WO2023174082A1 - 一种小颗粒碳酸盐矿石煅烧联产高纯co2反应器及其方法 - Google Patents

一种小颗粒碳酸盐矿石煅烧联产高纯co2反应器及其方法 Download PDF

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WO2023174082A1
WO2023174082A1 PCT/CN2023/079744 CN2023079744W WO2023174082A1 WO 2023174082 A1 WO2023174082 A1 WO 2023174082A1 CN 2023079744 W CN2023079744 W CN 2023079744W WO 2023174082 A1 WO2023174082 A1 WO 2023174082A1
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gas
reactor
moving bed
ore
purity
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PCT/CN2023/079744
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English (en)
French (fr)
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许光文
徐梓馥
韩振南
程继光
闫玉麟
贾鑫
张玉辉
王超
黄小锐
黄哲哲
梅杰
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沈阳化工大学
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Publication of WO2023174082A1 publication Critical patent/WO2023174082A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide

Definitions

  • the invention relates to a reactor for co-producing high-purity CO 2 and a method thereof, and in particular to a reactor for co-producing high-purity CO 2 by calcining small particle carbonate ores and a method thereof.
  • Carbonate ores are widely distributed, and their theoretical components are compounds composed of metal cations and carbonate ions. At present, more than 100 kinds of carbonate ores have been discovered, the common ones include magnesite MgCO 3 , calcite CaCO 3 , dolomite CaMg(CO 3 ) 2 , rhodochrosite ZnCO 3 , siderite FeCO 3 , and rhodochrosite MnCO 3 , cobaltite CoCO 3 , etc.
  • the calcination process of carbonate ore is the first step in its resource utilization, and it is widely used in many fields such as chemical industry, metallurgy, and construction.
  • Carbonate ores are calcined to produce solid metal oxides and gas CO 2 , of which solid metal oxides can be widely used in many fields such as chemical manufacturing, building materials industry, paper industry, food processing, and agricultural production; CO 2 as a High-quality raw materials with high application value have application examples in many industries such as oil exploration, agricultural fertilizer production, medical aid, artificial rainfall, chemical synthesis, food production, etc., and have good development prospects.
  • the traditional ore calcination process usually uses hot flue gas generated by fuel combustion as a heat source to directly heat the ore, so that the product CO 2 gas is mixed with a large amount of flue gas, and contains trace amounts of SO 2 , NO x and a large amount of dust, making CO 2 separation difficult Large and costly. Therefore, the gas products are usually simply processed and discharged directly into the atmosphere, causing resource waste and carbon emission problems. Therefore, co-production of high-purity CO2 by calcined carbonate ore has important research significance and application value.
  • reverberatory furnaces such as reverberatory furnaces, shaft kilns, suspension furnaces and rotary kilns.
  • reverberatory furnaces and shaft kilns are commonly used calcining devices, which are suitable for bulk materials with larger particle sizes and are difficult to process small particle ores and flotation mineral powder.
  • Chinese patent ZL201110049511.9 proposes a thermal separation method for light-burned magnesium oxide. and its device. Materials with a diameter of 60 to 300mm are calcined in a reverberatory kiln. The solid products are transported to a thermal screening screen for particle size classification.
  • Materials smaller than 40mm enter the heat pipe heat exchanger, exchange heat with cold air, and recycle the hot air as combustion-supporting air.
  • the cooled product is processed and stored in storage; for example, Chinese patent ZL201310371812.2 proposes an internal gas-fired shaft kiln and method for producing light-burned magnesium oxide.
  • the 30 ⁇ 80mm material is dried and preheated by hot flue gas in the preheating section, and then calcined in the calcining section, and then enters the cooling section downwards, where it exchanges heat with the incoming counter-current air.
  • the cooled material is discharged from the bottom of the furnace. Discharge from the material port.
  • the suspension furnace is very suitable for powdery materials.
  • Chinese patent ZL201610643705.4 proposes a light-burned magnesium oxide roasting kiln.
  • the preheated ore powder and air enter the furnace from the bottom.
  • the upward flowing gas in the furnace makes the ore powder rise in a suspended state.
  • the fuel is introduced into the furnace and burns with the oxygen in the air to generate heat.
  • the material is thermally decomposed during the rising process, and the product is removed from the upper part for gas and material separation.
  • the above-mentioned existing technologies all use hot flue gas as the heat source to directly contact the ore for heat transfer in the furnace.
  • the CO 2 produced by the decomposition of the ore is inevitably mixed with the flue gas, resulting in a low concentration of CO 2 in the gas product, making separation and purification difficult and costly.
  • direct emissions have brought about problems such as carbon emissions.
  • the rotary kiln is another commonly used calcining device for carbonate ores such as limestone, dolomite, and magnesite. The rotary kiln can calcine carbonate ores through indirect heating.
  • Chinese patent ZL201820558155.0 proposes a production device for light-burning MgO to co-produce high-purity CO2 , using a double-cylinder rotary kiln calcination system, in which the outer cylinder is composed of heat-resistant steel pipes and the inner cylinder is composed of heat-resistant ceramic pipes.
  • the combustion system burns in the inner cylinder and transfers the heat generated by combustion to the outer cylinder through the inner cylinder.
  • the magnesite in the outer cylinder is thermally decomposed to obtain light-burned MgO and high-purity CO 2 .
  • the rotary kiln has shortcomings such as high power consumption, and the calcination temperature is around 1000°C.
  • the material of the indirectly heated rotary kiln body cannot meet the long-term operation requirements, and the maintenance is difficult. Due to the limitation of equipment diameter, it is difficult to enlarge the device and cannot meet the requirements of large-scale operation. Production operation requirements.
  • the object of the present invention is to provide a small particle carbonate ore calcination co-production high-purity CO 2 reactor and its method.
  • a central gas collection chamber is installed as a gas product channel in the center of an externally heated moving bed reactor to change the flow direction of the gas product, thereby co-producing high-purity CO 2 while producing solid metal oxides.
  • the external heating method prevents the ore from being in direct contact with the hot flue gas.
  • the CO 2 concentration in the calcined gas product is high, and high-purity CO 2 can be obtained directly.
