CN103539146A - Ion hot method for continuously synthesizing SAPO-11 molecular sieves - Google Patents
Ion hot method for continuously synthesizing SAPO-11 molecular sieves Download PDFInfo
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- CN103539146A CN103539146A CN201310516817.XA CN201310516817A CN103539146A CN 103539146 A CN103539146 A CN 103539146A CN 201310516817 A CN201310516817 A CN 201310516817A CN 103539146 A CN103539146 A CN 103539146A
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Abstract
The invention discloses an ion hot method for continuously synthesizing SAPO-11 molecular sieves, relating to the technical field of molecular sieve synthesis. According to the ion hot method, an ion liquid is taken as a circulating solvent, reactants are treated through steps of continuous feeding, gelatinizing, crystallization and separation so as to obtain molecular sieve products, after distillation separation, the ion liquid and unreacted raw materials are recycled. The ion hot method is different from the traditional intermittent hydro-thermal method for synthesizing molecular sieves, the molecular sieves can be continuously synthesized almost at normal temperature, the unreacted components in a mother liquid can be recycled, continuous industrial production is realized, the production efficiency is high, the synthesis cost is lowered, the production cycle is shortened, and no liquid waste is discharged so that the ion hot method is environment-friendly.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, be specifically related to a kind of method with the synthetic SAPO-11 molecular sieve of the hot method continous way of ion.
Background technology
Aluminium phosphate molecular sieve is after Si-Al molecular sieve, and U.S. combinating carbide company is at the molecular sieve of new generation (USP4310440) of early eighties exploitation in last century.The aluminium silicophosphate SAPO(MAPO that silicon (or other metal heteroatom M) is introduced) molecular sieve, skeleton has acidic site, has therefore expanded the purposes of this molecular sieve.
2004, Morris professor's people from research group reported and used ionic liquid as the ion process for thermosynthesizing (Nature430,1012-1016 (2004)) of solvent and the synthetic microporous aluminium phosphate molecular sieve of template.Ion thermal synthesis can be carried out under normal pressure, and this is mainly because ionic liquid has insignificant saturated vapor pressure.The research of Tian Zhijian research group shows, ion thermal synthesis crystallization time can shorten to 1-10 minute (Xu, Y.P.et al.Angew.Chem., Int.Ed.45,3965-3970 (2006)).This also makes the fast rapid-result molecular sieve that produces of ionic liquid continous way become possibility.
At present, SAPO-11 molecular sieve adopts hydrothermal method synthetic more, and Guo Shoujie etc. also successfully synthesize SAPO-11 molecular sieve by microwave method.
No matter synthesizing of above-mentioned molecular sieve is that traditional hydrothermal synthesis method or ion thermal synthesis method is step synthesis technique.The mode of production operating in batches.This process, material adds in batches, emits in batches, and reaction process is without the turnover of material, and the reactor volume of scale operation is large, facility investment is high.
Summary of the invention
The object of the invention is for solving fast and quantity-produced problem, the method of the synthetic SAPO-11 aluminium phosphate molecular sieve of a kind of continous way is provided, it is circulating solvent that the method adopts ionic liquid, utilize ion thermal synthesis method reactant to obtain molecular sieve product through continous way charging, plastic, crystallization after separated, serialization industrial production, production efficiency is high, the recycle after fractionation by distillation of ionic liquid and unreacting material, greatly reduce synthetic cost, shorten the production cycle, and environmentally friendly without the discharge of waste liquid.
The present invention is a kind of method with the synthetic SAPO-11 molecular sieve of the hot method continous way of ion, it is characterized in that, employing ionic liquid is circulating solvent, the reactant of continuously feeding enters in tubular reactor crystallization rapidly through pre-plastic is laggard, after washing separation, obtain molecular sieve product, the recycle after fractionation by distillation of ionic liquid and unreacting material; Specifically comprise:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add to according to a certain percentage in the plastic cans containing ionic liquid and stir pre-plastic, and temperature is controlled at 60～120 ℃, pre-plastic 1～300 minute; Wherein said plastic cans Raw mixture has following mole of composition: ionic liquid: SiO
2: Al
2o
3: P
2o
5: mineralizer: template: H
2o=5～200:0～1.2:0.01～1.2:0.01～1.2:0.01～1.2:0.05～2.0:0.01～0.2;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor through fresh feed pump and is heated at 100～250 ℃ crystallization 1～300 minute, and more excellent crystallization temperature is 140～190 ℃, and crystallization time is 10～60 minutes;
C) and b) step, is fed to fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer in plastic cans simultaneously; Preferred feedstock flow velocity is 1-10ml/min.
D) separation after washing of the crystallization product mixtures after step b) crystallization obtains molecular sieve product;
E) water lotion is delivered to rectifying tower rectifying separation;
F) ionic liquid after rectifying and unreacted raw material cycling stream are continued to participate in reaction to plastic cans; Distilled water cycling stream after rectifying is washed reaction after product to filtration washing device;
Wherein, described silicon source is one or more in solid silicone, silicon sol, white carbon black, kaolin, polynite, water glass and tetraethoxy; Described aluminium source is one or more in aluminium powder, aluminum oxide, aluminium hydroxide, sodium metaaluminate, potassium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate and Burow Solution; Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate; Described ionic liquid is one or more in 1-butyl-3-methyl-bromination imidazoles, 1-propyl group-3-methyl-bromination imidazoles, 1-ethyl-3-methyl-bromination imidazoles, 1-butyl-3-methyl-imidazolitm chloride, 1-propyl group-3-methyl-imidazolitm chloride, 1-ethyl-3-methyl-imidazolitm chloride, and preferred ion liquid is one or more in 1-butyl-3-methyl-bromination imidazoles, 1-propyl group-3-methyl-bromination imidazoles, 1-ethyl-3-methyl-bromination imidazoles; Described masterplate agent is one or more in di-n-propylamine, diethylamine, triethylamine and 1,6-hexanediamine; The type of heating of described tubular reactor is conventional heating by electric cooker, steam-heated cal(l)andria, oil bath heating or Microwave-assisted firing, is preferably oil bath heating or Microwave-assisted firing; Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride and Potassium monofluoride.
The method of the synthetic SAPO-11 aluminium phosphate molecular sieve of continous way of the present invention, its beneficial effect is: 1) reactant obtains molecular sieve product through continous way charging, plastic, crystallization after separated, reaction is with Guan Suiting; 2) ionic liquid and unreacting material recycle after fractionation by distillation, reclaims the molecular sieve crystallite that has the reaction of having neither part nor lot in the raw material circulating, and can in circulation crystallization process, promote crystallization; Ionic liquid synthesis of molecular sieve can complete crystallization at normal pressure and within very short time, and this continous way is produced becomes possibility, greatly shortens the production cycle, and without the discharge of waste liquid waste water, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the method for the synthetic SAPO-11 molecular sieve of continous way of the present invention;
Fig. 2 is that the embodiment of the method 1 of the synthetic SAPO-11 molecular sieve of continous way of the present invention obtains sieve sample XRD figure.
In figure, 1. plastic cans, 2. fresh feed pump, 3. tubular reactor, 4. rectifying tower, 5. filtration washing device.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but not thereby limiting the invention.
Fig. 1 is the process flow diagram of the synthetic SAPO-11 molecular sieve of continous way of the present invention, in this technical process the reaction unit that adopts for teflon-lined tubular reactor 3, design parameter is that liner useful length is 127.4cm, the effective internal diameter of liner is 5mm, and tubular reactor 3 effective volumes are 100ml.
