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CN117401648A - Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2) - Google Patents

Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2) Download PDF

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CN117401648A
CN117401648A CN202210799115.6A CN202210799115A CN117401648A CN 117401648 A CN117401648 A CN 117401648A CN 202210799115 A CN202210799115 A CN 202210799115A CN 117401648 A CN117401648 A CN 117401648A
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gas
reactor
limestone
reducing agent
selectivity
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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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • 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

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
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Abstract

The invention relates to a method for preparing clinker by limestone reduction and decomposition under the catalysis of a thermal plasma coupling gas reducing agent and CO-producing CO/H-enriched gas 2 The method adopts one or more than two mixed gases of hydrogen, methane-enriched gas and ammonia gas as reducing agent, utilizes thermal plasma to supply heat, catalyzes the reducing agent and limestone to be subjected to one-step reduction decomposition in a reactor to generate clinker, and simultaneously CO-produces CO/H-enriched gas 2 Is a gas of (a) a gas of (b). The invention can avoid the generation of carbon dioxide by limestone thermal decomposition and CO-produce CO/H-enriched gas 2 The specific composition of the gas is related to the reducing agent and the reaction condition, and the gas can be used as a main component for supplying city gas or used as a synthesis raw material gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like. The invention has the electrothermal conversion efficiency>90 percent of the electrode has long service life, simple process, high added value of products, small industrialization difficulty and easy separation of productsGood process repeatability, safe and reliable operation and the like.

Description

Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2)
Technical Field
The invention belongs to the field of cement and slaked lime manufacturing, and in particular relates to a method for preparing clinker by one-step reduction and decomposition of limestone under the catalysis of a thermal plasma coupling gas reducer and combining CO/H-enriched components 2 Has high electrothermal conversion efficiency and high carbon neutralization efficiency.
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 and trafficCarbon neutralization for transportation of these two large emission households can be achieved by clean energy substitution, and carbon neutralization in the manufacturing and construction industries faces one of two major challenges: 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. The cement industry analysis shows that the cement yield of China is the first in the world for ten years, and is as low as 2017 at 6 months, the cement enterprises in China are 3465, the actual clinker yield in China is 20.2 hundred million tons, and the cement yield is 38.30 hundred million tons. 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 Emission, thus changing limestone calcination and decomposition process, reducing and even avoiding CO while preparing clinker 2 Emissions are a revolutionary technique, and are effective carbon neutralization techniques.
CN101987783a discloses a method for producing quick lime by calcining limestone with gas in a suspended state preheating decomposing furnace, which uses surplus gas produced by steelmaking to calcine limestone, so as to intensify the utilization rate, but cannot fundamentally solve the problem of CO 2 High emissions of (2). 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.
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 gas reducer on renewable electric plasmas to catalyze limestone to be subjected to one-step reductive decomposition.
The invention provides a method for catalyzing limestone to be reduced and decomposed in one step by coupling plasma and gas reducer and CO-producing CO/H-enriched material 2 The gas method utilizes thermal plasma to further thermally dissociate the gas reducer into free radicals and charged ions, and improves the reduction efficiency besides carrying a large amount of heat. The invention realizes the great reduction of carbon dioxide emission in cement industry and slaked lime industry, is a high-efficiency carbon neutralization technology, and simultaneously CO-produces CO-rich gas, which can be used as a main component for supplying city gas and can also 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 refers to the simultaneous combination of limestone decomposition into clinker under the same conditions of the same reactorAnd CO gas with high added value is produced, 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:
thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 The method adopts one or more than two mixed gases of hydrogen, methane-enriched gas and ammonia gas as reducing agent, and utilizes thermal plasma to catalyze the reducing agent and limestone in a reactor to generate clinker through one-step reduction decomposition, and CO-production of CO/H-enriched gas 2 Is a gas of (a) a gas of (b).
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 hot plasma working medium gas is utilized to bring one or two mixtures of reducing gases into the reactor for catalytic reduction and limestone decomposition; 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 Fast mixing with plasma jetCombining all of the natural gas and CO to be converted 2 Total enthalpy value Δh 15℃ ＜160kJ/mol。
Based on the above scheme, preferably, the electrode protecting gas of the arc discharge 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 above scheme, preferably, the method adopts metal and/or metal oxide as a catalyst, wherein 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-described scheme, preferably, the hydrogen gas is derived from hydrogen gas of fossil resources, hydrogen gas obtained by renewable electrowinning water, hydrogen gas obtained by photolysis water; the methane-rich gas comprises one or more than two mixed gases selected from pure methane gas, mixed gas of methane and low-carbon alkane, natural gas, shale gas and hydrate extracted methane; the mixed gas of one or more than two of hydrogen, rich methane gas and ammonia gas is used as an effective reducing agent to be mixed with one or more than two of inert atmosphere gas nitrogen, helium gas and argon gas, wherein the volume content of the effective reducing agent in the reaction raw material gas is 5-100%, and the volume content of the inert gas is 0-95%.
