CN109778222A - A kind of paired electrode prepare simultaneously aldehyde material and aromatic ester method and used electrode - Google Patents
A kind of paired electrode prepare simultaneously aldehyde material and aromatic ester method and used electrode Download PDFInfo
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Abstract
The present invention relates to the modified electrodes that a kind of paired electrode prepares the method for aldehyde material and aromatic ester and use simultaneously.For the present invention by adulterating other metals into metal electrode, the property for changing electrode realizes paired electrode synthesis.Electrolytic cell is divided into cathode chamber and anode chamber by ionic membrane, wherein reduction reaction occurs for cathode chamber, and acid is reduced to aldehyde material；Oxidation reaction occurs for anode chamber, and aromatic compound is transformed into aromatic ester.Paired electrode improves the utilization efficiency of electric energy, makes the cathode of electrode and anode that can be used effectively, and reduces the power consumption and cost of product, has good industrial prospect.
Description
Technical field
The invention belongs to Organic Electrochemical Synthesis fields, and in particular to a kind of paired electrode prepares aldehyde material and virtue simultaneously
The method of fragrant ester and used electrode.
Background technique
Aldehyde compound is a kind of important industrial chemicals, and glyoxalic acid, salicylide etc. all have important application.Glyoxalic acid
Structural formula are as follows: CHOCOOH can be used for preparing the fine chemical products such as vanillic aldehyde, allantoin.Glyoxalic acid mainly passes through at present
The preparation of glyoxal nitric acid oxidation method, but this method can generate the pollutants such as a large amount of three wastes, belong to high pollution industry.Specially
Sharp US4146731 reports a kind of technique that glyoxalic acid is prepared with nitric acid oxidation glyoxal, due to severe reaction conditions, side reaction
It is difficult to inhibit, the selectivity of target product is poor, and the dosage of nitric acid is very big, and many nitric acid are remained in product and are not easy to remove.And
And nitric acid, to the seriously corroded of equipment, the NOx generated in reaction process is the main source of acid rain, easily causes environmental pollution.
Patent US3779875 and CN1281063A, which are reported, prepares glyoxalic acid with oxalic acid cathode reduction method, used in the technique
Current density and current efficiency it is higher, partially solve the problems, such as that oxidation of glyoxal is brought, but oxalic acid cathodic reduction
Oxygen evolution reaction, anodic process utilization not yet in effect only occur for journey Anodic, and the oxygen of generation without utility value, wastes electricity substantially
Can, cause power consumption in oxalic acid electrolytic process higher, the production cost is very high for glyoxalic acid, and the technique is made not obtain large-scale application.Often
The power consumption of ton oxoacetic acid product is about 8000kWh, and the electric energy of every kilowatt hour can only generate 0.12-0.13kg product.
Salicylide is a kind of important fragrance intermediates, is mainly used for synthesizing coumarin etc..The conventional synthesis side of salicylide
Method is to be reacted to be made under sodium hydroxide solution with phenol and chloroform, and referred to as Reimer-Tiemann reaction, the method raw material disappears
Consumption is high, three-waste pollution is serious, and product quality is not high, needs to refine repeatedly.Salicylic acid electrolysis for preparing salicyic aldehyde is in recent years
The existing technique of exploitation, compare traditional handicraft, raw material salicylic at low cost, salicylide high income (yield > 75%), crude product
(purity > 90%) with high purity.
When electrolysis, salicylic acid is dissolved in the aqueous solution containing the substances such as sodium sulphate or sodium bisulfate, with aluminium amalgam, sodium mercury
It is electrolysed together as cathode material, dilute sulfuric acid is added in anode chamber as electrolyte.It is similar to the electrolytic process of oxalic acid reduction,
For cathode while reductic acid, anode carries out oxygen evolution reaction, and the electricity of about half is used to oxygen, leads to the life of salicylide
Produce high expensive.Unlike oxalic acid electrolysis, for cathode the accidents such as mercury poisoning easily occur for aluminium amalgam, sodium amalgam etc., easily
Cause mercury environmental pollution.
Therefore, organic acid electroreduction prepares aldehyde material at present, however it remains waste of energy, product power consumption are higher, electric
The problems such as pole material is not environmentally easily poisoned.Need to develop a kind of completely new electrode and its corresponding paired electrode electrolytic method, with
Solve presently, there are these problems.
