Method for preparing carbon monoxide by using sodium carbonate and manganese oxide thermochemical cycle
By using a thermochemical cycle of sodium carbonate and manganese oxide, carbon monoxide can be prepared at a lower temperature, solving the problems of high energy consumption and difficulty in scaling up traditional methods, and providing a stable energy supply solution.
Patent Information
- Application Number
- CN202310889985.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-07-19
- Publication Date
- 2026-02-10
- Estimated Expiration
- 2043-07-19
AI Technical Summary
Traditional methods for preparing carbon monoxide are energy-intensive, difficult to scale up, and require sophisticated equipment.
Carbon monoxide is prepared by a multi-step reaction using a thermochemical cycle of sodium carbonate and manganese oxide. This process includes the endothermic decomposition of manganese trioxide to produce manganese tetroxide and oxygen, the reaction of manganese tetroxide with sodium carbonate to produce NaMnO2, carbon dioxide, and carbon monoxide, and the reduction of carbon dioxide by recycling manganese trioxide and sodium carbonate.
It provides stable carbon monoxide at lower temperatures, achieves zero carbon emissions, utilizes carbon dioxide resources, reduces production costs and energy consumption, and is suitable for energy supply in regions with unbalanced energy supply and demand.
Smart Images
Figure CN116969459B_ABST
Abstract
Description
Technical Field
[0001] This disclosure relates to the field of fuel preparation technology, specifically to a method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide. Background Technology
[0002] Global energy supply currently relies primarily on burning fossil fuels; however, massive carbon emissions are exacerbating global warming. The resource utilization of carbon dioxide is a crucial pathway to achieving energy conservation, emission reduction, and sustainable development. Novel methods for using carbon dioxide as a raw material to produce carbon monoxide fuel have attracted widespread attention. Thermochemical cycles are a common method for decomposing carbon dioxide into carbon monoxide, encompassing various systems such as metal oxide systems, sulfur-containing systems, and halide metal systems. Among these, metal oxide systems have garnered significant attention due to their simple steps and lack of phase transitions. The thermochemical cycle for producing carbon monoxide fuel using metal oxide systems involves two steps: first, a high-temperature heat source decomposes the metal oxide, reducing it by losing oxygen atoms; second, the reduced metal oxide reacts with carbon dioxide, reducing it back to carbon monoxide, then oxidizes back to its pre-reduction state, endothermically resuming the first step of the reaction. While this two-step thermochemical cycle significantly lowers the reaction temperature, it remains relatively high (approximately 1500℃), requiring sophisticated equipment and hindering large-scale application. Summary of the Invention
[0003] (a) Technical problems to be solved
[0004] To address the aforementioned problems, this disclosure provides a method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide, which at least partially solves the technical problems of high energy consumption and difficulty in large-scale application of traditional carbon monoxide preparation methods.
[0005] (II) Technical Solution
[0006] This disclosure provides a method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide, comprising: S1, mixing sodium carbonate and manganese trioxide, heating to cause the manganese trioxide to undergo an endothermic decomposition reaction to obtain manganese tetroxide and oxygen; S2, heating to cause the manganese tetroxide and sodium carbonate to undergo an endothermic reaction to obtain NaMnO2, carbon dioxide and carbon monoxide; S3, introducing carbon dioxide to react with NaMnO2 to obtain manganese trioxide and sodium carbonate, wherein the manganese trioxide and sodium carbonate are recycled in S1 and S2.
[0007] Furthermore, concentrated solar energy is used for heating in S1, and the reaction temperature of the endothermic decomposition reaction is 700-1200℃.
[0008] Furthermore, the molar ratio of sodium carbonate to manganese trioxide in S1 is 1:1 to 1:6.
[0009] Furthermore, the oxygen obtained in S1 is separated and output as a product.
[0010] Furthermore, concentrated solar energy is used for heating in S2.
[0011] Furthermore, after S2, the process also includes: removing the carbon dioxide produced by S2 and collecting the carbon monoxide product.
