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CN117401919A - Method for preparing clinker and CO-producing CO by catalytic limestone reduction and decomposition through thermal plasma coupling solid reducing agent - Google Patents

Method for preparing clinker and CO-producing CO by catalytic limestone reduction and decomposition through thermal plasma coupling solid reducing agent Download PDF

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Publication number
CN117401919A
CN117401919A CN202210799110.3A CN202210799110A CN117401919A CN 117401919 A CN117401919 A CN 117401919A CN 202210799110 A CN202210799110 A CN 202210799110A CN 117401919 A CN117401919 A CN 117401919A
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gas
reactor
limestone
decomposition
selectivity
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Inventor
包信和
郭晓光
潘秀莲
夏维东
陈仙辉
王城
于洪飞
由灏盛
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • C04B7/4453—Burning; Melting using plasmas or radiations
    • 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
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/10—Preheating, burning calcining or cooling
    • C04B2/108—Treatment or selection of the fuel therefor
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • C04B7/4407—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for preparing clinker and CO-producing CO by catalyzing limestone reduction and decomposition through thermal plasma coupling solid reducing agent. The invention can avoid the generation of carbon dioxide by limestone thermal decomposition by coupling thermal plasma heating, and CO-produce CO-rich gas, wherein the specific composition of the gas is related to the reducing agent and the reaction condition. The invention has the characteristics of 90% of electrothermal conversion efficiency, long service life of electrodes, simple process, high added value of products, small industrialization difficulty, easy separation of products, good process repeatability, safe and reliable operation and the like, and the technology can realize the carbon dioxide emission reduction of cement industry and slaked lime industry by 60%, and has wide industrial application prospect.

Description

Method for preparing clinker and CO-producing CO by catalytic limestone reduction and decomposition through thermal plasma coupling solid reducing agent
Technical Field
The invention belongs to the technical field of cement and slaked lime manufacture, and particularly relates to a method for preparing clinker and CO-producing CO by catalyzing limestone through one-step reduction and decomposition by using a thermal plasma coupling solid reducing agent, which has high electrothermal conversion efficiency and high-efficiency carbon neutralization.
Background
12 months 2015, the Paris climate will pass Paris agreement, a long term goal of which is: "control the global average air temperature rise within 2 degrees celsius over the previous industrialized period, and strive to limit the temperature rise within 1.5 degrees celsius. The peak of greenhouse gas emission is realized as soon as possible, and the net zero emission of greenhouse gas is realized in the lower half of the century. Starting from 2023, global moves will be checked every 5 years to help each country increase the strength, strengthen international collaboration, and achieve the long-term goal of coping with climate change globally. To achieve this goal, 30 countries or regions have issued their carbon neutralization goals. The existing carbon emission structure in China is divided into three major blocks: 51% of power generation and heat supply, 28% of manufacturing and building industries and 10% of transportation. Thus, the pathways for achieving carbon neutralization mainly include the following: 1) Generating electricity and heating: mainly developing clean energy sources such as wind, light, water, nuclear energy and the like; 2) Manufacturing and construction industries: a. the carbon emission is reduced through energy structure optimization, energy conservation and emission reduction; b. neutralization is achieved by participating in carbon capture, carbon sink and carbon transaction; c, transportation: mainly realized by a new energy traffic mode and light weight.
The carbon emission of the manufacturing and building industries in China is high, and the path of carbon neutralization has objective technical problems. Is different from power generation, heat supply, transportation and transportationCarbon neutralization for two large emission households can be achieved by clean energy substitution, and one of two major difficulties are faced by carbon neutralization for manufacturing and construction industries: raw materials in the production process of industrial products (cement, steel and the like) react chemically to generate CO 2 Emissions are difficult to contain. Therefore, carbon neutralization in the manufacturing and construction industries is necessary to reform the existing industrial production technology.
Cement is an important basic raw material for national economy construction, and at present, no material can replace the cement at home and abroad. We divide the carbon emissions of the cement manufacturing industry into direct emissions and indirect emissions according to the source of carbon dioxide emissions. Direct emissions refer to the burning of fossil fuels and the production of CO from the thermal decomposition of raw materials 2 Discharging; indirect emission refers to CO generated by electric power support and heat energy loss required in the production or service process 2 And (5) discharging. Obtained by calculation and analysis, CO generated by raw material decomposition 2 The maximum emission ratio is about 63.01%, and the second is the emission of CO by heat supply 2 The ratio of the carbon dioxide to the catalyst is 31.57%, the total of direct carbon emissions is 96.51%, and the total of indirect emissions is only 3.49%. The carbon emission of cement accounts for 84.3 percent of the total carbon emission in the building material industry, 13.91 percent of the total carbon emission in China, and the 2 degree (2 DS) protocol of Paris protocol requires that the carbon dioxide emission is reduced to 520-524 kg per 1 ton of cement produced according to China cement society data. Currently, the carbon emission coefficient (accounting based on the yield of cement clinker) of the cement clinker in China is about 0.86, namely 860 kg of carbon dioxide is produced when one ton of cement is produced, which is obviously higher than the Paris protocol level, and the building industry is not exaggerated to realize carbon neutralization, so that the cement is the main battlefield. This means that there are two approaches to carbon neutralization in the cement industry: a revolution in production technology and fuel use technology; development of carbon capture and conversion technology at the back end. In the future, with the increase of various clean electric energy, fuel heat supply can be gradually replaced.
