CN103553076A - Method for continuously producing silicoaluminophosphate (SAPO-5) molecular sieve - Google Patents
Method for continuously producing silicoaluminophosphate (SAPO-5) molecular sieve Download PDFInfo
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- CN103553076A CN103553076A CN201310516837.7A CN201310516837A CN103553076A CN 103553076 A CN103553076 A CN 103553076A CN 201310516837 A CN201310516837 A CN 201310516837A CN 103553076 A CN103553076 A CN 103553076A
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Abstract
The invention discloses a method for continuously producing a silicoaluminophosphate (SAPO-5) molecular sieve and relates to the technical field of molecular sieve synthesis. The method comprises the following steps: with a low eutectic mixture as a circulating solvent; carrying out continuous feeding, gel formation, crystallization and separation on reactants to form a molecular sieve product; recycling the low eutectic mixture and un-reacted raw materials through distilling and separating. The method disclosed by the invention is different from the traditional method for intermittent hydrothermal synthesis of molecular sieves. Continuous synthesis of the molecular sieves under a near-atmospheric pressure condition can be achieved; components in mother liquor, which do not participate in reaction, can be recycled.
Description
Technical field
The present invention relates to Zeolite synthesis technical field, be specifically related to a kind of method that continous way is produced SAPO-5 molecular sieve.
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.
The conventional hydrothermal synthesis method of the many employings of SAPO-5 molecular sieve, Jhung etc. have also studied the synthetic of the SAPO-5 molecular sieve under microwave condition in great detail, find that microwave can be optionally for SAPO-5 Zeolite synthesis, and can carry out modulation crystal morphology by control condition.Mobil company adopts the compound two-phase medium of alcohol/water also successfully to synthesize the SAPO-5 molecular sieve of large crystal grain.
Synthesizing of above-mentioned molecular sieve, no matter be that traditional hydrothermal synthesis method or ion thermal synthesis method is step synthesis technique, the mode of production operating in batches, in this process, material adds in batches, emit in batches, 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, provide a kind of continous way to produce the method for aluminium phosphate molecular sieve, it is circulating solvent that the method adopts eutectic mixture, utilize eutectic mixture synthesis method reactant through continous way charging, plastic, crystallization with separated after obtain molecular sieve product, the recycle after fractionation by distillation of eutectic mixture and unreacting material, 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 the discharge without waste liquid is environmentally friendly.
The present invention is a kind of method that continous way is produced SAPO-5 molecular sieve, it is characterized in that, comprising:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add in the plastic cans containing eutectic mixture 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: eutectic mixture: SiO
2: Al
2o
3: P
2o
5: mineralizer: masterplate agent: 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 heating at 100-250 ℃ of crystallization 1～300min through fresh feed pump;
C) and b) simultaneously, fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer are fed in plastic cans by 1-15ml/min 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) eutectic mixture after rectifying and unreacted feedstream continue to participate in reaction to plastic cans; The distilled water that rectifying obtains flows to filtration washing device reaction after product is washed;
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 eutectic mixture is the mixture of etamon chloride and tetramethylolmethane or the mixture of tetraethylammonium bromide and tetramethylolmethane; Described masterplate agent is one or more in di-n-propylamine, diethylamine, triethylamine; Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride; Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate; The type of heating of described tubular reactor is heating by electric cooker, steam-heated cal(l)andria, oil bath heating or Microwave-assisted firing.
According to the present invention, above-mentioned continous way is produced the method for SAPO-5 molecular sieve, it is characterized in that, specifically comprises:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add in the plastic cans containing eutectic mixture and stir pre-plastic, and temperature is controlled at 60～120 ℃, pre-plastic 1～300 minute;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor heating at 140-190 ℃ of crystallization 10～60min through fresh feed pump;
C) and b) simultaneously, fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer are fed in plastic cans according to 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) eutectic mixture after rectifying and unreacted feedstream continue to participate in reaction to plastic cans; The distilled water that rectifying obtains flows to filtration washing device reaction after product is washed;
The type of heating of described tubular reactor is oil bath heating or Microwave-assisted firing;
Described eutectic mixture is the mixture of etamon chloride and tetramethylolmethane.
