CN104141148B - A kind of method of electrochemical synthesis trimethylamine - Google Patents
A kind of method of electrochemical synthesis trimethylamine Download PDFInfo
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- CN104141148B CN104141148B CN201410379019.1A CN201410379019A CN104141148B CN 104141148 B CN104141148 B CN 104141148B CN 201410379019 A CN201410379019 A CN 201410379019A CN 104141148 B CN104141148 B CN 104141148B
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Abstract
A kind of method of electrochemical synthesis trimethylamine is at normal temperatures and pressures, by N, dinethylformamide is mixed in proportion into solution with water, add supporting electrolyte tetramethyl ammonium chloride and be mixed into electrolyte, and add in airtight electrolyzer, it is sufficiently stirred for, then passes into nitrogen to above-mentioned electrolyzer and be electrochemically reacted, then gaseous product is carried out remove impurity by strong base solution, it is thus achieved that purity is the trimethylamine of 99%.This method technique is simple, easy to operate, obtains highly purified trimethylamine and easily collects, open a new way for the organic synthesis of amine, is a kind of process route having very much commercial synthesis to be worth.
Description
Technical field
The present invention relates to the synthetic method of a kind of trimethylamine, specifically a kind of technical scheme adopting electrochemical method synthesis trimethylamine.
Background technology
Trimethylamine and tertiary amine, molecular formula C3H9N, is a kind of important chemical products, for pesticide, dyestuff, medicine and organic synthesis etc.；As disinfectant, the alarm agent of natural gas, analytical reagent and organic synthesis raw material, it is also used for the raw material of medicine, pesticide, photographic material, rubber chemicals, explosive, chemical fibre solvent, surfactant and dyestuff.With the catalyst that the product of oxirane is used as polycondensation reaction；With the additive that the product choline chloride of ethylene chlorhydrin is used as chicken feed.Main organic synthesis raw material, can be used for producing various commercial auxiliaries, surfactant and dyestuff, ion exchange resin, flocculant, other cationic polymers etc..
The production method of existing trimethylamine requires to complete at high temperature under high pressure mostly, and equipment and energy resource consumption is all higher.The mixture of the various metal-oxide of activated alumina, silicon oxide, titanium dioxide, Tungstic anhydride., hargil, thorium oxide is adopted to make catalyst " adopting methanol vapor phase ammoniation process to prepare the device of methylamine " that publication number is CN203112720U.Reaction temperature is 250-5000C, reaction pressure 0.5-5.0MPa, air speed is 500-1500h-1.Methanol and ammonia reaction generate primary, secondary, tertiary amine mixture.The generation ratio of three kinds of amine is relevant with raw material, catalyst and reaction condition.The ratio of methanol and ammonia of can regulating obtains the product intentionally got, methanol: be the optimum condition generating monomethyl amine during ammonia=1:4, methanol: be the optimum condition generating trimethylamine during ammonia=1:1.5.The trimethylamine obtained often contains the impurity such as methanol, methylamine, dimethylamine, and available extractive distillation or azeotropic distillation are refined.Obtaining pure trimethylamine, can add acetic anhydride or chloroacetic chloride distills, primary amine, secondary amine generate acetylate, and boiling point height not easily steams.After being processed by the trimethylamine activated alumina distilled out, add Fluorenone sodium drying for standby.Additionally, passed through a drying tower equipped with solid potassium hydroxide, pure dry gaseous state trimethylamine can be obtained.This operating procedure is complex, and the energy and equipment requirements is higher.
The present invention is when carrying out " research of the paired electrochemical synthesis ethylene of acetylene and oxalic acid ", find that reaction has a large amount of gas to generate, gaseous product gas collector is directly collected, product gas chromatography mass spectrometry is detected, determine that product is trimethylamine, home and overseas correlative theses and patent are retrieved, it does not have find the report being electrochemically correlated with for Material synthesis trimethylamine with DMF.
