CN113549929B - Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration - Google Patents
Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration Download PDFInfo
- Publication number
- CN113549929B CN113549929B CN202110911758.0A CN202110911758A CN113549929B CN 113549929 B CN113549929 B CN 113549929B CN 202110911758 A CN202110911758 A CN 202110911758A CN 113549929 B CN113549929 B CN 113549929B
- Authority
- CN
- China
- Prior art keywords
- cathode
- liquid
- anode
- hydroxide
- organic matter
- 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
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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- 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
- C25B3/23—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
- 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
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Abstract
The invention relates to the technical field of electrochemical hydrogen production, and provides a method and a system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration 2 Generating hydrogen gas and hydroxide at the cathode; separating value-added oxide from the anode effluent, and heat treating the residual solution to obtain carbonate solution and CO 2 (ii) a The part of the cathode effluent is used as cathode inlet liquid for reflux, and the part of the cathode effluent is used as absorption liquid for capturing low-concentration CO 2 . The method can realize electrochemical coupling of hydrogen production, organic matter oxidation, carbon dioxide capture-desorption and hydroxide regeneration, can obtain value-added oxides while obtaining hydrogen, realizes carbon dioxide capture-desorption and hydroxide regeneration, reduces the comprehensive preparation cost of hydrogen, and realizes the multifunction of the electrolysis process.
Description
Technical Field
The invention relates to the technical field of electrochemical hydrogen production, in particular to a method and a system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration.
Background
Clean and green hydrogen energy, carbon capture and organic chemical technology are key elements for realizing carbon peak reaching and carbon neutralization and social sustainable development.
The hydrogen production by water electrolysis is a green and convenient method for producing hydrogen, and will become a main way for obtaining hydrogen energy in the future. However, the traditional hydrogen production function by water electrolysis is too single, the valuable product is only hydrogen, and the comprehensive cost of hydrogen production is higher.
Patent CN101043929A, CN101249976A reports that hydrogen can be obtained by electrolyzing sodium carbonate solution, oxygen evolution reaction occurs on an anode to generate oxygen and hydrogen ions, and sodium carbonate is converted into sodium bicarbonate and CO 2 The gas phase product of the anode is CO 2 And O 2 Mixing the gas; sodium ions migrate from the anode chamber to the cathode chamber, hydrogen evolution reaction occurs on the cathode to generate hydrogen and hydroxide ions, and the hydroxide ions and the sodium ions are combined to form sodium hydroxide to realize NaOH regeneration. However, the value product in this process is still only H 2 And the process anode O 2 And a cathode H 2 CO-production, potential safety hazard exists, and the gas-phase product of the anode of the process is CO 2 And O 2 Mixed gas of (2), difficult subsequent separation of CO 2 The desorption efficiency is low.
In a word, the current hydrogen production process by electrolysis has single function, fewer valuable products and CO 2 The desorption and separation efficiency is low, and the comprehensive cost of hydrogen is higher.
Disclosure of Invention
In view of the foregoing, the present invention provides a method and system for achieving hydrogen production, organic oxidation, carbon dioxide absorption-desorption, and hydroxide regeneration. The method provided by the invention can realize electrochemical coupling of hydrogen production, organic matter oxidation, carbon dioxide capture and hydroxide regeneration, can obtain value-added oxides while obtaining hydrogen, can realize capture-desorption of carbon dioxide and hydroxide regeneration, and reduces the comprehensive preparation cost of hydrogen.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration comprises the following steps:
using aqueous solution containing carbonate and water-soluble organic matter as anode feed liquor and using water or hydrogen and oxygenUsing the solution as cathode feed liquid, respectively introducing the anolyte and cathode feed liquid into anode chamber and cathode chamber of electrolytic bath to make electrolysis, and producing value-added oxide, bicarbonate and CO at anode 2 Generating hydrogen gas and hydroxide at the cathode;
separating the value-added oxide in the anode effluent generated after electrolysis, and carrying out heat treatment on the residual solution to obtain carbonate solution and CO 2 (ii) a Supplementing water-soluble organic matters into the carbonate solution, and then recycling the carbonate solution as anode feed liquor;
part of the cathode effluent generated after electrolysis is used as cathode inlet liquid to flow back, and part of the cathode effluent is used as absorption liquid to capture and absorb CO 2 。
Preferably, the carbonate is potassium carbonate and/or sodium carbonate; the hydroxide is potassium hydroxide and/or sodium hydroxide.
Preferably, the carbonate in the anode feed is replaced with bicarbonate.
Preferably, the total concentration of carbonate in the anode feed liquid is 0.3-6 mol/L, and the concentration of water-soluble organic matters is 0.01-3 mol/L; and when the hydroxide solution is used as cathode feed liquid, the concentration of the hydroxide in the cathode feed liquid is 0.1-7 mol/L.