Compared with prior art, its beneficial effect is as follows for the inventive method: 1) easy to operate: reactant obtains molecular sieve product through continous way charging, plastic, crystallization after separated, reaction is with Guan Suiting; 2) eutectic mixture 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; Eutectic mixture synthesis of molecular sieve can complete crystallization at normal pressure and within very short time, realizes the continous way of molecular sieve and produces, and 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 that continous way of the present invention is produced the method for SAPO-5 molecular sieve;
Fig. 2 is that the embodiment of the method 1 of continous way production SAPO-5 molecular sieve 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 inventive method is described further, but does not limit protection scope of the present invention.
In the following embodiment of the present invention the eutectic mixture that adopts for being that 1:1 mixes tetraethylammonium bromide and tetramethylolmethane heat slowly standby to molten state according to mass ratio.
Fig. 1 is the process flow diagram that continous way of the present invention is produced SAPO-5 molecular sieve, 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
According to mol ratio, be eutectic mixture: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=5.79:0:1:1:1:0.38 stirs plastic 30 minutes by 30g eutectic mixture, 3.8g aluminum isopropylate, 2.18g phosphoric acid, 0.5g hydrofluoric acid and 0.28g diethylamine in plastic cans 1, and temperature is at 60 ℃; By coutroi velocity, eutectic mixture, aluminum chloride, phosphoric acid and hydrofluoric acid, diethylamine are fed in plastic cans according to aforementioned proportion, make each material component keep constant; Colloidal sol in plastic cans 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 eutectic mixture 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-5 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 eutectic mixture: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=4.86:0.5:1:1:1:0.41,25.2g eutectic mixture, 2g silicon sol, 3.8g aluminum isopropylate, 2.18g phosphoric acid, 0.5g hydrofluoric acid and 0.3g diethylamine; Tubular reactor is at 160 ℃ of heating crystallizations, by coutroi velocity, is that to make crystallization time be 30 minutes to 3.3ml/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 eutectic mixture: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=3.83:0.6:1:1:1:0.5,18.6g eutectic mixture, 2.4g silicon sol, 3.8g aluminum isopropylate, 2.18g phosphoric acid, 0.5g hydrofluoric acid and 0.37g diethylamine; 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 eutectic mixture: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=4.75:0.8:1:1:1.07:0.62,24.6g eutectic mixture, 3.2g silicon sol, 3.8g aluminum isopropylate, 2.18g phosphoric acid, 0.54g hydrofluoric acid and 0.45g diethylamine; 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 tubular reactor type of heating is Microwave-assisted firing, and well heater is crystallization at 130 ℃, by coutroi velocity, is that to make crystallization time be 10 minutes to 10ml/min.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Embodiment 6
With embodiment 2, wherein aluminium source is aluminum chloride 2.5g.Sieve sample productive rate and relative crystallinity that the present embodiment is obtained are listed in table 1.
Embodiment 7
With embodiment 2, wherein template is dipropyl amine 0.42g.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 eutectic mixture: SiO
2: Al
2o
3: P
2o
5: HF: diethylamine=6.03:1:1:1:1.07:1.08.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 | 14 | 100 |
| 2 | 10 | 96 |
| 3 | 7.4 | 97 |
| 4 | 6.2 | 101 |
| 5 | 9.8 | 90 |
| 6 | 9.7 | 102 |
| 7 | 9.8 | 97 |
| 8 | 10.0 | 95 |
*note: the degree of crystallinity of embodiment 1 sieve sample of take is 100%.