In " a kind of improvement technique preparing tertiary amine " that publication number is CN102976950, primary response is fatty alcohol and dimethylamine prepares trimethylamine, it is characterized in that: as the reaction conversion ratio 80-90% of primary response, hydrogen in reactor, trimethylamine, a small amount of monomethyl amine, a small amount of dimethylamine gaseous mixture are passed into absorption tower, by one, two, after trimethylamine use water absorbs, obtain pure hydrogen to pass into again in reactor, proceed reaction, be finally separating to obtain trimethylamine.In " manufacture method of trimethylamine " that publication number is CN101062896A, it is provided that a kind of when manufacturing methylamine, by using zeolite catalyst, while reducing consumption energy cost, efficiency produces the method for the trimethylamine of insufficient section well.The manufacture method of this trimethylamine is characterized by, by methanol and ammonia, methanol and methylamine mixing and ammonia or methylamine mixture and ammonia, zeolite catalyst is used to manufacture in the method for methylamine, including separating-purifying methylamine from the reactant mixture obtained, after isolating ammonia and trimethylamine, make dimethylamine or containing the operation carrying out gas-phase reaction be more than or equal to mixture and the ammonia of 50 moles of % dimethylamine and MMA.Come et al. to be published in being entitled as on " Tianjin chemical industry " " course of industrialization of synthesis amine " with methanol and ammonia for raw material with 2003 by good fortune, under the high temperature of 400-420 DEG C and 5MPa high pressure, react with unformed aluminium silicate for catalyst, prepared thick mixed methylamine, dimethylamine, trimethylamine are the mixture of three kinds of main amine, are then fractionated into refining obtaining the methylamine of higher degree, dimethylamine, trimethylamine.These operating procedures are complex, and the energy and equipment requirements is higher.
Summary of the invention
The present invention provides a kind of method of electrochemical synthesis trimethylamine, with overcome prior art exists to equipment, severe reaction conditions, technological process is complicated, the deficiency of contaminated environment.
Realize above-mentioned purpose, the method for a kind of electrochemical synthesis trimethylamine of measure that the present invention takes, its described method is as follows:
(1) preparation of raw material
By N,N-dimethylformamide and anhydrous Na2CO3-Decompression distillation obtains highly purified N,N-dimethylformamide for twice and stores；Tetramethyl ammonium chloride is dissolved in ethanol, twice final vacuum stored dry of recrystallization；Cleaned by distilled water again after electrode polishing, remove surface oils and fats with acetone wiping；
(2) electrochemical reaction
At normal temperatures and pressures, by the N in step (), the ratio that dinethylformamide and water are 5:1-10:1 by volume is mixed into solution, and add supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L and be mixed into electrolyte, add an airtight electrolyzer, it is sufficiently stirred for, states electrolyzer then up and pass into the nitrogen of 1 hour, and with 140-450mA/cm2Electric current density be electrochemically reacted, finally gaseous product is carried out remove impurity by 3-6mol/L strong base solution, it is thus achieved that purity is the trimethylamine of 99%, is collected by gas collector.
Further technical scheme is as follows.
Described DMF and water are mixed into solution according to the ratio that volume ratio is 7:1, and add supporting electrolyte tetramethyl ammonium chloride 0.5mol/L and be mixed into electrolyte, it is thus achieved that trimethylamine.
The anode of described electrolyzer is the one in Pd, Pt, Au and Ti base oxide electrode.
The negative electrode of described electrolyzer is the one in Cu, Ag and Ni.
Described strong base solution is sodium hydroxide or potassium hydroxide.
The method realizing above-mentioned the provided a kind of electrochemical synthesis trimethylamine of the present invention, compared with prior art, its feature is as follows.
(1) prior art requires that this reaction carries out under normal temperature and pressure conditions under the high temperature of 400-420 DEG C and 5MPa high pressure, and reaction condition is gentle, and equipment requirements is very low.
(2) reducing agent required in course of reaction is to utilize electrochemical in-situ to generate, and original position utilization simultaneously is prepared trimethylamine, in-situ preparation and original position utilization and carried out in same system, simplifies reactions steps, reduces the response time.
(3) product that prior art generates is the mixture of monomethyl amine, dimethylamine, trimethylamine, and separation process is comparatively laborious, and this reaction is led to oversaturated strong base solution and be can be obtained by highly purified trimethylamine, and technological process is simple.
(4) prior art requires with unformed aluminium silicate is that catalyst reacts, and the reactant of this reaction is clean electronics, will not produce the by-product of secondary pollution, be a kind of eco-friendly reduction synthesis technology.
(5) prior art reaction is interrupted and stops more difficult control; this reaction is easily controlled; namely by control voltage can control reaction beginning, interruption and stopping, it is achieved that energy-conservation, reduce discharging, environmental protection can serialization, large-scale production an eco-friendly clean production method.
Detailed description of the invention
By specific examples below, the inventive method is further described.
A kind of method implementing electrochemical synthesis trimethylamine, its described method is at normal temperatures and pressures, by N, the ratio that dinethylformamide and water are 5:1-10:1 by volume is mixed into solution, add supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L and be mixed into electrolyte, and add in an airtight electrolyzer, be sufficiently stirred for, the nitrogen of 1 hour is passed into, then with 140-450mA/cm to above-mentioned electrolyzer2Electric current density be electrochemically reacted, then gaseous product is carried out remove impurity by 3-6mol/L strong base solution, it is thus achieved that purity is the trimethylamine of 99%, is collected by gas collector.
Embodiment 1
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 7:1, it is subsequently adding supporting electrolyte 0.5mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 350mA/cm2Electric current density be electrochemically reacted, select Pt electrode do anode, Cu electrode does negative electrode, gaseous product is carried out remove impurity by 5mol/L sodium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 95%, productivity 89%, and gas is carried out remove impurity with sodium hydroxide solution, obtains the trimethylamine that purity is 99% by current efficiency 76%.
Embodiment 2
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 6:1, it is subsequently adding supporting electrolyte 0.3mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 250mA/cm2Electric current density be electrochemically reacted, select Au electrode do anode, Pd electrode does negative electrode, gaseous product is carried out remove impurity by 4mol/L sodium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 93%, productivity 87%, and gas is carried out remove impurity with sodium hydroxide solution, obtains the trimethylamine that purity is 98% by current efficiency 75%.
Embodiment 3
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 5:1, it is subsequently adding supporting electrolyte 0.6mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 300mA/cm2Electric current density be electrochemically reacted, Ti base oxide electrode is selected to do anode, Ni electrode does negative electrode, gaseous product is carried out remove impurity by 5mol/L sodium hydroxide solution, it is collected by gas collector, then Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C are adopted；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 92%, productivity 81%, and gas is carried out remove impurity with sodium hydroxide solution, obtains the trimethylamine that purity is 97% by current efficiency 72%.
Embodiment 4
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 8:1, it is subsequently adding supporting electrolyte 0.7mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 240mA/cm2Electric current density be electrochemically reacted, Ti base oxide electrode is selected to do anode, Cu electrode does negative electrode, gaseous product is carried out remove impurity by 5mol/L sodium hydroxide solution, it is collected by gas collector, then Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C are adopted；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 90%, productivity 83%, and gas is carried out remove impurity with sodium hydroxide solution, obtains the trimethylamine that purity is 96% by current efficiency 72%.
Embodiment 5
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 9:1, it is subsequently adding supporting electrolyte 0.8mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 410mA/cm2Electric current density be electrochemically reacted, select Pt electrode do anode, Pd electrode does negative electrode, gaseous product is carried out remove impurity by 6mol/L sodium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 92%, productivity 84%, and gas is carried out remove impurity with sodium hydroxide solution, obtains the trimethylamine that purity is 98% by current efficiency 74%.
Embodiment 6
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 10:1, it is subsequently adding supporting electrolyte 0.3mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 400mA/cm2Electric current density be electrochemically reacted, select Pt electrode do anode, Ni electrode does negative electrode, gaseous product is carried out remove impurity by 6mol/L potassium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 93%, productivity 83%, and gas is carried out remove impurity with potassium hydroxide solution, obtains the trimethylamine that purity is 98.5% by current efficiency 70%.
Embodiment 7
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 6:1, it is subsequently adding supporting electrolyte 0.4mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 450mA/cm2Electric current density be electrochemically reacted, select Pt electrode do anode, Ag electrode does negative electrode, gaseous product is carried out remove impurity by 6mol/L potassium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 89%, productivity 84%, and gas is carried out remove impurity with potassium hydroxide solution, obtains the trimethylamine that purity is 97% by current efficiency 71%.
Embodiment 8
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 7:1, it is subsequently adding supporting electrolyte 0.5mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 400mA/cm2Electric current density be electrochemically reacted, select Pd electrode do anode, Cu electrode does negative electrode, gaseous product is carried out remove impurity by 6mol/L potassium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 87%, productivity 83%, and gas is carried out remove impurity with potassium hydroxide solution, obtains the trimethylamine that purity is 95% by current efficiency 70%.
Embodiment 9
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 7:1, it is subsequently adding supporting electrolyte 0.5mol/L tetramethyl ammonium chloride and is mixed into electrolyte, add in an airtight electrolyzer, it is sufficiently stirred for, passes into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 350mA/cm2Electric current density be electrochemically reacted, select Pd electrode do anode, Ag electrode does negative electrode, gaseous product is carried out remove impurity by 5mol/L potassium hydroxide solution, it is collected by gas collector, then adopts Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C；Ion source Ionization mode: EI, detects product, confirms that product is trimethylamine, conversion ratio 88%, productivity 83%, and gas is carried out remove impurity with potassium hydroxide solution, obtains the trimethylamine that purity is 93.5% by current efficiency 74%.
Claims (5)
1. a method for electrochemical synthesis trimethylamine, its described method is as follows:
(1) preparation of raw material
By N,N-dimethylformamide and anhydrous Na2CO3-Decompression distillation obtains highly purified N,N-dimethylformamide for twice and stores；Tetramethyl ammonium chloride is dissolved in ethanol, twice final vacuum stored dry of recrystallization；Cleaned by distilled water again after electrode polishing, remove surface oils and fats with acetone wiping；
(2) electrochemical reaction
At normal temperatures and pressures, by the N in step (), the ratio that dinethylformamide and water are 5:1-10:1 by volume is mixed into solution, and add supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L and be mixed into electrolyte, add an airtight electrolyzer, it is sufficiently stirred for, states electrolyzer then up and pass into the nitrogen of 1 hour, and with 140-450mA/cm2Electric current density be electrochemically reacted, finally gaseous product is carried out remove impurity by 3-6mol/L strong base solution, it is thus achieved that purity is the trimethylamine of 99%, is collected by gas collector.
2. the method for claim 1, is mixed into solution by described DMF and water according to the ratio that volume ratio is 7:1, and adds supporting electrolyte tetramethyl ammonium chloride 0.5mol/L and be mixed into electrolyte, it is thus achieved that trimethylamine.
3. the method for claim 1, the anode of described electrolyzer is the one in Pt, Pd, Au and Ti base oxide electrode.
4. the method for claim 1, the negative electrode of described electrolyzer is the one in Cu, Ag and Ni.
5. the method for claim 1, described strong base solution is sodium hydroxide or potassium hydroxide.
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| JP2006298820A (en) * | 2005-04-20 | 2006-11-02 | Mitsubishi Rayon Co Ltd | Production method of trimethylamine |
| CN101062896A (en) * | 2006-04-25 | 2007-10-31 | 三菱丽阳株式会社 | Method for manufacturing trimethylamine |
| CN102976950A (en) * | 2012-12-18 | 2013-03-20 | 天津天智精细化工有限公司 | Improved process for preparing tertiary amine |
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