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CN115403286A - Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose - Google Patents

Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose Download PDF

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CN115403286A
CN115403286A CN202110597395.8A CN202110597395A CN115403286A CN 115403286 A CN115403286 A CN 115403286A CN 202110597395 A CN202110597395 A CN 202110597395A CN 115403286 A CN115403286 A CN 115403286A
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reactor
gas
retention time
solid
bulk density
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包信和
郭晓光
潘秀莲
于洪飞
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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
    • C04B7/364—Avoiding environmental pollution during cement-manufacturing
    • C04B7/367—Avoiding or minimising carbon dioxide emissions
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • C01F11/06—Oxides or hydroxides by thermal decomposition of carbonates
    • 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
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/421—Inorganic materials
    • C04B7/422—Elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Geology (AREA)
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Abstract

The invention relates to a method for preparing clinker and CO-producing CO by catalytic limestone reductive decomposition, in particular to a method for directly reductive decomposition into clinker by using one or a mixture of coal and carbon as a reducing agent; furthermore, metal or metal oxide is used as a catalyst to catalyze the limestone reduction decomposition reaction, so that the reaction rate is accelerated, and the temperature for generating the reaction clinker is reduced. The technology can avoid the thermal decomposition of limestone to generate carbon dioxide, and simultaneously CO-produce CO-rich gas, wherein the specific composition of the gas is related to a reducing agent and reaction conditions, and the gas can be used as a main component to be supplied to city gas or used as a raw material of synthesis gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like. The invention can be realized in fluidized bed type, moving bed type, cyclone type, spouting type, boiling type and other decomposing furnaces, decomposing furnaces with preheating chambers, riser reactors, fixed bed type reactors and atmosphere flat kilns, and has the characteristics of simple process, high product added value, small industrialization difficulty, easy product separation, good process repeatability, safe and reliable operation and the like.

Description

Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose
Technical Field
The invention belongs to the field of cement and hydrated lime manufacturing, and particularly relates to a method for preparing clinker and CO-producing CO by catalyzing limestone through one-step reduction decomposition.
Background
In 12 months 2015, the paris climate has passed paris convention, which has long-term goals: "control the global average gas temperature to be within 2 ℃ compared with the prior industrialization period, and strive to limit the temperature rise to be within 1.5 ℃. The global emission of greenhouse gases reaches the peak as soon as possible, and the net zero emission of greenhouse gases is realized in the second half of the century. From 2023, the global action overall progress will be checked once every 5 years to help each country improve the strength, strengthen international cooperation and achieve the long-term goal of global coping with climate change. To achieve this goal, 30 countries or regions have promulgated their carbon neutralization goals in the near future.
The existing carbon emission structure in China is divided into three large blocks: 51% of power generation and heat supply, 28% of manufacturing and building industry and 10% of transportation. Therefore, the approach to carbon neutralization mainly includes the following aspects: 1) Power generation and heat supply: mainly develops clean energy sources, such as wind, light, water, nuclear energy and the like; 2) Manufacturing and construction industry: a. carbon emission is reduced through energy structure optimization and energy conservation and emission reduction; b. neutralization is realized by participating in carbon capture, carbon sequestration and carbon trading; c. transportation: mainly realized through new forms of energy traffic mode and lightweight.
The carbon emission ratio of the manufacturing and building industries of China is high, and the carbon neutralization way has objective technical problems. The carbon emission structure of China is greatly different from that of European and American countries, the carbon emission ratio of manufacturing industry and construction industry of China as a 'world factory' is about 28 percent, and the carbon emission ratio of European Union and the U.S. is only 13 percent and 9 percent. Carbon neutralization different from power generation, heat supply and transportation can be realized by replacing clean energy sources, and manufacturing and building are realizedCommercial carbon neutralization faces one of two major challenges: chemical reaction of raw materials in the production process of industrial products (cement, steel, etc.) to produce CO 2 Emissions are difficult to contain. Therefore, carbon neutralization in manufacturing and building industries inevitably requires reformation of the large broad-leaved hatchlings on the existing industrial production technology.
Cement is an important basic raw material for national economic construction, and at present, no material can replace the cement at home and abroad. I classify the carbon emissions of cement manufacturing into direct emissions and indirect emissions according to the emission source of carbon dioxide. Direct emission refers to combustion of fossil fuel and CO produced by thermal decomposition of the raw materials 2 Discharging; indirect emissions refer to CO produced by the loss of electrical power and heat energy required in the production or service process 2 And (4) discharging. Calculating and analyzing to obtain CO generated by decomposing raw materials 2 The emission ratio is at its maximum, about 63.01%, followed by the heating emission of CO 2 The ratio is 31.57%, the direct carbon emission accounts for 96.51% in total, and the indirect emission only accounts for 3.49%. The carbon emission of the cement accounts for 84.3 percent of the total carbon emission of the building material industry, the total carbon emission of China accounts for 13.91 percent, and according to the data of the China Cement Association, the 2 degree of intake (2 DS) protocol of the Paris protocol requires that the carbon dioxide emission must be reduced to 520-524 kg when 1 ton of cement is produced. Currently, the carbon emission coefficient of cement clinker (based on cement clinker yield accounting) in China is about 0.86, that is, 860 kilograms of carbon dioxide is generated when one ton of cement is produced, which is obviously higher than the Paris agreement level, and the cement is the main battlefield when the carbon neutralization is realized in the building industry. This means carbon neutralization in the cement industry, with two routes: a revolution in production technology and fuel usage technology; development of back-end carbon capture and conversion technologies. In the future, with the increase of various clean electric energy, fuel heating 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 dosage for producing cement, and a large amount of CO is generated along with the decomposition of the limestone when raw materials are cured 2 Discharge, thereby changing the limestone calcination decomposition process, reducing or even avoiding CO while preparing the clinker 2 The discharge, an innovative technique, is effectiveCarbon neutralization technology.
CN 10669887A discloses a calcium carbonate decomposition accelerator, which can reduce the decomposition temperature of calcium carbonate by mixing nitrate with water glass, consumes 0.7-1kg of accelerator per ton of calcium carbonate, has limited temperature reduction and can not effectively solve the problem of CO 2 High emissions, while producing large amounts of nitrogen oxides to exacerbate pollution. CN101987783A discloses a method for producing lime by calcining limestone with coal gas in a suspension state preheating decomposing furnace, which utilizes surplus coal gas generated by steel making to calcine limestone to enhance the utilization rate, but the method can not fundamentally solve the problem of CO 2 High emissions.
The invention provides a method for catalyzing limestone to be reduced and decomposed into clinker and CO-produce CO in one step, which adopts one or two of coal and carbon as a reducing agent, adopts metal or metal oxide as a catalyst, catalyzes the reduction reaction of the reducing agent and the limestone, accelerates the reaction rate, reduces the reaction temperature, and realizes the great emission reduction of carbon dioxide in the cement industry and the slaked lime industry; simultaneously CO-producing gas products with CO content of 69-100 percent 2 The content is less than 30 percent, the methane is less than 1 percent, the product can be supplied to city gas, and can also be used as feed gas to prepare high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like, thereby being a high-efficiency carbon neutralization technology.
Disclosure of Invention
The invention relates to a method for catalyzing limestone to be reduced and decomposed into clinker aggregate in one step and CO-producing gas rich in CO, which realizes great emission reduction of carbon dioxide in the cement industry and the slaked lime industry, is a high-efficiency carbon neutralization technology, CO-produces gas rich in CO, can be used as a main component to supply city gas, and can also be used as synthesis raw material gas of high-value chemicals such as olefin, oil, aromatic hydrocarbon and the like. The one-step method is that under the same condition of the same reactor, limestone is decomposed into clinker, and CO gas with high added value is CO-produced, and carbon dioxide is not discharged in the decomposition reaction.
The technical scheme of the invention is as follows:
a method for preparing clinker and CO-producing CO by catalytic limestone reduction decomposition adopts one or a mixture of two of coal and carbon as a reducing agent, catalyzes the reducing agent and limestone to generate the clinker by one-step reduction decomposition in a reactor, and CO-produces CO-rich gas.
Based on the scheme, preferably, metal or metal oxide is used as a catalyst to catalyze the reductive decomposition reaction of the reducing agent and limestone to generate clinker, so that the reaction rate is accelerated, the reaction temperature is reduced, the energy consumption is reduced, and meanwhile, CO-rich gas is CO-produced; 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、Si0 2 、Al 2 O 3 、ZrO 2 One or more than two of iron ore and manganese ore; more preferably, the catalyst is Fe or 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 scheme, preferably, the coal is one or a mixture of more than two of coal blocks and coal powder; the carbon comprises one or a mixture of more than two of activated carbon and non-activated carbon from fruit shells, waste wood, other biomass, coal and petroleum coke; as a further preferred, the carbon comprises one or both of activated carbon and graphite.
Based on the scheme, preferably, the calcination decomposition reactor is one or a combination of more than two of a fluidized bed type decomposition furnace, a moving bed type decomposition furnace, a cyclone type decomposition furnace, a spouted type decomposition furnace and a boiling type decomposition furnace, a decomposition furnace with a preheating chamber, a fixed bed type reactor and an atmosphere flat kiln; (ii) a The fluidized bed type reactor comprises a descending parallel fluidized bed type reactor and a riser reactor; further preferably, the reactor is a cyclone, a spouted, a boiling decomposition furnace or a riser reactor.
Based on the above scheme, preferably, the solid reducing agent is fed in powder form simultaneously with the limestone raw material, in a single powder feed or in multiple stages and fractions at different positions in the reactor.
Based on the above scheme, preferably, the metal or metal oxide catalyst comprises one or more than two of artificially synthesized metal or metal oxide, natural iron ore and manganese ore; the metal or metal oxide catalyst comprises a non-supported form, a support dispersed in 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 Iron ore and manganese ore on a composite oxide carrier.
Based on the above scheme, preferably, the metal or metal oxide catalyst comprises a particle with a certain particle size, ultrafine powder, and a monolithic column form; the metal or metal oxide catalyst can be packed in the reactor in different ways, including monolithic column form, coated on the reactor wall, directly mixed with limestone raw material and fed simultaneously, and catalyst powder separately fed into the reactor.