Based on the above scheme, preferably, the reactor is one or a combination of more than two of a fluidized bed type, a moving bed type, a cyclone type, a spouting 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. Further preferably, the reactor is a cyclone, a spray, a fluidized decomposing furnace or a riser reactor.
Based on the above, preferably, the metal or metal oxide catalyst comprises a particle of a certain size, ultrafine powder, monolithic column form; the metal or metal oxide catalyst may be packed in the reactor in various ways, including monolithic column form, coated on the reactor wall, directly mixed with limestone feed stock, powder fed separately into the reactor; the reactor is made of 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 normal pressure to 1MPa, and the reaction temperature is 300 to 500 ℃; most preferably the reaction pressure is 0.2 to 0.5MPa; the reaction temperature is 300-600 ℃.
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 0.1-10mm; 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 and 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 0.1-10mm; 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 and 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 0.1-5mm; 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 parallel 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 0.1-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Residence time is 1s-10s; the gas flow direction is parallel 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 0.1-10mm; 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 countercurrent, cocurrent and bubbling.
It is further preferred that the composition of the present invention,
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 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 of0.5-5g/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 acts on the working medium gas to simultaneously decompose the limestone to generate CO in one step besides providing the energy required by the limestone decomposition (strong endothermic process) 2 Reducing into CO, and converting the working medium gas into ions, free radicals and the like at high temperature in the plasma torch, wherein the ions and the free radicals catalyze and accelerate with the CO 2 The reaction and reduction process of the catalyst form a plasma enhanced coupling limestone reduction decomposition process. The beneficial effects of the invention are as follows:
(1) The thermal plasma can further thermally dissociate the gaseous reducing agent into free radicals and charged ions, and improves the reduction efficiency besides carrying a large amount of heat.
(2) The method for preparing clinker and CO-producing CO by coupling thermal plasma with one-step reduction and decomposition of limestone, and CO-producing CO/H-enriched material 2 The gas product composition of (1) gas contains CO 20-60%, H 2 The content of CO is 10-50 percent 2 Content of<20％，CH 4 Content of<10%, can be used as the main component to supply city gas or as the synthesis raw material gas of high-value chemicals such as olefin, oil, arene, etc., the technology of the invention can realize the emission reduction of 60% of carbon dioxide in cement industry and slaked lime industry, and has wide industrial application prospect.
(3) The invention can be realized in fluidized bed type, moving bed type, cyclone type, spray type, boiling type and other decomposing furnaces, decomposing furnace with preheating chamber, riser reactor, fixed bed reactor or atmosphere flat kiln, and has the characteristics of simple process, high added value of product, small industrialization difficulty, easy separation of product, 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 merely illustrative of the present inventionIt is intended that the scope of the invention shall include all of the claims and not be limited to the embodiments. In the following examples, each product was mass-detected and was based on the carbon balance before and after the reaction, H was 2 No calculation was made.
Comparative example 1
1g of heavy calcium carbonate (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 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 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed to obtain CO 2 。
Comparative example 2
Accurately weighing 1g of heavy calcium carbonate (0.08 mm) and 10mg of iron ore catalyst (0.08 mm), placing into a quartz fixed bed reactor, placing the reactor with bulk density of 0.78g/ml and gas-solid ratio of 80L/L, heating the reaction device to 900 ℃ (providing heat required for decomposition), replacing air in the reactor with 0.5L/min Ar gas for about 30 min, and introducing 1.25L/min Ar+ 25L/min NH 3 Is a mixed gas of (1); and after 30 minutes of hold, 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 1.5H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed, and the products are CO and H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 78%, CO 2 Selectivity of 21%, CH 4 The selectivity of (2) was 1%.
Example 1
Accurately weighing 1g of heavy calcium carbonate (0.08 mm) and 10mg of iron ore catalyst (0.08 mm), placing into a quartz fixed bed reactor, wherein the bulk density is 0.78g/ml, the gas-solid ratio is 80L/L, coupling an arc discharge plasma device, and using Ar gas displacement reaction of 0.5L/minAfter about 30 minutes of air in the reactor, the plasma parameters were adjusted as: the power is 0.3kW, and the Ar protecting gas is 0.5L/min; introducing Ar working medium gas 1.25L/min and NH 3 Reducing agent 1.25L/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 decomposed at 580 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 88%, CO 2 The selectivity of (2) is 11.5%, CH 4 The selectivity of (2) was 0.5%.
Example 2
1g of heavy calcium carbonate (0.1 mm) and 10mg of Fe were accurately weighed out 3 O 4 /Fe 2 O 3 The supported catalyst (0.1 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.75g/ml, the gas-solid ratio is 100L/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 0.38kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 retention time is 2H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 490 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 92%, CO 2 Has a selectivity of 7%, CH 4 The selectivity of (2) was 1%.
Example 3
Accurately weighing 1g of heavy calcium carbonate (0.12 mm) and 10mg of iron ore powder catalyst (0.12 mm), placing into a quartz fixed bed reactor, wherein the bulk density is 0.74g/ml, the gas-solid ratio is 110L/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 0.42kW, and the Ar shielding gas is 0.5L/min; introducing Ar working medium gas 1.5L/min, NH 3 Reducing agent 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 2.5H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 510 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be condensed to remove CO with a selectivity of 86 percent, CO 2 The selectivity of (2) was 14%.
Example 4
Accurately weighing 1g of heavy calcium carbonate (0.25 mm) and 20mg of Fe powder catalyst (0.25 mm), placing into a quartz fixed bed reactor, wherein the bulk density is 0.72g/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 0.5kW, and the Ar protecting gas is 0.5L/min; introducing H 2 Working medium gas 1.75L/min, ar reducer 0.25L/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 retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 595 ℃ to obtain H 2 、CO、H 2 O、CO 2 Wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) was 11%.
Example 5
Accurately weighing 1g of heavy calcium carbonate (0.33 mm) and 10mg of iron ore powder catalyst (0.33 mm), placing into a quartz fixed bed reactor, wherein the bulk density is 0.72g/ml, the gas-solid ratio is 140L/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 0.38kW, and the Ar shielding gas is 0.5L/min; introducing H 2 Working medium gas 1.2L/min, ar reducer 0.8L/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 decomposed at 480 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein CO is selected91% of the sex, CO 2 Has a selectivity of 9.8%, CH 4 The selectivity of (2) was 0.2%.
Example 6
Accurately weighing 1g of heavy calcium carbonate (0.38 mm) and 10mg of Ni powder catalyst (0.38 mm), placing into a quartz fixed bed reactor, wherein the bulk density is 0.71g/ml, the gas-solid ratio is 140L/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 0.44kW, and the Ar shielding gas is 0.5L/min; introducing Ar working medium gas 2.0L/min, CH 4 Reducing agent 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 0.9H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 600 ℃ and the product is H 2 、CO、H 2 O、CH 4 、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 7
Accurately weighing 1g of heavy calcium carbonate (0.25 mm) and 100mg of Cu powder catalyst (0.25 mm), placing into a silicon carbide fixed bed reactor, wherein the bulk density is 3g/ml, the gas-solid ratio is 85L/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 0.42kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.0L/min as working medium gas and reducing agent; 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 heavy calcium carbonate is completely decomposed at 580 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 90%, CO 2 The selectivity of (2) was 10%.
Example 8
1g of heavy calcium carbonate (0.3 mm) and 10mg of Fe were accurately weighed out 2 O 3 CaO supported catalyst (0.3 mm)Placing the mixture in a corundum fixed bed reactor, wherein the bulk density is 0.71g/ml, the gas-solid ratio is 100L/L, and the plasma parameters are adjusted after the air in the reactor is replaced by Ar gas of 0.5L/min for about 30 minutes by a coupled arc discharge plasma device: the power is 0.45kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.0L/min as working medium gas and reducing agent; 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 decomposed at 550 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 92%, CO 2 Has a selectivity of 7.7%, CH 4 The selectivity of (2) was 0.3%.
Example 9
1g of heavy calcium carbonate (0.08 mm) and 10mg of Fe were accurately weighed out 3 O 4 The powder catalyst (0.08 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 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 0.55kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 515 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 87%, CO 2 Has a selectivity of 12.7%, CH 4 The selectivity of (2) was 0.3%.
Example 10
Accurately weighing 1g of heavy calcium carbonate (0.15 mm) and 10mg Co 3 O 4 /Fe 2 O 3 The supported catalyst (0.15 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.74g/ml, and a coupled arc discharge plasma apparatus was used at 0.5. 0.5L/minAfter about 30 minutes of air in the Ar gas replacement reactor, the plasma parameters were adjusted as follows: the power is 0.59kW, and the Ar shielding gas is 0.5L/min; introducing H 2 Working medium gas 2.5L/min, NH 3 Reducing agent 1.5L/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 0.8H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 590 ℃ and the product is H 2 、 CO、H 2 O、CH 4 、N 2 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 82%, CO 2 Selectivity of 17%, CH 4 The selectivity of (2) is 0.3%, N 2 The selectivity of (2) was 0.7%.
Example 11
Accurately weighing 1g of heavy calcium carbonate (0.08 mm) and 10mg of manganese ore powder catalyst (0.08 mm), placing the heavy calcium carbonate and the manganese ore powder catalyst into a metal (Incoloy 800 HT) fixed bed reactor, wherein the bulk density is 0.78g/ml, the gas-solid ratio is 60L/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 0.59kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 heavy calcium carbonate is completely decomposed at 490 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) is 1.1%, N 2 Selectivity of 5%, CH 4 The selectivity of (2) was 0.9%.
Example 12
Accurately weighing 1g of heavy calcium carbonate (0.1 mm) and 15mg of manganese ore powder catalyst (0.1 mm), placing the heavy calcium carbonate and the manganese ore powder catalyst into a quartz moving bed reactor, wherein the bulk density is 0.75g/ml, the gas-solid ratio is 110L/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 0.66kW, and the Ar protecting gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 decomposed at 420 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 91%, CO 2 The selectivity of (2) is 8.8%, CH 4 The selectivity of (2) was 0.2%.
Example 13
Accurately weighing 1g of heavy calcium carbonate (0.1 mm) and 10mg of iron ore powder catalyst (0.1 mm), placing the heavy calcium carbonate and the iron ore powder catalyst into a quartz moving bed reactor, wherein the bulk density is 0.74g/ml, the gas-solid ratio is 120L/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 0.71kW, and the Ar protecting gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 decomposed at 381 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) is 10.8%, CH 4 The selectivity of (2) was 0.2%.
Example 14
Accurately weighing 1g of heavy calcium carbonate (0.05 mm) and 12mg of Ni/MgO supported catalyst (0.05 mm), placing the heavy calcium carbonate and the catalyst into a quartz moving bed reactor, wherein the bulk density is 0.8g/ml, the gas-solid ratio is 60L/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 0.82kW, and the Ar shielding gas is 0.5L/min; introducing H 2 3.5L/min as working medium gas and reducing agent; after 30 minutes of hold, the on-line analysis was started, during which time mass spectrometry was used to monitor the decomposition products at the beginning and end of the reactionRelative proportions in time. The residence time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 505 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 89%, CO 2 The selectivity of (2) is 10.4%, CH 4 The selectivity of (2) was 0.6%.
Example 15
Accurately weighing 10g heavy calcium carbonate (0.15 mm) and 100mg Cr/SiO 2 The supported catalyst (0.15 mm) is placed in a quartz moving bed reactor, the bulk density is 0.76g/ml, the gas-solid ratio is 100L/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 0.82kW, and the Ar shielding gas is 0.5L/min; ar working medium gas 2.0L/min, NH 3 Reducing agent 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 retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 478 ℃ to obtain H 2 、CO、H 2 O、N 2 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 85%, CO 2 The selectivity of (2) was 11.4%, N 2 The selectivity of (2) is 3%, CH 4 The selectivity of (2) was 0.6%.
Example 16
Accurately weighing 50g of heavy calcium carbonate (0.15 mm) and 0.5g of Fe/ZrO 2 The supported catalyst (0.15 mm) is placed in a quartz moving bed reactor, the bulk density is 0.75g/ml, the gas-solid ratio is 110L/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 1.2kW, and the Ar protecting gas is 0.5L/min; introducing H 2 5L/min as working medium gas and reducing agent; 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 decomposed at 560 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) is 6.4%, CH 4 The selectivity of (2) was 0.6%.
