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WO2018062952A1 - Procédé complexe pour réduire le dioxyde de carbone et produire de l'acide formique et du sulfate de potassium, et appareil pour ledit procédé complexe - Google Patents

Procédé complexe pour réduire le dioxyde de carbone et produire de l'acide formique et du sulfate de potassium, et appareil pour ledit procédé complexe Download PDF

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Publication number
WO2018062952A1
WO2018062952A1 PCT/KR2017/010997 KR2017010997W WO2018062952A1 WO 2018062952 A1 WO2018062952 A1 WO 2018062952A1 KR 2017010997 W KR2017010997 W KR 2017010997W WO 2018062952 A1 WO2018062952 A1 WO 2018062952A1
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potassium sulfate
formic acid
carbon dioxide
formate
reactor
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Korean (ko)
Inventor
신운섭
김범식
권순일
박미정
최명호
임정애
최지나
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Korea Research Institute of Chemical Technology KRICT
Sogang University Research Foundation
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Korea Research Institute of Chemical Technology KRICT
Sogang University Research Foundation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof

Definitions

  • the present application relates to a combined process of carbon dioxide reduction and formic acid and potassium sulfate production, and to an apparatus for the combined process.
  • Formic acid can be used for leather treatment, rubber coagulant, dyeing aid, hair dye, leather tanning, medicine, epoxy plasticizer, plating, disinfectant, fragrance, electroplating, dyeing and textile industry, organic raw materials, and inorganic / organic compound manufacturing. It is a compound used in the field. It is used 20,000 tons annually in Korea, and is mainly used in the process of producing leather products, and is produced in BASF, Kemira, and China, and consumes about 700,000 tons annually.
  • Conventional formic acid production methods include sodium formate technology, methyl formate hydrolysis technology, and polyhydric alcohol process by-products developed by BASF, Germany.
  • Many of the existing formic acid production processes are hydrolysed by synthesizing methyl formate from methanol and carbon monoxide as well as complex processes, and are synthesized under high temperature and high pressure conditions of 80 °C and 40 atm. There is a problem that the process must be high and continuous.
  • since there is a need for the continuous supply of harmful carbon monoxide a large amount of water is required for hydrolysis has a problem of wastewater treatment after use.
  • potassium sulfate can be used as a potassium fertilizer in crops in which chlorinated fertilizer cannot be used, and can be combined with various fertilizers because it has almost no smell.
  • the potassium sulfate is used as a fertilizer, the fertilizer effect appears quickly, and is known as a basic fertilizer together with ammonium sulfate and phosphoric acid peroxide.
  • the potassium sulfate can be used as a raw material of potassium alum, potassium bromide or pharmaceuticals for use other than the fertilizer, and is used in the world more than 4 million tons per year.
  • the existing sulfate, potassium sulfate was added to the potassium chloride is heated at high temperature to determine a metathesis from hydrochloric acid and a method of creating a potassium sulfate, Kai nitro, or key ISERE seat aqueous solution was added to potassium chloride to (MgSO 4 and H 2 O)
  • the method of making it precipitate, and the method of adding sulfuric acid to aqueous potassium chloride solution, making potassium hydrogen sulfate, crystallizing by adding equivalent potassium chloride, and recrystallizing in aqueous solution, etc. are mentioned.
  • About 50% of the process for producing potassium sulfate is a method of adding sulfuric acid to potassium chloride and heating at high temperature (600 ° C. to 700 ° C.), which is a Mannheim process for producing potassium sulfate. Since the Mannheim process uses a lot of energy, the production cost is high, and only a small process is possible.
  • the present inventors electrochemically reduce carbon dioxide to obtain a high concentration of formic acid (potassium formate, HCOOK), and then, when the formic acid is converted to formic acid, the separation and acidification process is performed effectively, high purity formic acid and potassium sulfate It was found that it can be obtained at the same time.
  • the new process is environmentally friendly and consumes less energy than existing processes for commercially producing formic acid.
  • US patent US 08562811 discloses a process for producing formic acid as an electrochemical process of carbon dioxide.
  • the present application provides a combined process of carbon dioxide reduction and formic acid and potassium sulfate production, and an apparatus for the combined process.
  • the first reactor for producing a formate by electrochemical reduction of carbon dioxide in an electrolyte containing potassium sulfate;
  • a concentrator connected to the first reactor and concentrating an electrolyte solution containing the formate and potassium sulfate prepared in the first reactor to a solid containing formate and potassium sulfate;
  • a second reactor connected to the concentrator, for adding sulfuric acid to the solid containing formate and potassium sulfate obtained in the concentrator to prepare a solution containing formic acid and potassium sulfate solids;
  • a separator connected to the second reactor and including a separator for separating the solution containing the formic acid and the potassium sulfate solid prepared in the second reactor into a formic acid-containing solution and potassium sulfate solid, respectively.
  • an apparatus for a complex process of preparing potassium sulfate is an apparatus for a complex process of preparing potassium sulfate.
  • a formate is obtained by electrochemical reduction of carbon dioxide in an electrolyte solution containing potassium sulfate in a first reactor, and the electrolyte solution including the formate and potassium sulfate obtained from the first reactor is obtained.
  • a complex process of producing formate by reduction of carbon dioxide, which is a greenhouse gas, and converting the formate into formic acid and potassium sulfate promotes reduction of carbon dioxide, which is a greenhouse gas, and proceeds in an aqueous solution. Because of the process, it is environmentally friendly and can reduce energy costs compared to the energy costs of the formic acid production process and the potassium sulfate production process.
  • the conventional formic acid manufacturing process is a high temperature process using CO and H 2 generated on the basis of petrochemical, whereas the complex process of the present application is an environmentally friendly and greenhouse gas gas at room temperature using CO 2 It is a process to reduce.
  • the reaction may be terminated in one step to obtain only formate, and the reaction may be performed up to two steps to obtain formic acid and potassium sulfate.
  • the obtained formic acid and potassium sulfate are very useful because of their high purity.
  • FIG. 1 is a schematic view showing a complex process of carbon dioxide reduction and formic acid and potassium sulfate production in one embodiment of the present application.
  • Figure 2 in one embodiment of the present application, is a process chart showing a combined process of carbon dioxide reduction and formic acid and potassium sulfate production.
  • 3 is, in one embodiment of the present application, a first reactor system for electrochemical CO 2 conversion.
  • FIG. 4 is a photograph showing a metal hydroxide supply chamber in a first reactor in one embodiment of the present application.
  • FIG. 6 shows electrolysis of CO 2 by amalgam coated foamed copper electrodes in a first reactor with 0.5 MK 2 SO 4 , in one embodiment of the present disclosure.
  • FIG. 7 shows long-term electrolysis of CO 2 in a first reactor (0.5 MK 2 SO 4 ) with a pH feedback system, in one embodiment of the present disclosure.
  • FIG. 8 is a graph showing a result of dissolving formic acid in a solvent using formic acid as a solvent and performing acidification with sulfuric acid in one example of the present application.
  • FIG. 9 illustrates the formic acid production process and energy consumption of each of Examples and Comparative Examples in Examples and Comparative Examples.
  • the term “combination of these” included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of the constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.
  • the first reactor for producing a formate by electrochemical reduction of carbon dioxide in an electrolyte containing potassium sulfate;
  • a concentrator connected to the first reactor and concentrating an electrolyte solution containing the formate and potassium sulfate prepared in the first reactor to a solid containing formate and potassium sulfate;
  • a second reactor connected to the concentrator, for adding sulfuric acid to the solid containing formate and potassium sulfate obtained in the concentrator to prepare a solution containing formic acid and potassium sulfate solids;
  • a separator connected to the second reactor, the separator comprising separating the solution containing the formic acid and the potassium sulfate solid prepared in the second reactor into a formic acid-containing solution and potassium sulfate solid, respectively.