Summary of the invention
Present invention aim to address above-mentioned prior art defect, a kind of paired electrode is provided and meanwhile prepare aldehyde material and
The method of aromatic ester, this method are included in cathode and reduction reaction occur, and are aldehyde material by the first organic acid reduction, send out in anode
Aromatic compound acyloxylation is generated aromatic ester by raw oxidation reaction.
Preferably, the general formula of the first organic acid is as follows:
R1-COOH
Wherein, R1Selected from substitution (such as hydroxyl replace) or unsubstituted C1-C10 alkyl, replace (such as hydroxyl replaces
) or unsubstituted C5-C12 aryl or C2-C10 acidic group.
Further, the first organic acid is selected from propionic acid, 2- rnethyl-propanoic acid, butyric acid, oxalic acid, benzoic acid, salicylic acid (adjacent hydroxyl
Yl benzoic acid), acetic acid, one of substances such as tartaric acid or a variety of, preferably one of oxalic acid, salicylic acid and tartaric acid or more
Kind.
Preferably, aromatic compound is selected from benzene, paraxylene, mesitylene, 1, one of 2,4,5- durenes, naphthalene etc.
Or it is a variety of.
Preferably, in the oxidation reaction of anode, using the second organic acid as anolyte, acyloxy occurs with aromatic compound
Change reaction and generates Ester.Further, Ester hydrolyzes, and is converted to phenolic substances.Second organic acid and aromatics
The molar ratio of object can be 10:1-40:1, preferably 20:1-30:1.The molar ratio of first organic acid and aromatic compound can be
1:0.5-1.5 preferably 1:0.8-1.2.
The general formula of second organic acid is as follows:
R3COOH
Wherein R3Selected from H or replace (such as halogen substitution) or unsubstituted C1-C6 alkyl (alkyl or alkenyl).
Second organic acid R3COOH is selected from one of formic acid, acetic acid, trifluoroacetic acid, propionic acid, n-butyric acie, 2 Methylpropionic acid
Or a variety of, preferably one of acetic acid, trifluoroacetic acid and propionic acid or a variety of.
Further, reduction reaction carries out in the cathodic compartment, and oxidation reaction carries out in the anode compartment, cathode chamber and anode chamber
It is separated with amberplex.
By analyzing electrode reaction, for organic acid when cathode carries out reduction reaction, anode carries out oxidation reaction simultaneously, electricity
Pole reaction equation is as follows:
Cathode reaction: R1-COOH+2H++2e→R1-CHO+H2O (1)
Anode reaction: H2O→0.5O2+2H++2e
By the way that the analysis of existing reaction is compared and is continuously attempted to, it has been found that its oxidation reaction attribute is utilized in anode,
Corresponding electrode reaction is designed, can make aromatic ring that acyloxylation reaction occur, electrode reaction is as follows:
Using organic acid as anolyte in reaction, the organic acid not only solvent as reaction, but also as the raw material of reaction, with virtue
Aroma compounds occur acyloxylation reaction and generate Ester, and Ester hydrolysis can be further converted into phenolic substances.
When fragrant cyclocomplex is naphthalene, product is naphthyl acetate, can be converted to alpha-Naphthol by straightforward procedure, this is a kind of important
Dyestuff and pesticide intermediate.Organic acid R3COOH is selected from formic acid, acetic acid, trifluoroacetic acid, propionic acid, n-butyric acie, 2- methyl-prop
One of acid is a variety of, preferably one of acetic acid, trifluoroacetic acid and propionic acid or a variety of.
Be independent of each other to make cathode chamber and anode chamber while reacting, preferably with amberplex by catholyte and
Anolyte separates, and amberplex is selected from cation-exchange membrane, anion-exchange membrane and Bipolar Membrane, preferred cationic exchange membrane.
Using cation-exchange membrane, the hydrogen ion that anode reaction generates can participate in reduction reaction, protect through ionic membrane and into cathode
The balance of material and charge is held.Cation-exchange membrane be selected from sulfonic acid type ion film, phosphatic type ionic membrane, carboxylic acid type ionic membrane,
The one or more of them such as phenols ionic membrane, preferably sulfonic acid type ion exchange membrane.
In order to increase the conductivity of anolyte, be preferably added to a kind of electrolyte, electrolyte be selected from cationic surfactant,
One of anionic surfactant, preferred cationic surfactant are further selected from tetramethyl ammonium acetate ((Me)4NOAc), tetraethyl trifluoroacetic acid ammonium ((Et)4NCF3COO), tetrabutyl tetrafluoride boron ammonium ((nBu)4NBF4), tetraethyl tetrafluoride
Boron ammonium ((Et)4NBF4), tetramethyl sulfate mono ammonium methyl ((Me)4NSO3Me one of) or a variety of, the dosage of electrolyte is preferred
It is the 0.1-50mol% of aromatic compound, preferably 1-20mol%, more preferable 2-15mol%.
W-response equation is as follows:
Cathode reaction: R1-COOH+2H++2e→R1-CHO+H2O
After paired electrode, the electricity of every kilowatt hour not only can generate 0.13kg aldehyde material in cathode, may be used also
To generate about 0.6-0.8kg aromatic ester in anode, the two does not interfere with each other, greatly improves the utilization rate of electric energy, reduce production
Product cost.
DSA electrode can be used for example in electrode of the invention, anode, and it is preferable to use alloy electrode of the invention, examples for cathode
It such as can be in the electric pressing operation of 5-10V.
The electrode mercurous using aluminium amalgam, sodium amalgam etc. is needed when salicylic acid electroreduction, these electrodes can not only make to grasp
Make personnel and mercury poisoning occurs, but also is easy to happen mercury leakage and causes environmental pollution.Therefore, the present invention additionally provides one kind to be used for
The alloy electrode of aldehyde material and aromatic ester is prepared, by electrode reduction-oxidation to substitute Amalgam electrode, the main body gold of electrode
Belong to is one of lead, titanium, copper, aluminium, zinc, preferably one of titanium, copper, lead；The metal of doping is nitrogen group element, chalcogen member
One of element, carbon group element are a variety of, preferably one or more of arsenic, bismuth, tellurium, silicon, germanium；The content of doped chemical is
0.1-10 mass %, preferably 0.2-1 mass %.
After novel alloy electrode, the use containing mercury electrode is not only avoided, current efficiency is increased to by 50%
95% or more, the hardness of electrode is also added, easy to clean or replacement is allowed to.
The purpose of the present invention is to provide a kind of electrochemical method for synthesizing of paired electrode, reduction reaction, which will occur, for cathode to have
Machine acid is reduced to aldehyde material, and oxidation reaction occurs for anode, and aromatic compound occurs acyloxylation reaction and generates aromatic ester, the two
It does not interfere with each other, improves utilization rate of electrical, reduce production cost.It also invented a kind of alloy electrode simultaneously, to substitute tradition
Contain mercury electrode, not only reduce environmental pollution, also improve current efficiency.
The beneficial effects of the present invention are:
While reduction reaction occurs for cathode chamber, using anode reaction, Oxygen anodic evolution reaction is become into aromatics
The acyloxylation of object reacts, and the two does not interfere with each other, improves the utilization rate of electric current, reduce production cost, for prepare aldehydes and
Fragrant phenol provides a kind of green, low-cost method, solves product power consumption height, production cost in existing production technology
The problems such as high, mercury electrode poisoning easy to pollute.Process flow is simple, not high to equipment requirement, is suitble to industrialized production.
Embodiment
Preparation method provided by present invention be described in more detail by the following examples, but the present invention not therefore and
It is any way limited.
Oxalic acid, salicylic acid, tartaric acid, benzoic acid, butyric acid, acetic acid, trifluoroacetic acid, propionic acid, formic acid；, 2 Methylpropionic acid purchase
It buys from Aladdin reagent, purity > 98.0%；
Benzene, paraxylene, mesitylene, 1,2,4,5- durenes, naphthalene: purchase producer: traditional Chinese medicines, purity > 99%；
Tetramethyl ammonium acetate, tetraethyl trifluoroacetic acid ammonium, tetrabutyl tetrafluoride boron ammonium, tetraethyl tetrafluoride boron ammonium, tetramethyl
Base sulfate mono ammonium methyl: purchase producer: lark prestige, purity > 98%；
Modified electrode: purchase producer, Suzhou Feng Gang titanium.
Embodiment 1
Into cathode chamber be added 100g 10wt% oxalic acid aqueous solution, to anode chamber be added 213.3g acetic acid, 6.94g benzene and
236.8mg tetramethyl ammonium acetate, anode chamber and cathode chamber are separated with Nafion ionic membrane.Cathode Ti electrode, wherein adulterating
0.2wt% arsenic, anode DSA electrode, control bath voltage are 5.3V, are electrolysed 1.0h at room temperature.It measures in catholyte, produces
Object acetaldehyde acid concentration is 5.2%, current efficiency 97%, and the concentration of acetic acid product phenol ester is 12.15% in anolyte, electric current effect
Rate is 96%.0.13kg glyoxalic acid and 0.42kg acetoxyphenyl can be generated in every kilowatt hour electric energy.