  • the central gas collection chamber can reduce the bed thickness and gas flow pressure drop, and is used for the calcination of small particle carbonate ores.
  • the central gas collection chamber regulates the gas products to flow laterally across the bed from the outer high-temperature zone to the inner low-temperature zone. zone, which reduces the temperature of the gas product while enhancing heat transfer in the inner layer; and the gas passes through the bed laterally to filter gas-entrained dust; the reactor can operate in a single group or in multiple groups, making it easy to scale up the model and large-scale industrialization.
  • a small particle carbonate ore calcination co-production high-purity CO 2 reactor the reactor includes an ore feed port, a moving bed reactor, a central gas collection chamber, a gas product outlet, a solid product outlet, an air inlet, Clean the gas inlet, flue gas outlet, combustion chamber, discharge device, and heat transfer wall;
  • the moving bed reactor is equipped with a central gas collection chamber inside and a combustion chamber outside;
  • the central gas collection chamber is placed at the center of the moving bed reactor, Set up evenly distributed gas channel holes to allow the gas product to flow transversely from the outer high-temperature zone through the bed to the inner low-temperature zone and enter the central gas collection chamber. This reduces the temperature of the gas product while enhancing heat transfer in the inner layer and entering the central gas collection chamber.
  • the gas products in the cavity are led out of the reactor through the gas product outlet;
  • the combustion chamber is located outside the moving bed reactor and is equipped with an air inlet, a clean gas inlet and a flue gas outlet;
  • the inner wall of the combustion chamber is the heat transfer wall, and the fuel combustion in the combustion chamber generates heat , transfer the heat required for calcination to the ore in the moving bed reactor through the heat transfer wall, so that it can be thermally decomposed.
  • the shape of the moving bed reactor is such as but not limited to a cylinder or a rectangular parallelepiped; the moving bed reactor operates in a single group of modules, or in multiple groups of modules Combined, or amplifier mode.
  • the central gas collection chamber is placed at the center of the moving bed reactor, and its shape is such as but not limited to cylindrical or rectangular shape. or more.
  • the combustion chamber is located outside the moving bed reactor, such as but not limited to opposite two sides, connected three sides or annular interconnected aisle.
  • the described combustion chamber has The temperature control range is, for example but not limited to, 800 to 1300°C.
  • the material of the combustion chamber and heat transfer wall is one or more of refractory bricks, refractory casting, or heat-resistant stainless steel.
  • the described small particle carbonate ore calcination co-production high purity CO 2 reactor the small particle carbonate ore, such as but not limited to magnesite MgCO 3 , calcite CaCO 3 , dolomite CaMg(CO 3 ) 2. Siderite ZnCO 3 and siderite FeCO 3 ore particles.
  • the gas dust removal device is a bag dust collector
  • the gas purification includes water washing dust removal, drying water removal, adsorption and impurity removal
  • the solid cooling device is air
  • the cooler is connected to the feed inlet, the solid product outlet of the moving bed reactor, and the solid product outlet of the gas dust removal device.
  • a method for co-producing high-purity CO2 by calcining small-particle carbonate ores includes the following steps: using small-particle carbonate ores as raw materials, quantitatively adding them to the moving bed reaction from the ore feed port through a feeding device.
  • the heat required for calcination is provided by the combustion of gas and air in the external combustion chamber.
  • the heat is transferred to the carbonate ore in the moving bed reactor through the heat transfer wall. Air and gas are introduced through the air inlet and the clean gas inlet respectively.
  • the generated flue gas is discharged through the flue gas outlet; the carbonate ore particles in the moving bed reactor are thermally decomposed, and the gas products pass through the bed laterally, and are discharged through the gas product outlet of the central gas collection chamber, and are cooled by the gas cooling system.
  • high-purity CO 2 is obtained.
  • the method described is a method for co-producing high-purity CO2 by calcining small particle carbonate ores.
  • the method achieves complete decomposition of the ores by controlling the residence time of the ores in the reactor, and the solid metal oxides are quantitatively removed from the moving bed through the discharge device.
  • the solid product outlet at the bottom of the reactor is discharged, and enters the solid cooling device together with the solid separated from the gas dust removal device. After cooling, the solid metal oxide product is collected and collected.
  • This invention installs a "central gas collecting chamber" in an externally heated moving bed reactor and designs a new type of calcination reactor suitable for small particle ores.
  • the flow direction of the gas product is changed through the central gas collecting chamber so that the gas can pass through the bed laterally. layer, and then discharged through the gas product outlet of the central gas collection chamber in the reactor.
  • This invention reduces the bed thickness and gas flow pressure drop, promotes the rapid derivation of CO 2 , and realizes the calcination of small particle carbonate ores;
  • the present invention controls the flow of gas from the outer high-temperature zone to the inner low-temperature zone, thereby enhancing the transfer of heat to the interior of the reactor. Shorten the calcination reaction time, reduce the energy consumption of product production, uniform the temperature gradient in the reactor, high product activity and uniform product properties;
  • the bed of the present invention plays a role in dust filtration to avoid gas dust entrainment and pipeline blockage;
  • the present invention can operate in a single group or multiple groups of modules, and is easy to model amplification and large-scale industrialization.
  • Figure 1 is a schematic structural diagram (front view) of the reactor of the present invention
  • Figure 2 is a schematic flow diagram of the present invention
  • Figure 3 is a schematic diagram (top view) of an embodiment of the multi-module combined structure of the reactor of the present invention
  • FIG 4 is a schematic diagram A of the reactor structure embodiment of the present invention (particle redistribution);
  • Figure 5 is a schematic diagram B (particle redistribution) of the reactor structure embodiment of the present invention.
  • Figure 6 is a schematic diagram of an embodiment of the reactor structure of the present invention (water vapor enhances heat transfer).
  • Components in the figure ore feed inlet 1, moving bed reactor 2, central gas collection chamber 3, gas product outlet 4, solid product outlet 5, air inlet 6, clean gas inlet 7, flue gas outlet 8, combustion chamber 9, Discharge device 10, heat transfer wall 11, baffle 12, upper discharge device 13, flue gas pipe 14, gas cooling system 15, gas dust removal device 16, gas purification system 17, solid cooling device 18, water vapor inlet 19.
