CN110158115B - Method for electrochemically preparing phenol - Google Patents
Method for electrochemically preparing phenol Download PDFInfo
- Publication number
- CN110158115B CN110158115B CN201910338064.5A CN201910338064A CN110158115B CN 110158115 B CN110158115 B CN 110158115B CN 201910338064 A CN201910338064 A CN 201910338064A CN 110158115 B CN110158115 B CN 110158115B
- Authority
- CN
- China
- Prior art keywords
- phenol
- anode
- benzene
- electrode material
- power supply
- 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.)
- Active
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 44
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 60
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003014 ion exchange membrane Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229940035674 anesthetics Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003193 general anesthetic agent Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
- C25B3/20—Processes
- C25B3/23—Oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for electrochemically producing phenol, comprising a step 1): adding an acetonitrile solution containing benzene with a certain mass concentration into an alkaline electrolyte solution, and keeping the conductivity above 10 mS/cm; step 2): taking a metallic nickel compound as an anode electrode catalyst, and taking a carbon material loaded with platinum black as a cathode electrode material; step 3): applying anode voltage through a power supply to control working voltage and working current; step 4): electrolyzing to generate a high-activity Ni ═ O active intermediate, and oxidizing benzene to phenol in one step; step 5): regulating the pH value of the aqueous electrolyte by using hydrochloric acid to regulate the state and solubility of the produced phenol; step 6): the product phenol is synchronously extracted through the upper acetonitrile organic phase, and the phenol is purified, and meanwhile, the organic extracting agent is recovered. The invention has the beneficial effects that: the invention adopts the one-step method to oxidize the benzene to prepare the phenol, and has the advantages of small equipment investment, low energy consumption, high conversion rate, few byproducts, recoverable organic solvent and the like.
Description
Technical Field
The invention relates to the field of dispersed electrochemical preparation of phenol, in particular to a method for preparing phenol by an electrochemical method.
Background
Phenol is one of the most important organic and high molecular chemical materials, and its applications mainly include phenolic resin, caprolactam, bisphenol A, adipic acid, aniline, alkylphenol and salicylic acid. The chemical products can be used for further producing high-value products such as pesticides, spices, dyes, bactericides, anesthetics, preservatives and the like. Phenol can also be used as a solvent and a reagent, and has wide application in scientific research. In recent years, the demand of the market for phenol is increasing, and the demand is in a short supply state.
The industrial production methods of phenol mainly include an cumene method, a toluene-benzoic acid method, a benzene sulfonation method, and the like. The cumene method is the current mature process and has the leading position in the world phenol industrial production. However, the cumene method has the problems of high energy consumption, low yield, large amount of acetone byproduct and the like. The toluene-benzoic acid method has the advantages of simple process flow, non-toxic raw materials, catalysts and products, low investment and capability of producing benzoic acid, benzaldehyde, benzyl alcohol and other chemical products with wide application according to market demands, but the generated phenol cannot leave a reactor quickly and is easy to generate tar, so that the yield of the phenol and the service life of the catalysts are influenced to a certain extent. Because the price of toluene is higher than that of benzene, the production cost of the toluene method is higher than that of the isopropyl benzene method, and only a few manufacturers such as Japan Qianye phenol company adopt the method to produce phenol at present. The benzene sulfonation method has the problems of corrosion, generation of three wastes and the like due to the fact that a large amount of sulfuric acid and sodium hydroxide are used in the preparation process, and is rarely used in recent years.
Electrochemical methods have a number of significant advantages. First, the use of toxic or hazardous oxidizing and reducing agents can be avoided. Because electrons are clean reaction reagents, the reaction system does not usually contain other reagents except raw materials and products, and the material consumption is reduced; and the product is easy to separate, has high purity and small environmental pollution. Secondly, in the electrochemical synthesis process, the two processes of electron transfer and chemical reaction can be carried out simultaneously, the electrode reaction speed can be effectively and continuously changed by controlling the electrode potential, and the side reaction is reduced, so that the yield and the selectivity of the target product are higher. Thirdly, the reaction can be carried out at normal temperature and normal pressure, and special heating and pressurizing equipment is not needed generally, so that the energy is saved, and the equipment investment is reduced.
Disclosure of Invention
The invention aims to overcome the defects and provide a method for electrochemically preparing phenol.