Embodiment 1
By 1-butyl-3-methyl-bromination imidazoles, aluminum chloride, phosphoric acid, hydrofluoric acid and diethylamine, according to mol ratio, be ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=6.5:0:1:1:1:0.38 stirs plastic 30 minutes in plastic cans 1, and temperature is at 60 ℃; By coutroi velocity, 1-butyl-3-methyl-bromination imidazoles, aluminum chloride, phosphoric acid, hydrofluoric acid and diethylamine are fed in plastic cans 1 according to aforementioned proportion, colloidal sol in plastic cans 1 is squeezed into tubular reactor 3 at 150 ℃ of heating crystallizations through fresh feed pump 2 simultaneously, by coutroi velocity be 5ml/min to make crystallization time be 20 minutes, the reactant after crystallization obtains zeolite product through washing; Washing obtains water lotion and is delivered to rectifying tower 4 rectifying separation, and the ionic liquid after rectifying and unreacted feedstream continue to participate in reaction to plastic cans 1, and the distilled water after rectifying flows to 5 pairs of reaction after products of filtration washing device and washes.To obtaining reaction product SAPO-11 sieve sample, carry out the test of productive rate and relative crystallinity.In the present invention, related productive rate is the butt weight/g of the sieve sample obtaining per hour, and relative crystallinity involved in the present invention is to stipulate that the degree of crystallinity of embodiment 1 gained sample is 100%, and other embodiment samples result is by comparison its relative crystallinity.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
With embodiment 1, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=6.8:0.5:1:1:1:0.41 wherein silicon source is silicon sol; Tubular reactor is that to make crystallization time be 30 minutes to 3.3ml/min by coutroi velocity.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.0:0.6:1:1:1:0.5, tubular reactor is at 170 ℃ of heating crystallizations, and by coutroi velocity 2.5ml/min, making crystallization time is 40 minutes.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Embodiment 4
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.2:0.8:1:1:1.07:0.38, tubular reactor is at 160 ℃ of heating crystallizations, by coutroi velocity, is that to make crystallization time be 50 minutes to 2ml/min.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.4:1:1:1:1.18:0.40.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Embodiment 6
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.6:1:1:1:1.07:0.42.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Embodiment 7
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.4:0.8:1:1:1.2:0.46.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
With embodiment 2, wherein material molar ratio is ionic liquid: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=7.5:0.8:1:1:1.07:0.5.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Table 1. embodiment 1-8 molecular sieve productive rate and relative crystallinity
| Sample | Productive rate (butt g/h) | Relative crystallinity % * |
| 1 | 15 | 100 |
| 2 | 9.9 | 98 |
| 3 | 7.5 | 95 |
| 4 | 6 | 102 |
| 5 | 9.9 | 97 |
| 6 | 9.7 | 101 |
| 7 | 9.8 | 95 |
| 8 | 10.0 | 96 |
*note: the degree of crystallinity of embodiment 1 sieve sample of take is 100%.
Claims (2)
1. the method with the synthetic SAPO-11 molecular sieve of the hot method continous way of ion, it is characterized in that, employing ionic liquid is circulating solvent, the reactant of continuously feeding enters in tubular reactor crystallization rapidly through pre-plastic is laggard, after washing separation, obtain molecular sieve product, the recycle after fractionation by distillation of ionic liquid and unreacting material; Specifically comprise:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add to according to a certain percentage in the plastic cans containing ionic liquid and stir pre-plastic, and temperature is controlled at 60～120 ℃, pre-plastic 1～300 minute; Wherein said plastic cans Raw mixture has following mole of composition: ionic liquid: SiO
2: Al
2o
3: P
2o
5: mineralizer: template: H
2o=5～200:0～1.2:0.01～1.2:0.01～1.2:0.01～1.2:0.05～2.0:0.01～0.2;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor through fresh feed pump and is heated at 100～250 ℃ crystallization 1～300 minute;
C) and b) step, is fed to fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer in plastic cans simultaneously;
D) separation after washing of the crystallization product mixtures after step b) crystallization obtains molecular sieve product;
E) water lotion is delivered to rectifying tower rectifying separation;
F) ionic liquid after rectifying and unreacted raw material cycling stream are continued to participate in reaction to plastic cans; Distilled water cycling stream after rectifying is washed reaction after product to filtration washing device;
Wherein, described silicon source is one or more in solid silicone, silicon sol, white carbon black, kaolin, polynite, water glass and tetraethoxy; Described aluminium source is one or more in aluminium powder, aluminum oxide, aluminium hydroxide, sodium metaaluminate, potassium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate and Burow Solution; Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate; Described ionic liquid is one or more in 1-butyl-3-methyl-bromination imidazoles, 1-propyl group-3-methyl-bromination imidazoles, 1-ethyl-3-methyl-bromination imidazoles, 1-butyl-3-methyl-imidazolitm chloride, 1-propyl group-3-methyl-imidazolitm chloride, 1-ethyl-3-methyl-imidazolitm chloride; Described masterplate agent is one or more in di-n-propylamine, diethylamine, triethylamine and 1,6-hexanediamine; The type of heating of described tubular reactor can be conventional heating by electric cooker, steam-heated cal(l)andria, oil bath heating or Microwave-assisted firing; Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride.