  • the present invention's small particle carbonate ore calcination co-production high-purity CO 2 reactor includes an ore feed port 1, a moving bed reactor 2, a central gas collection chamber 3, a gas product outlet 4, and a solid product Exit 5, air inlet 6, clean gas inlet 7, flue gas outlet 8, combustion chamber 9, discharge device 10, heat transfer wall 11.
  • the ore feed port 1 is located at the upper end of the moving bed reactor 2, and small particles of carbonate ore are quantitatively added to the moving bed reactor 2 from the ore feed port 1 through the feeding device.
  • the moving bed reactor 2 has a shape such as but not limited to a cylinder or a rectangular parallelepiped. It has a central gas collection chamber 3 inside and a combustion chamber 9 outside.
  • the central gas collection chamber 3 is placed at the center of the moving bed reactor 2, with a shape such as but not limited to one or more cylindrical and rectangular shapes; evenly distributed gas channel holes are provided to allow the gas products to pass through the outer high-temperature zone laterally. It flows through the bed to the inner low-temperature zone and enters the central gas collecting chamber 3, which lowers the temperature of the gas product while enhancing the heat transfer in the inner layer.
  • the gas product entering the central gas collecting chamber 3 is exported from the reactor through the gas product outlet 4.
  • the combustion chamber 9 is located outside the moving bed reactor 2, such as but not limited to two opposite sides, three connected sides or an annular interconnected channel; There is an air inlet 6, a clean gas inlet 7 and a flue gas outlet 8; the temperature control range is, for example, but not limited to 800-1300°C; the inner wall of the combustion chamber is the heat transfer wall 11, and the fuel combustion in the combustion chamber generates heat, which is transferred through the heat transfer wall.
  • the hot wall 11 transfers the heat required for calcination to the ore in the moving bed reactor 2, causing it to be thermally decomposed.
  • the material of the combustion chamber 9 and the heat transfer wall 11 can be one or more of refractory bricks, refractory casting, and heat-resistant stainless steel. kind.
  • the discharge device 10 is connected to the lower solid product outlet 5 and can be set to one or more. It is used to regulate the discharge of solid metal oxides, control the height of the bed in the moving bed, and reduce the phenomenon of raw and over-burning of materials in the bed. Improve product activity.
  • the process flow of the method for calcining small-particle carbonate ores to co-produce high-purity CO2 according to the present invention is shown in Figure 2.
  • the specific process is as follows: using small-particle carbonate ores as raw materials, through the feeding device, quantitatively measure from the ore feed port 1 Added into the moving bed reactor 2, the heat required for calcination is provided by the combustion of gas and air in the external combustion chamber 9. The heat is transferred to the carbonate ore in the moving bed reactor through the heat transfer wall 11, in which the air and gas pass through respectively.
  • the air inlet 6 and the clean gas inlet 7 take in air, and the generated flue gas is discharged through the flue gas outlet 8.
  • the carbonate ore particles in the moving bed reactor 2 are thermally decomposed, and the gas products pass through the bed laterally, are discharged through the gas product outlet 4 of the central gas collection chamber 3, and are cooled by the gas cooling system 15, the gas dust removal device 16 and the gas purification After the treatment of system 17, high-purity CO 2 is obtained; by controlling the residence time of the ore in the reactor, complete decomposition of the ore is achieved, and the solid metal oxide is quantitatively discharged from the solid product outlet 5 at the bottom of the moving bed reactor through the discharge device 10, and The solid separated by the gas dust removal device 16 enters the solid cooling device 18 together, and is collected after cooling to obtain a solid metal oxide product. This is the specific process of thermal decomposition of small particles of carbonate ore to obtain solid metal oxides and high-purity CO2 .
  • the multi-module combined structure (top view) of the reactor in this embodiment is shown in Figure 3.
  • the two moving bed reactors are placed longitudinally and connected through the combustion chamber. From a bird's-eye view, they form a multi-module combination of combustion chamber-reactor-combustion chamber-reactor-combustion chamber.
  • the small particle carbonate ore passes through the feeding device and is fed at the top of the moving bed reactor 2, which is fed from two external combustion chambers 9 and two moving bed reactors.
  • the combustion of gas and air in the connected combustion chambers 9 provides the heat required for calcination.
  • the heat is transferred to the carbonate ore in the moving bed reactor 2 through the heat transfer wall 11.
  • the air and gas in the three combustion chambers 9 pass through respectively.
  • the air inlet 6 and the clean gas inlet 7 take in air, and the generated flue gas is discharged through the flue gas outlet 8.
  • the carbonate ore particles in the two moving bed reactors 2 are thermally decomposed at the same time, and the gas products pass through the beds laterally and are discharged through the gas product outlet 4 of the central gas collection chamber 3. After cooling, they are dusted and purified. High-purity CO 2 is obtained; solid metal oxides are discharged from the bottom of the moving bed reactor, cooled together with the solids separated by gas product dust removal, and then collected.
  • Schematic diagram A of the reactor structure (particle redistribution) of this embodiment includes an ore feed inlet 1, a moving bed reactor 2, a central gas collection chamber 3, a gas product outlet 4, a solid product outlet 5, Air inlet 6, clean gas inlet 7, flue gas outlet 8, combustion chamber 9, discharge device 10, heat transfer wall 11, baffle 12.
  • the moving bed reactor is enlarged and extended longitudinally, and baffles 12 are placed transversely on each side at the center height of the reactor; the baffles 12 are horizontally equilateral trapezoids when viewed from the front, with one end of the long side fixed to the heat transfer wall 11 and one end of the short side. It is close to the central gas collection chamber 3, leaving a gap, and the diameter of the central gas collection chamber here can be appropriately reduced, so that the baffle can fully penetrate into the bed and play a role in particle redistribution of material particles.
  • the powder products will be concentrated in the moving bed reaction.