[0012] (III) Beneficial Effects
[0013] The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide disclosed herein employs a multi-step thermochemical cycle to decompose carbon dioxide into carbon monoxide fuel, providing a stable and sufficient supply of carbon monoxide at relatively low temperatures. This method only requires carbon dioxide and heat energy to be input into the system, while carbon monoxide and oxygen are output as products, achieving the goal of zero-carbon emission resource utilization of carbon dioxide and production of carbon monoxide fuel. The carbon monoxide produced by this method can be transported to energy-demanding areas, solving the problem of uneven distribution of energy supply and demand. Attached Figure Description
[0014] Figure 1 The illustration shows a schematic flow diagram of a method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to an embodiment of the present disclosure. Detailed Implementation
[0015] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments and the accompanying drawings.
[0016] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.
[0017] This disclosure provides a method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide. Please refer to [link to relevant documentation]. Figure 1 The process includes: S1, mixing sodium carbonate and manganese trioxide, heating to cause the manganese trioxide to undergo an endothermic decomposition reaction, yielding manganese tetroxide and oxygen; S2, heating to cause the manganese tetroxide and sodium carbonate to undergo an endothermic reaction, yielding NaMnO2, carbon dioxide and carbon monoxide; S3, introducing carbon dioxide to react with NaMnO2, yielding manganese trioxide and sodium carbonate, with the manganese trioxide and sodium carbonate being recycled in S1 and S2.
[0018] Specifically, in S1, sodium carbonate and manganese trioxide are mixed in a certain proportion to carry out an endothermic decomposition reaction of manganese trioxide, thereby obtaining manganese tetroxide. The generated oxygen is separated as a product. The reaction equation is as follows:
[0019] 3Mn₂O₃→2Mn₃P₄+0.5O₂
[0020] S2, manganese tetroxide and sodium carbonate undergo an endothermic reaction to produce NaMnO2, carbon dioxide and carbon monoxide. The reaction equation is as follows:
[0021] 2Mn3O4+3Na2CO3→6NaMnO2+2CO+CO2
[0022] In step S3, carbon dioxide is introduced and reacts with the NaMnO2 produced in step S2, generating manganese trioxide and sodium carbonate required for the first two steps, thus completing the cycle. The carbon dioxide from the second step is removed, and carbon monoxide is collected as a product. The reaction equation is as follows:
[0023] 6NaMnO2 + 3CO2 → 3Mn2P3 + 3Na2CO3
[0024] The generated manganese trioxide and sodium carbonate are used in the endothermic reactions of S1 and S2, respectively, thereby achieving the recycling of reactants.
[0025] Carbon monoxide is a pollution-free and renewable energy carrier that is convenient to transport and store and has high energy density. This disclosure uses a multi-step thermochemical cycle to decompose carbon dioxide to produce carbon monoxide fuel, which can provide a stable and sufficient supply of carbon monoxide at a relatively low temperature. This method only requires carbon dioxide and heat energy to be input into the system, and carbon monoxide and oxygen are output as products, achieving the goal of zero-carbon emission resource utilization of carbon dioxide and production of carbon monoxide fuel.
[0026] Based on the above embodiments, concentrated solar energy is used for heating in S1, and the reaction temperature of the endothermic decomposition reaction is 700-1200℃.
[0027] The thermochemical three-step cycle indirect decomposition method for producing carbon monoxide fuel from sodium carbonate and manganese oxide disclosed herein has a maximum reaction temperature of approximately 700–1200°C, which greatly reduces the reaction temperature and avoids the problem of not being able to produce carbon monoxide fuel on a large scale due to excessively high reaction temperatures. This provides a new solution for producing carbon monoxide fuel from carbon dioxide with low energy consumption.
[0028] Based on the above embodiments, the molar ratio of sodium carbonate to manganese trioxide in S1 is 1:1 to 1:6.
[0029] Maintaining a molar ratio of sodium carbonate to manganese trioxide within the above range helps ensure the stability of the cycle, covers material losses caused by various reasons, and ensures that sodium carbonate reacts fully to produce sufficient carbon monoxide.
[0030] Based on the above embodiment, the oxygen obtained in S1 is separated and output as a product.
[0031] During the cycle, oxygen and carbon monoxide are separated in sequence, thus solving the problem of product separation.
[0032] Based on the above embodiment, concentrated solar energy is used for heating in S2.
[0033] The reaction temperature is similar to that of S1 above, and will not be repeated here. Furthermore, the method disclosed herein does not involve fossil fuel input; only carbon dioxide and heat are input into the system, while carbon monoxide and oxygen are output as products, achieving the goal of zero-carbon emission resource utilization of carbon dioxide to produce carbon monoxide fuel.
[0034] Based on the above embodiments, after S2, the method further includes: removing the carbon dioxide generated in S2 and collecting the carbon monoxide product.
[0035] The present disclosure will be further described below through specific embodiments. The method for preparing carbon monoxide by the thermochemical cycle of sodium carbonate and manganese oxide described above will be specifically illustrated in the following examples. However, the following examples are merely illustrative of the present disclosure, and the scope of the present disclosure is not limited thereto.
[0036] Example 1:
[0037] The method for preparing carbon monoxide by thermochemical cycling of sodium carbonate and manganese oxide in this embodiment is as follows: Figure 1 As shown, the following steps are performed sequentially:
[0038] Step 11: Sodium carbonate and manganese trioxide are mixed in a molar ratio of 1:1 and fed into a tube furnace. The reaction temperature is 1000℃ and the reaction time is 50 minutes. Manganese trioxide decomposes upon heating to obtain manganese tetroxide. The reaction equation is as follows:
[0039] 3Mn₂O₃→2Mn₃O₄+0.5O₂
[0040] Oxygen is separated as a product.
[0041] Step 12: Continue heating and maintain the temperature at 1000℃ for 50 minutes to obtain NaMnO2, carbon dioxide, and carbon monoxide. The reaction is complete when no more gas is produced. The reaction equation is as follows:
[0042] 2Mn3O4+3Na2CO3→6NaMnO2+2CO+CO2
[0043] Step 13: Cool the solid product obtained in Step 12 to 300℃ and keep it at that temperature for 30 minutes, then introduce carbon dioxide to obtain manganese trioxide and sodium carbonate. The reaction equation is as follows:
[0044] 6NaMnO2 + 3CO2 → 3Mn2O3 + 3Na2CO3
[0045] Carbon monoxide was collected using a gas collection bag and detected by gas chromatography. The results showed that the generated gas was CO.
[0046] Step 14: The solid obtained in step 13 is recycled back to steps 11 and 12 as raw material.
[0047] Example 2:
[0048] The method for preparing carbon monoxide by thermochemical cycling of sodium carbonate and manganese oxide in this embodiment is as follows: Figure 1 As shown, the following steps are performed sequentially:
[0049] Step 21: Sodium carbonate and manganese trioxide are mixed in a molar ratio of 1:1. The reactor is heated under normal pressure using a Fresnel lens to carry out the reaction. The direct solar irradiance on that day was 500 W / m². 2 The concentration ratio was set to 500, the reaction temperature to 1000℃, and the reaction time to 50 minutes. Manganese trioxide decomposed upon heating to produce manganese trioxide. The reaction equation is as follows:
[0050] 3Mn₂O₃→2Mn₃O₄+0.5O₂
[0051] Oxygen is separated as a product.
[0052] Step 22: Continue to expose to sunlight and maintain the temperature at 1000℃ for 50 minutes to obtain NaMnO2, carbon dioxide, and carbon monoxide. The reaction is complete when no more gas is produced. The reaction equation is as follows:
[0053] 2Mn3O4+3Na2CO3→6NaMnP2+2CO+CO2
[0054] Step 23: After cooling the solid product obtained in Step 22 to 300℃ and holding it at that temperature for 30 minutes, carbon dioxide is introduced to obtain manganese trioxide and sodium carbonate. The reaction equation is as follows:
[0055] 6NaMnO2 + 3CO2 → 3Mn2O3 + 3Na2CO3
[0056] Carbon monoxide was collected using a gas collection bag as a product. The results showed that the gas produced was CO.
[0057] Step 24: The solid obtained in step 23 is recycled back to steps 21 and 22 as raw material.
[0058] In summary, the advantages of the method for preparing carbon monoxide by thermochemical cycling of sodium carbonate and manganese oxide disclosed herein are as follows:
[0059] 1. The thermochemical three-step cycle indirect decomposition method of sodium carbonate and manganese oxide to produce carbon monoxide fuel disclosed herein has a maximum reaction temperature of approximately 700–1200°C, which greatly reduces the reaction temperature and avoids the problem of not being able to produce carbon monoxide fuel on a large scale due to excessively high reaction temperatures. This provides a new solution for the low-energy decomposition of carbon dioxide to produce carbon monoxide fuel.
[0060] 2. The thermochemical three-step cyclic indirect decomposition method of sodium carbonate and manganese oxide to produce carbon monoxide fuel disclosed herein allows for the recycling of the reactants manganese trioxide and sodium carbonate, thereby reducing the production cost of carbon monoxide fuel. Furthermore, the use of commercially available raw materials for manganese trioxide and sodium carbonate eliminates the need for special processing and preparation, thus reducing the technical difficulty of producing carbon monoxide fuel.
[0061] 3. The thermochemical three-step cycle indirect decomposition method of sodium carbonate and manganese oxide to produce carbon monoxide fuel disclosed herein uses carbon dioxide as the only substance input, heat as the only energy input, and carbon monoxide and oxygen as the only two substances output, without the generation of by-products or impurities, thus improving atom utilization efficiency.
[0062] 4. The thermochemical three-step cyclic indirect decomposition method of sodium carbonate and manganese oxide to produce carbon monoxide fuel disclosed herein involves all three steps of reaction being carried out in one reactor, which reduces the energy input (thermal energy, electrical energy, and mechanical energy) required for the reaction process, thereby improving thermal efficiency and total heat utilization rate.
[0063] 5. The thermochemical three-step cycle of sodium carbonate and manganese oxide in this disclosure for the indirect decomposition of carbon dioxide to carbon monoxide fuel does not involve corrosive substances in the reaction, and the equipment in the system does not require anti-corrosion design, resulting in greater stability and wider applicability.
[0064] 6. The thermochemical three-step cycle indirect decomposition method of sodium carbonate and manganese oxide to produce carbon monoxide fuel disclosed herein has no fossil energy input, only carbon dioxide and heat energy input into the system, and carbon monoxide and oxygen as output products, thus achieving the goal of zero-carbon emission resource utilization of carbon dioxide to produce carbon monoxide fuel.
Claims
1. A method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide, characterized in that, include: S1, Sodium carbonate and manganese trioxide are mixed and heated to cause the manganese trioxide to undergo an endothermic decomposition reaction, yielding manganese tetroxide and oxygen; S2, heating causes the manganese tetroxide to react endothermically with the sodium carbonate to produce NaMnO2, carbon dioxide and carbon monoxide; S3, carbon dioxide is introduced to react with the NaMnO2 to obtain manganese trioxide and sodium carbonate, which are recycled in S1 and S2; The three reactions S1, S2, and S3 are all carried out in one reactor, and the highest reaction temperature in the three reactions is 700~1200℃.
2. The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to claim 1, characterized in that, In S1, concentrated solar energy is used for heating, and the reaction temperature of the endothermic decomposition reaction is 700~1200℃.
3. The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to claim 2, characterized in that, The molar ratio of sodium carbonate and manganese trioxide in S1 is 1:1 to 1:
6.
4. The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to claim 3, characterized in that, The oxygen obtained in S1 is separated and output as a product.
5. The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to claim 1, characterized in that, Concentrated solar energy is used for heating in S2.
6. The method for preparing carbon monoxide using a thermochemical cycle of sodium carbonate and manganese oxide according to claim 5, characterized in that, Following S2, the following also includes: Remove the carbon dioxide produced in S2 and collect the carbon monoxide product.