-4.11
22.30-22.45 4.00-3.91
23.10-23.33 3.90-3.81
23.45-23.60 3.82-3.75；
Molecular sieve described in the step a is to have an AEL topological framework, and through the SAPO-11 molecular sieve of at least 300 ℃ of roasting removed template methods, its crystalline structure is Pna2
1Spacer;
Alkaline compound solution described in the step a is the aqueous solution of inorganic alkaline compound or organic basic compound.
2. in accordance with the method for claim 1, it is characterized in that the mass ratio of alkaline compound solution and molecular sieve is 100～300: 1.
3. according to claim 1 or 2 described methods, it is characterized in that the pH of alkaline compound solution is 12-14.
4. according to claim 1 or 2 described methods, it is characterized in that the mass ratio of alkaline compound solution and molecular sieve is 200-250: 1.
5. in accordance with the method for claim 1, it is characterized in that inorganic alkaline compound is potassium hydroxide, sodium hydroxide, yellow soda ash or salt of wormwood, organic basic compound is aliphatic amide, hydramine or quaternary ammonium hydroxide compounds.
6. in accordance with the method for claim 1, it is characterized in that alkaline compound solution is the aqueous solution of inorganic alkaline compound.
7. in accordance with the method for claim 1, it is characterized in that mixing the temperature that stirs among the step a is 15-50 ℃.
8. according to claim 1 or 7 described methods, it is characterized in that mixing the temperature that stirs among the step a is 30-40 ℃.
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| CN103936028B (en) * | 2014-04-09 | 2016-05-18 | 中国华电集团科学技术研究总院有限公司 | A kind of preparation method of SAPO-11 molecular sieve |
| US10118166B2 (en) | 2014-06-06 | 2018-11-06 | Uop Llc | Zeolitic materials with modified surface composition, crystal structure, crystal size, and/or porosity, methods for making the same, and methods for converting oxygenates to olefins via reactions catalyzed by the same |
| CN110961149A (en) * | 2019-12-10 | 2020-04-07 | 中国石油大学(北京) | Modified SAPO-11 molecular sieve, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1283668A (en) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | Catalyst for hydroisomerizing paraffin |
| CN1289643A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Molecular sieve catalyst containing silicate, aluminate or phosphate and its preparing process and application |
| CN1363519A (en) * | 2001-10-17 | 2002-08-14 | 中国科学院兰州化学物理研究所 | Process for preparing SAPO molecular sieve |
| CN1392099A (en) * | 2002-07-30 | 2003-01-22 | 复旦大学 | SAPO-11 molecualr sieve and its preparing method |
-
2005
- 2005-04-25 CN CNB2005100669736A patent/CN100390056C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1283668A (en) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | Catalyst for hydroisomerizing paraffin |
| CN1289643A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Molecular sieve catalyst containing silicate, aluminate or phosphate and its preparing process and application |
| CN1363519A (en) * | 2001-10-17 | 2002-08-14 | 中国科学院兰州化学物理研究所 | Process for preparing SAPO molecular sieve |
| CN1392099A (en) * | 2002-07-30 | 2003-01-22 | 复旦大学 | SAPO-11 molecualr sieve and its preparing method |
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