Claims (2)
1. continous way is produced a method for SAPO-5 molecular sieve, it is characterized in that, specifically comprises:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add in the plastic cans containing eutectic mixture 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: eutectic mixture: SiO
2: Al
2o
3: P
2o
5: template: H
2o: mineralizer=5～200:0～1.2:0.01～1.2:0.01～1.2:0.05～2.0:0.01～0.2:0.01～1.2;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor heating at 100-250 ℃ of crystallization 1～300min through fresh feed pump;
C) and b) simultaneously, fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer are fed in plastic cans 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) eutectic mixture after rectifying and unreacted feedstream continue to participate in reaction to plastic cans; The distilled water that rectifying obtains flows to filtration washing device reaction after product is washed;
Wherein, described eutectic mixture is the mixture of etamon chloride and tetramethylolmethane or the mixture of tetraethylammonium bromide and tetramethylolmethane; 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 masterplate agent is one or more in di-n-propylamine, diethylamine, triethylamine; Described mineralizer is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride; Described phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, Secondary ammonium phosphate; The type of heating of described tubular reactor is heating by electric cooker, steam-heated cal(l)andria, oil bath heating or Microwave-assisted firing.
2. continous way according to claim 1 is produced the method for SAPO-5 molecular sieve, it is characterized in that, specifically comprises:
A) silicon source ,Lv source, masterplate agent, phosphorus source and mineralizer add in the plastic cans containing eutectic mixture and stir pre-plastic, and temperature is controlled at 60～120 ℃, pre-plastic 1～300 minute;
B) the pre-plastic product in plastic cans is squeezed into tubular reactor heating at 140-190 ℃ of crystallization 10～60min through fresh feed pump;
C) and b) simultaneously, fresh ,Lv source, silicon source, masterplate agent, phosphorus source and mineralizer are fed in plastic cans according to 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) eutectic mixture after rectifying and unreacted feedstream continue to participate in reaction to plastic cans; The distilled water that rectifying obtains flows to filtration washing device reaction after product is washed;
The type of heating of described tubular reactor is oil bath heating or Microwave-assisted firing;
Described eutectic mixture is the mixture of etamon chloride and tetramethylolmethane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629760A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Method for synthesizing AFI type SAPO (silicoaluminophosphate) molecular sieve |
| CN108473323A (en) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | The method for preparing synthetic mineral particle |
| CN110167881A (en) * | 2016-12-08 | 2019-08-23 | 巴斯夫公司 | The aluminosilicate zeolites of acceleration crystallize |
| CN115215351A (en) * | 2022-06-12 | 2022-10-21 | 中海油天津化工研究设计院有限公司 | Method and device for continuously producing molecular sieve in tubular reactor |
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| CN101602513A (en) * | 2009-07-18 | 2009-12-16 | 太原理工大学 | The method that in eutectic mixture, prepares aluminium phosphate molecular sieve |
| CN102583436A (en) * | 2011-01-06 | 2012-07-18 | 兰州理工大学 | Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body |
| 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 |
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2013
- 2013-10-28 CN CN201310516837.7A patent/CN103553076A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602513A (en) * | 2009-07-18 | 2009-12-16 | 太原理工大学 | The method that in eutectic mixture, prepares aluminium phosphate molecular sieve |
| CN102583436A (en) * | 2011-01-06 | 2012-07-18 | 兰州理工大学 | Quick synthesis method of heteroatomic aluminophosphate molecular sieve SAPO-5 in eutectic body |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473323A (en) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | The method for preparing synthetic mineral particle |
| CN108473323B (en) * | 2015-09-28 | 2022-07-01 | 国家科学研究中心 | Method for producing synthetic mineral particles |
| CN110167881A (en) * | 2016-12-08 | 2019-08-23 | 巴斯夫公司 | The aluminosilicate zeolites of acceleration crystallize |
| CN110167881B (en) * | 2016-12-08 | 2023-01-03 | 巴斯夫公司 | Accelerated aluminosilicate zeolite crystallization |
| CN106629760A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Method for synthesizing AFI type SAPO (silicoaluminophosphate) molecular sieve |
| CN106629760B (en) * | 2017-01-03 | 2018-10-02 | 兰州理工大学 | A method of synthesis AFI type silicoaluminophosphamolecular molecular sieves |
| CN115215351A (en) * | 2022-06-12 | 2022-10-21 | 中海油天津化工研究设计院有限公司 | Method and device for continuously producing molecular sieve in tubular reactor |
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Application publication date: 20140205 |