CN101660171A - Method for preparing aminopropanol by electrolysis - Google Patents
Method for preparing aminopropanol by electrolysis Download PDFInfo
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- CN101660171A CN101660171A CN200910144898A CN200910144898A CN101660171A CN 101660171 A CN101660171 A CN 101660171A CN 200910144898 A CN200910144898 A CN 200910144898A CN 200910144898 A CN200910144898 A CN 200910144898A CN 101660171 A CN101660171 A CN 101660171A
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- aminopropanol
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- electrolysis
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Abstract
A method for preparing aminopropanol by electrolysis comprises two steps, namely preparation of aminopropanol by electrolysis reduction of an amino acid cathode and purification; the method for preparing aminopropanol by electrolysis is characterized in that an ion exchange membrane is adopted to divide an electrolyzer into a negative chamber and a positive chamber; the concentration of the aminopropanol in catholyte is 0.3mol/L to 2.0mol/L; the pH of the catholyte is 1 to 4; the anolyte is sulfuric acid with mass percentage concentration of 2 percent to 20 percent; the temperature of the electrolyte is controlled to be from 30 DEG C to 60 DEG C; the current density is 200 A/m<2> to 2000 A/m<2>; and when electrolyte balance is reached, the aminopropanol is obtained after the catholyte experiences filtration, neutralization, re-filtration and distillation. The method for preparing aminopropanol by electrolysis has low production cost and no pollution in the production process.
Description
Technical field
The present invention relates to the preparation method of aminopropanol, more precisely is a kind of method for preparing aminopropanol with the water-soluble amino acid of electrolytic reduction.
Background technology
Aminopropanol has vast market prospect, fine chemistry industry and pharmaceutical industry in World chemical product market in 2002, and its sales volume reaches 7,000,000,000 and 1,590 hundred million dollars respectively.The L-aminopropanol is the important intermediate of synthetic third generation quinolones broad spectrum antibiotic Levofloxacin, its optical purity and price directly have influence on the quality and the price of Levofloxacin, it is important source material, intermediate and the chiral auxiliary(reagent) in pharmacy and the agribusiness simultaneously, has a wide range of applications as chiral source and chirality modifier in asymmetric synthesis.Its preparation is based on reduction method, as patent: 01127017.9; 200710190457.3; Disclosing with the L-alanine is starting raw material, prepares the method for aminopropanol with metal borohydride as reductive agent, and has obtained industrial application.The industrialization of still being unrealized of shortening method and biological synthesis process.Patent: 200610029053.1; 200710067973.7; Disclosing with the propylene oxide is starting raw material, prepares the method for aminopropanol through phase-transfer catalysis.Realized at present the method for industrialized production aminopropanol, its reductive agent consumption is big, cost an arm and a leg, and 1 ton of aminopropanol of every production will consume 2.5 tons of reductive agent KBH
4, this individual event cost promptly reaches 220,000 yuan, and reaction conditions requires height and long reaction time, and reaction efficiency is low, the residue contaminate environment.
Catalytic hydrogenating reduction just with its environmental friendliness, easy and simple to handlely be subjected to common concern.But up to now, the method for preparing aminopropanol with the water-soluble amino acid of electrolytic reduction does not have open report as yet.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, a kind of method of electrolytic preparation aminopropanol is provided, to reduce the production cost of aminopropanol, reducing the pollution of production process to environment.
The present invention adopts following technical scheme for the technical solution problem:
The method of electrolytic preparation aminopropanol of the present invention, comprise the amino acid catholyte reduction preparation aminopropanol and two steps of purifying, it is characterized in that adopting ion-exchange membrane that electrolyzer is divided into negative and positive two Room, the concentration of alanine is 0.3～2.0mol/L in the catholyte, and the pH of catholyte is 1～4; Described anolyte is that concentration is 2～20% sulfuric acid by mass percentage; The temperature of control electrolytic solution is 30～60 ℃, current density 200～2000A/m
2After reaching electrolytic equilibrium, with catholyte after filtration, neutralize, refilter, distill and promptly get aminopropanol.
The characteristics of electrolytic preparation aminopropanol method of the present invention also are:
Described catholyte consists of by mass ratio: alanine 15～35, water 80～60, sulfuric acid and vitriol 4～4.5, catalyzer 1～0.5.
The catalyzer that adds in the described catholyte is the loaded article of Re, Ru, Cu, Ni, Pd simple substance or its compound, and carrier is carbon, aluminum oxide or silica gel.
The cathode material that is provided with in the described electrolyzer is platinum, molybdenum, lead or the graphite with katalysis; Anode material is the inert material of acid corrosion-resistant.
Described anode material is platinum or molybdenum.