A method for electrochemically preparing phenol, comprising the steps of:
s1, adding an acetonitrile solution containing benzene with a certain mass concentration into an alkaline electrolyte solution, and keeping the conductivity above 10 mS/cm;
s2, taking a metallic nickel compound as an anode electrode catalyst and taking a carbon material loaded with platinum black as a cathode electrode material;
s3, applying anode voltage through a power supply, and controlling working voltage and working current;
s4, electrolyzing to generate a high-activity Ni ═ O active intermediate, and oxidizing benzene to phenol in one step;
s5, regulating the pH value of the aqueous electrolyte by hydrochloric acid to regulate the state and solubility of the produced phenol,
s6, synchronously extracting the product phenol through the upper acetonitrile organic phase, and purifying the phenol while recovering the organic extractant.
Preferably, the method comprises the following steps: in the step S1, the concentration of benzene in the benzene acetonitrile-containing solution is 10% -30%.
Preferably, the method comprises the following steps: in the step S1, the alkaline electrolyte is sodium hydroxide, potassium hydroxide or cesium hydroxide, and the concentration range is 0.1 to 1.0M.
Preferably, the method comprises the following steps: in step S2, the working electrode is nickel foam.
Preferably, the method comprises the following steps: in step S2, the working electrode is loaded with a special nickel complex represented by the chemical formula (Ni [ N (CH) ]2(N C5H4))2CH2(NC6H3O2)H2O]Cl。
Preferably, the method comprises the following steps: in step S3, the power supply is a dc operating power supply.
Preferably, the method comprises the following steps: in the step S3, the voltage is 2-5V, and the working current density is 1-8A/m2。
Preferably, the method comprises the following steps: in step S5, the pH of the aqueous electrolyte is adjusted to 7 using hydrochloric acid.
Preferably, the method comprises the following steps: in the step S6, the phenol purification method is cyclic heating or recrystallization.
Preferably, the method comprises the following steps: in the step S6, the organic extractant is recovered by condensation.
The invention has the beneficial effects that: the method for preparing phenol by oxidizing benzene by one-step method has the advantages of simple process, low equipment investment, low energy consumption, simple and convenient operation, high conversion rate, few byproducts, recoverable organic solvent and the like.
Drawings
FIG. 1 is a system flow diagram;
FIG. 2 is a molecular structure diagram of a supported specific nickel complex.
Description of reference numerals: the device comprises an anode conductive plate 1, an anode material 2, a heating plate 3, an anode electrolyte 4, a cathode electrolyte 5, a cathode conductive plate 6, an organic extraction chamber 7, an ion exchange membrane 8, a cathode material 9, a direct current power supply 10, a temperature control instrument 11, a thermocouple 12, a distillation separation chamber 13, a product pool 14 and a liquid guide pump 15.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
FIG. 1 is a system flow diagram;
the system mainly comprises an electrolytic cell part (an anode conductive plate 1, an anode material 2, a heating plate 3, an anode electrolyte 4, a cathode electrolyte 5, a cathode conductive plate 6, an organic extraction chamber 7, an ion exchange membrane 8, a cathode material 9, a direct current power supply 10, a temperature control instrument 11 and a thermocouple 12) and a product separation and purification part (a distillation separation chamber 13, a product pool 14 and a liquid guide pump 15). The electrolytic cell mainly comprises an anode conductive plate 1, a cathode conductive plate 6, an anode material 2, a cathode material 9, an anode electrolyte 4, a cathode electrolyte 5, an organic extraction chamber 7, an ion exchange membrane 8 and a heating plate 3. The specific working principle is as follows. A dc power supply 10 applies a positive voltage to the anode material 2 through the anode conductive plate 1 and cathode conductive plate 6 to oxidize the substrate benzene to produce product phenol which is extracted in an organic extraction chamber 7 above the anode of the cell and transferred out of the cell. The power supply applies a negative voltage across the cathode material 9, reducing the water to produce hydrogen gas as a by-product. The ion exchange membrane 8 between the two electrodes can transmit ions in the solution to form a complete electric loop. The optimal temperature of the electrode reaction is between 80 and 90 ℃, so that the electric heating plate 3 is wrapped on the outer layer of the battery plate, and the optimal temperature of the reaction is controlled by the temperature controller 11 and the thermocouple 12. After the phenol produced was transferred to the distillation chamber 13, the organic solvent was separated by distillation to finally obtain pure phenol 14. The distilled organic solution can be transported back to the electrolytic cell for reuse by means of a liquid-conducting pump 15.
Example 1
The working electrode material is nickel foam, and the carbon material loaded with platinum black is used as the cathode electrode material. 500mL of a 10% strength solution of benzene in acetonitrile was added to a sodium hydroxide electrolyte having a pH of 13. Setting the working voltage to 3.0V and regulating the working current to 1A/m2. The ratio of the area of the working electrode to the volume of the electrolyte solution was set to 1cm-2/1cm-3(100cm-2100 mL). After 10 hours of electrochemical treatment, the concentration of phenol in the aqueous phase reached 20 g/L. The average current efficiency was 40% during 10 hours of electrolysis, and the electricity consumption for producing phenol by this method was about 0.5 kwh/kg. The selectivity of phenol is as high as 90%, and the rest by-products are mainly hydroquinone and hydroquinone.