Embodiment 2
50g 10wt% aqueous solution of salicylic acid is added into cathode chamber, 49.5g trifluoroacetic acid, 4.62g is added to anode chamber
Paraxylene and 1586.5mg tetraethyl trifluoroacetic acid ammonium, anode chamber and cathode chamber are separated with Nafion ionic membrane.Cathode copper
Electrode is electrolysed 1.0h wherein doping 1wt% bismuth, anode DSA electrode, control bath voltage are 5.2V at room temperature.Measurement
In catholyte, product bigcatkin willow aldehyde concentration is 4.7%, current efficiency 95%, product trifluoroacetic acid 2 in anolyte, 5- dimethyl benzene
The concentration of phenolic ester is 13.58%, current efficiency 93%.0.21kg salicylide and 0.65kg tri- can be generated in every kilowatt hour electric energy
Fluoroacetic acid 2,5- dimethyl benzene phenolic ester.
Embodiment 3
100g 5wt% aqueous tartaric acid solution is added into cathode chamber, 49.3g propionic acid, 4g mesitylene is added to anode chamber
With 932.9mg tetrabutyl tetrafluoride boron ammonium, anode chamber and cathode chamber are separated with Nafion ionic membrane.Cathode lead electrode, wherein
0.6wt% tellurium, anode DSA electrode are adulterated, control bath voltage is 5.3V, is electrolysed 1.0h at room temperature.Measure catholyte
In, product 1- carbonyl -2,3- dihydroxy butyric acid density is 2.8%, current efficiency 96%, product propionic acid 2,4,6- tri- in anolyte
The concentration of methylbenzene phenolic ester is 5.8%, current efficiency 91%.0.23kg 1- carbonyl -2,3- can be generated in every kilowatt hour electric energy
Dihydroxy butyric acid and 0.60kg propionic acid 2,4,6- trimethylbenzene phenolic ester.
Embodiment 4
10g 10wt% benzoic acid aqueous solution is added into cathode chamber, 16.9g formic acid, 1.65g 1,2 is added to anode chamber,
4,5- durenes and 26.7mg tetraethyl tetrafluoride boron ammonium, anode chamber and cathode chamber are separated with Nafion ionic membrane.Cathode aluminium
Electrode is electrolysed 1.0h wherein doping 0.1wt% silicon, anode DSA electrode, control bath voltage are 5.3V at room temperature.It surveys
Determine in catholyte, product benzaldehyde concentration is 4.7%, current efficiency 98%, product formic acid -2,3 in anolyte, 5,6- tetramethyls
The concentration of phenol ester is 18.8%, current efficiency 87%.0.19kg benzaldehyde and 0.45kg can be generated in every kilowatt hour electric energy
Formic acid -2,3,5,6- durol phenolic ester.
Embodiment 5
100g 10wt% butyric acid aqueous solution is added into cathode chamber, 125g 2 Methylpropionic acid, 7.28g is added to anode chamber
Naphthalene and 2111.4mg tetramethyl sulfate mono ammonium methyl, anode chamber and cathode chamber are separated with Nafion ionic membrane.Cathode zinc electrode,
10wt% germanium, anode DSA electrode are wherein adulterated, control bath voltage is 5.3V, is electrolysed 1.0h at room temperature.Measure cathode
In liquid, product butyraldehyde concentration is 4.9%, current efficiency 99%, and the concentration of product 2 Methylpropionic acid -2'- naphthalene ester is in anolyte
17.54%, current efficiency 92%.0.13kg butyraldehyde and 0.63kg 2 Methylpropionic acid -2'- can be generated in every kilowatt hour electric energy
Naphthalene ester.
Comparative example
100g 10wt% oxalic acid aqueous solution is added into cathode chamber, 100g acetic acid, anode chamber and cathode is added to anode chamber
Room is separated with Nafion ionic membrane.The pure Ti electrode of cathode, anode DSA electrode, control bath voltage is 5.3V, in room temperature
Lower electrolysis 1.0h.It measures in catholyte, product acetaldehyde acid concentration is 2.5%, and current efficiency 48%, anolyte only has acetic acid.Often
0.06kg glyoxalic acid can be generated in kilowatt hour electric energy.
Claims (10)
1. a kind of method that paired electrode prepares aldehyde material and aromatic ester simultaneously, this method is included in cathode and reduction occurs instead
It answers, is aldehyde material by the first organic acid reduction, oxidation reaction occurs in anode, by aromatic compound acyloxylation, generates virtue
Fragrant ester.
2. according to the method described in claim 1, wherein, the first organic acid has following general formula:
R1-COOH
Wherein, R1Selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C5-C12 aryl or C2-C10 acidic group；
Preferably, the first organic acid is selected from propionic acid, 2- rnethyl-propanoic acid, butyric acid, oxalic acid, benzoic acid, salicylic acid, acetic acid, tartaric acid
One of or a variety of, preferably one of oxalic acid, salicylic acid and tartaric acid or a variety of.
3. method according to claim 1 or 2, wherein aromatic compound be selected from benzene, paraxylene, mesitylene, 1,2,
One of 4,5- durene, naphthalene are a variety of.
4. method according to any one of claim 1-3, wherein in the oxidation reaction of anode, with the second organic acid work
For anolyte, acyloxylation occurs with aromatic compound and reacts generation Ester.
5. being converted to phenolic substances according to the method described in claim 4, wherein, Ester further hydrolyzes.
6. the method according to after claim 45, wherein the second organic acid has following general formula:
R3COOH
Wherein R3Selected from H or replace (such as halogen substitution) or unsubstituted C1-C6 alkyl (alkyl or alkenyl)；
Preferably, the second organic acid R3COOH in formic acid, acetic acid, trifluoroacetic acid, propionic acid, n-butyric acie, 2 Methylpropionic acid one
Kind is a variety of, preferably one of acetic acid, trifluoroacetic acid and propionic acid or a variety of.
7. method according to claim 1 to 6, wherein the molar ratio of the second organic acid and aromatic compound is
10:1-40:1, preferably 20:1-30:1；The molar ratio of first organic acid and aromatic compound is 1:0.5-1.5, preferably 1:0.8-
1.2。
8. method according to any one of claims 1-7, wherein reduction reaction carries out in the cathodic compartment, oxidation reaction
It carries out in the anode compartment, cathode chamber and anode chamber are separated with amberplex.
9. method according to claim 1 to 8, wherein a kind of electrolyte is added in anolyte, electrolyte choosing
From one of cationic surfactant, anionic surfactant, preferred cationic surfactant is further selected from four
Methyl acetic acid ammonium ((Me)4NOAc), tetraethyl trifluoroacetic acid ammonium ((Et)4NCF3COO), tetrabutyl tetrafluoride boron ammonium ((nBu)4NBF4), tetraethyl tetrafluoride boron ammonium ((Et)4NBF4), tetramethyl sulfate mono ammonium methyl ((Me)4NSO3Me one of) or more
Kind, the dosage of electrolyte is preferably the 0.1-50mol% of aromatic compound, preferably 1-20mol%, more preferable 2-15mol%.
10. a kind of for preparing the alloy electrode of aldehyde material and aromatic ester by electrode reduction-oxidation, wherein the main body of electrode
Metal is one of lead, titanium, copper, aluminium, zinc or a variety of, preferably one of titanium, copper, lead；The metal of doping be nitrogen group element,
One of oxygen group elements, carbon group element are a variety of, preferably one or more of arsenic, bismuth, tellurium, silicon, germanium；Doped chemical contains
Amount is 0.1-10 mass %, preferably 0.2-1 mass %.
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| CN110284152A (en) * | 2019-07-15 | 2019-09-27 | 上海万华科聚化工科技发展有限公司 | A kind of lead dioxide electrode, preparation method and application |
| CN112824563A (en) * | 2019-11-19 | 2021-05-21 | 万华化学集团股份有限公司 | Method for simultaneously preparing picolinic acid and aromatic chloride dechlorination reduction products through paired electrolysis |
| CN113073346A (en) * | 2020-01-06 | 2021-07-06 | 万华化学集团股份有限公司 | Electrochemical method for simultaneously preparing o-diol and pyrrole methoxylation products |
| CN113755864A (en) * | 2021-09-27 | 2021-12-07 | 西安交通大学 | Method for synthesizing aryl trifluoromethoxy compound under electrochemical condition |
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| CN113755864A (en) * | 2021-09-27 | 2021-12-07 | 西安交通大学 | Method for synthesizing aryl trifluoromethoxy compound under electrochemical condition |
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