The principle of foundation of the present invention is: in electrolytic process, and the H of anolyte compartment
+Enter cathode compartment by cationic exchange membrane, at negative electrode H
+Get electronics and be reduced into atomic hydrogen and amino acid whose carboxyl generation reduction reaction.Electrode reaction is:
Anode: H
2O-2e=2H
++ 1/2O
2
Negative electrode: 2H
++ 2e=H
2
2H
2+R-CH(NH
2)-COOH→R-CH(NH
2)-CH
2OH+H
2O
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the inventive method is because of the inexpensive remarkable cost that reduces the preparation aminopropanol of raw material.
2, reaction conditions gentleness of the present invention, no residue.The oxyethane that adopts in the technology of having reported is inflammable explosive article; Borane reducing agent hydride is met wet inflammable, residue is arranged, contaminate environment after the reaction.
3, electrolytic reduction of the present invention carries out at normal pressure, room temperature condition, safety, easily control, and catalyzer can be reused.The catalytic hydrogenating reduction of report is to carry out under High Temperature High Pressure, and catalyzer can not be reused.
4, the inventive method is suitable for the preparation of water soluble amino alcohol, comprises that all water-soluble amino acids can adopt the inventive method to be prepared corresponding amino alcohol.
Embodiment
In the present embodiment, adopt ion-exchange membrane that electrolyzer is divided into cathode compartment and anolyte compartment, in cathode compartment and anolyte compartment, place 30～60 ℃ of the temperature that the prolong that is used to reduce utmost point room temp is regulated electrolytic solution respectively.
Cathode material adopts platinum, molybdenum, lead flake or graphite rod;
Anode material is corrosion resistant inert material, can be platinum or molybdenum sheet.
In the concrete preparation, the concentration of alanine is 0.3～2.0mol/L in the catholyte, and the pH of catholyte is 1～4; Anolyte is 2～20% sulfuric acid by the concentration of mass ratio; The temperature of control electrolytic solution is 30～60 ℃, current density 200～2000A/m
2After reaching electrolytic equilibrium, will neutralize, refilter with sodium hydroxide or yellow soda ash after the catholyte filtration and get aminopropanol through underpressure distillation.
In concrete the enforcement, catholyte consists of by mass ratio: alanine 15～35, water 80～60, sulfuric acid and vitriol 4～4.5, catalyzer 1～0.5.
The catalyzer that adds in catholyte is the loaded article of Re, Ru, Cu, Ni, Pd simple substance or its compound, and carrier is carbon, aluminum oxide or silica gel.
Embodiment 1:
Present embodiment is made electrolyzer with synthetic glass, is divided into cathode compartment and anolyte compartment with cationic exchange membrane, and anode and negative electrode adopt platinized platinum or molybdenum sheet to do electrode, and negative electrode and anodic useful area are 14cm
2, negative electrode and anodic spacing are 1.5cm.
With distilled water preparation 0.5mol/L L-L-Ala solution 100mL, add the 2mL vitriol oil and 2g sodium sulfate, add 0.1g gram palladium-carbon catalyst and get catholyte; Anolyte is 5% sulfuric acid, at current density 250A/m
2Electrolysis is 7 hours under the condition, with the efficient liquid phase chromatographic analysis feed stock conversion is 46.7%, catholyte after filtration, filtrate is neutralized to neutrality, refilters, 77～80 ℃/2.0KPa cut is collected in the filtrate decompression distillation obtained the L-aminopropanol with sodium hydroxide, and productive rate is 41.3%.
Embodiment 2:
Present embodiment electrolyzer and electrolytic solution initial composition are with embodiment 1, catalyzer adopts 0.1 gram ruthenium carbon, constant voltage 14V, electrolysis 9 hours, with the efficient liquid phase chromatographic analysis feed stock conversion is 67.8%, catholyte after filtration, filtrate is neutralized to neutrality, refilters, distills and obtain the L-aminopropanol with yellow soda ash, and productive rate is 64.7%.
Embodiment 3:
Present embodiment initial amino acid DL-alanine, catalyzer are 0.1 gram Raney's nickel, and other are as example 1, control current density 20A/dm
2, electrolysis 12 hours,, be 38.6% with the efficient liquid phase chromatographic analysis feed stock conversion, catholyte after filtration, neutralize, refilter, distill and obtain the DL-aminopropanol, productive rate is 35.4%.
Claims (5)
1, a kind of method of electrolytic preparation aminopropanol, comprise the amino acid catholyte reduction preparation aminopropanol and two steps of purifying, it is characterized in that adopting ion-exchange membrane that electrolyzer is divided into negative and positive two Room, the concentration of alanine is 0.3～2.0mo1/L in the catholyte, and the pH of catholyte is 1～4; Described anolyte is that concentration is 2～20% sulfuric acid by mass percentage; The temperature of control electrolytic solution is 30～60 ℃, current density 200～2000A/m
2After reaching electrolytic equilibrium, with catholyte after filtration, neutralize, refilter, distill and promptly get aminopropanol.
