Device and production process for realizing negative carbon emission and co-production of lime

Abstract

The invention discloses a device and a production process for realizing negative carbon emission and co-production of lime, the device can send high-temperature CO2 waste gas produced by a lime kiln into a CO2 conversion device to be converted into CO gas, and the high-temperature CO2 waste gas in a calcining zone of the lime kiln is sent into a fuel generation conversion device to be converted into combustible gas containing CO after being subjected to dust removal and purification; the combustible gas obtained through conversion is fed into the lime kiln to be combusted and heat is supplied to calcine the limestone, so that the high-temperature CO2 waste gas in lime production is used as a heat source and is subjected to decarburization conversion with biomass waste carbon or other carbon-containing fuel through a one-step method to generate the combustible gas and co-produce the lime; by applying the device disclosed by the invention, the problems of high external energy consumption, long conversion time and high conversion cost for converting CO2 into CO can be solved, the efficient industrialization realization of a negative carbon technology is promoted, and the aims of saving energy, reducing emission, replacing fossil fuel and realizing value-added, zero carbonization and negative carbonization are fulfilled.

Description

Technical Field

[0001] The present application relates to the field of lime kiln technology, and in particular to the recovery and application of CO2 in lime kilns, and specifically to a device and production process that can reduce production energy consumption, simplify production process flow, and achieve negative carbon emission and co-production of lime. Background Art

[0002] The increasingly mature carbon capture, storage and utilization technology faces strong resistance from the industry due to high costs and high energy consumption. Although carbon dioxide has adverse effects on the ecological environment when it is emitted in large quantities, it is one of the important resources in nature, so the rational use of CO2 is the key to effectively solve the problem.

[0003] Carbon dioxide resources can be comprehensively utilized in the following ways: (1) converting carbon dioxide into useful chemicals; (2) preparing organic compounds through electrochemical, photoelectrochemical and photochemical reactions; (3) preparing carbon dioxide polymers; (4) preparing fuel carbon; (5) supercritical carbon dioxide extraction. Supercritical CO2 extraction mainly utilizes the chemical inertness of CO2, but the existing technology for using CO2 as a reaction material is not mature enough, and the conversion and utilization rate of CO2 is also quite low.

[0004] At present, negative carbon technology is the key to achieving net zero carbon dioxide emissions and is also the most promising technology. It can integrate the technical points and advantages of multiple applications such as renewable resource utilization, clean energy production, and carbon dioxide emission reduction, and has huge advantages in creating and increasing negative carbon emissions.

[0005] Among them, carbon dioxide chemical utilization technology is the most typical negative carbon technology. It is characterized by the chemical conversion process, uses CO2 as a carbon and oxygen resource to convert it into other products, and has certain emission reduction benefits. It can not only directly consume CO2, but also replace traditional high-carbon raw materials, and has both direct and indirect emission reduction effects.

[0006] In recent years, C1 chemical science and technology ("C1 chemistry" refers to the chemical process of synthesizing industrial products using carbon or substances containing one carbon atom in the molecule (such as CO, CO2, CH4, CH3OH, etc.) as raw materials) has made great progress. CO2 is the cheapest and most abundant resource in the C1 family, and its utilization has naturally become one of the important topics of universal concern in countries around the world. Therefore, the more feasible way at this stage is to convert CO2 into CO fuel. The conversion method is to degrade CO2 into CO at high temperature (873K) by pyrolysis.

[0007] In the traditional method of CO production, reducing CO2 to produce CO using carbon-containing fuels such as coke and coal is a major production approach and important technology for converting CO2 into chemical raw materials and fuels. This process technology not only collects, captures and utilizes industrial exhaust gas containing CO2 gas, but also realizes the resource utilization of low-grade fuels such as coal powder and biomass powder.

[0008] At present, in many application research and production on the production of CO, whether coke or coal is used, in the gasification reaction of reducing CO2, the ideal reaction temperature is 900-1050°C. The higher the temperature, the shorter the required reaction time. However, the reduction process also requires the raw materials to be heated to a high temperature, which leads to the high energy consumption required for the above-mentioned method of reducing CO2 in actual production. Moreover, the reduction method is carried out in steps, which leads to serious problems of heat loss and energy waste. At the same time, there are also problems such as irrational energy utilization, and the entire process flow and equipment are relatively complicated, which seriously restricts the sustainable development of its technical application.

[0009] Therefore, from the perspective of energy efficiency in the above-mentioned CO2 conversion, external energy consumption is required or the economic efficiency becomes poor due to high energy consumption. From the perspective of protecting human natural resources and the ecological environment, a sustainable CO2 energy conversion system must be sought. The inventors have realized that how to change and reduce energy consumption or use the production system's own energy and waste heat energy to achieve energy self-sufficiency is an effective way.

[0010] As a new energy source, biomass energy is called the "fourth largest energy source". In the application of new energy in industrial production, biomass gasification is considered to be one of the important ways to utilize biomass energy due to its economy and carbon neutrality. It is also one of the important green and clean energy sources for the production of lime. A series of thermochemical reactions in the biomass gasification process can convert biomass raw materials into gaseous fuels for production, and can also be further converted into high value-added renewable liquid fuels or chemicals. The core advantage of CO2 reforming reduction synthesis gas in biomass gasification and production applications is carbon emission reduction and carbon recovery. The CO2 gas generated after the combustion of recycled lime kilns and other industrial furnaces is converted into water gas and catalytically converted into combustible gas for industrial production.

[0011] However, the main challenge of carbon dioxide resource utilization is to overcome the strong stability of carbon dioxide molecules, and breaking C=O requires high energy input. From a thermodynamic point of view, the bond energy of C=O is 783kJ / mol, and high temperature (1600-2000K) and high pressure conditions are required to break C=O. In the currently popular plasma methods, the core gas temperature of microwave plasma can reach 5000k or even higher, and the temperature of the surrounding area can reach more than 3000k. Obviously, in the current lime production (calcination temperature 890-1100℃) process, both the temperature and pressure environment and the energy consumption are unbearable. Therefore, it is urgent to propose a technical solution that can use the production system's own energy and waste heat energy to achieve energy self-sufficiency to bear the energy demand in the CO2 conversion process, thereby reducing the energy consumption in the CO2 conversion process, achieving the purpose of replacing fossil fuels and value-added and zero carbonization, negative carbonization, and achieving sustainable development. Summary of the invention

[0012] The present application provides a device and production process for achieving negative carbon emissions and co-producing lime, so as to solve the problems of high external energy consumption, long conversion time and high conversion cost required for converting CO2 into CO by traditional negative carbon technology.

[0013] In order to achieve the above objectives, this application provides the following technical solutions:

[0014] In one aspect, the present application provides a device for achieving negative carbon emission and co-production of lime, comprising a lime kiln, a CO2 conversion device and / or a fuel generation conversion device wherein:

[0015] The lime kiln has a kiln top gas collecting pipeline, which can send the CO2 gas produced by the lime kiln into the kiln top flue gas dust reduction and purification device for dust reduction and purification treatment, and the treated flue gas enters the CO2 conversion device along the descending flue gas conveying pipeline;

[0016] The CO2 conversion device comprises a low-temperature CO2 flue gas pressurizing device and a high-speed internal heating conversion device, wherein the low-temperature CO2 flue gas pressurizing device is used to pressurize the CO2 gas received from the descending flue gas conveying pipeline, and the high-speed internal heating conversion device is used to convert the pressurized CO2 gas into CO gas, and the converted CO gas is sent into the kiln chamber of the lime kiln for combustion and heat supply to calcine limestone;

[0017] The fuel generation and conversion device is a closed structure with two sections, the upper section is a cracking section, and the lower section is a conversion section. The cracking section and the conversion section are connected and cut off by a hot air shut-off valve. The top of the cracking section is provided with a biomass fuel inlet and a CO2 gasifying agent inlet, the bottom of the cracking section is provided with a cracking gas outlet, the conversion section has a CO conversion gas outlet and an air pipeline for inputting air gasifying agent, the bottom of the conversion section is provided with a high-temperature CO2 gas inlet, the CO2 gasifying agent inlet and the high-temperature CO2 gas inlet are respectively connected to the air pipeline for inputting air gasifying agent. The pyrolysis section is connected to a pipeline for high-temperature CO2 waste gas coming out of the calcining zone of the lime kiln. The pyrolysis section is used for pyrolysis the biomass fuel and high-temperature CO2 waste gas fed therein into pyrolysis gas containing CO, and the cracked CO is output to the kiln chamber of the lime kiln through the pyrolysis gas outlet; the conversion section is used for receiving the remaining biomass fuel (charcoal) after pyrolysis from the pyrolysis section and converting the high-temperature CO2 gas rising from its bottom into CO gas through the biomass fuel (charcoal), and the converted CO gas is output to the kiln chamber of the lime kiln through the CO conversion gas outlet.

[0018] On the other hand, the present application provides a production process for achieving negative carbon emission and co-production of lime, using the above-mentioned device for achieving negative carbon emission and co-production of lime, the production process comprises the following steps:

[0019] The high-temperature CO2 gas generated by the production of calcium oxide in the lime kiln is sent to a CO2 conversion device to be converted into CO gas, and the converted CO gas enters the fuel surrounding pipe of the lime kiln through a delivery pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln to burn and provide heat to calcine limestone; and / or,

[0020] The high-temperature CO2 waste gas from the lime kiln calcining zone is dust-removed and purified and then sent to the cracking section and conversion section of the fuel generation and conversion device. In the cracking section, the high-temperature CO2 gas is cracked by the biomass fuel sent to the fuel generation and conversion device, and the combustible gas obtained by the cracking is sent to the fuel surrounding pipe of the lime kiln body through a pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln body to burn and provide heat to calcine limestone; in the conversion section, the biomass fuel (charcoal) dropped from the cracking section and the CO2 rising from the bottom of the conversion section are subjected to countercurrent heat exchange to complete the conversion of CO2 to CO, and the converted CO is sent to the fuel surrounding pipe of the lime kiln body through a pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln body to burn and provide heat to calcine limestone.

[0021] Compared with the prior art, this application has at least the following beneficial effects:

[0022] 1. The present application provides a device for achieving negative carbon emission and co-production of lime, which can send the high-temperature CO2 gas produced by the production of calcium oxide in the lime kiln into a CO2 conversion device to convert it into CO gas, and / or, send the high-temperature CO2 waste gas from the lime kiln calcination zone to a fuel generation conversion device for dust removal and purification to convert it into a combustible gas containing CO, and send the CO gas converted from the CO2 conversion device and / or the combustible gas containing CO generated from the fuel generation conversion device into the lime kiln for combustion and heat supply to calcine limestone. That is, the present application utilizes the high-temperature CO2 waste gas in lime production as a heat source. The method is to decarbonize biomass waste carbon or other carbon-containing fuels (coal, coke) to generate CO2-containing combustible gas that can be used for production and co-produce lime, thereby realizing the conversion and reuse of CO2 waste gas from the lime kiln. Therefore, the device for achieving negative carbon emissions and co-producing lime provided by the present application can utilize the high-temperature CO2 waste gas in lime production as a heat source, thereby solving the problems of high external energy consumption, long conversion time and high conversion cost required for traditional negative carbon technology to convert CO2 into CO, promoting the efficient industrialization of negative carbon technology, achieving energy conservation and emission reduction, replacing fossil fuels, and realizing the goals of value-added, zero carbonization and negative carbonization.

[0023] 2. The CO2 conversion device and fuel generation conversion device in the present application utilize graphite electrodes and electromagnetic induction to react with cheap iron-based and zirconium-containing catalysts with CO2 waste gas to generate CO fuel gas for recycling, thereby achieving complete conversion and reuse of CO2 waste gas. This can offset the increased electricity cost of CO2 electrolysis, significantly reduce the fuel cost of lime production, and also achieve the purpose of CO2 "negative carbon" emissions.

[0024] 3. The present application uses biomass solid fuel as an energy source to provide a carbon and hydrogen source, and the fuel of the carbon and hydrogen source is prepared by catalytic cracking to calcine lime. The high-temperature biochar contacts the high-temperature CO2 waste gas from the lime kiln to produce a reduction reaction, and the obtained CO can be returned to the lime kiln as a fuel to be burned again to calcine lime. That is, the present application can convert more than 90% of the biochar produced in the process of biomass catalytic cracking into CO fuel, and at the same time, all the waste gas containing about 40% CO2 produced when calcining lime can be converted into CO fuel, which can achieve the purpose of recycling and converting waste carbon of biochar, and also effectively reduce the fuel cost of lime production and carbon emission reduction.

[0025] 4. The fuel generation and conversion device in the present application adopts a two-stage structure, in which the upper cracking section (i.e., the reduction device) and the lower conversion section (i.e., the synthesis device) are arranged in series from top to bottom. The cracking section of the upper section uses biomass solid fuel as raw material and uses coal and biomass composite series to produce fuel gas rich in CO and H2 gas through high-temperature cracking. The conversion section of the lower section uses the high-temperature hot biochar after cracking in the cracking section as the carbon source and heat source. By inputting high-temperature exhaust gas from the lime kiln circulation channel for C1 conversion, more than 90% of the biomass fuel can be converted into CO combustible gas; the external heat source of the conversion section of the lower section is provided by the sensible heat of high-temperature CO2 gas in the range of 1000-1100°C produced by the circulation channel in the middle of the lime kiln chamber, which can greatly reduce the energy consumption required for conversion. Not only does it not require an external energy heat source, but it can also release the carbon energy in the greenhouse gas CO2 and convert it into coal gas energy mainly composed of CO+H2.

[0026] 5. The present application mainly uses biomass fuel, and also provides a way and method of gasification using dry coal powder as raw material (fuel). The reaction temperature can be as high as 1300-1600°C, and it has good adaptability to coal types, can gasify a wide range of coal types, and has low requirements for ash content. Ash content below 30% can be gasified. During the gasification process, the carbon conversion rate is high and no organic pollutants are generated. The process meets the requirements of clean and efficient utilization of coal and environmental protection. The present application adopts a dry coal powder coupled with biomass composite serial method to achieve co-gasification of pulverized coal and biomass composite serial, that is, to achieve high-temperature gasification, and also solve the defects of low calorific value and low furnace temperature of biomass fuel, and also facilitates the temperature control of the gasifier and reduces energy consumption and improves efficiency, and also realizes the functions of independent use of biomass and independent use of coal powder for production.

[0027] 6. The high-speed internal heating conversion device in the CO2 conversion device of the present application is provided with a replaceable spherical solid inside the hollow graphite electrode. The high-entropy porous boride catalytic composite material is synthesized with zirconium oxide and zirconium phosphate materials as catalyst carriers and BaTiO3 and ultra-high temperature boride ceramic materials as auxiliary agents. The presence of the filling material increases the gas residence time, enhances the electric field strength and electron energy; and the electric field strength at the contact point of the spherical material is enhanced, the voltage is increased, and more micro-discharges are generated, thereby generating more plasma charges and micro-discharge filaments during discharge; in the conversion process, the factors affecting the conversion rate include the relative dielectric constant, porosity, and surface roughness of the filling material; materials with high porosity and large surface roughness help to enhance the electric field and generate higher current density, thereby improving the CO2 conversion rate and energy efficiency. In addition, the CO2 conversion device of the present application has a simple structure, good airtightness, no dead angles, and is conducive to uniform gas distribution and circulation. CO2 can be directly converted into CO and O2 in the reactor device.

[0028] 7. The low-speed external heating conversion device in the CO2 conversion device of the present application is designed as a filling device, which adopts a pipeline container structure. A certain height of filamentous catalyst and granular solid reactants are arranged inside the container to ensure that the flow velocity changes when the airflow flows through, thereby forming eddy currents and turbulence. The filamentous catalyst carrier is Fe fiber fleece, and the solid reactant is alumina particles containing zirconium and other components. An electromagnetic induction heating device is arranged outside the low-speed external heating conversion device. High-frequency magnetic lines are generated in the induction coil in the device, so that eddy currents are generated on the surface of the conductor workpiece in the induction coil, and heat is generated by self-generated internal resistance, and the heat is transferred to the device material by contact conduction. The Fe fiber catalyst and the solid reactant carrier are heated to the catalytic temperature through the device barrel. When the CO2 gas flows through this area, it is instantly heated to the catalytic temperature, and the CO2 gas is quickly converted into CO gas. The low-speed external heating conversion device in the present application has a simple structure, good airtightness, no dead angle, and is conducive to uniform gas distribution and circulation. The heating temperature is controlled by an external electric control box connected to the electromagnetic induction heating device. The heating area is segmented, and the power of each area (segment) can be adjusted. The temperature, protection and start-stop are automatically controlled, which improves the overall adaptive automation level of the device and can adapt to the needs of industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. It should be understood that the specific shapes and structures shown in the drawings should not usually be regarded as limiting conditions for implementing the present application; for example, based on the technical concepts and exemplary drawings disclosed in the present application, those skilled in the art are able to easily make routine adjustments or further optimizations to the increase / decrease / attribution division, specific shapes, positional relationships, connection methods, and dimensional ratios of certain units (components).

[0030] Figure 1 This is a schematic diagram of the overall structure of a device for achieving negative carbon emission and co-production of lime provided by the present application in an embodiment;

[0031] Figure 2 for Figure 1 A display diagram of the drawing in part A;

[0032] Figure 3 for Figure 1 The display diagram of the drawing in part B;

[0033] Figure 4 This is a schematic diagram of the overall structure of the fuel generation and conversion device in the present application in one embodiment;

[0034] Figure 5 for Figure 4 The display diagram of the drawing in part C;

[0035] Figure 6 for Figure 4 The display diagram of the D part;

[0036] Figure 7 This is a schematic diagram of the overall structure of the CO2 conversion device in this application in one embodiment.

[0037] Description of reference numerals:

[0038] 1. Double-chamber vertical kiln device for lime kiln;

[0039] 2. Fuel generation and conversion device; 2-1. Cracking section; 2-2. Conversion section; 2-3. Biomass fuel inlet; 2-4. CO2 gasification agent inlet; 2-5. Coal powder main spray gun; 2-5-1. Steam gasification agent inlet; 2-5-2. Coal powder surrounding pipe; 2-5-3. Coal powder auxiliary nozzle; 2-5-4. Fuel inlet; 2-5-5. Air inlet; 2-6. Hot air shut-off valve; 2-6-1. Cutting and crushing mechanism; 2-7. Cracking gas outlet; 2-8. CO conversion gas Outlet 1; 2-9, high-temperature CO2 gas inlet; 2-10, heat-resistant rotary sealed ash discharger; 2-11, air pressurizing device; 2-12, pneumatic conveying ring pipe; 2-13, slurry pump; 2-14, ash storage bin; 2-14-1, upper sealing plate; 2-14-2, lower sealing plate; 2-14-3, target liquid level position; 2-15, air duct 1; 2-15-1, air duct 2; 2-15-2, air gasification agent regulating injection port; 2-16, water inlet;

[0040] 3. CO2 conversion device; 3-1. Low-temperature CO2 flue gas pressurizing device; 3-2. High-speed internal heating conversion device; 3-2-1. High-speed internal heating conversion device shell; 3-3. Low-speed external heating conversion device; 3-4. Graphite electrode body; 3-4-1. Transformer; 3-5. Electrode vent; 3-6. Zirconium-based nano high-entropy porous ultra-high temperature catalytic material; 3-7. CO conversion gas outlet 2; 3-8. CO conversion gas connecting channel; 3-9. Hot air valve 4; 3-10. Hot air valve 5; 3-11. First-level Fe fiber wool catalyst; 3-12, first-level thermal storage particle catalyst; 3-13, second-level Fe fiber wool catalyst; 3-14, second-level thermal storage particle catalyst; 3-15, third-level Fe fiber wool catalyst; 3-16, third-level thermal storage particle catalyst; 3-17, fourth-level Fe fiber wool catalyst; 3-18, high-temperature electromagnetic induction heating device; 3-19, medium-temperature electromagnetic induction heating device; 3-20, low-temperature electromagnetic induction heating device; 3-21, electronic control device; 3-22, CO conversion gas outlet three;

[0041] 4. Gas collecting pipeline on the kiln roof; 5. Dust reduction and purification device for flue gas on the kiln roof; 6. Descending flue gas conveying pipeline; 7. CO conveying pipeline one; 8. CO conveying pipeline two; 9. Fuel surrounding pipe of lime kiln body; 10. Fuel spray gun; 11. CO conveying pipeline three; 12. Cracking gas output pipeline; 13. Lime kiln flue gas circulation channel; 14. Pulse control valve; 15. Ash removal conveying surrounding pipe; 16. Ash removal conveying pipeline; 17. High-temperature dust reduction device; 18. High-temperature CO2 gas conveying pipeline one; 19. Screw conveyor; 20. High-temperature CO2 gas conveying pipeline two; 21. High-temperature CO2 gas conveying pipeline three; 21-1. Adjusting the blowing port; 22. Hot air valve one; 23. Hot air valve two; 24. Hot air valve three; 25. Pneumatic ash conveying pipeline; 26. Waste gas valve one; 27. Waste gas valve two; 28. CO control valve; 29. ​​Waste gas external network pipeline one. DETAILED DESCRIPTION

[0042] The following is a description of the implementation of the present application by specific specific embodiments. People familiar with the technology can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are 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 the field without creative work are within the scope of protection of the present application.

[0043] The present application is further described below in detail through specific embodiments in conjunction with the accompanying drawings.

[0044] In the description of this application: unless otherwise specified, "plurality" means two or more. Terms in this application such as "pipeline one", "pipeline two", etc. are intended to distinguish the objects referred to, and do not have special meanings in terms of technical connotations (for example, they should not be understood as emphasizing the importance or order, etc.). Expressions such as "including", "comprising", "having", etc. also mean "not limited to" (certain units, components, materials, steps, etc.).

[0045] The terms such as "upper", "lower", "left", "right", "middle", etc. used in this application are usually used to facilitate intuitive understanding by comparing with the accompanying drawings, and are not absolute limitations on the positional relationship in the actual product. Without departing from the technical concept disclosed in this application, changes in these relative positional relationships should also be regarded as the scope of this application.

[0046] In order to solve the problems existing in the prior art, the inventors proposed that the development of applicable heating, catalytic methods and high-performance catalysts is the key to solving the above problems, combining the requirements of lime production process, CO2 conversion conditions and various energy supply methods. Common catalytic research systems can be divided into: electrocatalysis, thermal catalysis, photocatalysis and a combination of the three, and graphite heating is a technology commonly used in heating, smelting and sublimation processes, which can play an important role in different catalytic research systems. On this basis, the inventors proposed that graphite can be used as a resistive heating material, and when power is turned on, heat energy is generated due to resistance, thereby heating the surrounding objects; in addition, the inventors also proposed that electromagnetic induction self-heating technology can be used. Electromagnetic induction is a technology based on high-frequency alternating magnetic fields to generate induced eddy currents or relaxation oscillations inside ferromagnetic and paramagnetic materials, thereby achieving self-heating of materials, which has the advantages of fast heating speed and precise energy transmission.

[0047] The present application provides a method that can utilize high-temperature CO2 waste gas in lime production as a heat source without increasing external energy and heat energy, and decarbonize it with biomass waste carbon or other carbon-containing fuels (coal, coke) through a one-step method to convert it into C1 new energy to produce lime, and at the same time, use graphite electrodes and electromagnetic induction methods with cheap iron-based and zirconium-containing catalysts to continue to react with CO2 waste gas to generate CO fuel gas for recycling, so as to achieve the full conversion and reuse of CO2 waste gas, and achieve the purpose of replacing fossil fuels and value-added and zero carbonization and negative carbonization. The technical route of the present application is explained below:

[0048] Route 1: Biomass solid fuel is used as energy to provide a carbon and hydrogen source. First, the fuel of carbon and hydrogen source (mainly CO and H2, etc.) is prepared by catalytic cracking and then calcined lime. The calcination process produces 950-1200℃ high-temperature CO2 waste gas rich in 25-42% range. In the process of biomass catalytic cracking, 8-40% (adjustable) high-temperature biochar (waste carbon) can be produced. The high-temperature biochar and the CO2 waste gas of the same high temperature from the lime kiln waste gas circulation channel are contacted in a closed reactor to undergo a reduction reaction. High-quality CO gas fuel is prepared by adjusting the reaction temperature, reaction time, waste gas flow rate, etc. The obtained CO is used as fuel, and the fuel is returned to the lime kiln for burning and calcining lime again. This route 1 can convert more than 90% of the biochar produced in the process of biomass catalytic cracking into CO fuel, and at the same time, about 40% of the CO2 waste gas produced when calcining lime is converted into CO fuel, which can achieve the purpose of recycling and converting waste carbon of biochar, and also effectively reduce the fuel cost and carbon emission reduction of lime production.

[0049] Route 2: In order to balance and convert the CO2 gas generated by re-combustion, an electrolytic reduction reaction device is set up, using low-cost iron-based and zirconium-containing catalysts, and generating induced eddy currents through graphite electrode method + electromagnetic induction heating, thereby achieving self-heating of the material and converting the remaining CO2 into CO combustible gas for lime calcination production.

[0050] Therefore, this application can fully recover the CO2 gas in lime production through the above-mentioned route 1 and route 2 and convert it into combustible gas fuel with C1 as the main component, which can not only offset the increased electricity cost of electrolysis of CO2, but also significantly reduce the fuel cost of lime production, while also achieving the purpose of CO2 "negative carbon" emissions.

[0051] The process technology means and measures adopted in this application are described in detail below.

[0052] 1. Reaction mechanism of water gas (cracking gasification)

[0053] Carbon monoxide (CO) and hydrogen (H2) are both combustible gases, and such a mixture is called "water gas" in industry. Because there is one oxygen (O) atom and two hydrogen (H) atoms in the water (H2O) molecule, when water meets hot coal (C), the oxygen atom is immediately taken away by the coal (C), resulting in carbon monoxide (CO) and hydrogen (H2).

[0054] Water gas is a low calorific value gas, which is generally produced by the reaction of steam with hot carbon-containing fuel (such as coal or coke) or biomass. The present invention uses biomass solid fuel instead of coal or coke to produce water gas, the main components of which are hydrogen and carbon monoxide. In actual production, it may also contain a small amount of carbon dioxide, nitrogen and methane. The content of each component depends on the raw materials used and the gasification conditions.

[0055] In the gasifier, the carbon in the biomass fuel and the steam mainly undergo the following water-gas reaction:

[0056] C+H2O→CO+H2

[0057] C+2H2O→CO2+2H2

[0058] The above reactions are all endothermic reactions, so heat must be supplied to the gasifier.

[0059] 2. Reverse Water Gas Shift (RWGS) Reaction Mechanism

[0060] The RWGS reaction is the reverse reaction of the water-gas shift (WGS) reaction. CO2 can be converted into more active CO fuel gas through the RWGS reaction.

[0061] The reverse water gas shift reaction equation is as follows:

[0062] CO2+H2=CO+H2OΔH 0 298 =+42.1KJ / mol

[0063] The reaction is a reversible endothermic equimolar reaction, and high temperature is conducive to the reverse water gas shift reaction. The selection of the optimal conditions for the RWGS reaction is to achieve the best reaction performance. In this application, in terms of the adjustment of the reaction conditions, the key point is to control the molar ratio of CO2 and H2 in the reaction gas under gaseous conditions.

[0064] Experiments show that the catalyst reaction temperature gradient has an extremely important influence on the RWGS reaction. In the actual reaction process, the ideal reaction conditions can be achieved when the temperature is between 80℃ and 400℃, the pressure is between 1atm (0.101MPa) and 18atm (1.81MPa), and the gas flow rate is at a molar ratio of H2 and CO2 of 1:1.

[0065] 3. Application of electromagnetic induction heating technology

[0066] Electromagnetic induction is a technology that uses a high-frequency alternating magnetic field to generate induced eddy currents or relaxation oscillations inside ferromagnetic and paramagnetic materials, thereby achieving self-heating of the material. It has the advantages of fast heating speed and precise energy transmission.

[0067] The use of electromagnetic induction heating technology to drive the selective reduction of CO2 to produce CO can achieve electron enrichment on the catalyst surface in a high-frequency electromagnetic environment. The electron-rich surface of the catalyst helps to activate CO2 molecules, thereby promoting the reaction along a path with lower activation energy.

[0068] IV. Application of new cheap iron-based catalytic materials

[0069] In the method of reducing CO2 to produce CO by electromagnetic induction heating, Fe fiber wool is used as a catalyst carrier to prepare a monolithic catalytic material, and Ru 3+ The RuNPs (Ruthenium Nanoparticles) are modified on the surface of Fe fiber by substitution reaction with metal Fe. It is particularly important that Fe fiber fleece is a common mechanical polishing abrasive with low price. At the same time, the self-supporting structure of the fiber itself makes the catalyst structure strong and easy to shape. It can form a monolithic catalytic material, effectively reduce gas resistance, and meet the actual needs of industrial applications.

[0070] 5. Application of graphite electrode heating plasma conversion CO2 technology

[0071] Plasma is the fourth state of matter. It is a collection of particles such as electrons, ions, atoms (ground state or excited state), molecules (ground state or excited state), free radicals, etc. formed by the dissociation and ionization of gas molecules by heat or external electric field, radiation and other energy excitation. The plasma mentioned in this application is mainly produced by gas discharge ionization. During the discharge, free electrons gain energy from the given electric field and then lose energy by colliding with neutral gas molecules. The molecules gain energy and produce metastable molecules, atoms, free radicals, ions and other chemicals.

[0072] Graphite electrode is a high temperature resistant graphite conductive material made of petroleum coke and asphalt coke as aggregates and coal tar as binder, through raw material calcination, crushing and grinding, batching, kneading, molding, roasting, impregnation, graphitization and mechanical processing. Moreover, the melting point of graphite is 3850±50℃ and the boiling point is 4250℃. Even after ultra-high arc burning, the weight loss is very small and the thermal expansion coefficient is also very small. In particular, the strength of graphite increases with the increase of temperature. At 2000℃, the strength of graphite doubles, which is very suitable for the high temperature (1600~2 000K) conditions and environment required for CO2 pyrolysis.

[0073] 6. Application of zirconium-based nano-high entropy porous ultra-high temperature catalytic materials

[0074] The high-entropy porous boride catalytic composite material synthesized with zirconium oxide and zirconium phosphate materials as catalyst carriers and BaTiO3 and ultra-high temperature boride ceramic materials as additives has the characteristics of high temperature resistance, large specific surface area and surface charge density, and can be used for ion exchange; it also has strong thermal stability, chemical stability and mechanical strength, and strong acid and alkali resistance; in particular, its high-entropy porous and stable layered structure is not destroyed after the guest is introduced into the interlayer, and as a mesoporous material carrier, different metal ion organics can continue to be embedded into it, further improving the activity and selectivity of the original catalyst.

[0075] In particular, the ultra-high temperature boride ceramic material YB4 has a melting point of up to 2800°C, and its oxidation product is Y2O3, which also has a melting point of up to 2145°C. In addition, YB4 also has a low density (4.36g / cm 3 ) and a relatively low elastic modulus (350GPa). It fully meets the high temperature (1600-2000K) conditions and environment required for CO2 pyrolysis.

[0076] 7. Temperature balance control of CO2 to CO

[0077] The reaction of CO2 reducing CO adopts the Boudouard method, and the reaction formula is:

[0078] CO2+C=2CO-162.4Mj / kmol

[0079] In the reaction process, the key factors affecting the reduction rate are mainly temperature and carbon source quality. Carbon sources are generally selected from biomass (charcoal), coke, coal (anthracite), etc. The reduction rate is proportional to the temperature, and the reaction time in the low temperature section below 800°C often exceeds tens of seconds or longer, and it is difficult to achieve the balance of the reduction reaction. The ideal control temperature is in the range of 1000°C to 1100°C. At 1000°C, the conversion rate of CO2 reduction to CO can reach more than 99%, and at 1100°C, the conversion rate is close to 100%. The conversion rate of CO2 at different temperatures is shown in Table 1 below.

[0080] Table 1 Conversion rates of CO2 and CO at different temperatures

[0081] <![CDATA[Temperature (℃) > 450 600 700 750 800 850 900 1000 1100 <![CDATA[CO 2(％) ]]> 98.1 65.3 42.6 23.9 11.9 5.7 3.1 0.85 0.06 <![CDATA[CO (％) ]]> 1.9 34.7 57.4 76.1 88.1 94.3 96.9 99.15 99.94

[0082] When the reaction temperature is at the optimal reaction temperature of 1100°C, the properties of the carbon source (fuel) are also critical to the reaction rate of CO2 reducing CO. Table 2 below lists the reaction activity and reaction rate of different fuel properties.

[0083] Table 2 Comparison of reactivity and reaction rate of different fuel properties

[0084] <![CDATA[Time (秒) > 0 5 10 15 20 25 30 35 40 <![CDATA[Charcoal (co％) > 40-88 92-100 <![CDATA[Coke (co％) > 40-50 63-74 74-85 85-90 90-93 93-94 94-95 95 95 <![CDATA[Coal (co％) > 40-65 64-73 74-78 78-82 82-83 83 83 83

[0085] The data in the table show that charcoal can complete 88% CO conversion within 5 seconds and 100% CO conversion within 10 seconds, while the CO conversion rate of coke is only 40-50% within 5 seconds, 74-85% within 10 seconds, and 95% at most within 40 seconds. Coal does not convert CO within 5 seconds, and the conversion rate within 10 seconds is only 64-72%, and the conversion rate within 40 seconds is only 82% at most. It can be seen that in terms of reaction activity and reaction speed, charcoal>coke>coal, so the present application prefers charcoal (biomass) as a carbon source.

[0086] 8. Serial composite gasification of coal and biomass

[0087] Coal gasification technology in the clean conversion and utilization of coal is also the most effective way to clean and efficiently convert coal. The joint gasification of coal and biomass fuel can give full play to the characteristics of the two energy sources, effectively improve and improve the quality of synthesis gas, and overcome the difficulties in traditional biomass gasification technology, so as to achieve clean and efficient utilization of biomass and coal resources.

[0088] The present application mainly uses biomass fuel, and also provides a way and method of gasification using dry coal powder as raw (fuel). The reaction temperature is as high as 1300℃~1600℃, and it has good adaptability to coal types, can gasify a wide range of coal types, has low requirements for ash content, and can gasify coal with an ash content of less than 30%. During the gasification process, the carbon conversion rate is high and no organic pollutants are generated. The process meets the requirements of clean and efficient utilization of coal and environmental protection. In the present application, the dry coal powder is coupled with biomass composite serial to achieve the co-gasification of pulverized coal and biomass composite serial, that is, high-temperature gasification is achieved, and the defects of low calorific value and low furnace temperature of biomass fuel are solved. It is also convenient to realize the temperature control of the gasifier, reduce energy consumption, and improve efficiency, and it also realizes the functions of independent use of biomass and independent use of coal powder for production.

[0089] The energy conversion benefits brought about by this application are analyzed and calculated below.

[0090] 1. Energy conversion from charcoal directly to CO

[0091] The traditional biomass gasification process can produce 8-40% waste carbon residue (charcoal) after gasification, which cannot be consumed by the biomass itself and needs to be exported or processed, which wastes resources, increases environmental protection management, and also causes low energy conversion efficiency.

[0092] In this application, the charcoal slag produced during the gasification process is directly converted in the furnace, and the C1 component in the charcoal is fully converted into CO gas through the high-temperature thermochemical reaction of CO2 / charcoal. On average, 1kg of charcoal (waste carbon) can produce 3.50m 3 More than CO gas fuel.

[0093] According to the calculation of heat energy in lime production, the theoretical energy consumption of one ton of lime is 890,000 Kcal heat energy. The conversion of biomass heat energy (maximum 4200 Kcl / kg) requires 210 kg of biomass fuel, which can produce 45 kg (average) of charcoal after gasification. According to 1 kg of charcoal, 3.50 m 3 (Average) CO can be calculated as:

[0094] 45kg×3.50m 3 =157.5m 3 / ton ash

[0095] According to the calorific value of carbon monoxide (gas) 3500~4700Kcal / Nm 3 (air pressure is 1.0Kpa) calculation, the heat energy can be obtained:

[0096] 157.5m 3 / ton ash × (3500 ~ 4700Kcal / Nm 3 )=551250~740250Kcal

[0097] According to the calculation that one ton of ash requires 890,000Kcal of heat energy: 551,250~740,250Kcal / 890,000Kcal

[0098] The available heat energy is 0.62-0.83 tons of ash.

[0099] 2. Utilization of waste carbon thermal energy

[0100] In the traditional gasification process, when waste carbon is discharged from the furnace, it needs to be water-quenched in the furnace to achieve the purpose of liquid slag discharge. This not only consumes a lot of water resources and wastes a lot of thermal energy resources, but also causes water pollution and makes environmental protection management difficult.

[0101] In this application, a high temperature (900-1100°C) conversion method is adopted in the lower section (synthesis section) of the furnace, and the heat energy of the charcoal from the upper section of the furnace body and the sensible heat of the converted raw coal gas are fully recovered and utilized, with high thermal efficiency. In addition, since the sensible heat of the high temperature (1000-1200°C) CO2 waste gas from the lime kiln circulation channel is fully utilized for C1 conversion, more than 98% of the charcoal can be converted into CO gas, and "zero" external energy supply is achieved. Since most of the waste carbon is converted, compared with 8-40% waste carbon slag produced in the traditional gasification process, only 2-5% of the carbon-free ash slag (i.e., the ash in the raw material) is discharged.

[0102] 3. Energy balance of CO2 to CO

[0103] Chemical equation for carbon dioxide reducing carbon monoxide (coal gas):

[0104] C+1 / 2O2=CO+110.5kJ

[0105] C+O2=CO2+393.5kJ

[0106] CO + 1 / 2O2 = CO2 + 283 kJ

[0107] According to the Gays's law, we can know that: combining the first and second equations above and eliminating the O2 term (i.e. equation 1×2-equation 2) yields: C+CO2=2CO-172.5kJ

[0108] Therefore, it can be obtained that 1 mol of C reacts with 1 mol of CO2 and needs to absorb 172.5KJ of heat.

[0109] Calculate the energy cost required to convert 1 ton of CO2 using the formula:

[0110] Conversion energy = reaction molar energy * 10^6 / molar mass of molecule

[0111] Substituting the molar mass of CO2 as 44g / mol, it is calculated that the energy required to convert 1 ton of CO2 into CO and H2O is 3900000KJ (equivalent to 932100Kcal).

[0112] Energy of converted CO:

[0113] The calorific value of CO is 12.64MJ / Nm 3 , converted into mass calorific value is 10.112MJ / kg, equal to 10112KJ / kg, equivalent to 10112000KJ per ton (equivalent to: 2416768Kcal).

[0114] 4. Recover high-temperature CO2 energy from lime kiln

[0115] A large amount of high-temperature CO2 waste heat output from the waste gas circulation channel of the lime kiln calcining zone is directly converted into CO with charcoal without gas separation, and the mass ratio of CO2 to charcoal is 3.62:1, that is, it is converted into synthesis gas mainly composed of CO+H2. The thermal energy in the conversion process comes from the sensible heat of the CO2 waste gas at a temperature of 900-1300℃ in the lime kiln, which is the decomposition temperature of the lime calcined in the lime kiln, just the cracking temperature required for CO2 to convert CO. The reaction time is determined by the CO2 waste gas temperature, flow rate, and the height of the carbon reaction layer, and is generally adjusted within 5-40 seconds.

[0116] The key equipment and measures used to implement the production process of this application are described below.

[0117] 1. Lime kiln calcining device

[0118] An off-kiln channel-supported double-chamber lime kiln for mixing and blowing disclosed in the Chinese utility model patent CN202321555958.8 authorized by the applicant on November 17, 2023 can be used as a production device for producing lime (calcium oxide) and CO2 gas.

[0119] 2. Fuel generation and conversion device (segmented serial reduction integrated generation device)

[0120] The device adopts a two-stage structure, with an upper reduction device (cracking stage, i.e., a reduction gas generating device) and a lower synthesis device (conversion stage, i.e., a synthesis gas device) arranged in series from top to bottom. The upper reduction gas generating device uses biomass solid fuel as raw material and adopts a composite series of coal and biomass to generate CO and H2-rich combustion gas through high-temperature cracking. The lower synthesis gas device uses the high-temperature hot biochar cracked by the reduction gas generating device as a carbon source and heat source, and converts C1 by inputting high-temperature exhaust gas from a lime kiln circulation channel, so that more than 90% of the charcoal can be converted into CO combustible gas.

