CN115403282A - Clinker prepared by using gas reducing agent to catalyze limestone to reduce and decompose and CO-produce rich CO/H 2 Method (2) - Google Patents
Clinker prepared by using gas reducing agent to catalyze limestone to reduce and decompose and CO-produce rich CO/H 2 Method (2) Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 36
- 239000006028 limestone Substances 0.000 title claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 137
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 239000007789 gas Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000002829 reductive effect Effects 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 116
- 230000014759 maintenance of location Effects 0.000 claims description 94
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 239000010453 quartz Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 239000008187 granular material Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 238000006303 photolysis reaction Methods 0.000 claims description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 292
- 229910002091 carbon monoxide Inorganic materials 0.000 description 172
- 229910000019 calcium carbonate Inorganic materials 0.000 description 146
- 238000004458 analytical method Methods 0.000 description 78
- 238000009833 condensation Methods 0.000 description 76
- 230000005494 condensation Effects 0.000 description 76
- 238000004949 mass spectrometry Methods 0.000 description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 239000004568 cement Substances 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 238000006386 neutralization reaction Methods 0.000 description 11
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 229910001026 inconel Inorganic materials 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 229910001293 incoloy Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910002520 CoCu Inorganic materials 0.000 description 1
- 229910003336 CuNi Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910020413 SiO2—MgO Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/104—Ingredients added before or during the burning process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing clinker by catalytic limestone reduction decomposition and CO-producing rich CO/H 2 The method specifically relates to a method which adopts one or more than two mixed gases of hydrogen, methane and ammonia gas as a reducing agent to directly reduce and decompose the mixed gases into clinker; 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 of the invention can avoid the generation of carbon dioxide by limestone thermal decomposition and simultaneously CO-produce rich CO/H 2 The gas, the specific composition of which is related to the reducing agent and the reaction conditions, can be used as a main component to supply city gas or be used as synthesis raw material gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like. The invention can be used in fluidized bed type, moving bed type and rotary bed typeThe method is realized in a flow type decomposing furnace, a spouting type decomposing furnace, a boiling type decomposing furnace, a decomposing furnace with a preheating chamber, a riser reactor, a fixed bed type reactor and an atmosphere flat kiln, and has the characteristics of simple process, high added value of products, small industrialization difficulty, easy separation of products, good process repeatability, safe and reliable operation and the like.
Description
Technical Field
The invention belongs to the field of cement and hydrated lime manufacturing, and particularly relates to a method for preparing clinker by catalyzing limestone to reduce and decompose in one step and CO/H-rich clinker 2 The method of (1).
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 in the turn released their carbon neutralization goals.
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: 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 sink and carbon transaction; c. transportation: the novel energy traffic model and the light weight are mainly realized.
The carbon emission ratio of the manufacturing and building industries in China is high, and the objective technical problem exists in the way of carbon neutralization. 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 in two rows of households can be realized by replacing clean energy sourcesOne of two major challenges is faced in the carbon of construction and construction industries: chemical reaction of raw materials in the production process of industrial products (cement, steel and the like) to produce CO 2 Emissions are difficult to contain. Therefore, carbon neutralization in manufacturing and building industries necessitates reformation of the prior industrial production technology for the large broad axe.
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 the combustion of fossil fuels with CO produced by the thermal decomposition of the feedstock 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 the domestic cement accounts for 13.91 percent, and according to the data of the Chinese 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 kilograms for producing 1 ton of cement. Currently, the carbon emission coefficient of cement clinker (based on cement clinker yield accounting) in China is about 0.86, that is, producing one ton of cement will produce 860 kg of carbon dioxide, which is obviously higher than paris agreement level, and it is not exaggeration to say that the construction industry needs to realize carbon neutralization, and the cement is the main battlefield. 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 calcining decomposition process, reducing or even avoiding CO while preparing the clinker 2 The discharge is a revolutionary technology,is an effective carbon neutralization technique.
CN101987783A discloses a method for producing quicklime by calcining limestone with gas in a suspension state preheating decomposing furnace, which utilizes surplus gas generated by steel making to calcine limestone to enhance the utilization rate, but the method can not solve the problem of CO fundamentally 2 High emissions. CN 10669887A discloses a calcium carbonate decomposition accelerator, which can reduce the decomposition temperature of calcium carbonate by mixing nitrate with water glass, wherein 0.7-1kg of accelerator is consumed by each ton of calcium carbonate, the temperature reduction is limited, the high emission of CO2 cannot be effectively solved, and a large amount of oxynitride is generated to aggravate pollution.
The invention provides a method for catalyzing limestone to be reduced and decomposed into clinker in one step and CO/H-rich in CO/H 2 The gas method adopts one or more than two mixed gases of hydrogen, rich methane and ammonia gas as a reducing agent, adopts metal or metal oxide as a catalyst, and catalyzes the reduction reaction of the reducing agent and limestone, thereby not only accelerating the reaction rate and reducing the reaction temperature, but also realizing the great emission reduction of carbon dioxide in the cement industry and the hydrated lime industry; CO-producing a gaseous product having a composition, depending on the reducing agent and the reaction conditions, of approximately 20-60% CO and approximately H 2 Content of CO is 10-50% 2 Content < 20%, CH 4 The content is less than 10 percent, can be used as a main component to supply city gas, can also be used as feed gas to prepare high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like, and is 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 by one step and CO/H-rich product 2 The gas method realizes the great emission reduction of carbon dioxide in the cement industry and the hydrated lime industry, is an efficient carbon neutralization technology, and simultaneously coproduces rich CO/H 2 The gas of (2) can be used as a main component to supply city gas, and can also be used as a synthesis raw material gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like.
The technical scheme of the invention is as follows:
catalytic limestone reductive decomposition clinker preparation and CO-production of rich CO/H 2 The method of (1) is carried out,one or more than two mixed gases of hydrogen, methane-rich gas and ammonia gas are used as reducing agents, the reducing agents and limestone are catalyzed in a reactor to be reduced and decomposed in one step to generate clinker, and CO/H-rich gas is CO-produced 2 Of (2) is used.
Based on the above scheme, preferably, the reaction raw material gas takes one or a mixture of two or more of hydrogen, methane and ammonia gas as an effective reducing agent; the hydrogen is hydrogen from fossil resources, hydrogen obtained by renewable electrolysis of water, and hydrogen obtained by photolysis of water; the methane-rich gas comprises one or more than two of pure methane gas, methane and low-carbon alkane mixed gas, natural gas, shale gas and hydrate extracted methane; the effective reducing agent can be mixed with one or more than two of inert atmosphere gases of nitrogen, helium and argon, wherein the total volume content of the effective reducing agent is 5-100%; the volume content of the inert gas in the reaction raw material gas is 0-95%.
Based on the scheme, preferably, the method adopts metal and/or metal oxide as a catalyst, and 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; 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 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, coating on the reactor wall, direct mixing with limestone raw material, powder feeding into the reactor separately.
Based on the scheme, the calcination decomposition reactor is preferably 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 with a preheating chamber, a fixed bed type reactor and an atmosphere open kiln; 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, or a boiling decomposition furnace or a riser 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, preferably, the reaction conditions comprise that the operating pressure is normal pressure to 3MPa, and the temperature is 300 to 1000 ℃; preferably, the reaction pressure is normal pressure to 1MPa, and the reaction temperature is 300 to 500 ℃; or the reaction pressure is 0.2-0.5 MPa; the reaction temperature is 300-600 ℃.
Based on the above-described solution, it is preferable that,
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 size of the particles is 0.1-10mm; the density of the granules is 100-5000kg/m 3 (ii) a The retention time is 0.1-100h; the gas flow direction is divided into countercurrent and cocurrent;
the moving bed is used as a reactor, and the reaction conditions are as follows: qi (Qi)The 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 size of the particles is 0.1-10mm; the density of the granules is 100-5000kg/m 3 (ii) a The retention time is 0.1-100h; 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; 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 size of the particles is 0.1-5mm; the particle density is 1000-10000kg/m 3 (ii) a The retention time is 1s-5min; the gas flow direction is countercurrent;
a fluidized bed or a descending parallel fluidized bed is taken 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 size of the particles is 0.1-10mm; the density of the particles is 500-10000kg/m 3 (ii) a The retention time is 1s-10s; the gas flow direction is parallel flow;
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 size of the particles is 0.1-10mm; the particle density is 500-10000kg/m 3 (ii) a The retention time is 0.1-200h; the gas flow direction is countercurrent, cocurrent and bubbling.
As a further preference, it is possible to,
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 granule density 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, wherein the reaction conditions are as follows: the gas-solid ratio is 5-500L/L; the bulk density is 0.5-5g/ml; flow rate of solids0.5kg-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; 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 technology of the invention can avoid the generation of carbon dioxide by limestone thermal decomposition and simultaneously CO-produce rich CO/H 2 The gas of (1) consists of 20-60% of CO and H 2 Content of 10-50%, CO 2 Content < 20%, CH 4 The content is less than 10 percent, and the product can be used as a main component to be supplied to city gas or used as a synthesis feed gas of high-value chemicals such as olefin, oil products, aromatic hydrocarbon and the like.
(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) and 10mg of Fe were accurately weighed 2 O 3 The catalyst (0.05 mm) was placed in a quartz fixed bed reactor at a bulk density of 0.8g/ml, 100ml/min of hydrogen (99.9%) was continuously passed in cocurrent flow at atmospheric pressure at a gas-to-solid ratio of 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 reacted and decomposed at 550 ℃, and the products are CO and H 2 O、CH 4 、CO 2 ，H 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 Has a selectivity of 9%, CH 4 The selectivity of (2) is 1%.
Example 2 (fixed bed)
Accurately weighed 1g of heavy calcium carbonate (0.08 mm) and 10mg of iron ore catalyst (0.08 mm) into a quartz fixed bed reactor with a bulk density of 0.78g/ml, passed continuously at atmospheric pressure and in parallel into a volume of 50% H of 100ml/min 2 10% Ar/He, gas-solid ratio 80L/L, and raising the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the start and end of the reaction are monitored using mass spectrometry. The retention time is 1.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 580 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 85%, CO 2 Has a selectivity of 14.5%, CH 4 The selectivity of (A) was 0.5%.
Example 3 (fixed bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of Fe were accurately weighed 3 O 4 /Fe 2 O 3 Loading catalyst (0.1 mm) in a quartz fixed bed reactor with bulk density of 0.75g/ml, introducing 100ml/min hydrogen (99.9%) under normal pressure, gas-solid ratio of 100L/L, heating from 300 deg.C to 800 deg.C at 2 deg.C/min, and monitoring decomposition product by mass spectrometryRelative proportions at the beginning and end should be used. The retention time is 2H, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate at 490 ℃ are finished, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 89%, CO 2 Has a selectivity of 10%, CH 4 The selectivity of (A) was 1%.
Example 4 (fixed bed)
1g of ground calcium carbonate (0.12 mm) and 10mg of iron ore powder catalyst (0.12 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.74g/ml, 100ml/min of ammonia (99.9%) was continuously fed in cocurrent at atmospheric pressure, the gas-solid ratio was 110L/L, and the temperature was raised from 300 ℃ to 800 ℃ at 2 ℃/min, during which the relative proportion of the decomposition products at the beginning and at the end of the reaction was monitored by mass spectrometry. The retention time is 2.5H, and the analysis result shows that the heavy calcium carbonate is completely decomposed and ended at 510 ℃, and the products are CO and H 2 O、CO 2 In which H 2 The selectivity of O for removing CO by condensation is 84 percent, and CO 2 The selectivity of (a) was 16%.
Example 5 (fixed bed)
1g of ground calcium carbonate (0.15 mm) and 20mg of Cr were accurately weighed 2 O 3 A powder catalyst (0.15 mm) was placed in a quartz fixed-bed reactor at a bulk density of 0.74g/mi, 150ml/min of hydrogen (99.9%) was continuously fed in cocurrent at atmospheric pressure at a gas-solid ratio of 110L/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 1.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 570 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Has a selectivity of 11.8%, CH 4 The selectivity of (A) was 0.2%.
Example 6 (fixed bed)
1g of ground calcium carbonate (0.2 mm) and 20mg of Cr were accurately weighed 2 O 3 The powder catalyst (0.2 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.73g/ml and was continuously fed in cocurrent flow at atmospheric pressure100ml/min methane (99.9%), gas-to-solid ratio 150L/L, and heating from 300 deg.C to 800 deg.C at 2 deg.C/min, during which the relative proportions of the decomposition products at the beginning and end 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 630 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 89% and CO 2 Selectivity of (2) is 10.8%, CH 4 The selectivity of (A) was 0.2%.
Example 7 (fixed bed)
1g of ground calcium carbonate (0.25 mm) and 20mg of Fe powder catalyst (0.25 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.72g/ml, and passed continuously through a constant flow of atmospheric pressure cocurrent flow into a 70% H cell of 100ml/min 2 Ar, gas-solid ratio of 100L/L, and raising the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, and monitoring the relative proportion of the decomposition products at the beginning and the end by using mass spectrum in the process. The retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 595 ℃, and the products are CO and H 2 O、CO 2 Wherein the selectivity for CO is 89%, CO 2 The selectivity of (3) was 11%.
Example 8 (fixed bed)
Accurately weighing 1g of ground calcium carbonate (0.33 mm) and 10mg of iron ore powder catalyst (0.33 mm) in a quartz fixed bed reactor with a bulk density of 0.72g/ml, and continuously introducing 60% H of 100ml/min in cocurrent flow at normal pressure 2 Ar, gas-solid ratio 140L/L, and heating from 300 ℃ to 900 ℃ at 2 ℃/min, in the process, using mass spectrometry to monitor the relative proportion of decomposition products at the beginning and end. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 480 ℃ and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 89%, CO 2 Selectivity of (2) is 10.8%, CH 4 The selectivity of (2) was 0.2%.
Example 9 (fixed bed)
1g of ground calcium carbonate (0.38 mm) and 10mg of Ni powder catalyst (0.38 mm) were accurately weighed and placed in a quartz fixed bed reactor, and the reactor was packed denselyThe degree is 0.71g/ml, 100ml/min methane (99.9%) is continuously fed in cocurrent flow at atmospheric pressure, the gas-solid ratio is 140L/L, and the temperature is raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and the end of the decomposition products are monitored by mass spectrometry. The retention time is 0.9H, 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 H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 78% and CO 2 Selectivity of (2) is 21%, CH 4 The selectivity of (A) was 1%.
Example 10 (fixed bed)
1g of ground calcium carbonate (0.45 mm) and 10mg of Cr/Al were accurately weighed 2 O 3 The supported catalyst (0.45 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.71g/ml and passed in cocurrent flow at atmospheric pressure continuously into 80% H of 100ml/min 2 10% Ar/10% He, gas-solid ratio of 180L/L, and raising the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end are 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 625 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Selectivity of (2) is 11.7%, CH 4 The selectivity of (A) was 0.3%.
Example 11 (fixed bed)
Accurately weighed 1g of heavy calcium carbonate (0.2 mm) and 10mg of Cr powder catalyst (0.2 mm) into a quartz fixed-bed reactor at a bulk density of 0.74g/ml, and passed continuously in cocurrent flow at atmospheric pressure into a 90% H cell of 100ml/min 2 /10％NH 3 The gas-solid ratio was 80L/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 end 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 590 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Has a selectivity of 11%, CH 4 Has a selectivity of 0.3%, N 2 The selectivity of (2) was 0.7%.
Example 12 (fixed bed)
1g of ground calcium carbonate (0.25 mm) and 100mg of a Cu powder catalyst (0.25 mm) were accurately weighed, placed in a silicon carbide fixed bed reactor with a bulk density of 3g/ml, and 100ml/min of hydrogen (99.9%) was continuously fed in a concurrent manner at atmospheric pressure at a gas-solid ratio of 85L/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 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 580 ℃, and the products are CO and H 2 O、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 The selectivity of (3) was 12%.
Example 13 (fixed bed)
1g of ground calcium carbonate (0.3 mm) and 10mg of Fe were accurately weighed 2 O 3 The CaO supported catalyst (0.3 mm) is placed in a corundum fixed bed reactor, the bulk density is 0.71g/ml, 100ml/min hydrogen (99.9%) is continuously introduced at normal pressure in a concurrent flow mode, the gas-solid ratio is 100L/L, 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 is monitored by mass spectrometry in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 550 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 Has a selectivity of 9.7%, CH 4 The selectivity of (2) was 0.3%.
Example 14 (fixed bed)
1g of ground calcium carbonate (0.08 mm) and 10mg of Fe were accurately weighed 3 O 4 The powder catalyst (0.08 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 fed in cocurrent at atmospheric pressure at a gas-to-solid ratio of 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 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 515 ℃,the products are CO and H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation, with a CO selectivity of 85%, and CO 2 Has a selectivity of 14.7%, CH 4 The selectivity of (A) was 0.3%.
Example 15 (fixed bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of Fe were accurately weighed 3 O 4 /Al 2 O 3 The supported catalyst (0.1 mm) was placed in a zirconium oxide fixed bed reactor with a bulk density of 0.76g/ml, 100ml/min of hydrogen (99.9%) 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 relative proportions of the decomposition products at the beginning and end 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 630 ℃, and the products are CO and H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation with a CO selectivity of 86% and CO 2 Has a selectivity of 13.5%, CH 4 The selectivity of (A) was 0.5%.
Example 16 (fixed bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of Mn were accurately weighed 3 O 4 /Fe 2 O 3 The supported catalyst (0.1 mm) was placed in a zirconium oxide fixed bed reactor with a bulk density of 0.75g/ml, and 500ml/min of hydrogen (99.9%) was continuously fed in cocurrent at atmospheric pressure at a gas-solid ratio of 120L/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 end 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 580 ℃, and the products are CO and H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation with a CO selectivity of 88.5% and CO 2 Has a selectivity of 11%, CH 4 The selectivity of (2) was 0.5%.
Example 17 (fixed bed)
1g of ground calcium carbonate (0.15 mm) and 10mg of Co were accurately weighed 3 O 4 /Fe 2 O 3 The supported catalyst (0.15 mm) is placed on quartzIn a fixed bed reactor, the bulk density was 0.74g/ml, and 60% H of 300ml/min was continuously charged at normal pressure 2 /10％NH 3 Ar// He, gas-solid ratio of 180L/L, and raising the temperature from 200 ℃ to 900 ℃ at 5 ℃/min, during which the relative proportions of the decomposition products at the beginning and end are monitored using mass spectrometry. The retention time is 0.8H, and the analysis result shows that the complete reaction decomposition of the heavy calcium carbonate is finished at 590 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation, with a selectivity for CO of 78% 2 Has a selectivity of 21%, CH 4 Has a selectivity of 0.3%, N 2 The selectivity of (A) was 0.7%.
Example 18 (fixed bed)
2g of ground calcium carbonate (0.25 mm) and 20mg of iron ore: fe were accurately weighed 2 O 3 ∶Fe 3 O 4 Powder catalyst (0.25 mm) with mass ratio of 1: 3 is placed in a quartz fixed bed reactor with bulk density of 0.72g/ml, 400ml/min hydrogen (99.9%) is continuously fed in countercurrent at normal pressure, the gas-solid ratio is 110L/L, the temperature is raised from 200 ℃ to 900 ℃ at 2 ℃/min, and the relative proportion of decomposition products at the beginning and the end is monitored by 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 483 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 91% and CO 2 Selectivity of (2) is 8%, CH 4 Has a selectivity of 0.3%, N 2 The selectivity of (2) was 0.7%.
Example 19 (fixed bed)
1g of ground calcium carbonate (0.55 mm) and 10mg of Cu/MnO were accurately weighed 2 The supported catalyst (0.55 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.70g/ml, 300ml/min hydrogen (99.9%) is continuously introduced in a cocurrent manner at normal pressure, the gas-solid ratio is 200L/L, the temperature is increased from 200 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrum in the process. The retention time is 0.8H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 540 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Has a selectivity of 11.1%, CH 4 The selectivity of (2) was 0.9%.
Example 20 (fixed bed)
1g of limestone calcium (0.8 mm) and 10mg of NiO/CaO supported catalyst (0.8 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.69g/ml, and 200ml/min of ammonia (99.9%) was continuously introduced at atmospheric pressure in parallel with flow, with a gas-solid ratio of 500L/L, and the temperature was raised from 200 ℃ to 800 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and at the end were monitored by mass spectrometry. The retention time is 0.3H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 570 ℃, and the products are CO and H 2 O、N 2 、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 87% 2 Has a selectivity of 7.1%, a selectivity of N2 of 5%, CH 4 The selectivity of (a) was 0.9%.
Example 21 (fixed bed)
1g of limestone (0.1 mm) and 10mg of CaO/Al are accurately weighed 2 O 3 Loading the supported catalyst (0.1 mm) in a fixed bed metal reactor (Inconel 601 as the metal material) with a bulk density of 0.75g/ml, continuously introducing 300ml/min of 80% H at normal pressure 2 /10％NH 3 /N 2 The gas-solid ratio was 90L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end were monitored using mass spectrometry. The retention time is 0.3H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 560 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 85% and CO 2 Has a selectivity of 9.1%, N 2 Has a selectivity of 5% and CH 4 The selectivity of (2) was 0.9%.
Example 22 (fixed bed)
1g of ground calcium carbonate (0.08 mm) and 10mg of manganese ore powder catalyst (0.08 mm) were accurately weighed and placed in a metal (material Incoloy800 HT) fixed bed reverse reaction bedIn the reactor, a bulk density of 0.78g/ml, atmospheric pressure and concurrent continuous introduction of 300ml/min 85% 2 Ar, gas-solid ratio 60L/L, and 2 ℃/min from 300 ℃ to 900 ℃, in the process using mass spectrometry monitoring decomposition products at the beginning, end of the relative proportion. The retention time is 0.3H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 490 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a selectivity for CO of 91%, CO 2 Selectivity of (2) is 3.1%, N 2 Has a selectivity of 5% and CH 4 The selectivity of (a) was 0.9%.
Example 23 (fixed bed)
1g of limestone (0.1 mm) and 10mg of iron ore powder catalyst (0.1 mm) were accurately weighed, placed in a metal (metallic material Inconel 601) fixed bed reactor with a bulk density of 0.76g/ml, and 300ml/min of methane (99.9%) was continuously fed in 2 atm in countercurrent at a gas-solid ratio of 100L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end 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 460 ℃, and the products are CO and H 2 O、CH 4 、CO 2 The products are CO and H 2 O、CH 4 、CO 2 Wherein H is 2 O can be removed by condensation with a CO selectivity of 93%, CO 2 Has a selectivity of 6.8%, CH 4 The selectivity of (A) was 0.2%.