Preferably, the water-soluble organic compound comprises one or more of organic compounds of saccharides, alcohols and amines.
Preferably, the current density of the electrolysis is 100-8000A m -2 。
Preferably, the anode chamber and the cathode chamber are separated by an ionic membrane; the ion membrane is a potassium ion exchange membrane, a sodium ion exchange membrane or a proton exchange membrane.
Preferably, the concentration of the hydroxide in the cathode effluent is 2-15 mol/L; the volume of the part of the cathode effluent as the reflux of the cathode feed liquid is less than 50 percent of the total volume of the cathode effluent.
Preferably, the absorption liquid traps absorbed CO 2 As CO in air or flue gas 2 The absorption liquid traps and absorbs CO 2 The obtained solution is carbonate solution or carbonate-bicarbonate mixed solution; the absorption liquid is trappedAbsorption of CO 2 The obtained solution is used as anode feed liquor for recycling after being supplemented with water-based organic matters.
The invention also provides a system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration, which comprises an electrolytic bath; the electrolytic cell comprises an anode chamber, a cathode chamber and an ionic membrane, wherein the anode chamber is connected with an anode, and the cathode chamber is connected with a cathode; the anode chamber is provided with a liquid inlet and a liquid outlet, and the cathode chamber is provided with a liquid inlet and a liquid outlet;
an outlet of the anode liquid inlet tank is communicated with a liquid inlet of the anode chamber;
an anode effluent gas-liquid separator; the inlet of the anode liquid outlet gas-liquid separator is communicated with the liquid outlet of the anode chamber;
an organic matter separation device; the inlet of the organic matter separation device is communicated with the outlet of the anode liquid outlet gas-liquid separator;
a bicarbonate decomposer; the inlet of the bicarbonate decomposition tank is communicated with the outlet of the organic matter separation device; the liquid outlet of the bicarbonate decomposition tank is communicated with the inlet of the anode liquid inlet tank;
an organic matter feed tank; the organic matter feeding tank is communicated with the anode liquid inlet tank;
a cathode liquid inlet tank; the cathode liquid inlet tank is communicated with a liquid inlet of the cathode chamber;
a cathode effluent gas-liquid separator; the inlet of the cathode liquid outlet gas-liquid separator is communicated with the liquid outlet of the cathode chamber, and the liquid outlet of the cathode liquid outlet gas-liquid separator is communicated with the cathode liquid inlet tank;
a water storage tank; the water storage tank is communicated with the cathode liquid inlet tank;
a carbon dioxide absorption reactor; the liquid inlet of the carbon dioxide absorption reactor is communicated with the outlet of the cathode liquid inlet tank, and the gas inlet of the carbon dioxide absorption reactor is used for introducing air or flue gas; and a liquid outlet of the carbon dioxide absorber is communicated with the anode liquid inlet tank.
The present invention providesThe invention discloses a method for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration 2 Generating hydrogen gas and hydroxide at the cathode; separating the value-added oxide in the anode effluent generated after electrolysis, and carrying out heat treatment on the residual solution to obtain carbonate solution and CO 2 (ii) a Supplementing water-soluble organic matters into the carbonate solution, and then recycling the carbonate solution as anode feed liquor; part of the cathode effluent generated after electrolysis is used as cathode inlet liquid to flow back, and part of the cathode effluent is used as absorption liquid to capture and absorb CO 2 . The method provided by the invention can realize electrochemical coupling of hydrogen production, organic matter oxidation, carbon dioxide capture-desorption and hydroxide regeneration, wherein the anode does not generate oxygen evolution reaction under high potential but electrocatalysis organic matter oxidation reaction, thereby not only reducing total electrolysis voltage, but also avoiding safety risk caused by simultaneously generating oxygen and hydrogen in an electrolytic cell, and also lightening CO of the anode 2 And O 2 The problem of subsequent separation of gases; meanwhile, the anode of the invention not only carries out the oxidation reaction of organic matters, but also generates bicarbonate and CO along with the hydrogen ions generated by the carbonate combined oxidation reaction 2 Is beneficial to subsequent CO 2 Desorbing; furthermore, in the process of the invention, the cathode does not only react to produce H with evolution of hydrogen 2 OH produced during hydrogen evolution - The hydroxide is formed by combining with the transferred cations, so that the regeneration of the hydroxide is realized, the hydroxide in the cathode effluent is thickened, part of the cathode effluent is used as carbon dioxide absorption liquid after water is added, the carbon dioxide is captured and absorbed, and the solution after absorbing the carbon dioxide is reused as anode feed liquid, thereby further reducing the cost.
Drawings
Fig. 1 is a schematic structural diagram of a system for implementing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration provided by the present invention, wherein: 1-cathode feed tank, 2-CO 2 An absorption reactor, a 3-anode liquid inlet tank; 4-a cathode chamber, wherein the cathode chamber is provided with a cathode,5-anode chamber, 6-ionic membrane, 7-cathode, 8-anode, 9-anode effluent gas-liquid separator, 10-cathode effluent gas-liquid separator, 11-water storage tank, 12-organic matter feeding tank, 13-bicarbonate decomposer and 14-organic matter separator.
Detailed Description
The invention provides a method for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration, which comprises the following steps:
using aqueous solution containing carbonate and water-soluble organic matter as anode feed liquor, using water or hydroxide solution as cathode feed liquor, respectively introducing the described anolyte and cathode feed liquor into anode chamber and cathode chamber of electrolytic cell to make electrolysis so as to produce value-added oxide, bicarbonate and CO at anode 2 Generating hydrogen gas and hydroxide at the cathode;
separating the value-added oxide in the anode effluent generated after electrolysis, and performing heat treatment on the residual solution to obtain carbonate solution and CO 2 (ii) a Supplementing water-soluble organic matters into the carbonate solution, and then recycling the carbonate solution as anode feed liquor;
part of the cathode effluent generated after electrolysis is used as cathode inlet liquid to flow back, and part of the cathode effluent is used as absorption liquid to capture and absorb CO 2 。
The invention takes the water solution containing carbonate and water-soluble organic matters as the anode feed liquid. In the present invention, the carbonate is preferably potassium carbonate and/or sodium carbonate, more preferably potassium carbonate.
In the present invention, the carbonate in the anolyte feed may also be replaced by bicarbonate, preferably potassium bicarbonate or sodium bicarbonate.
In the present invention, the total concentration of carbonate in the anode feed liquid is preferably 0.3 to 6mol/L, more preferably 0.5 to 5mol/L, and when the salt in the anode feed liquid is bicarbonate, the total concentration of carbonate is the sum of the concentrations of carbonate and bicarbonate.
In the invention, the concentration of the water-soluble organic matters in the anode feed liquid is preferably 0.01-3 mol/L, and more preferably 0.05-2 mol/L; the aqueous solution organic matter preferably comprises one or more of organic compounds of saccharides, alcohols and amines; the saccharide is preferably glucose, and the alcohol is preferably glycerol or benzyl alcohol; the amine is preferably propylamine.
In the specific embodiment of the invention, water or hydroxide solution is preferably used as the cathode feed liquid in the first electrolysis, and a solution obtained by diluting the cathode effluent is used as the cathode feed liquid in the subsequent process, so as to reduce the cost, and the following specific description is provided. In the present invention, the hydroxide is preferably potassium hydroxide and/or sodium hydroxide; the concentration of the hydroxide in the cathode feed liquid is preferably 0.1 to 7mol/L, and more preferably 0.5 to 6mol/L.
The invention respectively leads the anode feed liquid and the cathode feed liquid into an anode chamber and a cathode chamber of the electrolytic cell for electrolysis. In the present invention, the current density of the electrolysis is preferably 100 to 8000Am -2 More preferably 500 to 7000Am -2 (ii) a The electrolysis temperature is preferably room temperature to 100 ℃, more preferably 30 to 50 ℃, and the distance between the anode and the cathode during electrolysis is preferably not more than 10mm; the anode chamber and the cathode chamber are separated by an ionic membrane; the ionic membrane is preferably a potassium ion exchange membrane, a sodium ion exchange membrane or a proton exchange membrane.
During the electrolysis, the oxidation reaction of organic matter occurs at the anode to obtain value-added oxide, and simultaneously the carbonate and hydrogen ions generated by the oxidation reaction are combined to generate bicarbonate and CO 2 (ii) a In the invention, when the water-soluble organic matter is glucose, the obtained value-added oxide is gluconic acid; when the water-soluble oxide is glycerol, the value-added oxide is dihydroxyacetone or formic acid; when the water-soluble organic matter is benzyl alcohol, the value-added oxide is benzoic acid; when the water-soluble oxide is propylamine, the value-added oxide is propionitrile, and the value-added oxide with higher value is obtained while hydrogen is prepared, so that the comprehensive cost of the hydrogen can be reduced, and the multi-functionalization of the electrochemical process is realized.
In the electrolysis process, hydrogen absorption reaction is carried out on the cathode, and meanwhile, generated hydroxide radicals react with cations (potassium ions or sodium ions) transferred to the cathode to obtain hydroxide (potassium hydroxide or sodium hydroxide), so that the hydroxide in cathode liquor is enriched.