  • a device for a complex process of preparing potassium is provided.
  • a formate is obtained by electrochemical reduction of carbon dioxide in an electrolyte solution containing potassium sulfate in a first reactor, and the electrolyte solution including the formate and potassium sulfate obtained from the first reactor is obtained. Transferred to a concentrator and concentrated to separate the formate and potassium sulfate solids respectively, and the solid containing formate and potassium sulfate obtained in the concentrator was transferred into a second reactor to add sulfuric acid to include formic acid and potassium sulfate solids.
  • Carbon dioxide reduction and formic acid comprising separating the solution comprising the formic acid and potassium sulfate solids obtained in the second reactor into a separator and separating the formic acid-containing solution and the potassium sulfate solid, respectively;
  • a complex process of preparing potassium sulfate comprising separating the solution comprising the formic acid and potassium sulfate solids obtained in the second reactor into a separator and separating the formic acid-containing solution and the potassium sulfate solid, respectively;
  • the first reactor 100 includes an electrolyte containing potassium sulfate, a cathode, an anode, and a membrane separating the cathode and the anode.
  • the first reactor system is connected to the reduction electrode unit to reduce the electrode portion injection line 160 for supplying carbon dioxide and a solution of the reduction electrode portion to the reduction electrode portion and the reduction to collect the materials supplied to the reduction electrode portion
  • a first chamber 150 connected to an electrode collection line 170, an anode electrode injection line 210 connected to the anode electrode to supply an anode electrode solution to the anode electrode, and an anode electrode
  • a second chamber 200 connected to the anode portion collection line 220 for collecting the prepared solution.
  • an electrolytic solution containing the formate and potassium sulfate is obtained through an electrochemical reduction reaction of carbon dioxide, and the electrolyte solution including the formate and potassium sulfate is obtained by using a concentrator injection line 250.
  • the electrolytic solution containing the formate and potassium sulfate is concentrated in the concentrator 300 to obtain a solid containing potassium formate and potassium sulfate, and the solid containing the formate and potassium sulfate is in the second reactor injection line ( Along the 320 is injected into the second reactor 350.
  • the second reactor (350) system includes a third chamber (400) for injecting sulfuric acid into the second reactor (350) by sulfuric acid injection line (410), the formate injected from the concentrator (300) And a solid containing potassium sulfate may react with the sulfuric acid in the second reactor 350 to obtain a solution containing formic acid and potassium sulfate solids.
  • the solution containing formic acid and potassium sulfate is injected into the separator 450 along the separator injection line 420, and the solution containing the formic acid and potassium sulfate solid in the separator 450 contains a formic acid-containing solution and potassium sulfate.
  • Each separated into solids, and the separated potassium sulfate solids are collected along the second potassium sulfate collection line 460, and the separated formic acid-containing solution is collected along the formic acid collection line 470, respectively.
  • the concentration may be performed by distillation, but is not limited thereto.
  • the purity of each of the formic acid and the potassium sulfate may be at least about 85% high purity independently of each other.
  • the purity of each of the formic acid and the potassium sulfate is independently about 85% to about 99.9%, about 86% to about 99.9%, about 87% to about 99.9%, about 88% to about 99.9%, about 89 %
  • the purity of each of the formic acid and the potassium sulfate is independently about 85% to about 99.9%, about 86% to about 99.9%, about 87% to about 99.9%, about 88% to about 99.9%, about 89 %
  • the purity of each of the formic acid and the potassium sulfate is independently about 85% to about 99.9%, about 86% to about 99.9%, about 87% to about 99.9%, about 88% to about 99.9%, about 89 %
  • the purity of each of the formic acid and the potassium sulfate is independently about 85% to about 99.9%, about 86% to about 99.
  • the first reactor is an electrochemical reduction reactor of carbon dioxide comprising an electrolyte solution containing potassium sulfate, an anode portion and a reducing electrode portion, supplying carbon dioxide to the cathode portion, the anode A metal hydroxide is continuously supplied to the part, and a voltage or a current is applied to the cathode and the anode to reduce the carbon dioxide so that the formate is continuously obtained.
  • the electrolytic solution included in the cathode electrode solution and the anode electrode solution comprises a selected from the group consisting of K 2 SO 4 , KHCO 3 , KCl, KOH, and combinations thereof It may be, but is not limited thereto.
  • KHCO 3 when KHCO 3 is used as the electrolyte, KCl may be used as an auxiliary electrolyte to increase conductivity, but is not limited thereto.
  • KHCO 3 and KCl are used as the electrolyte, carbon dioxide can be converted for a long time with stable current efficiency.
  • Cl - ions are transferred to the anode, and chlorine (Cl 2 ) is formed. May occur. The generation of chlorine may cause problems such as metal corrosion or tube melting.
  • the efficiency when using only KHCO 3 as the electrolyte, the efficiency may be reduced by about 10% because the conductivity is reduced. In one embodiment of the present application, when using K 2 SO 4 as the electrolyte, the efficiency is increased by about 5% to about 10% than when using KHCO 3 and KCl as the electrolyte, since chlorine does not occur, corrosion Problems can be solved. However, when K 2 SO 4 is used to obtain a formate of about 0.5 M or more, the K 2 SO 4 may precipitate. Because of this, K 2 SO 4 is precipitated inside the glass frit to supply the CO 2 gas, CO 2 is not properly supplied or the solution may not circulate due to the crystal. In one embodiment of the present application, by using K 2 SO 4 of 0.5 M or less can solve the problem of precipitation of K 2 SO 4 , but is not limited thereto.
  • the metal hydroxide may include a hydroxide of an alkali metal, but is not limited thereto.
  • the metal hydroxide may include, but is not limited to, one selected from the group consisting of KOH, NaOH, LiOH, and combinations thereof.
  • the concentration of the formate may be about 5% or more, but is not limited thereto.
  • the concentration of the formate is about 5% to about 30%, about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, about 25% to about 30%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, or about 5% to about 10%, but is not limited thereto.
  • a high concentration of formate of about 0.5 M or more may be continuously obtained by reduction of carbon dioxide, but is not limited thereto.
  • the voltage when formate is produced at a certain concentration or more during prolonged electrolysis, the voltage may change rapidly, which may be due to the sharp change in the pH of the electrode part solution.
  • the sharp change in pH is due to the breakage of the buffer solution of the cathode solution as the hydrogen ions generated in the anode solution are excessively supplied to the cathode solution through the separator. Therefore, when the metal hydroxide is continuously added to the anode portion solution, neutralizing the generated hydrogen ions to maintain the pH and voltage of the anode portion solution to adjust the amount of excess hydrogen ion For a long time, electrolysis can be made possible.
  • the metal cation of the metal hydroxide is also continuously supplied. As a result, a high concentration of formate of about 0.5 M or more can be obtained continuously for a long time.
  • the current density by applying a voltage to the cathode electrode portion and the anode portion may be about 350 mA / cm 2 or less, but is not limited thereto.
  • the current density is about 2 mA / cm 2 to about 350 mA / cm 2 , about 2 mA / cm 2 to about 300 mA / cm 2 , about 2 mA / cm 2 to about 250 mA / cm 2 , about 2 mA / cm 2 to about 200 mA / cm 2 , about 2 mA / cm 2 to about 150 mA / cm 2 , about 2 mA / cm 2 to about 100 mA / cm 2 , about 2 mA / cm 2 to about 50 mA / cm 2 , about 2 mA / cm 2 to about 10 mA / cm 2 , about 10 mA / cm 2 to about 350 mA / cm 2 , about 50 mA / cm 2 / cm
  • the cathode portion may include tin, mercury, lead, indium, or amalgam electrode, but is not limited thereto.
  • the amalgam electrode is a mixture, composite, or alloy containing Hg on the surface of the base electrode and a metal selected from the group consisting of Ag, In, Sn, Pb, Cu, and combinations thereof It may be to include that formed, but is not limited thereto.
  • the amalgam electrode may be to include a dental amalgam, but is not limited thereto.
  • the dental amalgam can provide a safe amalgam electrode that can ignore the toxicity caused by mercury.
  • the amalgam electrode has about 35 parts by weight to about 55 parts by weight of Hg, about 14 parts by weight to about 34 parts by weight of Ag, about 7 parts by weight to about 17 parts by weight of Sn, and about 4 parts by weight To about 24 parts by weight of Cu, but is not limited thereto.
  • the base electrode may be one having a porous, plate-like, rod-shaped, or foam type, but is not limited thereto.
  • the substrate electrode having porosity may include a granular assembly, a porous electrode by surface treatment, or a mesh metal electrode, but is not limited thereto.
  • the base electrode may include, but is not limited to, a group selected from the group consisting of copper, tin, nickel, carbon, free carbon, silver, gold, and combinations thereof.
  • the amalgam electrode may be formed using an amalgamator or by electroplating, but is not limited thereto.
  • the amount of sulfuric acid added to the formate-containing solution may be about 40 parts by weight to about 75 parts by weight based on 100 parts by weight of the formate-containing solution, but is not limited thereto.
  • the amount of sulfuric acid added to the formate-containing solution is about 40 parts by weight to about 75 parts by weight, about 45 parts by weight to about 75 parts by weight, about 100 parts by weight of the formate-containing solution.
  • FIGS. 1 and 2 showing the combined process of carbon dioxide reduction and formic acid and potassium sulfate production
  • first reactor electrochemical conversion of carbon dioxide using a flow cell (first reactor) for the production of high concentration of formate.
  • Amalgam coated rod electrode, amalgam coated foam electrode, or amalgam coated plate electrode were used as working electrodes, and a titanium mesh DSA electrode coated with IrOx was used as a counter electrode.
  • a constant current was applied and the voltage at both ends was measured.
  • the cathode electrode solution was supplied to the cathode electrode portion, the anode electrode solution was supplied to the anode electrode portion, and the shape of the carbon dioxide conversion system (first reactor system) used is shown in FIG. 3.
  • EG & G, 273A constant potentiometers
  • KS RnD constant current devices
  • CO 2 _ 10A constant current devices
  • a working electrode was used as a foam electrode (3 cm x 3 cm, 0.5 cm thick), and the electrolyte volume was used in a variety of 100 mL to 1,000 mL, but mainly 100 mL to 200 mL.
  • the electrolyte of the anode portion and the electrolyte of the cathode portion were separated and separated by a Nafion ® 117 membrane.
  • Ultra high purity carbon dioxide (purity 99.99%) was continuously supplied to the electrolyte of the cathode by using glass-frit, and ultra high purity argon (purity 99.99%) was supplied to the electrolyte of the anode, or gas was supplied. Electrolysis was performed without injection.
  • the pump for circulating the solution used a diaphragm pump and a peristaltic pump.
  • the product, formate, was quantitatively analyzed by liquid chromatography.
  • the formate Since the high concentration formate (1.6 M) obtained by electrochemical reduction of carbon dioxide using potassium sulfate as an electrolyte in Example 1 is dissolved in the potassium sulfate (0.2 M) solution, the formate is concentrated by concentration. Separated. In the potassium sulfate solution, the solubility of the formate is 3,400 g / L, the solubility of the potassium sulfate is 120 g / L, and when a high concentration of formate is dissolved in the potassium sulfate solution as in Example 1, Since the solubility of the potassium sulfate was further reduced, the formate could be easily separated into a liquid and the potassium sulfate could be separated into a solid by concentration.
  • the solid formate was obtained by evaporating the potassium sulfate solution in which the high concentration of formate was dissolved in order to conduct experiments at the laboratory level. Thereafter, the formate was dissolved in formic acid, and sulfuric acid was added in an equivalent ratio to prepare a mixed solution containing formic acid and potassium sulfate.
  • the reaction formula of the formate and sulfuric acid can be represented as in Scheme 1 below.
  • 8 is a graph showing the results of the acidification reaction with sulfuric acid by dissolving formate in the solvent using formic acid as a solvent. As shown in the graph of FIG. 8, it was confirmed that the reaction proceeded stably.
  • the mixed solution including the formic acid and potassium sulfate obtained through the reaction was distilled to separate the potassium sulfate as a solid and the formic acid as a liquid.
  • the obtained formic acid was 98%, the potassium sulfate was obtained as a purity of 97%, respectively, the result requested by the Korea Institute of Chemical Convergence Testing in order to confirm the purity of the formic acid (purity: 98.2 %) could be obtained.
  • the purity of the potassium sulfate was requested by the Korea Chemical Research Institute Chemical Analysis Center to obtain the results shown in Table 2.
  • the analysis of Table 2 was performed using Metrohm Ion Chromatograph C, and the analytical sample 1 contained 97.92% SO 4 2- in terms of SO 4 2- theoretical content of 55.17% in 100% K 2 SO 4 . , Sample 2 was confirmed to contain 97.86% SO 4 2- .
  • the electrolysis was stably possible with the amalgam electrode, and the electrolysis was performed at a constant voltage of about -1.9 V using an amalgam coated foam electrode, indicating that the efficiency was about 80% over 10 hours.
  • electrolysis proceeded at a current density of 30 mA ⁇ cm ⁇ 2 , and it was confirmed that electrolysis was possible at a higher current density than that of the rod type.
  • the current density As a method for increasing the current density, it was confirmed whether the current density can be increased by increasing the thickness of the amalgam-coated foam electrode having the same apparent area.
  • the amalgam electrode coated on the 5 mm thick foam base electrode has a current density of 100 mAcm -2 or higher, and the amalgam electrode coated on the 10 mm thick foam base electrode 150 mA cm -2.
  • the current efficiency was decreased when 200 mA ⁇ cm ⁇ 2 or more. The current density until such a rapid decrease in efficiency was defined as the 'limiting current density'.
  • Electrochemical reduction of carbon dioxide was carried out using the experimental method and apparatus presented in this example.
  • the effect of maintaining the pH of the anode portion and the formation of high concentration of formate in the cathode portion by continuously adding potassium hydroxide (KOH) to the anode portion was confirmed.
  • FIG. 7 is a graph obtained by prolonged electrolysis by continuously adding KOH to an anode part in the present embodiment.
  • KOH was continuously supplied to the anode for 34 hours and then electrolyzed for more than 34 hours, the pH and potential remained stable, and it was confirmed that more than 1 M of formate was produced with a current efficiency of 80% or more at the cathode.
  • the electrolysis was performed for a longer period, it was confirmed that the current efficiency was maintained at 80% or more even for about 2 M of the formate.
  • the energy consumption of each unit process was estimated to convert the energy saving amount according to the existing potassium sulfate manufacturing process and the development process.
  • the reaction proceeds at a high temperature (Mannheim furnace: 550 ° C.), but in the present embodiment, since the reaction proceeds at room temperature and atmospheric pressure, it was found to be superior to the existing process in terms of economy and stability.
  • formic acid is produced through electrochemical conversion, and formic acid and potassium sulfate are prepared by sulfation of the formate, and formic acid is produced in high purity through evaporation under reduced pressure. Produced and did not cost extra to produce potassium sulfate.

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Abstract

La présente invention concerne un procédé complexe pour réduire le dioxyde de carbone et produire de l'acide formique et du sulfate de potassium et un appareil pour ledit procédé complexe.
PCT/KR2017/010997 2016-09-30 2017-09-29 Procédé complexe pour réduire le dioxyde de carbone et produire de l'acide formique et du sulfate de potassium, et appareil pour ledit procédé complexe Ceased WO2018062952A1 (fr)

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