System and method for co-production of synthesis gas with controllable hydrogen-carbon ratio through carbonate reduction refining

Abstract

The invention provides a system and a method for co-production of synthesis gas with adjustable and controllable hydrogen-carbon ratio through carbonate reduction refining. The system comprises a hydrogen supply unit, a carbonate feeding unit and a carbonate fluidization hydrogenation reactor, the carbonate fluidization hydrogenation reactor comprises a first reaction chamber, a second reaction chamber and a cyclone separation unit; according to the system and the method for co-producing the synthesis gas with the adjustable hydrogen-carbon ratio through carbonate reduction refining, the reaction intensity of the first reaction cavity and the second reaction cavity of the carbonate fluidization hydrogenation reactor is adjusted and controlled, so that the hydrogen-carbon ratio in the product synthesis gas at the synthesis gas discharge hole can be accurately controlled; and proper reaction raw materials are directly provided for chemical synthesis of a series of subsequent high-added-value carbon derivatives.

Description

Technical Field

[0001] The present invention belongs to the technical field of resource utilization of waste carbon from high-carbon emission and energy-intensive industries, and specifically relates to a system and method for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio. Background Art

[0002] The extensive use of carbonate ore raw materials in the production of steel, cement, refractory materials, etc. inevitably causes a large amount of carbon dioxide (CO2) emissions: on the one hand, it comes from the thermal decomposition of the carbonate itself, and on the other hand, it comes from the energy combustion in the high-temperature production process. It accounts for 50% of my country's total industrial carbon emissions and needs to be solved urgently. Carbon dioxide capture, utilization and storage (CCUS) technology can first cool the high-temperature carbon-containing flue gas emitted by industry, capture carbon dioxide, and then purify, compress, and transport it, and finally store or utilize it geologically. However, the complex and lengthy process and the high capture cost make it difficult to be deployed on a large scale. It is urgent to develop new carbon-neutral technologies that are efficient and have industrial prospects.

[0003] The carbonate reduction refining technology aims to reduce the carbon in carbonates into high-value-added synthesis gas (CO+H2) in a hydrogen atmosphere, subverting the traditional way of thermal decomposition of carbonates in the air to produce carbon dioxide (CO2), and realizing the high-value utilization of the original waste carbon in the production process; at the same time, it effectively reduces the temperature required for carbonate decomposition, accelerates the carbonate decomposition conversion rate, and greatly reduces energy consumption and corresponding carbon emissions. More importantly, the originally energy-intensive carbonate decomposition reaction and carbon dioxide hydrogenation reaction are integrated into the same reactor and carried out simultaneously through carbonate hydrogenation reduction, which improves the low-carbon production efficiency while avoiding the high energy consumption and high cost associated with the carbon dioxide capture process and the cumbersome post-processing process. Therefore, carbonate reduction refining technology is currently receiving much attention.

[0004] CN115403282A and CN113582208A both disclose a method for producing metal oxides and co-producing synthesis gas by hydrogenation reduction of carbonates; CN116983912A discloses a system and method for catalytic conversion of carbonates by using hydrogen supply molecules (hydrogen or methane) in a fluidized bed reactor; CN117263183A discloses a method for applying electromagnetic induction heating technology to carbonate hydrogenation to prepare oxides and carbon monoxide. Although the above inventions optimize carbonate hydrogenation refining technology from the aspects of reaction equipment, heating method, catalyst and reducing gas type, however, due to the chemical inertness of carbonates and carbon dioxide themselves, in order to achieve the ideal carbon dioxide conversion rate and carbonate decomposition rate at the same time, it is necessary to feed a large excess of hydrogen gas, and use the chemical potential of hydrogen as a driving force to promote the efficient forward progress of carbonate hydrogenation reaction, which results in a huge demand for precious hydrogen resources in the production process and an excessively high molar ratio of H2 to CO (hydrogen-carbon ratio) of the output synthesis gas, which is not conducive to its further utilization and conversion. On the other hand, in order to meet the demand for industrial-scale metal oxide production, carbonate hydrogenation refining should be carried out in a fluidized bed mode: carbonate raw materials enter the reaction device in large quantities and continuously, and the gas (hydrogen)-solid (carbonate) phase fully contacts and reacts under the fluidized state, and metal oxides are quickly and efficiently produced; however, related research at home and abroad is still limited to the intermittent fixed bed reaction mode, and traditional carbonate thermal decomposition equipment such as rotary kilns have problems such as insufficient gas-solid contact and poor airtightness, which cannot meet the safe and large-scale continuous production of carbonate hydrogenation refining. Therefore, the continuous and efficient co-production of metal oxides and controllable hydrogen-carbon ratio synthesis gas with high hydrogen utilization efficiency under the fluidized mode is a problem and challenge that needs to be solved in the future industrial deployment of carbonate reduction refining technology. Summary of the invention

[0005] In view of the shortcomings of current carbonate reduction refining technology, the purpose of the present invention is to provide a system and method for carbonate reduction refining to co-produce synthesis gas with controllable hydrogen-carbon ratio, so as to achieve continuous and efficient co-production of metal oxides and synthesis gas with controllable hydrogen-carbon ratio with high hydrogen utilization efficiency in fluidized mode.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] The first aspect of the present invention is to provide a carbonate reduction refining and co-production system for synthesis gas with controllable hydrogen-carbon ratio, comprising a carbonate fluidized hydrogenation reaction unit, a hydrogen supply unit, a carbonate feed unit and a synthesis gas post-processing system;

[0008] The carbonate fluidized hydrogenation reaction unit comprises a first reaction chamber, a second reaction chamber and a cyclone separation unit;

[0009] The first reaction chamber is used for carbonate hydrogenation conversion; an air distribution plate is arranged at the bottom of the first reaction chamber, and the air distribution plate divides the first reaction chamber into an upper carbonate hydrogenation conversion zone and a lower solid product discharge zone; a hydrogen feed port is arranged on the side of the solid product discharge zone, and a metal oxide discharge port is arranged at the bottom; the hydrogen feed port is connected to a hydrogen supply unit; a carbonate feed port is arranged in the carbonate hydrogenation conversion zone; the carbonate feed port is connected to a carbonate feeding unit; the carbonate hydrogenation conversion zone is equipped with a first temperature control unit;

[0010] The second reaction chamber is used for enhanced conversion of the raw product gas to generate synthesis gas with controllable hydrogen-to-carbon ratio. A catalyst bed is provided in the second reaction chamber, and the catalyst bed is filled with a raw product gas enhanced conversion catalyst to form a raw product gas enhanced conversion zone; an air inlet is provided at the bottom of the second reaction chamber, and a product synthesis gas outlet is provided at the top; the raw product gas enhanced conversion zone is equipped with a second temperature control unit;

[0011] The cyclone separation unit has a feed inlet, a gas phase outlet and a solid phase outlet, wherein the feed inlet and the solid phase outlet are both connected to the carbonate hydroconversion zone, and the gas phase outlet is connected to the gas inlet; the cyclone separation unit is used for performing gas-solid separation on the raw product gas generated in the carbonate hydroconversion zone, and the raw product gas after gas-solid separation enters the second reaction chamber for enhanced conversion of the raw product gas, and the solid particles return to the carbonate hydroconversion zone for further hydrogenation conversion.

[0012] Furthermore, the carbonate hydroconversion zone is in the form of a fluidized bed, including but not limited to a bubbling fluidized bed, a turbulent fluidized bed, a dense phase transport bed or a dilute phase transport bed.

[0013] The carbonate hydroconversion zone adopts the above-mentioned fluidized bed form, so that the carbonate can be quickly and fully decomposed and converted into corresponding metal oxides and crude product gas through fluidized hydrogenation reaction refining in the carbonate hydroconversion zone.

[0014] Furthermore, the raw product gas enhanced conversion zone is in the form of a fixed bed or a fluidized bed, including but not limited to an axial fixed bed, a radial fixed bed, a shell-and-tube fixed bed, a bubbling fluidized bed or a turbulent fluidized bed.