The invention separates the value-added oxide in the anode effluent generated after electrolysis, and carries out heat treatment on the residual solution to obtain carbonate solution and CO 2 (ii) a And supplementing water-soluble organic matters into the carbonate solution, and then recycling the carbonate solution as anode feed liquor. The method for separating the organic oxide has no special requirement, and the value-added oxide can be separated by adopting a method well known by the technical personnel in the field, such as one or a combination of extraction, rectification and filtration.
In the present invention, the temperature of the heat treatment is preferably 70 to 99 ℃, more preferably 80 to 90 ℃; the invention has no special requirement on the time of the heat treatment, and the decomposition rate of the bicarbonate can be more than 50 percent.
In the present invention, CO generated at the anode 2 And CO produced by decomposition of bicarbonate 2 Is high concentration CO 2 Compared with CO in air and smoke before absorption 2 The concentration is obviously improved to more than 60 percent, and the part of high-concentration CO obtained by the invention 2 Can be directly recycled.
After the carbonate solution is obtained, the water-soluble organic matter is added into the carbonate solution and then the carbonate solution is used as anode feed liquor for recycling. The invention has no special requirement on the addition amount of the water-soluble organic matters, so that the contents of carbonate and the water-soluble organic matters in the anode feed liquid meet the requirements on the contents of carbonate and the water-soluble organic matters in the anode feed liquid.
The invention takes part of the cathode effluent generated after electrolysis as cathode inlet liquid to flow back, and part of the cathode effluent is taken as absorption liquid to capture and absorb CO 2 (ii) a In the invention, the volume of the part of the cathode effluent as the reflux of the cathode feed liquid is less than 50 percent of the total volume of the cathode effluent, and preferably 30 to 40 percent; in the invention, the concentration of hydroxide in the cathode effluent is preferably 2-15 mol/L, and more preferably 3-10 mol/L; the invention preferably adds part of water into the cathode effluent for dilutionAnd (3) releasing, and reducing the concentration of the hydroxide in the cathode liquid to meet the concentration requirement of the cathode liquid.
In the invention, part of cathode effluent is used as absorption liquid to capture and absorb CO 2 In particular to trap and absorb low-concentration CO in air or smoke 2 The flue gas can be flue gas of a thermal power plant, flue gas of a smelting plant and the like; the absorption liquid absorbs low-concentration CO in air or flue gas 2 Then repeatedly used, and high-concentration and purer CO is obtained by electrolysis and bicarbonate decomposition 2 Thereby realizing CO 2 To carry out CO purification and concentration 2 Resource utilization is carried out; the invention preferably dilutes the cathode effluent to a supplementary part of water and then uses the diluted cathode effluent for absorbing CO 2 Absorption of CO 2 The latter solution is carbonate solution or carbonate-bicarbonate mixed solution; the absorption liquid is used for capturing and absorbing CO 2 The obtained solution is supplemented with water-based organic matters and then is used as anode feed liquor for recycling, so that the cost is further reduced.
The invention also provides a system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration, which has a schematic structural diagram as shown in figure 1, wherein: 1-cathode feed tank, 2-CO 2 An absorption reactor, a 3-anode liquid inlet tank; 4-cathode chamber, 5-anode chamber, 6-ionic membrane, 7-cathode, 8-anode, 9-anode effluent gas-liquid separator, 10-cathode effluent gas-liquid separator, 11-water storage tank, 12-organic matter feeding tank, 13-bicarbonate decomposer and 14-organic matter separator.
The following is described in detail with reference to fig. 1:
the system provided by the invention comprises an electrolytic cell. In the present invention, the electrolytic cell comprises an anode chamber, a cathode chamber and an ionic membrane separating the anode chamber and the cathode chamber; the anode chamber is connected with the anode, and the cathode chamber is connected with the cathode; the anode chamber is provided with a liquid inlet and a liquid outlet, and the cathode chamber is provided with a liquid inlet and a liquid outlet.
The system provided by the invention comprises an anode liquid inlet tank, wherein an outlet of the anode liquid inlet tank is communicated with a liquid inlet of the anode chamber.
Hair brushThe system provided by the invention comprises an anode effluent gas-liquid separator; and the inlet of the anode liquid outlet gas-liquid separator is communicated with the liquid outlet of the anode chamber. The invention has no special requirements on the gas-liquid separator, can realize gas-liquid separation, and can separate CO in the effluent liquid 2 And separating to obtain the product.
The system provided by the invention comprises an organic matter separation device; the inlet of the organic matter separation device is communicated with the outlet of the anode liquid outlet gas-liquid separator; the invention has no special requirements on the organic matter separation device, and can select a proper device according to the organic matter separation method, such as an extraction tank, a filter or a rectifying tower.
