Method for heat capture-conversion of green CO2 to synthesis gas by electromagnetic induction

Abstract

The invention discloses a method for capturing-converting green CO2 into synthesis gas by utilizing electromagnetic induction heat. The electromagnetic induction heat takes hysteresis loss heating as a main component, and a multifunctional material takes a Co base as a main electromagnetic induction heating component, a CaO base as a main adsorbent and a Fe base as a main catalytic component. By changing a template agent, adding an auxiliary agent for inhibiting Co oxidation, introducing a component for inhibiting CaO high-temperature sintering and adjusting the heating power and frequency of an electromagnetic inductor, the energy consumption in the reaction process is jointly reduced, and the CO2 yield, the catalytic activity, the selectivity and the stability of the multifunctional material are improved. The method has the advantages that the method for capturing-converting the green CO2 into the synthesis gas by utilizing the electromagnetic induction heat is provided, and the captured CO2 is converted into the synthesis gas in situ in the electromagnetic inductor by designing the multifunctional material which has the electromagnetic induction heating capacity (magnetic hysteresis loss heating) and is used for capturing and catalytically converting the CO2. And the problems of high energy consumption, non-uniform heating, fast heat dissipation, slow heating / cooling speed and the like in a traditional heating mode can be effectively improved.

Description

Technical Field

[0001] The present application relates to the technical field of CO2 capture-conversion to synthesis gas, and in particular to a method for capturing and converting green CO2 to synthesis gas using electromagnetic induction heat. Background Art

[0002] Against the backdrop of increasingly severe global climate change issues, carbon neutrality has become a common goal pursued by the international community. To achieve this goal, CO2 capture, utilization and storage (CCUS) provides strong technical support. However, high costs and high energy consumption restrict the large-scale promotion of this technology.

[0003] The integrated CO2 capture-conversion technology is an integrated route developed within the CCUS framework. It can significantly reduce investment in gas compression, transportation and storage processes. It is a low-energy and more efficient CO2 emission reduction technology. The Chinese invention patent (CN112569896A) discloses a calcium oxide-based bifunctional material for high-temperature capture of CO2 and in-situ catalytic conversion into synthesis gas. Among them, the carbonation reaction between CaO and CO2 needs to be carried out at 600-700°C, and the decomposition of CaCO3 into CaO is a strong endothermic reaction, requiring a high temperature of 800-900°C. In addition, the reverse water gas reaction is also a high-temperature favorable reaction, and the required temperature is as high as 500-700°C. Therefore, under the existing technical path, effectively solving the problems of uneven heating, rapid heat loss and low energy utilization in traditional heating methods is of great significance to the large-scale development of CO2 capture and conversion.

[0004] Electromagnetic induction heating technology is a heating method that directly converts electromagnetic energy into thermal energy. Heat is quickly induced on the magnetic material without heating the entire reactor, which improves energy transfer efficiency and high heat dissipation. The process is safer and cleaner. To date, CO2 capture-conversion integrated technology has been carried out using traditional heating methods. Therefore, it is crucial to design and develop a sustainable path that uses electromagnetic induction heat to capture and convert green CO2 into high value-added products. Summary of the invention

[0005] The present invention aims at the problem of high energy consumption in capturing and converting CO2 into synthesis gas, and provides a method for capturing and converting green CO2 into synthesis gas using electromagnetic induction heat. By designing a multifunctional material with electromagnetic induction heating capability (hysteresis loss heating), CO2 capture and catalytic conversion of CO2, the captured CO2 is converted into synthesis gas in situ in an electromagnetic inductor. The present invention can effectively improve the problems of high energy consumption, uneven heating, fast heat dissipation and slow heating / cooling speed in traditional heating methods.

[0006] The electromagnetic induction heat capture-conversion of green CO2 to synthesis gas is carried out in an electromagnetic inductor, an infrared temperature controller is used to control the temperature, and a non-scattering infrared spectrometer is used to monitor the exhaust gas components online. A certain amount of multifunctional material (40-60 mesh) is weighed and placed in a quartz tube, and then the quartz tube is placed in the copper coil of the electromagnetic inductor. Set the target temperature, heating power and frequency, and heat to the set temperature under a 50mL / min N2 atmosphere, and then capture and convert CO2. The first stage: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and keep it for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. The second stage: CO2 conversion, switch the gas to 30mL / min H2 for CO2 hydrogenation to synthesis gas.