[0015] Furthermore, the cyclone separation unit is a single-stage cyclone separator or a multi-stage cyclone separator; the single-stage cyclone separator is provided with a feed inlet on the side, a gas phase outlet on the top, and a solid phase outlet on the bottom; the multi-stage cyclone separator is formed by connecting multiple single-stage cyclone separators in series.

[0016] Furthermore, the cyclone separation unit is an external cyclone separation unit; the external cyclone separation unit is arranged outside the carbonate hydroconversion zone;

[0017] The carbonate hydroconversion zone is provided with a crude product gas outlet and a solid phase material return port;

[0018] When the cyclone separation unit is a single-stage cyclone separator, the feed inlet of the single-stage cyclone separator is connected to the crude product gas outlet, the gas phase outlet is connected to the air inlet, and the solid phase outlet is connected to the solid phase material return port; when the cyclone separation unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator is connected to the crude product gas outlet, the gas phase outlet of the previous-stage cyclone separator is connected to the feed inlet of the next-stage cyclone separator, the gas phase outlet of the last-stage cyclone separator is connected to the air inlet, and the solid phase outlets of the cyclone separators at each stage are connected to the solid phase material return port through pipelines.

[0019] Furthermore, the cyclone separation unit is a built-in cyclone separation unit; the built-in cyclone separation unit is fixed on the top of the carbonate hydroconversion zone;

[0020] When the built-in cyclone separation unit is a first-stage cyclone separator, the feed inlet and the solid phase outlet of the first-stage cyclone separator are both located inside the carbonate hydroconversion zone and do not contact the inner wall of the carbonate hydroconversion zone, and the gas phase outlet is connected to the air inlet; when the cyclone separation unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator and the solid phase outlets of each stage of cyclone separator are both located inside the carbonate hydroconversion zone and do not contact the inner wall of the carbonate hydroconversion zone, the gas phase outlet of the upper stage cyclone separator is connected to the feed inlet of the lower stage cyclone separator, and the gas phase outlet of the last stage cyclone separator is connected to the air inlet.

[0021] Furthermore, the carbonate reduction refining and co-production system of synthesis gas with controllable hydrogen-to-carbon ratio also includes a preheating system for preheating feed hydrogen;

[0022] The preheating system has a high-temperature fluid inlet, a high-temperature fluid outlet, a low-temperature fluid inlet and a low-temperature fluid outlet. The product synthesis gas outlet is connected to the high-temperature fluid inlet through a first pipeline, and the high-temperature fluid outlet is connected to the synthesis gas post-processing system through a second pipeline. The hydrogen supply unit is connected to the low-temperature fluid inlet through a third pipeline, and the low-temperature fluid outlet is connected to the hydrogen feed port through a fourth pipeline.

[0023] The feed hydrogen is preheated by the preheating system so that the feed hydrogen can quickly reach the hydrogenation conversion temperature after entering the carbonate hydrogenation conversion zone, which helps to accelerate the carbonate hydrogenation conversion reaction, increase the reaction rate and conversion rate, and thus optimize the entire carbonate hydrogenation conversion process; and the preheating system preheats the hydrogen by heat exchanging the product synthesis gas with the feed hydrogen, which can realize the utilization of the waste heat of the product synthesis gas, and at the same time, the high-temperature product synthesis gas is initially cooled, which is beneficial for the post-processing system to further process the product synthesis gas.

[0024] Furthermore, the air distribution plate is a porous plate type air distribution plate, a multi-tube type air distribution plate, a microporous plate type air distribution plate, a bubble type air distribution plate, a float valve type air distribution plate or a multi-layer plate type air distribution plate; the pore size of the air distribution plate is 50 to 100 μm.

[0025] The aperture size of the air distribution plate is set to 50-100 μm, so that the feed hydrogen can be used as a fluidizing gas after being evenly distributed through the air distribution plate to enhance the fluidization quality of the carbonate solid particles, so as to ensure sufficient contact reaction between the gas phase reactant (hydrogen) and the solid phase reactant (carbonate), while supporting the buffer solid to prevent it from falling quickly to the solid product discharge area and blocking the hydrogen feed port; and when the carbonate particles are converted into metal oxide particles, the particle size decreases but the density increases, and they can smoothly pass through the air distribution plate into the solid product discharge area for discharge and collection.

[0026] Furthermore, the crude product gas enhanced conversion catalyst is a metal and / or metal oxide; the metal includes but is not limited to one or more of Fe, Co, Ni, and Cu; the metal oxide includes but is not limited to one or more of Na2O, K2O, MgO, CaO, and CeO2; the loading amount of the crude product gas enhanced conversion catalyst in the catalyst bed is 30kg-5t.

[0027] Furthermore, the preheating system is equipped with an additional heat source.

[0028] The preheating system is equipped with an additional heat source. When the waste heat in the output product synthesis gas is not sufficient to provide preheating heat for the feed hydrogen, the feed hydrogen is preheated by the additional heat source, which is beneficial to the smooth progress of the carbonate hydrogenation reduction refining reaction.

[0029] Furthermore, the preheating system is a shell and tube heat exchanger, a fin heat exchanger, a plate heat exchanger or a coil heat exchanger.

[0030] Furthermore, the synthesis gas post-processing system includes a condenser and a turbine compressor connected in sequence, and the high-temperature fluid outlet is connected to the condenser through a second pipeline.

[0031] The product synthesis gas is further cooled and condensed by a condenser to remove moisture from the product synthesis gas, and then compressed and stored by a turbine compressor, which is conducive to the large-scale continuous production of carbonate hydrogenation reduction refining.

[0032] Furthermore, the metal oxide discharge port is provided with a discharge valve.

[0033] By setting a discharge valve at the metal oxide discharge port and controlling the discharge valve at the beginning of the reaction, a certain amount of metal oxide particles form a particle accumulation below the hydrogen feed port in the solid product discharge zone, which plays a sealing role and prevents hydrogen leakage; then the discharge valve is opened to discharge normally, while ensuring the normal operation of the system and material balance.

[0034] A second aspect of the present invention is to provide a method for refining and co-producing synthesis gas with a controllable hydrogen-to-carbon ratio by carbonate reduction, wherein the system for refining and co-producing synthesis gas with a controllable hydrogen-to-carbon ratio by carbonate reduction comprises the following steps:

[0035] S1. Preheat the hydrogen gas to the first temperature at 250-150000m 3 / h flow rate from the hydrogen feed port into the solid product discharge zone, and carbonate with a particle size of 50 to 150 μm is fed into the carbonate hydrogenation conversion zone from the carbonate feed port at a feed rate of 5 to 70 t / h;

[0036] S2. The temperature of the carbonate hydroconversion zone is controlled at a second temperature by the first temperature control unit, and the hydrogen is uniformly distributed through the air distribution plate as both a reaction gas and a fluidizing gas to fully contact and collide with the feed carbonate solid particles in the carbonate hydroconversion zone to perform fluidized hydrogenation of the carbonate, completely decompose it and convert it into metal oxides, and generate a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor;

[0037] S3. The metal oxide passes through the air distribution plate into the solid product discharge area and is discharged through the metal oxide discharge port; the crude product gas mixed with a small amount of solid particles enters the cyclone separation unit for gas-solid separation;

[0038] S4. After gas-solid separation, the raw product gas enters the raw product gas enhanced conversion zone, and the temperature of the raw product gas enhanced conversion zone is controlled at a third temperature by the second temperature control unit. The raw product gas is subjected to enhanced conversion in the raw product gas enhanced conversion zone, and the carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the raw product gas enhanced conversion zone; the solid particles return to the carbonate hydrogenation conversion zone for further hydrogenation conversion;

[0039] S5. The hydrogen-carbon ratio controllable synthesis gas generated in the raw product gas enhanced conversion zone enters the synthesis gas post-processing system for processing and storage.