The system provided by the invention comprises a bicarbonate decomposition tank; the inlet of the bicarbonate decomposition tank is communicated with the outlet of the organic matter separation device; and the liquid outlet of the bicarbonate decomposition tank is communicated with the inlet of the anode liquid inlet tank.
The system provided by the invention comprises an organic matter feeding tank; the organic matter feeding tank is communicated with the anode liquid inlet tank; and a water-soluble organic matter solution is stored in the organic matter feeding tank and is used for feeding to the anode liquid feeding tank.
The system provided by the invention comprises a cathode liquid inlet tank; and the outlet of the cathode liquid inlet tank is communicated with the liquid inlet of the cathode chamber.
The system provided by the invention comprises a cathode effluent gas-liquid separator; the inlet of the cathode liquid outlet gas-liquid separator is communicated with the liquid outlet of the cathode chamber, and the liquid outlet of the cathode liquid outlet gas-liquid separator is communicated with the cathode liquid inlet tank.
The system provided by the invention comprises a water storage tank; the water storage tank is communicated with the cathode liquid inlet tank.
The system provided by the invention comprises a carbon dioxide absorption reactor; the liquid inlet of the carbon dioxide absorption reactor is communicated with the outlet of the cathode liquid inlet tank, and the gas inlet of the carbon dioxide absorption reactor is used for introducing air or flue gas; and a liquid outlet of the carbon dioxide absorber is communicated with the anode liquid inlet tank.
The invention is described below with reference to FIG. 1The method of the invention is explained in detail: the cathode inlet liquid enters the cathode chamber 4 from the cathode inlet liquid tank, the anode inlet liquid enters the anode chamber 5 from the anode inlet liquid tank 3, after electrolysis, the cathode outlet liquid enters the cathode outlet liquid gas-liquid separator 10 for gas-liquid separation to generate hydrogen, part of the liquid returns to the cathode inlet liquid tank for reuse (water is supplemented in the water storage tank 11 phase cathode inlet liquid tank), and part of the liquid enters the carbon dioxide absorption reactor 2 as the carbon dioxide absorption liquid to absorb low-concentration CO in air or flue gas 2 Then the mixture enters an anode liquid inlet tank for recycling; the anode effluent enters an anode effluent gas-liquid separator 9 for gas-liquid separation to generate high-concentration CO 2 The liquid enters an organic matter separation device 14 to separate organic matters, and the residual liquid enters a bicarbonate decomposition tank 13 to be decomposed to generate high-concentration CO 2 And carbonate solution, the carbonate solution returns to the anode liquid inlet tank 3 for recycling, and the organic matter feeding tank 12 adds water-soluble organic matter solution into the anode liquid inlet tank.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Taking an aqueous solution containing potassium carbonate and glycerol as an anode feed liquid (the concentration of potassium carbonate is 2.5mol/L, the concentration of glycerol is 1.2 mol/L) and a potassium hydroxide solution (the concentration is 6 mol/L) as a cathode feed liquid, respectively introducing the anode feed liquid and the cathode feed liquid into an anode chamber and a cathode chamber of an electrolytic cell for electrolysis, wherein the current density is 3000A/m 2 At the anode, oxidation of glycerol takes place to form mainly dihydroxyacetone, while potassium carbonate is converted to potassium bicarbonate and CO 2 (ii) a Hydrogen evolution reaction takes place at the cathode to produce H 2 And KOH;
the concentration of potassium hydroxide in the cathode effluent is increased to 7-7.8 mol/L,20 percent of potassium hydroxide is diluted to 6mol/L by adding water and flows back to the cathode feed liquor, 80 percent of potassium hydroxide is diluted to 5.0-5.1 mol/L by adding water and is used for CO 2 The trapping and absorption of (1).
Absorbing CO in air by using 5.0-5.1 mol/L potassium hydroxide solution 2 Obtaining a potassium carbonate-potassium bicarbonate mixed solution, wherein the concentration of the potassium carbonate is 2.3mol/L, and the concentration of the potassium bicarbonate is 0.4mol/L, and adding the potassium carbonate-potassium bicarbonate mixed solution into the mixed solutionAdding glycerol to form a potassium carbonate-potassium bicarbonate mixed solution with 1.2mol/L of glycerol concentration, and recycling by taking the mixed solution as anolyte.
Analysis of the organic oxidation products in the effluent from the anode showed a selectivity for the dihydroxyacetone product of about 82% and the formic acid product of about 16%. KHCO obtained after rectification and separation of oxidation products 3 Heating the solution to 90 deg.C to make KHCO 3 Decomposition to K 2 CO 3 And CO 2 And CO 2 Further release to obtain CO 2 Gas, and K 2 CO 3 The solution is pumped back to the anode liquid inlet tank to realize cyclic utilization, and the anode and the KHCO are 3 High concentration of CO produced by decomposition 2 And carrying out resource utilization.
Example 2
Taking an aqueous solution containing sodium carbonate and glucose as an anode feed liquid (the concentration of sodium carbonate is 1.5mol/L, the concentration of glucose is 1 mol/L) and a sodium hydroxide solution (the concentration is 6 mol/L) as a cathode feed liquid, respectively introducing the anode feed liquid and the cathode feed liquid into an anode chamber and a cathode chamber of an electrolytic cell for electrolysis, wherein the current density is 1500A/m 2 The oxidation reaction of glucose at the anode takes place mainly to form gluconic acid and simultaneously to form NaHCO 3 And release CO 2 A gas; hydrogen evolution reaction takes place at the cathode to produce H 2 And NaOH.
The concentration of sodium hydroxide in the cathode effluent is increased to 3.2-4 mol/L, 10 percent of the cathode effluent is diluted to 2mol/L by adding water and flows back to the cathode feed liquor, 90 percent of the cathode effluent is diluted to 2.9-3 mol/L by adding water and is used for CO 2 The capture and absorption of (2).
Absorbing CO in air by using 2.9-3 mol/L sodium hydroxide solution 2 To obtain 1.4 to 1.5mol/L sodium carbonate, glucose was added to the sodium carbonate solution to form an aqueous solution containing sodium carbonate having a glucose concentration of about 1 mol/L. The solution is used as anolyte for cyclic utilization.
And analyzing the organic oxidation products in the anode effluent, wherein the selectivity of the gluconic acid product is about 91 percent. NaHCO after rectification separation of oxidation products 3 The solution was heated to 90 ℃ to allow NaHCO 3 Decomposition to Na 2 CO 3 And CO 2 And CO 2 Further release to obtain CO 2 Gas, and Na 2 CO 3 The solution is pumped back to the anode liquid inlet tank to realize cyclic utilization, and the anode and NaHCO are used 3 High concentration of CO produced by decomposition 2 And carrying out resource utilization.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration is characterized by comprising the following steps:
using water solution containing carbonate and water-soluble organic matter as anode feed liquor, using water or hydroxide solution as cathode feed liquor, respectively introducing the described anode feed liquor and cathode feed liquor into anode chamber and cathode chamber of electrolytic cell to make electrolysis so as to produce value-added oxide, bicarbonate and CO at anode 2 Generating hydrogen gas and hydroxide at the cathode; the water-soluble organic matter is one or more of organic compounds of saccharides and amines;
separating the value-added oxide in the anode effluent generated after electrolysis, and carrying out heat treatment on the residual solution to obtain carbonate solution and CO 2 (ii) a Supplementing water-soluble organic matters into the carbonate solution, and then recycling the carbonate solution as anode feed liquor;
part of the cathode effluent generated after electrolysis is used as cathode feed liquid to flow back, and part of the cathode effluent is used as absorption liquid to capture and absorb CO 2 。
2. The process according to claim 1, characterized in that the carbonate is potassium carbonate and/or sodium carbonate; the hydroxide is potassium hydroxide and/or sodium hydroxide.
3. The method of claim 1, wherein carbonate in the anode feed is replaced with bicarbonate.
4. A method according to claim 1, 2 or 3, characterised in that the total concentration of carbonate in the anolyte feed liquor is 0.3 to 6mol/L and the concentration of water-soluble organic substances is 0.01 to 3mol/L; and when the hydroxide solution is used as cathode feed liquid, the concentration of the hydroxide in the cathode feed liquid is 0.1-7 mol/L.
5. The method of claim 1, wherein the current density of the electrolysis is from 100 to 8000Am -2 。
6. The method of claim 1 wherein the anode and cathode compartments are separated by an ionic membrane; the ion membrane is a potassium ion exchange membrane, a sodium ion exchange membrane or a proton exchange membrane.
7. The method according to claim 1, wherein the hydroxide concentration in the cathode effluent is 2-15 mol/L; the volume of the part of the cathode effluent as the reflux of the cathode feed liquid is less than 50 percent of the total volume of the cathode effluent.
8. The method of claim 1, wherein the absorption liquid captures absorbed CO 2 Is CO in air or flue gas 2 The absorption liquid traps and absorbs CO 2 The obtained solution is carbonate solution or carbonate-bicarbonate mixed solution;
the absorption liquid is used for capturing and absorbing CO 2 And supplementing aqueous organic matters into the obtained solution, and recycling the solution as anode feed liquor.
9. A system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration is characterized by comprising an electrolytic bath; the electrolytic cell comprises an anode chamber, a cathode chamber and an ionic membrane, wherein the anode chamber is connected with an anode, and the cathode chamber is connected with a cathode; the anode chamber is provided with a liquid inlet and a liquid outlet, and the cathode chamber is provided with a liquid inlet and a liquid outlet;
an outlet of the anode liquid inlet tank is communicated with a liquid inlet of the anode chamber;
an anode effluent gas-liquid separator; the inlet of the anode liquid outlet gas-liquid separator is communicated with the liquid outlet of the anode chamber;
an organic matter separation device; the inlet of the organic matter separation device is communicated with the outlet of the anode liquid outlet gas-liquid separator;
a bicarbonate decomposition tank; the inlet of the bicarbonate decomposition tank is communicated with the outlet of the organic matter separation device; the liquid outlet of the bicarbonate decomposition tank is communicated with the inlet of the anode liquid inlet tank;
an organic matter charging tank; the organic matter feeding tank is communicated with the anode liquid inlet tank;
a cathode liquid inlet tank; the cathode liquid inlet tank is communicated with a liquid inlet of the cathode chamber;
a cathode effluent gas-liquid separator; the inlet of the cathode liquid outlet gas-liquid separator is communicated with the liquid outlet of the cathode chamber, and the liquid outlet of the cathode liquid outlet gas-liquid separator is communicated with the cathode liquid inlet tank;
a water storage tank; the water storage tank is communicated with the cathode liquid inlet tank;
a carbon dioxide absorption reactor; the liquid inlet of the carbon dioxide absorption reactor is communicated with the outlet of the cathode liquid inlet tank, and the gas inlet of the carbon dioxide absorption reactor is used for introducing air or flue gas; and a liquid outlet of the carbon dioxide absorption reactor is communicated with the anode liquid inlet tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110911758.0A CN113549929B (en) | 2021-08-10 | 2021-08-10 | Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110911758.0A CN113549929B (en) | 2021-08-10 | 2021-08-10 | Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113549929A CN113549929A (en) | 2021-10-26 |
| CN113549929B true CN113549929B (en) | 2022-10-21 |
Family
ID=78133730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110911758.0A Active CN113549929B (en) | 2021-08-10 | 2021-08-10 | Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113549929B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116135785A (en) * | 2021-11-17 | 2023-05-19 | 国家电投集团科学技术研究院有限公司 | Carbon dioxide trapping method for coupling graded electrolysis/pyrolysis hydrogen production |
| CN114000172B (en) * | 2021-12-16 | 2023-03-07 | 东北大学 | Method for trapping and reducing carbon dioxide and co-producing oxygen or chlorine |
| CN114351188B (en) * | 2022-01-10 | 2023-08-01 | 青岛中石大环境与安全技术中心有限公司 | Method and device for producing hydrogen by electrolysis of water and capturing carbon dioxide |
| CN114645290B (en) * | 2022-02-25 | 2023-06-30 | 东南大学 | CO (carbon monoxide) 2 Synchronous conversion system and method for trapping and electric regeneration |
| CN116855964A (en) * | 2022-03-28 | 2023-10-10 | 势加透博（北京）科技有限公司 | Carbon dioxide capturing method and system capable of co-producing carbon monoxide and hydrogen |
| CN114870602B (en) * | 2022-05-31 | 2023-08-22 | 江苏科技大学 | Carbon capture system for regulating pH value based on potassium carbonate absorbent combined with capacitive deionization technology |
| CN117358037A (en) * | 2022-06-30 | 2024-01-09 | 中国石油天然气集团有限公司 | Carbon dioxide capturing method and system thereof |
| CN115123997A (en) * | 2022-07-15 | 2022-09-30 | 江西新节氢能源科技有限公司 | Vehicle-mounted hydrogen production integrated machine and hydrogen production method |
| WO2024016114A1 (en) * | 2022-07-18 | 2024-01-25 | 势加透博（北京）科技有限公司 | Method and device for carbon capture coupled hydrogen production |
| WO2024016115A1 (en) * | 2022-07-18 | 2024-01-25 | 国家电投集团科学技术研究院有限公司 | Co2 capture and desorption apparatus and method |
| WO2024016502A1 (en) * | 2022-07-18 | 2024-01-25 | 势加透博（北京）科技有限公司 | Carbon dioxide trapping method and gas absorption system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101043929A (en) * | 2004-08-20 | 2007-09-26 | 环球研究技术有限公司 | Removal of carbon dioxide from air |
| CN102605383A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Method and device for hydrogen-circulating electrolysis and application of the method and device in production of aluminum oxide |
