System and method for producing synthesis gas with controllable hydrogen-carbon ratio by carbonate reduction smelting

Abstract

This invention provides a system and method for producing syngas with an adjustable hydrogen-to-carbon ratio through carbonate reduction refining, comprising a hydrogen supply unit, a carbonate feeding unit, and a carbonate fluidized bed hydrogenation reactor. The carbonate fluidized bed hydrogenation reactor includes a first reaction chamber, a second reaction chamber, and a cyclone separation unit. By adjusting the reaction intensity of the first and second reaction chambers of the carbonate fluidized bed hydrogenation reactor, this system and method can achieve precise control of the hydrogen-to-carbon ratio in the syngas at the syngas outlet, thus providing suitable reaction feedstocks for the subsequent chemical synthesis of a series of high-value-added carbon derivatives.

Description

Technical Field

[0001] This invention belongs to the field of waste carbon resource utilization technology in energy-intensive industries with high carbon emissions, and specifically relates to a system and method for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining. Background Technology

[0002] The extensive use of carbonate ore raw materials in the production processes of steel, cement, and refractory materials inevitably leads to substantial carbon dioxide (CO2) emissions. These emissions originate from both the thermal decomposition of carbonates themselves and the combustion of energy during high-temperature production processes, accounting for 50% of my country's total industrial carbon emissions and urgently requiring a solution. Carbon dioxide capture, utilization, and storage (CCUS) technology can first cool and capture the carbon dioxide in high-temperature carbon-containing flue gas emitted from industry, then purify, compress, and transport it before finally geologically storing or utilizing it. However, the complex and lengthy process, along with the high capture cost, makes large-scale deployment difficult. Therefore, developing efficient and industrially viable new carbon neutrality technologies is urgently needed.

[0003] Carbonate reduction refining technology aims to convert carbon in carbonates into high-value-added syngas (CO + H2) in a hydrogen atmosphere, overturning the traditional method of carbon dioxide (CO2) production through the thermal decomposition of carbonates in air. This technology achieves high-value utilization of previously waste carbon during production. Simultaneously, it effectively lowers the temperature required for carbonate decomposition, accelerates the conversion rate, and significantly reduces energy consumption and corresponding carbon emissions. More importantly, the previously energy-intensive carbonate decomposition and carbon dioxide hydrogenation reactions are integrated into a single reactor, proceeding simultaneously through carbonate hydrogenation and reduction. This improves low-carbon production efficiency while avoiding the high energy consumption and costs associated with carbon dioxide capture and cumbersome post-processing. Therefore, carbonate reduction refining technology is currently attracting considerable attention.

[0004] CN115403282A and CN113582208A both disclose a method for the hydrogenation reduction of carbonates to produce metal oxides and co-produce syngas; CN116983912A discloses a system and method for the catalytic conversion of carbonates using hydrogen-donating molecules (hydrogen or methane) in a fluidized bed reactor; CN117263183A discloses a method for applying electromagnetic induction heating technology to the hydrogenation of carbonates to produce oxides and carbon monoxide. Although the above inventions have optimized the carbonate hydrogenation refining technology in terms of reaction equipment, heating method, catalyst, and type of reducing gas, due to the chemical inertness of carbonates and carbon dioxide themselves, in order to simultaneously achieve the ideal carbon dioxide conversion rate and carbonate decomposition rate, a large excess of hydrogen must be fed in. The chemical potential of hydrogen is used as a driving force to promote the efficient forward reaction of carbonate hydrogenation. This results in a huge demand for valuable hydrogen resources in the production process and an excessively high H2 to CO molar ratio (hydrogen-carbon ratio) in the output syngas, which is not conducive to its further utilization and conversion. On the other hand, to match the demand for industrial-scale metal oxide production, carbonate hydrogenation refining should be carried out in a fluidized bed mode: large quantities and continuously of carbonate feedstock enter the reactor, and the gas (hydrogen) and solid (carbonate) phases fully contact and react in a fluidized state, rapidly and efficiently producing metal oxides. However, relevant research both domestically and internationally is still limited to intermittent fixed-bed reaction modes, while traditional carbonate thermal decomposition equipment, such as rotary kilns, suffers from insufficient gas-solid phase contact and poor sealing, failing to meet the requirements for safe, large-scale, continuous production of carbonate hydrogenation refining. Therefore, achieving continuous and efficient co-production of metal oxides and controllable hydrogen-to-carbon ratio syngas with high hydrogen utilization efficiency in a fluidized bed mode is a pressing problem and challenge that needs to be addressed for the future industrial deployment of carbonate reduction refining technology. Summary of the Invention

[0005] To address the shortcomings of current carbonate reduction refining technology, the present invention aims to provide a system and method for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining, so as to achieve continuous and efficient co-production of metal oxides and syngas with a controllable hydrogen-to-carbon ratio under fluidized bed mode with high hydrogen utilization efficiency.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] The first aspect of the present invention is to provide a system for producing syngas with a controllable hydrogen-to-carbon ratio by reducing carbonates, comprising a carbonate fluidized hydrogenation reaction unit, a hydrogen supply unit, a carbonate feeding unit, and a syngas post-treatment system.

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

[0009] The first reaction chamber is used for carbonate hydrogenation conversion; a wind distribution plate is provided at the bottom of the first reaction chamber, which divides the first reaction chamber into an upper carbonate hydrogenation conversion zone and a lower solid product discharge zone; a hydrogen inlet is provided on the side of the solid product discharge zone, and a metal oxide outlet is provided at the bottom; the hydrogen inlet is connected to a hydrogen supply unit; the carbonate hydrogenation conversion zone is provided with a carbonate inlet; the carbonate inlet is connected to a carbonate feeding unit; a first temperature control unit is configured in the carbonate hydrogenation conversion zone.

[0010] The second reaction chamber is used for the enhanced conversion of crude product gas into syngas with a controllable hydrogen-to-carbon ratio. The second reaction chamber is equipped with a catalyst bed, which is filled with a crude product gas enhanced conversion catalyst to form a crude product gas enhanced conversion zone. The bottom of the second reaction chamber is equipped with an inlet and the top is equipped with a product syngas outlet. The crude 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. The feed inlet and solid phase outlet are both connected to the carbonate hydrogenation conversion zone, and the gas phase outlet is connected to the gas inlet. The cyclone separation unit is used to perform gas-solid separation on the crude product gas generated in the carbonate hydrogenation conversion zone. The crude product gas after gas-solid separation enters the second reaction chamber for enhanced conversion of the crude product gas, and the solid particles are returned to the carbonate hydrogenation conversion zone for further hydrogenation conversion.