[0040] Furthermore, the first temperature is 300-750°C, the second temperature is 500-850°C, and the third temperature is 350-800°C.

[0041] Furthermore, the carbonate includes but is not limited to calcium carbonate, magnesium carbonate, ferrous carbonate and / or corresponding natural ores with calcium carbonate, magnesium carbonate or ferrous carbonate as main components; including a combination of one or more of dolomite, calcite, limestone, magnesite and siderite.

[0042] Further, when the carbonate is calcium carbonate or a natural ore with calcium carbonate as the main component, including a combination of one or more of dolomite, calcite, and limestone, the first temperature is 600-750° C., the second temperature is 650-850° C., and the third temperature is 700-800° C.;

[0043] When the carbonate is magnesium carbonate or natural ore magnesite with magnesium carbonate as the main component, the first temperature is 320-380° C., the second temperature is 500-550° C., and the third temperature is 350-400° C.;

[0044] When the carbonate is ferrous carbonate or natural ore siderite with ferrous carbonate as the main component, the first temperature is 400-460°C, the second temperature is 500-520°C, and the third temperature is 650-700°C.

[0045] Furthermore, the sources of hydrogen include but are not limited to hydrogen produced from fossil fuels such as petroleum, coal and natural gas, hydrogen produced from water electrolysis using renewable energy sources such as wind power and photovoltaics, and hydrogen produced from algae photosynthesis and biomass reforming.

[0046] Compared with the prior art, the present invention has at least the following beneficial effects:

[0047] 1. The carbonate reduction refining and co-production system of the hydrogen-carbon ratio controllable synthesis gas of the present invention ensures that carbonates are quickly and fully decomposed and converted into corresponding metal oxides and preliminary product gas through fluidized hydrogenation refining, and CO2 in the preliminary product gas that is not converted in time can be further catalytically converted into CO in the product gas enhanced conversion zone composed of subsequent catalysts. Through the provision of the product gas enhanced conversion zone, part of the carbon source that should be relatively slowly reduced and converted in the carbonate hydrogenation conversion zone can be more efficiently and thoroughly catalytically converted into CO in the catalyst bed of the product gas enhanced conversion zone in the form of CO2, thereby improving the CO2 conversion rate and reducing the reaction load of the carbonate hydrogenation conversion zone, thereby effectively reducing the hydrogen feed demand (i.e., the feed molar ratio of hydrogen: carbonate), thereby reducing the hydrogen-carbon ratio of the product synthesis gas at the synthesis gas outlet, which is beneficial to the further utilization and conversion of the product synthesis gas.

[0048] 2. The carbonate reduction refining and co-production system of the present invention for controlling the hydrogen-carbon ratio of synthesis gas performs fluidized hydrogenation conversion on carbonate in the carbonate hydrogenation conversion zone, and the hydrogen fully preheated by the preheating system enters the solid product discharge zone from the hydrogen feed port. The hydrogen is evenly distributed through the air distribution plate as a reaction gas and the fluidizing gas at the same time, and fully contacts and collides with the feed carbonate solid particles in the carbonate hydrogenation conversion zone, completely decomposing and converting them into metal oxides; at this time, the carbonate hydrogenation reaction (MCO3+H2→MO+H2O+CO, M is a metal ion) and the carbonate thermal decomposition reaction (MCO3 →MO+CO2) and a small amount of reverse water-gas shift reaction (CO2+H2→CO+H2O) compete with each other and are all strongly endothermic reactions, generating preliminary product gas composed of CO, H2, water vapor and CO2 that is not converted in time; the three strongly endothermic reactions are carried out simultaneously in the same reaction area (carbonate hydrogenation conversion zone), which can avoid the additional energy consumption caused by repeated temperature changes when the three reactions are carried out independently; the hydrogenation conversion of carbonate and carbon dioxide promotes the positive shift of the carbonate decomposition reaction equilibrium, reduces the temperature required for carbonate decomposition, and accelerates the carbonate decomposition rate.

[0049] 3. The carbonate reduction refining and co-production system of the hydrogen-carbon ratio controllable synthesis gas of the present invention has two different reaction zones: a carbonate hydrogenation conversion zone and a product gas enhanced conversion zone. By regulating the reaction conditions (including but not limited to the feed molar ratio of hydrogen and carbonate, carbonate particle size, reaction temperature of each reaction zone, catalyst bed form and catalyst bed weight hourly space velocity, etc.), the reaction intensity of the carbonate hydrogenation conversion zone and the product gas enhanced conversion zone can be regulated, thereby achieving precise control of the hydrogen-carbon ratio of the final output product synthesis gas, and directly providing suitable reaction raw materials for the subsequent chemical synthesis of a series of high value-added carbon derivatives.

[0050] 4. The carbonate reduction refining and co-production system of the hydrogen-carbon ratio controllable synthesis gas of the present invention can effectively avoid the problem of difficult separation of catalyst and carbonate after mixing by carrying out the carbonate hydrogenation conversion process and the catalyst catalytic conversion process in different areas, which is beneficial to the replacement and regeneration of the catalyst bed. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic flow diagram of a system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-to-carbon ratio according to Example 1 of the present invention.

[0052] Figure 2 It is a schematic diagram of the structure of the carbonate fluidized hydrogenation reaction unit of Example 1 of the present invention.

[0053] Figure 3 It is a structural schematic diagram of the preheating system of Example 1 of the present invention.

[0054] Figure 4 It is a schematic diagram of the process of the post-processing system of Example 1 of the present invention.

[0055] Figure 5 It is a schematic structural diagram of the carbonate fluidized hydrogenation reaction unit of Example 2 of the present invention.

[0056] Figure 6 It is a schematic diagram of the structure of the carbonate fluidized hydrogenation reaction unit of Example 4 of the present invention.

[0057] In the figure: 10-first reaction chamber; 11-carbonate feed port; 12-rough product gas outlet; 13-air distribution plate; 14-hydrogen feed port; 15-metal oxide discharge port; 16-solid phase material return port;

[0058] 20-first-stage cyclone separator; 21-feeding port; 22-gas phase outlet; 23-solid phase outlet;

[0059] 30-second reaction chamber; 31-catalyst bed; 32-gas inlet; 33-product synthesis gas outlet;

[0060] Ⅰ-①-carbonate hydroconversion zone; Ⅰ-②-solid product discharge zone; Ⅱ-crude product gas enhanced conversion zone;

[0061] 40-preheating system; 41-high temperature fluid inlet; 42-high temperature fluid outlet; 43-low temperature fluid inlet; 44-low temperature fluid outlet;

[0062] 51-first pipeline; 52-second pipeline; 53-third pipeline; 54-fourth pipeline;

[0063] 60-condenser;

[0064] 70-Turbo compressor;

[0065] F1-carbonate; F2-raw product gas enhanced conversion catalyst; P1-metal oxide. DETAILED DESCRIPTION

[0066] The present invention will be further described below by specific embodiments in conjunction with the accompanying drawings. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0067] Example 1

[0068] 1.1. Carbonate reduction refining and co-production system of synthesis gas with controllable hydrogen-carbon ratio

[0069] refer to Figures 1 to 4 The carbonate reduction refining and co-production system of the present embodiment of the invention for controllable hydrogen-carbon ratio synthesis gas comprises a hydrogen supply unit (not shown in the figure), a carbonate feeding unit (not shown in the figure), a carbonate fluidized hydrogenation reaction unit, a preheating system 40 for preheating the feed hydrogen, and a synthesis gas post-treatment system for treating the product synthesis gas;

[0070] See also Figure 2 , the carbonate fluidized hydrogenation reaction unit includes a first reaction chamber 10, a second reaction chamber 30 and a cyclone separation unit 20;