In the cement production process, limestone, clay, iron ore, coal, and the like are required. Limestone is the raw material with the largest cement production amount, and generates a large amount of CO along with the decomposition of the raw material slaked limestone 2 Emissions, thus changing the limestone calcining and decomposing process, reducing the production of clinker at the same timeTo avoid CO 2 Emissions are a revolutionary technique, and are effective carbon neutralization techniques.
CN106698987A discloses a calcium carbonate decomposition accelerator which can reduce the decomposition temperature of calcium carbonate by mixing nitrate and water glass, and consumes 0.7-1kg of accelerator per ton of calcium carbonate, the temperature reduction is limited and CO can not be effectively solved 2 Is increased, and a large amount of oxynitride is generated to exacerbate pollution. CN101987783a discloses a method for producing quick lime by calcining limestone with gas in a suspended state preheating decomposing furnace, which uses the surplus gas produced by steelmaking to calcine limestone, uses the internal combustion of coal dust to supply heat, and generates a large amount of CO in the heat supply process 2 。
Disclosure of Invention
The invention researches the heat supply of the limestone suspension decomposing furnace, and the traditional limestone suspension decomposing furnace utilizes the internal combustion of coal dust to supply heat, and generates a large amount of CO in the heat supply process 2 In order to solve the problems of carbon emission and heat supply in a new process, the invention carries out heat supply coupling catalysis on the renewable electric plasma to realize one-step reductive decomposition of limestone.
The invention provides a method for preparing clinker and CO-producing CO by catalyzing limestone reduction and decomposition with a solid reducing agent through thermal plasma coupling. The invention not only realizes the great reduction of carbon dioxide emission in cement industry and slaked lime industry, but also is a high-efficiency carbon neutralization technology, and CO-produces CO-rich gas, which can be used as a main component for supplying city gas and also can be used as synthesis raw material gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like. The one-step method is to decompose limestone into clinker under the same condition of the same reactor and CO-produce CO gas with high added value, and the decomposition reaction does not discharge carbon dioxide.
For CFD simulation of traditional electric heating or internal heating, it can be seen that the temperature distribution in the reactor is very uneven, greatly limiting the limestone decomposition process of strong heat absorption. The heating efficiency of the traditional heating process is still about 40-50%.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for preparing clinker and CO-producing CO by catalyzing limestone reduction and decomposition through thermal plasma coupling solid reducing agent adopts one or two mixtures of coal and carbon as the reducing agent, utilizes thermal plasma to supply heat, catalyzes the reducing agent and limestone to perform one-step reduction and decomposition in a reactor to generate clinker, and CO-produces CO.
Based on the above, preferably, the thermal plasma includes one or a combination of two of arc discharge plasma and inductively coupled plasma.
Based on the above scheme, preferably, the power of the thermal plasma is 0.1kW-100MW; the thermal plasma adopts direct current, the current is 10-10000A, and the voltage is 10-10000V;
based on the scheme, preferably, the working medium gas carrier gas of the thermal plasma is Ar, he and CH 4 、CO 2 、 CO、H 2 One or a combination of two or more of them.
Based on the above scheme, preferably, the working medium gas of the thermal plasma is part of natural gas and CO to be converted 2 Natural gas and CO to be converted 2 Rapidly mixing with the plasma jet, all the natural gas and CO to be converted 2 Total enthalpy value Δh 15℃ ＜160kJ/mol。
Based on the above scheme, preferably, the working medium gas of the thermal plasma is converted synthesis gas, and natural gas and CO to be converted 2 Rapidly mixing with the plasma jet, all the natural gas and CO to be converted 2 Total enthalpy value Δh 15℃ ＜160kJ/mol。
Based on the above scheme, preferably, the electrode protection gas of the thermal plasma is Ar, he, CO, H 2 One or a combination of two or more of them.
Based on the above scheme, preferably, the cathode and anode materials of the thermal plasma are one or more of copper, tungsten, silver, hafnium, alloy and graphite.
Based on the scheme, preferably, the mixture of one or two of coal and carbon is brought into the reactor by using hot plasma working medium gas carrier gas to catalyze, reduce and decompose limestone;
based on the above scheme, preferably, the coal is one or a mixture of more than two of coal blocks and pulverized coal; the carbon comprises one or more than two of shell carbon, waste wood carbon, coal, petroleum coke and non-activated carbon; as a further preference, the carbon comprises one or both of activated carbon and graphite.
Based on the above, preferably, the process employs a metal and/or metal oxide as a catalyst; the metal is one or more than two of Fe, mn, cr, ni, cu, co and alloy steel; the metal oxide is Fe 2 O 3 、 Fe 3 O 4 、Mn 3 O 4 、MnO 2 、Cr 2 O 3 、NiO、CuO、Co 3 O 4 、CaO、MgO、SiO 2 、Al 2 O 3 、ZrO 2 One or more of iron ore and manganese ore. Further preferably, the catalyst is Fe, fe 2 O 3 、 Fe 3 O 4 One or more than two of CaO, iron ore, manganese ore and alloy steel.
Based on the above scheme, preferably, the reactor is one or more than two of fluidized bed type, moving bed type, cyclone type, spray type and boiling type decomposing furnace, decomposing furnace with preheating chamber, fixed bed type reactor and atmosphere flat kiln; the fluidized bed decomposing furnace reactor comprises a downstream parallel fluidized bed type reactor and a riser reactor.
Further preferably, the reactor is a cyclone type decomposing furnace, a spouting type decomposing furnace, a boiling type decomposing furnace or a riser reactor.
Based on the above, it is preferable that the reducing agent is fed in powder form simultaneously with the limestone raw material, single powder at one time or in multiple stages at different positions of the reactor; the catalyst comprises particles, superfine powder and a monolithic column form; the catalyst is filled in the reactor in different modes, including a monolithic column form, coated on the wall of the reactor, directly mixed with limestone raw material, simultaneously fed, and catalyst powder is singly fed in the reactor; the material of the reactor comprises one or more than two of quartz, silicon carbide, zirconia, corundum and alloy steel.
Based on the above scheme, preferably, the reaction pressure is between normal pressure and 3MPa; the reaction temperature is 300-1000 ℃. Further preferably, the reaction pressure is from normal pressure to 1MPa, and the reaction temperature is from 500 to 800 ℃.
Based on the scheme, a fixed bed is preferably used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; bulk density of 0.5-5g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 100-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-100h; the gas flow direction is divided into countercurrent or cocurrent;
the moving bed is taken as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 100-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-10h; the gas flow direction is divided into countercurrent or cocurrent;
taking a riser as a reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 5-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-500 m 3 /h; the particle size of the particles is 0.001-5mm; the particle density is 1000-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 1s-5min; the gas flow direction is countercurrent;
the fluidized bed or the descending fluidized bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-300 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 1s-5min; the gas flow direction is parallel flow or countercurrent flow;
the atmosphere flat kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-200t/h; the gas flow is 0.01-500 m 3 /h; particles ofThe grain diameter is 0.001-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.1-200h; the gas flow direction is counter-current, co-current or bubbling.
As further preferred:
the fixed bed is taken as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; bulk density of 0.5-3g/ml; the solid flow is 0.5kg-50t/h; the gas flow is 0.1-100 m 3 /h; the particle size of the particles is 0.01-5mm; the particle density is 200-2000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-10h;
the moving bed is taken as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; bulk density of 0.5-3g/ml; the solid flow is 0.5kg-50t/h; the gas flow is 0.1-100 m 3 /h; the particle size of the particles is 0.01-1mm; the particle density is 200-2000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-2h;
taking a riser as a reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 5-500L/L; bulk density of 0.5-5g/ml; the solid flow is 0.5kg-50t/h; the gas flow is 0.1-150 m 3 /h; the particle size of the particles is 0.05-1mm; the particle density is 2000-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Residence time is 1s-60s;
the fluidized bed or the descending fluidized bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-800L/L; bulk density of 0.5-5g/ml; the solid flow is 0.5kg-50t/h; the gas flow is 0.1-100 m 3 /h; the particle size of the particles is 0.01-2mm; the particle density is 500-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 1s-30s;
the atmosphere flat kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; bulk density of 0.5-5g/ml; the solid flow is 0.5kg-50t/h; the gas flow is 0.1-150 m 3 /h; the particle size of the particles is 0.01-3mm; the particle density is 500-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.1-50h.
The principle of the invention is as follows: the thermal plasma is utilized to gasify the coal dust or the carbon powder, and besides providing the energy required by limestone decomposition (strong endothermic process), the CO generated by limestone decomposition is simultaneously carried out in one step 2 Reduction to CO, wherein the gasified coal dust or carbon powder contains a large amount of gas-phase carbon radical which catalyzes and accelerates the CO 2 Is also of (1)The original process forms a plasma enhanced coupling limestone reduction decomposition process.
The beneficial effects of the invention are as follows:
(1) The thermal plasma can further gasify solid coal dust or carbon powder, carries a large amount of heat, and simultaneously reduces solid-gas into gas-gas, thereby improving the reduction efficiency.
(2) The method for preparing clinker and CO-producing CO by coupling thermal plasma with one-step reduction and decomposition of limestone can avoid carbon dioxide generated by limestone thermal decomposition, and the CO content in CO-producing gas products is 69-100%, and CO is produced 2 Content of<30％，CH 4 Content of<1, can be used for supplying city gas or as the synthesis raw material gas of high-value chemicals such as olefin, oil, aromatic hydrocarbon, etc. The technology can realize 60% of carbon dioxide emission reduction in cement industry and slaked lime industry, and has wide industrial application prospect.
(3) The invention can be reversely caused in fluidized bed type, moving bed type, rotational flow type, spray type, boiling type reactors and decomposing furnaces with preheating chambers, and is realized in a lifting pipe type reactor, a fixed bed type reactor or an atmosphere flat kiln, and has the characteristics of simple process, high added value of products, small industrialization difficulty, easy separation of products, good process repeatability, safe and reliable operation and the like.
(4) The catalyst of the invention can further accelerate the reaction rate, reduce the reaction temperature, be favorable for reducing the energy consumption and improve the reaction efficiency.
Detailed Description
The following examples are intended to be illustrative of the invention and the scope of the invention is to be construed as including the full breadth of the claims and not to be limited to the examples alone. The products in the following examples are each detected by gas chromatography and mass spectrometry.
Comparative example 1
Accurately weighing 1g of heavy calcium carbonate, placing the heavy calcium carbonate into a quartz fixed bed reactor, coupling an arc discharge plasma device, replacing air in the reactor by 0.5L/min Ar gas for about 30 minutes, and adjusting plasma parameters to be: the power is 0.45kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 3.0L/min; after 30 minutes, start to be onlineAnalysis, during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. Mass spectrometry was used in this process to monitor the relative proportions of the decomposition products at the beginning and end of the reaction. Analysis results show that the heavy calcium carbonate is completely decomposed at 900 ℃ and the product is CO 2 。
Comparative example 2
1g of heavy calcium carbonate (0.05 mm), 1g of activated carbon (0.05 mm) and 10mg of Fe were accurately weighed out 2 O 3 The catalyst (0.05 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.8g/ml and a gas-solid ratio of 50L/L, the reactor was warmed up to 900 c (to provide the heat required for decomposition), the air in the reactor was replaced with 0.5L/min Ar gas for about 30 minutes, and after 30 minutes the on-line analysis was started, during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 8%, CO 2 The selectivity of (C) is 91%, CH 4 The selectivity of (2) was 1%.
Example 1
1g of heavy calcium carbonate (0.05 mm), 1g of activated carbon (0.05 mm) and 10mg of Fe were accurately weighed out 2 O 3 The catalyst (0.05 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.8g/ml, the gas-solid ratio is 50L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.3kW, and the Ar protecting gas is 0.5L/min; ar working medium gas is 2.5L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 82%, CO 2 Selectivity of 17%, CH 4 The selectivity of (2) was 1%.
Example 2
Accurately weighing 1g of heavy calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 10mg of iron ore catalyst (0.08 mm) and placing the mixture in Dan YingguIn the fixed bed reactor, the bulk density is 0.75g/ml, the gas-solid ratio is 50L/L, the arc discharge plasma device is coupled, and after the Ar gas of 0.5L/min is used for replacing the air in the reactor for about 30 minutes, the plasma parameters are adjusted as follows: the power is 0.35kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.5L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 84%, CO 2 The selectivity of (2) was 16%.
Example 3
Accurately weighing 1g of heavy calcium carbonate (0.1 mm), 1g of graphite (0.1 mm) and 10mg of Fe 3 O 4 /Fe 2 O 3 The catalyst (0.1 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.72g/ml, the gas-solid ratio is 45L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.38kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1.5h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 84%, CO 2 Selectivity of 15%, CH 4 The selectivity of (2) was 1%.
Example 4
1g of heavy calcium carbonate (0.2 mm), 1g of graphite/activated carbon=1:1 (mass ratio) (0.05 mm) and 10mg of iron ore catalyst (0.1 mm) were accurately weighed into a quartz fixed bed reactor, the bulk density was 0.71g/ml, the gas-solid ratio was 40L/L, the arc discharge plasma apparatus was coupled, and after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the plasma parameters were adjusted to: the power is 0.35kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry.The residence time is 2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 84%, CO 2 The selectivity of (2) was 16%.
Example 5
Accurately weighing 1g of heavy calcium carbonate (0.09 mm), 1g of coal (0.09 mm) and 20mg of iron ore (0.05 mm), placing the heavy calcium carbonate, the coal and the iron ore into a quartz fixed bed reactor, wherein the bulk density is 0.73g/ml, the gas-solid ratio is 100L/L, coupling an arc discharge plasma device, and after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes, adjusting plasma parameters to be: the power is 0.35kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 90%, CO 2 The selectivity of (2) was 10%.
Example 6
Accurately weighing 1g of heavy calcium carbonate (0.1 mm), 1g of coal/activated carbon=1:1 (mass ratio) (0.05 mm) and 10mg of iron ore catalyst (0.05 mm), placing the materials in a zirconia fixed bed reactor, wherein the bulk density is 0.70g/ml, the gas-solid ratio is 120L/L, coupling an arc discharge plasma device, and adjusting plasma parameters after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.5h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 91%, CO 2 The selectivity of (2) was 9%.
Example 7
1g of heavy calcium carbonate (0.5 mm), 1g of coal/activated carbon/graphite=1:1 (mass ratio) (0.05 mm) and 10mg of iron ore catalyst (0.5 mm) are accurately weighed and placed in a corundum fixed bed reactor, the bulk density is 0.68g/ml, the gas-solid ratio is 110L/L, and a coupled arc discharge plasma device is used with 0.5LAfter about 30 minutes of Ar gas replacement of air in the reactor, the plasma parameters were adjusted as follows: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 88%, CO 2 The selectivity of (2) is 12%.
Example 8
1g of heavy calcium carbonate (0.6 mm), 1g of coal (0.6 mm) and 10mg of Fe were accurately weighed out 2 O 3 CaO catalyst (0.5 mm) is placed in a silicon carbide fixed bed reactor, the bulk density is 0.67g/ml, the gas-solid ratio is 200L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.45kW, and the Ar shielding gas is 0.5L/min; h 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 87%, CO 2 The selectivity of (2) was 13%.
Example 9
1g of heavy calcium carbonate (0.05 mm), 1g of activated carbon (0.05 mm) and 10mg of Fe were accurately weighed out 3 O 4 The catalyst (0.05 mm) is placed in an alloy steel (Incoloy 800 HT) fixed bed reactor, the bulk density is 0.8g/ml, the gas-solid ratio is 300L/L, an arc discharge plasma device is coupled, and after the air in the reactor is replaced by Ar gas of 0.5L/min for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; h 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.3h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (1) is7％，CH 4 The selectivity of (2) was 1%.
Example 10
1g of heavy calcium carbonate (0.08 mm), 1g of activated carbon (0.07 mm) and 10mg of Fe were accurately weighed out 3 O 4 /Al 2 O 3 The catalyst (0.06 mm) is placed in a zirconia fixed bed reactor, the bulk density is 0.78g/ml, the gas-solid ratio is 300L/L, the arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.42kW, and the Ar shielding gas is 0.5L/min; h 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) is 10.5%, CH 4 The selectivity of (2) was 0.5%.
Example 11
Accurately weighing 100g of heavy calcium carbonate (0.08 mm), 200g of coal (0.08 mm) and 2g of Mn 3 O 4 The catalyst (0.08 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.77g/ml, the gas-solid ratio is 500L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO+H 2 2.0L/min of working medium gas in a molar ratio of 1:1; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) is 10%, CH 4 The selectivity of (2) was 1%.
Example 12
Accurately weighing 1g of heavy calcium carbonate (1 mm), 1g of coal (1 mm) and 10mg of manganese ore catalyst (1 mm), placing into a metal (Incoloy 800 HT) fixed bed reactor, wherein the bulk density is 0.62g/ml, the gas-solid ratio is 100L/L, and couplingThe arc discharge plasma apparatus was configured to replace air in the reactor with 0.5L/min Ar gas for about 30 minutes, and then to adjust plasma parameters as follows: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO+H 2 3.0L/min of working medium gas in a molar ratio of 1:1; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.8h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 87%, CO 2 The selectivity of (2) was 13%.
Example 13
1g of heavy calcium carbonate (0.08 mm), 2g of coal (0.08 mm) and 15mg of manganese ore catalyst (0.08 mm) are accurately weighed and placed in a quartz moving bed reactor, the bulk density is 0.79g/ml, the gas-solid ratio is 50L/L, an arc discharge plasma device is coupled, and after the air in the reactor is replaced by Ar gas of 0.5L/min for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.35kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) was 11%.
Example 14
Accurately weighing 1g of heavy calcium carbonate (0.06 mm), 1g of active carbon (0.06 mm) and 10mg of iron ore catalyst (0.06 mm), placing the heavy calcium carbonate, the active carbon and the iron ore catalyst into a corundum moving bed reactor, wherein the bulk density is 0.79g/ml, the gas-solid ratio is 55L/L, coupling an arc discharge plasma device, and adjusting plasma parameters after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、 CO 2 Wherein the selectivity of CO is 85%, CO 2 The selectivity of (2) was 14.8％，CH 4 The selectivity of (2) was 0.2%.
Example 15
Accurately weighing 1g of heavy calcium carbonate (0.1 mm), 1g of active carbon/graphite=1:1 (mass ratio) (0.1 mm) and 12mg of Ni/MgO catalyst (0.1 mm), placing the heavy calcium carbonate, the active carbon/graphite and the catalyst in a silicon carbide moving bed reactor, wherein the bulk density is 0.75g/ml, the gas-solid ratio is 100L/L, coupling an arc discharge plasma device, and adjusting plasma parameters after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.5h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 85%, CO 2 The selectivity of (2) was 15%.
Example 16
Accurately weighing 10g of heavy calcium carbonate (1 mm), 10g of active carbon/graphite/coal=1:1:1 (mass ratio) (1 mm) and 100mg of iron ore catalyst (1 mm), placing the materials in a quartz moving bed reactor, wherein the bulk density is 0.68g/ml, the gas-solid ratio is 100L/L, coupling an arc discharge plasma device, and adjusting plasma parameters after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.5h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 84%, CO 2 The selectivity of (2) was 16%.
Example 17
1g of heavy calcium carbonate (0.5 mm), 1g of activated carbon (0.5 mm) and 10mg of MnO were accurately weighed 2 :Mn 3 O 4 : Fe 2 O 3 Co=1:1:3:1 catalyst (mass ratio) (0.5 mm) was placed in a silicon carbide moving bed reactor, bulk density was 0.72g/ml, gas-solid ratio was 200L/L, and an arc discharge plasma apparatus was coupled to replace the air in the reactor with 0.5L/min Ar gas for about 30 minutesAfter the clock, the plasma parameters were adjusted as follows: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.2h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 18
Accurately weigh 1g heavy calcium carbonate (0.1 mm), 1g activated carbon/coal = 1:3 (mass ratio) (0.1 mm) and 10mg iron ore catalyst (0.1 mm) were placed in a moving bed reactor of alloy steel (Incoloy 800 HT), the bulk density was 0.71g/ml, the gas-solid ratio at 15 atmospheres was 300L/L, and after coupling an arc discharge plasma apparatus, the air in the reactor was replaced with 0.5L/min Ar gas for about 30 minutes, the plasma parameters were adjusted to: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.5h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) is 6.3%, CH 4 The selectivity of (2) was 0.7%.
Example 19
Accurately weighing 10g of heavy calcium carbonate (0.08 mm), 10g of coal (0.08 mm) and 10mg of Fe/ZrO 2 -Al 2 O 3 The catalyst (0.08 mm) is placed in a zirconia moving bed reactor, the bulk density is 0.78g/ml, the gas-solid ratio is 150L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.2h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 21
Accurately weighing 1g of heavy calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 10mg of MnO 2 Cu: fe: co=1:1:1:5 catalyst (mass ratio) (0.08 mm) was placed in a moving bed reactor of metal (GH 2302 material), bulk density was 0.78g/ml, gas-solid ratio under 14 atmospheres was 250L/L, and after coupling an arc discharge plasma apparatus, air in the reactor was replaced with 0.5L/min Ar gas for about 30 minutes, the plasma parameters were adjusted to: the power is 0.55kW, and the Ar shielding gas is 0.5L/min; CO 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.08 and h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 96%, CO 2 The selectivity of (2) was 4%.
Example 22
Accurately weighing 1g of heavy calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 11mg of MnO 2 Ni: mn=3:1:2 (mass ratio) (0.08 mm) is placed in a quartz cyclone decomposing furnace reactor, bulk density is 0.78g/ml, gas-solid ratio is 50L/L, an arc discharge plasma device is coupled, and after air in the reactor is replaced by Ar gas of 0.5L/min for about 30 minutes, plasma parameters are adjusted to be: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is decomposed completely and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 87%, CO 2 Has a selectivity of 12.5%, CH 4 The selectivity of (2) was 0.5%.
Example 23
Accurately weighing 1g of heavy calcium carbonate (0.1 mm), 1.5g of active carbon/coal=1:1 (mass ratio) (0.1 mm) and 12mg of NiO: mn=3:1 catalyst (mass ratio) (0.1 mm), placing into a corundum cyclone type decomposing furnace reactor, wherein the bulk density is 0.75g/ml, the gas-solid ratio is 100L/L, and coupling an arc discharge plasma device to ensure thatAfter replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the plasma parameters were adjusted as follows: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.7h, and the analysis result shows that the heavy calcium carbonate is decomposed completely and the products are CO and CO 2 Wherein the selectivity of CO is 82%, CO 2 The selectivity of (2) was 18%.
Example 24
Accurately weighing 10g of heavy calcium carbonate (0.25 mm), 10g of active carbon/coal=1:1 (mass ratio) (0.25 mm) and 2g of NiO: mn=3:1 (mass ratio) (0.25 mm), placing the heavy calcium carbonate, the active carbon/coal=1:1 (mass ratio) and the 2g of NiO: mn=3:1 (mass ratio) in a silicon carbide cyclone decomposing furnace reactor, wherein the bulk density is 0.72g/ml, the gas-solid ratio is 100L/L, coupling an arc discharge plasma device, and adjusting plasma parameters after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes: the power is 0.45kW, and the Ar shielding gas is 0.5L/min; h 2 Working medium gas 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.6h, and the analysis result shows that the heavy calcium carbonate is decomposed completely and the products are CO and CO 2 Wherein the selectivity of CO is 87%, CO 2 The selectivity of (2) was 13%.
Example 25
50g of heavy calcium carbonate (0.08 mm), 50g of activated carbon/coal=1:1 (mass ratio) (0.08 mm) and 200mg of iron ore (0.08 mm) are accurately weighed into a metal (material of Incoloy800 HT) spouted decomposing furnace reactor, the bulk density is 0.79g/ml, the gas-solid ratio is 150L/L, an arc discharge plasma device is coupled, and after air in the reactor is replaced by 0.5L/min Ar gas for about 30 minutes, plasma parameters are adjusted to be: the power is 0.4kW, and the Ar shielding gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.1h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate are finished, and the products are CO and CO 2 Wherein the selectivity of CO is 92%,CO 2 the selectivity of (2) was 8%.
Example 26
200g of heavy calcium carbonate (0.1 mm), 200g of activated carbon/coal=1:1 (mass ratio) (0.1 mm) and 2g of MnO were accurately weighed out 2 Iron ore=3:1 catalyst (mass ratio) (0.1 mm) was placed in a silicon carbide totem-pole decomposing furnace reactor, bulk density was 0.72g/ml, gas-solid ratio under 5 atmospheres was 250L/L, an arc discharge plasma apparatus was coupled, and after using 0.5L/min Ar gas to displace air in the reactor for about 30 minutes, the plasma parameters were adjusted to: the power is 0.62kW, and the Ar shielding gas is 0.5L/min; CO working medium gas 3.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.1 and h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 27
Accurately weighing 1kg of heavy calcium carbonate (0.2 mm), 1kg of active carbon/coal=1:1 (mass ratio) (0.2 mm) and 10g of CuO, wherein iron ore=1:1 (mass ratio) (0.2 mm) are placed in a metal (material is Inconel 601) spouted decomposing furnace reactor, the bulk density is 0.71g/ml, the gas-solid ratio under 5 atmospheric pressure is 150L/L, an arc discharge plasma device is coupled, and after air in the reactor is replaced by Ar gas of 0.5L/min for about 30 minutes, plasma parameters are adjusted to be: the power is 0.71kW, and the Ar protecting gas is 0.5L/min; h 2 +CO 2 The molar ratio of the working medium gas to the water is 1:1, and the working medium gas is 4.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 0.6h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 92%, CO 2 Has a selectivity of 7.5%, CH 4 The selectivity of (2) was 0.5%.
Example 28
Accurately weighing 1g heavy calcium carbonate (1 mm), 1g activated carbon/coal=1:1 (mass ratio) (1 mm) and 10mg Fe/Al 2 O 3 The catalyst (1 mm) was placed in an alloy steel (Incoloy 800 HT) in a boiling decomposing furnace reactor, the bulk density is 0.68g/ml, the gas-solid ratio is 150L/L under 20 atmospheric pressure, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.71kW, and the Ar protecting gas is 0.5L/min; CO 2 3.0L/min of working medium gas; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 29
Accurately weighing 1g heavy calcium carbonate (2 mm), 1g activated carbon/coal=1:1 (mass ratio) (2 mm) and 10mg Mn 2 O 3 /Fe 2 O 3 -Al 2 O 3 The catalyst (2 mm) is placed in a quartz zone preheating chamber decomposing furnace reactor, the bulk density is 0.67 and g/ml, the gas-solid ratio is 80L/L, an arc discharge plasma device is coupled, and after 0.5L/min Ar gas is used for replacing air in the reactor for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.51kW, and the Ar protecting gas is 0.5L/min; ar working medium gas is 2.0L/min; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 30
Accurately weighing 1g heavy calcium carbonate (0.08 mm), 1g coal (0.08 mm) and 10mg Mn 3 O 4 NiO: cuO: fe=1:2:6:2 (mass ratio) (0.08 mm) was placed in a metal (material: incoloy800 HT) riser reactor, the bulk density was 0.79g/ml, the gas-solid ratio at 10 atm was 60L/L, an arc discharge plasma apparatus was coupled, and after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the plasma parameters were adjusted to: the power is 0.85kW, and the Ar shielding gas is 0.5L/min; h 2 Working medium gas is 5.0L/min; the on-line analysis was started after 30 minutes of hold,mass spectrometry was used in this process to monitor the relative proportions of the decomposition products at the beginning and end of the reaction. The residence time is 1min, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selectivity of CO is 97%, CO 2 The selectivity of (2) was 3%.
Example 31
Accurately weighing 1g of heavy calcium carbonate (0.05 mm), 2g of coal (0.05 mm) and 10mg of iron ore, wherein Fe=1:2 (mass ratio) (0.05 mm) are placed in a metal (material is Incoloy800 HT) atmosphere flat kiln reactor, the bulk density is 0.8g/ml, the gas-solid ratio under 10 atmospheric pressure is 50L/L, an arc discharge plasma device is coupled, and after the air in the reactor is replaced by 0.5L/min Ar gas for about 30 minutes, the plasma parameters are adjusted to be: the power is 0.75kW, and the Ar shielding gas is 0.5L/min; CH (CH) 4 3.0L/min of working medium gas; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 3h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CO 2 Wherein the selection of CO is 88%, CO 2 The selectivity of (2) was 10%.
Example 32
Accurately weighing 1g of heavy calcium carbonate (0.1 mm) and 1g of active carbon, wherein coal=1:1 (0.1 mm), placing the heavy calcium carbonate and the active carbon into a quartz fixed bed reactor, wherein the bulk density is 0.76g/ml, the gas-solid ratio is 80L/L, coupling an arc discharge plasma device, and after using 0.5L/min Ar gas to replace air in the reactor for about 30 minutes, adjusting plasma parameters to be: the power is 0.75kW, and the Ar shielding gas is 0.5L/min; CH (CH) 4 3.0L/min of working medium gas; the on-line analysis was started after 30 minutes of hold during which the relative proportions of the decomposition products at the beginning and end of the reaction were monitored using mass spectrometry. The residence time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 80%, CO 2 Selectivity of 19%, CH 4 The selectivity of (2) was 1%.

Claims (10)

1. A method for preparing clinker and CO-producing CO by catalyzing limestone reduction and decomposition through thermal plasma coupling solid reducing agent is characterized by comprising the following steps: one or a mixture of two of coal and carbon is used as a reducing agent, thermal plasma is used for supplying heat, and the reducing agent and limestone are catalyzed in a reactor to be subjected to one-step reduction decomposition to generate clinker, and CO is CO-produced.
2. The method according to claim 1, characterized in that: the thermal plasma comprises one or a combination of two of an arc discharge plasma and an inductively coupled plasma.
3. The method according to claim 1, characterized in that: the power of the thermal plasma is 0.1kW-100MW; the thermal plasma adopts direct current, the current is 10-10000A, and the voltage is 10-10000V.
4. The method according to claim 1, characterized in that: the working medium gas carrier gas of the thermal plasma is Ar, he and CH 4 、CO 2 、CO、H 2 One or a combination of two or more of them.
5. The method according to claim 1, characterized in that: and (3) carrying one or two mixtures of coal and carbon into a reactor by using hot plasma working medium gas carrier gas to catalyze, reduce and decompose limestone.
6. The method according to claim 1, characterized in that: the method adopts metal and/or metal oxide as a catalyst; the metal is one or more than two of Fe, mn, cr, ni, cu, co and alloy steel;
the metal oxide is Fe 2 O 3 、Fe 3 O 4 、Mn 3 O 4 、MnO 2 、Cr 2 O 3 、NiO、CuO、Co 3 O 4 、CaO、MgO、SiO 2 、Al 2 O 3 、ZrO 2 One or more of iron ore and manganese ore.
7. The method according to claim 1, characterized in that: the reactor is one or the combination of more than two of a fluidized bed type, a moving bed type, a cyclone type, a spray type and a boiling type decomposing furnace, a decomposing furnace with a preheating chamber, a fixed bed type reactor and an atmosphere flat kiln;
the fluidized bed decomposing furnace reactor comprises a downstream parallel fluidized bed type reactor and a riser reactor.
8. The method according to claim 1, characterized in that: the reducing agent is fed with limestone raw materials in a powder form at the same time, and is fed in a single powder mode or fed in multiple sections at different positions of the reactor;
the catalyst comprises particles, superfine powder and a monolithic column form;
the catalyst is filled in the reactor in different modes, including a monolithic column form, coated on the wall of the reactor, directly mixed with limestone raw material, simultaneously fed, and catalyst powder is singly fed in the reactor;
the material of the reactor comprises one or more than two of quartz, silicon carbide, zirconia, corundum and alloy steel.
9. The method according to claim 1, characterized in that: the reaction pressure is normal pressure to 3MPa; the reaction temperature is 300-1000 ℃.
10. The method according to claim 1, characterized in that:
the fixed bed is taken as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; bulk density of 0.5-5g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 100-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-100h; the gas flow direction is divided into countercurrent or cocurrent;
the moving bed is taken as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 /h; particle size of the particles0.001-10mm; the particle density is 100-5000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.01-10h; the gas flow direction is divided into countercurrent or cocurrent;
taking a riser as a reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 5-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-500 m 3 /h; the particle size of the particles is 0.001-5mm; the particle density is 1000-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 1s-5min; the gas flow direction is countercurrent;
the fluidized bed or the descending fluidized bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-300 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 1s-5min; the gas flow direction is parallel flow or countercurrent flow;
the atmosphere flat kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; bulk density of 0.5-10g/ml; the solid flow is 0.05kg-200t/h; the gas flow is 0.01-500 m 3 /h; the particle size of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The residence time is 0.1-200h; the gas flow direction is counter-current, co-current or bubbling.
CN202210799110.3A 2022-07-06 2022-07-06 Method for preparing clinker and CO-producing CO by catalytic limestone reduction and decomposition through thermal plasma coupling solid reducing agent Pending CN117401919A (en)

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