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

[0013] The carbonate hydrogenation conversion zone adopts the above-mentioned fluidized bed form, which enables carbonates to be rapidly and fully decomposed into corresponding metal oxides and crude product gas through fluidized hydrogenation reaction in the carbonate hydrogenation conversion zone.

[0014] Furthermore, the crude product gas enhanced conversion zone is in the form of a fixed bed or a fluidized bed, including but not limited to axial fixed bed, radial fixed bed, tubular fixed bed, bubbling fluidized bed or 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 has a feed inlet on the side, a gas phase outlet at the top, and a solid phase outlet at the bottom; the multi-stage cyclone separator is composed of multiple single-stage cyclone separators connected in series.

[0016] Furthermore, the cyclone separation unit is an external cyclone separation unit; the external cyclone separation unit is located outside the carbonate hydrogenation conversion zone;

[0017] The carbonate hydrogenation conversion zone is equipped with a crude product gas outlet and a solid 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 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 final-stage cyclone separator is connected to the air inlet, and the solid phase outlets of each stage of the cyclone separator are connected to the solid material return port via pipelines.

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

[0020] When the built-in cyclone separator unit is a single-stage cyclone separator, the feed inlet and solid phase outlet of the single-stage cyclone separator are both located inside the carbonate hydrogenation conversion zone and do not contact the inner wall of the carbonate hydrogenation conversion zone, and the gas phase outlet is connected to the gas inlet; when the cyclone separator unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator and the solid phase outlet of each stage of the cyclone separator are both located inside the carbonate hydrogenation conversion zone and do not contact the inner wall of the carbonate hydrogenation conversion zone, the gas phase outlet of the previous stage cyclone separator is connected to the feed inlet of the next stage cyclone separator, and the gas phase outlet of the final stage cyclone separator is connected to the gas inlet.

[0021] Furthermore, the system for producing hydrogen-to-carbon ratio controllable syngas by carbonate reduction refining also includes a preheating system for preheating the 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 syngas outlet is connected to the high-temperature fluid inlet via a first pipeline. The high-temperature fluid outlet is connected to the syngas post-processing system via a second pipeline. The hydrogen supply unit is connected to the low-temperature fluid inlet via a third pipeline. The low-temperature fluid outlet is connected to the hydrogen feed port via a fourth pipeline.

[0023] By preheating the feed hydrogen through a preheating system, the feed hydrogen can quickly reach the hydrogenation conversion temperature after entering the carbonate hydrogenation conversion zone. This helps to accelerate the carbonate hydrogenation conversion reaction, improve the reaction rate and conversion rate, and thus optimize the entire carbonate hydrogenation conversion process. In addition, the preheating system preheats the hydrogen by exchanging heat between the product syngas and the feed hydrogen, which enables the utilization of the waste heat of the product syngas. At the same time, it provides preliminary cooling of the high-temperature product syngas, which is beneficial for the post-processing system to further process the product syngas.

[0024] Furthermore, the air distribution plate is a perforated plate type air distribution plate, a multi-tube type air distribution plate, a micro-perforated plate type air distribution plate, a bubble cap type air distribution plate, a floating valve type air distribution plate, or a multi-layer plate type air distribution plate; the pore size of the air distribution plate is 50-100μm.

[0025] The aperture size of the air distribution plate is set to 50-100 μm, so that the feed hydrogen, after being evenly distributed through the air distribution plate, can enhance the fluidization quality of the carbonate solid particles as a fluidizing gas, thereby ensuring sufficient contact and reaction between the gaseous reactants (hydrogen) and the solid reactants (carbonates). At the same time, it supports and buffers the solid material, preventing it from falling rapidly into the solid product discharge area and clogging the hydrogen inlet. Furthermore, when the carbonate particles are converted into metal oxide particles, the particle size decreases but the density increases, allowing them to pass smoothly 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 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; and the loading of the crude product gas enhanced conversion catalyst in the catalyst bed is 30 kg to 5 t.

[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 residual heat in the output 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.

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

[0030] Furthermore, the syngas aftertreatment system includes a condenser and a turbine compressor connected in sequence, and the high-temperature fluid outlet is connected to the condenser via a second pipeline.

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

[0032] Furthermore, the metal oxide outlet is equipped with a discharge valve.

[0033] By setting a discharge valve at the metal oxide outlet, the discharge valve is controlled at the beginning of the reaction, so that a certain amount of metal oxide particles form a particle accumulation below the hydrogen inlet 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 provides a method for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining, using the aforementioned system for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining, comprising the following steps:

[0035] S1. Preheat hydrogen gas to the first temperature at a speed of 250-150000m 3 A flow rate of 50-150 μm of carbonate particles is introduced into the solid product discharge zone from the hydrogen inlet at a flow rate of 5-70 t / h.

[0036] S2. The temperature of the carbonate hydrogenation conversion zone is controlled at the second temperature by the first temperature control unit. Hydrogen gas, as a reaction gas and fluidizing gas, is evenly distributed by the air distribution plate and then fully contacts and collides with the feed carbonate solid particles in the carbonate hydrogenation conversion zone to carry out fluidized hydrogenation of carbonate, completely decompose it into metal oxide, and at the same time generate crude product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor.

[0037] S3. The metal oxide enters the solid product discharge zone through the air distribution plate and is discharged through the metal oxide discharge port; the coarse product gas containing a small amount of solid particles enters the cyclone separation unit for gas-solid separation.

[0038] S4. After gas-solid separation, the crude product gas enters the crude product gas enhanced conversion zone. The temperature of the crude product gas enhanced conversion zone is controlled at the third temperature by the second temperature control unit. The crude product gas undergoes enhanced conversion in the crude product gas enhanced conversion zone. The carbon dioxide that was not hydrogenated in time is further catalyzed into carbon monoxide in the crude product gas enhanced conversion zone. The solid particles are returned to the carbonate hydrogenation conversion zone for further hydrogenation conversion.