Based on the above scheme, preferably, the material of the calcination decomposition reactor includes one or a combination of two or more of quartz, silicon carbide, zirconia, corundum, and alloy steel.
Based on the scheme, the reaction conditions preferably comprise that the operation pressure is normal pressure to 3MPa; the temperature is 300-1000 ℃; more preferably, the reaction pressure is from normal pressure to 1MPa, and the reaction temperature is from 500 to 800 ℃.
Based on the scheme, preferably, a fixed bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; the bulk density is 0.5-5g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 H; the particle diameter of the particles is 0.001-10mm; the granule density is 100-5000kg/m 3 (ii) a The retention time is 0.01 to 100 hours; the gas flow direction is divided into countercurrent or cocurrent;
the method comprises the following steps of (1) using a moving bed reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 H; the particle diameter of the particles is 0.001-10mm; the granule density is 100-5000kg/m 3 (ii) a The retention time is 0.01-100h; the gas flow direction is divided into countercurrent or cocurrent flow;
taking a riser as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 5-2000L/L; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-500 m 3 H; the particle diameter of the particles is 0.001-5mm; the particle density is 1000-10000kg/m 3 (ii) a The retention 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; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-300 m 3 H; the particle diameter of the particles is 0.001-10mm; the granule density is 500-10000kg/m 3 (ii) a The retention time is 1s-5min; the gas flow direction is cocurrent or countercurrent;
an atmosphere open kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-200t/h; the gas flow is 0.01-500 m 3 H; the particle diameter of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 (ii) a The retention time is 0.1-200h; the gas flow direction is countercurrent, cocurrent or bubbling.
As further preferred:
the fixed bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 density of the granules is 200-2000kg/m 3 (ii) a The retention time is 0.01-10h;
the method comprises the following steps of (1) using a moving bed reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 granule density is 200-2000kg/m 3 (ii) a The retention time is 0.01-2h;
taking a riser as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 5-500L/L; the bulk density is 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 density of the granules is 2000-5000kg/m 3 (ii) a The retention 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; the bulk density is 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 granule density is 500-5000kg/m 3 (ii) a The retention time is 1s-30s;
an atmosphere open kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 granule density is 500-5000kg/m 3 (ii) a The retention time is 0.1-50h.
Advantageous effects
(1) The method for preparing clinker and CO-producing CO by one-step reductive decomposition of limestone can avoid the generation of carbon dioxide by thermal decomposition of limestone, and CO-producing CO with the CO content of 69-100% in gas products 2 Content < 30%, CH 4 The content is less than 1, and the product can be supplied to city gas or used as synthesis raw material gas of high-value chemicals such as olefin, oil product, aromatic hydrocarbon and the like. The technology of the invention can realize 60% carbon dioxide emission reduction in cement industry and slaked lime industry, and has wide industrial application prospect.
(2) The invention can be realized in fluidized bed type, moving bed type, cyclone type, spurting type, boiling type and other decomposing furnaces, decomposing furnaces with preheating chambers, riser reactors, fixed bed type reactors and atmosphere flat kilns, 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.
(3) The use of the catalyst of the invention can further accelerate the reaction rate, reduce the reaction temperature, be beneficial to reducing the energy consumption and improve the reaction efficiency.
Detailed Description
The following examples are only illustrative of the present invention, and the scope of the present invention shall include the full contents of the claims, and is not limited to the examples. In the following examples, each product was detected by gas chromatography and mass spectrometry.
Example 1 (fixed bed)
1g of ground calcium carbonate (0.05 mm), 1g of activated carbon (0.05 mm) and 10mg of Fe were accurately weighed 2 O 3 The catalyst (0.05 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.8g/ml, 100ml/min argon was continuously passed in cocurrent at atmospheric pressure, the gas-solid ratio was 50L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and at the end of the reaction were monitored by mass spectrometry. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate is completely decomposed and ended at 650 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 75%, CO 2 Has a selectivity of 24%, CH 4 The selectivity of (A) was 1%.
Example 2 (fixed bed)
1g of ground calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 10mg of iron ore catalyst (0.08 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.75g/ml, fed with He at 100ml/min continuously at atmospheric pressure in cocurrent flow at a gas-solid ratio of 50L/L, and heated at 2 ℃/min from 300 ℃ to 900 ℃ during which the relative proportion of the decomposition products at the start and end of the reaction was monitored by mass spectrometry. The retention time is 2h, and the analysis result shows that the heavy calcium carbonate is completely decomposed and ended at 690 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 78%, CO 2 The selectivity of (2) was 22%.
Example 3 (fixed bed)
1g of ground calcium carbonate (0.1 mm), 1g of graphite (0.1 mm) and 10mg of Fe were accurately weighed 3 O 4 /Fe 2 O 3 The catalyst (0.1 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.72g/ml, 100ml/min argon was continuously passed in cocurrent at atmospheric pressure, the gas-solid ratio was 45L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and at the end of the reaction were monitored by mass spectrometry. The retention time is 1.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 680 ℃, and the products are CO and CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 82% and CO 2 Selectivity of (2) CH 4 The selectivity of (A) was 1%.
Example 4 (fixed bed)
1g of ground 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 and placed in a quartz fixed bed reactor with a bulk density of 0.71g/ml, 100ml/min of argon was continuously fed in cocurrent at atmospheric pressure, with a gas-solid ratio of 40L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the start and end of the reaction were monitored by mass spectrometry. The retention time is 2h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 650 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 82%, CO 2 The selectivity of (2) is 18%.
Example 5 (fixed bed)
1g of ground calcium carbonate (0.09 mm), 1g of coal (0.09 mm) and 20mg of iron ore (0.05 mm) were accurately weighed, placed in a quartz fixed-bed reactor with a bulk density of 0.73g/ml, 100ml/min of argon was continuously fed in cocurrent at atmospheric pressure at a gas-solid ratio of 100L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 655 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 89%, CO 2 The selectivity of (3) was 11%.
Example 6 (fixed bed)
1g of ground 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) were accurately weighed into a zirconia fixed bed reactor, with a bulk density of 0.70g/ml, 100ml/min of argon was continuously passed in cocurrent at atmospheric pressure, with a gas-to-solid ratio of 120L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of decomposition products were monitored by mass spectrometry. The retention time is 0.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 610 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 88%, CO 2 The selectivity of (3) was 12%.
Example 7 (fixed bed)
1g of ground calcium carbonate (0.5 mm), 1g of coal/activated carbon/graphite = 1: (weight ratio)1 (mass ratio) (0.05 mm) and 10mg of iron ore catalyst (0.5 mm) are placed in a corundum fixed bed reactor, the bulk density is 0.68g/ml, 100ml/min of argon is continuously introduced under normal pressure in a concurrent flow mode, the gas-solid ratio is 110L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at the temperature of 630 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 85%, CO 2 The selectivity of (A) is 15%.
Example 8 (fixed bed)
1g of ground calcium carbonate (0.6 mm), 1g of coal (0.6 mm) and 10mg of Fe were accurately weighed 2 O 3 the/CaO catalyst (0.5 mm) was placed in a silicon carbide fixed bed reactor with a bulk density of 0.67g/ml, 100ml/min of hydrogen (99.9%) was continuously fed co-currently at atmospheric pressure with a gas-solid ratio of 200L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 650 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 85%, CO 2 The selectivity of (3) was 15%.
Example 9 (fixed bed)
1g of ground calcium carbonate (0.05 mm), 1g of activated carbon (0.05 mm) and 10mg of Fe were accurately weighed 3 O 4 The catalyst (0.05 mm) was placed in an alloy steel (Incoloy 800 HT) fixed bed reactor with a bulk density of 0.8g/ml, 100ml/min hydrogen (99.9%) was continuously passed in cocurrent flow at atmospheric pressure with a gas-to-solid ratio of 300L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.3h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 640 ℃ and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (3) was 10%.
Example 10 (fixed bed)
1g of ground calcium carbonate (0.08 mm), 1g of activated carbon (0.07 mm) and 10mg of Fe were accurately weighed 3 O 4 /Al 2 O 3 Catalyst (0.06 mm) is placed inIn a zirconia fixed bed reactor, the bulk density is 0.78g/mi, 100ml/min of hydrogen (99.9%) is continuously introduced at normal pressure in a cocurrent manner, the gas-solid ratio is 300L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 0.2h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 650 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 86%, CO 2 Has a selectivity of 13.5%, CH 4 The selectivity of (2) was 0.5%.
Example 11 (fixed bed)
100g of ground calcium carbonate (0.08 mm), 200g of coal (0.08 mm) and 2g of Mn were accurately weighed 3 O 4 The catalyst (0.08 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.77g/ml, 1L/min of argon was continuously passed in cocurrent flow at atmospheric pressure, the gas-solid ratio was 500L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 633 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 85%, CO 2 Has a selectivity of 14%, CH 4 The selectivity of (2) is 1%.
Example 12 (fixed bed)
1g of ground calcium carbonate (1 mm), 1g of coal (1 mm) and 10mg of manganese ore catalyst (1 mm) were accurately weighed, placed in a metal (material Incoloy800 HT) fixed bed reactor, with a bulk density of 0.62g/ml, argon gas was continuously passed in cocurrent flow at 20 atm and 200ml/min at a gas-solid ratio of 100L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.8h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at the temperature of 630 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 85%, CO 2 The selectivity of (3) was 15%.
Example 13 (moving bed)
1g of ground 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 fixed bed reactor,the bulk density is 0.79g/ml, argon gas of 120ml/min is continuously introduced in a normal-pressure countercurrent manner, the gas-solid ratio is 50L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by using mass spectrometry in the process. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 680 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 86%, CO 2 The selectivity of (3) was 14%.
Example 14 (moving bed)
1g of ground calcium carbonate (0.06 mm), 1g of activated carbon (0.06 mm) and 10mg of iron ore catalyst (0.06 mm) were accurately weighed and placed in a corundum fixed bed reactor with a bulk density of 0.79g/ml, argon gas was continuously introduced at 130ml/min in a countercurrent manner at normal pressure with a gas-solid ratio of 55L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of decomposition products were monitored by mass spectrometry. The retention time is 2h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 630 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 81%, CO 2 Has a selectivity of 18.8%, CH 4 The selectivity of (2) was 0.2%.
Example 15 (moving bed)
1g of ground calcium carbonate (0.1 mm), 1g of activated carbon/graphite = 1: 1 (mass ratio) (0.1 mm) and 12mg of Ni/MgO catalyst (0.1 mm) were accurately weighed and placed in a silicon carbide fixed bed reactor with a bulk density of 0.75g/ml, argon gas was continuously fed at 120ml/min in a countercurrent manner at normal pressure at a gas-solid ratio of 100L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 635 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 83%, CO 2 The selectivity of (3) was 17%.
Example 16 (moving bed)
Accurately weighing 10g of ground calcium carbonate (1 mm), 10g of activated carbon/graphite/coal = 1: 1 (mass ratio) (1 mm) and 100mg of iron ore catalyst (1 mm) in a quartz fixed bed reactor, wherein the bulk density is 0.68g/ml, continuously introducing 1L/min of argon under normal pressure in a counter-current manner, and the gas-solid ratio100L/L and increasing the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products are monitored using mass spectrometry. The retention time is 0.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 708 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 650%, CO 2 The selectivity of (A) was 19%.
Example 17 (moving bed)
1g of ground 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: 3: 1 catalyst (mass ratio) (0.5 mm) was placed in a moving bed reactor of silicon carbide with a bulk density of 0.72g/ml, 100ml/min argon was continuously passed in countercurrent at atmospheric pressure with a gas-solid ratio of 200L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.2h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 610 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (3) was 10%.
Example 18 (moving bed)
1g of ground calcium carbonate (0.1 mm), 1g of activated carbon/coal = 1: 3 (mass ratio) (0.1 mm) and 10mg of iron ore catalyst (0.1 mm) were accurately weighed and placed in an alloy steel (Incoloy 800 HT) moving bed reactor with a bulk density of 0.71g/ml, 100ml/min of helium was continuously fed in countercurrent at 15 atm at a gas-solid ratio of 300L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of decomposition products were monitored using mass spectrometry. The retention time is 0.5h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 635 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 90%, CO 2 Has a selectivity of 9.3%, CH 4 The selectivity of (2) was 0.7%.
Example 19 (moving bed)
10g of ground calcium carbonate (0.08 mm), 10g of coal (0.08 mm) and 10mg of Fe/ZrO were accurately weighed 2 -Al 2 O 3 The catalyst (0.08 mm) was placed in a moving bed zirconia reactor with a bulk density of 0.78g/ml, argon gas of 500ml/min was continuously introduced in countercurrent at normal pressure, the gas-solid ratio was 150L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.2h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 630 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (3) was 10%.
Example 21 (moving bed)
1g of ground calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 10mg of MnO were accurately weighed 2 Cu: fe: co = 1: 5 catalyst (mass ratio) (0.08 mm) was placed in a moving bed metal (GH 2302) reactor with a bulk density of 0.78g/ml, argon gas was continuously introduced into the reactor at a pressure of 14 atm in a countercurrent flow of 200ml/min at a gas-solid ratio of 250L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.08h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 590 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 94%, CO 2 The selectivity of (3) was 6%.
Example 22 (cyclone decomposition furnace)
1g of ground calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 11mg of MnO were accurately weighed 2 Ni: mn = 3: 1: 2 (mass ratio) (0.08 mm) in a quartz cyclone decomposing furnace reactor with a bulk density of 0.78g/ml, introducing 120ml/min argon continuously in a countercurrent manner at normal pressure with a gas-solid ratio of 50L/L, raising the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, and monitoring the beginning, the end and the relative proportion of decomposed products by using mass spectrometry in the process. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 670 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 85%, CO 2 Has a selectivity of 14.5%, CH 4 The selectivity of (A) was 0.5%.
Example 23 (cyclone decomposition furnace)
1g of ground calcium carbonate (0.1 mm), 1.5g of activated carbon/coal = 1: 1 (mass ratio) (0.1 mm) and 12mg of NiO: mn = 3: 1 catalyst (mass ratio) (0.1 mm) were accurately weighed and placed in a steel flaskIn the reactor of the jade cyclone decomposing furnace, the bulk density is 0.75g/ml, argon gas with the volume of 120ml/min is continuously introduced in a cocurrent flow mode at normal pressure, the gas-solid ratio is 100L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 0.7h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 645 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 80%, CO 2 The selectivity of (2) is 20%.
Example 24 (cyclone decomposition furnace)
10g of ground calcium carbonate (0.25 mm), 10g of activated carbon/coal = 1: 1 (mass ratio) (0.25 mm) and 2g of NiO: mn = 3: 1 (mass ratio) (0.25 mm) were accurately weighed and placed in a silicon carbide cyclone decomposing furnace reactor with a bulk density of 0.72g/ml, 1L/min of argon was continuously fed in a countercurrent manner at normal pressure at a gas-solid ratio of 100L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.6h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 728 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 85%, CO 2 The selectivity of (2) is 15%.
Example 25 (spurting type decomposing furnace)
50g of ground 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) were accurately weighed into a metal (material Incoloy800 HT) spouted calciner reactor, the bulk density was 0.79 g/mi, 6L/min of argon was continuously fed in a countercurrent manner at normal pressure, the gas-solid ratio was 150L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 550 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (2) is 10%.
Example 26 (spurting type decomposing furnace)
200g of ground calcium carbonate (0.1 mm), 200g of activated carbon/coal = 1: 1 (mass ratio) (0.1 mm), and 2g of MnO were accurately weighed 2 Iron ore = 3: 1 catalyst (mass ratio) (0.1 mm)Placing the silicon carbide in a reactor of a silicon carbide spurting decomposing furnace, wherein the bulk density is 0.72g/ml, 5 atmospheres are reversely and continuously introduced with 10L/min of argon, the gas-solid ratio is 250L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 0.1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 615 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (2) is 10%.
Example 27 (boiling decomposition furnace)
1kg of ground calcium carbonate (0.2 mm), 1kg of activated carbon/coal = 1: 1 (mass ratio) (0.2 mm) and 10g of CuO: iron ore = 1: 1 (mass ratio) (0.2 mm) were accurately weighed and placed in a metal (material Inconel 601) spouted calciner reactor with a bulk density of 0.71g/ml, 20L/min of argon was continuously fed in countercurrent at 5 atm and a gas-solid ratio of 150L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 0.6h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 580 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 89%, CO 2 Selectivity of (2) is 10.5%, CH 4 The selectivity of (A) was 0.5%.
Example 28 (boiling decomposition furnace)
1g of ground calcium carbonate (1 mm), 1g of activated carbon/coal = 1: 1 (mass ratio) (1 mm), and 10mg of Fe/Al were accurately weighed 2 O 3 The catalyst (1 mm) was placed in a boiling decomposition furnace reactor of alloy steel (Incoloy 800 HT) at a bulk density of 0.68g/ml, with 20 atmospheres of counter-current continuous argon flow at 100ml/min, a gas-to-solid ratio of 150L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 625 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 91%, CO 2 The selectivity of (3) was 9%.
Example 29 (decomposing furnace with preheating chamber)
Accurately weigh 1g of heavyCalcium 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) was placed in a quartz belt preheat chamber decomposition furnace reactor at a bulk density of 0.67g/ml, 300ml/min argon was continuously passed in countercurrent at atmospheric pressure at a gas-to-solid ratio of 80L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 2h, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate at 704 ℃ are finished, and the products are CO and CO 2 Wherein the selectivity for CO is 90%, CO 2 The selectivity of (2) is 10%.
Example 30 (decomposing furnace with preheating chamber)
1g limestone (0.5 mm), 1.5g coal (0.5 mm) and FeCr/SiO were accurately weighed 2 -ZrO 2 The catalyst (0.5 mm) was placed in a metal (Inconel 601 metal material) preheat chamber decomposition reactor with a bulk density of 0.70g/ml, 300ml/min argon was continuously fed in countercurrent at atmospheric pressure at a gas-to-solid ratio of 120L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 690 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 91%, CO 2 Has a selectivity of 8.5%, CH 4 The selectivity of (2) was 0.5%.
Example 31 (riser reactor)
1g of ground calcium carbonate (0.08 mm), 1g of coal (0.08 mm) and 10mg of Mn were accurately weighed 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 with a bulk density of 0.79g/ml, 300ml/min argon was continuously fed counter-currently at 10 atm at a gas-to-solid ratio of 60L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 1min, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 600 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 95%, CO 2 Selectivity of (2)The content was 5%.
Example 32 (riser reactor)
1g limestone (0.15 mm), 1g coal/graphite = 1: 1 (mass ratio) (0.15 mm) and 10mg Ni: fe: co = 1: 2: 9 catalyst (mass ratio) (0.15 mm) were accurately weighed into a metal (metal material is Inconel 601) riser reactor, 300ml/min of argon gas was continuously fed in counter-current at 2 atm, the gas-solid ratio was 100L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of decomposition products were monitored using mass spectrometry. The retention time is 0.5min, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 590 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity of CO is 96 percent, and CO 2 Has a selectivity of 3.7%, CH 4 The selectivity of (2) was 0.3%.
Example 33 (riser reactor)
1g of ground calcium carbonate (0.5 mm), 1g of coal/graphite = 1: 1 (mass ratio) (0.5 mm), and 10mg of Mn were accurately weighed 3 O 4 Ni: cu: fe = 1: 7: 2 catalyst (mass ratio) (0.5 mm) was placed in a metal riser reactor (made of GH 2302) with a bulk density of 0.70g/ml, argon gas was continuously introduced at 200ml/min in a countercurrent of 4 atmospheres at a gas-solid ratio of 150L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 1min, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 600 ℃, and the products are CO and CH 4 、 CO 2 Wherein the selectivity for CO is 94%, CO 2 Has a selectivity of 5.5%, CH 4 The selectivity of (2) was 0.5%.
Example 34 (riser reactor)
1g of limestone (1 mm), 1.5g of coal/graphite = 1: 1 (mass ratio) (1 mm), and 10mg of NiCu/Fe were accurately weighed 2 O 3 The catalyst (1 mm) is placed in a silicon carbide riser reactor, the bulk density is 0.70g/ml, argon gas with the volume of 250ml/min is continuously introduced in a countercurrent way at 2 atmospheric pressures, the gas-solid ratio is 200L/L, the temperature is increased from 300 ℃ to 900 ℃ at 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The residence time was set at 45s and,the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 609 ℃ and the products are CO and CO 2 Wherein the selectivity for CO is 93%, CO 2 The selectivity of (2) was 7%.
Example 36 (riser reactor)
1g of ground calcium carbonate (0.25 mm), 2g of coal (0.25 mm) and 10mg of MgO: ni: cu: fe were accurately weighed 3 O 4 = 1: 3: 2 (mass ratio) (0.25 mm) was placed in a metallic (material Hastelloy C) riser reactor with a bulk density of 0.73g/ml, argon was continuously introduced in a countercurrent of 5 atmospheres at a gas-solid ratio of 400L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of the decomposition products were monitored by mass spectrometry. The retention time is 10s, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 585 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 93%, CO 2 The selectivity of (3) was 7%.
Example 37 (riser reactor)
1g limestone (0.55 mm), 2g coal (0.55 mm) and MnO were accurately weighed 2 /Al 2 O 3 The catalyst (0.55 mm) was placed in a metal (material Incoloy800 HT) riser reactor with a bulk density of 0.73g/ml,25 atmospheres counter-current flow of 250ml/min argon gas continuously with a gas-to-solid ratio of 200L/L and a 2 ℃/min temperature increase from 300 ℃ to 900 ℃ during which the start, end and relative proportions of the decomposition products were monitored using mass spectrometry. The retention time is 30s, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 610 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 80%, CO 2 The selectivity of (2) is 20%.
Example 38 (atmosphere flat kiln)
1g of ground calcium carbonate (0.05 mm), 2g of coal (0.05 mm) and 10mg of iron ore, fe = 1: 2 (mass ratio) (0.05 mm) were accurately weighed into a metal (material Incoloy800 HT) atmosphere open kiln reactor, the bulk density was 0.8g/ml, 250ml/min of hydrogen (99.9%) was continuously fed at 10 atmospheres, the gas-solid ratio was 50L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportion of decomposition products were monitored by mass spectrometry. Residence timeThe reaction time is 3h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 730 ℃, and the products are CO and CO 2 Wherein the selectivity of CO is 88 percent, CO 2 The selectivity of (3) was 12%.
Example 39 (atmosphere flat kiln)
1g of ground calcium carbonate (0.1 mm), 2g of coal (0.1 mm) and 10mg of NiFe/MgO-Al were accurately weighed 2 O 3 The catalyst (0.1 mm) is placed in a quartz atmosphere open kiln reactor, the bulk density is 0.74g/ml, 300ml/min argon is continuously introduced in a countercurrent way under normal pressure, the gas-solid ratio is 80L/L, the temperature is increased from 200 ℃ to 900 ℃ at the speed of 5 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 30s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 630 ℃, and the products are CO and CO 2 Wherein the selectivity for CO is 91%, CO 2 The selectivity of (3) was 9%.
Example 40 (atmosphere flat kiln)
Accurately weighed 100g of ground calcium carbonate (0.5 mm), 150g of coal/activated carbon = 1: 2 (mass ratio) (0.5 mm) and 10mg of Cu (0.5 mm) were placed in a corundum atmosphere open kiln reactor with a bulk density of 0.71g/ml, 400ml/min of argon was continuously fed in countercurrent at normal pressure, the gas-solid ratio was 120L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportion of decomposition products were monitored by mass spectrometry. The retention time is 5h, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 613 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 94%, CO 2 Selectivity of (2) is 5%, CH 4 The selectivity of (A) was 1%.
Example 41 (atmosphere flat kiln)
10kg of limestone calcium (1 mm), 10kg of coal/activated carbon = 1: 2 (mass ratio) (1 mm) and 100g of Fe/SiO2-MgO catalyst (1 mm) were accurately weighed into a metal (material Incoloy800 HT) atmosphere open kiln reactor, the bulk density was 0.69g/ml, 20L/min of argon was continuously fed in countercurrent at 10 atm, the gas-solid ratio was 300L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the start, end and relative proportions of decomposition products were monitored by mass spectrometry. The retention time is 3h, and the analysis result shows that the heavy carbon is generatedThe calcium carbonate completely reacts and decomposes at 670 ℃ to obtain products of CO and CO 2 Wherein the selectivity for CO is 96%, CO 2 Has a selectivity of 3%, CH 4 The selectivity of (A) was 1%.
Example 42 (atmosphere flat kiln)
Accurately weighed 100kg limestone (3 mm), 110kg coal/activated carbon = 1: 2 (mass ratio) (3 mm) and 1kg MgO: fe 2 O 3 Catalyst (mass ratio) = 1: 3 (3 mm) is placed in a metal (metal material is Inconel 601) fixed bed reactor, the bulk density is 0.65 g/ml,30 atmospheres are continuously introduced with 30L/min of argon, the gas-solid ratio is 80L/L, the temperature is increased from 200 ℃ to 900 ℃ at 2 ℃/min, and the beginning, the end and the relative proportion of decomposition products are monitored by mass spectrometry in the process. The retention time is 10h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 560 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 90%, CO 2 Has a selectivity of 9.2%, CH 4 The selectivity of (2) was 0.8%.
Example 43
1g of ground calcium carbonate (0.1 mm) and 1g of activated carbon coal = 1: 1 (0.1 mm) were accurately weighed into a quartz fixed bed reactor with a bulk density of 0.76g/ml, 100ml/min of argon was continuously passed in cocurrent flow at atmospheric pressure at a gas-solid ratio of 80L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min for a residence time of 8h, during which the relative proportions of the decomposition products at the start and end of the reaction were monitored by mass spectrometry. The retention time is 1h, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 800 ℃, and the products are CO and CH 4 、CO 2 Wherein the selectivity for CO is 75%, CO 2 Has a selectivity of 24%, CH 4 The selectivity of (A) was 1%.
Comparative example 1
1g of ground calcium carbonate is accurately weighed and placed in a quartz fixed bed reactor, 100ml/min of argon is continuously introduced at normal pressure, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of decomposition products at the beginning and the end of the reaction is monitored by mass spectrometry in the process. The analysis result shows that the heavy calcium carbonate is completely decomposed at 900 ℃, and the product is CO 2 。

Claims (10)

1. A method for preparing clinker and CO-producing CO by catalytic limestone reductive decomposition is characterized in that: one or a mixture of coal and carbon is used as a reducing agent, the reducing agent and limestone are catalyzed in a reactor to be reduced and decomposed in one step to generate clinker, and CO is CO-produced.
2. The method of claim 1, wherein: the carbon comprises one or two of activated carbon and graphite; 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 than two of iron ore and manganese ore.
3. The method of claim 2, wherein: the catalyst is Fe or Fe 2 O 3 、Fe 3 O 4 One or more than two of CaO, iron ore, manganese ore and alloy steel.
4. The method of claim 1, wherein: the reactor is one or the 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 reactor comprises a descending parallel fluidized bed type and a riser reactor.
5. The method of claim 4, wherein: the reactor is a spiral-flow type, a spouting type or a boiling type decomposing furnace or a riser reactor.
6. The method of claim 1, wherein: the reducing agent is fed with limestone raw materials in a powder form at the same time, is fed with single powder at one time or is fed with multiple sections and times at different positions of the reactor;
the metal or metal oxide catalyst comprises particles with certain particle size, ultrafine powder and an integral column form;
the metal or metal oxide catalyst is filled in the reactor in different modes, including an integral column form, coated on the wall of the reactor, directly mixed with limestone raw material and fed simultaneously, and catalyst powder is independently fed in the reactor;
the material of the reactor comprises one or the combination of more than two of quartz, silicon carbide, zirconia, corundum and alloy steel.
7. The method of claim 1, wherein: the reaction pressure is normal pressure to 3MPa; the reaction temperature is 300-1000 ℃.
8. The method of claim 7, wherein: the reaction pressure is normal pressure-1 MPa, and the reaction temperature is 500-800 ℃.
9. The method of claim 1, wherein:
the fixed bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; the bulk density is 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 granule density is 100-5000kg/m 3 (ii) a The retention time is 0.01-100h; the gas flow direction is divided into countercurrent or cocurrent;
the method comprises the following steps of (1) using a moving bed reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 2-2000L/L; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-200 m 3 H; the particle diameter of the particles is 0.001-10mm; the granule density is 100-5000kg/m 3 (ii) a The retention time is 0.01-10h; the gas flow direction is divided into countercurrent or cocurrent;
taking a riser as a reactor, and 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 (ii) a The retention time is 1s-5min; the gas flow direction is counter-current;
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; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-100t/h; the gas flow is 0.01-300 m 3 H; the particle diameter of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 (ii) a The retention time is 1s-5min; the gas flow direction is cocurrent or countercurrent;
an atmosphere open kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-2000L/L; the bulk density is 0.5-10g/ml; the solid flow is 0.05kg-200t/h; the gas flow is 0.01-500 m 3 H; the particle diameter of the particles is 0.001-10mm; the particle density is 500-10000kg/m 3 (ii) a The retention time is 0.1-200h; the gas flow direction is counter current, co-current or bubbling.
10. The method of claim 9, wherein:
a fixed bed is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 density of the granules is 200-2000kg/m 3 (ii) a The retention time is 0.01-10h;
the method comprises the following steps of (1) using a moving bed reactor, wherein the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 density of the granules is 200-2000kg/m 3 (ii) a The retention time is 0.01-2h;
taking a riser as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 5-500L/L; the bulk density is 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 granule density is 2000-5000kg/m 3 (ii) a The retention 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; the bulk density is 0.5-5g/ml; fixing deviceThe volume 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 granule density is 500-5000kg/m 3 (ii) a The retention time is 1s-30s;
an atmosphere open kiln is used as a reactor, and the reaction conditions are as follows: the gas-solid ratio is 10-500L/L; the bulk density is 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 granule density is 500-5000kg/m 3 (ii) a The retention time is 0.1-50h.
CN202110597395.8A 2021-05-28 2021-05-28 Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose Pending CN115403286A (en)

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