Example 2
The working electrode material is nickel foam, and the carbon material loaded with platinum black is used as the cathode electrode material. A 20% strength solution of benzene in acetonitrile was added to a pH 13 sodium hydroxide electrolyte. Setting the working voltage to 3.0V and regulating the working current to 1.5A/m2. The ratio of the area of the working electrode to the volume of the electrolyte solution was set to 1cm-2/1cm-3(100cm-2100 mL). After 8 hours of electrochemical treatment, the concentration of phenol in the aqueous phase reached 20 g/L. The average current efficiency was 50% during 8 hours of electrolysis, and the electricity consumption for producing phenol by this method was about 0.4 kwh/kg. The selectivity of phenol reaches 90%, and the main byproducts are hydroquinone and hydroquinone.
Example 3
The working electrode material is a special nickel complex (Ni [ N (CH) supported as shown in figure 22(N C5H4))2CH2(NC6H3O2)H2O]A titanium alloy material of Cl, and a carbon material supporting platinum black as a cathode electrode material. A 20% strength solution of benzene in acetonitrile was added to a pH 13 sodium hydroxide electrolyte. Setting the working voltage to 3.0V and regulating the working current to 1.0A/m2. The ratio of the area of the working electrode to the volume of the electrolyte solution was set to 1cm-2/1cm-3. After electrochemical treatment for 12 hours, the concentration of phenol in the aqueous phase reached more than 20 g/L. The average current efficiency was 50% during the 12 hour electrolysis, and the electricity consumption for producing phenol by this method was about 0.75 kwh/kg. The selectivity of phenol reaches 70%, and the main byproducts are hydroquinone, resorcinol and hydroquinone.
The novel method for preparing phenol by oxidizing benzene in one step through electrochemical catalysis not only improves the conversion efficiency of benzene, but also realizes the aims of emission reduction, energy conservation and green chemistry.
Claims (3)
1. The method for electrochemically preparing the phenol is characterized by comprising an anode conducting plate, an anode electrode material, an anode electrolyte, an ion exchange membrane, a cathode electrolyte, a cathode electrode material and a cathode conducting plate which are sequentially arranged in an electrolytic cell; the direct current power supply passes positive voltage through the anode conductive plate; a direct current power supply applies negative voltage on the cathode electrode material; the ion exchange membrane between the anode electrode material and the cathode electrode material transmits ions in the electrolytic cell to form a complete electric loop; the method comprises the following steps:
s1, adding an acetonitrile solution containing benzene with a certain mass concentration into an alkaline electrolyte solution, and keeping the conductivity above 10 mS/cm; the mass concentration of benzene in the acetonitrile solution containing benzene is 10-30 percent; the alkaline electrolyte is sodium hydroxide, potassium hydroxide or cesium hydroxide, and the concentration range is 0.1-1.0M;
s2, taking a metallic nickel compound as an anode electrode catalyst and taking a carbon material loaded with platinum black as a cathode electrode material; the anode is nickel foam or a chemical formulaIs (Ni [ N (CH)2(N C5H4))2CH2(NC6H3O2)H2O]Cl and the structural formula is
The supported special nickel complex;
s3, applying anode voltage through a power supply, and controlling working voltage and working current; in the step S3, the voltage is 2-5V, and the working current density is 1-8A/m2；
S4, electrolyzing to generate a high-activity Ni ═ O active intermediate, and oxidizing benzene to phenol in one step;
s5, regulating the pH value of the aqueous electrolyte by using hydrochloric acid to regulate the state and solubility of the produced phenol; regulating the pH value of the aqueous electrolyte to 7 by using hydrochloric acid;
s6, synchronously extracting the product phenol through an upper acetonitrile organic phase, purifying the phenol, and simultaneously recovering an organic extractant; the phenol purification method is cyclic heating or recrystallization.
2. The method for electrochemically producing phenol according to claim 1, wherein in step S3, the power supply is a dc operating power supply.
3. The method for electrochemically preparing phenol according to claim 1, wherein in step S6, the organic extractant is recovered by condensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910338064.5A CN110158115B (en) | 2019-04-25 | 2019-04-25 | Method for electrochemically preparing phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910338064.5A CN110158115B (en) | 2019-04-25 | 2019-04-25 | Method for electrochemically preparing phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110158115A CN110158115A (en) | 2019-08-23 |
| CN110158115B true CN110158115B (en) | 2020-07-03 |
Family
ID=67640068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910338064.5A Active CN110158115B (en) | 2019-04-25 | 2019-04-25 | Method for electrochemically preparing phenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110158115B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529111B (en) * | 2021-06-30 | 2023-10-27 | 东华理工大学 | Process and device for preparing phenol by using benzene through electric catalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730872A (en) * | 1970-05-27 | 1973-05-01 | Rhone Poulenc Sa | Electric cells |
| CN105951121A (en) * | 2016-05-27 | 2016-09-21 | 安庆师范大学 | Method for preparing phenol by ionic liquid assisted electric catalytic oxidation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10026940A1 (en) * | 2000-05-30 | 2001-12-06 | Creavis Tech & Innovation Gmbh | Electrochemical cell for the oxidation of organic compounds and electrocatalytic oxidation process |
-
2019
- 2019-04-25 CN CN201910338064.5A patent/CN110158115B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730872A (en) * | 1970-05-27 | 1973-05-01 | Rhone Poulenc Sa | Electric cells |
| CN105951121A (en) * | 2016-05-27 | 2016-09-21 | 安庆师范大学 | Method for preparing phenol by ionic liquid assisted electric catalytic oxidation |
Non-Patent Citations (3)
| Title |
|---|
| AN ATTEMPT TO DEFINE BENZENE AND PHENOL ELECTROCHEMICAL OXIDATION MECHANISM;BOLESLAW FLESZAR等;《Electrochimica Acta》;19851231;第30卷(第1期);第32-33页、图6、摘要 * |
| ELECTROLYTIC PRODUCTION OF PHENOLS FROM BENZENE USING Cu(I)/Cu(II) COUPLE;Kazuo SASAKI等;《CHEMISTRY LETTERS》;19831231;第446页 * |
| One-Step Hydroxylation of Benzene to Phenol Induced by Glow Discharge Plasma in an Aqueous Solution;Yong-Jun Liu等;《Plasma Chem Plasma Process》;20070524;第27卷;第496-503页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110158115A (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102912374B (en) | An electrochemical reduction CO2 electrolytic cell with a bipolar membrane as a diaphragm and its application | |
| CN103160849B (en) | The method of Carbon dioxide electrochemical reduction trans-utilization | |
| CN103160851B (en) | Membrane reactor | |
| CN111254456B (en) | Electrochemical synthesis method of 2-nitro-4-methylsulfonylbenzoic acid | |
| CN110791773A (en) | Method and device for producing hydrogen by electrolyzing water | |
| CN103436910B (en) | The preparation method of a kind of gluconic acid and glucaric acid | |
| CN102877086A (en) | Method for preparing cyclic carbonate from olefin and carbon dioxide by electrochemical method | |
| CN110158115B (en) | Method for electrochemically preparing phenol | |
| US4589963A (en) | Process for the conversion of salts of carboxylic acid to their corresponding free acids | |
| CZ20011317A3 (en) | Process for preparing sodium and potassium peroxodisulfates and ammonium peroxodisulfate | |
| CN105696017B (en) | A novel technical method for iron reduction of nitrobenzene | |
| CA2413727A1 (en) | Electrochemical cell | |
| US20230151500A1 (en) | Novel electrocatalytic membrane reactor and use thereof in preparation of high-purity hydrogen | |
| WO2023082884A1 (en) | New electrocatalytic membrane reactor and use thereof in preparation of high-purity hydrogen | |
| CN105862072B (en) | A kind of new technique method of zinc reduction nitrobenzene | |
| CN115928110A (en) | Hydrogenation dechlorination method of high-concentration chlorinated aromatic compound | |
| Pletcher et al. | Organic electrosynthesis | |
| CN114134522A (en) | A kind of electrochemical synthesis method of 4,4'-bipyridine | |
| CN114314765A (en) | Method and device for producing hydrogen by combining electrochemical resource desulfurization wastewater and application | |
| CN113430571A (en) | Method for recovering metal lithium in photo-assisted waste lithium iron phosphate battery | |
| EP3854910A1 (en) | Electrochemical production of formaldehyde | |
| WO2025045280A2 (en) | Off-site electro-catalytic reaction method and reaction system | |
| CN102358943A (en) | Method for synthesizing ethylene and oxalic acid from acetylene by bipolar electrochemical technology | |
| CN102560522A (en) | Method for electrochemically preparing potassium ferrate with increased yield | |
| CN117867532A (en) | A method for synthesizing p-aminophenol and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |