CN100358882C - Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid - Google Patents
Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid Download PDFInfo
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- CN100358882C CN100358882C CNB2006100421932A CN200610042193A CN100358882C CN 100358882 C CN100358882 C CN 100358882C CN B2006100421932 A CNB2006100421932 A CN B2006100421932A CN 200610042193 A CN200610042193 A CN 200610042193A CN 100358882 C CN100358882 C CN 100358882C
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- tetrahydrofuran
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- butyleneglycol
- granule type
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention discloses a method for catalyzing and synthesizing tetrahydrofuran by using granular solid super strong acids, which comprises the steps of adding catalysts, heating, supplying nitrogen, inputting 1.4-butanediol, generating products, postprocessing the products, distilling and purifying the products, etc. The method of the present invention has the advantages of high catalysis efficiency, low reaction temperature, single raw material, simple technology, high yield, high output rate, low cost, etc., and is favorable for industrial production.
Description
Technical field
The present invention relates to a kind of process for catalytic synthesis of organic solvent, relate in particular to a kind of method of utilizing the solid superacid as catalyst synthesizing tetrahydrofuran.
Background technology
Tetrahydrofuran (THF) (THF) is a kind of high polarity, lower boiling amphoteric solvent commonly used in organic scientific research and industry, also is important medicine synthetic intermediate and Organic Chemicals.Tetrahydrofuran (THF) is used for the solvent of synthetic pentoxiverin, sharp multiple enzyme element, Progesterone and some hormone medicines in medicine industry; Tetrahydrofuran (THF) also can be used for the ply of paper of synthetic leather surface treatment agent and amino peptide and analyses etc.
At present, the main method of synthetic THF has: furfural method, dichlorobutylene method, cis-butenedioic anhydride shortening method, Reppe, butadiene oxidation method and 1,4-butyleneglycol cyclodehydration method.In aforesaid method, with 1, the 4-butyleneglycol is raw material synthetic THF product purity height, technology is simple.But this technology adopts sulfuric acid catalysis usually, etching apparatus, and coking is serious, and easily causes environmental pollution.The employing strong-acid ion exchange resin (Zhu Chongye, Chen Zhumin, Li Quanzhi, petrochemical complex, nineteen ninety the 19th rolls up 518) and η-Al
2O
3, heteropolyacid etc. replaces sulfuric acid catalysis, effectively solved equipment corrosion and coking problem, reduced environmental pollution, but that production technique changes is little, still has catalyzer and reaction system separation problem.X-Al
2O
3Or H-Y molecular sieve fixed bed (Wang Haijing, Duan Qiwei, chemical industry progress, 934 pages of 2002 the 21st 12 phases of volume) the synthetic THF of catalysis has the catalytic efficiency height, but continuous production, catalyzer such as must not separate at advantage, but catalytic temperature is higher.
Summary of the invention
The purpose of invention is at the existing deficiency of the synthetic method of above-mentioned tetrahydrofuran (THF), provides a kind of catalytic efficiency higher, and temperature of reaction is lower, is more suitable for the method for the fixed-bed catalytic synthesizing tetrahydrofuran of industrial application.
Patent of the present invention adopts the method for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid, is made up of following steps:
(1) adds catalyzer: in reactor, add the granule type SO of 3-5mm
4 2-/ MxOy solid super acid catalyst 80-120g;
(2) heating; Heating makes the temperature life to 200-300 ℃;
(3) feed nitrogen: in reactor, import nitrogen with air speed 60-80ml/h, and make catalyzer all the time at the nitrogen protection state;
(4) input 1.4-butyleneglycol: after the air of reaction system is drained, in reactor, import the 1.4-butyleneglycol with weight space velocity 20-35g/h;
(5) product generates: the 1.4-butyleneglycol generates product under the effect of catalyzer;
(6) product aftertreatment: after above-mentioned reaction, the product aqueous solution that the still discharge port that responds is sent is collected in the flask through the condensing works condensation;
(7) fractionation is purified: above-mentioned thick product is shunted, collected 64-67 ℃ of cut, obtain the thick product of tetrahydrofuran (THF).
Preferably, the described SO of above-mentioned steps (1)
4 2-/ MxOy class solid super acid catalyst is meant SO
4 2-/ Al
2O
3Solid super acid catalyst.
Preferably, the described SO of step (1)
4 2-The add-on of/MxOy class solid super acid catalyst is 80-100g.
Preferably, during the described Heating temperature of step (2) 220-300 ℃.
Preferably, it is characterized in that step (2) is described to be heated to be with the nichrome wire heating under the controller control.
Preferably, the air speed of the described input nitrogen of step (3) is 60-80ml/h.
Preferably, step (4) 1.4-butyleneglycol input air speed is weight space velocity 20-35ml/h.
Preferably, it is characterized in that the 1.4-butyleneglycol of step (4) input is a 1.4-butyleneglycol steam.
Preferably, the product in the step (7) is and water azeotropic product.
The method of the catalyzed by particle type solid superacid agent catalysis synthesizing tetrahydrofuran that the present invention is used is at normal pressure, the fixed-bed catalytic under the gas phase condition.Used SO
4 2-/ MxOy class solid super acid catalyst has excellent catalytic activity, catalytic stability and anti-carbon deposition ability, does not occur the active sign that reduces more than 300 hours 200-300 ℃ of catalysis, the renewable and recycling of catalyzer.The method of the catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid that the present invention is used, it is single also to have a raw material, and technology is easy, can synthesize the characteristics that productive rate is high continuously.Yield calculates by tetrahydrofuran (THF) and reaches 99% in the thick product, and gas chromatography-mass spectrum logotype instrument analytical results shows through the U.S., contains tetrahydrofuran (THF) in the thick product, and all the other products are water.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.But the invention is not restricted to this.
Embodiment 1:
(1) adds catalyzer: in reactor, add the granule type SO of 3-5mm
4 2-/ Al
2O
3Solid super acid catalyst 80g.
(2) with the nichrome wire heating under the controller control; Heating makes temperature life to 250 ℃;
(3) feed nitrogen: in reactor, import nitrogen with air speed 60ml/h, and make catalyzer all the time at the nitrogen protection state;
(4) input 1.4-butyleneglycol: after the air of reaction system is drained, in reactor, import 1.4-butyleneglycol steam with weight space velocity 25g/h;
(5) product generates: the 1.4-butyleneglycol generates product under the effect of catalyzer;
(6) product aftertreatment: after above-mentioned reaction, the product aqueous solution that the still discharge port that responds is sent is collected in the flask through the condensing works condensation,
(7) shunting is purified: above-mentioned thick product is shunted, collected the 64-67C cut, obtain the thick product of tetrahydrofuran (THF).Yield calculates by tetrahydrofuran (THF) and reaches 99% in the thick product, and gas chromatography-mass spectrum logotype instrument analytical results shows through the U.S., contains tetrahydrofuran (THF) in the thick product, and all the other products are water.
Embodiment 2
(1) adds catalyzer: in reactor, add the granule type SO of 3-5mm
4 2-/ MxOy solid super acid catalyst 100g.
(2) just with the nichrome wire heating under the controller control; Heating makes temperature life to 280 ℃
(3) feed nitrogen: in reactor, import nitrogen with air speed 80ml/h, and make catalyzer all the time at the nitrogen protection state;
(4) input 1.4-butyleneglycol: after the air of reaction system is drained, in reactor, import 1.4-butyleneglycol steam with weight space velocity 30g/h;
(5) product generates: the 1.4-butyleneglycol generates product under the effect of catalyzer;
(6) product aftertreatment: after above-mentioned reaction, the product aqueous solution that the still discharge port that responds is sent is collected in the flask through the condensing works condensation,
(7) shunting is purified: above-mentioned thick product is shunted, collected 64-67 ℃ of cut, obtain the thick product of tetrahydrofuran (THF).
Yield calculates by tetrahydrofuran (THF) and reaches 99% in the thick product, and gas chromatography-mass spectrum logotype instrument analytical results shows through the U.S., contains tetrahydrofuran (THF) in the thick product, and all the other products are water.