[0071] The first reaction chamber 10 is used for carbonate hydrogenation conversion; an air distribution plate 13 is arranged at the bottom of the first reaction chamber 10, and the air distribution plate 13 divides the first reaction chamber 10 into a solid product discharge area I-② and a carbonate hydrogenation conversion area I-① located above the solid product discharge area I-②; a hydrogen feed port 14 is arranged at the side of the solid product discharge area I-②, and a metal oxide discharge port 15 is arranged at the bottom; the hydrogen feed port 14 is connected to the hydrogen supply unit, and is used to pass feed hydrogen into the carbonate fluidized hydrogenation reaction unit; the carbonate hydrogenation conversion area I-① The side is provided with a carbonate feed port 11, a crude product gas outlet 12 and a solid phase material return port 16; the carbonate feed port 11 is connected to the carbonate feeding unit, and is used to introduce carbonate into the carbonate fluidized hydrogenation reaction unit; the carbonate hydrogenation conversion zone I-① is equipped with a first temperature control unit (not shown in the figure); the first reaction chamber 10 is used for the fluidized hydrogenation reaction of carbonate, which can fully decompose carbonate into metal oxides P1 and generate a crude product gas containing carbon monoxide, carbon dioxide, hydrogen and water vapor; the carbonate is fully preheated by the preheating system 40. The heated hydrogen enters the solid product discharge zone Ⅰ-② from the hydrogen feed port 14. The hydrogen is evenly distributed as a reaction gas and a fluidizing gas through the air distribution plate 13, and then fully contacts and collides with the feed carbonate solid particles in the carbonate hydrogenation conversion zone Ⅰ-① to carry out fluidized hydrogenation of the carbonate, and completely decompose it into the corresponding metal oxide; at this time, the carbonate hydrogenation reaction (MCO3+H2→MO+H2O+CO, M is a metal ion), the carbonate thermal decomposition reaction (MCO3→MO+CO2) and a small amount of reverse water gas shift reaction (CO2+H2→CO+H2O) compete with each other, and all of them are strongly endothermic reactions, generating a crude product gas composed of CO, H2, water vapor and CO2 that is not converted in time; the three strongly endothermic reactions are carried out simultaneously in the same reaction area (carbonate hydrogenation conversion zone Ⅰ-①), which can avoid the additional energy consumption caused by repeated temperature changes when the three are carried out independently; the carbonate and carbon dioxide hydrogenation conversion promotes the positive shift of the carbonate decomposition reaction equilibrium, reduces the temperature required for carbonate decomposition, and accelerates the carbonate decomposition rate;

[0072] The cyclone separation unit is an external cyclone separation unit and is a first-stage cyclone separator 20. The first-stage cyclone separator 20 is provided with a feed port 21 on the side, a gas phase outlet 22 on the top, and a solid phase outlet 23 on the bottom; the feed port 21 is connected to the raw product gas outlet 12; the cyclone separation unit performs gas-solid separation on the raw product gas generated in the carbonate hydroconversion zone I-①, separates and removes solid particles mixed in the raw product gas, and the raw product gas after gas-solid separation enters the second reaction chamber 30 for enhanced conversion of the raw product gas; the solid phase outlet 23 is connected to the solid phase material return port 16, so that the carbonate solid particles that are not timely hydrogenated and converted and are carried into the cyclone separation unit by the raw product gas can be returned to the carbonate hydroconversion zone I-① through the solid phase material return port 16 for hydrogenation conversion;

[0073] The second reaction chamber 30 is used for the enhanced conversion of the raw product gas to generate synthesis gas with a controllable hydrogen-to-carbon ratio. A catalyst bed 31 is provided in the second reaction chamber 30. The catalyst bed 31 is filled with a raw product gas enhanced conversion catalyst F2 to form a raw product gas enhanced conversion zone II. An air inlet 32 ​​is provided at the bottom of the second reaction chamber 30, and a product synthesis gas outlet 33 is provided at the top. The air inlet 32 ​​is connected to the gas phase outlet 22. The raw product gas enhanced conversion zone II is equipped with a second temperature control unit (not shown in the figure). The second reaction chamber 30 is used to further catalytically convert the CO2 in the raw product gas that has not been converted in time into CO, which can improve the CO2 conversion rate. At the same time, the reaction load of the carbonate hydroconversion zone is reduced, thereby effectively reducing the hydrogen feed demand (i.e., the feed molar ratio of hydrogen and carbonate), thereby reducing the hydrogen-to-carbon ratio of the product synthesis gas at the synthesis gas outlet, which is conducive to the further utilization and conversion of the product synthesis gas; and the carbonate hydroconversion zone I-① and the raw product gas enhanced conversion zone II work synergistically, and by regulating the reaction intensity of the carbonate hydroconversion zone I-① and the raw product gas enhanced conversion zone II, the hydrogen-to-carbon ratio in the product synthesis gas at the product synthesis gas outlet can be precisely controlled; directly providing suitable reaction raw materials for the subsequent chemical synthesis of a series of high value-added carbon derivatives;

[0074] See also Figure 3 The preheating system 40 has a high-temperature fluid inlet 41, a high-temperature fluid outlet 42, a low-temperature fluid inlet 43 and a low-temperature fluid outlet 44. The product synthesis gas outlet 33 is connected to the high-temperature fluid inlet 41 through a first pipeline 51, and the high-temperature fluid outlet 42 is connected to the synthesis gas post-processing system through a second pipeline 52; the hydrogen supply unit is connected to the low-temperature fluid inlet 43 through a third pipeline 53, and the low-temperature fluid outlet 44 is connected to the hydrogen feed port 14 through a fourth pipeline 54. The product synthesis gas is heat-exchanged with the feed hydrogen to preheat the hydrogen, which can realize the utilization of the waste heat of the product synthesis gas, and at the same time, the high-temperature product synthesis gas is initially cooled, which is conducive to the synthesis gas post-processing system to further process the product synthesis gas.

[0075] join Figure 4 The synthesis gas post-processing system includes a condenser 60 for further cooling the product synthesis gas and condensing to remove moisture in the product synthesis gas, and a turbine compressor 70 for compressing the product synthesis gas for storage; the product synthesis gas is further cooled and condensed to remove moisture in the product synthesis gas by the condenser 60, and then the product synthesis gas is compressed and stored by the turbine compressor 70, which is conducive to the large-scale continuous production of carbonate hydrogenation reduction refining.

[0076] Furthermore, the carbonate reduction refining and co-production system of the hydrogen-to-carbon ratio controllable synthesis gas of the present invention can effectively avoid the problem of difficult separation of the raw product gas enhanced conversion catalyst F2 and carbonate after mixing, by carrying out the carbonate hydrogenation conversion process and the raw product gas catalytic enhanced conversion process in different areas, which is beneficial to the replacement and regeneration of the catalyst bed 31.