[0039] S5. The hydrogen-to-carbon ratio controlled syngas generated in the crude product gas enhanced conversion zone enters the syngas post-processing system for treatment 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 carbonates include, but are not limited to, calcium carbonate, magnesium carbonate, ferrous carbonate and / or corresponding natural minerals whose main components are calcium carbonate, magnesium carbonate or ferrous carbonate; including one or more combinations of dolomite, calcite, limestone, magnesite and siderite.

[0042] Furthermore, when the carbonate is calcium carbonate or a natural mineral with calcium carbonate as the main component, including one or more combinations 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 magnesite, a natural ore with magnesium carbonate as the main component, the first temperature is 320-380℃, the second temperature is 500-550℃, and the third temperature is 350-400℃.

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

[0045] Furthermore, the sources of hydrogen include, but are not limited to, hydrogen production from fossil fuels such as petroleum, coal, and natural gas; hydrogen production from water electrolysis generated by renewable energy sources such as wind power and photovoltaic power; and hydrogen production from algal photosynthesis and biomass reforming.

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

[0047] 1. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining of the present invention ensures rapid and complete decomposition of carbonates into corresponding metal oxides and preliminary product gas through fluidized hydrorefining. The 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. By setting up the product gas enhanced conversion zone, some carbon sources that should have been reduced and converted relatively slowly 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. This improves the CO2 conversion rate while reducing the reaction load in the carbonate hydrogenation conversion zone, thereby effectively reducing the hydrogen feed demand (i.e., the hydrogen:carbonate feed molar ratio), and thus reducing the hydrogen-to-carbon ratio of the product syngas at the syngas outlet, which is beneficial for the further utilization and conversion of the product syngas.

[0048] 2. The system for producing controlled hydrogen-to-carbon ratio syngas by carbonate reduction refining of the present invention performs fluidized hydrogenation conversion of carbonate in the carbonate hydrogenation conversion zone. Hydrogen gas, fully preheated by the preheating system, enters the solid product discharge zone from the hydrogen inlet. Simultaneously, the hydrogen gas, as a reactant gas, is evenly distributed with the fluidizing gas via a distribution plate and fully contacts and collides with the feed carbonate solid particles in the carbonate hydrogenation conversion zone, completely decomposing them into metal oxides. At this time, the carbonate hydrogenation reaction (MCO3 + H2 → MO + H2O + CO, where M is a metal ion) and the carbonate thermal decomposition reaction (MCO3 + H2 → MO + H2O + CO) occur simultaneously. →MO+CO2) and a small amount of reverse water-gas shift reaction (CO2+H2→CO+H2O) compete with each other and are both strongly endothermic reactions, producing a preliminary product gas composed of CO, H2, water vapor, and unconverted CO2; the three strongly endothermic reactions occur simultaneously in the same reaction zone (carbonate hydrogenation conversion zone), which can avoid the extra energy consumption caused by repeated temperature changes when the three are carried out independently; the carbonate and carbon dioxide hydrogenation conversion drive the equilibrium of the carbonate decomposition reaction to the positive side, reducing the temperature required for carbonate decomposition while accelerating the carbonate decomposition rate.

[0049] 3. The system for producing hydrogen-to-carbon ratio controllable syngas by carbonate reduction refining of the present invention has two different reaction zones: a carbonate hydrogenation conversion zone and a product gas enhanced conversion zone. By adjusting 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 controlled, thereby achieving precise control of the hydrogen-to-carbon ratio of the final output product syngas. This provides suitable reaction raw materials for the subsequent chemical synthesis of a series of high-value-added carbon derivatives.

[0050] 4. The system for producing hydrogen-carbon ratio controllable syngas by carbonate reduction refining of the present invention can effectively avoid the problem of difficulty in separating catalyst and carbonate after mixing by separating the carbonate hydrogenation conversion process and the catalyst catalytic conversion process in separate regions, which is beneficial to the replacement and regeneration of catalyst bed. Attached Figure Description

[0051] Figure 1 This is a schematic diagram of the process for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining, as described in Embodiment 1 of the present invention.

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

[0053] Figure 3 This is a schematic diagram of the preheating system in Embodiment 1 of the present invention.

[0054] Figure 4 This is a flowchart of the post-processing system of Embodiment 1 of the present invention.

[0055] Figure 5 This is a schematic diagram of the structure of the carbonate fluidized hydrogenation reaction unit in Embodiment 2 of the present invention.

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

[0057] In the diagram: 10-First reaction chamber; 11-Carbonate inlet; 12-Crude product gas outlet; 13-Air distribution plate; 14-Hydrogen inlet; 15-Metal oxide outlet; 16-Solid material return outlet;

[0058] 20 - Primary cyclone separator; 21 - Feed inlet; 22 - Gas phase outlet; 23 - Solid phase outlet;

[0059] 30 - Second reaction chamber; 31 - Catalyst bed; 32 - Gas inlet; 33 - Product syngas outlet;

[0060] Ⅰ-①- Carbonate hydrogenation conversion 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-Turbine compressor;

[0065] F1 - Carbonate; F2 - Crude product gas enhanced conversion catalyst; P1 - Metal oxide. Detailed Implementation

[0066] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0067] Example 1

[0068] 1.1 System for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining

[0069] refer to Figures 1-4 The system for producing hydrogen-carbon ratio controllable syngas by carbonate reduction refining in this embodiment includes 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 syngas post-treatment system for processing the product syngas.

[0070] See 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; a wind distribution plate 13 is provided at the bottom of the first reaction chamber 10, which divides the first reaction chamber 10 into a solid product discharge zone I-② and a carbonate hydrogenation conversion zone I-① located above the solid product discharge zone I-②; a hydrogen inlet 14 is provided on the side of the solid product discharge zone I-②, and a metal oxide outlet 15 is provided at the bottom; the hydrogen inlet 14 is connected to a hydrogen supply unit and is used to introduce feed hydrogen into the carbonate fluidized hydrogenation reaction unit; the carbonate hydrogenation conversion zone I-① The side is equipped with a carbonate inlet 11, a crude product gas outlet 12, and a solid material return outlet 16; the carbonate inlet 11 is connected to the carbonate feeding unit and is used to feed 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 oxide P1, and at the same time generate crude product gas containing carbon monoxide, carbon dioxide, hydrogen and water vapor; after being fully preheated by the preheating system 40 Heated hydrogen enters the solid product discharge zone I-② through the hydrogen inlet 14. Simultaneously, the hydrogen, acting as both reactant and fluidizing gas, is evenly distributed via the air distribution plate 13 and then fully contacts and collides with the fed carbonate solid particles in the carbonate hydrogenation conversion zone I-①, undergoing fluidized hydrogenation of the carbonate and completely decomposing it into the corresponding metal oxides. At this time, the carbonate hydrogenation reaction (MCO3+H2→MO+H2O+CO, where 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 are all strongly endothermic reactions, generating a crude product gas composed of CO, H2, water vapor, and unconverted CO2. The simultaneous occurrence of these three strongly endothermic reactions in the same reaction zone (carbonate hydrogenation conversion zone I-①) avoids the additional energy consumption caused by repeated temperature changes when they occur independently. The carbonate and carbon dioxide hydrogenation conversion shifts the carbonate decomposition reaction equilibrium to the positive side, lowering the temperature required for carbonate decomposition while accelerating the decomposition rate.

[0072] The cyclone separation unit is an external cyclone separation unit and a first-stage cyclone separator 20. The first-stage cyclone separator 20 has a feed inlet 21 on the side, a gas phase outlet 22 at the top, and a solid phase outlet 23 at the bottom. The feed inlet 21 is connected to the crude product gas outlet 12. The cyclone separation unit performs gas-solid separation on the crude product gas generated in the carbonate hydrogenation conversion zone I-①, separating and removing solid particles entrained in the crude product gas. The crude product gas after gas-solid separation enters the second reaction chamber 30 for enhanced conversion. The solid phase outlet 23 is connected to the solid material return port 16, so that carbonate solid particles that are not hydrogenated in time and are carried into the cyclone separation unit by the crude product gas can return to the carbonate hydrogenation conversion zone I-① for hydrogenation conversion through the solid material return port 16.

[0073] The second reaction chamber 30 is used for the enhanced conversion of crude product gas into syngas with a controllable hydrogen-to-carbon ratio. The second reaction chamber 30 contains a catalyst bed 31 filled with a crude product gas enhanced conversion catalyst F2, forming a crude product gas enhanced conversion zone II. The second reaction chamber 30 has an inlet 32 ​​at the bottom and a product syngas outlet 33 at the top, with the inlet 32 ​​connected to the gas phase outlet 22. The crude 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 unconverted CO2 in the crude product gas into CO, thereby improving the CO2 conversion rate. Simultaneously, it reduces the reaction load in the carbonate hydrogenation conversion zone, thereby effectively reducing the hydrogen feed demand (i.e., the molar ratio of hydrogen to carbonate feed), and consequently reducing the hydrogen-to-carbon ratio of the product syngas at the syngas outlet, which is beneficial for the further utilization and conversion of the product syngas. Furthermore, the carbonate hydrogenation conversion zone I-① and the crude product gas enhanced conversion zone II work synergistically. By regulating the reaction intensity of the carbonate hydrogenation conversion zone I-① and the crude product gas enhanced conversion zone II, precise control of the hydrogen-to-carbon ratio in the product syngas at the syngas outlet can be achieved. This directly provides suitable reaction raw materials for the subsequent chemical synthesis of a series of high-value-added carbon derivatives.

[0074] See 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 syngas outlet 33 is connected to the high-temperature fluid inlet 41 via a first pipeline 51, and the high-temperature fluid outlet 42 is connected to the syngas post-processing system via a second pipeline 52. The hydrogen supply unit is connected to the low-temperature fluid inlet 43 via a third pipeline 53, and the low-temperature fluid outlet 44 is connected to the hydrogen inlet 14 via a fourth pipeline 54. By exchanging heat between the product syngas and the feed hydrogen, the hydrogen is preheated, enabling the utilization of the waste heat of the product syngas. Simultaneously, the high-temperature product syngas is initially cooled, which is beneficial for further processing by the syngas post-processing system.

[0075] join Figure 4 The syngas after-treatment system includes a condenser 60 for further cooling and condensing the product syngas to remove moisture, and a turbine compressor 70 for compressing and storing the product syngas. The further cooling and condensing of the product syngas by the condenser 60 to remove moisture, followed by compression and storage by the turbine compressor 70, facilitates the large-scale continuous production of carbonate hydrogenation refining.

[0076] Furthermore, the system for producing hydrogen-to-carbon ratio controllable syngas by carbonate reduction refining of the present invention can effectively avoid the problem of difficulty in separating the crude product gas enhanced conversion catalyst F2 after being mixed with carbonate by carrying out the carbonate hydrogenation conversion process and the crude product gas catalytic enhancement conversion process in separate regions, which is beneficial to the replacement and regeneration of catalyst bed 31.

[0077] Based on the above design, the carbonate in the carbonate feeding unit enters the carbonate hydrogenation conversion zone I-① through the carbonate inlet 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 inlet 14; the temperature of the carbonate hydrogenation conversion zone I-① is controlled at the second temperature by the first temperature control unit, and the hydrogen, after being evenly distributed by the air distribution plate 13, is simultaneously used as both the reaction gas and the fluidizing gas in the carbonate hydrogenation conversion zone I-①, making full contact and collision with the fed carbonate solid particles to carry out the carbonate fluidized hydrogenation reaction, generating metal oxide P1 solid particles and a crude product composed of hydrogen, carbon monoxide, carbon dioxide and water vapor. Gas; metal oxide P1 enters the solid product discharge zone I-② through the air distribution plate 13 and exits 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 inlet 21 for gas-solid separation; 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 the third temperature by the second temperature control unit; under the action of the crude product gas enhanced conversion catalyst F2, the CO2 in the crude product gas that has not been converted in time is further catalytically converted into CO, improving the CO2 conversion rate while reducing the reaction load of the carbonate hydrogenation conversion zone I-①, thereby effectively reducing the hydrogen content. The feed requirements (i.e., the molar ratio of hydrogen to carbonate) are controlled, thereby reducing the hydrogen-to-carbon ratio of the product syngas at product syngas outlet 33. This facilitates further utilization and conversion of the product syngas. Furthermore, by controlling reaction conditions (such as the molar ratio of hydrogen to carbonate feed, the reaction temperature in each reaction zone, the catalyst bed type and heavy space velocity in the crude product gas enhanced conversion zone, etc.), the reaction intensity in carbonate hydrogenation conversion zone I-① and crude product gas enhanced conversion zone II can be controlled. This allows for precise control of the hydrogen-to-carbon ratio of the final output product syngas, directly providing suitable reaction feedstocks for the subsequent chemical synthesis of a series of high-value-added carbon derivatives. The product syngas exits through product syngas 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, realizing the utilization of the waste heat of the product syngas and performing preliminary cooling. Then, it flows out from the high-temperature fluid outlet 42 and enters the condenser 60 for further cooling and condensation to remove moisture from the product syngas. Finally, it is compressed by the turbine compressor 70 and stored. The timely processing of the product syngas by the syngas post-processing system is conducive to the large-scale continuous production of carbonate hydrogenation reduction refining. The carbonate F1 solid particles that are not hydrogenated in time and are carried into the cyclone separation unit by the crude product gas can be returned to the carbonate hydrogenation conversion zone I-① for hydrogenation conversion through the solid material return port 16.