Embodiment 3
(1) adds catalyzer: in reactor, add the granule type SO of 3-5mm
4 2-/ MxOy solid super acid catalyst 120g;
(2) with the nichrome wire heating under the controller control; Heating makes temperature life to 300 ℃
(3) feed nitrogen: in reactor, import nitrogen with air speed 70ml/h, and make catalyzer all the time at the nitrogen protection state;
(4) input 1.4-butyleneglycol: after the air of reaction system is drained, in reactor, import 1.4-butyleneglycol steam with weight space velocity 35g/h;
(5) product generates: the 1.4-butyleneglycol generates product under the effect of catalyzer;
(6) product aftertreatment: after above-mentioned reaction, the product aqueous solution that the still discharge port that responds is sent is collected in the flask through the condensing works condensation,
(7) shunting is purified: above-mentioned thick product is shunted, collected 64-67 ℃ of cut, obtain the thick product of tetrahydrofuran (THF).
Yield calculates by tetrahydrofuran (THF) and reaches 99% in the thick product, and gas chromatography-mass spectrum logotype instrument analytical results shows through the U.S., contains tetrahydrofuran (THF) in the thick product, and all the other products are water.
Claims (4)
1. method with catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid may further comprise the steps:
(1) adds catalyzer: in reactor, add the granule type SO of 3-5mm
4 2-/ MxOy solid super acid catalyst 80-120g; SO
4 2-/ MxOy class solid super acid catalyst is meant SO
4 2-/ Al
2O
3Solid super acid catalyst;
(2) heating; Heating makes temperature rise to 220-300 ℃;
(3) feed nitrogen: in reactor, import nitrogen with air speed 60-80ml/h, and make catalyzer all the time at the nitrogen protection state;
(4) input 1,4-butyleneglycol: after the air of reaction system is drained, in reactor, import 1, the 4-butyleneglycol with weight space velocity 20-35g/h;
(5) product generates: 1, and the 4-butyleneglycol generates product under the effect of catalyzer;
(6) product aftertreatment: after above-mentioned reaction, the product aqueous solution process condensing works condensation by the reactor discharge port is discharged is collected in the flask;
(7) shunting is purified: above-mentioned thick product is shunted, collected 64-67 ℃ of cut, obtain the thick product of tetrahydrofuran (THF).
2. the method with catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid as claimed in claim 1 is characterized in that the described SO of step (1)
4 2-The add-on of/MxOy class solid super acid catalyst is 80-100g.
3. the method with catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid as claimed in claim 1 is characterized in that, step (2) is described to be heated to be with the nichrome wire heating under the controller control.
4. the method with catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid as claimed in claim 1 is characterized in that, 1 of step (4) input, and the 4-butyleneglycol is 1,4-butyleneglycol steam.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100421932A CN100358882C (en) | 2006-01-09 | 2006-01-09 | Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid |
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| CNB2006100421932A CN100358882C (en) | 2006-01-09 | 2006-01-09 | Process for catalyzing synthesizing tetrahydrofuran by granule type solid super strengthen acid |
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| CN1793133A CN1793133A (en) | 2006-06-28 |
| CN100358882C true CN100358882C (en) | 2008-01-02 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108912079A (en) * | 2018-07-25 | 2018-11-30 | 铜仁学院 | A kind of method that fixed-bed catalytic prepares oxinane |
| CN114805250B (en) * | 2022-05-24 | 2023-12-29 | 中化学科学技术研究有限公司 | Tetrahydrofuran preparation process and device |
| CN115043795B (en) * | 2022-07-28 | 2023-07-25 | 中化学科学技术研究有限公司 | Tetrahydrofuran production process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
| CN1675190A (en) * | 2002-08-20 | 2005-09-28 | 巴斯福股份公司 | Method for producing tetrahydrofuran |
-
2006
- 2006-01-09 CN CNB2006100421932A patent/CN100358882C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208410A (en) * | 1996-01-16 | 1999-02-17 | 林德股份公司 | Process and device for the preparation of tetrahydrofuran |
| CN1675190A (en) * | 2002-08-20 | 2005-09-28 | 巴斯福股份公司 | Method for producing tetrahydrofuran |
Non-Patent Citations (2)
| Title |
|---|
| 1，4-丁二醇气相脱水环化制四氢呋喃催化剂和工艺的研究. 王海京，段启伟.化工进展，第21卷第12期. 2002 * |
| 负载型硅钨酸催化1，4-丁二醇环化脱水制备四氢呋喃. 李海霞等.精细石油化工，第2期. 2005 * |
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