2, the method for electrolytic preparation aminopropanol according to claim 1 is characterized in that described catholyte consisting of by mass ratio: alanine 15～35, water 80～60, sulfuric acid and vitriol 4～4.5, catalyzer 1～0.5.
3, the method for electrolytic preparation aminopropanol according to claim 2 is characterized in that the catalyzer that adds in the described catholyte is the loaded article of Re, Ru, Cu, Ni, Pd simple substance or its compound, and carrier is carbon, aluminum oxide or silica gel.
4, the method for electrolytic preparation aminopropanol according to claim 1, the cathode material that it is characterized in that being provided with in the described electrolyzer is platinum, molybdenum, lead or the graphite with katalysis; Anode material is the inert material of acid corrosion-resistant.
5, the method for electrolytic preparation aminopropanol according to claim 4 is characterized in that described anode material is platinum or molybdenum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101448989A CN101660171B (en) | 2009-09-09 | 2009-09-09 | Method for preparing aminopropanol by electrolysis |
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|---|---|---|---|
| CN2009101448989A CN101660171B (en) | 2009-09-09 | 2009-09-09 | Method for preparing aminopropanol by electrolysis |
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| CN101660171B CN101660171B (en) | 2011-01-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229536A (en) * | 2011-04-25 | 2011-11-02 | 上虞市众昌化工有限公司 | Method for separating amino alkyl alcohol through membrane electrodialysis |
| CN102344378A (en) * | 2010-08-03 | 2012-02-08 | 江苏康恒化工有限公司 | Amino alcohol preparation method using aqueous amino acid |
| CN102584606A (en) * | 2011-12-28 | 2012-07-18 | 浙江工业大学 | Method for preparing aminopropanol by bipolar membrane electrodialysis |
| CN109996905A (en) * | 2016-11-15 | 2019-07-09 | 国立大学法人横浜国立大学 | The manufacturing method of organic hydride material producing device and organic hydride |
| CN110016684A (en) * | 2019-04-08 | 2019-07-16 | 天津大学 | A method of by amino acid electrolytic preparation enamine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2513132A (en) * | 1947-02-10 | 1950-06-27 | Shell Dev | Preparation of amino alcohols |
| DE3928290A1 (en) * | 1989-08-26 | 1991-02-28 | Basf Ag | METHOD FOR PRODUCING AMINOBENZYL ALCOHOLS |
| CN1641071A (en) * | 2004-01-18 | 2005-07-20 | 浙江工业大学 | Alkyl hydroxylamine and its salt electrochemical synthesis method |
-
2009
- 2009-09-09 CN CN2009101448989A patent/CN101660171B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344378A (en) * | 2010-08-03 | 2012-02-08 | 江苏康恒化工有限公司 | Amino alcohol preparation method using aqueous amino acid |
| CN102344378B (en) * | 2010-08-03 | 2013-12-18 | 江苏康恒化工有限公司 | Amino alcohol preparation method using aqueous amino acid |
| CN102229536A (en) * | 2011-04-25 | 2011-11-02 | 上虞市众昌化工有限公司 | Method for separating amino alkyl alcohol through membrane electrodialysis |
| CN102229536B (en) * | 2011-04-25 | 2013-11-13 | 上虞市众昌化工有限公司 | Method for separating amino alkyl alcohol through membrane electrodialysis |
| CN102584606A (en) * | 2011-12-28 | 2012-07-18 | 浙江工业大学 | Method for preparing aminopropanol by bipolar membrane electrodialysis |
| CN109996905A (en) * | 2016-11-15 | 2019-07-09 | 国立大学法人横浜国立大学 | The manufacturing method of organic hydride material producing device and organic hydride |
| CN109996905B (en) * | 2016-11-15 | 2021-05-11 | 国立大学法人横浜国立大学 | Organic hydride manufacturing device and organic hydride manufacturing method |
| US11519082B2 (en) | 2016-11-15 | 2022-12-06 | National University Corporation Yokohama National University | Organic hydride production apparatus and method for producing organic hydride |
| CN110016684A (en) * | 2019-04-08 | 2019-07-16 | 天津大学 | A method of by amino acid electrolytic preparation enamine |
| CN110016684B (en) * | 2019-04-08 | 2021-03-16 | 天津大学 | Method for preparing enamine by electrolyzing amino acid |
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| CN101660171B (en) | 2011-01-05 |
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