CN101508683B - Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol - Google Patents
Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol Download PDFInfo
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- CN101508683B CN101508683B CN2009101197957A CN200910119795A CN101508683B CN 101508683 B CN101508683 B CN 101508683B CN 2009101197957 A CN2009101197957 A CN 2009101197957A CN 200910119795 A CN200910119795 A CN 200910119795A CN 101508683 B CN101508683 B CN 101508683B
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- tetrahydropyrrole
- butyleneglycol
- water
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Abstract
The present invention relates to a method for producing tetrahydropyrrole. The method comprises the following steps: taking 1,4-butyleneglycol, ammonia and water with the mol ratio of 1:1.3-2:0.4-3 as raw materials, heating and vaporizing to reach reaction temperature of 240-330 DEG C, introducing into a reactor at the weight space velocity of 0.6-0.7g/min under the protection of nitrogen, passing through a gas-phase fixed bed filled with an SO4<2->/TiO2-SnO2-Al2O3 solid super acidic catalyst or SO4<2->/CuO-ZnO-Al2O3 solid super acidic catalyst, performing catalytic reaction at the reaction pressure of 0-0.1MPa, condensing a reactant to obtain a solvent mixture, distilling and purifying the solvent mixture, and collecting a distillate with the temperature of 86-90 DEG C to obtain crude tetrahydropyrrole. In the method, the tetrahydropyrrole is synthesized by reaction in a low pressure state, a little water is added in the synthesis process to reduce difficulty in purifying and separating the product, and the method has the advantages of safety and high efficiency, simple production process, low production cost, energy conservation, easy wastewater treatment, easy environmental protection, and high raw material conversion rate and yield.
Description
Technical field
The invention belongs to a kind of method of producing Pyrrolidine.
Background technology
Pyrrolidine is a cyclic secondary amine, and pKb=2.9 has the character of general amine, in fields such as medicine, agricultural chemicals, weaving, printing and dyeing, household chemicals, coating, macromolecular material, sensitive materials, additive, sweetening agents purposes is widely arranged.
Its past, the preparation method mainly contained: tetrahydrofuran (THF) and ammonia catalysis synthesis process, hydrodenitrification method etc.Also can carry out the synthetic of tetrahydropyrrole compounds by additive method, wherein more representational have: 1, and 4-butanediamine shortening denitrogenation, 1,4-succinonitrile hydrogenation method, pyrroles's hydrogenation method, pyrrolidone hydrogenation method etc.These methods are mainly reacted under hydro condition, have condition harshness, matching requirements height, shortcoming such as not easy to operate, generally can not react under normal pressure.Reaction under high pressure requires safe, and device fabrication and productive expense costliness are unfavorable for improving production capacity, are unfavorable for large-scale commercial production.Existing synthesis method mostly is the mesohigh reaction greatly, and big water gaging participates in reaction in the building-up process, wastes energy, and increases product purification difficulty, has also increased waste water control difficulty and cost.
Summary of the invention
The objective of the invention is to design a kind of by 1, the method of Pyrrolidine is produced in the ammonification of 4-butanediol dehydrogenation, and this method is reacted the tetrahydrobiopterin synthesis pyrroles under low-pressure state, add entry in the building-up process less, reduce product purification separating difficulty, have safe and efficiently, production link is simple, and production cost is low, save energy, be easy to waste water control, be easy to environment protection standard, the advantage that feed stock conversion and productive rate are high.
For this reason; raw material of the present invention adopts 1, and the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.3～2: 0.4～3, and the vaporization of heating reaches temperature of reaction; 240～330 ℃ of temperature of reaction, under nitrogen protection with weight space velocity 0.6～0.7g/min input reactor by SO is housed
4 2-/ TiO
2-SnO
2-Al
2O
3Solid super acid catalyst, or SO
4 2-/ CuO-ZnO-Al
2O
3The gas phase fixed bed of solid super acid catalyst, reaction pressure 0～0.1MPa is through catalyzed reaction, reacted object obtains admixture solvent after condensation, the admixture solvent fractionation is purified, collect 86～90 ℃ of cuts, the thick product of Pyrrolidine, described 1, the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.3: 0.4, or described 1, the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.5: 1, or described 1, and the mol ratio of 4-butyleneglycol, ammonia and water is 1: 2: 3.Aforesaid method has reached purpose of the present invention.
Advantage of the present invention is reaction tetrahydrobiopterin synthesis pyrroles under low-pressure state, add entry in the building-up process less, reduce product purification separating difficulty, have safe and efficiently, production link is simple, and production cost is low, save energy, be easy to waste water control, be easy to environment protection standard, the advantage that feed stock conversion and productive rate are high.
Specific embodiments
Embodiment 1: make reactor with the gas phase fixed bed, add 3～5mm particulate state SO in the gas phase fixed bed
4 2-/ TiO
2-SnO
2-Al
2O
3Solid super acid catalyst 150g; Heating makes temperature rise to 280 ℃, with air speed 50～55cm
3/ min imports nitrogen in reactor, catalyzer is under the nitrogen protection all the time.With volume pump with 1,4-butyleneglycol and water, ratio (mol ratio) is by 1: 0.4, with weight space velocity 0.6g/min with 1, in the steam of 4-butyleneglycol and the water input reactor.And feed ammonia simultaneously, and making 1, the mol ratio of 4-butyleneglycol and ammonia is 1: 1.3, and makes 1, the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.3: 0.4.Reaction pressure 0～0.1MPa.Above-mentioned raw materials generates the mixing object under the effect of catalyzer, through the condensing works condensation, get admixture solvent from the effusive object of reactor discharge port, purifies through fractionation again, collects 86～90 ℃ of cuts, gets the thick product of Pyrrolidine.Through gas Chromatographic Determination: 1,4-butyleneglycol transformation efficiency 100%, the Pyrrolidine productive rate is 92%, by product is mainly water.
Embodiment 2: SO as different from Example 1
4 2-/ CuO-ZnO-Al
2O
3Solid super acid catalyst; Described 1, the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.5: 1.290 ℃ of temperature of reaction.1,4-butyleneglycol transformation efficiency 100%, the Pyrrolidine productive rate is 91%, by product is mainly water.All the other are identical.So be not repeated.
Embodiment 3: SO as different from Example 1
4 2-/ TiO
2-SnO
2-Al
2O
3Solid super acid catalyst; Described 1, the mol ratio of 4-butyleneglycol, ammonia and water is 1: 2: 3.With 1, the steam of 4-butyleneglycol and water is imported in the reactor with weight space velocity 0.7g/min.320 ℃ of temperature of reaction.1,4-butyleneglycol transformation efficiency 100%, the Pyrrolidine productive rate is 90.5%, by product is mainly water.All the other are identical.So be not repeated.
SO
4 2-/ TiO
2-SnO
2-Al
2O
3Solid super acid catalyst and SO
4 2-/ CuO-ZnO-Al
2O
3Solid super acid catalyst is existing procucts.
In above-mentioned detailed concrete real-time mode,, can under the prerequisite that does not deviate from its aim and scope, implement although invention has been described with preferred form with characteristic to a certain degree.Various visibly different embodiment of the present invention should understand under the situation that does not depart from claim thereafter, and invention is not limited to specific embodiment.
In a word, the present invention reacts the tetrahydrobiopterin synthesis pyrroles under low-pressure state, add less entry in the building-up process, reduces product purification separating difficulty, have safe and efficiently, production link is simple, and production cost is low, energy savings, be easy to waste water control, be easy to environment protection standard, the advantage that feed stock conversion and productive rate are high.
Claims (1)
1. method of producing Pyrrolidine by the ammonification of 4-butanediol dehydrogenation; it is characterized in that: raw material adopts 1; the mol ratio of 4-butyleneglycol, ammonia and water is 1: 1.3～2: 0.4～3; the vaporization of heating reaches temperature of reaction; 240～330 ℃ of temperature of reaction, under nitrogen protection with weight space velocity 0.6～0.7g/min input reactor by SO is housed
4 2-/ TiO
2-SnO
2-Al
2O
3Solid super acid catalyst, or SO
4 2-/ CuO-ZnO-Al
2O
3The gas phase fixed bed of solid super acid catalyst, reaction pressure 0～0.1MPa, through catalyzed reaction, reacted object obtains admixture solvent after condensation, and the admixture solvent fractionation is purified, and collects 86～90 ℃ of cuts, gets the thick product of Pyrrolidine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101197957A CN101508683B (en) | 2009-03-30 | 2009-03-30 | Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101197957A CN101508683B (en) | 2009-03-30 | 2009-03-30 | Dehydrogenation ammoniation method for producing pyrrolidine with 1,4butanediol |
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| Publication Number | Publication Date |
|---|---|
| CN101508683A CN101508683A (en) | 2009-08-19 |
| CN101508683B true CN101508683B (en) | 2011-10-26 |
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| CN110746377B (en) * | 2019-11-07 | 2023-03-31 | 中国科学院兰州化学物理研究所 | Method for synthesizing 1-substituted pyrrolidine/piperidine derivative by supported metal catalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN101343258A (en) * | 2008-08-20 | 2009-01-14 | 曲阜师范大学 | Method for synthesis of pyrrolidine with particle type solid ultra-corrosive acid catalysis |
-
2009
- 2009-03-30 CN CN2009101197957A patent/CN101508683B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN101343258A (en) * | 2008-08-20 | 2009-01-14 | 曲阜师范大学 | Method for synthesis of pyrrolidine with particle type solid ultra-corrosive acid catalysis |
Non-Patent Citations (1)
| Title |
|---|
| 郭锡坤 等.Cu/SO42-/TiO2-Al2O3催化剂的制备及其催化性能研究.《汕头大学学报（自然科学版）》.2007,第22卷(第4期),71-75，80. * |
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