2. method according to claim 1, is characterized in that: specifically comprise:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add in the plastic cans containing ionic liquid and stir pre-plastic, and temperature is controlled at 80～110 ℃, pre-plastic 20～200 minutes;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor through fresh feed pump and be heated to 140-190 ℃ of crystallization 10～60min;
C) and b) simultaneously, fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer are fed in plastic cans with 1-10ml/min flow velocity step, make each material component keep constant;
D) separation after washing of the reaction mixture after crystallization obtains molecular sieve product;
E) water lotion step d) being obtained is delivered to rectifying tower rectifying separation;
F) ionic liquid after rectifying and unreacted raw material cycling stream are continued to participate in reaction to plastic cans; Distilled water cycling stream after rectifying is washed reaction after product to filtration washing device;
The type of heating of described tubular reactor is oil bath heating or Microwave-assisted firing;
Described ionic liquid is one or more of 1-butyl-3-methyl-bromination imidazoles, 1-propyl group-3-methyl-bromination imidazoles and 1-ethyl-3-methyl-bromination imidazoles.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609439A (en) * | 2015-02-16 | 2015-05-13 | 黑龙江大学 | Method for ionothermal synthesis of SAPO-31 molecular sieve nanorod |
| CN108473323A (en) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | The method for preparing synthetic mineral particle |
| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834015A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院大连化学物理研究所 | Synthetic process of SAPO-11 Molecular sieve |
| CN1884076A (en) * | 2006-05-25 | 2006-12-27 | 中国科学院大连化学物理研究所 | Method for synthesizing P-Al molecular sieve by microwave heating |
| WO2012056118A1 (en) * | 2010-10-28 | 2012-05-03 | IFP Energies Nouvelles | Izm-4 crystallized solid and process for preparing same |
| CN102452657A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Equipment for preparing molecular sieve |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN103241745A (en) * | 2013-04-16 | 2013-08-14 | 中国海洋石油总公司 | Synthesis method and application of small-particle-size SAPO-11 molecular sieve |
-
2013
- 2013-10-28 CN CN201310516817.XA patent/CN103539146B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834015A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院大连化学物理研究所 | Synthetic process of SAPO-11 Molecular sieve |
| CN1884076A (en) * | 2006-05-25 | 2006-12-27 | 中国科学院大连化学物理研究所 | Method for synthesizing P-Al molecular sieve by microwave heating |
| CN102452657A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Equipment for preparing molecular sieve |
| WO2012056118A1 (en) * | 2010-10-28 | 2012-05-03 | IFP Energies Nouvelles | Izm-4 crystallized solid and process for preparing same |
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN103241745A (en) * | 2013-04-16 | 2013-08-14 | 中国海洋石油总公司 | Synthesis method and application of small-particle-size SAPO-11 molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| YUN-PENG XU ET AL.: "Microwave-Enhanced Ionothermal Synthesis of Aluminophosphate Molecular Sieves", 《ANGEW. CHEM. INT. ED.》, vol. 45, 9 May 2006 (2006-05-09), pages 3965 - 3970, XP002615848, DOI: doi:10.1002/anie.200600054 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609439A (en) * | 2015-02-16 | 2015-05-13 | 黑龙江大学 | Method for ionothermal synthesis of SAPO-31 molecular sieve nanorod |
| CN104609439B (en) * | 2015-02-16 | 2017-02-01 | 黑龙江大学 | Method for ionothermal synthesis of SAPO-31 molecular sieve nanorod |
| CN108473323A (en) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | The method for preparing synthetic mineral particle |
| US11352264B2 (en) | 2015-09-28 | 2022-06-07 | Centre National De La Recherche Scientifique | Method for preparing synthetic mineral particles |
| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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