Example 24 (fixed bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of Fe were accurately weighed 2 O 3 /Al 2 O 3 The supported catalyst (0.1 mm) is placed in a fixed bed metal reactor (made of GH 2302) and has a bulk density of 0.75g/ml, and 200ml/min methane (99.9%) is continuously introduced into the reactor at 4 atm in a cocurrent manner, wherein the gas-solid ratio is 300L/L, and the temperature is raised from 300 ℃ to 900 ℃ at 2 ℃/min, and the relative proportion of the decomposition products at the beginning and at the end is monitored by mass spectrometry. The analysis result shows that the heavy calcium carbonate is completely decomposed at 450 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 92% and CO 2 Has a selectivity of 8.8%, CH 4 The selectivity of (2) was 0.2%.
Example 25 (moving bed)
1g of ground calcium carbonate (0.1 mm) and 15mg of manganese ore powder catalyst (0.1 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.75g/ml, and 120ml/min of hydrogen (99.9%) was continuously fed in a countercurrent manner at normal pressure with a gas-solid ratio of 110L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and the end 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 is completely reacted and decomposed at the temperature of 420 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 The selectivity of (3) is 9.8%, CH 4 The selectivity of (2) was 0.2%.
Example 26 (moving bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of iron ore powder catalyst (0.1 mm) were accurately weighed, placed in a quartz fixed bed reactor with a bulk density of 0.74g/mi, and 130ml/min of hydrogen (99.9%) was continuously fed in countercurrent at normal pressure, the gas-solid ratio was 120L/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 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 381 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 The selectivity of (A) is 11.8%, CH 4 The selectivity of (A) was 0.2%.
Example 27 (moving bed)
1g of heavy calcium carbonate (0.05 mm) and 12mg of Ni/MgO supported catalyst (0.05 mm) are accurately weighed and placed in a quartz fixed bed reactor, the bulk density is 0.8g/ml, 120ml/min of hydrogen (99.9%) is continuously introduced in a normal-pressure countercurrent manner, the gas-solid ratio is 60L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative ratio of the beginning and the end of the decomposition product is monitored by mass spectrometry in the processFor example. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 505 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 86% and CO 2 Has a selectivity of 13.4%, CH 4 The selectivity of (2) was 0.6%.
Example 28 (moving bed)
10g of ground calcium carbonate (0.15 mm) and 100mg of Cr/SiO were accurately weighed 2 The supported catalyst (0.15 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.76g/ml, ammonia gas (99.9%) is continuously introduced into the reactor at 1L/min in a countercurrent way 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 relative proportion of the decomposition products at the beginning and the end is 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 478 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 80% and CO 2 Selectivity of (2) is 16.4%, N 2 Selectivity of (2) is 3%, CH 4 The selectivity of (a) was 0.6%.
Example 29 (moving bed)
50g of ground calcium carbonate (0.15 mm) and 0.5g of Fe/ZrO were accurately weighed 2 Loading the supported catalyst (0.15 mm) in a quartz fixed bed reactor with a bulk density of 0.75g/ml, feeding continuously in a countercurrent at normal pressure of 6L/min at 55% 2 /10％NH 3 The gas-solid ratio of the decomposition product is 110L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition product at the beginning and the end is monitored by using a mass spectrum in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 560 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Selectivity of (2) is 6.4%, N 2 Has a selectivity of 5%, CH 4 The selectivity of (a) was 0.6%.
Example 30 (moving bed)
Accurately weighed 12g of ground calcium carbonate (0.5 mm) and 1g of Co/ZrO 2 The supported catalyst (0.5 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.7g/ml, 1.5L/min methane (99.9%) is continuously introduced at normal pressure, the gas-solid ratio is 200L/L, the temperature is raised from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 565 ℃, and the products are CO and H 2 O、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 The selectivity of (2) is 12%.
Example 31 (moving bed)
200g of ground calcium carbonate (0.2 mm) and 2g of iron ore: fe were accurately weighed 2 O 3 = 1: 1 (mass ratio) powder catalyst (0.2 mm) was placed in a quartz fixed bed reactor with a bulk density of 0.75g/ml, and passed continuously through a constant pressure cocurrent flow of 10L/min 80% 2 Ar, gas-solid ratio 500L/L, and 2 ℃/min from 300 ℃ to 900 ℃, in the process using mass spectrometry monitoring decomposition products at the beginning, end of the relative proportion. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely decomposed in the reaction at 465 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90%, CO 2 The selectivity of (3) was 10%.
Example 32 (moving bed)
1kg of ground calcium carbonate (0.25 mm) and 1g of Fe were accurately weighed 3 O 4 ∶Cr 2 O 3 Powder catalyst (0.25 mm) = 1: 1 (mass ratio) is placed in a quartz fixed bed reactor, the bulk density is 0.74g/ml, 20L/min ammonia gas (99.9%) is continuously introduced in a countercurrent way under normal pressure, the gas-solid ratio is 150L/L, 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 is monitored by mass spectrometry in the process. The retention time is 0.6H, and the analysis result shows that the heavy calcium carbonate is completely decomposed in the reaction at 520 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 87% 2 The selectivity of (A) is 6.3％，N 2 Selectivity of (2) is 6%, CH 4 The selectivity of (A) was 0.7%.
Example 33 (moving bed)
200g of ground calcium carbonate (0.55 mm) and 2g of Cu: cr were accurately weighed 2 O 3 Powder catalyst (0.25 mm) = 1: 3 (mass ratio) is placed in a quartz fixed bed reactor, the bulk density is 0.72g/ml, 5L/min of hydrogen (99.9%) is continuously fed in a countercurrent way under normal pressure, the gas-solid ratio is 150L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrum in the process. The retention time is 1H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 540 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Has a selectivity of 5.3%, N 2 Has a selectivity of 6%, CH 4 The selectivity of (A) was 0.7%.
Example 34 (moving bed)
1g of ground calcium carbonate (0.35 mm) and 2g of Mn were accurately weighed 3 O 4 /ZrO 2 The supported catalyst (0.1 mm) is placed in a quartz fixed bed reactor, the bulk density is 0.75g/ml, ammonia gas (99.9%) of 100ml/min is continuously introduced in a countercurrent way at normal pressure, the gas-solid ratio is 190L/L, the temperature is increased from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrum in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 470 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 91% and CO 2 Has a selectivity of 8.3%, CH 4 The selectivity of (A) was 0.7%.
Example 35 (moving bed)
1g of ground calcium carbonate (0.3 mm) and 10mg of MnO were accurately weighed 2 ∶Mn 3 O 4 ∶Fe 2 O 3 Putting powder catalyst (0.1 mm) with mass ratio of 1: 2: 3 in a quartz fixed bed reactor with bulk density of 0.74g/ml, continuously introducing 100ml/min methane (99.9%) under normal pressure in countercurrent mode, and gas-solid ratio of160L/L and a temperature increase of 2 ℃/min from 300 ℃ to 900 ℃ during which the relative proportions of the decomposition products at the beginning and at the end are 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 470 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 90%, and CO 2 Has a selectivity of 9.3%, CH 4 The selectivity of (A) was 0.7%.
Example 36 (moving bed)
1g of ground calcium carbonate (0.2 mm) and 10mg of MnO were accurately weighed 2 ∶Mn 3 O 4 ∶Fe 2 O 3 Co = 1: 3: 1 (mass ratio) powder catalyst (0.1 mm) was placed in a silicon carbide moving bed reactor with a bulk density of 0.77g/ml, and 90% H of 100ml/min was continuously fed at normal pressure 2 Ar, gas-solid ratio of 120L/L, and raising the temperature from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and monitoring the relative proportion of the decomposition products at the beginning and the end by using mass spectrum in the process. The retention time is 0.1H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 480 ℃ and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 91% and CO 2 Has a selectivity of 8.3%, CH 4 The selectivity of (2) was 0.7%.
Example 37 (moving bed)
1g of ground calcium carbonate (0.2 mm) and 10mg of CoCu/ZrO were accurately weighed 2 -Al 2 O 3 The supported catalyst (0.2 mm) is placed in a corundum moving bed reactor, the bulk density is 0.77g/ml, 100ml/min hydrogen (99.9%) is continuously introduced into the reactor in a normal-pressure countercurrent manner, the gas-solid ratio is 110L/L, 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 is monitored by 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 the temperature of 610 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 91% and CO 2 Has a selectivity of 8.3%, CH 4 The selectivity of (A) was 0.7%.
Example 38 (moving bed)
1g of ground calcium carbonate (0.5 mm) and 50mg of MnO were accurately weighed 2 ∶Mn 3 O 4 ∶Fe 2 O 3 Co: cu = 1: 3: 1: 2 (mass ratio) powdered catalyst (0.1 mm) was placed in an alloy steel (Incoloy 800 HT) moving bed reactor with a bulk density of 3g/ml, 200ml/min ammonia gas (99.9%) was continuously fed in countercurrent at atmospheric pressure at a gas-to-solid ratio of 110L/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 end 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 495 ℃ after the reaction is finished, and the products are CO and H 2 O、N 2 、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 90%, CO 2 Has a selectivity of 6.3%, N 2 Has a selectivity of 3%, CH 4 The selectivity of (2) was 0.7%.
Example 39 (moving bed)
1g of ground calcium carbonate (1 mm) and 10mg of Fe/ZrO were accurately weighed 2 -Al 2 O 3 The supported catalyst (0.2 mm) was placed in a moving bed zirconia reactor with a bulk density of 3g/ml, 500ml/min methane (99.9%) was continuously fed at atmospheric pressure at a gas-to-solid ratio of 200L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and end 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 is completely reacted and decomposed at 460 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 92%, CO 2 The selectivity of (3) is 7.6%, CH 4 The selectivity of (2) was 0.4%.
Example 40 (moving bed)
1g limestone (0.3 mm) and 10mg Ni/Fe were accurately weighed 3 O 4 Loading the supported catalyst (0.3 mm) in a moving bed reactor of metal (the metal material is Inconel 601), with a bulk density of 0.76g/ml, and feeding the catalyst into the reactor at normal pressure in countercurrent at 300ml/min continuously to 85% 2 /15％NH 3 The gas-solid ratio is 220L/L and is 2The temperature was increased from 200 ℃ to 900 ℃ during which the relative proportions of the decomposition products at the beginning and at the end 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 530 ℃ and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 89% and CO 2 Has a selectivity of 6.5%, N 2 Selectivity of (2) is 4%, CH 4 The selectivity of (2) was 0.5%.
Example 41 (moving bed)
1g limestone (0.2 mm) and 10mg MnO were accurately weighed 2 /ZrO 2 The MgO supported catalyst (0.2 mm) is placed in a metal (the metal material is Inconel 601) moving bed reactor, the bulk density is 0.76g/ml, hydrogen (99.9%) with the flow rate of 300ml/min is continuously introduced in a countercurrent way under 2 atmospheric pressures, the gas-solid ratio is 180L/L, the temperature is increased from 200 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 0.3H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 500 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 93%, CO 2 Has a selectivity of 6.5%, CH 4 The selectivity of (A) was 0.5%.
Example 42 (moving bed)
1g of ground calcium carbonate (0.1 mm) and 10mg of MnO were accurately weighed 2 Cu: fe: co = 1: 5 (mass ratio) A powder catalyst (0.1 mm) was placed in a moving bed reactor of metal (material GH 2302) with a bulk density of 0.78g/ml, and 14 atmospheres was counter-currently passed continuously through a 200ml/min 5-th-H 2 Ar, gas-solid ratio of 180L/L, and heating from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportion of the decomposition products at the beginning and end is 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 430 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 94%, CO 2 The selectivity of (a) is 5.5%,CH 4 the selectivity of (A) was 0.5%.
Example 43 (moving bed)
1g of limestone (0.2 mm) and 10mg of Co: cu: fe: co: cr = 1: 2: 1 (mass ratio) of a powder catalyst (mass ratio) (0.1 mm) were accurately weighed and placed in a SiC moving bed reactor at a bulk density of 0.78g/ml, and 250ml/min of hydrogen (99.9%) was continuously introduced at 2 atm at a gas-solid ratio of 200L/L and heated from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end 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 449 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 92% and CO 2 The selectivity of (2) was 8%.
Example 44 (moving bed)
1g of ground calcium carbonate (0.2 mm) and 10mg of Cr were accurately weighed 2 O 3 ∶Fe 2 O 3 Powder catalyst (0.1 mm) = 1: 2 (mass ratio) is placed in a metal (material is Hastelloy C) moving bed reactor, the bulk density is 0.76g/ml, ammonia gas (99.9%) of 250ml/min is continuously introduced into the reactor under 18 atm, the gas-solid ratio is 200L/L, the temperature is raised from 300 ℃ to 900 ℃ at 2 ℃/min, and the relative proportion of decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 475 ℃ and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 91%, CO 2 Has a selectivity of 4.5%, N 2 The selectivity of (2) was 4.5%.
Example 45 (moving bed)
1g of ground calcium carbonate (0.2 mm) and 10mg of iron ore: fe were accurately weighed 2 O 3 Putting a powder catalyst (0.2 mm) = 1: 4 (mass ratio) in a metal (made of Incoloy800 HT) moving bed reactor, wherein the bulk density is 0.74g/ml, introducing hydrogen (99.9%) with the concentration of 250ml/min into the reactor continuously in a countercurrent way at 25 atmospheric pressures, the gas-solid ratio is 120L/L, and raising the temperature from 300 ℃ to 900 ℃ at the temperature of 2 ℃/min, wherein mass spectrometry is used for monitoringRelative proportion of decomposition products at the beginning and end. The retention time is 0.1H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 485 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 93%, CO 2 The selectivity of (3) was 7%.
Example 46 (moving bed)
1g limestone (0.3 mm) and 10mg iron ore: fe were accurately weighed 2 O 3 Putting powder catalyst (0.2 mm) = 1: 4 (mass ratio) in metal (material Incoloy 909) moving bed reactor, with bulk density of 0.76g/ml, continuously introducing 15 atm countercurrent into 250ml/min 60% H 2 /10％NH 3 The gas/solid ratio was 150L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative ratio of the decomposition products at the beginning and end was 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 465 ℃ and the products are CO and H 2 O、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 94% and CO 2 Selectivity of (2%), N 2 The selectivity of (2) is 4%.
Example 47 (moving bed)
1g of ground calcium carbonate (0.3 mm) and 15mg of Fe were accurately weighed 3 O 4 Ni: cu = 1: 2 (mass ratio) (catalyst 0.4 mm) was placed in a moving bed metal (material Incoloy800 HT) reactor with a bulk density of 0.73g/ml, and 250ml/min methane (99.9%) was continuously fed in a countercurrent of 30 atmospheres at a gas-to-solid ratio of 100L/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 end 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 480 ℃ and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 92%, CO 2 Has a selectivity of 7.5%, CH 4 The selectivity of (2) was 0.5%.
Example 48 (cyclone decomposition furnace)
1g of ground calcium carbonate (0.1 mm) and 11mg of MnO were accurately weighed 2 Ni: mn = 3: 1: 2 (mass ratio) a powder catalyst (0.1 mm) was placed in a quartz cyclone type decomposing furnace reactor with a bulk density of 0.75g/ml, 120ml/min of hydrogen (99.9%) was continuously fed at normal pressure, a gas-solid ratio was 160L/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 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 570 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 92%, and CO 2 Has a selectivity of 7.5%, CH 4 The selectivity of (2) was 0.5%.
Example 49 (cyclone decomposition furnace)
1g of ground calcium carbonate (0.1 mm) and 11mg of CuNi/ZrO were accurately weighed 2 Loading the supported catalyst (0.1 mm) in a quartz cyclone decomposing furnace reactor with a bulk density of 0.79g/ml, feeding 120ml/min of 85% H in a countercurrent manner at normal pressure 2 Ar, gas-solid ratio of 100L/L, and raising the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, in the process, monitoring the relative proportion of the decomposition products at the beginning and the end by using mass spectrum. The analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 660 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 85%, CO 2 Has a selectivity of 14.5%, CH 4 The selectivity of (2) was 0.5%.
Example 50 (cyclone decomposition furnace)
1g of ground calcium carbonate (0.2 mm) and 12mg of NiO: mn = 3: 1 (mass ratio) catalyst (0.2 mm) were accurately weighed and placed in a corundum cyclone furnace reactor with a bulk density of 0.76g/ml, 120ml/min of ammonia gas (99.9%) was continuously fed in countercurrent at normal pressure, the gas-solid ratio was 300L/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 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 655 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 88% and CO 2 Selectivity of (2) is 8%, N 2 The selectivity of (2) is 4%.
Example 51 (cyclone decomposition furnace)
Accurately weighed 10g of heavy calcium carbonate (0.3 mm) and 90mg of NiO: mn = 3: 1 (mass ratio) powder catalyst (0.1 mm) were placed in a silicon carbide cyclone decomposing furnace reactor with a bulk density of 0.75g/ml, and fed continuously at 85% H of 1L/min in a countercurrent of atmospheric pressure 2 /15％NH 3 The gas-solid ratio was 500L/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 end were monitored using mass spectrometry. The retention time is 0.2H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 608 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 89% and CO 2 Selectivity of (2) is 5.5%, N 2 Selectivity of (2) is 5%, CH 4 The selectivity of (A) was 0.5%.
Example 52 (spurting type decomposing furnace)
50g of ground calcium carbonate (1 mm) and 200mg of iron ore powder catalyst (1 mm) were accurately weighed and placed in a metal (material quality Incoloy800 HT) spouted-type decomposing furnace reactor, the bulk density was 0.69g/ml, 6L/min of hydrogen (99.9%) was continuously fed in a normal-pressure countercurrent manner, the gas-solid ratio was 300L/L, the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, and the relative proportions of the beginning and the end of the decomposition products were monitored by mass spectrometry during the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 660 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 Selectivity of (2) is 5%, N 2 The selectivity of (3) is 5%.
Example 53 (spurting type decomposing furnace)
Accurately weighed 12g of ground calcium carbonate (0.45 mm) and 200mg of NiO/SiO 2 The supported catalyst (0.15 mm) is placed in a corundum spurting type decomposing furnace reactor, the bulk density is 0.74g/ml, and ammonia gas (9) of 1.5L/min is continuously introduced at normal pressure9.9%) and a gas-solid ratio of 210L/L, and the temperature was increased from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end were monitored by mass spectrometry. The retention time is 0.5H, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate at 605 ℃ is finished, and the products are CO and H 2 O、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 88% and CO 2 Has a selectivity of 5%, N 2 The selectivity of (3) was 7%.
Example 54 (spurting type decomposing furnace)
200g of ground calcium carbonate (0.2 mm) and 2g of MnO were accurately weighed 2 Iron ore = 3: 1 (mass ratio) powder catalyst (0.2 mm) was placed in a silicon carbide spouted hearth reactor with a bulk density of 0.75g/ml, and 80% H of 10L/min was continuously introduced into a reactor with a counter-current flow of 5 atm 2 Ar, gas-solid ratio 180L/L, and 2 ℃/min from 300 ℃ to 900 ℃, in the process using mass spectrometry monitoring decomposition products at the beginning, end of the relative proportion. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 560 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 The selectivity of (2) is 10%.
Example 55 (boiling decomposition furnace)
1kg of ground calcium carbonate (0.33 mm) and 10g of CuO: iron ore = 1: 1 (mass ratio) powder catalyst (0.33 mm) were accurately weighed and placed in a metal (material Inconel 601) spouted type decomposing furnace reactor with a bulk density of 0.73g/ml, and 80 h-h of 20L/min was continuously fed in a countercurrent manner under normal pressure 2 Ar, gas-solid ratio 160L/L, and 2 ℃/min from 300 ℃ to 900 ℃, in the process using mass spectrometry monitoring decomposition products at the beginning, end of the relative proportion. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 490 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 92%, CO 2 Selectivity of (2) is 7.5%, CH 4 The selectivity of (A) was 0.5%.
Example 56 (boiling decomposition furnace)
200g of ground calcium carbonate (0.1 mm) and 200mg of NiO: iron ore = 3: 1 (mass ratio) powder catalyst (0.1 mm) were accurately weighed and placed in a quartz boiling decomposition furnace reactor with a bulk density of 0.78g/ml, 5L/min of hydrogen (99.9%) was continuously fed in countercurrent at normal pressure and with a gas-solid ratio of 160L/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 end 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 630 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90%, CO 2 The selectivity of (2) is 10%.
Example 57 (boiling decomposition furnace)
1g of ground calcium carbonate (0.55 mm) and 10mg of NiO: cr were accurately weighed 2 O 3 The catalyst (mass ratio) = 6: 1 (0.15 mm) is placed in a corundum boiling decomposing furnace reactor, the bulk density is 0.74g/ml, 100ml/min of pure hydrogen (99.9%) is continuously introduced under normal pressure, the gas-solid ratio is 160L/L, 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 is monitored by using mass spectrometry in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at the temperature of 610 ℃, and the products are CO and H 2 O、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 81% and CO 2 The selectivity of (A) was 19%.
Example 58 (boiling decomposition furnace)
1g of ground calcium carbonate (0.3 mm) and 10mg of Fe/Al were accurately weighed 2 O 3 The supported catalyst (0.1 mm) was placed in a boiling type decomposing furnace reactor of alloy steel (Incoloy 800 HT) with a bulk density of 0.76g/ml, and 95% H of 100ml/min was continuously charged at normal pressure 2 Ar, gas-solid ratio 100L/L, and 2 ℃/min from 300 ℃ to 900 ℃, in the process using mass spectrometry monitoring decomposition products at the beginning, end of the relative proportion. The retention time is 0.6H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 555 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 91%, and CO 2 The selectivity of (2) was 9%.
Example 59 (boiling decomposition furnace)
1g of ground calcium carbonate (0.15 mm) and 10mg of Fe-Cu-Ni/Al were accurately weighed 2 O 3 The supported catalyst (0.25 mm) was placed in a boiling type decomposing furnace reactor with a bulk density of 0.73g/ml, and 300ml/min of pure ammonia gas was continuously used to bring the iron ore catalyst (120 mesh) into the decomposing furnace at a gas-solid ratio of 160L/L at counter-current normal pressure, and the temperature was raised from 200 ℃ to 900 ℃ at 5 ℃/min, during which the relative proportions of the beginning and end 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 560 ℃ and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 92% and CO 2 The selectivity of (2) was 8%.
Example 60 (decomposing furnace with preheating chamber)
1g of ground calcium carbonate (0.25 mm) and 10mg of Mn were accurately weighed 2 O 3 /Fe 2 O 3 -Al 2 O 3 The supported catalyst (0.15 mm) was placed in a quartz zone preheat chamber decomposition furnace reactor at a bulk density of 0.76g/ml, 300ml/min ammonia (99.9%) was continuously fed at atmospheric pressure at a gas-to-solid ratio of 180L/L, and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and end 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 completely reacts and decomposes at 640 ℃ and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 90% and CO 2 Selectivity of (2) is 5%, N 2 The selectivity of (3) is 5%.
Example 61 (decomposing furnace with preheating chamber)
1g of limestone calcium (1 mm) and 10mg of Mn were accurately weighed 3 O 4 NiO = 1: 7 catalyst (mass ratio) (1 mm) is placed in a quartz-belt preheating-chamber decomposing furnace reactor, the bulk density is 0.69g/ml, and the normal pressure is realized200ml/min of methane (99.9%) were continuously fed in countercurrent at a gas-to-solid ratio of 140L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and at the end 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 590 ℃, and the products are CO and H 2 O、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 92% and CO 2 The selectivity of (3) was 7%.
Example 62 (decomposing furnace with preheating chamber)
1g limestone (0.25 mm) and FeCr/SiO were accurately weighed 2 -ZrO 2 Loading the supported catalyst (0.15 mm) in a metal (Inconel 601) preheating chamber decomposing furnace reactor with a bulk density of 0.75g/ml, and continuously introducing 300ml/min 85% H under normal pressure in countercurrent 2 /N 2 The gas-solid ratio was 140L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end 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 the temperature of 520 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 91%, CO 2 Has a selectivity of 8.5%, CH 4 The selectivity of (2) was 0.5%.
Example 63 (riser reactor)
1g of ground 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 (material Incoloy800 HT) riser reactor, the bulk density was 0.81g/ml, 300ml/min of hydrogen (99.9%) was continuously introduced counter-currently at 20 atm, the gas-solid ratio was 80L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and end of the decomposition products were monitored by mass spectrometry. The retention time is 30s, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 480 ℃ and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 98% and CO 2 The selectivity of (2%).
Example 64 (riser reactor)
1g of limestone (0.15 mm) and 10mg of 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 at a bulk density of 0.78g/ml, and 2 atm was continuously passed through a flow of 85 h of 300ml/min 2 /15％NH 3 The gas-solid ratio was 100L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end were monitored by mass spectrometry. The retention time is 35s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 460 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation, with a CO selectivity of 92%, CO 2 Selectivity of (2%), N 2 Selectivity of (2) is 5.7%, CH 4 The selectivity of (A) was 0.3%.
Example 65 (riser reactor)
1g of ground calcium carbonate (0.25 mm) and 10mg of Mn were accurately weighed 3 O 4 Ni: cu: fe = 1: 7: 2 catalyst (mass ratio) (0.25 mm) was placed in a metal (material GH 2302) riser reactor with a bulk density of 0.78g/ml, 200ml/min methane (99.9%) was continuously fed in counter-current at 4 atmospheres with a gas-solid ratio of 130L/L and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the beginning and end of the decomposition products were monitored by mass spectrometry. The retention time is 60s, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at the temperature of 450 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 94%, CO 2 Has a selectivity of 5.5%, CH 4 The selectivity of (2) was 0.5%.
Example 66 (riser reactor)
Accurately weighing 1g of heavy calcium carbonate (0.45 mm) and 10mg of NiO: cuO = 1: 6 (mass ratio) powder catalyst (0.45 mm) and placing the heavy calcium carbonate and the powder catalyst into a metal (made of Inconel 600) riser reactor, wherein the bulk density is 0.74g/ml, ammonia gas (99.9%) with the concentration of 250ml/min is continuously introduced into the riser reactor in a counter-current manner at 2 atmospheric pressures, and the gas-solid ratio is 200L-L and increasing the temperature from 300 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and at the end are monitored using mass spectrometry. The retention time is 20s, and the analysis result shows that the complete reaction and decomposition of the heavy calcium carbonate at 545 ℃ are finished, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 92% and CO 2 Has a selectivity of 3%, N 2 Selectivity of (2) is 4.7%, CH 4 The selectivity of (2) was 0.3%.
Example 67 (riser reactor)
1g limestone (0.15 mm) and 10mg NiCu/Fe were accurately weighed 2 O 3 The supported catalyst (0.15 mm) was placed in a silicon carbide riser reactor at a bulk density of 0.78g/mi, with 2 atmospheres of continuous introduction of 250ml/min of hydrogen (99.9%) at a gas-to-solid ratio of 220L/L, and with a temperature rise of 2 ℃/min from 300 ℃ to 900 ℃, during which the relative proportions of the decomposition products at the beginning and end were monitored by mass spectrometry. The retention time is 30s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at the temperature of 539 ℃ and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 93%, CO 2 Has a selectivity of 2%, N 2 Selectivity of (2) is 4.7%, CH 4 The selectivity of (2) was 0.3%.
Example 68 (riser reactor)
1g of ground calcium carbonate (0.75 mm) and 10mg of MgO: ni: cu: fe were accurately weighed 3 O 4 Powder catalyst (0.75 mm) = 1: 3: 2 (mass ratio) is placed in a metal (material is Hastelloy C) riser reactor, the bulk density is 0.72g/ml,5 atmospheres are reversely and continuously fed with 250ml/min ammonia (99.9%), the gas-solid ratio is 220L/L, the temperature is raised from 300 ℃ to 900 ℃ at 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 45s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 435 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation, with COSelectivity 93%, CO 2 Selectivity of (2) is 3%, N 2 The selectivity of (2) is 3%.
Example 69 (riser reactor)
1g of ground calcium carbonate (0.15 mm) and MnO were accurately weighed 2 /Al 2 O 3 The supported catalyst (0.15 mm) was placed in a metal (material Incoloy800 HT) riser reactor with a bulk density of 0.78g/ml and 25 atm countercurrent flows continuously through 250ml/min of 90% H 2 /10％NH 3 The gas-solid ratio was 500L/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 end 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 the temperature of 450 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 96% and CO 2 Selectivity of (2) is 1%, N 2 The selectivity of (3%).
Example 70 (riser reactor)
1g limestone (0.85 mm) and 10mg iron ore: cr were accurately weighed 2 O 3 Cu: cr = 2: 1: 2 (mass ratio) powder catalyst (0.85 mm) is placed in a metal (material is Incoloy 909) riser reactor, the bulk density is 0.71g/ml, hydrogen (99.9%) of 250ml/min is continuously introduced in a counter-current manner at 15 atmospheric pressures, the gas-solid ratio is 320L/L, the temperature is raised from 300 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 15s, and the analysis result shows that the heavy calcium carbonate is completely reacted and decomposed at 435 ℃, and the products are CO and H 2 O、CO 2 In which H 2 O can be removed by cold condensation with CO selectivity of 96% and CO 2 The selectivity of (3) was 4%.
Example 71 (atmosphere flat kiln)
1g of heavy calcium carbonate (0.15 mm) and 10mg of iron ore, fe = 1: 2 (mass ratio) powder catalyst (0.15 mm) are accurately weighed and placed in a metal (material is Incoloy800 HT) atmosphere open kiln reactor, the bulk density is 0.79g/ml,30 atmospheric pressure countercurrent flows are continuously introduced with 250ml/min of hydrogen (99.9%), and gas and solid are filledThe ratio was 160L/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 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 ℃, and the products are CO and H 2 O、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 94%, CO 2 The selectivity of (3) was 6%.
Example 72 (atmosphere flat kiln)
1g of ground calcium carbonate (0.25 mm) and 10mg of NiFe/MgO-Al were accurately weighed 2 O 3 The supported catalyst (0.25 mm) is placed in a quartz-atmosphere open kiln reactor, the bulk density is 0.76g/ml, 300ml/min ammonia gas is continuously introduced in a normal-pressure countercurrent mode, the gas-solid ratio is 150L/L, the temperature is increased from 200 ℃ to 900 ℃ at the speed of 5 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is 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 590 ℃, and the products are CO and H 2 O、N 2 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 91% and CO 2 Has a selectivity of 4%, N 2 The selectivity of (3) is 5%.
Example 73 (atmosphere flat kiln)
2g of heavy calcium carbonate (0.15 mm) and 10mg of iron ore powder catalyst (0.15 mm) are accurately weighed and placed in a corundum atmosphere open kiln reactor, the bulk density is 0.79g/ml, 400ml/min of methane is continuously fed in a normal-pressure countercurrent manner, the gas-solid ratio is 190L/L, the temperature is increased from 200 ℃ to 900 ℃ at the speed of 2 ℃/min, and the relative proportion of the decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 0.5H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 463 ℃ and the products are CO and H 2 O、CH 4 、CO 2 In which H is 2 O can be removed by condensation with a CO selectivity of 94%, CO 2 Selectivity of (2) is 5%, CH 4 The selectivity of (A) was 1%.
Example 74 (atmosphere flat kiln)
1g of ground calcium carbonate (1 mm) and 10mg of Mn were accurately weighed 3 O 4 /SiO 2 MgO supported catalyst (1 mm) in a silicon carbide atmosphere open kiln reactor with a bulk density of 0.69g/ml,2 atmospheres continuously charged at 85% H of 300ml/min 2 /10％NH 3 /5％CH 4 The gas-solid ratio was 110L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end 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 540 ℃, and the products are CO and H 2 O、CH 4 、N 2 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 94%, CO 2 Has a selectivity of 3%, a selectivity of N2 of 2%, CH 4 The selectivity of (2) is 1%.
Example 75 (atmosphere flat kiln)
10kg of limestone calcium (0.25 mm) and 10g of Fe/SiO2-MgO supported catalyst (0.25 mm) are accurately weighed and placed in a metal (material is Incoloy800 HT) atmosphere open kiln reactor, the bulk density is 0.75g/ml, 20L/min of methane is continuously introduced at 10 atmospheric pressures, the gas-solid ratio is 200L/L, the temperature is increased from 200 ℃ to 900 ℃ at 2 ℃/min, and the relative proportion of decomposition products at the beginning and the end is monitored by mass spectrometry in the process. The retention time is 0.45H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 500 ℃, and the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 96% and CO 2 Has a selectivity of 3%, CH 4 The selectivity of (A) was 1%.
Example 76 (atmosphere flat kiln)
Accurately weigh 100kg limestone (0.65 mm) and 1kg MgO: fe 2 O 3 Powder catalyst (mass ratio) = 1: 3 (0.65 mm) placed in a metal (metal material is Inconel 601) fixed bed reactor with a bulk density of 0.70g/ml, and 20 atm continuous passage of 30L/min 85% H 2 /15％CH 4 The gas-solid ratio was 400L/L and the temperature was raised from 200 ℃ to 900 ℃ at 2 ℃/min, during which the relative proportions of the decomposition products at the beginning and end were monitored by mass spectrometry. The retention time is 0.45h, and the analysis result shows that the heavy calcium carbonate is completely reversed at 460 DEG CAfter the decomposition is finished, the products are CO and H 2 O、CH 4 、CO 2 In which H 2 O can be removed by condensation with a CO selectivity of 93%, CO 2 Has a selectivity of 6.2%, CH 4 The selectivity of (a) was 0.8%.
Example 77
1g of ground calcium carbonate (0.1 mm) was accurately weighed out and placed in a quartz fixed-bed reactor with a bulk density of 0.78g/ml, 100ml/min of hydrogen (99.9%) was continuously fed in cocurrent flow at atmospheric pressure at a gas-solid ratio of 60L/L, and the temperature was raised from 300 ℃ to 900 ℃ at 2 ℃/min, 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 6H, and the analysis result shows that the heavy calcium carbonate completely reacts and decomposes at 800 ℃, and the products are CO and H 2 O、CH 4 、CO 2 ，H 2 O can be removed by condensation with a CO selectivity of 66%, CO 2 Selectivity of (2) is 33%, 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 850 ℃, and the product is CO 2 。
Claims (10)
1. Catalytic limestone reductive decomposition clinker preparation and CO-production of rich CO/H 2 The method is characterized in that: one or more than two mixed gases of hydrogen, rich methane and ammonia are used as reducing agents, the reducing agents and limestone are catalyzed in a reactor to be reduced and decomposed in one step to generate clinker, and CO/H rich is CO-produced 2 The gas of (2).
2. The method of claim 1, wherein: 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 goldThe metal oxide being 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 、A1 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 hydrogen is hydrogen from fossil resources, hydrogen obtained by renewable electrolysis of water, and hydrogen obtained by photolysis of water;
the methane-rich gas comprises one or more than two of pure methane gas, methane and low-carbon alkane mixed gas, natural gas, shale gas and hydrate extracted methane;
the hydrogen and the mixed gas rich in one or more than two of methane gas and ammonia gas are used as effective reducing agents and are mixed with one or more than two of inert atmosphere gases of nitrogen, helium and argon, wherein the volume content of the effective reducing agents in the reaction raw material gas is 5-100%, and the volume content of the inert gases is 0-95%.
5. 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; preferably a cyclone, a spurt, a boiling decomposing furnace or a riser 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 can be filled in the reactor by different modes, including a monolithic column form, coating on the wall of the reactor, directly mixing with limestone raw material, and independently feeding powder into 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.
6. The method of claim 1, wherein: the reaction pressure is normal pressure to 3MPa; the reaction temperature is 300-1000 ℃.
7. The method of claim 6, wherein: the reaction pressure is normal pressure to 1MPa; the reaction temperature is 300-500 ℃.
8. The method of claim 6, wherein: the reaction pressure is 0.2-0.5 MPa; the reaction temperature is 300-600 ℃.
9. The method of claim 1, wherein:
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 size of the particles is 0.1-10mm; 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 and cocurrent;
the moving 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 0.5-10g/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 granule density is 100-5000kg/m 3 (ii) a The retention 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; 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 size of the particles is 0.1-5mm; density of particles1000-10000kg/m 3 (ii) a The retention time is 1s-5min; the gas flow direction is counter-current;
a fluidized bed or a descending parallel fluidized bed is taken 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 size of the particles is 0.1-10mm; the particle density is 500-10000kg/m 3 (ii) a Residence time 1s-1os; the gas flow direction is parallel flow;
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 size of the particles is 0.1-10mm; the particle density is 500-10000kg/m 3 (ii) a The retention time is 0.1-200h; the gas flow direction is countercurrent, cocurrent and bubbling.
10. The method of claim 9, wherein:
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 granule density 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, wherein 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; 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.
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| GB712929A (en) * | 1951-02-08 | 1954-08-04 | Texaco Development Corp | Improvements in or relating to process for the reduction of reducible metal oxides and the production of carbon monoxide and hydrogen |
| US4594236A (en) * | 1982-09-07 | 1986-06-10 | Skf Steel Engineering Ab | Method of manufacturing calcium carbide from powdered lime and/or limestone |
| CN1995291A (en) * | 2006-01-05 | 2007-07-11 | 尹小林 | Method for producing CO cleaning gas catalyzed by carbonate ore and carbon |
| CN110512043A (en) * | 2019-09-11 | 2019-11-29 | 中南大学 | A kind of method of gas-based shaft kiln calcined limestone coproduction iron ore prereduction product |
| GB202005728D0 (en) * | 2020-04-20 | 2020-06-03 | Univ Oxford Innovation Ltd | Process and catalyst |
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2021
- 2021-05-28 CN CN202110598385.6A patent/CN115403282A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB712929A (en) * | 1951-02-08 | 1954-08-04 | Texaco Development Corp | Improvements in or relating to process for the reduction of reducible metal oxides and the production of carbon monoxide and hydrogen |
| US4594236A (en) * | 1982-09-07 | 1986-06-10 | Skf Steel Engineering Ab | Method of manufacturing calcium carbide from powdered lime and/or limestone |
| CN1995291A (en) * | 2006-01-05 | 2007-07-11 | 尹小林 | Method for producing CO cleaning gas catalyzed by carbonate ore and carbon |
| CN110512043A (en) * | 2019-09-11 | 2019-11-29 | 中南大学 | A kind of method of gas-based shaft kiln calcined limestone coproduction iron ore prereduction product |
| GB202005728D0 (en) * | 2020-04-20 | 2020-06-03 | Univ Oxford Innovation Ltd | Process and catalyst |
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