[0077] According to the above concept, the carbonate in the carbonate feeding unit enters the carbonate hydroconversion zone I-① through the carbonate feed port 11; the hydrogen in the hydrogen supply unit is preheated to the first temperature by the preheating system 40, and then enters the solid product discharge zone I-② through the hydrogen feed port 14; the temperature of the carbonate hydroconversion zone I-① is controlled at the second temperature by the first temperature control unit, and the hydrogen evenly distributed by the air distribution plate 13 is evenly distributed in the carbonate hydroconversion zone I-① as a reaction gas and a fluidizing gas, and fully contacts and collides with the feed carbonate solid particles, and performs carbonate fluidization hydrogenation reaction to generate metal oxide P1 solid particles and a crude product composed of hydrogen, carbon monoxide, carbon dioxide and water vapor. Gas; metal oxide P1 enters solid product discharge zone Ⅰ-② through air distribution plate 13, and is discharged through metal oxide discharge port 15; crude product gas mixed with a small amount of solid particles enters primary cyclone separator 20 through crude product gas outlet 12 and feed port 21 for gas-solid separation; the crude product gas after gas-solid separation enters crude product gas enhanced conversion zone Ⅱ, and the temperature of crude product gas enhanced conversion zone Ⅱ is controlled at the third temperature by the second temperature control unit; under the action of crude product gas enhanced conversion catalyst F2, CO2 in the crude product gas that is not converted in time is further catalytically converted into CO, which improves the CO2 conversion rate while reducing the reaction load of carbonate hydrogenation conversion zone Ⅰ-①, thereby effectively reducing hydrogen The feed demand (i.e., the feed molar ratio of hydrogen and carbonate) can be reduced to reduce the hydrogen-to-carbon ratio of the product synthesis gas at the product synthesis gas outlet 33, which is beneficial to the further utilization and conversion of the product synthesis gas. By adjusting the reaction conditions (such as the feed molar ratio of hydrogen and carbonate, the reaction temperature of each reaction zone, the catalyst bed form and the catalyst bed weight hourly space velocity of the raw product gas enhanced conversion zone, etc.), the reaction intensity of the carbonate hydrogenation conversion zone I-① and the raw product gas enhanced conversion zone II can be adjusted to achieve precise control of the hydrogen-to-carbon ratio of the final output product synthesis gas, which can directly provide suitable reaction raw materials for the subsequent chemical synthesis of a series of high value-added carbon derivatives; the product synthesis gas is discharged through the product synthesis gas outlet 33, The first pipeline 51 and the high-temperature fluid inlet 41 enter the preheating system 40 to exchange heat with the feed hydrogen to realize the waste heat utilization of the product synthesis gas, and at the same time perform preliminary cooling, and then flow out from the high-temperature fluid outlet 42, enter the condenser 60 for further cooling and condensation to remove moisture in the product synthesis gas, and finally are compressed by the turbine compressor 70 and stored. The timely treatment of the product synthesis gas by the synthesis gas post-treatment system is beneficial to the large-scale continuous production of carbonate hydrogenation reduction refining; the carbonate F1 solid particles that are not timely hydrogenated and converted and are carried into the cyclone separation unit by the crude product gas can be returned to the carbonate hydrogenation conversion zone I-① through the solid phase material return port 16 for hydrogenation conversion.

[0078] In the above system, the air distribution plate 13 is a porous plate type air distribution plate, a multi-tube type air distribution plate, a microporous plate type air distribution plate, a bubble type air distribution plate, a float valve type air distribution plate or a multi-layer plate type air distribution plate; the pore size of the air distribution plate 13 is 50-100μm.

[0079] The aperture size of the air distribution plate 13 is set to 50-100 μm, so that the feed hydrogen can be used as a fluidizing gas after being evenly distributed through the air distribution plate to enhance the fluidization quality of the carbonate solid particles, so as to ensure sufficient contact reaction between the gas phase reactant (hydrogen) and the solid phase reactant (carbonate), while supporting the buffer solid to prevent it from falling quickly to the solid product discharge area and blocking the hydrogen feed port; and when the carbonate particles are converted into metal oxide particles, the particle size decreases but the density increases, and they can smoothly pass through the air distribution plate into the solid product discharge area for discharge and collection.

[0080] In the above system, the carbonate hydroconversion zone Ⅰ-① is in the form of a fluidized bed, including but not limited to a bubbling fluidized bed, a turbulent fluidized bed, a dense phase transport bed or a dilute phase transport bed; by adopting the above fluidized bed form, the carbonate F1 can be rapidly and fully decomposed and converted into corresponding metal oxides and crude product gas through fluidized hydrogenation reaction refining in the carbonate hydroconversion zone Ⅰ-①.

[0081] In the above system, the raw product gas enhanced conversion zone II is in the form of a fixed bed or a fluidized bed, including but not limited to an axial fixed bed, a radial fixed bed, a shell-and-tube fixed bed, a bubbling fluidized bed or a turbulent fluidized bed.

[0082] In the above system, the raw product gas enhanced conversion catalyst F2 is a metal and / or metal oxide; the metal includes but is not limited to one or more of Fe, Co, Ni, and Cu; the metal oxide includes but is not limited to one or more of Na2O, K2O, MgO, CaO, and CeO2.

[0083] In the system and method of the present invention, the weight hourly space velocity of the catalyst bed 31 is regulated by the hydrogen flow rate at the hydrogen feed port 14 and the loading amount of the raw product gas enhanced conversion catalyst F2.

[0084] In the above system, the loading amount of the raw product gas enhanced conversion catalyst F2 in the catalyst bed 31 is 30kg-5t.

[0085] In the above system, the preheating system 40 is equipped with an additional heat source (not shown in the figure). When the heat of the generated product synthesis gas is insufficient to provide preheating heat for the feed hydrogen, the feed hydrogen is preheated by the additional heat source, which is beneficial to the smooth progress of the carbonate hydrogenation reduction refining reaction.

[0086] In the above system, the preheating system 40 is a shell and tube heat exchanger, a fin heat exchanger, a plate heat exchanger or a coil heat exchanger.

[0087] In the above system, the metal oxide discharge port 15 is provided with a discharge valve (not shown in the figure).

[0088] By setting a discharge valve at the metal oxide discharge port 15 and controlling the discharge valve before the reaction starts, a certain amount of metal oxide P1 particles form a particle accumulation below the hydrogen feed port 14 of the solid product discharge zone Ⅰ-②, which plays a sealing role and prevents hydrogen leakage; then the discharge valve is opened to discharge normally, while ensuring the normal operation of the system and material balance.

[0089] 1.2. Method for producing synthesis gas with controllable hydrogen-carbon ratio by carbonate reduction refining

[0090] Continue to see Figure 1 Based on the above 1.1 carbonate reduction and refining system for co-producing synthesis gas with adjustable hydrogen-carbon ratio, this embodiment further provides a method for carbonate reduction and refining for co-producing synthesis gas with controllable hydrogen-carbon ratio, including the following steps:

[0091] S1. Preheat the hydrogen gas to 350-750°C by the preheating system 40 at 250-150000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the carbonate F1 with a particle size of 50-150 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 5-70 t / h;

[0092] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 500-850° C. by the first temperature control unit, and the hydrogen is uniformly distributed as a reaction gas and a fluidizing gas through the air distribution plate 13, and then fully contacts and collides with the solid particles of the feed carbonate F1 in the carbonate hydroconversion zone I-①, and the carbonate is fluidized and hydrogenated to completely decompose and convert it into the metal oxide P1, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0093] S3. The metal oxide P1 enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0094] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 400-800°C by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II, and the carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0095] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0096] By this method, the carbonate hydrogenation reduction refining reaction is divided into two areas, namely, carbonate hydrogenation conversion zone I-① and crude product gas enhanced conversion zone II. By regulating the reaction conditions (such as the feed molar ratio of hydrogen and carbonate, the reaction temperature of each reaction zone, the catalyst bed form and the catalyst bed weight hourly space velocity of the crude product gas enhanced conversion zone, etc.), the reaction intensity of carbonate hydrogenation conversion zone I-① and crude product gas enhanced conversion zone II can be regulated, so that the hydrogen-carbon ratio of the final output product synthesis gas can be accurately controlled, and suitable reaction raw materials can be directly provided for the subsequent chemical synthesis of a series of high value-added carbon derivatives. In addition, by carrying out the carbonate hydrogenation conversion process and the crude product gas catalytic enhanced conversion process in different areas, the problem of difficult separation of the crude product gas enhanced conversion catalyst F2 and carbonate after mixing can be effectively avoided, which is beneficial to the replacement and regeneration of the catalyst bed 31.

[0097] Furthermore, in the above method, the carbonate includes but is not limited to calcium carbonate, magnesium carbonate, ferrous carbonate and / or corresponding natural ores with calcium carbonate, magnesium carbonate or ferrous carbonate as the main components; including a combination of one or more of dolomite, calcite, limestone, magnesite and siderite.

[0098] Furthermore, in the above method, when the carbonate is calcium carbonate or a natural ore with calcium carbonate as the main component, including a combination of one or more of dolomite, calcite, and limestone, the first temperature is 600-750°C, the second temperature is 650-850°C, and the third temperature is 700-800°C;

[0099] When the carbonate is magnesium carbonate or natural ore magnesite with magnesium carbonate as the main component, the first temperature is 320-380° C., the second temperature is 500-550° C., and the third temperature is 350-400° C.;

[0100] When the carbonate is ferrous carbonate or natural ore siderite with ferrous carbonate as the main component, the first temperature is 400-460°C, the second temperature is 500-520°C, and the third temperature is 650-700°C.

[0101] Furthermore, the sources of hydrogen in the above method include but are not limited to hydrogen produced from fossil fuels such as oil, coal and natural gas, hydrogen produced from water electrolysis using renewable energy sources such as wind power and photovoltaics, and hydrogen produced from algae photosynthesis and biomass reforming.

[0102] Example 2

[0103] See also Figure 5 , which is different from Example 1, in the carbonate reduction refining and co-production of hydrogen-to-carbon ratio controllable synthesis gas system of this embodiment, the cyclone separation unit is an external cyclone separation unit and is a multi-stage cyclone separator (composed of multiple first-stage cyclone separators 20 connected in series), the feed inlet 21 of the first-stage cyclone separator is connected to the raw product gas outlet 12, the gas phase outlet 22 of the upper-stage cyclone separator is connected to the feed inlet 21 of the lower-stage cyclone separator, the gas phase outlet 22 of the last-stage cyclone separator is connected to the air inlet 32, and the solid phase outlets 23 of the cyclone separators at each stage are connected to the solid phase material return port 16 through pipelines.

[0104] Example 3

[0105] Different from Example 1, in the carbonate reduction refining and co-production system of hydrogen-carbon ratio controllable synthesis gas in this embodiment, the carbonate hydroconversion zone I-① is not provided with a raw product gas outlet 12 and a solid phase material return port 16;

[0106] The cyclone separation unit is a built-in cyclone separation unit and is a first-stage cyclone separator 20. The feed inlet 21 and the solid phase outlet 23 of the first-stage cyclone separator 20 are both located inside the carbonate hydroconversion zone Ⅰ-① and do not contact the inner wall of the carbonate hydroconversion zone Ⅰ-①. The gas phase outlet 22 is connected to the gas inlet 32.

[0107] Example 4

[0108] See also Figure 6 , which is different from Example 1, in the carbonate reduction refining and co-production system of hydrogen-carbon ratio controllable synthesis gas in this embodiment, the carbonate hydroconversion zone Ⅰ-① is not provided with a raw product gas outlet 12 and a solid phase material return port 16;

[0109] The cyclone separation unit is a built-in cyclone separation unit and a multi-stage cyclone separator (composed of multiple first-stage cyclone separators 20 connected in series). The feed inlet 21 of the first-stage cyclone separator and the solid phase outlets 23 of each stage of cyclone separators are both located inside the carbonate hydroconversion zone Ⅰ-① and do not contact the inner wall of the carbonate hydroconversion zone Ⅰ-①. The gas phase outlet 22 of the upper-stage cyclone separator is connected to the feed inlet 21 of the lower-stage cyclone separator, and the gas phase outlet 22 of the final-stage cyclone separator is connected to the gas inlet 32.

[0110] Specific application examples are provided below.

[0111] Application Example 1

[0112] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0113] S1. Preheat the hydrogen gas to 650°C in the preheating system 40 at 48000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and calcium carbonate with a particle size of 70 to 100 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0114] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 700°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a dense phase transport bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas to fully contact and collide with the calcium carbonate solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 65 μm), and the calcium carbonate is fluidized and hydrogenated to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0115] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0116] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 750° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed form, and the catalyst bed 31 is loaded with 4t of FeNi / MgCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0117] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0118] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0119] Application Example 2

[0120] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0121] S1. Preheat the hydrogen gas to 650°C in the preheating system 40 at 32000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and calcium carbonate with a particle size of 70 to 100 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0122] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 700°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a turbulent fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as both a reaction gas and a fluidizing gas, and then fully contacts and collides with the calcium carbonate solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 60 μm), and fluidized hydrogenation of the calcium carbonate is performed to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0123] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0124] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 750° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a radial fixed bed form, and the catalyst bed 31 is loaded with 4t of FeCo / CaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0125] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0126] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0127] Application Example 3

[0128] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0129] S1. Preheat the hydrogen gas to 750°C in the preheating system 40 at 48000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and calcium carbonate with a particle size of 100-150 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0130] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 800°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a dense phase transport bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas to fully contact and collide with the calcium carbonate solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 90 μm), and the calcium carbonate is fluidized and hydrogenated to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0131] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0132] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 750° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed form, and the catalyst bed 31 is loaded with 4t of FeNi / MgCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0133] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0134] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0135] Application Example 4

[0136] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0137] S1. Preheat the hydrogen gas to 750°C in the preheating system 40 at 48000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and calcium carbonate with a particle size of 100-150 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0138] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 850°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a dense phase transport bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas to fully contact and collide with the calcium carbonate solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 90 μm), and the calcium carbonate is fluidized and hydrogenated to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0139] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0140] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 800° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed, and the catalyst bed 31 is loaded with 5t of FeNi / MgCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0141] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0142] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0143] Application Example 5

[0144] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0145] S1. Preheat the hydrogen gas to 680°C in the preheating system 40 at 48000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the limestone with a particle size of 70 to 100 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0146] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 700°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a dense phase transport bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas to fully contact and collide with the limestone solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 65 μm), and the calcium carbonate is fluidized and hydrogenated to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0147] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0148] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 750° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed form, and the catalyst bed 31 is loaded with 4t of FeNi / MgCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0149] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0150] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0151] Application Example 6

[0152] The method for reducing and refining calcium carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthetic gas with an adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0153] S1. Preheat the hydrogen gas to 600°C in the preheating system 40 at 32000m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and dolomite with a particle size of 70 to 100 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 70 t / h;

[0154] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 650°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a turbulent fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and a fluidizing gas, and then fully contacts and collides with dolomite solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 60 μm), and fluidized hydrogenation of calcium carbonate is performed to completely decompose and convert it into calcium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated at the same time;

[0155] S3. Calcium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0156] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 700°C by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts an axial fixed bed form, and the catalyst bed 31 is loaded with 5t of FeCo / CaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0157] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0158] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining calcium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of calcium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0159] Application Example 7

[0160] The method for reducing and refining magnesium carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in 1.1, and includes the following steps:

[0161] S1. Preheat the hydrogen gas to 380°C in the preheating system 40 at 400m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the magnesium carbonate with a particle size of 90-110 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 5 t / h;

[0162] S2. The temperature of carbonate hydroconversion zone I-① is controlled at 550°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a dilute phase transport bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas to fully contact and collide with magnesium carbonate solid particles in carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 80 μm), and fluidized hydrogenation of magnesium carbonate is performed to completely decompose and convert it into magnesium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0163] S3. Magnesium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0164] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 400° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a turbulent fluidized bed, and the catalyst bed 31 is loaded with 35 kg of NiCo / NaMgO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0165] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0166] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the calcium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining magnesium carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of magnesium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0167] Application Example 8

[0168] The method for reducing and refining magnesium carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in 1.1, and includes the following steps:

[0169] S1. Preheat the hydrogen gas to 380°C at 270m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the magnesium carbonate with a particle size of 90-110 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 5 t / h;

[0170] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 550°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a turbulent fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and a fluidizing gas, and then fully contacts and collides with the solid particles of magnesium carbonate in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 80 μm), and the magnesium carbonate is fluidized and hydrogenated to completely decompose and convert it into magnesium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0171] S3. Magnesium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0172] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 400° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed, and the catalyst bed 31 is loaded with 35 kg of CuFe / KMgO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0173] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0174] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the magnesium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining magnesium carbonate to co-produce synthesis gas with adjustable hydrogen-to-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of magnesium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0175] Application Example 9

