CN104141148A - Method for electrochemically synthesizing trimethylamine - Google Patents
Method for electrochemically synthesizing trimethylamine Download PDFInfo
- Publication number
- CN104141148A CN104141148A CN201410379019.1A CN201410379019A CN104141148A CN 104141148 A CN104141148 A CN 104141148A CN 201410379019 A CN201410379019 A CN 201410379019A CN 104141148 A CN104141148 A CN 104141148A
- Authority
- CN
- China
- Prior art keywords
- trimethylamine
- mixed
- solution
- electrolyzer
- ammonium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for electrochemically synthesizing trimethylamine. At normal temperature and pressures, N, N-dimethyl formamide and water are mixed to solution according to a proportion, then supporting electrolyte tetramethyl ammonium chloride is added to the solution to be mixed to electrolyte, the electrolyte is added to a sealed electrolytic tank and fully mixed, nitrogen is led to the electrolytic tank for an electrochemical reaction, then a gaseous product is subjected to purification through strong base solution, and trimethylamine with the purity being 99% is obtained. The method is simple in process and convenient to operate, the obtained high-purity trimethylamine is easy to collect, a new path is developed for synthesis of organic amines, and the method is a process route with high industrial synthesis value.
Description
Technical field
The present invention relates to a kind of synthetic method of Trimethylamine 99, is a kind of technical scheme that adopts the synthetic Trimethylamine 99 of electrochemical method specifically.
Background technology
Trimethylamine 99 is tertiary amine, molecular formula C
3h
9n is a kind of important Chemicals, for agricultural chemicals, dyestuff, medicine and organic synthesis etc.; As alarm agent, analytical reagent and the organic synthesis raw material of sterilizing agent, Sweet natural gas, also for the raw material of medicine, agricultural chemicals, photographic material, rubber ingredients, explosive, chemical fibre solvent, tensio-active agent and dyestuff.With the reaction product of the oxyethane catalyzer as polycondensation; With the reaction product choline chloride of the ethylene chlorhydrin additive as chicken feed.Main organic synthesis raw material, can be used for producing various industrial auxiliary agents, tensio-active agent and dyestuff, ion exchange resin, flocculation agent, other cationic polymerss etc.
The production method of existing Trimethylamine 99 requires to complete under High Temperature High Pressure mostly, all higher to equipment and energy consumption." adopting methanol vapor phase ammoniation process to prepare the device of methylamine " of being CN 203112720 U at publication number adopts the mixture of activated alumina, silicon oxide, titanium dioxide, tungstic oxide, carclazyte, the various metal oxides of Thorotrast to make catalyzer.Temperature of reaction is 250-500
0c, reaction pressure 0.5-5.0MPa, air speed is 500-1500h
-1.Methyl alcohol and ammonia react generate primary, secondary, tertiary amine mixture.The generation ratio of three kinds of amine is relevant with raw material, catalyzer and reaction conditions.Can regulate the ratio of methyl alcohol and ammonia to obtain the product that hope obtains, methyl alcohol: when ammonia=1:4, be the top condition that generates Monomethylamine, methyl alcohol: be the top condition that generates Trimethylamine 99 when ammonia=1:1.5.The Trimethylamine 99 obtaining often contains the impurity such as methyl alcohol, methylamine, dimethylamine, can utilize extractive distillation or component distillation to refine.Obtain pure Trimethylamine 99, can add aceticanhydride or Acetyl Chloride 98Min. to distill, primary amine, secondary amine generate acetylate, and high being difficult for of boiling point steams.After the Trimethylamine 99 distilling out is processed with activated alumina, add Fluorenone sodium drying for standby.In addition, it,, by a drying tower that solid potassium hydroxide is housed, can be obtained to pure dry gaseous state Trimethylamine 99.This operating procedure is comparatively complicated, higher to the energy and equipment requirements.
The present invention is in carrying out " research of the paired electrochemical synthesis ethene of acetylene and oxalic acid ", find that reaction has a large amount of gas to generate, gaseous product is directly collected with gas collector, product gas chromatography mass spectrometry is detected, determine that product is Trimethylamine 99, the relevant paper of home and overseas and patent are retrieved, do not found to synthesize taking DMF as raw material with electrochemical method the relevant report of Trimethylamine 99.
At publication number be CN 102976950 " a kind of improvement technique of preparing tertiary amine ", main reaction is that fatty alcohol and dimethylamine are prepared Trimethylamine 99, it is characterized in that: as the reaction conversion ratio 80-90% of main reaction, hydrogen in reactor, Trimethylamine 99, a small amount of Monomethylamine, a small amount of dimethylamine gas mixture are passed into absorption tower, by one, two, after Trimethylamine 99 water absorbs, obtain pure hydrogen and pass into again in reactor, proceed reaction, finally separate and obtain Trimethylamine 99." manufacture method of Trimethylamine 99 " that is CN101062896A at publication number, provides a kind of in the time manufacturing methylamine, and by using zeolite catalyst, in reducing consumption energy cost, efficiency produces the method for the Trimethylamine 99 of insufficient section well.The manufacture method feature of this Trimethylamine 99 is, by methyl alcohol and ammonia, methyl alcohol and methylamine mixing and ammonia or methylamine mixture and ammonia, use zeolite catalyst to manufacture in the method for methylamine, comprise separating-purifying methylamine the reaction mixture from obtaining, isolate after ammonia and Trimethylamine 99, make dimethylamine or contain the operation that is more than or equal to the mixture of 50 % by mole of dimethylamine and MMA and ammonia and carries out gas-phase reaction.Waits people and 2003 to be published in being entitled as on " Tianjin chemical industry " by good fortune and " synthesize the course of industrialization of amine " taking methyl alcohol and ammonia as raw material, under the high temperature of 400-420 DEG C and 5MPa high pressure, react taking unformed pure aluminium silicate as catalyzer, make the mixture that thick mixed methylamine, dimethylamine, Trimethylamine 99 is three kinds of amine of master, then through refining methylamine, dimethylamine, the Trimethylamine 99 that obtains higher degree of fractionation.These operating procedures are comparatively complicated, higher to the energy and equipment requirements.
Summary of the invention
The invention provides a kind of method of electrochemical synthesis Trimethylamine 99, with overcome in prior art, exist to equipment, severe reaction conditions, technical process complexity, the deficiency of contaminate environment.
Realize above-mentioned purpose, the method for a kind of electrochemical synthesis Trimethylamine 99 of measure that the present invention takes, described in it, method is as follows:
(1) preparation of raw material
By DMF and anhydrous Na
2cO
3-underpressure distillation obtains highly purified DMF for twice and stores; Tetramethyl ammonium chloride is dissolved in ethanol to twice final vacuum stored dry of recrystallization; After electrode polishing, cleaned by distilled water again, remove surperficial grease with acetone wiping;
(2) electrochemical reaction
At normal temperatures and pressures, by the N in step (), dinethylformamide and water are by volume for the ratio of 5:1-10:1 is mixed into solution, and add supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L to be mixed into electrolytic solution, add again an airtight electrolyzer, fully stir, then pass into the nitrogen of 1 hour to above-mentioned electrolyzer, and with 140-450mA/cm
2current density carry out electrochemical reaction, finally gaseous product is carried out to removal of impurities by 3-6mol/L strong base solution, to obtain purity be 99% Trimethylamine 99, collects by gas collector.
Further technical scheme is as follows.
The described ratio that is 7:1 according to volume ratio by DMF and water is mixed into solution, and adds supporting electrolyte tetramethyl ammonium chloride 0.5 mol/L to be mixed into electrolytic solution, obtains Trimethylamine 99.
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.
Realize the method for a kind of electrochemical synthesis Trimethylamine 99 that the present invention is above-mentioned provided, compared with prior art, its feature is as follows.
(1) prior art requires under the high temperature and 5MPa high pressure of 400-420 DEG C, and this reaction is carried out under normal temperature and pressure conditions, and reaction conditions gentleness is very low to equipment requirements.
(2) in reaction process, required reductive agent is to utilize electrochemical in-situ to generate, and Trimethylamine 99 is prepared in original position utilization simultaneously, and original position generates and original position utilization is carried out in same system, has simplified reactions steps, has reduced the reaction times.
(3) product that prior art generates is the mixture of Monomethylamine, dimethylamine, Trimethylamine 99, and sepn process is more loaded down with trivial details, and the logical oversaturated strong base solution of this reaction just can obtain highly purified Trimethylamine 99, and technical process is simple.
(4) prior art requirement is that catalyzer reacts with unformed pure aluminium silicate, and the reagent of this reaction is clean electronics, can not produce the by product of secondary pollution, is a kind of eco-friendly reduction synthetic technology.
(5) prior art is reacted interruption and is stopped more difficult control; this reaction is easily controlled; can control by controlling voltage reaction beginning, interrupt and stop, having realized energy-conservation, reduction of discharging, environmental protection can serialization, an eco-friendly clean production method of large-scale production.
Embodiment
By following specific embodiment, the inventive method is further described.
Implement a kind of method of electrochemical synthesis Trimethylamine 99, described in it, method is at normal temperatures and pressures, by N, dinethylformamide and water are by volume for the ratio of 5:1-10:1 is mixed into solution, add again supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L to be mixed into electrolytic solution, and add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 140-450mA/cm
2current density carry out electrochemical reaction, then gaseous product is carried out to removal of impurities by 3-6mol/L strong base solution, to obtain purity be 99% Trimethylamine 99, collects 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, then add supporting electrolyte 0.5mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 350mA/cm
2current density carry out electrochemical reaction, select Pt electrode to do anode, Cu electrode does negative electrode, gaseous product is carried out to removal of impurities by 5mol/L sodium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 95%, and productive rate 89%, current efficiency 76%, carries out removal of impurities to gas with sodium hydroxide solution, obtains purity and be 99% Trimethylamine 99.
