CN114525536A - Thermal-electric coupling fused salt electrolysis CO2/CH4Preparation method and application of cathode material for preparing synthetic gas - Google Patents
Thermal-electric coupling fused salt electrolysis CO2/CH4Preparation method and application of cathode material for preparing synthetic gas Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 title claims abstract description 20
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 25
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 25
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 2
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a method for electrolyzing CO by using a thermal-electric coupling molten salt2/CH4A preparation method and application of a cathode material for preparing synthesis gas, belonging to the field of electrochemistry. The method is characterized in that nickel nitrate and potassium hexacyanocobaltate (III) are used as raw materials, a Ni-Co organic framework precursor is obtained at room temperature, and the NiO/Co organic framework precursor is formed by roasting at low temperature in air atmosphere3O4Nanocubes, then subjected to low temperature H2And activating the plasma in situ to obtain Ni-Co surface alloy catalyst powder. The invention has the advantages that the synthesis method can realize that the Ni-Co surface alloy catalyst has higher stability under electric field and high temperature, can effectively maintain the surface structure, and inhibit the inactivation caused by the migration and aggregation of surface active components Ni and Co, and the highest methane conversion rate, the carbon dioxide conversion rate and the CO yield can respectively reach 45 percent, 51 percent and 49 percent in a 400 ℃ molten salt electrolytic cellThe reaction is continued for 60 hours and is kept relatively stable in CO2/CH4The low-temperature electric reforming synthesis gas has wide application prospect in the field of synthesis gas preparation.
Description
Technical Field
The application relates to a method for electrolyzing CO by using a thermal-electric coupling fused salt2/CH4A method for preparing cathode material of synthetic gas. Belongs to the field of electrochemistry.
Background
Carbon dioxide is a typical greenhouse gas and is an important carbon-containing resource. Therefore, the emission reduction and resource utilization of carbon dioxide are the hot problems of the research in the scientific community at present. Introducing CO2By H2Or CH4The conversion of hydrogen sources into more valuable CO is an effective way, which is not only favorable for reducing the emission of greenhouse gases, but also is a process of changing waste into valuable, and the CO can be further used as raw material gas of Fischer-Tropsch synthesis reaction to synthesize various fuels and basic chemicals. CO 22A non-polar, symmetrical linear molecular structure in which the C atom and two O atoms form two 3-center 4-electron delocalized large pi bonds, the structure of which determines CO2Is strong electron acceptor and weak electron donor. In view of CO2High stability of the molecule and thermodynamic equilibrium, conventional CO2/CH4In the thermal reforming synthesis process, the high-temperature condition is generally required to be carried out>700 c), which is a significant challenge to the thermal stability of the catalytic material and to the production costs. In addition, the high reaction temperature tends to cause sintering of the active metal and the generation of carbon deposition, and the formed fibrous carbon has high mechanical strength and can cause mechanical damage to the catalyst, thereby leading to rapid deactivation of the catalyst.
Xie et al (high efficiency electrochemical reforming of the CH)4/CO2 in a solid oxide electrolyser[J]Science advance,2018,4(3):5100.) electrochemical reforming of CO in solid oxide electrolysis of all perovskite SOE electrolysis for the first time2/CH4The prepared synthesis gas has excellent carbon deposition resistance and active component agglomeration inhibition performance in the reaction process of the all-perovskite SOE catalyst electrode, has high-temperature reaction stability of 300h, and aims to solve the problem of conventional thermal reforming of CO2/CH4Provides a new idea for the problems of stability and carbon deposition resistance of the catalyst for preparing the synthesis gas. However, the solid oxide electrolysis reaction temperature is as high as 800 ℃, even higher than the traditional thermal reforming reaction temperature, so that the reaction needs huge energy consumption and has poor economic benefit.
CO electrolysis with high temperature heat2/CH4Compared with reforming technology, the method for reforming CO by adopting thermo-electric coupling under mild reaction conditions is economical and energy-saving2/CH4Has greater development potential and application prospect. In the process of thermo-electric reforming, CO2The reduction reaction is carried out at the cathode of the electrolytic cell to generate CO and CH4Partial oxidation to CO and H at the anode of the cell2. First step CO of the electric reforming reaction2Reduction to CO and O2-O generated as a prerequisite step2-Further generation of CH by migration to the anode in the electrolyte4Partial oxidation to CO and H2. In the actual reaction process, CO generated by the cathode can further undergo disproportionation reaction to generate C, and the C is deposited on the surface of the electrode, so that the catalyst electrode is deactivated. Therefore, there is a need to develop a new type of low temperature high activity thermo-electric coupling reformed CO2/CH4A cathode material.
Disclosure of Invention
The invention aims to provide a novel thermo-electric coupling fused salt electric reforming CO2/CH4A method for preparing cathode material of synthetic gas. The electrode has the advantages of high CO selectivity and low reaction temperature.
The technical scheme of the invention is as follows:
fused salt electrolysis of CO by thermo-electric coupling2/CH4The preparation method of the cathode material for preparing the synthesis gas comprises the following steps:
1) adding metered PVP and Nickel nitrate to HNO3Continuously stirring the solution to obtain a solution A;
2) dissolving metered potassium hexacyanocobaltate (III) in HNO3Continuously stirring the solution to obtain a solution B;
3) mixing the solution A and the solution B prepared in the previous step at room temperature under the condition of strong stirring, and continuously stirring until a clear solution C is obtained;
4) aging, centrifuging, washing and drying the prepared clear solution C to obtain a Ni-Co PBA precursor;
5) directly roasting the prepared Ni-Co PBA precursor to obtain NiO/Co3O4Nano cubeAnd (3) a body. Then, NiO/Co is subjected to cold plasma3O4Activating the nanocubes to obtain Ni-Co surface alloy catalyst powder;
6) the Ni-Co surface alloy catalyst powder prepared by the method is tableted into an electrode, and the CO is electrolyzed by the thermal-electric coupling molten salt2An electrode of CO.
The continuous stirring time is 15-45 min;
the aging temperature is 50-100 ℃, the aging time is 10-30h, the washing liquid is deionized water and ethanol, and the drying temperature is 50-100 ℃;
the roasting atmosphere is air, the roasting temperature is 250-500 ℃, and the roasting time is 0.5-1.5 h;
the plasma atmosphere is H2The pressure of the plasma activated gas is 300-500mTorr, the activation power is 100-300W, and the activation time is 5-15 min.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a method for electrically reforming CO by using heat-electricity coupled molten salt2/CH4The prepared Ni-Co surface alloy catalyst has higher stability under electric field and high temperature, can effectively maintain the surface structure and inhibit the inactivation caused by the migration and aggregation of surface active components Ni and Co;
(2) the Ni-Co surface alloy catalyst cathode material prepared by the invention has the advantages that the highest methane conversion rate, the carbon dioxide conversion rate and the CO yield can respectively reach 45%, 51% and 49% in a 400 ℃ molten salt electrolytic cell, and the continuous reaction can be kept relatively stable for 60 hours. The cathode material is used for reforming CO2/CH4The reaction for preparing the synthesis gas has obvious low-temperature characteristics.
Drawings
FIG. 1 is a diagram of thermal-electric coupling of molten salt reforming CO2/CH4A schematic diagram of a reaction device for preparing synthesis gas;
FIG. 2 is a schematic diagram of the thermal-electric coupling molten salt electric reforming of CO in example 1 of the present invention2/CH4Preparing a synthetic gas reaction stability diagram;
FIG. 3 is a scanning electron microscope image of the cathode material in example 1 of the present invention;
Detailed Description
The technical solutions of the present invention will be further described below with reference to preferred embodiments, but the technical contents of the present invention are not limited to the described ranges.
Example 1
1) Adding metered PVP and Nickel nitrate to HNO3Continuously stirring the solution for 15-45min to obtain a solution A;
2) dissolving metered potassium hexacyanocobaltate (III) in HNO3Continuously stirring the solution for 15-45min to obtain a solution B;
3) mixing the prepared solution A and solution B at room temperature under strong stirring, and continuously stirring for 15-45min until a clear solution C is obtained;
4) aging the prepared clear solution at 50-100 ℃ for 10-30h, centrifuging, washing with deionized water and ethanol for several times, and drying overnight at 50-100 ℃ to obtain a Ni-Co PBA precursor;
5) directly roasting the prepared Ni-Co PBA precursor for 0.5-1.5h at the temperature of 250-500 ℃ to obtain NiO/Co3O4A nanocube. Then, through H2Cold plasma at 300-500mTorr and 100-300W for Ag/Co3O4Activating the nanocubes for 5-15min to obtain Ni-Co surface alloy catalyst powder;
6) the Ni-Co surface alloy catalyst powder prepared by the method is tableted into an electrode, and the CO is electrolyzed by the thermal-electric coupling molten salt2/CH4The cathode electrode of (1).
The electrolysis reaction is carried out in a molten salt electrolytic cell device shown in figure 1 at 400 ℃ -2SO4) Introducing CO to the cathode and anode respectively2、CH4And blowing off air in the electrolyte, and finally applying a voltage of-1V between the anode and the cathode to perform an electrolysis test.
Recording the electrolytic reaction of an electrolytic cell under the voltage of-1 to 1V by adopting an electrochemical workstationThe current density of the conductive paste is 50 to 200mA/cm2(ii) a Detecting the volume contents of the products at the cathode and anode outlets respectively by gas chromatography, and calculating the CO content2、CH4Conversion and CO yield.
Respectively keeping CO at 400 deg.C and 0.8V2、CH4Gas flow rate of 20mL/min, CO2And CH4The conversion reached a maximum of 51% and 45%, respectively, with a CO yield of 49%.
FIG. 2 shows thermo-electrically coupled molten salt electrolysis of CO prepared according to the method of example 12/CH4The reaction stability of the cathode electrode of the synthesis gas is prepared. It can be seen that CO is maintained at 400 deg.C and 0.8V respectively2、CH4When the gas flow rate is 20mL/min, the reaction is continued for 60 hours, the current density is kept relatively stable, and CO is2And CH4Still has higher conversion rate.
FIG. 3 shows thermo-electrically coupled molten salt electrolysis of CO prepared according to the method of example 12/CH4Scanning electron microscope images before and after the synthesis gas cathode electrode is continuously reacted for 60 hours show that the surface of the electrode is still loose and porous before and after the reaction, which shows that the cathode material has better porous structure stability.
Comparative example 1
1) Measured amounts of nickel nitrate and potassium hexacyanocobaltate (III) were dissolved in HNO3Continuously stirring for 15-45min in the solution until the solution is clear, aging the obtained clear solution at 50-100 ℃ for 10-30h, centrifuging, washing with deionized water and ethanol for several times, and drying overnight at 50-100 ℃ to obtain a Ni-Co precursor;
2) the Ni-Co precursor obtained by the preparation is directly roasted for 0.5 to 1.5 hours at the temperature of 250-500 ℃ to obtain NiO/Co3O4A nanocube. Then, through H2Cold plasma on Ag/Co at 300-500mTorr and 100-300W3O4Activating the nanocubes for 5-15min to obtain Ni-Co surface alloy catalyst powder;
3) the Ni-Co surface alloy catalyst powder prepared by the method is tableted into an electrode, and the CO is electrolyzed by the thermal-electric coupling molten salt2/CH4The cathode electrode of (1).
The electrolysis reaction is carried out in a molten salt electrolytic cell device shown in figure 1 at 400 ℃ -2SO4) Introducing CO to the cathode and anode respectively2、CH4And blowing off air in the electrolyte, and finally applying a voltage of-1V between the anode and the cathode to perform an electrolysis test.
Recording CO of the electrolytic cell at 400 ℃ and 0.8V by using an electrochemical workstation2、CH4The gas flow rate of (2) is 20 mL/min; detecting the volume contents of the products at the cathode and anode outlets respectively by gas chromatography, and calculating CO2、CH4The conversion rates were 29% and 23%, respectively, and the yield of CO was 19%.
Comparative example 2
1) Adding metered PVP and Nickel nitrate to HNO3Continuously stirring the solution for 5 to 15min to obtain a solution A;
2) dissolving metered potassium hexacyanocobaltate (III) in HNO3Continuously stirring the solution for 5 to 15min to obtain a solution B;
3) mixing the prepared solution A and solution B at room temperature under strong stirring, and continuously stirring for 5-15min until a clear solution C is obtained;
4) aging the prepared clear solution C at 50-100 ℃ for 10-30h, centrifuging, washing with deionized water and ethanol for several times, and drying overnight at 50-100 ℃ to obtain a Ni-Co PBA precursor;
5) performing high-temperature H on the Ni-Co PBA precursor prepared by the method2Carrying out thermal reduction for 1-3h to obtain Ni-Co surface alloy catalyst powder;
6) the Ni-Co surface alloy catalyst powder prepared by the method is tableted into an electrode, and the CO is electrolyzed by the thermal-electric coupling molten salt2An electrode of CO.
The electrolysis reaction is carried out in a molten salt electrolytic cell device shown in figure 1 at the temperature of 400-/Ag2SO4) Introducing CO to the cathode and anode respectively2、CH4And blowing off air in the electrolyte, and finally applying a voltage of-1V between the anode and the cathode to perform an electrolysis test.
Recording CO of the electrolytic cell at 400 ℃ and 0.8V by using an electrochemical workstation2、CH4The gas flow rate of (2) is 20 mL/min; detecting the volume contents of the products at the cathode and anode outlets respectively by gas chromatography, and calculating CO2、CH4The conversion rates were 34% and 19%, respectively, and the yield of CO was 24%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (7)
1. Novel CO electrolysis by using thermal-electric coupling molten salt2/CH4A preparation method and application of cathode material for preparing synthesis gas,
the method is characterized by comprising the following steps:
a. adding metered PVP and Nickel nitrate to HNO3Continuously stirring the solution to obtain a solution A;
b. dissolving metered potassium hexacyanocobaltate (III) in HNO3Continuously stirring the solution to obtain a solution B;
c. mixing the solution A obtained in the step a and the solution B obtained in the step B under the condition of strong stirring at room temperature, and continuously stirring until a clear solution C is obtained;
d. c, aging, centrifuging, washing and drying the clear solution C obtained in the step C to obtain a Ni-Co PBA precursor;
e. directly roasting the Ni-Co PBA precursor obtained in the step d to obtain NiO/Co3O4A nanocube. Then, the Ag/Co is treated by cold plasma3O4Activating the nanocubes to obtain Ni-Co surface alloy catalyst powder;
f. pressing Ni-Co surface alloy catalyst powder obtained in the step e into an electrode, namely obtaining CO electrolyzed by the thermal-electric coupling molten salt2/CH4And preparing the cathode electrode of the synthesis gas.
2. The novel thermo-electric coupling fused salt electrolysis (CO) according to claim 12/CH4The preparation method and the application of the cathode material for preparing the synthesis gas are characterized in that the continuous stirring time is 15-45 min.
3. The novel thermo-electric coupling fused salt electrolysis (CO) according to claim 12/CH4The preparation method and the application of the cathode material for preparing the synthesis gas are characterized in that the aging temperature is 50-100 ℃, the aging time is 10-30h, the washing liquid is deionized water and ethanol, and the drying temperature is 50-100 ℃.
4. The novel thermo-electric coupling molten salt electrolysis of CO of claim 12/CH4The preparation method and the application of the cathode material for preparing the synthesis gas are characterized in that the roasting atmosphere is air, the roasting temperature is 250-500 ℃, and the roasting time is 0.5-1.5 h.
5. The novel thermo-electric coupling molten salt electrolysis of CO of claim 12/CH4The preparation method and the application of the cathode material for preparing the synthesis gas are characterized in that the plasma atmosphere is H2The pressure of the plasma activated gas is 300-500mTorr, the activation power is 100-300W, and the activation time is 5-15 min.
6. The novel thermo-electric coupling fused salt electrolysis (CO) according to claim 12/CH4The preparation method and application of the cathode material for preparing the synthesis gas are characterized in that the highest methane conversion rate, the carbon dioxide conversion rate and the CO yield can be divided in a 400 ℃ molten salt electrolytic cellRespectively reaches 45%, 51% and 49%.
7. The novel thermo-electric coupling fused salt electrolysis (CO) according to claim 12/CH4The preparation method and the application of the cathode material for preparing the synthesis gas are characterized in that the continuous reaction is kept relatively stable for 60 hours.
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