WO2020220183A1 - Réacteur à membrane électrocatalytique à étages multiples, son utilisation et procédé associé dans une réaction électrochimique organique - Google Patents

Réacteur à membrane électrocatalytique à étages multiples, son utilisation et procédé associé dans une réaction électrochimique organique Download PDF

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WO2020220183A1
WO2020220183A1 PCT/CN2019/084950 CN2019084950W WO2020220183A1 WO 2020220183 A1 WO2020220183 A1 WO 2020220183A1 CN 2019084950 W CN2019084950 W CN 2019084950W WO 2020220183 A1 WO2020220183 A1 WO 2020220183A1
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chamber
porous membrane
stage
membrane
electrode
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PCT/CN2019/084950
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English (en)
Chinese (zh)
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李建新
张玉军
王虹
尹振
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天津工业大学
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Priority to PCT/CN2019/084950 priority Critical patent/WO2020220183A1/fr
Priority to CN201990000272.8U priority patent/CN211886777U/zh
Publication of WO2020220183A1 publication Critical patent/WO2020220183A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • 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
    • 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
    • C25B3/25—Reduction
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • This application belongs to the technical field of organic electrochemical synthesis, and in particular relates to a multi-stage electrocatalytic membrane reactor and its application and method in organic electrochemical reactions.
  • Organic electrochemical synthesis uses electrons as reagents. It is a new technology that realizes the synthesis of organic substances through the gains and losses of electrons. It is called "ancient method, new technology” and has been widely used in medicine, Perfume, auxiliary agent, dye intermediate and other industries.
  • membrane separation As a new type of separation technology with high efficiency, energy saving and environmental friendliness, membrane separation has been widely used in various fields such as petroleum, chemical industry, medicine, biology, food and water treatment.
  • the electrochemical technology and membrane separation technology are combined to construct an electrocatalytic membrane reactor.
  • the high specific surface area of the porous membrane electrode is used to load more catalysts to further increase the number of active sites.
  • the process of reactants passing through the membrane surface strengthens the The flow mass transfer effect increases the efficiency of electron transfer, and the product is separated from the membrane surface in time to prevent excessive oxidation, while improving the conversion rate of raw materials and the selectivity of target products.
  • reactors there are many types of reactors in the chemical industry.
  • Traditional reactors include: tubular reactors, tank reactors, tower reactors, fixed bed reactors, fluidized bed reactors, etc. These reactors will involve one or more problems of high temperature, high pressure, oxidant, reducing agent, and catalyst loss. In the future energy saving, green and high efficiency process requirements, there is an urgent need to develop new and efficient new reactors.
  • Chinese invention patent CN101597096A discloses an electrocatalytic membrane reactor, which includes adjustable DC stabilized power supply, connecting wires, electrocatalytic composite membrane, auxiliary electrode, liquid tank, vacuum gauge, peristaltic pump, permeate tank and other parts.
  • Chinese invention patent CN102634815A discloses a method for preparing sodium tetrafluoropropionate by oxidation of tetrafluoropropanol by electrocatalytic membrane. It is characterized in that reaction and separation are integrated to synthesize sodium tetrafluoropropionate.
  • the invention uses a titanium-based electrocatalytic membrane as an anode and an auxiliary electrode as a cathode to form an electrocatalytic membrane reactor; the reactant or feed liquid is a mixed aqueous solution of tetrafluoropropanol and sodium salt.
  • the fluoropropanol is catalyzed and oxidized to the intermediate product tetrafluoropropionic acid on the surface of the membrane.
  • the tetrafluoropropionic acid reacts with the electrolyte sodium salt in the feed solution to produce sodium tetrafluoropropionate.
  • the reactant tetrafluoropropanol and the product sodium tetrafluoropropionate are separated in real time; the membrane permeate is collected, the pH value is adjusted to about 7-8, and then concentrated to obtain the sodium tetrafluoropropionate product.
  • Chinese invention patent CN103436910A discloses a method for preparing gluconic acid and glucaric acid by electrocatalytic membrane oxidation of glucose.
  • the utility model is characterized in that the electrocatalytic membrane is used as the anode, and the auxiliary electrode is used as the cathode.
  • the electrocatalytic membrane reactor is constructed by connecting with a stabilized voltage through a wire to catalyze the oxidation of glucose.
  • Chinese invention patent CN104032327A discloses a method for preparing cyclohexanol and cyclohexanone by electrocatalytic oxidation of alkanes.
  • the method uses a porous metal electrocatalytic membrane loaded with metal oxides as the anode, and the auxiliary electrode is the cathode to form an electrocatalytic membrane reactor;
  • the reaction raw material liquid is a mixed aqueous solution of cyclohexane, organic solvent and electrolyte, at a certain working voltage and current
  • cyclohexane is catalyzed and oxidized by metal oxides on the membrane surface and in the pores to the products cyclohexanol and cyclohexanone.
  • this application proposes a multi-stage electrocatalytic membrane reactor and its application and method in organic electrochemical reactions.
  • One aspect of this application provides a multi-stage electrocatalytic membrane reactor, including:
  • the reactor body which has a chamber for electrochemical reaction
  • a pair of porous membrane electrodes of two or more stages are arranged in the chamber;
  • the pair of porous membrane electrodes includes a porous membrane electrode and an auxiliary electrode arranged oppositely;
  • the porous membrane electrode includes a supporting membrane and a support on the Support the catalyst on the membrane;
  • a feeding unit which is arranged on one side of the reactor body and communicates with the chamber, and is used to provide reaction raw materials to the chamber;
  • a product collection unit which is arranged on the other side of the reactor body and communicates with the chamber, and is used to collect products generated in the chamber;
  • the power source, the positive electrode and the negative electrode of which are respectively connected to the porous membrane electrode and the auxiliary electrode, or the auxiliary electrode and the porous membrane electrode of each stage of the porous membrane electrode pair, to form an electrode pair.
  • the porous membrane electrode pairs of two or more stages are arranged in a manner such that the cathode and the anode are staggered with each other, and the step spacing of adjacent porous membrane electrode pairs is 1-100 mm.
  • the supporting membrane is one of a titanium membrane, a nickel membrane, and a carbon membrane
  • the porous membrane electrode has an average pore diameter of 0.1-10 ⁇ m, a thickness of 1-20 mm, and a porosity of 5-40%.
  • the catalyst is an electrochemical oxidation catalyst or an electrochemical reduction catalyst;
  • the electrochemical oxidation catalyst includes CeO 2 , MnO 2 , Mn 2 O 3 , Mn 3 O 4 , MoO 3 , PbO 2 , SnO 2 , TiO 2.
  • the electrochemical reduction catalyst includes at least one of Au, Pb, In, Cd, Sn, Zn, Ru, Cu, and oxides thereof.
  • the auxiliary electrode is one of stainless steel or titanium metal.
  • a sampling point for sampling is provided between each stage of the porous membrane electrode pair or multiple stages of the porous membrane electric stage pair.
  • the multi-stage electrocatalytic membrane reactor is further provided with a temperature control device, and the temperature control device is arranged outside the feeding unit and/or the reactor body.
  • the feeding unit is in communication with the lower end of the chamber, and the product collection unit is in communication with the upper end of the chamber, so that the entire system circulates in a bottom-up path.
  • a pump is provided on the communication path between the feeding unit and the chamber for pumping reaction raw materials into the chamber of the reactor body.
  • Another aspect of this application provides an application of the multi-stage electrocatalytic membrane reactor described in any one of the above in organic electrochemical oxidation or organic electrochemical reduction reactions.
  • the organic matter oxidized in the organic electrochemical oxidation reaction includes alcohols, aldehydes, alkanes, and phenols; the alcohols include methanol, ethanol, propanol, butanol, cyclohexanol, benzyl alcohol, etc.
  • the aldehydes include one of benzaldehyde and pentahydroxymethyl furfural; the alkanes include one of pentane, hexane, cyclohexane, and octane; the phenols include phenol.
  • the organic matter reduced in the organic electrochemical reduction reaction includes acid gas and organic acid;
  • the acid gas includes CO 2 ;
  • the organic acid includes formic acid, acetic acid, butyric acid, benzoic acid, fatty acid, and unsaturated fatty acid Or a kind of grease.
  • Another aspect of the present application provides a method for performing organic electrochemical oxidation or organic electrochemical reduction in the multi-stage electrocatalytic membrane reactor according to any one of the above, and the method includes the following steps:
  • the porous membrane electrode pair According to the product, select the support membrane of the porous membrane electrode and the type of the catalyst supported on it, and confirm the auxiliary electrode type; the two or more porous membrane electrode pairs are cathode and anode Arranged in a staggered manner in the chamber of the reactor body;
  • reaction raw materials are selected and placed in the feeding unit, and the corresponding electrolyte solution is placed in the chamber;
  • the product generated in the chamber is collected by the product collection unit.
  • the reaction raw materials are pumped in through the lower end of the chamber, and sequentially pass through various levels of porous membrane electrode pairs from bottom to top to perform a multi-stage catalytic electrochemical reaction, and the product is collected by the product collection unit through the upper end of the chamber.
  • the operating voltage range of the control power supply is 0.5-20V
  • the control current density range is 0.5-20mA/cm 2 .
  • the residence time of the reaction raw materials in the chamber is controlled by a pump to be 1 to 50 minutes.
  • the method further includes controlling the temperature in the feeding unit and/or the chamber to be 0-80°C through a temperature control device arranged outside the feeding unit and/or the reactor body.
  • the method further includes the step of collecting samples at different positions for detection by sampling points arranged between the porous membrane electrode pairs at each stage or the porous membrane electrical stage pairs at multiple stages.
  • the catalyst is immobilized on a supporting membrane with good conductivity to form a porous membrane electrode, which has good stability and can be used repeatedly, and the electrochemical oxidation or reduction reaction can be achieved by installing two or more porous membrane electrode pairs. High efficiency.
  • the reaction is mainly controlled by voltage or current density, the voltage or current density used is low, and the energy consumption is low.
  • Fig. 1 is a schematic diagram of the structure of a multi-stage electrocatalytic membrane reactor of this application.
  • the embodiments of the present application provide a multi-stage electrocatalytic membrane reactor, as shown in FIG. 1, including:
  • the reactor body 1 has a chamber 11 for electrochemical reaction
  • the porous membrane electrode pair 2 of two or more stages is arranged in the chamber 11; the porous membrane electrode pair includes a porous membrane electrode and an auxiliary electrode arranged oppositely; the porous membrane electrode includes a supporting membrane and a load Catalyst on the supporting membrane;
  • a feeding unit 3 which is arranged on one side of the reactor body 1 and communicates with the chamber 11, and is used to provide reaction raw materials to the chamber 11;
  • the product collection unit 4 which is arranged on the other side of the reactor body 1 and communicates with the chamber 11, is used to collect the products generated in the chamber 11;
  • the power supply 5 has its positive electrode and negative electrode respectively connected to the porous membrane electrode and the auxiliary electrode, or the auxiliary electrode and the porous membrane electrode of each stage of the porous membrane electrode pair 2 to form an electrode pair.
  • 21 in FIG. 1 is an anode connected to the positive electrode of the battery
  • 22 is a cathode connected to the negative electrode of the battery.
  • the porous membrane electrode in the porous membrane electrode pair 2 is used as the cathode 22
  • the auxiliary electrode is used as the anode 21
  • the porous membrane electrode in the porous membrane electrode pair 2 It is used as the anode 21, and the auxiliary electrode is used as the cathode 22.
  • the multi-stage electrocatalytic membrane reactor provided by the above-mentioned embodiments is provided with two or more porous membrane electrode pairs, and the catalyst is immobilized on the supporting membrane, which has good stability and can be used repeatedly, and the reactants will gradually Grade through the porous membrane electrode pair to carry out the organic electrosynthesis reaction, to achieve the high efficiency of electrochemical oxidation or reduction; use electrons as the "reagent”, do not use strong oxidizing or strong reducing reagents, polluting any pollutant discharge, and environmental protection; It has the advantages of high efficiency, high selectivity, simple operation, etc., and is suitable for industrial production and application.
  • the porous membrane electrode pairs 2 of two or more stages are arranged in such a way that the cathode 22 and the anode 21 are staggered with each other, and the step distance between adjacent porous membrane electrode pairs 2 is 1-100 mm.
  • the electrode pairs are arranged in the manner of anode 21, cathode 22, anode 21, cathode 22, etc., to achieve stepwise oxidation or reduction reactions.
  • the stage spacing within the above range, on the one hand, the overall volume of the reactor can be controlled, and on the other hand, the continuity of the stepwise organic electrosynthesis reaction can be ensured; it is understandable that the adjacent porous membrane electrode pair 2
  • the spacing can also be 20mm, 40mm, 60mm, 80mm, etc., and those skilled in the art can select within the above range.
  • the supporting membrane is one of a titanium membrane, a nickel membrane, and a carbon membrane
  • the porous membrane electrode has an average pore diameter of 0.1-10 ⁇ m, a thickness of 1-20 mm, and a porosity of 5 ⁇ 40%.
  • a material with good conductivity is selected as the supporting film to ensure the progress of the electrochemical reaction and can be used repeatedly. Controlling the average pore size, thickness and porosity of the porous membrane electrode within the above range can ensure that the reactants smoothly permeate the porous membrane electrode for electrochemical reactions, and are beneficial to the screening and adsorption of the membrane, and increase electrons. The transfer efficiency is enhanced by convection and mass transfer.
  • the average pore diameter of the porous membrane electrode can also be 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 6 ⁇ m, 8 ⁇ m, etc.
  • the thickness can also be 5mm, 10mm, 15mm, etc.
  • the porosity can also be 10%, 20%. %, 30%, etc.
  • the catalyst is an electrochemical oxidation catalyst or an electrochemical reduction catalyst;
  • the electrochemical oxidation catalyst includes CeO 2 , MnO 2 , Mn 2 O 3 , Mn 3 O 4 , MoO 3 , PbO 2 At least one of SnO 2 , TiO 2 , and V 2 O 5 ;
  • the electrochemical reduction catalyst includes at least one of Au, Pb, In, Cd, Sn, Zn, Ru, Cu and their oxides .
  • high-activity electrochemical oxidation catalyst and reduction catalyst are selected, and on the basis of the prior art, the reduction function of the reactor is realized.
  • the auxiliary electrode is one of stainless steel or titanium metal.
  • each stage of the porous membrane electrode pair 2 or multiple stages of the porous membrane electrode pair 2 is provided with a sampling point 6 for sampling, which can detect samples taken at different positions, thereby Control the reaction process, in addition to kinetic studies.
  • the multi-stage electrocatalytic membrane reactor is further provided with a temperature control device 7 which is provided outside the feed unit 3 and/or the reactor body 1.
  • the temperature affects the conversion rate of the electrochemical reaction and the catalytic efficiency of the catalyst.
  • the temperature control device 7 is provided to better realize the control of the organic electrochemical synthesis reaction.
  • the temperature control device 7 may be an ordinary instrument or be controlled by PLC.
  • the feeding unit 3 communicates with the lower end of the chamber 11, and the product collection unit 4 communicates with the upper end of the chamber 11, so that the entire system is in a bottom-up manner.
  • Path circulation This embodiment takes fluid mechanics into consideration and is verified by experiments. The bottom-up path shown in Fig. 1 has the best effect.
  • the reaction raw materials enter the chamber 11 from the lower end of the reactor body 1, and pass through the porous membrane electrode pair 2 from bottom to top to chemically react, and the final product enters the product collection unit 4 from the upper end of the chamber 11.
  • other circulation paths such as left to right, right to left, front to back, back to front, top to bottom are also feasible. of.
  • a pump 8 is provided on the communication path between the feeding unit 3 and the chamber 11 for pumping reaction raw materials into the chamber 11 of the reactor body 1.
  • a pump 8 is provided on the communication path between the feeding unit 3 and the chamber 11 for pumping reaction raw materials into the chamber 11 of the reactor body 1.
  • a control valve 9 is provided on the communication path between the chamber and the feed unit 3 and the product collection unit 4 to control the supply of reaction raw materials and the output of products.
  • Another aspect of the embodiments of the present application provides an application of the multi-stage electrocatalytic membrane reactor according to any of the above embodiments in organic electrochemical oxidation or organic electrochemical reduction reactions.
  • the organic matter oxidized in the organic electrochemical oxidation reaction in the above application includes alcohols, aldehydes, alkanes, and phenols; the alcohols include methanol, ethanol, propanol, butanol, cyclohexanol, and benzyl alcohol.
  • the aldehydes include one of benzaldehyde and pentahydroxymethyl furfural; the alkanes include one of pentane, hexane, cyclohexane, and octane; the phenols include phenol.
  • the organic matter reduced in the organic electrochemical reduction reaction of the above application includes acid gas and organic acid; the acid gas includes CO 2 ; the organic acid includes formic acid, acetic acid, butyric acid, benzoic acid, fatty acid, unsaturated fatty acid or A kind of grease.
  • Another aspect of the embodiments of the present application provides a method for performing organic electrochemical oxidation or organic electrochemical reduction in the multi-stage electrocatalytic membrane reactor according to any of the above embodiments.
  • the method includes the following steps:
  • Configure the porous membrane electrode pair 2 According to the product, select the support membrane of the porous membrane electrode and the type of the catalyst supported on it, and confirm the auxiliary electrode type; as shown in Figure 1, the two or more porous The membrane electrode pair 2 is arranged in the chamber 11 of the reactor body 1 in a manner that the cathode and the anode are staggered with each other;
  • reaction raw materials are selected and placed in the feeding unit 3, and the corresponding electrolyte solution is placed in the chamber;
  • the product generated in the chamber 11 is collected by the product collection unit 4.
  • the reaction raw materials are pumped in through the lower end of the chamber 11, and pass through the porous membrane electrode pairs 2 at various levels from bottom to top to perform a multi-stage catalytic electrochemical reaction, and the product is processed through the upper end of the chamber 11.
  • the collection unit 4 collects.
  • the operating voltage range of the control power supply 5 is 0.5-20 V
  • the control current density range is 0.5-20 mA/cm 2 .
  • the reaction is mainly controlled by voltage or current density, the voltage or current density used is low, and the energy consumption is low.
  • the method further includes controlling the temperature in the feeding unit 3 and/or the chamber 11 to be 0 through a temperature control device 7 provided outside the feeding unit 3 and/or the reactor body 1. ⁇ 80°C.
  • the residence time of the reaction raw materials in the chamber 11 is controlled by the pump 8 to be 1-50 min.
  • the method further includes collecting samples at different positions for detection by setting a sampling point 6 between each stage of the porous membrane electrode pair 2 or multiple stages of the porous membrane electric stage pair 2 A step of.
  • the electrochemical oxidation or reduction method provided in the above embodiments is carried out using a multi-stage electrocatalytic membrane reactor.
  • the type, number, and distribution of porous membrane electrodes are controlled, and the voltage range, current density, and raw materials of the reaction are controlled.
  • Residence time, temperature, etc. so as to control the conversion rate of raw materials and the yield of products, and realize the high efficiency of electrochemical oxidation or reduction.
  • it operates under normal temperature and pressure, and does not use strong oxidants or strong reducing agents. It is highly efficient, green, simple to operate, safe and reliable, suitable for industrial implementation, and can be widely used in the organic electrosynthesis industry.
  • the porous titanium film with in-situ supported Cu nano-catalyst is used as the cathode (high electrochemical reduction activity), and the auxiliary conductive titanium metal mesh is used as the anode (only as the counter electrode, forming a current path, electrochemical oxidation is small), and the cathode is used
  • a five-stage electrocatalytic membrane reactor is assembled in a staggered manner with the anode, which has a strong electrochemical reduction effect. Stable current is provided by the DC power supply.
  • the raw material liquid enters the chamber from the bottom of the reactor body under the action of the peristaltic pump, and gradually penetrates each pair of porous membrane electrode pairs to realize the multi-stage catalytic electrochemical reaction, and finally enters the permeate Tank (product collection unit).
  • the electrolyte is 15g/L Na 2 SO 4 , the initial concentration of acetic acid is 20 mmol/L, the current density of the membrane reactor is 1.0 mA/cm 2 , and the residence time is 10 min.
  • the temperature is used as a variable to control the multi-stage electrocatalytic membrane reactor. It can be seen from Table 1 that the temperature increased from 15°C to 35°C, correspondingly, the conversion rate of acetic acid first increased and then decreased. Among them, when the temperature is 25°C, the conversion rate of acetic acid reaches 95.5%, and the selectivity of ethanol is greater than 99%.
  • the porous titanium film with Au nano-catalyst supported in situ is used as the cathode (high electrochemical reduction activity), and the auxiliary conductive titanium metal mesh is used as the anode (only as the counter electrode, forming a current path, with little electrochemical oxidation), using the cathode
  • a forty-stage electrocatalytic membrane reactor is assembled in a staggered manner with the anode, which has a strong electrochemical reduction effect. Stable current is provided by the DC power supply.
  • the raw material liquid enters the chamber from the bottom of the reactor body under the action of the peristaltic pump, and gradually penetrates each pair of porous membrane electrode pairs to realize the multi-stage catalytic electrochemical reaction, and finally enters the permeate tank.
  • the Na 2 CO 3 solution is fed with a saturated CO 2 solution, the current density of the membrane reactor is 1.0 mA/cm 2 , and the residence time is 20 min.
  • the temperature is 25°C, the CO 2 conversion rate reaches 96.0%, and the selectivity between formic acid and CO is 95%, of which CO accounts for about 10%.
  • the porous titanium membrane with in-situ supported V 2 O 5 nano-catalyst is used as the anode (with high electrochemical oxidation activity), and the auxiliary conductive stainless steel mesh is used as the cathode (only as the counter electrode, forming a current path, electrochemical reduction effect is small),
  • a ten-stage electrocatalytic membrane reactor is assembled in a staggered cathode and anode manner, which has strong electrochemical oxidation. Stable current is provided by the DC power supply.
  • the raw material liquid enters the chamber from the bottom of the reactor body under the action of the peristaltic pump, and gradually penetrates each pair of porous membrane electrode pairs to realize the multi-stage catalytic electrochemical reaction, and finally enters the permeate tank. Under normal pressure, the initial concentration of cyclohexanol is 5mmol/L, the electrolyte is 5g/L NaOH, the residence time is 40min, and the reaction temperature is 30°C.
  • the current density is used as a variable to control the multi-stage electrocatalytic membrane reactor. It can be seen from Table 2 that as the current density increases, the conversion efficiency first increases and then decreases. Among them, when the current density is 2.0 mA/cm 2 , the conversion rate of cyclohexanol reaches 95.0%, and the selectivity of cyclohexanone is as high as 99.4%. The good performance is better than most precious metal catalysts reported in the literature.
  • the porous titanium membrane with in-situ supported V 2 O 5 nano-catalyst is used as the anode (with high electrochemical oxidation activity), and the auxiliary conductive stainless steel mesh is used as the cathode (only as the counter electrode, forming a current path, electrochemical reduction effect is small),
  • the multi-stage electrocatalytic membrane reactor is assembled separately by adopting the alternate method of cathode and anode. Stable current is provided by the DC power supply.
  • the raw material liquid enters the chamber from the bottom of the reactor body under the action of the peristaltic pump, and gradually penetrates each pair of porous membrane electrode pairs to realize the multi-stage catalytic electrochemical reaction, and finally enters the permeate tank.
  • the initial concentration of cyclohexane is 20mmol/L
  • the electrolyte is 5g/L NaOH
  • the current density of the membrane reactor is 1.0mA/cm
  • the residence time is 10min
  • the temperature is 30 °C.
  • the multi-stage reactor is controlled with the number of porous membrane electrode pairs (number of porous membrane electrode pairs) as a variable. It can be seen from Table 3 that the more stages of the porous membrane electrode pair, the higher the conversion efficiency. Among them, when the number of reactor stages is 50, the conversion rate of cyclohexane reaches 96.0%, and the total selectivity of cyclohexanol and cyclohexanone is as high as 99.9%.
  • Cyclohexane is a bulk chemical raw material. Cyclohexanone and cyclohexanol (KA oil) are prepared by oxidation of cyclohexane, and adipic acid is further oxidized to produce nylon 66. At present, the industrially oxidizing cyclohexane to prepare KA oil mainly includes cobalt salt oxidation, boric acid oxidation, and non-catalytic oxidation.
  • Chinese invention patent CN104032327A also discloses a method for preparing cyclohexanol and cyclohexanone by electrocatalytic oxidation of alkanes, but the conversion rate of cyclohexane is only 9.37%, and the total selectivity of cyclohexanol and cyclohexanone is 94.2%.
  • the conversion rate of cyclohexane in this example is much higher than the conversion rate of the existing method, and can be as high as 96.0%, which can realize the efficient conversion of cyclohexane.
  • the total selectivity of cyclohexanol and cyclohexanone is as high as 99.9%, the reaction efficiency is obviously improved, the good performance is better than most cyclohexane oxidation processes reported in the literature, and it has a wide range of application prospects.

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Abstract

La présente invention concerne un réacteur à membrane électrocatalytique à étages multiples et son utilisation et un procédé associé dans une réaction électrochimique organique. Le réacteur à membrane électrocatalytique à étages multiples comprend : un corps de réacteur, ayant une chambre pour effectuer une réaction électrochimique ; au moins deux étages de paires d'électrodes à membrane poreuse, disposés dans la chambre ; une unité d'alimentation, disposée sur un côté du corps de réacteur, étant en communication avec la chambre et utilisée pour fournir des matières premières de réaction à la chambre ; et une unité de collecte de produit, disposée de l'autre côté du corps de réacteur, étant en communication avec la chambre et utilisée pour collecter des produits générés dans la chambre ; et une alimentation électrique, l'électrode positive et l'électrode négative de celle-ci étant respectivement connectées à une électrode à membrane poreuse et à une électrode auxiliaire ou à une électrode auxiliaire et à une électrode à membrane poreuse de chaque étage de la paire d'électrodes à membrane poreuse, de manière à former des paires d'électrodes. Le réacteur à membrane électrocatalytique à étages multiples de la présente invention présente les avantages d'un taux de conversion élevé et d'une stabilité élevée et d'être sûr, fiable, écologique, respectueux de l'environnement et réutilisable.
PCT/CN2019/084950 2019-04-29 2019-04-29 Réacteur à membrane électrocatalytique à étages multiples, son utilisation et procédé associé dans une réaction électrochimique organique WO2020220183A1 (fr)

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CN201990000272.8U CN211886777U (zh) 2019-04-29 2019-04-29 多级电催化膜反应器

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PCT/CN2019/084950 WO2020220183A1 (fr) 2019-04-29 2019-04-29 Réacteur à membrane électrocatalytique à étages multiples, son utilisation et procédé associé dans une réaction électrochimique organique

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