[0176] The method for reducing and refining magnesium carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in this embodiment adopts the system for reducing and refining carbonate to produce a synthesis gas with an adjustable hydrogen-to-carbon ratio in 1.1, and includes the following steps:

[0177] S1. Preheat the hydrogen gas to 320°C at 270m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the magnesite with a particle size of 90-110 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 5 t / h;

[0178] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 510°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a turbulent fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and a fluidizing gas, and then fully contacts and collides with the solid particles of magnesite in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 80 μm), and fluidized hydrogenation of magnesium carbonate is performed to completely decompose and convert it into magnesium oxide, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0179] S3. Magnesium oxide enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0180] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 350° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts an axial fixed bed form, and the catalyst bed 31 is loaded with 60 kg of CuCe / KMgO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0181] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0182] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the magnesium carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining magnesium carbonate to co-produce synthesis gas with adjustable hydrogen-to-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of magnesium carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0183] Application Example 10

[0184] The method of reducing ferrous carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment adopts the system of reducing carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0185] S1. Preheat the hydrogen gas to 400°C in the preheating system 40 at 11600m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the ferrous carbonate with a particle size of 100-120 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 20 t / h;

[0186] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 520°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a turbulent fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and a fluidizing gas, and then fully contacts and collides with the ferrous carbonate solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 95 μm), and the ferrous carbonate is fluidized and hydrogenated to completely decompose and convert it into iron, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0187] S3. Iron enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0188] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 650° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a bubbling fluidized bed, and the catalyst bed 31 is loaded with 1 t of FeCo / CeCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0189] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0190] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the ferrous carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining ferrous carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of ferrous carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0191] Application Example 11

[0192] The method of reducing ferrous carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment adopts the system of reducing carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0193] S1. Preheat the hydrogen gas to 400°C by the preheating system 40 at 7800m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the ferrous carbonate with a particle size of 100-120 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 20 t / h;

[0194] S2. The temperature of carbonate hydroconversion zone I-① is controlled at 520°C by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a bubbling fluidized bed form), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and fluidizing gas, and then fully contacts and collides with ferrous carbonate solid particles in carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 90 μm), and fluidized hydrogenation of ferrous carbonate is performed to completely decompose and convert it into iron, and a crude product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0195] S3. Iron enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0196] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 650° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a radial fixed bed form, and the catalyst bed 31 is loaded with 1 t of FeCo / CeCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0197] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0198] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the ferrous carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining ferrous carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of ferrous carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0199] Application Example 12

[0200] The method of reducing ferrous carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment adopts the system of reducing carbonate to refine and co-produce synthesis gas with adjustable hydrogen-carbon ratio in 1.1, and includes the following steps:

[0201] S1. Preheat the hydrogen gas to 460°C by the preheating system 40 at 7800m 3 / h flow rate from the hydrogen feed port 14 into the solid product discharge zone I-②, and the siderite with a particle size of 100-120 μm is fed into the carbonate hydrogenation conversion zone I-① from the carbonate feed port 11 at a feed rate of 20 t / h;

[0202] S2. The temperature of the carbonate hydroconversion zone I-① is controlled at 500° C. by the first temperature control unit (the carbonate hydroconversion zone I-① adopts a bubbling fluidized bed), and hydrogen is uniformly distributed through the air distribution plate 13 as a reaction gas and a fluidizing gas, and then fully contacts and collides with the siderite solid particles in the carbonate hydroconversion zone I-① (the aperture size of the air distribution plate 13 is 90 μm), and the ferrous carbonate is fluidized and hydrogenated to completely decompose and convert it into iron, and a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated;

[0203] S3. Iron enters the solid product discharge zone Ⅰ-② through the air distribution plate 13 and is discharged through the metal oxide discharge port 15; the crude product gas mixed with a small amount of solid particles enters the primary cyclone separator 20 through the crude product gas outlet 12 and the feed port 21 for gas-solid separation;

[0204] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II, and the temperature of the crude product gas enhanced conversion zone II is controlled at 700° C. by the second temperature control unit. The crude product gas is subjected to enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a radial fixed bed form, and the catalyst bed 31 is loaded with 1 t of FeCo / CeCaO catalyst). The carbon dioxide that is not hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone II; the solid particles after gas-solid separation are returned to the carbonate hydrogenation conversion zone I-① for further hydrogenation conversion;

[0205] S5. The synthesis gas with controllable hydrogen-carbon ratio generated in the raw product gas enhanced conversion zone II is heat exchanged with the feed hydrogen through the preheating system 40, and the residual heat is recovered and supplied to the preheating system 40; it then enters the synthesis gas post-processing system for processing and storage.

[0206] The solid at the metal oxide discharge port 15 is collected for thermogravimetric analysis of the ferrous carbonate content. After removing the moisture, the synthesis gas product enters the mass spectrometer for gas composition and concentration analysis. Based on this, the process indicators of the method for reducing and refining ferrous carbonate to co-produce synthesis gas with adjustable hydrogen-carbon ratio in this embodiment can be obtained within a reaction time of 0.5 to 1.5 hours: the decomposition rate of ferrous carbonate, the conversion rate of carbon dioxide and the composition of the product synthesis gas, see Table 1.

[0207] Table 1

[0208]

[0209] Comparative Example 1

[0210] The difference between this comparative example and Example 1 is that the product gas enhanced conversion zone does not load a catalyst and by adjusting the hydrogen feed, the conversion rate of carbon dioxide within 0.5 to 1.5 hours of reaction is similar to that of Example 1. The main parameters and performance indicators involved in this comparative example are shown in Table 2.

[0211] Comparative Example 2

[0212] The difference between the comparative example and Example 1 is that the product gas enhanced conversion zone does not carry a catalyst and the hydrogen feed is adjusted so that the composition of the synthesis gas within 0.5 to 1.5 hours of reaction is similar to that of Example 1. The main parameters and performance indicators involved in this comparative example are shown in Table 2.

[0213] Table 2

[0214]

[0215] Combining Table 1 and Table 2, it can be seen that when there is no catalyst-catalyzed conversion process coupled with the carbonate hydrogenation conversion process, due to the chemical inertness of carbonate and carbon dioxide themselves, in order to simultaneously achieve the ideal carbonate decomposition rate and CO2 conversion rate, the hydrogen feed amount needs to be far in excess of the carbonate feed amount, increasing from 3:1 (hydrogen: carbonate feed molar ratio) in Example 1 to 8:1 in Comparative Example 1, which inevitably results in huge hydrogen consumption and the hydrogen-carbon ratio of the synthesis gas product is too high to be further utilized later. On the other hand, as shown in the performance indicators of Comparative Example 2 in Table 2, in order to output a synthesis gas product with an ideal hydrogen-to-carbon ratio, it is necessary to reduce the amount of hydrogen feed, but it is difficult to simultaneously achieve efficient metal oxide production and CO2 resource conversion; the system and method for carbonate reduction refining and co-production of adjustable hydrogen-to-carbon ratio synthesis gas of the present invention can effectively reduce the hydrogen feed demand (i.e., the feed molar ratio of hydrogen: carbonate), thereby reducing the hydrogen-to-carbon ratio of the product synthesis gas at the synthesis gas outlet, which is beneficial to the further utilization and conversion of the product synthesis gas; and by regulating the reaction conditions (such as the feed molar ratio of hydrogen: carbonate, the reaction temperature of each reaction zone, the catalyst bed weight hourly space velocity of the product gas enhanced conversion zone, etc.) to regulate the reaction intensity of the carbonate hydrogenation conversion zone and the product gas enhanced conversion zone, the hydrogen-to-carbon ratio of the final output product synthesis gas can be accurately controlled, directly providing suitable reaction raw materials for the subsequent chemical synthesis of a series of high value-added carbon derivatives.

[0216] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio, characterized in that: It includes a carbonate fluidized hydrogenation reaction unit, a hydrogen supply unit, a carbonate feed unit and a synthesis gas post-processing system; The carbonate fluidized hydrogenation reaction unit comprises a first reaction chamber, a second reaction chamber and a cyclone separation unit; The first reaction chamber is used for carbonate hydrogenation conversion; an air distribution plate is arranged at the bottom of the first reaction chamber, and the air distribution plate divides the first reaction chamber into an upper carbonate hydrogenation conversion zone and a lower solid product discharge zone; a hydrogen feed port is arranged on the side of the solid product discharge zone, and a metal oxide discharge port is arranged at the bottom; the hydrogen feed port is connected to a hydrogen supply unit; a carbonate feed port is arranged in the carbonate hydrogenation conversion zone; the carbonate feed port is connected to a carbonate feeding unit; the carbonate hydrogenation conversion zone is equipped with a first temperature control unit; The second reaction chamber is used for enhanced conversion of the raw product gas to generate synthesis gas with controllable hydrogen-carbon ratio. A catalyst bed is provided in the second reaction chamber, and the catalyst bed is filled with a raw product gas enhanced conversion catalyst to form a raw product gas enhanced conversion zone; an air inlet is provided at the bottom of the second reaction chamber, and a product synthesis gas outlet is provided at the top; the raw product gas enhanced conversion zone is equipped with a second temperature control unit; The cyclone separation unit has a feed inlet, a gas phase outlet and a solid phase outlet, wherein the feed inlet and the solid phase outlet are both connected to the carbonate hydroconversion zone, and the gas phase outlet is connected to the gas inlet; the cyclone separation unit is used for performing gas-solid separation on the raw product gas generated in the carbonate hydroconversion zone, and the raw product gas after gas-solid separation enters the second reaction chamber for enhanced conversion of the raw product gas, and the solid particles return to the carbonate hydroconversion zone for further hydrogenation conversion.

2. The carbonate reduction refining and co-production system of hydrogen-carbon ratio controllable synthesis gas according to claim 1, characterized in that: The carbonate hydrogenation conversion zone is in the form of a fluidized bed, including but not limited to a bubbling fluidized bed, a turbulent fluidized bed, a dense phase transport bed or a dilute phase transport bed; the raw product gas enhanced conversion zone is in the form of a fixed bed or a fluidized bed, including but not limited to an axial fixed bed, a radial fixed bed, a shell and tube fixed bed, a bubbling fluidized bed or a turbulent fluidized bed.

3. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The cyclone separation unit is a single-stage cyclone separator or a multi-stage cyclone separator; the single-stage cyclone separator is provided with a feed inlet on the side, a gas phase outlet on the top, and a solid phase outlet on the bottom; the multi-stage cyclone separator is formed by connecting multiple single-stage cyclone separators in series.

4. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The cyclone separation unit is an external cyclone separation unit; the external cyclone separation unit is arranged outside the carbonate hydroconversion zone; The carbonate hydroconversion zone is provided with a crude product gas outlet and a solid phase material return port; When the cyclone separation unit is a single-stage cyclone separator, the feed inlet of the single-stage cyclone separator is connected to the crude product gas outlet, the gas phase outlet is connected to the air inlet, and the solid phase outlet is connected to the solid phase material return port; when the cyclone separation unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator is connected to the crude product gas outlet, the gas phase outlet of the previous-stage cyclone separator is connected to the feed inlet of the next-stage cyclone separator, the gas phase outlet of the last-stage cyclone separator is connected to the air inlet, and the solid phase outlets of the cyclone separators at each stage are connected to the solid phase material return port through pipelines.

5. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The cyclone separation unit is a built-in cyclone separation unit; the built-in cyclone separation unit is fixed on the top of the carbonate hydroconversion zone; When the built-in cyclone separation unit is a first-stage cyclone separator, the feed inlet and the solid phase outlet of the first-stage cyclone separator are both located inside the carbonate hydroconversion zone and do not contact the inner wall of the carbonate hydroconversion zone, and the gas phase outlet is connected to the air inlet; when the cyclone separation unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator and the solid phase outlets of each stage of cyclone separator are both located inside the carbonate hydroconversion zone and do not contact the inner wall of the carbonate hydroconversion zone, the gas phase outlet of the upper stage cyclone separator is connected to the feed inlet of the lower stage cyclone separator, and the gas phase outlet of the last stage cyclone separator is connected to the air inlet.

6. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-to-carbon ratio also includes a preheating system for preheating feed hydrogen; The preheating system has a high-temperature fluid inlet, a high-temperature fluid outlet, a low-temperature fluid inlet and a low-temperature fluid outlet. The product synthesis gas outlet is connected to the high-temperature fluid inlet through a first pipeline, and the high-temperature fluid outlet is connected to the synthesis gas post-processing system through a second pipeline. The hydrogen supply unit is connected to the low-temperature fluid inlet through a third pipeline, and the low-temperature fluid outlet is connected to the hydrogen feed port through a fourth pipeline.

7. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The air distribution plate is a porous plate type air distribution plate, a multi-tube type air distribution plate, a microporous plate type air distribution plate, a bubble type air distribution plate, a float valve type air distribution plate or a multi-layer plate type air distribution plate; the pore size of the air distribution plate is 50-100 μm.

8. The system for carbonate reduction refining and co-production of synthesis gas with controllable hydrogen-carbon ratio according to claim 1, characterized in that: The crude product gas enhanced conversion catalyst is a metal and / or a metal oxide; the metal includes but is not limited to one or more of Fe, Co, Ni, and Cu; the metal oxide includes but is not limited to one or more of Na2O, K2O, MgO, CaO, and CeO2; the loading amount of the crude product gas enhanced conversion catalyst in the catalyst bed is 30kg-5t.

9. A method for refining and co-producing synthesis gas with controllable hydrogen-carbon ratio by carbonate reduction, characterized in that: A system for refining and co-producing synthesis gas with controllable hydrogen-to-carbon ratio by carbonate reduction according to any one of claims 1 to 8 comprises the following steps: S1. Preheat the hydrogen to 300-750℃ at 250-150000m 3 / h flow rate from the hydrogen feed port into the solid product discharge zone, and carbonate with a particle size of 50 to 150 μm is fed into the carbonate hydrogenation conversion zone from the carbonate feed port at a feed rate of 5 to 70 t / h; S2. The temperature of the carbonate hydroconversion zone is controlled at 500-850° C. by the first temperature control unit, and hydrogen is uniformly distributed as a reaction gas and a fluidizing gas through the air distribution plate to fully contact and collide with the feed carbonate solid particles in the carbonate hydroconversion zone, completely decomposing and converting them into metal oxides, and generating a raw product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor; S3. The metal oxide passes through the air distribution plate into the solid product discharge area and is discharged through the metal oxide discharge port; the crude product gas mixed with a small amount of solid particles enters the cyclone separation unit for gas-solid separation; S4. After gas-solid separation, the crude product gas enters the crude product gas enhanced conversion zone, and the temperature of the product gas enhanced conversion zone is controlled at 350-800°C by the second temperature control unit. The carbon dioxide in the crude product gas that has not been hydrogenated and reduced in time is further catalytically converted into carbon monoxide in the crude product gas enhanced conversion zone; the solid particles return to the carbonate hydrogenation conversion zone for further hydrogenation conversion; S5. The hydrogen-carbon ratio controllable synthesis gas generated in the raw product gas enhanced conversion zone enters the synthesis gas post-processing system for processing and storage.

10. The method for refining and co-producing synthesis gas with controllable hydrogen-to-carbon ratio by carbonate reduction according to claim 9, characterized in that: The carbonate includes but is not limited to calcium carbonate, magnesium carbonate, ferrous carbonate and / or corresponding natural ores with the carbonate as the main component.

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