Example 17
Accurately weighing 1g of heavy calcium carbonate (0.1 mm) and 11mg of MnO 2 Ni: mn=3:1:2 (mass ratio) powder catalyst (0.1 mm) is placed in a quartz cyclone decomposing furnace reactor, the bulk density is 0.75g/ml, the gas-solid ratio is 160L/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 0.58kW, and the Ar shielding gas is 0.5L/min; introducing H 2 2.5L/min as working medium gas and reducing agent; 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 decomposed at 570 ℃ and the product is H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) is 6.5%, CH 4 The selectivity of (2) was 0.5%.
Example 18
Accurately weighing 1g of heavy calcium carbonate (0.1 mm) and 11mg of CuNi/ZrO 2 The supported catalyst (0.1 mm) is placed in a quartz cyclone decomposing furnace reactor, the bulk density is 0.79g/ml, the gas-solid ratio is 100L/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 0.62kW, and the Ar shielding gas is 0.5L/min; ar+H 2 2.5L/min of working medium gas in a molar ratio of 1:5; 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. Analysis results show that the heavy calcium carbonate is completely reacted and decomposed at 660 ℃ and the product is H 2 、CO、 H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 86%, CO 2 The selectivity of (2) is 13.5%, CH 4 Selectivity of (2)0.5%.
Example 19
Accurately weighing 50g of heavy calcium carbonate (1 mm) and 200mg of iron ore powder catalyst (1 mm), placing the heavy calcium carbonate and the iron ore powder catalyst into a metal (the material is Incoloy800 HT) spouted decomposing furnace reactor, wherein the bulk density is 0.69g/ml, the gas-solid ratio is 300L/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 0.8kW, and the Ar protecting gas is 0.5L/min; introducing H 2 3.5L/min as working medium gas and reducing agent; 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 decomposed at 660 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 92%, CO 2 The selectivity of (2) was 8%.
Example 20
Accurately weigh 12g heavy calcium carbonate (0.45 mm) and 200mg NiO/SiO 2 The supported catalyst (0.15 mm) is placed in a corundum spray type decomposing furnace reactor, the bulk density is 0.74g/ml, the gas-solid ratio is 210L/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 to be: the power is 0.58kW, and the Ar shielding gas is 0.5L/min; introducing Ar working medium gas 2.5L/min, NH 3 Reducing agent 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 decomposed at 605 ℃ and the product is H 2 、CO、H 2 O、N 2 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 90%, CO 2 Selectivity of 5%, N 2 The selectivity of (2) was 5%.
Example 21
1g of heavy calcium carbonate (0.25 mm) and 10mg Mn were accurately weighed 2 O 3 /Fe 2 O 3 -Al 2 O 3 The supported catalyst (0.15 and mm) is placed in a quartz zone preheating chamber decomposing furnace reactor, the bulk density is 0.76g/ml, the gas-solid ratio is 180L/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 to be: the power is 0.92kW, and the Ar shielding gas is 0.5L/min; introducing H 2 Working medium gas 2.5L/min, CH 4 Reducing agent 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 0.8H, and the analysis result shows that the heavy calcium carbonate is completely decomposed at 640 ℃ and the products are CO and H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) was 7%.
Example 22
Accurately weighing 1g of limestone calcium (1 mm) and 10mg of Mn 3 O 4 NiO=1:7 catalyst (mass ratio) (1 mm) is placed in a quartz zone preheating chamber decomposing furnace reactor, the bulk density is 0.69g/ml, the gas-solid ratio is 140L/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 0.92kW, and the Ar shielding gas is 0.5L/min; introducing H 2 Working medium gas 2.5L/min, CH 4 3.0L/min of reducing agent; 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 heavy calcium carbonate is completely decomposed at 590 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 94%, CO 2 The selectivity of (2) was 6%.
Example 23
1g of heavy calcium carbonate (0.08 mm) and 10mg of iron ore (NiO: cuO: fe=1:2:6:2 (mass ratio) catalyst (0.08 mm) were accurately weighed and placed in a metal (Incoloy 800 HT) riser reactor, the bulk density was 0.81g/ml, the gas-solid ratio was 80L/L at 20 atmospheres, and an arc discharge plasma apparatus was coupled, using 0.5L/min Ar gas displacement reactionAfter about 30 minutes of air in the reactor, the plasma parameters were adjusted as: the power is 0.92kW, and the Ar shielding gas is 0.5L/min; introducing H 2 5L/min as working medium gas and reducing agent; 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 30s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 480 ℃ and the product is H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 98%, CO 2 The selectivity of (2%).