[0121] The external heat source of the synthesis gas device in the lower section is provided by the sensible heat of high-temperature CO2 gas in the range of 1000-1100℃ produced by the circulation channel in the middle of the lime kiln, which greatly reduces energy consumption. Not only does it not require an external energy heat source, but it can also release the carbon energy in the greenhouse gas CO2 and convert it into coal gas energy mainly composed of CO+H2.

[0122] 3. High-speed internal heating conversion device (internal heating electrolysis CO2 conversion CO device)

[0123] The heating method of the device adopts the method of setting a hollow graphite electrode in the device. The graphite body of the graphite electrode is composed of carbon atoms and has good electrical conductivity, thermal conductivity and high temperature resistance. Among them, thermal conductivity is one of the important conditions for realizing graphite heating. Heat energy can be effectively transferred to surrounding objects, allowing the surrounding objects to be heated. When the electrode is energized, resistance is generated to generate heat energy, thereby heating the surrounding objects. At the same time, the graphite material has a strong infrared spectrum absorption capacity and can absorb high-intensity infrared radiation, thereby realizing rapid heating of surrounding objects. This is also one of the important reasons why it plays a role in the heating process.

[0124] A replaceable spherical solid high-entropy porous boride catalytic composite material is arranged inside the hollow graphite electrode, which is made of zirconium oxide and zirconium phosphate materials as catalyst carriers and BaTiO3 and ultra-high temperature boride ceramic materials as additives. The presence of the filler material increases the gas residence time, enhances the electric field strength and electron energy; and the electric field strength at the contact point of the spherical material is enhanced, the voltage is increased, and more micro-discharges are generated, so more plasma charges and micro-discharge filaments are generated during discharge; in the conversion process, the conversion rate is affected by the relative dielectric constant, porosity, surface roughness, etc. of the filler material; materials with high porosity and large surface roughness help to enhance the electric field and generate higher current density, thereby improving the CO2 conversion rate and energy efficiency.

[0125] The conversion method uses plasma catalysis technology, which improves the conversion rate of reactants, the selectivity of target products and the energy efficiency through any combination of plasma and catalyst. Adding catalysts to the reaction system enhances the plasma reaction, and the catalyst can also be activated in the plasma area. As far as the CO2 conversion process is concerned, the role of adding catalysts is mainly to improve the energy efficiency of the reaction.

[0126] When the reaction gas CO2 passes through the inside of the electrode, when a sufficiently high voltage is applied to the electrode, the gas is broken down, forming a discharge channel so that the plasma can produce a large number of high-energy active particles, and the discharge is uniform and stable. The high-energy active particles are activated and catalyzed by a high-entropy porous boride catalytic composite material synthesized with zirconium oxide and zirconium phosphate materials as catalyst carriers and BaTiO3 and ultra-high temperature boride ceramic materials as additives, thereby achieving a thorough cracking of CO2 and generating CO gas. The reactor of the present application has a simple structure, good airtightness, no dead angles, and is conducive to uniform gas distribution and circulation. CO2 can be directly converted into CO and O2 in the reactor device.

[0127] 4. Low-speed external heating conversion device (externally heated adjustable CO2 electromagnetic induction conversion CO reactor)

[0128] The reaction device adopts a filling device and a pipeline container structure. The container is filled with a certain height of silk flocculent catalyst and granular solid reactant, which ensures that the flow rate changes when the airflow flows through, thereby forming eddy currents and turbulence. The silk flocculent catalyst carrier is Fe fiber wool, and the solid reactant is alumina particles containing zirconium and other components. An electromagnetic induction heating device is arranged outside the reactor. The induction coil in the device generates high-frequency magnetic lines, so that the surface of the conductor workpiece in the induction coil generates eddy currents to generate heat by self-generated internal resistance, and the heat is transferred to the barrel by contact conduction. Then, the internal Fe fiber wool catalyst and the solid reactant carrier are heated to the catalytic temperature through the barrel. When CO2 gas flows through this area, it is instantly heated to the catalytic temperature, and CO2 gas is converted into CO gas. The reactor of the present application has a simple structure, good airtightness, no dead angle, and is conducive to uniform gas distribution and circulation. The heating temperature is controlled by an electric control box connected to the electromagnetic induction heating device outside. The heating area is segmented, and the power size of each area (segment) can be adjusted, and the temperature, protection and start and stop are automatically controlled.

[0129] The structural principle and process flow of the solution provided in this application are described in detail below.

[0130] The device for realizing negative carbon emission and co-production of lime provided in the present application mainly comprises: a lime kiln double-chamber vertical kiln device 1, a fuel generation and conversion device 2 and a CO2 conversion device 3. The production process completed by the device can be divided into three systems, which can realize the closed-loop production of the three systems as a whole, and can also realize the independent production of a single system. The three systems are: a. Independent lime kiln double-chamber vertical kiln production system; b. Independent fuel generation and conversion production system; c. Independent CO2 conversion CO production system.

[0131] The process principle of the closed-loop production of the three systems is as follows:

[0132] Limestone begins to decompose initially at 890℃ in a double-chamber lime kiln, and is completely decomposed at 950-1100℃. In the process of decomposing limestone into calcium oxide (lime), 35-44% carbon dioxide (CO2) gas is produced, which enters the kiln top flue gas dust reduction purification device through the lime kiln top gas collection pipeline, and enters the CO2 conversion device through the descending flue gas transmission pipeline for CO2 conversion to CO. The converted CO gas enters the lime kiln body fuel enclosure pipe through the transmission pipeline, and then is distributed to the fuel spray gun, which is transported to the kiln by the fuel spray gun for combustion and heat calcination of limestone. The cracked gas produced by the fuel generation and conversion device also enters the lime kiln body fuel enclosure pipe through the CO transmission pipeline, and enters the fuel spray gun after mixing with the CO gas.

[0133] During the ash cleaning process, the 1100℃ high-temperature and high-pressure (30-35KPa) flue gas in the flue gas circulation channel of the lime kiln body is transported to the CO2 conversion device at the lower section of the fuel generation and conversion device through the ash cleaning conveying pipe, ash cleaning conveying pipeline and high-temperature dust suppression device to convert CO2 and waste carbon into CO. The generated CO fuel also enters the lime kiln body fuel pipe through the conveying pipeline, completing the entire closed-loop fuel conversion process.

[0134] A high-temperature ash collection device can be installed on the ash cleaning and conveying pipeline to collect lime powder (dust). After collection, the powder is transported by a screw conveyor to the belt conveyor at the bottom of the lime kiln to complete the transfer and transportation together with the finished lime.

[0135] In the present application, the fuel generation and conversion device is a two-stage closed structure, and the upper and lower sections are controlled by electric (or hydraulic, pneumatic) hot air shut-off valves, which can realize the composite serial production of the upper and lower sections and the independent operation and production of the upper and lower sections. The upper section is a cracking device, which adopts a downdraft structure and is divided into four areas from top to bottom: drying layer, pyrolysis layer, oxidation layer, and reduction layer. The biomass fuel and the reducing gas are in a parallel downward flow mode, and the temperature of the pyrolysis layer is controlled in the range of 500 to 600°C. The final oxidation layer formation temperature can reach a high temperature of 1000°C.

[0136] The lower section is a generating device with an upward suction structure. Its raw material comes from the waste carbon generated after the upper section cracking the biomass, mainly solid granular biochar. The channel entering the lower section is controlled by the hot air shut-off valve between the upper and lower sections. When the waste carbon enters the lower section, it slowly descends and performs countercurrent heat exchange with the CO2 reducing gas rising from the lower part to complete the CO conversion work. The conversion process does not require an external heat source, and all comes from the waste heat inside the entire production system. The waste heat mainly comes from three aspects: one is the 900-1000℃ heat energy from the upper waste carbon itself, the second is the 1100℃ high-temperature CO2 waste gas temperature in the lime kiln flue gas circulation channel, and the third is the exothermic heat energy from the continued combustion of the waste carbon. The combustion temperature after the three are mixed is exactly the temperature required for the waste carbon to convert CO, achieving a balance in heat energy supply. The converted waste carbon ash (furnace ash) accounts for only about 3% of the weight ratio before the waste carbon conversion, and enters the ash storage box through the ash unloading device at the bottom of the fuel generation conversion device, and is transported to the lime kiln bottom ash discharge system or other downstream devices by a pneumatic conveying device or a slurry pump.

[0137] The structure and main process flow of the solution provided by the present application are described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0138] Embodiment 1

[0139] Based on the device for achieving negative carbon emission and co-production of lime provided by the present application, the present application can directly produce CO fuel and co-production lime by using the waste heat of lime kiln + biomass waste carbon and graphite electrode + electromagnetic induction. This embodiment describes in detail the process flow of overall closed-loop production using the present device.

[0140] See also Figures 1 to 3 When lime is produced by the double-chamber vertical kiln device 1, the primary CO2 gas in the range of 35-44% is obtained from the kiln top gas collecting pipe 4 into the kiln top flue gas dust reduction and purification device 5 for dust reduction and purification treatment. The treated flue gas temperature is in the range of 70-250℃, and the flue gas particulate matter is less than 50mg / m 3 The flue gas enters the low-temperature CO2 flue gas pressurizing device 3-1 along the descending flue gas conveying pipeline 6, and the pressurized CO2 gas enters the high-speed internal heating conversion device 3-2 for CO gas conversion. Figure 7During the conversion process, the gas first enters the graphite electrode body 3-4. The inside of the graphite electrode body 3-4 is hollow and filled with spherical zirconium-based nano-high entropy porous ultra-high temperature catalytic materials 3-6. A plurality of electrode vents 3-5 are arranged on the electrode body. When the gas passes through the graphite electrode body 3-4, the transformer 3-4-1 energizes the graphite electrode body 3-4. The energized graphite electrode body quickly reaches a temperature greater than 1800°C within 1 to 2 seconds. At the same time, the zirconium-based nano-high entropy porous ultra-high temperature catalytic materials 3-6 in the graphite electrode body also reach the same temperature at the same time, catalyzing the CO2 gas and instantly converting it into a gas with a CO content greater than 90%. The converted gas enters the interior of the high-speed internal heating conversion device shell 3-2-1 through several electrode vents 3-5. See Figure 1 Then the gas enters the CO delivery pipeline 2 8 through the CO conversion gas outlet 2 3-7, and then enters the kiln chamber (kiln chamber 1 and kiln chamber 2) of the lime kiln double-chamber vertical kiln device 1 through the lime kiln body fuel surrounding pipe 9.

[0141] When the converted CO gas needs to be further increased in content, it enters the low-speed external heating conversion device 3-3 through the CO conversion gas connection channel 3-8 for further conversion. Figure 7 The low-speed external heating conversion device 3-3 is internally provided with catalytic materials of different heights and numbers, such as the first-level Fe fiber wool catalyst 3-11, the first-level heat storage particle catalyst 3-12, the second-level Fe fiber wool catalyst 3-13, the second-level heat storage particle catalyst 3-14, the third-level Fe fiber wool catalyst 3-15, the third-level heat storage particle catalyst 3-16, and the fourth-level Fe fiber wool catalyst 3-17. The gaps and particle sizes of the catalysts at different levels are different, and they decrease step by step from bottom to top. Among them, the fiber wool catalyst is a flocculent body with different diameters, and the heat storage particle catalyst is a round particle. The combination of the two objects forms a material space with different resistances to meet the gas residence time and heat storage and catalytic time. During the heating process, the gas passes through the entire container from bottom to top, and its gas flow, pressure and opening and closing are controlled by the hot air valve four 3-9 and the hot air valve five 3-10. The overall heating of the low-speed external heating conversion device 3-3 is achieved by a three-stage heating device, namely a high-temperature electromagnetic induction heating device 3-18, a medium-temperature electromagnetic induction heating device 3-19 and a low-temperature electromagnetic induction heating device 3-20. The three-stage heating device is separate and gradually heats and regulates from bottom to top. It can also heat a single stage. The heating power supply is controlled by an electronic control device 3-21. The content of CO gas after conversion can reach more than 99%. The converted CO gas fuel enters the CO delivery pipeline 2 8 from the CO conversion gas outlet 3 3-22 and the CO delivery pipeline 1 7.

[0142] The fuel (heat energy) required by the double-chamber vertical kiln device 1 of the lime kiln comes from the fuel generation and conversion device 2, see Figures 4 to 6The fuel generation and conversion device 2 is configured as two areas with different functions, namely, the cracking section 2-1 and the conversion section 2-2. The two areas control the material descending flow rate and opening and closing through the hot air shut-off valve 2-6. A cutting and crushing mechanism 2-6-1 is provided at the connection between the two areas.

[0143] Granular biomass fuel (which can be charcoal with a particle size of 30 to 100 mm) enters from biomass fuel inlet 2-3, CO2 gasifier enters from CO2 gasifier inlet 2-4, and steam gasifier enters from steam gasifier inlet 2-5-1. Steam gasifier inlet 2-5-1 is used as a backup and when coal powder is gasified. The gasifier in production is mainly CO2 gasifier. The biomass fuel entering from biomass fuel inlet 2-3 slowly descends and enters the four areas of drying layer, pyrolysis layer, oxidation layer, and reduction layer from top to bottom. During the cracking process of biomass fuel, the biomass fuel and the reducing gas are in a parallel downward flow mode, and the main components of the cracked gas (average values ​​of different biomass fuels) are: hydrogen 15.27%, oxygen 3.12%, nitrogen 56.22%, methane 1.57%, carbon monoxide 9.76%, carbon dioxide 13.75%, ethylene 0.10%, ethane 0.13%, propane 0.03%, propylene 0.05%, totaling 100%. The cracked gas enters the cracked gas output pipeline 12 from the cracked gas outlet 2-7, and is also transported to the CO transport pipeline 28.

[0144] The remaining charcoal after cracking accounts for about 8-40% of the dry weight of the fuel (which can be adjusted according to the production process). It enters the upper part of the hot air shut-off valve 2-6 through the charcoal's own gravity and the positive pressure inside the device. Opening and adjusting different channel areas of the hot air shut-off valve 2-6 can control its descending speed and enter the conversion section 2-2. The charcoal slowly descends from top to bottom in the conversion section 2-2 and performs combustion heat exchange with the high-temperature CO2 waste gas in the range of more than 1000-1200°C from the high-temperature CO2 gas transmission pipeline-18. During the exchange process, the CO2 gas is converted into CO gas.

[0145] The conversion process uses air and CO2 gas as gasifying agents, and adopts the bottom blowing method. The high-temperature CO2 waste gas enters the device from the high-temperature CO2 gas inlet 2-9. The high-temperature CO2 gasifying agent entering the conversion section 2-2 is the high-temperature CO2 waste gas in the range of 950 to 1200°C, which comes from the high-temperature waste gas in the lime kiln calcining zone (i.e., the temperature of the lime kiln decomposing limestone). Figure 1 , 2, enters the ash cleaning and conveying pipe 15 through the lime kiln flue gas circulation channel 13 which is interconnected between the lime kiln body 1 and the kiln body 2. A plurality of pulse control valves 14 are arranged on the ash cleaning and conveying pipe 15 which are connected with the lime kiln flue gas circulation channel 13. The flue gas flow and pressure in the ash cleaning and conveying pipe 15 are controlled by controlling the opening number and the opening and closing times of the pulse control valves 14. The flue gas then enters the ash cleaning and conveying pipe 16 and is conveyed to the high-temperature dust reduction device 17 for dust reduction and purification treatment. The purified high-temperature CO2 waste gas is conveyed to the CO2 gasification agent inlet 2-4 through the high-temperature CO2 gas conveying pipe 18. High-temperature CO2 gas delivery pipeline 1 18 is also provided with high-temperature CO2 gas delivery pipeline 2 20 and high-temperature CO2 gas delivery pipeline 3 21. High-temperature CO2 gas delivery pipeline 2 20 controls and adjusts hot air valve 2 23 to deliver a part of CO2 gas to the low-speed external heating conversion device 3-3 for conversion. The gas in high-temperature CO2 gas delivery pipeline 3 21 enters high-temperature CO2 gas delivery pipeline 3 21 through hot air valve 3 24, a part of which enters the CO2 gasification agent inlet 2-4, and a part of which enters the conversion section 2-2. Figure 3 The high-temperature CO2 gas transmission pipeline 3 21 is provided with upper, middle and lower three-layer regulating injection ports 21-1 to assist the conversion section 2-2 device in blowing, so as to achieve the purpose of regulation and optimization control. Figure 3 The air gasifier enters from the air pipe 1 2-15, and the air source is provided by the air pressurizing device 2-11. The air pipe 1 2-15 is provided with a branch pipe air pipe 2 2-15-1, and also has upper, middle and lower three-layer regulating blowing ports 2-15-2 for auxiliary blowing of air and oxygen injection.

[0146] The remaining charcoal ash (slag) after the charcoal is fully converted accounts for about 2-3% of the dry weight of the fuel. Its particle size is relatively fine and is discharged into the ash storage bin through the heat-resistant rotary sealed ash discharger 2-10. Figure 6 , an upper sealing plate 2-14-1 is provided on the upper part of the ash storage bin, and a lower sealing plate 2-14-2 is provided on the lower part, forming an independent sealed space to ensure that gas and dust do not leak out. When pneumatically conveying dust, its high-pressure air source is provided by the air pressurizing device 2-11, blown into the ash storage bin through the pipeline, forming a high-pressure airflow of dust-gas mixing and boiling and blown into the pneumatic conveying ring pipe 2-12. The pneumatic conveying ring pipe 2-12 is provided with multiple interfaces connected to the ash storage bin 2-14, forming a pressure-equalized airflow discharged into the pneumatic ash conveying pipeline 25 and then entering the lower ash bin of the high-temperature dust reduction device 17, and together with the dust-removed surface ash, it is transported to the upper part of the ash belt at the bottom of the lime kiln by the screw conveyor 19, and transported to the downstream system together with the finished lime. When the slurry ash discharge method is adopted, water is injected through the water inlet 2-16 and the water level is maintained at the target liquid level position 2-14-3, and then the slurry pump 2-13 is turned on to suck the mixture of carbon ash and water out of the device, and then stored or transported.

[0147] All CO gas that has completed the conversion process in the conversion section 2-2 is output from the CO conversion gas outlet 1 2-8 outside the device, enters the cracking gas output pipeline 12 through the CO delivery pipeline 3 11, and is then mixed and then delivered to the CO delivery pipeline 2 8.

[0148] All the converted combustible gases enter the CO conveying pipeline 2 8 for mixing, and the mixed gas enters the fuel surrounding pipe 9 of the lime kiln body, and then is sprayed into the double-bore vertical kiln device 1 of the lime kiln by several fuel spray guns 10 arranged around the lime kiln body to calcine lime. The CO2 gas decomposed during the calcination process enters the gas collecting pipeline 4 on the kiln top, and the powder ash (dust) purified in the high-temperature dust reduction device 17 enters the screw conveyor 19 from its bottom, and is transported to the belt conveyor of the ash discharge system at the bottom of the lime kiln, and is transported to the downstream users together with the finished lime. At this point, the production cycle of the entire system is completed.

[0149] Embodiment 2

[0150] Based on a device for achieving negative carbon emission and co-production of lime provided in the present application, this embodiment describes the process of using the device to carry out closed-loop production of a lime kiln double-chamber vertical kiln device 1 and a fuel generation and conversion device 2.

[0151] The CO2 outlet of the low-temperature CO2 flue gas pressurizing device 3-1 is connected to the CO2 inlet of the high-speed internal heating conversion device 3-2 through an exhaust valve 26. A hot air valve 4 3-9 is provided at the CO conversion gas outlet 2 3-7 at the bottom of the high-speed internal heating conversion device 3-2. The bottom of the low-speed external heating conversion device 3-3 is connected to the high-temperature CO2 gas delivery pipeline 2 20 through a hot air valve 2 23. The top of the low-speed external heating conversion device 3-3 is connected to the CO delivery pipeline 7 through a CO regulating valve 28.

[0152] In this embodiment, on the basis of the process described in the first embodiment, the exhaust gas valve 1 26, the hot air valve 4 3-9, the hot air valve 2 23 and the CO regulating valve 28 are closed to stop the exhaust gas from entering the CO2 conversion device 3 and stop the output of CO gas, and the exhaust gas valve 2 27 is opened to allow the exhaust gas to enter the exhaust gas external network pipe 1 29 and then be discharged into a separately arranged chimney or other emission facilities, so that the lime kiln double-chamber vertical kiln device 1 and the fuel generation and conversion device 2 form an independent closed-loop production system.

[0153] Embodiment 3

[0154] Based on a device for achieving negative carbon emissions and co-producing lime provided in the present application, this embodiment illustrates the process of using the device to carry out serial production of synthesis gas using biomass and coal powder.

[0155] When the fuel generation and conversion device 2 is operating normally with biomass fuel, pulverized coal fuel is introduced into the furnace, and the coal and air undergo combustion reaction to release heat. This stage is mainly to increase the temperature in the furnace. First, the pulverized coal main spray gun 2-5, the pulverized coal surrounding pipe 2-5-2, the pulverized coal auxiliary nozzle 2-5-3, the fuel inlet 2-5-4 and the air inlet 2-5-5 are turned on to carry out composite serial production of pulverized coal injection and biomass fuel. When the temperature rises to the predetermined parameter, the air inlet 2-5-5 is closed to stop the air supply, and the furnace temperature is turned on. The CO2 gasifier inlet 2-4 and the steam gasifier inlet 2-5-1 are opened to react with the unburned coal char that is flowing downward, and then react with the pyrolyzed biomass char to produce medium-calorific combustible gas rich in CO and H2. Since the gasification reaction is an endothermic reaction, the furnace temperature will gradually decrease. When the furnace temperature reaches the preset value, the system opens the air inlet 2-5-5 again to continue supplying air to increase the furnace temperature. In this way, the two-stage reciprocating cycle to produce fuel gas constitutes a composite serial gasification process of coal and biomass.

[0156] Embodiment 4

[0157] Based on a device for achieving negative carbon emissions and co-producing lime provided in the present application, this embodiment describes a process for producing cracking gas by independently using biomass fuel using the device.

[0158] In the process described in Example 3, the pulverized coal main spray gun 2-5, the pulverized coal surrounding pipe 2-5-2, the pulverized coal auxiliary nozzle 2-5-3, the fuel inlet 2-5-4 and the air inlet 2-5-5 are closed to restore the single-row gasification process using biomass fuel independently.

[0159] Compared with the prior art, the solution provided by this application has at least the following beneficial effects:

[0160] (1) This application uses biomass raw materials (charcoal) with "zero carbon" properties to gasify into gas mainly composed of CO2 to produce lime, which changes the production method of traditional lime shaft kilns using petrochemical energy such as anthracite or coke, and realizes the transformation from traditional energy to green energy application.

[0161] (2) The present application adopts the same device for producing gasification gas and synthesis gas, which solves the problem that different devices are required in the traditional gasification process and coal gas production process, resulting in large equipment footprint, complicated process and high equipment cost. It simplifies the production process and energy loss, and also greatly reduces equipment investment.

[0162] (3) The present application realizes the composite serial cracking and gasification of biomass and coal by directly injecting coal powder and other fuels during the biomass gasification and cracking process, thereby achieving the purpose of multi-path application of fuel and realizing two functions in the same device, thereby achieving the purpose of reducing equipment investment.

[0163] (4) The present application uses the high-temperature CO2 gas in the circulation channel of the lime kiln as a high-calorific value gas fuel for reforming with biomass coke (charcoal) to generate CO, which not only saves the external heat energy consumption required in the conversion process, but also solves the problem of "black pollution" caused by the large amount of "waste coke" generated in the traditional biomass cracking production method that cannot be treated. This is one of the original innovation cores of the present application.

[0164] (5) Compared with traditional biomass gasifiers, due to the reforming effect of "waste charcoal", more than 95% of biomass fuel is gasified into high calorific value combustible gases such as CO, and the calorific value of the gas can be increased by more than 15%. The calorific value of biomass gas has increased from the original ≥1200Kcal / Nm 3 Increase to ≥1800Kcal / Nm 3 .

[0165] (6) In this application, since the CO2 waste gas is converted into CO fuel and directly mixed with biomass pyrolysis gas for lime calcination production, its calorific value increases from ≥1800Kcal / Nm 3 Increase again to ≥3000Kcal / Nm of mixed gas 3 Calorific value, saving a lot of energy consumption in lime production.

[0166] (7) The internal heating electrode high voltage electricity + plasma technology adopted in the present application converts CO2 into CO fuel, and utilizes the high energy electrons and active species generated by high voltage discharge to activate energy small molecules, thereby instantly and rapidly cracking CO2, thereby achieving the rapid breaking of CO2's inert chemical bonds and improving the catalytic reaction capacity. In particular, the application of high entropy porous boride catalytic composite materials synthesized with zirconium oxide and zirconium phosphate materials as catalyst carriers and BaTiO3 and ultra-high temperature boride ceramic materials as additives reduces the reaction energy consumption and reaction time, and the materials are easily available and inexpensive, which is also one of the original innovation cores of the present application.

[0167] (8) The present application adopts the external heating electromagnetic induction method + staged product circulation cracking to separate CO2 into CO fuel. Through the reasonable distribution of the internal temperature of the reactor and the staged temperature adjustment and the timely withdrawal of the product, the CO2 is completely cracked, and the production of high-purity CO and the recycling of CO2 raw gas are achieved. In addition, sufficient reaction time is required for the CO2 cracking process. In particular, the cheap and easily available silk-like catalyst carrier Fe fiber fleece is selected to greatly reduce the catalytic cost. This is also one of the original innovation cores of the present application.

[0168] (9) In the "electrolysis" method of the present application, since the converted CO2 gas is directly used to produce lime, its electrical energy and thermal energy consumption is replaced by the converted CO2 gas, achieving energy consumption balance and surplus, without increasing costs with external energy.

[0169] (10) The present application has the advantages of simple structure, controllable and easy control of electrical conversion intensity, large flue gas treatment flux, and good CO2 cracking effect.

[0170] (11) In this application, all CO2 waste gas is converted into CO gas for lime calcination, realizing the circular application within the production system and achieving the true purpose of "zero carbon emissions". In addition, the remaining CO gas can also be stored and used externally or sold, realizing the "negative carbon" emissions of lime production.

[0171] (12) Compared with the traditional method of calcining lime with coal, the present application adopts a closed-loop production method and does not require the investment in environmental management equipment such as bag filters, desulfurization and denitrification, thereby effectively reducing the investment in environmental management equipment.

[0172] (13) The present application adopts a variety of different production process methods to realize a lime production system, a gas preparation system, and a CO2 conversion system that can operate independently, thereby facilitating production management and operation.

[0173] (14) The device in the present application is also suitable for the transformation and application of traditional lime kilns, and is easier to promote industrialization.

[0174] (15) The principles and application solutions of this application can also be expanded to other waste carbon conversion and gaseous product conversion processes dominated by technologies such as electrolysis, which can be easily converted and applied in industry.

[0175] The technical features of the above embodiments may be arbitrarily combined (as long as there is no contradiction in the combination of these technical features). To make the description concise, not all possible combinations of the technical features in the above embodiments are described; these embodiments that are not explicitly written should also be considered to be within the scope of this specification.

[0176] The above is a relatively specific and detailed description of the present application through general description and specific embodiments. It should be understood that, based on the technical concept of the present application, several conventional adjustments or further innovations can be made to these specific embodiments; however, as long as they do not deviate from the technical concept of the present application, the technical solutions obtained by these conventional adjustments or further innovations also fall within the scope of protection of the claims of the present application.

Claims

1. A device for achieving negative carbon emission and co-production of lime, characterized in that: It comprises a lime kiln, a CO2 conversion device (3) and / or a fuel generation conversion device (2) wherein: The lime kiln has a kiln top gas collecting pipeline (4), and the kiln top gas collecting pipeline (4) can send the CO2 gas produced by the lime kiln to the kiln top flue gas dust reduction and purification device (5) for dust reduction and purification treatment, and the treated flue gas enters the CO2 conversion device (3) along the descending flue gas conveying pipeline (6); The CO2 conversion device (3) comprises a low-temperature CO2 flue gas pressurizing device (3-1) and a high-speed internal heating conversion device (3-2), wherein the low-temperature CO2 flue gas pressurizing device (3-1) is used to pressurize the CO2 gas received from the descending flue gas conveying pipeline (6), and the high-speed internal heating conversion device (3-2) is used to convert the pressurized CO2 gas into CO gas, and to send the converted CO gas into the kiln chamber of the lime kiln for combustion and heat supply to calcine limestone; The fuel generation and conversion device (2) is a closed structure with two upper and lower sections, wherein the upper section is a cracking section (2-1) and the lower section is a conversion section (2-2). The cracking section (2-1) and the conversion section (2-2) are connected and cut off by a hot air shut-off valve (2-6). The top of the cracking section (2-1) is provided with a biomass fuel inlet (2-3) and a CO2 gasifying agent inlet (2-4). The bottom of the cracking section (2-1) is provided with a cracking gas outlet (2-7). The conversion section (2-2) has a CO conversion gas outlet (2-8) and an air duct for inputting an air gasifying agent. The bottom of the conversion section (2-2) is provided with a high-temperature CO2 gas inlet (2-9). The O2 gasifying agent inlet (2-4) and the high-temperature CO2 gas inlet (2-9) are respectively connected to the pipeline for outputting the high-temperature CO2 waste gas from the lime kiln calcining zone; the cracking section (2-1) is used to crack the biomass fuel and the high-temperature CO2 waste gas fed therein into cracking gas containing CO, and the cracked CO is output to the kiln chamber of the lime kiln through the cracking gas outlet (2-7); the conversion section (2-2) is used to receive the remaining biomass fuel after cracking from the cracking section (2-1) and convert the high-temperature CO2 gas rising from its bottom into CO gas through the biomass fuel, and the converted CO gas is output to the kiln chamber of the lime kiln through the CO conversion gas outlet 1 (2-8).

2. The device for achieving negative carbon emission and co-production of lime according to claim 1, characterized in that: The lime kiln is a double-chamber vertical kiln or a single-chamber vertical kiln; A plurality of fuel spray guns (10) are arranged around the kiln body of the lime kiln, each of the fuel spray guns (10) is connected to a lime kiln body fuel surrounding pipe (9) arranged on the outer wall of the kiln body, the fuel spray gun (10) is used to spray combustible gas into the kiln chamber of the lime kiln, and the lime kiln body fuel surrounding pipe (9) is used to receive the cracking gas discharged from the cracking gas outlet (2-7), the CO gas discharged from the CO conversion gas outlet 1 (2-8), and the CO gas discharged from the CO2 conversion device (3); A lime kiln flue gas circulation channel (13) connected to the kiln chamber is arranged on the outer wall of the kiln body of the lime kiln. The lime kiln flue gas circulation channel (13) is connected to the ash cleaning and conveying enclosure pipe (15) through a plurality of pulse control valves (14). The ash cleaning and conveying enclosure pipe (15) is connected to the ash cleaning and conveying pipeline (16). The high-temperature exhaust gas from the lime kiln calcining zone is sent to the high-temperature dust reduction device (17) for dust reduction and purification treatment through the lime kiln flue gas circulation channel (13), the pulse control valve (14), the ash cleaning and conveying enclosure pipe (15) and the ash cleaning and conveying pipeline (16). The purified high-temperature CO2 exhaust gas is sent to the CO2 gasification agent inlet (2-4) and the high-temperature CO2 gas inlet (2-9).

3. The device for achieving negative carbon emission and co-production of lime according to claim 2, characterized in that: The low-temperature CO2 flue gas pressurizing device (3-1) has a CO2 inlet end, a first CO2 outlet end and a second CO2 outlet end, the CO2 inlet end is connected to the descending flue gas conveying pipeline (6), the first CO2 outlet end is connected to the CO2 inlet of the high-speed internal heating conversion device (3-2) through a waste gas valve 1 (26), and the second CO2 outlet end is connected to a waste gas external network pipeline 1 (29) through a waste gas valve 2 (27); The high-speed internal heating conversion device (3-2) comprises a high-speed internal heating conversion device shell (3-2-1), a graphite electrode body (3-4) is arranged in the high-speed internal heating conversion device shell (3-2-1), the graphite electrode body (3-4) has a hollow inner cavity, the hollow inner cavity is filled with spherical zirconium-based nano high-entropy porous ultra-high temperature catalytic material (3-6), a plurality of electrode vents (3-5) are arranged on the side wall of the graphite electrode body (3-4), the electrode vents (3-5) are connected to the high-speed internal heating conversion device shell (3-2-1); the graphite electrode body (3-4) is electrically connected to a transformer (3-4-1), and the transformer (3- 4-1) is used to energize the graphite electrode body (3-4) when the gas passes through the graphite electrode body (3-4); the converted CO enters the shell (3-2-1) of the high-speed internal heating conversion device through the electrode vent hole (3-5), and enters the CO delivery pipeline (8) through the CO conversion gas outlet (3-7) on the shell (3-2-1) of the high-speed internal heating conversion device, and then enters the lime kiln chamber through the lime kiln body fuel surrounding pipe (9); the CO conversion gas outlet (3-7) is connected to the CO delivery pipeline (8) through the hot air valve (3-9), and the CO delivery pipeline (8) is connected to the lime kiln body fuel surrounding pipe (9).

4. The device for achieving negative carbon emission and co-production of lime according to claim 3, characterized in that: The CO2 conversion device (3) further comprises a low-speed external heating conversion device (3-3), wherein a plurality of layers of catalysts are arranged in sequence from bottom to top in the low-speed external heating conversion device (3-3), and the gaps and particle sizes of the catalysts at different levels decrease step by step from bottom to top; The several layers of catalysts include, arranged in order from bottom to top, a primary Fe fiber fleece catalyst (3-11), a primary heat storage particle catalyst (3-12), a secondary Fe fiber fleece catalyst (3-13), a secondary heat storage particle catalyst (3-14), a tertiary Fe fiber fleece catalyst (3-15), a tertiary heat storage particle catalyst (3-16) and a quaternary Fe fiber fleece catalyst (3-17).

5. The device for achieving negative carbon emission and co-production of lime according to claim 4, characterized in that: The low-speed external heating reforming device (3-3) has a first CO inlet, which is close to the bottom of the low-speed external heating reforming device (3-3). The first CO inlet is connected to the CO reforming gas outlet of the high-speed internal heating reforming device (3-2) through a CO reforming gas connecting channel (3-8). A hot air valve five (3-10) is provided on the CO reforming gas connecting channel (3-8); A second CO inlet is provided at the bottom of the low-speed external heating conversion device (3-3), and the second CO inlet is connected to a second high-temperature CO2 gas delivery pipeline (20) through a second hot air valve (23), and the second high-temperature CO2 gas delivery pipeline (20) is connected to a first high-temperature CO2 gas delivery pipeline (18), and the first high-temperature CO2 gas delivery pipeline (18) is connected to the gas outlet of the high-temperature dust reduction device (17); The high-temperature CO2 gas delivery pipeline one (18) is connected to the CO2 gasification agent inlet (2-4) through the high-temperature CO2 gas delivery pipeline three (21), and the high-temperature CO2 gas delivery pipeline three (21) is provided with a hot air valve three; one end of the high-temperature CO2 gas delivery pipeline one (18) is connected to the high-temperature CO2 gas inlet (2-9) through the hot air valve one (22).

6. The device for achieving negative carbon emission and co-production of lime according to claim 5, characterized in that: A high-temperature electromagnetic induction heating device (3-18), a medium-temperature electromagnetic induction heating device (3-19) and a low-temperature electromagnetic induction heating device (3-20) are sequentially arranged on the outer wall of the low-speed external heating conversion device (3-3) from bottom to top, and the heating power supplies of the three electromagnetic induction heating devices are respectively controlled by an electric control device (3-21). The three electromagnetic induction heating devices are used to heat the gas in the low-speed external heating conversion device (3-3); A CO output port is provided at the top of the low-speed external heating conversion device (3-3), and the CO output port is connected to the CO delivery pipeline 1 (7) through a CO control valve (28), and the CO delivery pipeline 1 (7) is connected to the CO delivery pipeline 2 (8) through a cracked gas output pipeline (12).

7. The device for achieving negative carbon emission and co-production of lime according to claim 1, characterized in that: A main coal powder spray gun (2-5) is arranged on the top of the fuel generation and conversion device (2), and a steam gasification agent inlet (2-5-1) and a fuel inlet (2-5-4) are arranged on the main coal powder spray gun (2-5). An air inlet (2-5-5) is opened on the side wall of the fuel generation and conversion device (2) close to the cracking section (2-1). A coal powder surrounding pipe (2-5-2) is arranged on the top of the cracking section (2-1), and the coal powder surrounding pipe (2-5-2) is connected to the inner cavity of the cracking section (2-1) through a plurality of coal powder auxiliary nozzles (2-5-3). The cracking section (2-1) is divided into a drying layer, a pyrolysis layer, an oxidation layer and a reduction layer from top to bottom.

8. The device for achieving negative carbon emission and co-production of lime according to claim 1, characterized in that: The outer wall of the conversion section (2-2) is provided with three layers of regulating blowing ports (21-1) from top to bottom, each regulating blowing port (21-1) is connected to the inner cavity of the conversion section (2-2), each regulating blowing port (21-1) is connected to a high-temperature CO2 gas delivery pipeline three (21), and the high-temperature CO2 gas delivery pipeline three (21) performs auxiliary blowing on the conversion section (2-2) through the regulating blowing ports (21-1); The outer wall of the conversion section (2-2) is also provided with multiple layers of air gasification agent regulating blowing ports (2-15-2) from top to bottom, each of the air gasification agent regulating blowing ports (2-15-2) is connected to the second air duct (2-15-1), the second air duct (2-15-1) is connected to the first air duct (2-15), and the first air duct (2-15) is connected to the outlet end of the air pressurizing device (2-11); The CO gas converted in the conversion section (2-2) is transported to the CO transport pipeline three (11) through the CO conversion gas outlet one (2-8), and the CO transport pipeline three (11) is connected to the CO transport pipeline two (8) through the cracked gas output pipeline (12).

9. The device for achieving negative carbon emission and co-production of lime according to claim 8, characterized in that: An ash outlet is formed below the conversion section (2-2), and a heat-resistant rotary sealed ash outlet is provided at the ash outlet. The heat-resistant rotary sealed ash outlet (2-10) is used to discharge the carbon ash after the biomass fuel is converted into a sealed ash storage bin (2-14) below. The ash storage bin (2-14) is connected to the air pressurizing device (2-11) through a pipeline, and the air pressurizing device (2-11) can pneumatically convey the carbon ash in the ash storage bin (2-14) to the pneumatic conveying ring pipe (2-12). The pneumatic conveying ring pipe (2-12) is connected to the ash storage bin (2-14) through multiple interfaces. The pneumatic conveying ring pipe (2-12) is connected to the lower ash bin of the high-temperature dust removal device (17) through a pneumatic ash conveying pipeline (25). A screw conveyor (19) is arranged below the high-temperature dust removal device (17). The screw conveyor (19) is used to convey the fly ash discharged from the high-temperature dust removal device (17) to the belt conveyor of the ash discharge system at the bottom of the lime kiln; The ash storage bin (2-14) is provided with a water inlet (2-16) and a water outlet. Water is injected into the ash storage bin (2-14) through the water inlet (2-16) and the water level is maintained at a target liquid level position (2-14-3). A slurry pump (2-13) is provided at the water outlet. A mixture of carbon ash and water is sucked out through the slurry pump (2-13).

10. A production process for achieving negative carbon emissions and co-producing lime, characterized in that: The device for achieving negative carbon emission and co-production of lime according to any one of claims 1 to 9 is used, and the production process comprises the following steps: The high-temperature CO2 gas generated by the production of calcium oxide in the lime kiln is sent to a CO2 conversion device to be converted into CO gas, and the converted CO gas enters the fuel surrounding pipe of the lime kiln through a delivery pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln to burn and provide heat to calcine limestone; and / or, The high-temperature CO2 waste gas from the lime kiln calcining zone is dust-removed and purified and then sent to the cracking section and conversion section of the fuel generation and conversion device. In the cracking section, the high-temperature CO2 gas is cracked by the biomass fuel sent to the fuel generation and conversion device, and the combustible gas obtained by the cracking is sent to the fuel surrounding pipe of the lime kiln body through a pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln body for combustion and heat supply to calcine limestone; in the conversion section, the biomass fuel dropped from the cracking section and the CO2 rising from the bottom of the conversion section are subjected to countercurrent heat exchange to complete the conversion of CO2 to CO, and the converted CO is sent to the fuel surrounding pipe of the lime kiln body through a pipeline, and is transported to the kiln through a fuel spray gun arranged on the fuel surrounding pipe of the lime kiln body for combustion and heat supply to calcine limestone.

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