CN110016688A - Electrochemical preparation method of alcohol substance - Google Patents
Electrochemical preparation method of alcohol substance Download PDFInfo
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- CN110016688A CN110016688A CN201910276285.4A CN201910276285A CN110016688A CN 110016688 A CN110016688 A CN 110016688A CN 201910276285 A CN201910276285 A CN 201910276285A CN 110016688 A CN110016688 A CN 110016688A
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- fatty acid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
The invention discloses a preparation method of alcohol substances, which takes an inert electrode as a working electrode and a counter electrode, takes a solution of a mixture of unit fatty acid and dibasic fatty acid of a proton or aprotic solvent as an electrolyte, and carries out electrolysis under the condition that the working voltage is not more than 3.0V to obtain the alcohol substances. In particular, alcohols having a carbocyclic ring or a branched chain can be obtained. The invention adopts an electrochemical method to prepare the alcohol substances for the first time, the monocarboxylic acid and the dicarboxylic acid are renewable green raw materials, an aqueous solution system can be completely adopted, the obtained alcohol products are naturally separated, and the product purity is high.
Description
Technical field
The invention belongs to electrochemistry formated technical fields, and in particular to a kind of electrochemical preparation method of alcohols material.
Background technique
Increasingly depleted and problem of environmental pollution with non-renewable fossil becomes increasingly conspicuous, and researchs and develops reproducible
The chemical products of neutral carbon, for alleviating oil crisis, improving environmental situation, realization sustainable development with strategic meaning
Justice
In organic synthesis, the building of carbon skeleton is an extremely important step, this has related to the growth of carbochain.Traditional
Carbochain growing method is much weaker along with toxic, harmful reagent use or carbochain growing ability, can only such as increase a carbon
Atom etc..The method that the present invention uses electrochemistry uses aseptate glass electrolytic cell to hold as reaction under three-electrode system
Device, the alcohol product being synthesized in the present invention.And improve efficiently the shortcoming in above-mentioned technique.
The method of electrochemistry organic synthesis has the advantages that following prominent: required instrument is compared with simple, preparatory process is less, anti-
Shorter and product postprocessing is simple the time required to answering mild condition, obtaining reaction product, does not need extra catalyst, original
Subeconomy height, reaction process green etc..Kolbe reaction can use monocarboxylic acid R-COOH and be electrolysed to obtain R-R alkane.
Palkovits et al. is electrolysed R under the electric current of 200mA1- COOH and HOOC-R2- COOH obtains R1-R1And esters.But utilize one
First carboxylic acid R1- COOH and dicarboxylic acids HOOC-R2The mixture of-COOH is electrolysed to obtain alcohols material mesh at different conditions
Before there is no report.
It is raw material electro-catalysis preparation present invention firstly provides the mixture of the monocarboxylic acid of originated biomass and dicarboxylic acids
The method of alcohols material.
Summary of the invention
The present invention uses for the first time from the extensive unit of biomass source or dicarboxylic acids for raw material electro-catalysis and prepares alcohols object
Matter.Technical scheme is as follows:
The present invention discloses a kind of preparation method of alcohols material, which is characterized in that using inert electrode as working electrode and right
Electrode, the solution using the unit fatty acid and di-fatty acid blend of proton or aprotic solvent is electrolyte in operating voltage
No more than being electrolysed to obtain alcohols material under the conditions of 3.0V.The molecular formula of unit fatty acid is R1- COOH, binary of fatty acids
Molecular formula is HOOC-R2- COOH, wherein R, R1And R2Be each independently alkyl, can be saturated hydrocarbyl or unsaturated alkyl,
The present invention obtains carbochain by addition after electrolytic catalysis unit and di-fatty acid decarboxylation and increases alcohols material.
Wherein the alcohols material includes the alcohols material with carbocyclic ring or branch.
Preferably, in the unit fatty acid and di-fatty acid blend unit fatty acid and binary of fatty acids mole
Than for 0.1:1-1:0.1.Under normal circumstances, the total concentration of the carboxylic acid solution is not less than 0.01mol/L.
Preferably, the proton or aprotic compound solvent be one of deionized water, methanol, acetone or acetonitrile or
It is several.