Example 24
Accurately weighing 1g of limestone (0.15 mm) and 10mg of Ni: fe: co=1:2:9 catalyst (mass ratio) (0.15 mm), placing the limestone and the 10mg of Ni: fe: co=1:2:9 catalyst in a metal (the metal material is Inconel 601) riser reactor, wherein the bulk density is 0.78g/ml, the gas-solid ratio of 2 atmospheres 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 to obtain the following components: the power is 0.92kW, and the Ar shielding gas is 0.5L/min; introducing Ar working medium gas 1L/min, H 2 Reducing agent 1L/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 35s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 460 ℃ to obtain H 2 、CO、H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 The selectivity of (2) is 6%, CH 4 The selectivity of (2) was 0.3%.
Example 25
Accurately weighing 1g of heavy calcium carbonate (0.15 mm) and 10mg of iron ore: fe=1:2 (mass ratio) powder catalyst (0.15 mm), placing the mixture into a metal (material is Incoloy800 HT) atmosphere flat kiln reactor, wherein the bulk density is 0.79g/ml, the gas-solid ratio of 30 atmospheres is 160L/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 1.1kW, and the Ar shielding gas is 0.5L/min; introducing H 2 5L/min as working medium gas and reducing agent;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 retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 530 ℃ to obtain H 2 、CO、H 2 O、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 95%, CO 2 The selectivity of (2) was 5%.
Example 26
Accurately weighing 1g of heavy calcium carbonate (0.25 mm) and 10mg of NiFe/MgO-Al 2 O 3 The supported catalyst (0.25 mm) is placed in a quartz atmosphere flat kiln reactor, the bulk density is 0.76g/ml, the gas-solid ratio is 150L/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 0.56kW, and the Ar shielding gas is 0.5L/min; introducing H 2 Working medium gas 5L/min, NH 3 Reducing agent 1.5L/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 at 590 ℃ to obtain H 2 、CO、H 2 O、N 2 、CO 2 Wherein H is 2 O can be removed by condensation, wherein the selectivity of CO is 93%, CO 2 Selectivity of 4%, N 2 The selectivity of (2) was 3%.

Claims (10)

1. Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is characterized in that: the method comprises the steps of adopting one or more than two mixed gases of hydrogen, methane-enriched gas and ammonia gas as a reducing agent, utilizing thermal plasma to supply heat, catalyzing the reducing agent and limestone in a reactor to perform one-step reduction decomposition to generate clinker, and simultaneously CO-producing CO/H-enriched gas 2 Is a gas of (a) a gas of (b).
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: carrying one or two mixtures of reducing gases into a reactor by utilizing hot plasma working medium gas to catalyze, reduce and decompose limestone; 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: the method adopts metal and/or metal oxide as a catalyst, wherein 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.
6. The method according to claim 1, characterized in that:
the hydrogen is from hydrogen of fossil resources, hydrogen obtained by renewable electroelectrolysis of water and hydrogen obtained by photolysis of water;
the methane-rich gas comprises one or more than two mixed gases selected from pure methane gas, mixed gas of methane and low-carbon alkane, natural gas, shale gas and hydrate extracted methane;
the mixed gas of one or more than two of hydrogen, rich methane gas and ammonia gas is used as an effective reducing agent to be mixed with one or more than two of inert atmosphere gas nitrogen, helium gas and argon gas, wherein the volume content of the effective reducing agent in the reaction raw material gas is 5-100%, and the volume content of the inert gas is 0-95%.
7. The method according to claim 1, characterized in that: the reactor is one or more than two of fluidized bed type, moving bed type, cyclone type, spray type and boiling type decomposing furnaces, decomposing furnaces with preheating chambers, fixed bed type reactors and atmosphere flat kiln reactors; 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 metal or metal oxide catalyst comprises particles with certain granularity, superfine powder and a monolithic column form;
the metal or metal oxide catalyst may be packed in the reactor in various ways, including monolithic column form, coated on the reactor wall, directly mixed with limestone feed stock, powder fed separately into the reactor;
the reactor is made of 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 0.1-10mm; 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 and 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 0.1-10mm; 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 and 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 0.1-5mm; 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 parallel 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 0.1-10mm; the particle density is 500-10000kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Residence time is 1s-10s; the gas flow direction is parallel 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 0.1-10mm; 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 countercurrent, cocurrent and bubbling.
CN202210799115.6A 2022-07-06 2022-07-06 Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2) Pending CN117401648A (en)

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