[0078] In the above system, the air distribution plate 13 is a perforated plate type air distribution plate, a multi-pipe type air distribution plate, a micro-perforated plate type air distribution plate, a bubble cap type air distribution plate, a floating 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 gas, after being evenly distributed through the air distribution plate, can enhance the fluidization quality of the carbonate solid particles as a fluidizing gas, thereby ensuring sufficient contact and reaction between the gas phase reactant (hydrogen) and the solid phase reactant (carbonate). At the same time, it supports and buffers the solid material, preventing it from falling rapidly into the solid product discharge area and clogging the hydrogen inlet. Furthermore, when the carbonate particles are converted into metal oxide particles, the particle size decreases but the density increases, allowing them to pass smoothly through the air distribution plate into the solid product discharge area for discharge and collection.

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

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

[0082] In the above system, the crude product gas enhanced conversion catalyst F2 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.

[0083] In the system and method of this invention, the weight space velocity of the catalyst bed 31 is controlled by the hydrogen flow rate at the hydrogen inlet 14 and the loading of the crude product gas enhanced conversion catalyst F2.

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

[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 syngas 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 finned heat exchanger, a plate heat exchanger, or a coil heat exchanger.

[0087] In the above system, the metal oxide outlet 15 is equipped 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 begins, a certain amount of metal oxide P1 particles are allowed to accumulate below the hydrogen inlet 14 in the solid product discharge zone I-②, which acts as a seal to prevent hydrogen leakage. Then, the discharge valve is opened to discharge the material normally, while ensuring the normal operation of the system and the material balance.

[0089] 1.2 Method for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining

[0090] See also Figure 1 Based on the above-described system for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining, this embodiment further provides a method for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining, comprising the following steps:

[0091] S1. Hydrogen gas, preheated to 350–750°C by the preheating system 40, is then introduced at a flow rate of 250–150000 m³ / h. 3 A flow rate of 50-150 μm of carbonate F1 is introduced into the solid product discharge zone I-② from the hydrogen inlet 14 at a flow rate of 5-70 t / h. The carbonate F1 with a particle size of 50-150 μm is introduced into the carbonate hydrogenation conversion zone I-① from the carbonate inlet 11 at a feed rate of 5-70 t / h.

[0092] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 500-850℃ by the first temperature control unit. Hydrogen gas is used as a reaction gas and fluidizing gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the feed carbonate F1 solid particles in carbonate hydrogenation conversion zone I-① to carry out fluidized hydrogenation of carbonate and completely decompose it into metal oxide P1. At the same time, crude product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor is generated.

[0093] S3. 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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0094] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 400-800℃ by the second temperature control unit. The crude product gas undergoes enhanced conversion in the crude product gas enhanced conversion zone II. The carbon dioxide that has not been hydrogenated in time is further catalyzed 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0096] This method divides the carbonate hydrogenation reduction refining reaction into two zones: carbonate hydrogenation conversion zone I-① and crude product gas enhanced conversion zone II. By controlling 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 heavy hourly space velocity of the catalyst bed in the crude product gas enhanced conversion zone), the reaction intensity of carbonate hydrogenation conversion zone I-① and crude product gas enhanced conversion zone II can be controlled. This allows for precise control of the hydrogen-to-carbon ratio of the final output product syngas, directly providing suitable reaction raw materials for the subsequent chemical synthesis of a series of high-value-added carbon derivatives. Furthermore, by separating the carbonate hydrogenation conversion process and the crude product gas catalytic enhanced conversion process into separate zones, the problem of difficulty in separating the crude product gas enhanced conversion catalyst F2 from the carbonate after mixing can be effectively avoided, which is beneficial for the replacement and regeneration of 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 minerals whose main components are calcium carbonate, magnesium carbonate or ferrous carbonate; including one or more combinations of dolomite, calcite, limestone, magnesite and siderite.

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

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

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

[0101] Furthermore, the hydrogen sources for the above methods include, but are not limited to, hydrogen production from fossil fuels such as petroleum, coal, and natural gas; hydrogen production from water electrolysis generated by renewable energy sources such as wind power and photovoltaic power; and hydrogen production from algal photosynthesis and biomass reforming.

[0102] Example 2

[0103] See Figure 5 Unlike Example 1, in the system for producing controlled hydrogen-to-carbon ratio syngas by carbonate reduction refining in this example, the cyclone separation unit is an external 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 is connected to the crude product gas outlet 12. The gas phase outlet 22 of the previous-stage cyclone separator is connected to the feed inlet 21 of the next-stage cyclone separator. The gas phase outlet 22 of the final-stage cyclone separator is connected to the air inlet 32. The solid phase outlet 23 of each stage of the cyclone separator is connected to the solid material return port 16 through pipelines.

[0104] Example 3

[0105] Unlike Example 1, in the carbonate reduction refining and co-production of hydrogen-carbon ratio controllable syngas system of this example, the carbonate hydrogenation conversion zone I-① does not have a crude product gas outlet 12 and a solid material return port 16.

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

[0107] Example 4

[0108] See Figure 6 Unlike Example 1, in the carbonate reduction refining and co-production of hydrogen-carbon ratio controllable syngas system of this example, the carbonate hydrogenation conversion zone I-① does not have a crude product gas outlet 12 and a solid 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 outlet 23 of each stage cyclone separator are located inside the carbonate hydrogenation conversion zone I-① and do not contact the inner wall of the carbonate hydrogenation conversion zone I-①. The gas phase outlet 22 of the previous stage cyclone separator is connected to the feed inlet 21 of the next stage cyclone separator. The gas phase outlet 22 of the final stage cyclone separator is connected to the air inlet 32.

[0110] The following provides specific application examples.

[0111] Application Example 1

[0112] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

[0113] S1. Hydrogen gas preheated to 650°C by the preheating system is then transported at 48000m... 3 A flow rate of 70 t / h is introduced from hydrogen inlet 14 into solid product discharge zone I-②, and calcium carbonate with a particle size of 70-100 μm is introduced from carbonate inlet 11 into carbonate hydrogenation conversion zone I-① at a feed rate of 70 t / h.

[0114] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 700℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a dense phase conveying bed form). Hydrogen gas is used as a reaction gas and fluidizing gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the calcium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 65μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0116] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 750℃ by the second temperature control unit. The crude product gas undergoes 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 has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0118] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0119] Application Example 2

[0120] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

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

[0122] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 700℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts turbulent fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with calcium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 60μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0124] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 750℃ by the second temperature control unit. The crude product gas undergoes 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 has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0126] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0127] Application Example 3

[0128] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

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

[0130] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 800℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a dense phase conveying bed form). Hydrogen gas is used as a reaction gas and fluidizing gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the calcium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 90μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0132] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 750℃ by the second temperature control unit. The crude product gas undergoes 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 has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0134] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0135] Application Example 4

[0136] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

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

[0138] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 850℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a dense phase conveying bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the calcium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 90μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0140] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 800℃ by the second temperature control unit. The crude product gas undergoes 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 5t of FeNi / MgCaO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0142] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0143] Application Example 5

[0144] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

[0145] S1. Hydrogen gas preheated to 680°C by the preheating system is introduced at a speed of 48000m. 3 A flow rate of 70 t / h is introduced from hydrogen inlet 14 into solid product discharge zone I-②, and limestone with a particle size of 70-100 μm is introduced from carbonate inlet 11 into carbonate hydrogenation conversion zone I-① at a feed rate of 70 t / h.

[0146] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 700℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a dense phase conveying bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with limestone solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 65μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0148] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 750℃ by the second temperature control unit. The crude product gas undergoes 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 has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0150] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0151] Application Example 6

[0152] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by calcium carbonate reduction refining in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by carbonate reduction refining, and includes the following steps:

[0153] S1. Hydrogen gas preheated to 600℃ by the preheating system 40 is then pumped at 32000m... 3 A flow rate of 70 t / h is introduced from hydrogen inlet 14 into solid product discharge zone I-②, and dolomite with a particle size of 70-100 μm is introduced from carbonate inlet 11 into carbonate hydrogenation conversion zone I-① at a feed rate of 70 t / h.

[0154] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 650℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts turbulent fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the dolomite solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 60μm) to carry out fluidized hydrogenation of calcium carbonate, which is completely decomposed into calcium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor is generated.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0156] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 700℃ by the second temperature control unit. The crude product gas undergoes 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 has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0158] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the calcium carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment can be obtained within 0.5 to 1.5 hours of reaction: calcium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0159] Application Example 7

[0160] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing magnesium carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

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

[0162] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 550℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a dilute phase conveying bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with magnesium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 80μm) to carry out fluidized hydrogenation of magnesium carbonate, which is completely decomposed into magnesium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas 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 containing a small amount of solid particles enters the first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0164] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 400℃ by the second temperature control unit. The crude product gas undergoes enhanced conversion in the crude product gas enhanced conversion zone II (the crude product gas enhanced conversion zone II adopts a turbulent fluidized bed form, and the catalyst bed 31 is loaded with 35kg of NiCo / NaMgO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0166] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the calcium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the magnesium carbonate reduction refining and co-production of controllable hydrogen-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: magnesium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0167] Application Example 8

[0168] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing magnesium carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

[0169] S1. Hydrogen gas preheated to 380°C by the preheating system 40 is introduced at a speed of 270m... 3 A flow rate of 5 t / h is introduced from hydrogen inlet 14 into solid product discharge zone I-②, and magnesium carbonate with a particle size of 90-110 μm is introduced from carbonate inlet 11 into carbonate hydrogenation conversion zone I-① at a feed rate of 5 t / h.

[0170] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 550℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a turbulent fluidized bed form). Hydrogen gas, as a reaction gas, is uniformly distributed with the fluidizing gas through the air distribution plate 13 and then fully contacts and collides with the magnesium carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 80μm) to carry out fluidized hydrogenation of magnesium carbonate, which is completely decomposed into magnesium oxide, and at the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas 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 containing a small amount of solid particles enters the first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0172] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 400℃ by the second temperature control unit. The crude product gas undergoes 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 35kg of CuFe / KMgO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0174] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the magnesium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the magnesium carbonate reduction refining and co-production of controllable hydrogen-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: magnesium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0175] Application Example 9

[0176] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing magnesium carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

[0177] S1. Hydrogen gas preheated to 320°C by the preheating system 40 is introduced at 270m... 3 A flow rate of 5 t / h is introduced from hydrogen inlet 14 into solid product discharge zone I-②, and magnesite with a particle size of 90-110 μm is introduced from carbonate inlet 11 into carbonate hydrogenation conversion zone I-① at a feed rate of 5 t / h.

[0178] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 510℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts turbulent fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the magnesite solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 80μm) to carry out fluidized hydrogenation of magnesium carbonate, which is completely decomposed into magnesium oxide. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas 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 containing a small amount of solid particles enters the first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0180] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 350℃ by the second temperature control unit. The crude product gas undergoes 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 60kg of CuCe / KMgO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0182] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the magnesium carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the magnesium carbonate reduction refining and co-production of controllable hydrogen-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: magnesium carbonate decomposition rate, carbon dioxide conversion rate, and product syngas composition, as shown in Table 1.

[0183] Application Example 10

[0184] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing ferrous carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

[0185] S1. Hydrogen gas preheated to 400℃ by the preheating system 40 is introduced at 11600m 3A flow rate of 100-120 μm of ferrous carbonate is introduced into the solid product discharge zone I-② from the hydrogen inlet 14 at a flow rate of 20 t / h. Ferrous carbonate with a particle size of 100-120 μm is introduced into the carbonate hydrogenation conversion zone I-① from the carbonate inlet 11 at a feed rate of 20 t / h.

[0186] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 520℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts turbulent fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the ferrous carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 95μm) to carry out fluidized hydrogenation of ferrous carbonate, completely decompose it into iron, and at the same time generate crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas and water vapor.

[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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0188] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 650℃ by the second temperature control unit. The crude product gas undergoes 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 1t of FeCo / CeCaO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0190] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the ferrous carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the ferrous carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: ferrous carbonate decomposition rate, carbon dioxide conversion rate, and syngas composition, as shown in Table 1.

[0191] Application Example 11

[0192] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing ferrous carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

[0193] S1. Hydrogen gas preheated to 400°C by the preheating system is introduced at 7800m... 3 A flow rate of 100-120 μm of ferrous carbonate is introduced into the solid product discharge zone I-② from the hydrogen inlet 14 at a flow rate of 20 t / h. Ferrous carbonate with a particle size of 100-120 μm is introduced into the carbonate hydrogenation conversion zone I-① from the carbonate inlet 11 at a feed rate of 20 t / h.

[0194] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 520℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a bubbling fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the ferrous carbonate solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 90μm) to carry out fluidized hydrogenation of ferrous carbonate, which is completely decomposed into iron. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas 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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0196] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 650℃ by the second temperature control unit. The crude product gas undergoes 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 1t of FeCo / CeCaO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0198] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the ferrous carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the ferrous carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: ferrous carbonate decomposition rate, carbon dioxide conversion rate, and syngas composition, as shown in Table 1.

[0199] Application Example 12

[0200] The method for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing ferrous carbonate in this embodiment uses the system described in 1.1 above for producing syngas with an adjustable hydrogen-to-carbon ratio by reducing carbonate, and includes the following steps:

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

[0202] S2. The temperature of carbonate hydrogenation conversion zone I-① is controlled at 500℃ by the first temperature control unit (carbonate hydrogenation conversion zone I-① adopts a bubbling fluidized bed form). Hydrogen gas is used as a reaction gas and fluidized gas. After being evenly distributed by the air distribution plate 13, it fully contacts and collides with the siderite solid particles in carbonate hydrogenation conversion zone I-① (the pore size of the air distribution plate 13 is 90μm) to carry out fluidized hydrogenation of ferrous carbonate, which is completely decomposed into iron. At the same time, a crude product gas containing carbon dioxide, carbon monoxide, hydrogen gas 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 first-stage cyclone separator 20 through the crude product gas outlet 12 and the feed inlet 21 for gas-solid separation.

[0204] S4. The crude product gas after gas-solid separation enters the crude product gas enhanced conversion zone II. The temperature of the crude product gas enhanced conversion zone II is controlled at 700℃ by the second temperature control unit. The crude product gas undergoes 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 1t of FeCo / CeCaO catalyst). The carbon dioxide that has not been 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 hydrogen-to-carbon ratio controllable syngas generated in the crude product gas enhanced conversion zone II is preheated and heat-exchanged with the feed hydrogen through the preheating system 40 to recover waste heat and supply it to the preheating system 40; then it enters the syngas post-processing system for processing and storage.

[0206] The solids collected at the metal oxide outlet 15 were subjected to thermogravimetric analysis to determine the ferrous carbonate content. After removing moisture, the syngas product was analyzed by mass spectrometry for gas composition and concentration. Based on this, the process parameters of the ferrous carbonate reduction refining and co-production of controllable hydrogen-to-carbon ratio syngas in this embodiment during the reaction time of 0.5 to 1.5 hours are as follows: ferrous carbonate decomposition rate, carbon dioxide conversion rate, and syngas composition, as shown in 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 is not loaded with a catalyst and the conversion rate of carbon dioxide within 0.5 to 1.5 hours of reaction is similar to that of Example 1 by adjusting the hydrogen feed. 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 is not loaded with a catalyst and the composition of the syngas is similar to that of Example 1 within 0.5 to 1.5 hours of reaction by adjusting the hydrogen feed. The main parameters and performance indicators involved in this comparative example are shown in Table 2.

[0213] Table 2

[0214]

