Carbon dioxide high-temperature capture and utilization method and reactor thereof

Abstract

The invention discloses a carbon dioxide high-temperature capture and utilization method and a reactor thereof. CO2 is captured from the high-temperature gas and converted into CO or synthesis gas in situ. CO2-containing high-temperature flue gas enters the reactor and enters the adsorption reaction tube from one end of the adsorption reaction tube after being distributed, CO2 in the flue gas is subjected to adsorption reaction by the catalytic material filled in the adsorption reaction tube, and decarbonized gas is discharged from the other end of the adsorption reaction tube and is discharged from the reactor through decarbonized gas collection equipment; the reducing gas enters the conversion reaction tube from one end of the conversion reaction tube after being distributed, the catalytic material in the conversion reaction tube is subjected to conversion reaction, CO2 adsorbed by the catalytic material in the conversion reaction tube is converted into CO, the catalytic material in the conversion reaction tube is converted and regenerated, and CO-containing product gas is discharged from the other end of the reaction tube; product gas is discharged from the reactor through product gas collecting equipment, and the adsorption reaction tube and the conversion reaction tube periodically switch feeding and subsequent processes. By using the method, the energy utilization rate can be fully increased, the emission reduction cost can be effectively reduced, high energy consumption caused by capture cooling / conversion heating can be avoided, and the high cost of purification and transportation after CO2 capture and potential safety hazards caused by CO2 burying are solved.

Description

Technical Field

[0001] The present invention belongs to the field of chemical industry and relates to a method for capturing carbon dioxide from high-temperature gas and converting it into synthesis gas in situ (synthesis gas here and hereinafter refers to CO or a mixture of CO and hydrogen, water vapor, etc.), and specifically relates to a high-temperature capture and utilization method of carbon dioxide and a reactor thereof. Background Art

[0002] Carbon capture, utilization and storage (CCUS) is the most important technical path to address global climate change and control greenhouse gas emissions. 2 There are many sources of CO emissions, such as cement, steel, electricity, coal chemical industry and refineries. 2 Major emitters of CO 2 Emissions issues, all industries have carried out CO 2 Each industry has formed a variety of CO2 capture, utilization and storage according to its own characteristics. 2 Technological approaches to capture, utilization and storage.

[0003] At present, the focus of large-scale research on carbon capture is on the power industry. Among them, the chemical absorption capture method for flue gas after combustion in coal-fired power plants is a relatively mature technology. However, high-temperature flue gas requires step-by-step heat exchange to be absorbed at low temperatures, and its solvent cost is high and the regeneration energy consumption is high, resulting in an additional increase of about 30% in the energy consumption of coal-fired power plants. At the same time, the captured CO 2 Offsite storage requires high transportation costs and is also subject to questionable safety issues. Adsorption is also relatively mature in technology, but is generally only used in conditions where the gas composition is determined. The capacity of the adsorbent and CO 2 The selectivity is low, the cost is high, and it is generally only used for low-temperature gases. Membrane methods usually cannot achieve a high degree of separation and require multiple stages and / or recycling, which leads to increased complexity, energy consumption and cost. At the same time, impurities in the gas may also cause blockage. After the above methods are captured, only high-concentration CO 2 Gas, subsequent transportation, and utilization are also issues that deserve attention. 2 The key is the technology to capture and convert it into high value-added chemicals.

[0004] In recent years, with the strong support of the Chinese government, enterprises, scientific research institutions and universities have jointly participated in a series of studies on supporting policies, related theories and key technologies, established a professional research team, and achieved a number of results and progress. The details of major domestic industrial pilot and demonstration projects are as follows: The CO2-based power plant launched by Huaneng Group at Shanghai Shidongkou Second Power Plant in December 20092 The capture demonstration project used a CO 2 Capture technology, CO captured annually 2 The scale reaches 120,000 tons, capturing CO 2 The purity reaches over 99.5%. The captured CO 2 Some of it is used in the food processing industry after passing through the refining system, and the rest is used in industrial production. When it was put into operation, the capture device was the largest coal-fired power plant flue gas CO 2 The 250MW IGCC unit of Huaneng Tianjin Green Coal Power was completed and put into operation in 2011, and the 400MW unit with CO 2 The IGCC unit with capture device is designed to research, develop, demonstrate and promote CO 2 The near-zero-emission coal-based power generation system can significantly improve power generation efficiency and master the design, construction and operation technologies of large-scale coal gasification projects.

[0005] Three companies have established calcium cycle CO capture technology. 2 The pilot demonstration adopts the calcium circulation double fluidized bed circulation capture system to achieve CO 2 Capture and regeneration.

[0006] All of the above technologies focus on CO 2 In terms of capture, it does not involve conversion and subsequent utilization. 2 Most of the research on capture and conversion focuses on catalysts. 2 Capture is a highly exothermic reaction, and the conversion process is a highly endothermic reaction. The temperature and heat control of the reaction process is extremely critical. The process design and reactor type are the key to determining whether the technology is feasible. For highly endothermic and exothermic reactions, the measures usually taken include: using coils to take heat / supplement heat, using direct combustion heating, using fluidized beds, moving beds, etc. These methods are used for CO 2 There are some problems in both capture and conversion. On the one hand, the coils absorb heat and take heat as the capture / conversion process switches, which makes control difficult. On the other hand, due to the uneven reaction in the catalyst bed, it is difficult to avoid local overheating / overcooling. Direct supplementary heating often causes the problem of overheating of the gas after combustion. Taking the commonly used CaO / CaCO 3 For example, when the temperature is > 850-900°C, the adsorbent will melt and sinter, while CO 2The conversion process generally requires a reaction temperature of 500-700℃ or above. If direct supplementary combustion is used for heating, the temperature is too high and the adsorbent will melt, sinter and become inactive. If the temperature is controlled to less than 800℃, the supplementary heat is very limited due to the temperature difference, or too much fuel gas and combustion-supporting gas are required, resulting in serious dilution of the product and a decrease in the effective gas concentration. If the reactor adopts a fluidized bed, moving bed or other form, since most industrial flue gas is at normal pressure or low pressure, it is basically impossible to achieve this by conventional means due to pressure limitations.

[0007] CN202110287520.5 discloses a method for reducing carbon monoxide synthesis gas with a high-temperature molten heat carrier, carbon dioxide and carbon powder. The method uses carbon dioxide and carbon powder to absorb the sensible heat and latent heat emitted by the high-temperature heat carrier and heat it to the reduction temperature to instantly reduce it to carbon monoxide high-energy synthesis gas, and uses the high-temperature volumetric heat capacity of carbon dioxide to circulate heat exchange on the granulated high-temperature heat carrier. The whole process is long, and the core equipment is similar to a fluidized bed, with a large pressure drop. The process temperature changes frequently between 50℃ and 1500℃, and the drastic temperature change will inevitably bring energy consumption problems; and the longer process will bring pressure drop problems. Usually, the flue gas pressure is low, and the large pressure drop also limits the use of this technology.

[0008] CN201821322948.9 discloses a catalytic reaction device, wherein a methane + water vapor hydrogen production catalyst is provided at the bottom to produce hydrogen, carbon dioxide is introduced into the middle, and a carbon dioxide hydrogenation catalyst is provided at the top. Carbon dioxide reacts with hydrogen to produce carbon monoxide gas at the top. The main problem with this patent is that, first, carbon dioxide hydrogenation is a strongly endothermic reaction, and the equivalent ratio of CO 2 and H 2 Every 5% reaction will cause a temperature drop of about 150°C. Under this type of reactor, the reaction is actually unsustainable and will soon terminate due to the temperature drop. Second, this reactor does not involve carbon capture, but is merely a carbon dioxide hydrogenation reactor.

[0009] CN201410202280.4 discloses a method based on manganese and lanthanide metal catalysts to hydrogenate carbon dioxide and perform a reverse water gas reaction to generate carbon monoxide. The main problems of this patent are similar to those of CN201821322948.9. First, the hydrogenation of carbon dioxide is a strongly endothermic reaction. The equivalent ratio of CO 2 and H 2 Every 5% reaction will cause a temperature drop of about 150°C. Under this type of reactor, the reaction is actually unsustainable and will soon terminate due to the temperature drop. Second, this reactor does not involve carbon capture, but is merely a carbon dioxide hydrogenation reactor.

[0010] At present, the patents and documents published at home and abroad are concentrated in CO 2 Capture and CO2 In the study of the hydrogenation reverse water gas reaction, 2 There are few studies on capture and in-situ conversion. 2 Efficient capture of CO 2 In-situ conversion into synthesis gas products is convenient for the subsequent synthesis of light olefins and other chemical products with high added value. This can not only fully improve energy utilization and effectively reduce emission reduction costs, but also avoid the high energy consumption of capture cooling / conversion heating, and solve the problem of CO 2 The high cost of post-capture purification and transportation, as well as the safety risks of storage, are expected to increase the overall CO 2 The feasibility and economy of the emission reduction process are of great significance. Summary of the invention

[0011] The purpose of the present invention is to provide a method for capturing and utilizing carbon dioxide at high temperature and a reactor thereof to capture CO from high temperature gas. 2 and convert it into CO or syngas in situ.

[0012] To achieve the above-mentioned object of the invention, the technical solution of the present invention is as follows.

[0013] A method for capturing and utilizing carbon dioxide at high temperature, characterized in that: the method comprises a reactor, wherein a plurality of reaction tubes are arranged in the reactor, a part of the plurality of reaction tubes are used as adsorption reaction tubes, and another part of the plurality of reaction tubes are used as conversion reaction tubes, and the outside of the reaction tubes is preferably filled with a heat-conducting medium;

[0014] 1) Containing CO 2 The high-temperature flue gas enters the reactor and enters the adsorption reaction tube from one end of the adsorption reaction tube after being distributed by the carbon dioxide-containing gas distribution equipment. The CO in the flue gas 2 The catalytic material filled in the adsorption reaction tube undergoes adsorption reaction, and the decarbonized gas is discharged from the other end of the adsorption reaction tube and comes out of the reactor through the decarbonized gas collection device;

[0015] 2) After being distributed by the reducing gas distribution equipment, the reducing gas enters the conversion reaction tube from one end of the conversion reaction tube, and performs a conversion reaction on the catalytic material in the conversion reaction tube. The CO adsorbed by the catalytic material in the conversion reaction tube 2 It is converted into CO, and the catalytic material in the conversion reaction tube is converted and regenerated. The product gas containing CO is discharged from the other end of the reaction tube and comes out of the reactor through the product gas collection equipment;

[0016] 3) Regularly switch the feed and subsequent processes of the adsorption reaction tube and the conversion reaction tube;

[0017] The catalytic material filled in the adsorption reaction tube and the conversion reaction tube is a material having dual functions of carbon dioxide adsorption and catalytic conversion, preferably a CaO material loaded with one or more active components such as Co, Ni and lanthanide metals.

[0018] The carbon dioxide-containing gas distribution equipment and reducing gas distribution equipment described in the present invention can both be in the form of a distribution plate or a distributor.

[0019] The post-decarburization gas collection equipment and the product gas collection equipment described in the present invention can both be in the form of a gas collection box, a gas collection plate or a gas collection pipe.

[0020] The adsorption reaction temperature of the present invention is room temperature to 800°C, preferably in the range of 600 to 750°C.

[0021] The conversion reaction temperature of the present invention is 100-950°C, preferably 600-800°C.

[0022] The high temperature carbon dioxide capture and utilization method of the present invention, when the catalytic material in the adsorption reaction tube in the adsorption mode reaches CO 2 After adsorption saturation capacity, CO 2 The high-temperature flue gas switches to the conversion reaction tube. At this time, the adsorption reaction tube changes from adsorption mode to conversion regeneration mode. The feed gas of the adsorption reaction tube becomes reducing gas. The reducing gas in the adsorption reaction tube (in conversion regeneration mode) converts the saturated CO adsorbed on the catalyst into 2 Converted into CO; To ensure safety, the adsorption mode and conversion regeneration mode should be purged with high-temperature inert gas before switching, and then repeated in sequence.

[0023] The present invention also provides a reactor for a high-temperature capture and utilization method of carbon dioxide. The reactor includes a shell, a gas inlet and a gas outlet, and is characterized in that: the reactor also includes a plurality of reaction tubes, a carbon dioxide-containing gas distribution device, a reducing gas distribution device, a decarbonized gas collection device and a product gas collection device arranged in the shell, the reaction tubes are filled with catalytic materials, a part of the plurality of reaction tubes is used as an adsorption reaction tube, and the other part is used as a conversion reaction tube, the gas inlet includes a carbon dioxide-containing gas inlet and a reducing gas inlet, the gas outlet includes a decarbonized gas outlet and a product gas outlet, the carbon dioxide-containing gas inlet is connected to the adsorption reaction tube inlet through the carbon dioxide-containing gas distribution device, the reducing gas inlet is connected to the conversion reaction tube inlet through the reducing gas distribution device, the adsorption reaction tube outlet is connected to the decarbonized gas outlet through the decarbonized gas collection device, and the conversion reaction tube outlet is connected to the product gas outlet through the product gas collection device.

[0024] A reactor described in the present invention has further technical characteristics in that, in order to enhance the heat transfer effect, the adsorption reaction tube (adsorption reaction mode) and the conversion reaction tube for carrying out the conversion process (conversion regeneration mode) can be arranged crosswise, or can be arranged crosswise in rows with intervals, or other arrangements such as a plum blossom shape can be adopted.

[0025] The reactor of the present invention is further characterized in that: in order to enhance the heat transfer effect, a heat-conducting medium such as a heat-conducting salt can be filled outside the reaction tube in the reactor shell. The heat-conducting salt can be KNO 3 、NaNO 3 、BaCl 2 、BaCO 3 、LiCO 3 etc., or a mixture of multiple salts.

[0026] The reactor described in the present invention has a further technical feature that in order to enhance the heat transfer effect, the outer wall of the reaction tube can be in the form of a finned tube or the like.

[0027] A reactor described in the present invention has a further technical feature that, in order to enhance the heat transfer effect, baffles and other measures may be added to the heat-conducting medium (such as heat-conducting salt, etc.) in the reactor shell.

[0028] The adsorption process in the high-temperature carbon dioxide capture and utilization method of the present invention is a strong exothermic reaction, and the conversion process is a strong endothermic reaction, and the heat absorbed by the conversion process is much greater than the heat released by the adsorption process. The insufficient heat can be supplemented by a heating device (such as an electric heater, etc.), or the heat-conducting medium in the reactor shell can be drawn out and circulated back after external heating. Therefore, the reactor of the present invention also includes a heating device (such as an electric heater, etc.). When the heat released by the adsorption process cannot meet the heat required by the conversion process, the insufficient heat is supplemented by an electric heater, or the heat-conducting medium in the reactor shell is drawn out and circulated back after external heating.

[0029] The adsorption reaction tube and the conversion reaction tube described in the present invention use different names only for the convenience of description. When the adsorption reaction tube and the conversion reaction tube are regularly switched for feeding and subsequent processes, the functions of the adsorption reaction tube and the conversion reaction tube are interchanged.

[0030] The reaction tube of the present invention is further provided with a support grid and a pressure cover, and the catalytic material is filled between the support grid and the pressure cover, the support grid is provided under the catalytic material, and the pressure cover is provided on the top of the catalytic material.

[0031] The reducing gas in the present invention refers to a gas that can react with CO 2 Gases that react to produce CO or synthesis gas, such as H 2 , CH 4 , C 2 H 6It can also be a mixture of one or more of these gases, or a mixture of an inert gas (such as nitrogen) and one or more of these gases. When these gases are introduced separately, the following reactions will occur:

[0032] CO 2 +2H 2 =CO+H 2 O+H 2 or CO 2 +H 2 =CO+H 2 O

[0033] CO 2 +CH 4 =2CO+2H 2

[0034] 2CO 2 +C 2 H 6 =4CO+3H 2

[0035] The present invention is applicable to the treatment of carbon dioxide-containing gas (such as high-temperature flue gas containing CO2, etc.), so as to capture CO2 from the carbon dioxide-containing gas and convert it into synthesis gas in situ. When the temperature of the gas to be treated is too high, the temperature can be reduced to a suitable temperature range by recovering heat or the like; when the temperature is too low, the temperature can be raised to a suitable temperature range by heating or the like.

[0036] Compared with the prior art, the advantages of the present invention are as follows: 1. The carbon dioxide adsorption and conversion are completed in situ under similar temperature and pressure conditions, which can fully improve the energy utilization rate and effectively reduce the emission reduction cost, and avoid the high energy consumption of capture cooling / conversion heating, solving the problem of CO 2 The high cost of post-capture purification and transportation, as well as the high cost of CO 2 1. The reactor is inherently safe, and the heat transfer medium acts as a heat buffer, which can effectively avoid temperature fluctuations during the adsorption process of the reaction tube; 2. The in-situ coupled utilization of heat from the adsorption exothermic / conversion endothermic process can be achieved to achieve energy conservation and emission reduction effects; 3. The pressure drop of the reaction tube is low, and the temperature is easy to control and adjust, which can be applied to most flue gas conditions; 4. The process is simple, automatic sequential control can be realized, it is easy to operate and maintain, with low investment and small footprint.

[0037] The present invention will be further described in detail below with the accompanying drawings and specific embodiments, but the scope of the present invention is not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The figure is a simple process flow diagram of a method for high-temperature capture and utilization of carbon dioxide according to the present invention.

[0039] Figure 2 It is a schematic diagram of a single reaction tube in the reactor of the present invention.

[0040] Figure 3 This is a schematic diagram of the distribution of the reaction tubes in the reactor cross section of the present invention.

[0041] Figure 4 It is a schematic diagram of the structure of the reaction tube and the distribution plate at the upper end of the reactor of the present invention.

[0042] Figure 5 It is a schematic diagram of the structure of the reaction tube and the distribution plate at the lower end of the reactor of the present invention.

[0043] Figure 6 This is a schematic diagram of the structure of a product gas collecting plate of the present invention.

[0044] Figure 7 This is a schematic diagram of the structure of a gas collecting plate after decarburization of the present invention.

[0045] Figure 8 It is an oblique view of the reaction tube and distribution plate structure at the upper part of the reactor of the present invention.

[0046] Fig. 9 It is a schematic diagram of the 3D model of the reactor of the present invention.

[0047] Fig.10 This is a schematic diagram of the 3D model of the reaction tube of the reactor of the present invention.

[0048] Fig.11 It is a schematic diagram of the 3D model of the reaction tube and the end portion in the reactor of the present invention.

[0049] The reference numerals shown in the figures are:

[0050] 1. High-temperature flue gas, 2. Decarbonized gas, 3. Reducing gas, 4. Product gas, 5. Reactor, 6. Reaction tube, 6-1. Support grid, 6-2. Catalytic material, 6-3. Pressure cover, 7. Electric heater, 8-1. Carbon dioxide-containing gas distribution plate, 8-2. Reducing gas distribution plate, 8-3. Decarbonized gas collecting plate, 8-4. Product gas collecting plate, 9-1 / 2. Reactor gas outlet, 9-3 / 4. Reactor gas inlet, 11~18. Control valve. DETAILED DESCRIPTION

[0051] The present invention is further described below in conjunction with specific examples. The examples are only implementation methods of the present invention under certain specific conditions and should not be regarded as limiting the protection content of the present invention.

[0052] like Figure 1 As shown, a simple process flow of a high-temperature carbon dioxide capture and utilization method of the present invention.

[0053] like Figure 2-11 As shown, the layout, appearance and 3D schematic diagram of a reactor, reaction tube and distribution plate / gas collecting plate of the present invention.

[0054] The catalytic material is adsorbed saturated, and the time for switching the reaction tube adsorption reaction mode and the conversion regeneration mode can be designed according to the material adsorption capacity to perform timing control; 2 content, perform online control, and switch the operation mode of the reaction tube.

[0055] Example:

[0056] Raw material high temperature flue gas 66000m 3 Take n / h as an example, the flue gas composition is as follows:

[0057]

[0058]

[0059] For detailed process, see Figure 1 .

[0060] In the reactor 5, the flue gas temperature is 640°C and the flue gas pressure is 10 kPa. In the initial state, the control valves 11, 13, 15, and 17 are in the open state, and the control valves 12, 14, 16, and 18 are in the closed state.

[0061] 1). 640℃ high temperature flue gas 1 enters adsorption reactor 5 from the bottom through control valve 1 via reactor air inlet 9-3, and enters 10,000 reaction tubes 6 (used as adsorption reaction tubes for adsorption reaction) via carbon dioxide containing gas distribution plate 8-1.

[0062] 2). See Figure 2-Figure 8 The reaction tube 6 is a DN25 finned tube with a fin ratio of 2.46 and is equipped with The CaO-based catalytic material 6-2 has Co active centers loaded on it for catalyzing CO 2 With H 2 The catalyst material 6-2 is provided with a support grid 6-1 at the bottom and a pressure cover 6-3 at the top to fix the catalyst material. After the high-temperature flue gas 1 passes through the reaction tube 6 as the adsorption reaction tube from bottom to top, the CO in the flue gas 2 The decarbonized gas 2 is collected by the decarbonized gas collecting plate 8-3 and then leaves the reactor through the reactor gas outlet 9-2 via the control valve 13.

[0063] 3).24200m 3n / h, 730°C reducing gas 3 (in this embodiment, high temperature hydrogen) enters the reactor 5 from the lower part of the reactor through the control valve 15 and the reactor inlet 9-4, and enters the other 10,000 reaction tubes 6 (as the conversion reaction tubes for conversion regeneration) through the reducing gas distribution plate 8-2. After the reducing gas 3 passes through the reaction tubes 6 as the conversion reaction tubes from bottom to top, the CO adsorbed on the catalytic material 6-2 is 2 The product gas 4 is reduced to synthesis gas as product gas 4, and the catalytic material 6-2 is regenerated at the same time. The product gas 4 is collected by the product gas collecting plate 8-4 and then leaves the reactor from the reactor gas outlet 9-1 through the control valve 17. The composition of the synthesis gas (product gas 4) is as follows:

[0064] Element composition CO 31.67v％ <![CDATA[H 2 ]]> 35.00v％ <![CDATA[CO 2 ]]> 1.67v％ <![CDATA[H 2 The]]> 31.67v％ total 100v％

[0065] 4). See Figure 3 The 10,000 reaction tubes 6 used as adsorption reaction tubes in the above step 2) and the 10,000 reaction tubes 6 used as conversion reaction tubes in step 3) are arranged in rows and crosswise.

[0066] 5). See Figure 4 and Figure 6 The product gas collecting plate 8-4 in the above step is directly connected to the reaction tube 6, the reaction tube is opened on the product gas collecting plate 8-4, and the opening is directly connected to the top space of the reactor 5;

[0067] 6). See Figure 4 and Figure 7 , the decarburized gas collecting plate 8-3 in the above steps is directly connected to the reaction tube 6, wherein part of the reaction tube 6 passes through the decarburized gas collecting plate 8-3 and is then connected to the opening on the product gas collecting plate 8-4; part of the reaction tube 6 opens on the decarburized gas collecting plate 8-3 and is connected to the space separated by the decarburized gas collecting plate 8-3 and the product gas collecting plate 8-4 on the reactor 5;

[0068] 7) The carbon dioxide-containing gas distribution plate 8-1 and the reducing gas distribution plate 8-2 described in the above steps have the same structure as the decarburized gas collecting plate 8-3 and the product gas collecting plate 8-4, and can be regarded as their mirror images. The reaction tube 6 opening on the product gas collecting plate 8-4 corresponds to the opening on the reducing gas distribution plate 8-2 at the lower part of the reactor; the reaction tube 6 opening on the decarburized gas collecting plate 8-3 corresponds to the opening on the carbon dioxide gas distribution plate 8-1 at the lower part of the reactor; thereby achieving the separation between the gas medium of the adsorption reaction and the gas medium of the conversion reaction.

[0069] 8) Fill LiCO in the shell outside the reaction tube 6 above the carbon dioxide gas distribution plate 8-1 of the reactor 5 and below the decarbonized gas collecting plate 8-3. 3The molten salt is heated to 695°C by the electric heater 7. The electric heater 7 has an expected heating load of 18.2MW.

[0070] 9). After 2 hours, the reactor is purged with hot nitrogen, control valves 11, 13, 15, and 17 are closed, control valves 12, 14, 16, and 18 are opened, and the high-temperature flue gas 1 and reducing gas 3 are fed interchangeably through the valves. Then the process is circulated in sequence according to the timing control.

[0071] 10) The names of the aforementioned distribution plates / gas collection plates 8-1 to 8-4 are only for convenience of description and do not represent the actual medium for distribution / gas collection. For example, after the first switch, the carbon dioxide-containing gas distribution plate 8-1 actually distributes reducing gas 3, and after the next switch, it redistributes high-temperature flue gas 1. The other distribution / gas collection situations are similar.

[0072] The flue gas treated by this embodiment can achieve CO 2 Emissions are reduced by 200,000 tons / year, and 220,000 tons / year of synthesis gas are produced as a by-product.

Claims

1. A method for capturing and utilizing carbon dioxide at high temperature, characterized in that: The high-temperature carbon dioxide capture and utilization method comprises a reactor, wherein a plurality of reaction tubes are arranged in the reactor, a part of the plurality of reaction tubes is used as an adsorption reaction tube, and another part is used as a conversion reaction tube; 1) High-temperature flue gas containing CO2 enters the reactor, and enters the adsorption reaction tube from one end of the adsorption reaction tube after being distributed by the carbon dioxide-containing gas distribution equipment. The CO2 in the flue gas is adsorbed by the catalytic material filled in the adsorption reaction tube, and the decarbonized gas is discharged from the other end of the adsorption reaction tube and comes out of the reactor through the decarbonized gas collection equipment; 2) The reducing gas enters the conversion reaction tube from one end of the conversion reaction tube after being distributed by the reducing gas distribution device, and performs a conversion reaction on the catalytic material in the conversion reaction tube. The CO2 adsorbed by the catalytic material in the conversion reaction tube is converted into CO, and the catalytic material in the conversion reaction tube is converted and regenerated. The product gas containing CO is discharged from the other end of the conversion reaction tube and comes out of the reactor through the product gas collection device; 3) Regularly switch the feed and subsequent processes of the adsorption reaction tube and the conversion reaction tube; The catalytic material filled in the adsorption reaction tube and the conversion reaction tube is a material having dual functions of carbon dioxide adsorption and catalytic conversion.

2. A method for high temperature capture and utilization of carbon dioxide according to claim 1, characterized in that: The adsorption reaction temperature is between room temperature and 800°C; the conversion reaction temperature is between 100°C and 950°C.

3. A method for high temperature capture and utilization of carbon dioxide according to claim 1 or 2, characterized in that: The adsorption reaction temperature is 600-750°C; the conversion reaction temperature is 600-800°C.

4. The method for high-temperature capture and utilization of carbon dioxide according to claim 1, characterized in that: The reducing gas refers to a gas that can react with CO2 to generate CO, or a mixture of one or more of these gases, or a mixed gas of an inert gas and one or more of these gases.

5. The method for high-temperature capture and utilization of carbon dioxide according to claim 1, characterized in that: The catalytic material is a CaO material loaded with one or more than two active components of Co, Ni and lanthanide metals.

6. A method for high temperature capture and utilization of carbon dioxide according to claim 4, characterized in that: The gases that can react with CO2 to generate CO are H2, CH4 and C2H6.

7. A reactor for use in the high-temperature capture and utilization method of carbon dioxide according to claim 1, the reactor comprising a shell, a gas inlet and a gas outlet, characterized in that: The reactor also includes multiple reaction tubes, carbon dioxide-containing gas distribution equipment, reducing gas distribution equipment, decarbonized gas collection equipment and product gas collection equipment arranged in the shell. Catalytic materials are filled in the reaction tubes. Some of the multiple reaction tubes are used as adsorption reaction tubes, and the other part is used as conversion reaction tubes. The gas inlet includes a carbon dioxide-containing gas inlet and a reducing gas inlet. The gas outlet includes a decarbonized gas outlet and a product gas outlet. The carbon dioxide-containing gas inlet is connected to the adsorption reaction tube inlet through the carbon dioxide-containing gas distribution equipment, the reducing gas inlet is connected to the conversion reaction tube inlet through the reducing gas distribution equipment, the adsorption reaction tube outlet is connected to the decarbonized gas outlet through the decarbonized gas collection equipment, and the conversion reaction tube outlet is connected to the product gas outlet through the product gas collection equipment.

8. A reactor according to claim 7, characterized in that: The carbon dioxide-containing gas distribution equipment and the reducing gas distribution equipment are both of the type using distribution plates or distributors; the post-decarbonization gas collection equipment and the product gas collection equipment are both of the type using gas collection boxes, gas collection plates or gas collection pipes.

9. A reactor according to claim 7, characterized in that: The adsorption reaction tubes and the conversion reaction tubes are arranged crosswise, or arranged crosswise with intervals in rows, or arranged in a plum blossom shape.

10. A reactor according to claim 7, characterized in that: The outside of the reaction tube in the reactor shell is filled with a heat-conducting medium.

11. A reactor according to claim 10, characterized in that: The heat conducting medium is selected from one or a mixture of two or more salts of KNO3, NaNO3, BaCl2, BaCO3 and LiCO3.

12. A reactor according to claim 7, characterized in that: The outer wall of the reaction tube is in the form of a finned tube.

13. A reactor according to claim 10, characterized in that: Add baffles to the heat transfer medium in the reactor shell.

14. A reactor according to claim 7, characterized in that: The reactor also includes a heating device. When the heat released by the adsorption process cannot meet the heat required by the conversion process, the insufficient heat is supplemented by the heating device, or the heat-conducting medium in the reactor shell is drawn out and circulated back after external heating.

15. A reactor according to claim 7, characterized in that: A supporting grid and a pressure cover are also arranged in the reaction tube, and the catalytic material is filled between the supporting grid and the pressure cover. The supporting grid is arranged at the bottom of the catalytic material, and the pressure cover is arranged at the top of the catalytic material.

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