Preferably, also it is added supportive electrolyte into the electrolyte, the supportive electrolyte strong electrolyte, usually
The electrolyte for ionizing out ion completely under aqueous solution or molten condition is known as strong electrolyte.
Preferably, the inert electrode is metal platinum or graphite.
Preferably, by selecting graphite electrode to imitate for working electrode come the selectivity for improving product alcohols material and faraday
Rate.
Preferably, the faradic efficiency and product alcohols material of the preparation method are improved by increasing operating voltage
Selectivity.
The present invention can be used or without using reference electrode.Common laboratory uses reference electrode, and industrialized production is not required to
Want reference electrode.
Beneficial effects of the present invention:
1, the present invention does raw material using the mixture of unit and dicarboxylic acids for the first time and prepares alcohols, uses electric current as reaction
Reagent and catalyst are added without dangerous toxic additive, have reaction process is simple, reaction can occur at normal temperatures and pressures,
Generate that less waste, reaction time is short, reaction conversion rate is high, reaction cost is lower compared with conventional method, does not arrange in reaction process
Put environmentally harmful tail gas, the advantages that reaction process is green.
2, traditional Kolbe reaction is electrolysis monocarboxylate (RCOOH) in methanol solution, and obtain its decarboxylation dimerization it
Product (R-R) afterwards.Present inventors have unexpectedly found that electrochemical method is used in the present invention, with unit carboxylic acid (R1- COOH) and binary
Carboxylic acid (HOOC-R2- COOH) mixture be raw material prepare alcohols material, can especially obtain the alcohol with carbocyclic ring or branch
Substance.For example, with n-butyric acie (C3H7) and adipic acid (HOOC-C COOH4H8- COOH) it is that raw material can obtain 3,4- dimethyleyelohexane
Alcohol (C8H16O), with acetic acid (CH3) and adipic acid (HOOC-C COOH4H8- COOH) it is that raw material can obtain 4- methylpentane -1- alcohol
(C6H14O)。
3, the present invention does raw material using the mixture of unit and dicarboxylic acids for the first time and prepares alcohols.Unit and dicarboxylic acids are equal
Be reproducible green material, have many advantages, such as that source is wide, inexpensive, biodegradable, nontoxic, can from cellulose, half fiber element,
The fermentation such as plant amylum obtains.
4, method of the invention can prepare alcohols as electrolyte using water solution system completely.Water is as a kind of environment
Friendly solvent does the requirement that solvent not only meets " Green Chemistry " with water, and the long-chain alcohol-based liquid generated is not soluble in water, can
With aqueous solution natural separation, product purity height.Therefore the collection process of product becomes compared to traditional preparation after the completion of being electrolysed
Method is more simplified, and a large amount of time is not only saved, and also reduces the energy consumption of whole process, environmental-friendly, at low cost.It is easy to
Industrialized production.
Specific embodiment
Specific example below embodies process described in the invention, but the present invention is not limited to these examples.
The mixture through catalytic decarboxylation of unit and dicarboxylic acids is obtained alcohols material using electro-catalysis by the present invention.Reaction terminates
Generating afterwards can be with aqueous solution natural separation, product purity height.Entire electrolytic process can carry out in aqueous solution.
Embodiment 1
Drug: deionized water (18.2M Ω, Merck Mi Libo Milli-Q Advantage A10 ultrapure water system), it is used
Glutamic acid, potassium hydroxide, potassium sulfate, sulfuric acid be after buying back directly use without being further purified.
Electrolytic cell: electrolytic cell used in this reaction is 50mm3Screw socket can closed no diaphragm Orion Pax glass electrolytic cell.Electrolysis
System is three-electrode system, wherein being worked electrode with graphite flake (1cm × 1cm), is done with Pt net (60 mesh, 1cm × 1cm) to electricity
Pole, using Hg/HgO (1M KOH) electrode as reference electrode.
The adipic acid of 1.1g, the caprylic acid and 15.0mm of 2.2g are weighed respectively32molcm-3KOH aqueous solution, successively plus
Enter in beaker and mix, afterwards plus ultrapure water is settled to 30mm-3.Magneton is put into beaker, is added after opening 600rpm stirring 10min
In above-mentioned electrolytic cell.Electrolytic cell is placed in 30 DEG C or so water-baths, and three electrodes are successively connected to work station.First recycle
Volt-ampere (CV) test, CV scanning range are 0V-4V, sweep speed: 5mV/s, scanning circle number: 5 circles.Then carry out constant potential electricity
Solution, the constant-potential electrolysis 30min at 1.5V.