  • the unreacted small particles of ore will be redistributed to the outside of the moving bed reactor, where they will be thermally decomposed in contact with the high-temperature heat transfer wall, greatly improving the overall heat transfer efficiency and processing capacity of the device, reducing production energy consumption, and solid metal oxides
  • the quality is uniform and stable. Air and gas are introduced through the air inlet 6 and the clean gas inlet 7 respectively, and the generated flue gas is discharged through the flue gas outlet 8.
  • the carbonate ore particles in the moving bed reactor 2 are thermally decomposed, and the gas products pass through the bed laterally and flow to the central gas collection chamber 3. After being cooled by the inner low-temperature bed, they flow into the central gas collection chamber through the gas channel holes. 3. It is discharged from the gas product outlet 4 of the central gas collection chamber 3. After cooling, it is dusted and purified to obtain high-purity CO 2 ; by controlling the residence time of the ore in the reactor, the ore is completely decomposed, and the solid metal oxide is discharged The device 10 quantitatively discharges the solid product from the two solid product outlets 5 at the bottom of the moving bed reactor and collects it after cooling. Solid metal oxides and high-purity CO 2 can be obtained.
  • Schematic diagram B (particle redistribution) of the reactor structure of this embodiment, as shown in Figure 5, includes an ore feed inlet 1, a moving bed reactor 2, a central gas collection chamber 3, a gas product outlet 4, a solid product outlet 5, air in Port 6, clean gas inlet 7, flue gas outlet 8, combustion chamber 9, discharge device 10, heat transfer wall 11, upper discharge device 13, flue gas pipe 14.
  • the moving bed reactor is divided into two sections, the upper and lower sections, connected through the upper section discharge device 13 and the flue gas pipe 14, and the gas product outlet position of the central gas collection chamber in the lower section of the moving bed is opposite to that of the upper section.
  • the upper discharging device 13 plays a role in particle redistribution of material particles.
  • the carbonate ore particles in the upper moving bed reactor 2 are thermally decomposed, and the gas products pass through the bed laterally and flow to the central gas collection chamber 3. After being cooled by the inner low-temperature bed, they flow into the central gas collection through the gas channel holes. Chamber 3 is discharged through the gas product outlet 4 of the central gas collection chamber 3. After cooling, it is dusted and purified to obtain high-purity CO 2 .
  • the outer ore in the upper reactor is first heated to decompose and crush, and the powder product formed will seriously hinder the heat transfer. The bed moves downward, and the powder product and unreacted large-grained ore are discharged into the lower reactor through the upper discharge device 13.
  • a stacking angle will be formed at the top of the lower reactor, allowing the powder product to move downward from the center normally, while the unreacted large particles of ore inside are redistributed to the outside near the combustion chamber, and continue to provide heat through the outer combustion chamber 9 to cause thermal decomposition. Improve the overall heat transfer efficiency and processing capacity of the device, reduce production energy consumption, and ensure uniform and stable quality of solid metal oxides.
  • the lower combustion chamber is connected to the upper combustion chamber through a flue gas pipe 14, and air and gas are provided through the air inlet 6 and clean gas inlet 7 of the lower combustion chamber. The burned flue gas is discharged from the flue gas outlet 8 of the upper combustion chamber.
  • the carbonate ore particles in the lower moving bed reactor 2 are thermally decomposed, and the gas products pass through the bed laterally and flow to the central gas collection chamber 3. After being cooled by the inner low-temperature bed, they flow into the central gas collection through the gas channel holes. Chamber 3 is discharged through the gas product outlet 4 of the central gas collection chamber 3. After cooling, it is dusted and purified to obtain high-purity CO 2 ; by controlling the residence time of the ore in the reactor, the ore is completely decomposed, and the solid metal oxide is discharged through The material device 10 quantitatively discharges the solid product from the two solid product outlets 5 at the bottom of the moving bed reactor, and collects it after cooling. Solid metal oxides and high-purity CO 2 can be obtained.
  • the schematic diagram of the reactor structure of this embodiment (water vapor enhanced heat transfer), as shown in Figure 6, includes an ore feed inlet 1, a moving bed reactor 2, a central gas collection chamber 3, a gas product outlet 4, and a solid product outlet 5 , air inlet 6, clean gas inlet 7, flue gas outlet 8, combustion chamber 9, discharge device 10, heat transfer wall 11, water vapor inlet 19.
  • water vapor is passed into the reactor from multiple water vapor inlets 19 to improve the heat transfer efficiency and allow small particles of carbonate ore to be heated quickly and evenly.
  • small particles of ore are quantitatively added into the moving bed reactor 2 from the upper ore feed port 1 .
  • the heat required for calcination is provided by the combustion of gas and air in the external combustion chamber 9.
  • the heat is transferred to the carbonate ore in the moving bed reactor through the heat transfer wall 11.
  • the air and gas enter through the air inlet 6 and the clean gas inlet 7 respectively.
  • the generated flue gas is discharged through the flue gas outlet 8.
  • Water vapor is passed into the reactor from multiple water vapor inlets.
  • the water vapor transfers the high-temperature heat from the outside to the low-temperature bed inside, improving the heat transfer efficiency. At the same time, it reduces the partial pressure of the gas around the ore, lowers the decomposition temperature, and increases the decomposition speed.
  • the small particles of carbonate ore are heated quickly and evenly, and gradually decompose into gas CO 2 and solid metal oxide.
  • the gas and water vapor pass through the bed laterally and flow to the central gas collecting chamber 3. After being cooled by the inner low-temperature bed, they flow into the central gas collecting chamber 3 through the gas channel hole and pass through the gas product outlet 4 of the central gas collecting chamber 3.
  • high-purity CO 2 After being discharged, cooled and subjected to dust removal and purification, high-purity CO 2 is obtained; by controlling the residence time of the ore in the reactor, complete decomposition of the ore is achieved, and the solid metal oxide is quantified from the two solids at the bottom of the moving bed reactor through the discharging device 10 The product is discharged from outlet 5 and collected after cooling. Solid metal oxides and high-purity CO 2 can be obtained.
  • the present invention uses specific examples to illustrate the principles and implementation methods of the invention.
  • the above examples are only used to help understand the method and its core idea of the present invention.
  • the above are only preferred embodiments of the present invention. It should be pointed out that due to the limitations of written expressions, there are objectively unlimited specific structures.
  • Several improvements, modifications or changes can also be made, or the above technical features can be combined in an appropriate manner; these improvements, modifications or combinations, or the principle concepts and technical solutions can be directly applied to other situations without improvement, All should be regarded as the protection scope of the present invention.

Abstract

一种小颗粒碳酸盐矿石煅烧联产高纯CO 2反应器，所述反应器包括有矿石进料口(1)、移动床反应器(2)、中心集气腔(3)、气体产物出口(4)、固体产物出口(5)、空气进口(6)、清洁燃气进口(7)、烟气出口(8)、燃烧室(9)、排料装置(10)、传热壁(11)及气体除尘装置(16)和固体冷却装置(18)；所述移动床反应器(2)内部设置中心集气腔(3)，外部设置燃烧室(9)；气体产物由外层高温区横向穿过床层流向内层低温区，并进入中心集气腔(3)，降低气体产物温度的同时强化内层传热，进入中心集气腔(3)的气体产物由气体产物出口(4)导出反应器；以及利用该反应器进行小颗粒碳酸盐矿石煅烧联产高纯CO 2方法。

Description

一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器及其方法 技术领域
本发明涉及一种联产高纯CO2反应器及其方法，特别是涉及一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器及其方法。
背景技术
碳酸盐矿石分布广泛，其理论成分是由金属阳离子与碳酸根离子组成的化合物。目前，已发现的碳酸盐矿石超过100种，常见的包括菱镁矿MgCO3、方解石CaCO3、白云石CaMg(CO3)2菱锌矿ZnCO3、菱铁矿FeCO3、菱锰矿MnCO3、菱钴矿CoCO3等。通常，碳酸盐矿石煅烧过程是其资源化利用的第一步，被广泛应用于化工、冶金、建筑等众多领域。
碳酸盐矿石通过煅烧产出固体金属氧化物以及气体CO2，其中固体金属氧化物可以广泛地应用于化工制造、建材工业、造纸行业、食品加工以及农业生产等众多领域；CO2作为一种具有较高的应用价值的优质原料，在石油开采、农业制肥、医疗救助、人工降雨、化工合成、食品生产等众多行业范围内都有着应用实例，具备着良好的发展前景。而传统的矿石煅烧过程通常采用燃料燃烧产生热烟气作为热源直接加热矿石，使产物CO2气体中于混有大量烟气，并含有微量SO2、NOx以及大量粉尘，使得CO2分离难度大、成本高。因此，气体产物通常经过简单处理，直接排入大气中，造成了资源浪费以及碳排放问题。因此，煅烧碳酸盐矿石联产高纯CO2具有重要的研究意义和应用价值。
目前，规模化碳酸盐矿石煅烧装置有许多种，如反射炉、竖窑、悬浮炉和回转窑等。其中，反射炉和竖窑作为常用煅烧装置，适用于粒径较大的块状物料，难以处理小颗粒矿石及浮选矿粉，如中国专利ZL201110049511.9提出了轻烧氧化镁的热选方法及其装置，将60～300mm的物料在反射窑中煅烧，固体产物输送到热选筛进行粒度分级，小于40mm的进入热管换热器，与冷空气进行热量交换，回收热空气作为助燃空气，冷却后的产物处理后入库；如中国专利ZL201310371812.2提出了一种用于生产轻烧氧化镁的内燃气烧竖窑及方法，取 30～80mm物料，在预热段经热烟气进行干燥预热，然后在煅烧段进行煅烧，后向下进入冷却段，与通入的逆流空气进行热交换，冷却后的物料由炉底出料口排出。悬浮炉非常适用于粉料状物料，具有反应时间短，产品活性高、单台套处理量大等优点，同时可处理小颗粒矿石，如中国专利ZL201610643705.4提出了轻烧氧化镁焙烧窑炉悬浮焙烧装置，预热后的矿石粉与空气从下部进入炉内，炉内向上流动的气体使矿石粉呈上升的悬浮态，同时通入燃料于炉内与空气中的氧气燃烧产生热量，使物料在上升过程中受热分解，产物从上部移出后进行气料分离。
上述现有技术均采用热烟气作为热源在炉内与矿石直接接触传热，矿石分解产生的CO2不可避免与烟气混合，造成气体产物中CO2浓度低，分离提纯难度大、成本高，直接排放又带来了碳排放等问题。回转窑是石灰石、白云石、菱镁矿等碳酸盐矿石的另一种常用煅烧装置，回转窑可以通过间接加热煅烧碳酸盐矿石。如中国专利ZL201820558155.0提出了一种轻烧MgO联产高纯CO2的生产装置，采用双筒回转窑煅烧系统，其中外筒由耐热钢管构成，内筒由耐热陶瓷管构成。燃烧系统在内筒里燃烧，并将燃烧产生的热量通过内筒传递给外筒，外筒里的菱镁矿受热分解获得轻烧MgO和高纯CO2。但是，回转窑存在动力消耗大等缺点，并且煅烧温度在1000℃左右，间接加热回转窑炉体材料难以满足长时间运行要求，维护难度高，由于装备直径限制难以进行装置放大，无法满足大规模生产运行需求。
现有的碳酸盐矿石煅烧存在问题归纳如下：矿石原料使用范围小，许多小颗粒矿石无法得到有效利用而废弃，资源严重浪费；煅烧过程中产生粉尘，易造成设备损坏以及环境污染；热烟气作为热源直接加热矿石，使煅烧气体产物被大量烟气稀释，使得气体中CO2分离难度大、成本高，易造成碳排放问题；外热式(回转窑)装置模式放大具有局限性，运转动力消耗大，占地面积大，维修护理难等问题。针对以上问题，目前已有许多在传统煅烧设备的基础上，结合复杂的后处理工序进行改进的研究成果，但始终无法从根本上解决问题，因此需要研究开发高效低耗、可规模化的小颗粒碳酸盐矿石煅烧联产高纯CO2反应器及方法。
发明内容
本发明的目的在于提供一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器 及其方法，本发明通过在外热式移动床反应器中心加装中心集气腔作为气体产物通道，改变气体产物流动方向，在生产固体金属氧化物的同时联产高纯CO2。一方面，外加热方式使矿石不与热烟气直接接触，煅烧气体产物中CO2浓度高，可直接得到高纯CO2。另一方面，中心集气腔可以降低床层厚度和气体流动压降，用于小颗粒碳酸盐矿石煅烧，中心集气腔调控气体产物由外层高温区横向穿过床层流向内层低温区，降低气体产物温度的同时对内层起到强化传热作用；且气体横向穿过床层过滤气体夹带粉尘；该反应器可以单组运行，也可以多组联合，易于模式放大和大规模工业化。
本发明的目的是通过以下技术方案实现的：
一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述反应器包括有矿石进料口、移动床反应器、中心集气腔、气体产物出口、固体产物出口、空气进口、清洁燃气进口、烟气出口、燃烧室、排料装置、传热壁；所述移动床反应器内部设置中心集气腔，外部设置燃烧室；中心集气腔置于移动床反应器中心处，设置均匀分布的气体通道孔，使气体产物由外层高温区横向穿过床层流向内层低温区，并进入中心集气腔，降低气体产物温度的同时强化内层传热，进入中心集气腔的气体产物由气体产物出口导出反应器；燃烧室位于移动床反应器外侧，设有空气进口、清洁燃气进口以及烟气出口；燃烧室的内壁即为传热壁，燃烧室内燃料燃烧产生热量，通过传热壁将煅烧所需热量传递至移动床反应器内的矿石，使其受热分解。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述移动床反应器形状例如但不限于圆柱体或长方体；移动床反应器单组模块运行，或多组模块联合，或放大装置模式。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述中心集气腔置于移动床反应器中心处，其形状例如但不限于圆柱形、长方体形的一种或多种。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述燃烧室位于移动床反应器外侧，例如但不限于相对的两侧、相连的三侧或环形相互连通的通道。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述燃烧室其 温度控制范围，例如但不限于在800～1300℃。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述燃烧室和传热壁材质为耐火砖或耐火浇筑或耐热不锈钢的一种或多种。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述小颗粒碳酸盐矿石，例如但不限于菱镁矿MgCO3、方解石CaCO3、白云石CaMg(CO3)2、菱锌矿ZnCO3、菱铁矿FeCO3矿石颗粒。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，所述气体除尘装置为布袋除尘器，气体净化包括水洗除尘、干燥除水、吸附除杂质；固体冷却装置为空气冷却机，与进料口和移动床反应器的固体产物出口、气体除尘装置的固体产物出口相连。
一种小颗粒碳酸盐矿石煅烧联产高纯CO2方法，所述方法包括如下步骤：以小颗粒碳酸盐矿石为原料，通过进料装置，从矿石进料口定量加入于移动床反应器内，由外部燃烧室中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁传递于移动床反应器内的碳酸盐矿石，其中空气和燃气分别通过空气进口与清洁燃气进口进气，产生的烟气通过烟气出口排出；移动床反应器内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，经中心集气腔的气体产物出口排出，经气体冷却系统冷却、气体除尘装置和气体净化系统处理后，获得高纯CO2。
所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2方法，所述方法通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置定量从移动床反应器底部的固体产物出口排出，与气体除尘装置分离出的固体一同进入固体冷却装置，冷却后收集得到固体金属氧化物产品。
本发明的优点与效果是：
本发明在外热式移动床反应器内加装“中心集气腔”，设计一种适用于小颗粒矿石的新型煅烧反应器，通过中心集气腔改变气体产物流动方向，使气体横向穿过床层，再经反应器内中心集气腔的气体产物出口排出。
具体优点如下：
1.本发明降低床层厚度和气体流动压降，促进CO2快速导出，实现小颗粒碳酸盐矿石煅烧；
2.本发明调控气体由外层高温区流向内层低温区，强化热量向反应器内部传递， 缩短煅烧反应时间、降低产品生产能耗、均一反应器内温度梯度，产物活性高、产物性质均一；
3.本发明床层起到粉尘过滤作用，避免气体粉尘夹带和管路堵塞；
4.本发明可以单组或多组模块运行，易于模式放大和大规模工业化。
附图说明
图1为本发明反应器结构示意图(正视图)；
图2为本发明流程示意图；
图3为本发明反应器多模块组合结构实施例示意图(俯视图)；
图4为本发明反应器结构实施例示意图A(颗粒再分布)；
图5为本发明反应器结构实施例示意图B(颗粒再分布)；
图6为本发明反应器结构实施例示意图(水蒸气强化传热)。
图中构件：矿石进料口1、移动床反应器2、中心集气腔3、气体产物出
口4、固体产物出口5、空气进口6、清洁燃气进口7、烟气出口8、燃烧室9、排料装置10、传热壁11、挡板12、上段排料装置13、烟气管道14、气体冷却系统15、气体除尘装置16、气体净化系统17、固体冷却装置18、水蒸气进口19。
具体实施方式
下面结合附图所示实施例对本发明进行详细说明。
本发明小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，如图1所示，包括矿石进料口1、移动床反应器2、中心集气腔3、气体产物出口4、固体产物出口5、空气进口6、清洁燃气进口7、烟气出口8、燃烧室9、排料装置10、传热壁11。矿石进料口1位于移动床反应器2上端，小颗粒碳酸盐矿石通过进料装置，从矿石进料口1定量加入于移动床反应器2内。移动床反应器2，形状例如但不限于圆柱体或长方体，内部设置中心集气腔3，外部设置燃烧室9。中心集气腔3置于移动床反应器2中心处，形状例如但不限于圆柱形、长方体形的一种或多种；设置均匀分布的气体通道孔，使气体产物由外层高温区横向穿过床层流向内层低温区，并进入中心集气腔3，降低气体产物温度的同时强化内层传热，进入中心集气腔3的气体产物由气体产物出口4导出反应器。燃烧室9位于移动床反应器2外侧，例如但不限于相对的两侧、相连的三侧或环形相互连通的通道；设 有空气进口6、清洁燃气进口7以及烟气出口8；其温度控制范围，例如但不限于在800～1300℃；燃烧室的内壁即为传热壁11，燃烧室内燃料燃烧产生热量，通过传热壁11将煅烧所需热量传递至移动床反应器2内的矿石，使其受热分解，燃烧室9和传热壁11的材质可以是耐火砖、耐火浇筑、耐热不锈钢的一种或多种。排料装置10与下部固体产物出口5相连，可设为一个或多个，用于调控固体金属氧化物的排出量，控制移动床内床层高度，减少床内物料生烧和过烧现象，提高产物活性。
本发明小颗粒碳酸盐矿石煅烧联产高纯CO2方法流程，如图2所示，具体过程如下：以小颗粒碳酸盐矿石为原料，通过进料装置，从矿石进料口1定量加入于移动床反应器2内，由外部燃烧室9中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁11传递于移动床反应器内的碳酸盐矿石，其中空气和燃气分别通过空气进口6与清洁燃气进口7进气，产生的烟气通过烟气出口8排出。移动床反应器2内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，经中心集气腔3的气体产物出口4排出，经气体冷却系统15冷却、气体除尘装置16和气体净化系统17处理后，获得高纯CO2；通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置10定量从移动床反应器底部的固体产物出口5排出，与气体除尘装置16分离出的固体一同进入固体冷却装置18，冷却后收集得到固体金属氧化物产品。此即小颗粒碳酸盐矿石受热分解获得固体金属氧化物以及高纯CO2具体流程。
实施例1
本实施例的反应器的多模块组合结构(俯视图)，如图3所示。两个移动床反应器纵向放置，通过燃烧室连接，从俯视角度看形成燃烧室-反应器-燃烧室-反应器-燃烧室的多模块组合形式。使用该移动床反应器煅烧小颗粒碳酸盐矿石时，小颗粒碳酸盐矿石通过进料装置，于移动床反应器2顶部进料，由两个外部燃烧室9和两个移动床反应器相连的燃烧室9中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁11传递于移动床反应器2内的碳酸盐矿石，其中的三个燃烧室9的空气和燃气都分别通过空气进口6和清洁燃气进口7进气，产生的烟气通过烟气出口8排出。两个移动床反应器2内的碳酸盐矿石颗粒同时受热分解，气体产物横向穿过床层，经中心集气腔3的气体产物出口4排出，冷却后经除尘、净化， 获得高纯CO2；固体金属氧化物由移动床反应器底部排出，与气体产物除尘分离出的固体一同冷却后收集。
实施例2
本实施例的反应器结构示意图A(颗粒再分布)，如图4所示，包括矿石进料口1、移动床反应器2、中心集气腔3、气体产物出口4、固体产物出口5、空气进口6、清洁燃气进口7、烟气出口8、燃烧室9、排料装置10、传热壁11、挡板12。
其中移动床反应器纵向放大延长，在反应器中心高度处各侧横向放置挡板12；挡板12从正视角度看呈横放等边梯形，长边一端固定在传热壁11，短边一端靠近中心集气腔3，并留有间距，且此处中心集气腔的直径可适当减少，使挡板充分深入床层，对物料颗粒起到颗粒再分布的作用。使用该移动床反应器煅烧碳酸盐矿石时，小颗粒矿石从上端矿石进料口1定量加入于移动床反应器2内，由外部燃烧室9中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁11传递于移动床反应器内的碳酸盐矿石，上段反应器中外侧矿石先分解破碎，形成的粉末产物会严重阻碍热量传递，床层向下移动，粉末产物和未反应大颗粒矿石都经过挡板12排出到下部反应器内，下段反应器顶部会形成堆积角，由于小颗粒矿石和粉末产物的粒径和密度不同，经过堆积角后，粉末产物会集中于移动床反应器中心，而未反应的小颗粒矿石会被再分布至移动床反应器外侧，与高温传热壁接触受热分解，大幅提高装置整体传热效率和处理量，降低生产能耗，固体金属氧化物品质均一稳定。其中空气和燃气分别通过空气进口6与清洁燃气进口7进气，产生的烟气通过烟气出口8排出。移动床反应器2内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，流向中心集气腔3，并经过内层低温床层冷却后，经气体通道孔流进中心集气腔3，由中心集气腔3的气体产物出口4排出，冷却后经除尘、净化，获得高纯CO2；通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置10定量从移动床反应器底部的两个固体产物出口5排出，冷却后收集。即可获得固体金属氧化物以及高纯CO2。
实施例3
本实施例的反应器结构示意图B(颗粒再分布)，如图5所示，包括矿石进料口1、移动床反应器2、中心集气腔3、气体产物出口4、固体产物出口5、空气进 口6、清洁燃气进口7、烟气出口8、燃烧室9、排料装置10、传热壁11、上段排料装置13、烟气管道14。
其中移动床反应器分上下两段，通过上段排料装置13和烟气管道14连接，且下段移动床内的中心集气腔的气体产物出口位置与上部相反。其中所述上段排料装置13对物料颗粒起到颗粒再分布的作用。使用该移动床反应器煅烧碳酸盐矿石时，小颗粒矿石从上端矿石进料口1定量加入于上段的移动床反应器2内，由外部燃烧室9中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁11间接传递于移动床反应器内。上段移动床反应器2内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，流向中心集气腔3，并经过内层低温床层冷却后，经气体通道孔流进中心集气腔3，通过中心集气腔3的气体产物出口4排出，冷却后经除尘、净化，获得高纯CO2。上段反应器中外侧矿石先受热分解破碎，形成的粉末产物会严重阻碍热量传递，床层向下移动，粉末产物和未反应大颗粒矿石都经过上段排料装置13排出到下段反应器内，这样下段反应器顶部会形成堆积角，使粉末产物正常从中心处向下移动，而内部未反应大颗粒矿石再分布至外侧靠近燃烧室，继续通过外层燃烧室9提供热量使之受热分解，大幅提高装置整体传热效率和处理量，降低生产能耗，固体金属氧化物品质均一稳定。其中下段燃烧室与上段燃烧室通过烟气管道14相连，且通过下段燃烧室空气进口6和清洁燃气进口7提供空气和燃气，燃烧后的烟气由上部燃烧室的烟气出口8排出。下段移动床反应器2内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，流向中心集气腔3，并经过内层低温床层冷却后，经气体通道孔流进中心集气腔3，通过中心集气腔3的气体产物出口4排出，冷却后经除尘、净化，获得高纯CO2；通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置10定量从移动床反应器底部的两个固体产物出口5排出，冷却后收集。即可获得固体金属氧化物以及高纯CO2。
实施例4
本实施例的反应器结构示意图(水蒸气强化传热)，如图6所示，包括矿石进料口1、移动床反应器2、中心集气腔3、气体产物出口4、固体产物出口5、空气进口6、清洁燃气进口7、烟气出口8、燃烧室9、排料装置10、传热壁11、水蒸气进口19。
在普通型反应器结构的基础上，从多个水蒸气进口19通水蒸气于反应器内，提高传热效率，使小颗粒碳酸盐矿石快速均匀受热。使用该移动床反应器煅烧碳酸盐矿石时，小颗粒矿石从上端矿石进料口1定量加入于移动床反应器2内。由外部燃烧室9中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁11传递于移动床反应器内的碳酸盐矿石，其中空气和燃气分别通过空气进口6与清洁燃气进口7进气，产生的烟气通过烟气出口8排出。并从多个水蒸气进口19通水蒸气于反应器内，水蒸气将外侧高温热量传递至内部低温床层，提高传热效率，同时减少矿石周围气体分压，降低分解温度、提高分解速度，使小颗粒碳酸盐矿石快速均匀受热，逐渐分解成气体CO2和固体金属氧化物。气体与水蒸气横向穿过床层，流向中心集气腔3，并经过内层低温床层冷却后，经气体通道孔流进中心集气腔3，通过中心集气腔3的气体产物出口4排出，冷却后经除尘、净化，获得高纯CO2；通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置10定量从移动床反应器底部的两个固体产物出口5排出，冷却后收集。即可获得固体金属氧化物以及高纯CO2。
本发明应用了具体个例对发明原理及实施方式进行了阐述，以上实例的说明只是用于帮助理解本发明的方法及其核心思想。以上仅是本发明的优选实施方式，应当指出，由于文字表达的有限性，而客观上存在无限的具体结构，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进、润饰或变化，也可以将上述技术特征以适当的方式进行组合；这些改进润饰、变化或组合，或未经改进将原理的构思和技术方案直接应用于其它场合的，均应视为本发明的保护范围。

Claims (10)

  1. 一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述反应器包括有矿石进料口(1)、移动床反应器(2)、中心集气腔(3)、气体产物出口(4)、固体产物出口(5)、空气进口(6)、清洁燃气进口(7)、烟气出口(8)、燃烧室(9)、排料装置(10)、传热壁(11)及气体除尘装置和固体冷却装置；所述移动床反应器(2)内部设置中心集气腔(3)，外部设置燃烧室(9)；中心集气腔(3)置于移动床反应器(2)中心处，设置均匀分布的气体通道孔，使气体产物由外层高温区横向穿过床层流向内层低温区，并进入中心集气腔(3)，降低气体产物温度的同时强化内层传热，进入中心集气腔(3)的气体产物由气体产物出口(4)导出反应器；燃烧室(9)位于移动床反应器(2)外侧，设有空气进口(6)、清洁燃气进口(7)以及烟气出口(8)；燃烧室的内壁即为传热壁(11)，燃烧室内燃料燃烧产生热量，通过传热壁(11)将煅烧所需热量传递至移动床反应器(2)内的矿石，使其受热分解。
  2. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述移动床反应器(2)形状例如但不限于圆柱体或长方体；移动床反应器单组模块运行，或多组模块联合，或放大装置模式。
  3. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述中心集气腔(3)置于移动床反应器(2)中心处，形状例如但不限于圆柱形、长方体形的一种或多种。
  4. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述燃烧室(9)位于移动床反应器(2)外侧，例如但不限于相对的两侧、相连的三侧或环形相互连通的通道。
  5. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述燃烧室(9)其温度控制范围，例如但不限于在800～1300℃。
  6. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述燃烧室(9)和传热壁(11)材质为耐火砖或耐火浇筑或耐热不锈钢的一种或多种。
  7. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述小颗粒碳酸盐矿石，例如但不限于菱镁矿MgCO3、方解石CaCO3、 白云石CaMg(CO3)2、菱锌矿ZnCO3、菱铁矿FeCO3矿石颗粒。
  8. 根据权利要求1所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2反应器，其特征在于，所述气体除尘装置为布袋除尘器，气体净化包括水洗除尘、干燥除水、吸附除杂质；固体冷却装置为空气冷却机，与进料口和移动床反应器的固体产物出口、气体除尘装置的固体产物出口相连。
  9. 一种小颗粒碳酸盐矿石煅烧联产高纯CO2方法，其特征在于，所述方法包括如下步骤：
    以小颗粒碳酸盐矿石为原料，通过进料装置，从矿石进料口(1)定量加入于移动床反应器(2)内，由外部燃烧室(9)中燃气与空气燃烧提供煅烧所需热量，热量通过传热壁(11)传递于移动床反应器内的碳酸盐矿石，其中空气和燃气分别通过空气进口(6)与清洁燃气进口(7)进气，产生的烟气通过烟气出口(8)排出；移动床反应器(2)内的碳酸盐矿石颗粒受热分解，气体产物横向穿过床层，经中心集气腔(3)的气体产物出口(4)排出，经气体冷却系统(15)冷却、气体除尘装置(16)和气体净化系统(17)处理后，获得高纯CO2。
  10. 根据权利要求8所述的一种小颗粒碳酸盐矿石煅烧联产高纯CO2方法，其特征在于，所述方法通过控制矿石在反应器内停留时间，实现矿石完全分解，固体金属氧化物通过排料装置(10)定量从移动床反应器底部的固体产物出口(5)排出，与气体除尘装置(16)分离出的固体一同进入固体冷却装置(18)，冷却后收集得到固体金属氧化物产品。
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