| CN102701312A (en) * | 2012-05-30 | 2012-10-03 | 中国科学院广州能源研究所 | Method for producing hydrogen by using dye-sensitized photocatalytic fuel cell and degrading organic dye wastewater simultaneously |
| CN102839383A (en) * | 2012-09-24 | 2012-12-26 | 山东东岳高分子材料有限公司 | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299744B1 (en) * | 1997-09-10 | 2001-10-09 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
| US6994839B2 (en) * | 2001-08-15 | 2006-02-07 | Ovonic Battery Company, Inc. | Carbonate recycling in a hydrogen producing reaction |
| CN101275233B (en) * | 2007-12-27 | 2010-12-15 | 复旦大学 | Hydrogen production method using alcohol as raw material |
| CN102125793A (en) * | 2010-12-23 | 2011-07-20 | 中山大学 | Method for capturing and purifying carbon dioxide |
| US20170096742A1 (en) * | 2015-10-02 | 2017-04-06 | Waste Hub | Electrochemical processes for acid whey treatment and reuse |
| CN109778218B (en) * | 2019-02-01 | 2021-04-06 | 南京大学 | Device and method for co-production of hydrogen production and lithium extraction by electrochemistry |
| CN110616438B (en) * | 2019-08-19 | 2021-09-28 | 南京宁智高新材料研究院有限公司 | Device and method for electrochemically preparing high-purity battery-grade lithium hydroxide |
-
2021
- 2021-08-10 CN CN202110911758.0A patent/CN113549929B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101043929A (en) * | 2004-08-20 | 2007-09-26 | 环球研究技术有限公司 | Removal of carbon dioxide from air |
| CN102605383A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Method and device for hydrogen-circulating electrolysis and application of the method and device in production of aluminum oxide |
| CN102701312A (en) * | 2012-05-30 | 2012-10-03 | 中国科学院广州能源研究所 | Method for producing hydrogen by using dye-sensitized photocatalytic fuel cell and degrading organic dye wastewater simultaneously |
| CN102839383A (en) * | 2012-09-24 | 2012-12-26 | 山东东岳高分子材料有限公司 | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113549929A (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113549929B (en) | Method and system for realizing hydrogen production, organic matter oxidation, carbon dioxide absorption-desorption and hydroxide regeneration | |
| US8658016B2 (en) | Carbon dioxide capture and conversion to organic products | |
| US20210047743A1 (en) | Method for electrochemically reducing carbon dioxide | |
| CN102240497A (en) | Method and device for preparing methanoic acid from carbon dioxide recovered from flue gas by utilizing electric power at night | |
| CN108728860A (en) | A kind of riboflavin promotion low concentration CO2The method of electrochemistry trapping | |
| CN114214638B (en) | Method and equipment for enriching carbon dioxide and co-producing hydrogen and oxygen or chlorine | |
| US20200023309A1 (en) | Device and method for purifying sulfur dioxide and nitrogen oxide in flue gas | |
| JP2008100211A (en) | Mixed gas separation method and system | |
| CN114000172B (en) | Method for trapping and reducing carbon dioxide and co-producing oxygen or chlorine | |
| CN105169890A (en) | Electrochemical method capable of regenerating amino carbon dioxide rich liquor | |
| CN106039964B (en) | A kind of method of desulfurization co-producing hydrogen and sulfuric acid | |
| US20160222528A1 (en) | Method for electrochemical reduction of co2 in an electrochemical cell | |
| CN105964127A (en) | SO2 absorbing and converting technological method | |
| JPH04290526A (en) | Method for separating and reutilizing carbon dioxide | |
| CN114351188B (en) | Method and device for producing hydrogen by electrolysis of water and capturing carbon dioxide | |
| CN113617192B (en) | Electrochemical cyclic trapping SO by utilizing PCET reaction 2 Is a method of (2) | |
| CN110311146B (en) | Carbon dioxide mineralization power generation method using organic matter as catalyst | |
| JP2023051705A (en) | Method for recovering lithium from waste lithium-ion battery | |
| WO2024002310A1 (en) | Method for coupling carbon dioxide capture and hydrogen production, and system therefor | |
| KR102656514B1 (en) | An electrochemical method capable of processing alkali metal sulfate and simultaneously producing hydrogen, sulfuric acid, alkali metal hydroxide, and high value-added compounds within an electrodialysis stack | |
| CN217410318U (en) | Carbon dioxide recovery system | |
| WO2024016115A1 (en) | Co2 capture and desorption apparatus and method | |
| TWI795890B (en) | How to make ethylene oxide | |
| KR20130000534A (en) | Apparatus and method for making useful materials from carbon dioxide | |
| CN117443162A (en) | CO 2 Trapping and desorbing device and method |
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 |