Embodiment 2
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 6:1, then add supporting electrolyte 0.3mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 250mA/cm
2current density carry out electrochemical reaction, select Au electrode to do anode, Pd electrode does negative electrode, gaseous product is carried out to removal of impurities by 4mol/L sodium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 93%, and productive rate 87%, current efficiency 75%, carries out removal of impurities to gas with sodium hydroxide solution, obtains purity and be 98% Trimethylamine 99.
Embodiment 3
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 5:1, then add supporting electrolyte 0.6mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 300mA/cm
2current density carry out electrochemical reaction, select Ti base oxide electrode to do anode, Ni electrode does negative electrode, gaseous product is carried out to removal of impurities by 5mol/L sodium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 92%, and productive rate 81%, current efficiency 72%, carries out removal of impurities to gas with sodium hydroxide solution, obtains purity and be 97% Trimethylamine 99.
Embodiment 4
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 8:1, then add supporting electrolyte 0.7mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 240mA/cm
2current density carry out electrochemical reaction, select Ti base oxide electrode to do anode, Cu electrode does negative electrode, gaseous product is carried out to removal of impurities by 5mol/L sodium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 90%, and productive rate 83%, current efficiency 72%, carries out removal of impurities to gas with sodium hydroxide solution, obtains purity and be 96% Trimethylamine 99.
Embodiment 5
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 9:1, then add supporting electrolyte 0.8mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 410mA/cm
2current density carry out electrochemical reaction, select Pt electrode to do anode, Pd electrode does negative electrode, gaseous product is carried out to removal of impurities by 6mol/L sodium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 92%, and productive rate 84%, current efficiency 74%, carries out removal of impurities to gas with sodium hydroxide solution, obtains purity and be 98% Trimethylamine 99.
Embodiment 6
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 10:1, then add supporting electrolyte 0.3mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 400mA/cm
2current density carry out electrochemical reaction, select Pt electrode to do anode, Ni electrode does negative electrode, gaseous product is carried out to removal of impurities by 6mol/L potassium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 93%, and productive rate 83%, current efficiency 70%, carries out removal of impurities to gas with potassium hydroxide solution, obtains purity and be 98.5% Trimethylamine 99.
Embodiment 7
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 6:1, then add supporting electrolyte 0.4mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 450mA/cm
2current density carry out electrochemical reaction, select Pt electrode to do anode, Ag electrode does negative electrode, gaseous product is carried out to removal of impurities by 6mol/L potassium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 89%, and productive rate 84%, current efficiency 71%, carries out removal of impurities to gas with potassium hydroxide solution, obtains purity and be 97% Trimethylamine 99.
Embodiment 8
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 7:1, then add supporting electrolyte 0.5mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 400mA/cm
2current density carry out electrochemical reaction, select Pd electrode to do anode, Cu electrode does negative electrode, gaseous product is carried out to removal of impurities by 6mol/L potassium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 87%, and productive rate 83%, current efficiency 70%, carries out removal of impurities to gas with potassium hydroxide solution, obtains purity and be 95% Trimethylamine 99.
Embodiment 9
At normal temperatures and pressures, by N, dinethylformamide and water are mixed into 30mL solution according to volume ratio 7:1, then add supporting electrolyte 0.5mol/L tetramethyl ammonium chloride to be mixed into electrolytic solution, add in an airtight electrolyzer, fully stir, pass into the nitrogen of 1 hour to above-mentioned electrolyzer, then with 350mA/cm
2current density carry out electrochemical reaction, select Pd electrode to do anode, Ag electrode does negative electrode, gaseous product is carried out to removal of impurities by 5mol/L potassium hydroxide solution, collect by gas collector, then adopt Agilent company of U.S. gas chromatograph-mass spectrometer, model: 7890A-5975C; Ion source ionization mode: EI, detects product, confirms that product is Trimethylamine 99, transformation efficiency 88%, and productive rate 83%, current efficiency 74%, carries out removal of impurities to gas with potassium hydroxide solution, obtains purity and be 93.5% Trimethylamine 99.