[0215] As can be seen from Tables 1 and 2, when the catalytic conversion process is coupled with the carbonate hydrogenation process without a catalyst, due to the chemical inertness of carbonates and carbon dioxide, the amount of hydrogen feed needs to be far greater than the amount of carbonate feed to achieve the ideal carbonate decomposition rate and CO2 conversion rate at the same time. The ratio of hydrogen to carbonate feed molar ratio increases from 3:1 in Example 1 to 8:1 in Comparative Example 1. This inevitably results in huge hydrogen consumption and an excessively high hydrogen-to-carbon ratio in the syngas product, making it difficult to utilize further. On the other hand, as shown in the performance indicators of Comparative Example 2 in Table 2, to output a syngas product with an ideal hydrogen-to-carbon ratio, it is necessary to reduce the hydrogen feed rate, but it is difficult to simultaneously achieve efficient metal oxide production and CO2 resource conversion. The system and method of the present invention for producing syngas with adjustable hydrogen-to-carbon ratio through carbonate reduction refining can effectively reduce the hydrogen feed demand (i.e., the hydrogen:carbonate feed molar ratio), thereby reducing the hydrogen-to-carbon ratio of the syngas at the syngas outlet, which is beneficial for the further utilization and conversion of the syngas. Furthermore, by controlling the reaction conditions (such as the hydrogen:carbonate feed molar ratio, the reaction temperature of each reaction zone, and the heavy hourly space velocity of the catalyst bed in the product gas enhanced conversion zone), the reaction intensity of the carbonate hydrogenation conversion zone and the product gas enhanced conversion zone can be controlled, thus achieving precise control of the hydrogen-to-carbon ratio of the final output syngas. This provides 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 are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent transformations or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining, characterized in that, It includes a preheating system, a carbonate fluidized hydrogenation reaction unit, a hydrogen supply unit, a carbonate feeding unit, and a syngas post-treatment system; The carbonate fluidized hydrogenation reaction unit includes a first reaction chamber, a second reaction chamber, and a cyclone separation unit; The first reaction chamber is used for carbonate hydrogenation conversion; a wind distribution plate is provided at the bottom of the first reaction chamber, which divides the first reaction chamber into an upper carbonate hydrogenation conversion zone and a lower solid product discharge zone; a hydrogen inlet is provided on the side of the solid product discharge zone, and a metal oxide outlet is provided at the bottom; the hydrogen inlet is connected to a hydrogen supply unit; the carbonate hydrogenation conversion zone is provided with a carbonate inlet; the carbonate inlet is connected to a carbonate feeding unit; a first temperature control unit is configured in the carbonate hydrogenation conversion zone. The second reaction chamber is used for the enhanced conversion of crude product gas to generate syngas with a controllable hydrogen-to-carbon ratio. The second reaction chamber is equipped with a catalyst bed, which is filled with a crude product gas enhanced conversion catalyst to form a crude product gas enhanced conversion zone. The bottom of the second reaction chamber is equipped with an inlet and the top is equipped with a product syngas outlet. The crude 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. The feed inlet and solid phase outlet are both connected to the carbonate hydrogenation conversion zone, and the gas phase outlet is connected to the gas inlet. The cyclone separation unit is used to perform gas-solid separation on the crude product gas generated in the carbonate hydrogenation conversion zone. The crude product gas after gas-solid separation enters the second reaction chamber for enhanced conversion of the crude product gas, and the solid particles are returned to the carbonate hydrogenation conversion zone for further hydrogenation conversion. The preheating system is used to preheat the feed hydrogen. It has a high-temperature fluid inlet, a high-temperature fluid outlet, a low-temperature fluid inlet, and a low-temperature fluid outlet. The product syngas outlet is connected to the high-temperature fluid inlet through a first pipeline. The high-temperature fluid outlet is connected to the syngas post-processing system through a second pipeline. The hydrogen supply unit is connected to the low-temperature fluid inlet through a third pipeline. The low-temperature fluid outlet is connected to the hydrogen feed inlet through a fourth pipeline.

2. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining 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 bubbling fluidized bed, turbulent fluidized bed, dense phase transport bed or dilute phase transport bed; the crude product gas enhanced conversion zone is in the form of a fixed bed or fluidized bed, including but not limited to axial fixed bed, radial fixed bed, tubular fixed bed, bubbling fluidized bed or turbulent fluidized bed.

3. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining 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 has a feed inlet on the side, a gas phase outlet at the top, and a solid phase outlet at the bottom; the multi-stage cyclone separator is composed of multiple single-stage cyclone separators connected in series.

4. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining according to claim 1, characterized in that, The cyclone separation unit is an external cyclone separation unit; the external cyclone separation unit is located outside the carbonate hydrogenation conversion zone; The carbonate hydrogenation conversion zone is equipped with a crude product gas outlet and a solid 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 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 final-stage cyclone separator is connected to the air inlet, and the solid phase outlets of each stage of the cyclone separator are connected to the solid material return port via pipelines.

5. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining 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 to the top of the carbonate hydrogenation conversion zone; When the built-in cyclone separator unit is a single-stage cyclone separator, the feed inlet and solid phase outlet of the single-stage cyclone separator are both located inside the carbonate hydrogenation conversion zone and do not contact the inner wall of the carbonate hydrogenation conversion zone, and the gas phase outlet is connected to the gas inlet; when the cyclone separator unit is a multi-stage cyclone separator, the feed inlet of the first-stage cyclone separator and the solid phase outlet of each stage of the cyclone separator are both located inside the carbonate hydrogenation conversion zone and do not contact the inner wall of the carbonate hydrogenation conversion zone, the gas phase outlet of the previous stage cyclone separator is connected to the feed inlet of the next stage cyclone separator, and the gas phase outlet of the final stage cyclone separator is connected to the gas inlet.

6. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining according to claim 1, characterized in that, The air distribution plate is a perforated plate type air distribution plate, a multi-tube type air distribution plate, a micro-perforated plate type air distribution plate, a bubble cap type air distribution plate, a floating valve type air distribution plate, or a multi-layer plate type air distribution plate; the pore size of the air distribution plate is 50~100μm.

7. The system for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining according to claim 1, characterized in that, The crude product gas enhanced conversion catalyst is selected from one or more of Fe, Co, Ni, Cu, Na2O, K2O, MgO, CaO, and CeO2; the loading of the crude product gas enhanced conversion catalyst in the catalyst bed is 30 kg to 5 t.

8. A method for producing syngas with a controllable hydrogen-to-carbon ratio through carbonate reduction refining, characterized in that, The system for producing hydrogen-to-carbon ratio controllable syngas by carbonate reduction refining according to any one of claims 1-7 includes the following steps: S1. Preheat hydrogen gas to 300~750℃ at a speed of 250~150000m 3 A flow rate of 50-150 μm of carbonate particles is introduced into the solid product discharge zone from the hydrogen inlet at a flow rate of 5-70 t / h. S2. The temperature of the carbonate hydrogenation conversion zone is controlled at 500~850℃ by the first temperature control unit. Hydrogen gas is used as a reaction gas and fluidizing gas. After being evenly distributed by the air distribution plate, it fully contacts and collides with the feed carbonate solid particles in the carbonate hydrogenation conversion zone, completely decomposes them into metal oxides, and generates crude product gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor. S3. The metal oxide enters the solid product discharge zone through the air distribution plate and is discharged through the metal oxide discharge port; the coarse product gas containing 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. The temperature of the enhanced conversion zone is controlled at 350~800℃ by the second temperature control unit. The carbon dioxide in the crude product gas that has not been hydrogenated in time is further catalyzed into carbon monoxide in the enhanced conversion zone. The solid particles are returned to the carbonate hydrogenation conversion zone for further hydrogenation conversion. S5. The hydrogen-to-carbon ratio controlled syngas generated in the crude product gas enhanced conversion zone enters the syngas post-processing system for treatment and storage.

9. The method for producing syngas with a controllable hydrogen-to-carbon ratio by carbonate reduction refining according to claim 8, characterized in that, The carbonates include, but are not limited to, calcium carbonate, magnesium carbonate, ferrous carbonate and / or the corresponding natural minerals in which they are the main components.

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