Product processing: after the completion of electrolysis, since density is lower than water, meeting nature floats on solution the oil-phase product of generation
Side.0.2mm is taken with liquid-transfering gun-3Upper layer oil product is weighed in chromatogram bottle.0.2mm is pipetted again-3Internal standard compound is in upper
It states in chromatogram bottle, and carries out heavy.Then 1.5mm is added-3Isopropanol is vibrated into chromatogram bottle, and on the oscillator, is shaken up.
Product analysis: the synthetic product obtained in internal standard method for gas chromatography instrument analysis chromatography.Wherein, gas phase is utilized
Mass spectrometry in chromatography and mass spectrometer goes out why product plants substance, utilizes the meteorology in internal standard method for gas chromatography instrument
Chromatogram quantification obtains the distribution percentage of product.The results are shown in Table 1.As can be seen from the results, by the mixing of adipic acid and caprylic acid
Object obtains C after being electrolysed at 1.5V18H38O and C18H36O is mainly alcohols material known to analysis, does not meet unit acid
Kolbe reaction rule separately has the by-products such as a small amount of other aldehyde, ether, ketone and acid.Alcohols material with carbocyclic ring or branch is in head
It is secondary not only to provide molecular formula but also provide its systematic nomenclature when occurring, it is subsequent then only to provide molecular formula when occurring again, similarly hereinafter.
Embodiment 2-15
After carrying out cell reaction as mixture using different unit carboxylic acid and dicarboxylic acids, the composition of products therefrom and its choosing
Selecting property is shown in Table 1.Wherein for embodiment 1-8 and 10-15 using working electrode with embodiment 1, the working electrode that embodiment 9 uses is platinum
Electrode.Other are the same as embodiment 1.
1 embodiment 1-15 of table
Embodiment 16-21
After carrying out cell reaction as mixture using the caprylic acid of various concentration and adipic acid, the composition of products therefrom and its choosing
Selecting property is shown in Table 2.Other are the same as embodiment 1.
2 embodiment 16-21 of table
It is wherein found through analysis, the carbochain of the part alcohol product in the above product has carbocyclic ring or branch.
By the data of table 1 it can be seen that in the case where solvent is certain for deionized water other conditions, unit carboxylic acid
Carbon chain lengths are longer, and faradic efficiency and alcohols material selectivity of product are higher.In the case where other conditions are certain, voltage is got over
Height, faradic efficiency and alcohols material selectivity of product are lower；When voltage is lower than 3V, faradic efficiency and alcohols material product
Selectivity is higher；When voltage is 0.5V, alcohols material selectivity of product is more than 90%, and faradic efficiency is more than 93%；It examines
Consider other factors, voltage selects 3V or less.When solvent is the organic solvents such as methanol, acetone or acetonitrile, faradic efficiency and alcohol
Substance selectivity is not high instead, such as embodiment 10-12；Consider environmentally protective factor, does not use organic solvent generally, but select
Deionized water is selected as solvent.By embodiment 1 and embodiment 9 it is found that in the case where other conditions are certain, working electrode is stone
It is platinum electrode that electrode ink faradic efficiency and alcohols material selectivity of product, which are higher than working electrode,；Work is selected under normal circumstances
Electrode is graphite electrode.It can be seen from embodiment 16 and example 17 in the case where other conditions are certain, the concentration of dicarboxylic acids
Higher than unit carboxylic acid concentration when, be more likely in product generate the longer product of carbochain.By embodiment 16-21 it is found that at it
In the case that his condition is certain, in 0.01-1mol/L within the scope of this, this is anti-for the concentration of the concentration of unit carboxylic acid and dicarboxylic acids
Ying Junke is efficiently carried out, and the influence of concentration is little.
Although specific embodiment of the invention is described for purposes of illustration here, in the Yu Benfa that is not contrary to
In the case where bright, many variations in details be will be apparent to the person skilled in the art.
Claims (8)
1. a kind of preparation method of alcohols material, which is characterized in that using inert electrode as working electrode and to electrode, with proton or
The unit fatty acid of aprotic solvent and the solution of di-fatty acid blend are not more than 3.0V item in operating voltage for electrolyte
It is electrolysed to obtain alcohols material under part.
2. preparation method according to claim 1, which is characterized in that the alcohols material includes the alcohol with carbocyclic ring or branch
Substance.
3. preparation method according to claim 1, which is characterized in that in the unit fatty acid and di-fatty acid blend
The molar ratio of unit fatty acid and binary of fatty acids is 0.1:1-1:0.1.
4. preparation method according to claim 1, which is characterized in that the proton or aprotic compound solvent are deionization
One or more of water, methanol, acetone or acetonitrile.
5. preparation method according to claim 1, which is characterized in that supportive electrolyte is also added into the electrolyte,
The supportive electrolyte is strong electrolyte.
6. preparation method according to claim 1, which is characterized in that the inert electrode is metal platinum or graphite.
7. preparation method according to claim 6, which is characterized in that by selecting graphite electrode be working electrode to improve
State the faradic efficiency of preparation method and the selectivity of product alcohols material.
8. preparation method according to claim 1, which is characterized in that improve the preparation method by reducing operating voltage
Faradic efficiency and product alcohols material selectivity.
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Citations (7)
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|---|---|---|---|---|
| JPS51113836A (en) * | 1975-03-28 | 1976-10-07 | San Ei Chem Ind Ltd | Preparation of dihydrocapasaicine |
| JPS51113835A (en) * | 1975-03-28 | 1976-10-07 | San Ei Chem Ind Ltd | Preparation of capsaicine and homologues |
| CN1950317A (en) * | 2004-03-26 | 2007-04-18 | 珀杜研究基金会 | Processes for the production of xylitol |
| CN101132765A (en) * | 2005-03-04 | 2008-02-27 | 考格尼斯知识产权管理有限责任公司 | Emollients and cosmetic compositions based on special branched hydrocarbons |
| CN102471903A (en) * | 2009-07-23 | 2012-05-23 | 塞拉曼技术股份有限公司 | Decarboxylation cell for production of coupled radical products |
| CN102782191A (en) * | 2010-04-23 | 2012-11-14 | 塞拉曼技术公司 | Electrochemical synthesis of aryl-alkyl surfactant precursor |
| DE102015207581A1 (en) * | 2015-04-24 | 2016-10-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the electrochemical conversion of fatty acids and plant for carrying out the process |
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2019
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|---|---|---|---|---|
| JPS51113836A (en) * | 1975-03-28 | 1976-10-07 | San Ei Chem Ind Ltd | Preparation of dihydrocapasaicine |
| JPS51113835A (en) * | 1975-03-28 | 1976-10-07 | San Ei Chem Ind Ltd | Preparation of capsaicine and homologues |
| CN1950317A (en) * | 2004-03-26 | 2007-04-18 | 珀杜研究基金会 | Processes for the production of xylitol |
| CN101132765A (en) * | 2005-03-04 | 2008-02-27 | 考格尼斯知识产权管理有限责任公司 | Emollients and cosmetic compositions based on special branched hydrocarbons |
| CN102471903A (en) * | 2009-07-23 | 2012-05-23 | 塞拉曼技术股份有限公司 | Decarboxylation cell for production of coupled radical products |
| CN102782191A (en) * | 2010-04-23 | 2012-11-14 | 塞拉曼技术公司 | Electrochemical synthesis of aryl-alkyl surfactant precursor |
| DE102015207581A1 (en) * | 2015-04-24 | 2016-10-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the electrochemical conversion of fatty acids and plant for carrying out the process |
| EP3286357A1 (en) * | 2015-04-24 | 2018-02-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for the electrochemical conversion of fatty acids and equipment for carrying out the method |
Non-Patent Citations (3)
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| V.N.ANDREEW ET AL.: "Application of vegetable Oils for Electrocatalytic Synthesis of Hydrocarbons", 《RUSSIAN JOURNAL OF ELECTROCHEMISTRY》 * |
| 叶文法等: "《基础有机化学反应》", 31 October 1996 * |
| 王兴国: "《油料科学原理》", 31 August 2017 * |
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Address after: 300452 Binhai Industrial Research Institute Campus of Tianjin University, No. 48 Jialingjiang Road, Binhai New Area, Tianjin Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |