CN103628086B - A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously - Google Patents
A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously Download PDFInfo
- Publication number
- CN103628086B CN103628086B CN201310640283.1A CN201310640283A CN103628086B CN 103628086 B CN103628086 B CN 103628086B CN 201310640283 A CN201310640283 A CN 201310640283A CN 103628086 B CN103628086 B CN 103628086B
- Authority
- CN
- China
- Prior art keywords
- usp mannitol
- electrode
- sorbyl alcohol
- glucose
- anode
- 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.)
- Expired - Fee Related
Links
Abstract
A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously first processes cationic membrane; The preparation of laggard column electrode and pre-treatment; Finally carry out paired electrosynthesis, described paired electrosynthesis is that H type diaphragm sell is loaded onto cationic exchange membrane, yin, yang the two poles of the earth electrolyzer is all supporting electrolyte with metabisulfite solution, with sodium hydroxide adjustment solution basicity, then in anode pool, phenylcarbinol is added, glucose is added at cathode pool, after stirring, temperature of reaction is regulated by water bath with thermostatic control, setting Faradaic current carries out constant-current electrolysis, phenylcarbinol is selectively oxidized as phenyl aldehyde at anode, and glucose is reduced to sorbyl alcohol and N.F,USP MANNITOL at negative electrode.Present method is in an electrolytic process, respectively with phenylcarbinol and glucose two kinds of compounds for raw material, obtain phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously, drastically increase current efficiency and spatiotemporal efficiency, reduce production cost and energy consumption, cathode product transformation efficiency improves more than 10%, and economic benefit is very remarkable.
Description
Technical field
The present invention relates to a kind of method preparing phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL, especially a kind of paired electrosynthesis method adopting paired electrosynthesis technology simultaneously to prepare phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL.
Technical background
Phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL are all important fine-chemical intermediate and raw material, are widely used in the fields such as medicine, food, agricultural chemicals dyestuff.
Due to electrochemical method mild condition, simple to operate, environmentally safe, it is a kind of green synthesis techniques, especially paired electrosynthesis technology, it is except the general advantage with electrosynthesis, also has that current efficiency is high, spatiotemporal efficiency is high, production cost is low, saves electric energy, the concern of electric energy efficiency advantages of higher and extremely people.
The electrosynthesis of existing phenyl aldehyde mainly with Mn (III)/Mn (II), Ce (IV)/Ce (III) plasma to for medium, metallic lead is the indirect electrooxidation toluene method of anode, as " modern chemical industry ", 1996, (6): P
33-35" the Indirect Electrooxidation synthesizing benzaldehyde " of upper report, also has and adopts metallic nickel to be anode, and in basic solution, phenyl aldehyde prepared by selective oxidation phenylcarbinol, as " chemical journal ", and 2010,68(16): P
1649-1652" in basic solution, the selectivity catalytic oxidation of phenylcarbinol is studied " of upper report;
About the electrosynthesis method of sorbyl alcohol and N.F,USP MANNITOL mainly obtains with electro-reduction glucose, as " fine chemistry industry ", 2000,17(S1): P
49-51,57" research of electro-reduction synthesis N.F,USP MANNITOL and sorbyl alcohol " of upper report, " fine-chemical intermediate ", 2001,31(5): P
: 30-32" research of Synthesis of Sorbitol by Electro-Reduction from Glucose " of upper publication etc.;
And the application of paired electrosynthesis technology to be also detected in glucose be raw material, synthesize the relevant report of sorbyl alcohol and gluconic acid or N.F,USP MANNITOL, sorbyl alcohol and gluconic acid in cathode and anode, as " fine chemistry industry ", 2000,17(10 simultaneously): P
576-580" paired electrolysis Simultaneous Synthesis of Mannitol, sorbyl alcohol and the gluconate " of upper report, " Qingtao Chemical Engineering College's journal ", 2002,23(2): P
: 43-47.On " the electrolysis glucose synthesis sorbyl alcohol and gluconic acid " delivered etc.
By existing documents and materials, it is no matter the synthesis of phenyl aldehyde, or the preparation of N.F,USP MANNITOL and sorbyl alcohol, mainly based on one pole electrosynthesis method, and this method is compared with paired electrosynthesis technology, not only current efficiency and spatiotemporal efficiency lower, and production cost and energy consumption also all higher; And the processing condition of paired electrosynthesis are also relatively harsh, its productive rate or transformation efficiency are also not high enough.Therefore, adopt paired electrosynthesis technology to research and develop further to prepare phenyl aldehyde and N.F,USP MANNITOL, the method for sorbyl alcohol has certain realistic meaning.
Summary of the invention
The concrete technical problems that the present invention will solve how to adopt phenylcarbinol and glucose by paired electrosynthesis technology synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously, and then provide a kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously.
The technical scheme that the present invention deals with problems is as follows.
A method for paired electrolysis simultaneously synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL, method described in it follows these steps to carry out:
(1) pre-treatment of cationic membrane:
Nafion117 cationic membrane is put into the H of 5%
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling; Then the H of 0.5mol/L is put into
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times, stand-by;
(2) preparation of electrode and pre-treatment
Anode: nickel foam is cut into pole plate, successively with alcohol, dilute hydrochloric acid cleaning, then is cleaned by pure water, stand-by; Take nickel foam as working electrode, saturated calomel electrode is reference electrode, and nickel plate is supporting electrode, and employing Faradaic current is 0.3A, and electrolytic solution consists of 0.1mol/LNiSO
4+ 0.1mol/LCH
3cOONa+0.5mol/LNaOH, carries out constant-current electrolysis until electrode surface generates the NiOOH of black, is NiOOH electrode, stand-by;
Negative electrode: by purity be the stereotype electrode of 99.9% by sand papering light, with alcohol washes, then with dilute hydrochloric acid cleaning, finally washing is clean, stand-by;
(3) paired electrosynthesis phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL
H type diaphragm sell is loaded onto cationic exchange membrane, take NiOOH as anode, and Pd plate is negative electrode, respectively adds 40mL pure water in pond, yin, yang the two poles of the earth, supporting electrolyte sodium sulfate 2.0g, and appropriate solid NaOH, opens induction stirring and makes it dissolve completely; Then in anode pool, add the phenylcarbinol of 5 times, add the glucose of 2 ~ 3 times at cathode pool, stir after 5 minutes, by water bath with thermostatic control, reacting liquid temperature is adjusted to 25 DEG C, Faradaic current is set as 0.1A, carries out constant-current electrolysis; Phenylcarbinol is selectively oxidized as phenyl aldehyde at anode, and glucose is reduced to sorbyl alcohol and N.F,USP MANNITOL at negative electrode;
After electrolytic reaction terminates, take out electrode alcohol washes clean, then spend pure water cleaning, stand-by;
Anolyte acid neutralization proceeds in 100mL separating funnel after pH is 2-3, with ethyl acetate carry out extracting, separatory, then to aqueous phase back extraction twice, combined ethyl acetate, washes three times; By extraction liquid anhydrous Na
2sO
4carry out drying, then after it is separated, distills, obtained products benzene formaldehyde;
Catholyte proceeds in beaker, with dilute sulphuric acid neutralization, adds gac and decolours, then carry out filtering, concentrating, when filtrate volume is concentrated into original 1/3, then add isopyknic dehydrated alcohol, be incubated one hour, filtered while hot, removing sodium sulfate, filtrate slowly cools to crystallization and generates, and filters and obtains N.F,USP MANNITOL crude product and Sorbitol Solution USP, secondary recrystallization is carried out, obtained N.F,USP MANNITOL after being dissolved by the N.F,USP MANNITOL crude product distilled water obtained again.
Realize the method for a kind of paired electrolysis that the invention described above provides synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously, in an electrolytic process, respectively with phenylcarbinol and glucose two kinds of compounds for raw material, not only obtain phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL three kinds of high value-added products in yin, yang the two poles of the earth simultaneously, and anodic current efficiency is between 81.1% ~ 87.4%, cathode efficiency is between 88.7% ~ 93.4%, and the total current of electrolytic reaction is most effective reaches more than 180%; Compared with one pole electrosynthesis method, the method not only can obtain one to two kind of product more, and current efficiency and spatiotemporal efficiency are all greatly improved, and production cost and energy consumption also reduce greatly; And compared with existing paired electrosynthesis method, temperature of reaction reduces 25 DEG C, its processing condition are made to be more prone to control, handled easily; Meanwhile, the transformation efficiency of cathode product also improves more than 10%, and its economic benefit is very remarkable.
Embodiment
Below the specific embodiment of the present invention is further illustrated.
Implement a kind of method of paired electrolysis simultaneously synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL, take NiOOH as anode, Pd plate is negative electrode, phenylcarbinol and glucose are respectively raw material, be the electrolyzer of barrier film and sodium sulfate at cationic exchange membrane be in the basic solution of supporting electrolyte, phenylcarbinol is selectively oxidized obtained phenyl aldehyde at anode, and glucose is reduced at negative electrode and obtains sorbyl alcohol and N.F,USP MANNITOL.The method is compared with the method for N.F,USP MANNITOL with existing one pole electrosynthesis phenyl aldehyde or sorbyl alcohol, and current efficiency and spatiotemporal efficiency are all greatly improved.Its concrete grammar step is as follows:
The pre-treatment of step one, cationic membrane
Nafion117 cationic membrane is put into the H of 5%
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling; Then the H of 0.5mol/L is put into
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times, stand-by.
The preparation of step 2, electrode and pre-treatment
Anode: nickel foam is cut into 2 × 2.5cm rectangle, successively with alcohol, dilute hydrochloric acid cleaning, finally cleans with pure water, stand-by; Take nickel foam as working electrode, saturated calomel electrode is reference electrode, and nickel plate is supporting electrode, and employing Faradaic current is 0.3A, and electrolytic solution consists of 0.1mol/LNiSO
4+ 0.1mol/LCH
3cOONa+0.5mol/LNaOH, carries out constant-current electrolysis until electrode surface generates the NiOOH of black, is NiOOH electrode, stand-by.
Negative electrode: by purity be 99.9% stereotype be cut into 3 × 3.5cm rectangle, with sand papering light, with alcohol washes, then with dilute hydrochloric acid cleaning, finally washing is clean, stand-by.
Step 3, paired electrosynthesis phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL
H type diaphragm sell is loaded onto cationic exchange membrane, take NiOOH as anode, and Pd plate is negative electrode, respectively adds 40mL pure water in pond, yin, yang the two poles of the earth, supporting electrolyte sodium sulfate 2.0g, and appropriate solid NaOH, opens induction stirring and makes it dissolve completely; Then in anode pool, be incorporated as the phenylcarbinol of theoretical amount 5 times, be incorporated as the glucose of theoretical amount 2 ~ 3 times at cathode pool, stir after 5 minutes, by water bath with thermostatic control, reacting liquid temperature is adjusted to 25 DEG C, Faradaic current is set as 0.1A, carries out constant-current electrolysis; Phenylcarbinol is selectively oxidized as phenyl aldehyde at anode, and glucose is reduced to sorbyl alcohol and N.F,USP MANNITOL at negative electrode.After electrolytic reaction terminates, take out electrode alcohol washes clean, then spend pure water cleaning, stand-by.
Anolyte acid neutralization proceeds in 100mL separating funnel after pH is 2-3, with ethyl acetate carry out extracting, separatory, then to aqueous phase back extraction twice, combined ethyl acetate, washes three times; By extraction liquid anhydrous Na
2sO
4carry out drying, then after being separated it, distilling, obtained products benzene formaldehyde, adopts rp-hplc determination product yield.
Liquid phase chromatogram condition is Shim-packVP-ODSC
18chromatographic column (150 × 4.6um), moving phase is acetonitrile: water=55:45, flow velocity 0.8mL/min, column temperature 40 DEG C, and determined wavelength is 250nm, and sample size is 20.00 μ L.
Catholyte proceeds in beaker, neutralize with dilute sulphuric acid, add gac to decolour, then carry out filtering, concentrating, when filtrate volume is concentrated into original 1/3, add isopyknic dehydrated alcohol again, be incubated one hour, filtered while hot, removing sodium sulfate, filtrate slowly cools to crystallization and generates, filtration obtains N.F,USP MANNITOL crystal and Sorbitol Solution USP, carry out secondary recrystallization after being dissolved by the N.F,USP MANNITOL crude product distilled water obtained, N.F,USP MANNITOL sterling can be obtained, adopt the transformation efficiency of spectrophotometry product.
With 3,5-dinitrosalicylic acid for developer, adopt calibration curve method to measure the absorbance of surplus stock glucose in product in wavelength 540nm place, calculate its content according to Law of Lambert-Beer, by the transformation efficiency obtaining product sorbyl alcohol and N.F,USP MANNITOL that converts.
Specific embodiment is as follows.
Embodiment 1
The cationic exchange membrane handled well is placed in the diaphragm sell of H type, Pd plate is adopted to be negative electrode, NiOOH is anode, the sodium sulfate of 40mL pure water and 2.0g is added respectively in pond, yin, yang the two poles of the earth, and solid NaOH0.1g(cathode pool) and 1.2g(anode pool), starting induction stirring instrument makes it dissolve completely, then in cathode pool, glucose 5.41g is added, phenylcarbinol 5.40g is added in anode pool, stir after 5 minutes, by water bath with thermostatic control, reacting liquid temperature is adjusted to 25 DEG C, Faradaic current is set as 0.1A, constant-current electrolysis 19320s; Electrolytic reaction is complete, and anolyte is added H
2sO
4solution is neutralized to pH and proceeds in 100mL separating funnel after 2-3, with ethyl acetate carry out extracting, separatory, again to aqueous phase back extraction twice, combined ethyl acetate, wash three times (each 10mL), by anhydrous sodium sulphate, drying and dehydrating is carried out to it, then after being separated, distilling, obtain products benzene formaldehyde.Adopt reversed-phased high performace liquid chromatographic to analyze product, its purity can reach more than 99.0%, and the yield of phenyl aldehyde is 87.40%.
Catholyte proceeds in beaker, neutralize with dilute sulphuric acid, add gac to decolour, then filter, concentrated, when filtrate volume is concentrated into original 1/3, add isopyknic dehydrated alcohol again, be incubated one hour, filtered while hot, removing sodium sulfate, filtrate slowly cools to crystallization and generates, filtration obtains N.F,USP MANNITOL crystal and Sorbitol Solution USP, secondary recrystallization is carried out after being dissolved by the N.F,USP MANNITOL crude product distilled water obtained, N.F,USP MANNITOL sterling can be obtained, adopt remaining glucose amount in this solution of spectrophotometry, through converting, the transformation efficiency obtaining sorbyl alcohol and N.F,USP MANNITOL is 93.45%.
The inventive method reaches 180.85% in the total current efficiency of whole paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously.
Embodiment 2
Experimentation only changes the add-on of solid NaOH in cathode pool, increases to 0.2g by 0.1g, and all the other are with embodiment 1.Analytical results shows, the yield of phenyl aldehyde is 85.35%, and the transformation efficiency of sorbyl alcohol and N.F,USP MANNITOL is 91.63%, the total current efficiency of whole electrolytic reaction be 176.98%. it can thus be appreciated that, the hydrolysis reaction of glucose is accelerated by the alkali consumption increasing catholyte, improve the productive rate of product, its effect is also not obvious.Illustrate in cathode pool that the NaOH adding 0.1g can meet the hydrolysis reaction of glucose, meanwhile, because the liberation of hydrogen side reaction of negative electrode also can generate OH
-, and be conducive to the hydrolysis of glucose.
Embodiment 3
Experimentation only changes the add-on of glucose in cathode pool, reduces to 3.60g by 5.41g, and all the other are with embodiment 1.Analytical results shows, the yield of phenyl aldehyde is 81.14%, the transformation efficiency of sorbyl alcohol and N.F,USP MANNITOL is then 88.74%, the total current efficiency of its electrolytic reaction be 169.88%. this also illustrate when in catholyte, the concentration of glucose is lower, the consumption of electric energy is not only for the reduction of glucose, also may be used for the precipitation of electrode side reaction hydrogen, thus cause the current efficiency of negative electrode slightly to decrease.
Claims (1)
1. a method for paired electrolysis simultaneously synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL, method described in it follows these steps to carry out:
(1) pre-treatment of cationic membrane:
Nafion117 cationic membrane is put into the H of 5%
2o
2boil 30 minutes in the aqueous solution, cleaned with pure water after cooling; Then the H of 0.5mol/L is put into
2sO
4boil one hour in solution, then clean with pure water, finally soak 24 hours in pure water, change water therebetween three times, stand-by;
(2) preparation of electrode and pre-treatment
Anode: nickel foam is cut into pole plate, successively with alcohol, dilute hydrochloric acid cleaning, then is cleaned by pure water, stand-by; Take nickel foam as working electrode, saturated calomel electrode is reference electrode, and nickel plate is supporting electrode, and electrolytic solution consists of 0.1mol/LNiSO
4+ 0.1mol/LCH
3cOONa+0.5mol/LNaOH, with current density 0.06A/cm
2carry out constant-current electrolysis, until electrode surface generates the NiOOH of black, be NiOOH electrode, stand-by;
Negative electrode: by purity be the stereotype electrode of 99.9% by sand papering light, with alcohol washes, then with dilute hydrochloric acid cleaning, finally washing is clean, stand-by;
(3) paired electrosynthesis phenyl aldehyde and sorbyl alcohol, N.F,USP MANNITOL
H type diaphragm sell is loaded onto cationic exchange membrane, take NiOOH as anode, and Pd plate is negative electrode, respectively adds 40mL pure water in pond, yin, yang the two poles of the earth, supporting electrolyte sodium sulfate 2.0g, and appropriate solid NaOH, opens induction stirring and makes it dissolve completely; Then in anode pool, add the phenylcarbinol of 5 times, add the glucose of 2 ~ 3 times at cathode pool, stir after 5 minutes, by water bath with thermostatic control, reacting liquid temperature is adjusted to 25 DEG C, Faradaic current is set as 0.1A, carries out constant-current electrolysis; Phenylcarbinol is selectively oxidized as phenyl aldehyde at anode, and glucose is reduced to sorbyl alcohol and N.F,USP MANNITOL at negative electrode;
After electrolytic reaction terminates, take out electrode alcohol washes clean, then with pure water cleaning, stand-by;
Anolyte acid neutralization proceeds in 100mL separating funnel after pH is 2-3, with ethyl acetate carry out extracting, separatory, then to aqueous phase back extraction twice, combined ethyl acetate, washes three times; By extraction liquid anhydrous Na
2sO
4carry out drying, then after it is separated, distills, obtained products benzene formaldehyde;
Catholyte proceeds in beaker, with dilute sulphuric acid neutralization, adds gac and decolours, then carry out filtering, concentrating, when filtrate volume is concentrated into original 1/3, then add isopyknic dehydrated alcohol, be incubated one hour, filtered while hot, removing sodium sulfate, filtrate slowly cools to crystallization and generates, and filters and obtains N.F,USP MANNITOL crude product and Sorbitol Solution USP, secondary recrystallization is carried out, obtained N.F,USP MANNITOL after being dissolved by the N.F,USP MANNITOL crude product distilled water obtained again.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310640283.1A CN103628086B (en) | 2013-12-04 | 2013-12-04 | A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310640283.1A CN103628086B (en) | 2013-12-04 | 2013-12-04 | A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103628086A CN103628086A (en) | 2014-03-12 |
CN103628086B true CN103628086B (en) | 2016-01-20 |
Family
ID=50209527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310640283.1A Expired - Fee Related CN103628086B (en) | 2013-12-04 | 2013-12-04 | A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103628086B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104328453A (en) * | 2014-11-05 | 2015-02-04 | 太原理工大学 | Method for paired electrosynthesis of benzaldehyde and tetramethyl piperidinol |
CN109778222B (en) * | 2017-11-13 | 2020-08-28 | 万华化学集团股份有限公司 | Method for preparing aldehyde substance and aromatic ester simultaneously by paired electrodes and used electrodes |
CN111101145B (en) * | 2018-10-29 | 2021-05-14 | 万华化学集团股份有限公司 | Method for preparing aromatic halide and aldehyde substance simultaneously by paired electrodes |
CN111748825B (en) * | 2019-03-28 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing epsilon-caprolactone through paired electrode reaction |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
CN101078128A (en) * | 2007-06-30 | 2007-11-28 | 广西壮族自治区化工研究院 | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4306859B2 (en) * | 1999-03-02 | 2009-08-05 | ペルメレック電極株式会社 | Process for producing 1,2-diols and equivalents thereof |
-
2013
- 2013-12-04 CN CN201310640283.1A patent/CN103628086B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
CN101078128A (en) * | 2007-06-30 | 2007-11-28 | 广西壮族自治区化工研究院 | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs |
Non-Patent Citations (7)
Title |
---|
在线超声成对电合成苯甲醛和丁二酸;李彦威等;《高等学校化学学报》;20120131;第33卷(第1期);第66-70页 * |
成对电合成技术;张宏坤等;《电化学》;19990831;第5卷(第3期);第304-309页 * |
成对电合成技术的新进展;顾登平等;《精细化工》;20000630;第17卷(第6期);第336-338页 * |
成对电解同时合成甘露醇、山梨醇和葡萄糖酸盐;顾登平等;《精细化工》;20001031;第17卷(第10期);第576-580页 * |
成对电解法制取葡萄糖酸和山梨醇;姜力夫等;《曲阜师范大学学报》;19950731;第21卷(第3期);第66-70页 * |
苯甲醛电合成技术的新进展;李彦威等;《现代化工》;20060131;第26卷(第1期);第15-19页 * |
苯甲醛的电合成技术;胡万里等;《精细石油化工》;19980531(第3期);第47-53页 * |
Also Published As
Publication number | Publication date |
---|---|
CN103628086A (en) | 2014-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103628086B (en) | A kind of method of paired electrolysis synthesizing benzaldehyde and sorbyl alcohol, N.F,USP MANNITOL simultaneously | |
CN110656345B (en) | Electrolytic synthesis method of 4-amino-3, 6-dichloropicolinic acid | |
KR20140048967A (en) | Method for producing vanillin by electrochemically oxidizing aqueous lignin solutions or suspensions | |
CN103603006B (en) | A kind of electrolytic synthesis technique of 3,6-lontrel | |
CN103012026B (en) | Bromination reaction method | |
CN104495925B (en) | The preparation method of sodium metavanadate | |
CN110777391B (en) | Electric reduction preparation method of gefitinib intermediate | |
CN109371259A (en) | A method of going dechlorination from solution of zinc sulfate | |
CN101078128B (en) | Method and device for preparing mannitol and potassium iodate by electrolysis in pairs | |
CN101525754B (en) | Method for preparing solid state powder of potassium ferrate by adopting one-step method and electricity chemistry method | |
CN104357874A (en) | Method for preparing nickel molybdate by using cationic membrane electrolysis process | |
CN102442950A (en) | Ionic liquid synthesis method based on strong alkaline anion exchange resin | |
CN103113250A (en) | Preparation method of D-para hydroxybenzene glycine methyl ester | |
CN101979713A (en) | Method for electrolytic synthesis of parahydroxybenzaldehyde | |
CN104831305A (en) | Method for preparing liver tungstate by cation membrane electrolytic method | |
CN111005033A (en) | Electro-reduction preparation method of sildenafil intermediate | |
CN102839383B (en) | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane | |
CN102977031A (en) | Method for synthesizing ionic liquid | |
CN106894037B (en) | A method of electrolysis method produces high concentration ferrate step by step | |
CN110698439B (en) | Process for preparing D-pantolactone by bipolar membrane method | |
CN104789982A (en) | Method for preparing silver molybdate with cationic membrane electrolysis method | |
CN103668312B (en) | A kind of maleic acid cis-trans isomerization prepares the electrochemical process of fumaric acid | |
CN102560527B (en) | Direct electrochemical synthesis method of 5-nitro-1, 4-naphthoquinone | |
CN108084006B (en) | Preparation method of trimethylbenzoquinone and trimethylhydroquinone | |
CN104328453A (en) | Method for paired electrosynthesis of benzaldehyde and tetramethyl piperidinol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | 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: 20160120 Termination date: 20181204 |
|
CF01 | Termination of patent right due to non-payment of annual fee |