[0007] The technical solution adopted in this application is: a method for capturing and converting green CO2 into synthesis gas using electromagnetic induction heat. The electromagnetic induction heat is mainly hysteresis loss heating, and the multifunctional material is mainly Co-based electromagnetic induction heating component, CaO-based adsorbent, and Fe-based catalytic component.

[0008] The following four factors are mainly used to jointly promote and improve the electromagnetic induction heating temperature, CO2 capture amount, CO2 conversion rate, CO selectivity and stability of electromagnetic induction thermal capture-conversion of green CO2 to synthesis gas.

[0009] First, since the capture and conversion of green CO2 into synthesis gas needs to be carried out in the temperature range of 600-700℃, the electromagnetic induction heating component in the multifunctional material is mainly based on the magnetic material Co (the Curie temperature of Co is 1130℃), and one or two of the magnetic-assisting components Fe and Ni are added to inhibit the slow oxidation of metal Co in the CO2 atmosphere to keep the electromagnetic induction heating temperature constant;

[0010] Second, using CaO as the main adsorption component, one or more of Mg, Al, Ga, and Y are added to inhibit the high-temperature sintering of CaO and enhance the cycle stability of CO2 capture;

[0011] Third, adding a template agent: one of cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and the template agent: CaO (mass ratio) = 1:1 to 3:1, to enhance the dispersion of the components in the multifunctional material, improve the pore structure and increase the specific surface area, and promote the multifunctional material to have a higher CO2 adsorption capacity, catalytic activity and stability;

[0012] Fourthly, the temperature and heating rate are adjusted by adjusting the heating frequency and power of the electromagnetic inductor. When the target temperature can be heated, the heating power is reduced as much as possible, thereby reducing energy consumption.

[0013] The method comprises the following steps:

[0014] 1. Synthesis of multifunctional materials:

[0015] (1) Dissolve the template in deionized water to obtain solution A.

[0016] (2) Adding the precursor salt of the catalytic component, ferric nitrate nonahydrate, to the solution A, fully dissolving and stirring to obtain a solution B.

[0017] (3) Adding the precursor salt of the electromagnetic induction heating component, cobalt nitrate hexahydrate, into the solution B, fully dissolving and stirring to obtain a solution C.

[0018] (4) Adding the precursor salt of the CO2 adsorption component, calcium nitrate tetrahydrate, to the solution C, fully dissolving it, and stirring it at 25°C for 1 hour to obtain a solution D.

[0019] (5) Solution D was placed in a freeze dryer for 48 h, calcined in a muffle furnace at 800 °C for 2 h (heating rate of 1 °C / min), and then transferred to a tubular furnace for reduction at 600 °C for 1 h (100 mL / min) under pure H2 atmosphere to obtain a multifunctional material.

[0020] The template in step (1) is one of cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and the template:CaO (mass ratio) is 1:1 to 3:1.

[0021] The amount of ferric nitrate nonahydrate added in step (2) is Fe:CaO (molar ratio) = 1:5 to 1:15.

[0022] In step (3), the amount of cobalt nitrate hexahydrate added is Co:CaO (molar ratio) = 1:5 to 1:15, and the amount of nickel nitrate hexahydrate added is Ni:CaO (molar ratio) = 0:5 to 1:10.

[0023] In step (4), one or more of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, gallium nitrate hexahydrate or yttrium nitrate hexahydrate are added, and the amount of stabilizer precursor salt added is M:CaO (molar ratio) = 1:5 to 1:15.

[0024] The reduction temperature used in the tubular furnace in step (5) is 500-700°C.

[0025] 2. Performance test of electromagnetic induction heat capture and conversion of green CO2 into syngas

[0026] (1) Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of an electromagnetic inductor.

[0027] (2) Set the target temperature, heating power and frequency, and heat to the set temperature in a 50 mL / min N2 atmosphere.

[0028] (3) For CO2 capture, the gas was switched to 15% CO2 / N2 (30 mL / min) and maintained for 20 min, and then 50 mL / min N2 was used to purge the CO2 in the pipeline.

[0029] (4) To carry out CO2 conversion, the gas was switched to 30 mL / min H2 for CO2 hydrogenation to produce synthesis gas.

[0030] The target temperature range set in step (2) is 600-700° C., the power adjustment range is 0-10 kW, and the frequency adjustment range is 100-200 kHz.

[0031] At least one of the above technical solutions adopted in this application can achieve the following beneficial effects:

[0032] This application proposes a method for capturing and converting green CO2 into synthesis gas using electromagnetic induction heat. The multifunctional material has Co as the main magnetic induction heating component, CaO as the main adsorbent, and Fe as the main catalytic component. After the modification of four factors, the performance of capturing and converting green CO2 into synthesis gas using electromagnetic induction heat is optimal. When the power of the electromagnetic inductor is 50KW and the frequency is 100KHZ, it only takes 16s for the multifunctional material to heat from 25°C to 650°C, and it can be stably maintained at 650°C for 500h. At the same time, the multifunctional material shows 10.9mmol g -1 100% CO2 adsorption, 100% CO2 conversion, 100% CO selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 .FeCoNiMgCaO x The relationship between the conversion rate and selectivity of CO2 hydrogenation to CO over time (500h).

[0034] Figure 2 .FeCoNiMgCaO x The relationship between the amount of CO2 adsorbed by the catalyst and time (500h). DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solution and advantages of the present application clearer, the technical solution of the present application will be clearly and completely described below in combination with the specific embodiments of the present application and the corresponding drawings. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present application.

[0036] Example 1. Using Fe1Co1Ca 10 O is a multifunctional material that uses electromagnetic induction heat to capture and convert green CO2 into syngas

[0037] (1) Preparation of multifunctional materials

[0038] Weigh 4.7230g P123 and fully dissolve it in 20mL deionized water. Add 0.4040g ferric nitrate nonahydrate, 0.2910g cobalt nitrate hexahydrate, and 2.3615g calcium nitrate tetrahydrate to the above solution, and then stir the above solution vigorously at 25°C for 1h. Place the above solution in a freeze dryer for 48h, calcine at 800°C in a muffle furnace for 2h (heating rate of 1°C / min), and then transfer it to a tube furnace in a pure H2 atmosphere and reduce it at 600°C for 1h (100mL / min) to obtain Fe1Co1Ca 10 oMultifunctional material.

[0039] (2) Performance test of using electromagnetic induction heat to capture and convert green CO2 into synthesis gas

[0040] Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor. Set the target temperature to 650°C, the heating power to 5KW, the heating frequency to 100KHZ, and raise the temperature to the set temperature of 650°C under a 50mL / min N2 atmosphere, and then perform CO2 capture and conversion. Stage 1: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and maintain for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. Stage 2: CO2 conversion, switch the gas to 30mL / min H2 to hydrogenate CO2 to synthesis gas. Repeat this cycle. The evaluation results of the CO2 capture performance, CO2 conversion rate, CO selectivity and stability of the multifunctional material are as follows:

[0041]

[0042] Example 2. Fe1Co1Ni1Ca 10 O is a multifunctional material that uses electromagnetic induction heat to capture and convert green CO2 into syngas

[0043] (1) Preparation of multifunctional materials

[0044] Weigh 4.7230g P123 and fully dissolve it in 20mL deionized water. Add 0.4040g ferric nitrate nonahydrate, 0.2910g cobalt nitrate hexahydrate, 0.2908g nickel nitrate hexahydrate, and 2.3615g calcium nitrate tetrahydrate to the above solution, and then stir the above solution vigorously at 25°C for 1h. Place the above solution in a freeze dryer for 48h, calcine at 800°C in a muffle furnace for 2h (heating rate of 1°C / min), and then transfer it to a tube furnace in a pure H2 atmosphere and reduce it at 600°C for 1h (100mL / min) to obtain Fe1Co1Ni1Ca 10 oMultifunctional material.

[0045] (2) Performance test of using electromagnetic induction heat to capture and convert green CO2 into synthesis gas

[0046] Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor. Set the target temperature to 650°C, the heating power to 5KW, the heating frequency to 100KHZ, and raise the temperature to the set temperature of 650°C under a 50mL / min N2 atmosphere, and then perform CO2 capture and conversion. Stage 1: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and maintain for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. Stage 2: CO2 conversion, switch the gas to 30mL / min H2 to hydrogenate CO2 to synthesis gas. Repeat this cycle. The evaluation results of the CO2 capture performance, CO2 conversion rate, CO selectivity and stability of the multifunctional material are as follows:

[0047]

[0048] Example 3. Fe1Co1Ni1Mg1Ca 10 O is a multifunctional material that uses electromagnetic induction thermal capture to convert green CO2 into syngas

[0049] (1) Preparation of multifunctional materials

[0050] Weigh 4.7230g P123 and fully dissolve it in 20mL deionized water. Add 0.4040g ferric nitrate nonahydrate, 0.2910g cobalt nitrate hexahydrate, 0.2908g nickel nitrate hexahydrate, 2.3615g calcium nitrate tetrahydrate and 0.2564g magnesium nitrate hexahydrate to the above solution, and then stir the above solution vigorously at 25°C for 1h. Place the above solution in a freeze dryer for 48h, calcine at 800°C in a muffle furnace for 2h (heating rate of 1°C / min), and then transfer it to a tube furnace for reduction at 600°C for 1h (100mL / min) under pure H2 atmosphere to obtain Fe1Co1Ni1Mg1Ca 10 oMultifunctional material.

[0051] (2) Performance test of using electromagnetic induction heat to capture and convert green CO2 into synthesis gas

[0052] Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor. Set the target temperature to 650°C, the heating power to 5KW, the heating frequency to 100KHZ, and raise the temperature to the set temperature of 650°C under a 50mL / min N2 atmosphere, and then perform CO2 capture and conversion. Stage 1: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and maintain for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. Stage 2: CO2 conversion, switch the gas to 30mL / min H2 to hydrogenate CO2 to synthesis gas. Repeat this cycle. The evaluation results of the CO2 capture performance, CO2 conversion rate, CO selectivity and stability of the multifunctional material are as follows:

[0053]

[0054] Example 4. Fe1Co1Ni1Mg1Ca 10 O-700℃ reduction to multifunctional materials, using electromagnetic induction heat to capture and convert green CO2 into syngas

[0055] (1) Preparation of multifunctional materials

[0056] Weigh 4.7230g P123 and fully dissolve it in 20mL deionized water. Add 0.4040g ferric nitrate nonahydrate, 0.2910g cobalt nitrate hexahydrate, 0.2908g nickel nitrate hexahydrate, 2.3615g calcium nitrate tetrahydrate and 0.2564g magnesium nitrate hexahydrate to the above solution, and then stir the above solution vigorously at 25°C for 1h. Place the above solution in a freeze dryer for 48h, calcine at 800°C in a muffle furnace for 2h (heating rate of 1°C / min), and then transfer it to a tubular furnace for reduction at 700°C for 1h (100mL / min) under pure H2 atmosphere to obtain Fe1Co1Ni1Mg1Ca 10 O-700℃ multifunctional material.

[0057] (2) Performance test of using electromagnetic induction heat to capture and convert green CO2 into synthesis gas

[0058] Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor. Set the target temperature to 650°C, the heating power to 5KW, the heating frequency to 100KHZ, and raise the temperature to the set temperature of 650°C under a 50mL / min N2 atmosphere, and then perform CO2 capture and conversion. Stage 1: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and maintain for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. Stage 2: CO2 conversion, switch the gas to 30mL / min H2 to hydrogenate CO2 to synthesis gas. Repeat this cycle. The evaluation results of the CO2 capture performance, CO2 conversion rate, CO selectivity and stability of the multifunctional material are as follows:

[0059]

[0060] Example 5. Fe1Co1Ni1Mg1Ca 10 O is a multifunctional material that uses electromagnetic induction heat to capture and convert green CO2 into syngas

[0061] (1) Preparation of multifunctional materials

[0062] Weigh 4.7230g P123 and fully dissolve it in 20mL deionized water. Add 0.4040g ferric nitrate nonahydrate, 0.2910g cobalt nitrate hexahydrate, 0.2908g nickel nitrate hexahydrate, 2.3615g calcium nitrate tetrahydrate and 0.2564g magnesium nitrate hexahydrate to the above solution, and then stir the above solution vigorously at 25°C for 1h. Place the above solution in a freeze dryer for 48h, calcine at 800℃ in a muffle furnace for 2h (heating rate of 1℃ / min), and then transfer it to a tubular furnace for reduction at 600℃ for 1h (100mL / min) under pure H2 atmosphere to obtain Fe1Co1Ni1Mg1Ca 10 oMultifunctional material.

[0063] (2) Performance test of using electromagnetic induction heat to capture and convert green CO2 into synthesis gas

[0064] Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor. Set the target temperature to 650°C, the heating power to 7KW, the heating frequency to 150KHZ, and raise the temperature to the set temperature of 650°C under a 50mL / min N2 atmosphere, and then perform CO2 capture and conversion. Stage 1: CO2 capture, switch the gas to 15% CO2 / N2 (30mL / min) and maintain for 20min, then use 50mL / min N2 to purge the CO2 in the pipeline. Stage 2: CO2 conversion, switch the gas to 30mL / min H2 for CO2 hydrogenation to synthesis gas. Repeat this cycle. The evaluation results of the CO2 capture performance, CO2 conversion rate, CO selectivity and stability of the multifunctional material are as follows:

[0065]

[0066] The above is only an embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims

1. A method for capturing and converting green CO2 into synthesis gas using electromagnetic induction heat. The electromagnetic induction heat is mainly hysteresis loss heating, and the multifunctional material is mainly Co-based electromagnetic induction heating component, CaO-based adsorbent, and Fe-based catalytic component. The method comprises the following steps: 1.1 Synthesis of multifunctional materials: (1) Dissolve the template in deionized water to obtain solution A. (2) adding the precursor salt of the catalyst component, ferric nitrate nonahydrate, to the solution A, fully dissolving and stirring to obtain a solution B; (3) adding cobalt nitrate hexahydrate, a precursor salt of the electromagnetic induction heating component, to the solution B, fully dissolving and stirring to obtain a solution C; (4) adding calcium nitrate tetrahydrate, a precursor salt of the CO2 adsorption component, to the solution C, fully dissolving it, and stirring at 25° C. for 1 h to obtain a solution D; (5) Solution D was placed in a freeze dryer for 48 h, calcined in a muffle furnace at 800 °C for 2 h (heating rate of 1 °C / min), and then transferred to a tube furnace for reduction at 600 °C for 1 h (100 mL / min) under pure H2 atmosphere to obtain a multifunctional material; 1.2 Performance test of electromagnetic induction heat capture and conversion of green CO2 into syngas (6) Weigh a certain amount of multifunctional material (40-60 mesh) and place it in a quartz tube, and then place the quartz tube in the copper coil of the electromagnetic inductor; (7) Set the target temperature, heating power and frequency, and heat to the set temperature under 50 mL / min N2 atmosphere; (8) For CO2 capture, switch the gas to 15% CO2 / N2 (30 mL / min) and maintain for 20 min, then use 50 mL / min N2 to purge the CO2 in the pipeline; (9) For CO2 conversion, switch the gas to 30 mL / min H2 to hydrogenate CO2 into synthesis gas.

2. The method according to claim 1, characterized in that The template in step (1) is one of cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and the template:CaO (mass ratio) is 1:1 to 3:

1.

3. The method according to claim 1, characterized in that The amount of ferric nitrate nonahydrate added in step (2) is Fe:CaO (molar ratio) = 1:5 to 1:

15.

4. The method according to claim 1, characterized in that In step (3), the amount of cobalt nitrate hexahydrate added is Co:CaO (molar ratio) = 1:5 to 1:15, and the amount of nickel nitrate hexahydrate added is Ni:CaO (molar ratio) = 0:5 to 1:

10.

5. The method according to claim 1, characterized in that The target temperature range set in step (7) is 600-700° C., the power adjustment range is 0-10 kW, and the frequency adjustment range is 100-200 kHz.

6. The method according to claim 1, characterized in that The electromagnetic induction heat capture-conversion of green CO2 to synthesis gas is carried out in an electromagnetic inductor, an infrared temperature controller is used to control the temperature, and a non-scattering infrared spectrometer is used to monitor the exhaust gas components online. A certain amount of multifunctional material (40-60 mesh) is weighed and placed in a quartz tube, and then the quartz tube is placed in the copper coil of the electromagnetic inductor, and the target temperature, heating power and frequency are set. In a 50mL / min N2 atmosphere, the temperature is raised to the set temperature, and then CO2 is captured and converted. The first stage: CO2 capture, the gas is switched to 15% CO2 / N2 (30mL / min) and maintained for 20min, and then 50mL / min N2 is used to purge the CO2 in the pipeline. The second stage: CO2 conversion, the gas is switched to 30mL / min H2 for CO2 hydrogenation to synthesis gas.

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