Claims (5)
1. a method for electrochemical synthesis Trimethylamine 99, described in it, method is as follows:
(1) preparation of raw material
By DMF and anhydrous Na
2cO
3-underpressure distillation obtains highly purified DMF for twice and stores; Tetramethyl ammonium chloride is dissolved in ethanol to twice final vacuum stored dry of recrystallization; After electrode polishing, cleaned by distilled water again, remove surperficial grease with acetone wiping;
(2) electrochemical reaction
At normal temperatures and pressures, by the N in step (), dinethylformamide and water are by volume for the ratio of 5:1-10:1 is mixed into solution, and add supporting electrolyte tetramethyl ammonium chloride 0.1-1.0mol/L to be mixed into electrolytic solution, add again an airtight electrolyzer, fully stir, then pass into the nitrogen of 1 hour to above-mentioned electrolyzer, and with 140-450mA/cm
2current density carry out electrochemical reaction, finally gaseous product is carried out to removal of impurities by 3-6mol/L strong base solution, to obtain purity be 99% Trimethylamine 99, collects by gas collector.
2. the method for claim 1, the described ratio that is 7:1 according to volume ratio by DMF and water is mixed into solution, and adds supporting electrolyte tetramethyl ammonium chloride 0.5 mol/L to be mixed into electrolytic solution, obtains Trimethylamine 99.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410379019.1A CN104141148B (en) | 2014-08-04 | 2014-08-04 | A kind of method of electrochemical synthesis trimethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410379019.1A CN104141148B (en) | 2014-08-04 | 2014-08-04 | A kind of method of electrochemical synthesis trimethylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104141148A true CN104141148A (en) | 2014-11-12 |
| CN104141148B CN104141148B (en) | 2016-06-29 |
Family
ID=51850477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410379019.1A Expired - Fee Related CN104141148B (en) | 2014-08-04 | 2014-08-04 | A kind of method of electrochemical synthesis trimethylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104141148B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2259373C1 (en) * | 2004-04-12 | 2005-08-27 | Дзержинский опытный завод авиационных материалов Открытое акционерное общество "Авиабор" | Trimethylaminoborane preparation method |
| 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 |
-
2014
- 2014-08-04 CN CN201410379019.1A patent/CN104141148B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2259373C1 (en) * | 2004-04-12 | 2005-08-27 | Дзержинский опытный завод авиационных материалов Открытое акционерное общество "Авиабор" | Trimethylaminoborane preparation method |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| MOHAMMAD BEHBAHANI ET AL: "A novel electrochemical method for the synthesis of 2,4-diamino-6-hydroxybenzofuro[2,3-b]pyridine-3-carbonitrile derivatives", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| SERGE SCHREINER ET AL: "Carbon dioxide reduction via homogeneous catalytic synthesis and hydrogenation of N,N-dimethylformamide", 《INORGANICA CHIMICA ACTA》 * |
| 陈洪龄 等: "三甲胺氧化制备N,N-二甲基甲酰胺的研究", 《化学工程师》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104141148B (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2591703C2 (en) | Method for preparation of 3,3-dimethylbutyraldehyde | |
| CN106588758A (en) | Synthetic process for 2-hydrazinylpyridine derivative | |
| CN102718633B (en) | Hydroquinone preparation method | |
| CN103143381B (en) | Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method | |
| CN104803958A (en) | Preparation technique for florosa | |
| CN105601588A (en) | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production | |
| CN103044190B (en) | Preparation method of trifluoroethylene | |
| CN104562073A (en) | System for preparing hydrocarbon by virtue of high-temperature electrolysis of CO2/H2O and application thereof | |
| CN103819344A (en) | Synthesis method of 1,2-propane diamine | |
| CN104141148A (en) | Method for electrochemically synthesizing trimethylamine | |
| CN101126163A (en) | Method for preparing aldehyde by using glow discharging to electrolyze ethanol solution | |
| CN102442992A (en) | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate | |
| CN101928222A (en) | Synthesis method of N, N, N', N'-tetraisopropyl ethylene diamine | |
| CN101723797A (en) | Method for producing tetrafluoromethane by gas phase catalysis | |
| CN102674253A (en) | Preparation method of hydroiodic acid | |
| CN102452890B (en) | Method for preparing methylcyclohexane through hydrogenolysis of methylcyclohexanol | |
| CN113149827A (en) | Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide | |
| CN103724210A (en) | Production method of N-ethyl-n-butylamine | |
| CN103664520A (en) | Method for preparing isopropyl alcohol through hydration reaction of propylene | |
| CN110862296A (en) | Method for separating reaction product in chloromethane production process | |
| CN109250694A (en) | A method of hydroxylamine hydrochloride is prepared using hydrogen chloride dry gas | |
| CN112299998B (en) | Preparation method of deuterated dimethyl carbonate, product obtained by preparation method and application of product | |
| CN110563580A (en) | synthesis method of high-purity propyl propionate | |
| CN112939804B (en) | Preparation method of organic amine oxide | |
| CN104649994A (en) | Low-cost environment-friendly preparation method of 4-methyl-5-alkoxy oxazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160629 Termination date: 20190804 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |