CN117401648A - Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2) - Google Patents
Thermal plasma coupled gas reducer catalyzed limestone reduction and decomposition to prepare clinker and CO-produce CO/H-enriched product 2 Is a method of (2) Download PDFInfo
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- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 45
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 32
- 239000006028 limestone Substances 0.000 title claims abstract description 32
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 176
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 37
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- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 7
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000012159 carrier gas Substances 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
- 238000009616 inductively coupled plasma Methods 0.000 claims description 2
- 239000011261 inert 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 76
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 36
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 114
- 238000004458 analytical method Methods 0.000 description 58
- 229910000019 calcium carbonate Inorganic materials 0.000 description 57
- 229910002091 carbon monoxide Inorganic materials 0.000 description 39
- 238000004949 mass spectrometry Methods 0.000 description 29
- 230000001681 protective effect Effects 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 238000009833 condensation Methods 0.000 description 26
- 230000005494 condensation Effects 0.000 description 26
- 239000004568 cement Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 19
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001293 incoloy Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000000149 penetrating effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003336 CuNi Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 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
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/108—Treatment or selection of the fuel therefor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域Technical field
本发明属于水泥、熟石灰制造领域，具体涉及一种热等离子体耦合气体还原剂催化石灰石一步还原分解制熟料并联产富含CO/H2的方法，具有高电热转化效率和高效碳中和。The invention belongs to the field of cement and slaked lime manufacturing, and specifically relates to a method for producing clinker through one-step reduction and decomposition of limestone by thermal plasma coupling gas reducing agent and co-production of CO/ H2- rich, which has high electrothermal conversion efficiency and efficient carbon neutralization. .
背景技术Background technique
2015年12月，巴黎气候大会通过了《巴黎协定》，协定的长期目标是：“将全球平均气温较前工业化时期上升幅度控制在2摄氏度以内，并努力将温度上升幅度限制在1.5摄氏度以内。全球尽快实现温室气体排放达峰，本世纪下半叶实现温室气体净零排放”。从2023年开始，每5年将对全球行动总体进展进行一次盘点，以帮助各国提高力度、加强国际合作，实现全球应对气候变化的长期目标。为了实现该目标，先后有30国或地区发布其碳中和目标。我国现有碳排放结构分为三大块：发电与供热 51％，制造与建筑业28％，交通运输10％。因此，实现碳中和的途径主要包括如下几方面：1)发电与供热：主要发展清洁能源，如风、光、水、核能等；2)制造与建筑业：a.通过能源结构优化和节能减排降低碳排放；b.通过参与碳捕捉、碳汇、碳交易实现中和；c.交通运输：主要通过新能源交通模式和轻量化实现。In December 2015, the Paris Climate Conference adopted the Paris Agreement. The long-term goal of the agreement is: "to control the increase in global average temperature to less than 2 degrees Celsius compared with the pre-industrial period, and to strive to limit the temperature increase to less than 1.5 degrees Celsius." The world should reach the peak of greenhouse gas emissions as soon as possible and achieve net-zero greenhouse gas emissions in the second half of this century." Starting from 2023, an inventory of the overall progress of global actions will be conducted every five years to help countries increase their efforts, strengthen international cooperation, and achieve the long-term goal of global response to climate change. In order to achieve this goal, 30 countries or regions have released their carbon neutrality goals. my country's current carbon emission structure is divided into three major parts: power generation and heating 51%, manufacturing and construction 28%, and transportation 10%. Therefore, the ways to achieve carbon neutrality mainly include the following aspects: 1) Power generation and heating: mainly develop clean energy, such as wind, light, water, nuclear energy, etc.; 2) Manufacturing and construction industry: a. Through energy structure optimization and Energy conservation and emission reduction reduce carbon emissions; b. Neutralization is achieved by participating in carbon capture, carbon sinks, and carbon trading; c. Transportation: mainly achieved through new energy transportation modes and lightweighting.
我国制造与建筑业的碳排放占比较高，碳中和之路存在客观技术难题。有别于发电与供热、交通运输这两个排放大户的碳中和可以通过清洁能源替代实现，制造与建筑业的碳中和面临两大难题之一：工业产品(水泥和钢铁等)生产工艺中的原料化学反应产生CO2，排放难以遏制。因此，制造与建筑业的碳中和，势必需要对现有工业生产技术进行大刀阔斧的改革。my country's manufacturing and construction industries account for a high proportion of carbon emissions, and there are objective technical difficulties on the road to carbon neutrality. Unlike power generation, heating, and transportation, the two major emitters, where carbon neutrality can be achieved through clean energy substitution, carbon neutrality in the manufacturing and construction industries faces one of two major problems: the production of industrial products (cement, steel, etc.) The chemical reaction of raw materials in the process produces CO 2 , and the emissions are difficult to contain. Therefore, achieving carbon neutrality in the manufacturing and construction industries will inevitably require drastic reforms in existing industrial production technologies.
水泥是国民经济建设的重要基础原材料，目前国内外尚无一种材料可以替代它的地位。我国是水泥大国，受益于经济高速增长，对水泥的需求量不断攀升，水泥行业分析表示，我国水泥产量已连续十多年位居世界第一，截至2017年 6月底，全国水泥企业共3465家，全国实际熟料产能20.2亿吨，水泥产能38.30亿吨。我们按照二氧化碳的排放来源，将水泥制造业的碳排放分为直接排放和间接排放。直接排放是指燃烧化石燃料与原料受热分解产生的CO2排放；间接排放是指在生产或服务过程中所需的电力支持及热能损耗而产生的CO2排放。计算分析获得，原料分解产生的CO2排放占比最大，约为63.01％，其次是供热排放CO2占比31.57％，直接碳排放合计占到96.51％，间接排放仅占到3.49％。水泥碳排放占比建筑材料行业碳排放总量的84.3％，国内碳排总量的13.91％，根据中国水泥协会数据，巴黎协议的摄2度 (2DS)协议要求每生产1吨水泥，二氧化碳排放量必须降到520-524公斤之间。当前，我国水泥熟料碳排放系数(基于水泥熟料产量核算)约为0.86，即生产一吨水泥将产生860公斤二氧化碳，明显高于巴黎协议水平，不夸张的说建筑行业要实现碳中和，水泥便是主战场。这意味着水泥行业的碳中和，有两条途径：生产工艺和燃料使用技术的变革；后端的碳捕集和转化技术的发展。未来随着多种清洁电能的增加，燃料供热可逐渐被取代。Cement is an important basic raw material for national economic construction. Currently, there is no material at home and abroad that can replace its status. my country is a big cement country. Benefiting from rapid economic growth, the demand for cement continues to rise. Cement industry analysis shows that my country's cement production has ranked first in the world for more than ten consecutive years. As of the end of June 2017, there were 3,465 cement companies nationwide. , the national actual clinker production capacity is 2.02 billion tons, and the cement production capacity is 3.830 billion tons. We divide carbon emissions from the cement manufacturing industry into direct emissions and indirect emissions according to the source of carbon dioxide emissions. Direct emissions refer to CO 2 emissions produced by the thermal decomposition of fossil fuels and raw materials; indirect emissions refer to CO 2 emissions produced from the power support and heat energy loss required in the production or service process. Calculation and analysis revealed that CO 2 emissions from raw material decomposition accounted for the largest proportion, about 63.01%, followed by CO 2 emissions from heating, which accounted for 31.57%. Direct carbon emissions totaled 96.51%, and indirect emissions accounted for only 3.49%. Cement carbon emissions account for 84.3% of the total carbon emissions of the building materials industry and 13.91% of the total domestic carbon emissions. According to data from the China Cement Association, the Paris Agreement’s 2DS agreement requires that for every ton of cement produced, carbon dioxide emissions The amount must be reduced to between 520-524 kg. Currently, my country's cement clinker carbon emission coefficient (based on cement clinker production accounting) is about 0.86, that is, producing one ton of cement will produce 860 kilograms of carbon dioxide, which is significantly higher than the level of the Paris Agreement. It is no exaggeration to say that the construction industry must achieve carbon neutrality , cement is the main battlefield. This means that there are two ways to achieve carbon neutrality in the cement industry: changes in production processes and fuel usage technologies; and the development of back-end carbon capture and conversion technologies. In the future, with the increase of various types of clean electric energy, fuel heating can be gradually replaced.
在水泥生产过程中，需要石灰石、黏土、铁矿石及煤等。石灰石是生产水泥用量最大的原料，伴随生料熟化石灰石分解产生大量CO2排放，因此改变石灰石煅烧分解工艺，在制备熟料的同时，降低甚至避免CO2排放，是一项变革性技术，是有效的碳中和技术。In the cement production process, limestone, clay, iron ore and coal are required. Limestone is the largest raw material used in the production of cement. With the decomposition of raw meal slaking limestone, a large amount of CO2 emissions are generated. Therefore, changing the limestone calcination and decomposition process to reduce or even avoid CO2 emissions while preparing clinker is a transformative technology. Effective carbon neutral technology.
CN101987783A揭示一种在悬浮态预热分解炉利用煤气煅烧石灰石生产生石灰的方法，其利用炼钢所产生的富余煤气煅烧石灰石，强化了利用率，但其也不能从根本上解决CO2的高排放。CN106698987A揭示了一种碳酸钙分解促进剂，其利用硝酸盐和水玻璃混合可降低碳酸钙分解温度，每吨碳酸钙需消耗0.7-1kg促进剂，温度降低有限且不能有效解决CO2的高排放，同时产生大量氮氧化合物加重污染。CN101987783A discloses a method of using gas to calcine limestone in a suspended preheating decomposition furnace to produce limestone. It uses the surplus gas generated from steelmaking to calcine limestone, which enhances the utilization rate, but it cannot fundamentally solve the high emission of CO 2 . CN106698987A discloses a calcium carbonate decomposition accelerator that uses nitrate and water glass to mix to reduce the calcium carbonate decomposition temperature. Each ton of calcium carbonate requires 0.7-1kg of accelerator. The temperature reduction is limited and cannot effectively solve the high emission of CO2 . , and at the same time produce a large amount of nitrogen oxides to aggravate pollution.
发明内容Contents of the invention
本发明对石灰石分解悬浮炉的供热进行了研究，传统石灰石悬浮分解炉利用煤粉内燃烧进行供热，供热过程中产生大量CO2，为了解决碳排放和新过程的供热，本发明将可再生电等离子体进行供热耦合气体还原剂催化石灰石一步还原分解。The present invention studies the heat supply of limestone decomposition suspension furnace. The traditional limestone suspension decomposition furnace uses internal combustion of pulverized coal for heat supply. A large amount of CO 2 is generated during the heating process. In order to solve the problem of carbon emissions and heat supply in the new process, the present invention The renewable electric plasma is used for heat supply and coupled with gas reducing agent to catalyze the one-step reduction and decomposition of limestone.
本发明提供一种耦合等离子体耦合气体还原剂催化石灰石一步还原分解成熟料并联产富含CO/H2气体的方法，利用热等离子体进一步将气体还原剂热解离成自由基、带电离子，除携带大量热量外，同时提高了还原效率。本发明实现水泥工业、熟石灰工业二氧化碳大幅度减排，是一种高效的碳中和技术，同时联产富含CO的气体，既可作为主要成分供给城市煤气，也可作为烯烃、油品、芳烃等高值化学品的合成原料气。所述的一步法是指在同一个反应器同样的条件下石灰石分解成熟料的同时联产高附加值CO气体，分解反应本身不排放二氧化碳。The invention provides a method for coupling plasma and coupling gas reductant to catalyze the one-step reduction and decomposition of limestone to clinker and co-produce CO/ H2- rich gas, and utilizes thermal plasma to further thermally dissociate the gas reductant into free radicals and charged ions. , in addition to carrying a large amount of heat, it also improves the reduction efficiency. The invention realizes a substantial reduction of carbon dioxide emissions in the cement industry and slaked lime industry. It is an efficient carbon neutralization technology and co-produces CO-rich gas, which can be used as the main component to supply city gas, or as olefins, oil products, Synthesis feed gas for high-value chemicals such as aromatics. The one-step method means that limestone decomposes clinker under the same conditions in the same reactor and simultaneously produces high value-added CO gas. The decomposition reaction itself does not emit carbon dioxide.
对于传统电加热或内供热的CFD模拟，可以看出，反应器内温度分布极不均匀，极大地限制了强吸热的石灰石分解过程。传统供热热过程，其供热效率仍约40-50％。For the CFD simulation of traditional electric heating or internal heating, it can be seen that the temperature distribution in the reactor is extremely uneven, which greatly limits the strongly endothermic limestone decomposition process. The heating efficiency of traditional heating process is still about 40-50%.
为了实现上述目的，本发明技术方案具体如下：In order to achieve the above objects, the technical solutions of the present invention are as follows:
一种热等离子体耦合气体还原剂催化石灰石还原分解制熟料并联产富含CO/H2的方法，采用氢气、富含甲烷气、氨气中的一种或两种以上的混合气作为还原剂，利用热等离子，在反应器中催化所述还原剂与石灰石一步还原分解生成熟料，同时联产富含CO/H2的气体。A method for thermal plasma coupled gas reducing agent to catalyze the reduction and decomposition of limestone to produce clinker and co-produce rich CO/H 2 , using one or a mixture of two or more of hydrogen, methane-rich gas, and ammonia as the The reducing agent uses thermal plasma to catalyze the one-step reduction and decomposition of the reducing agent and limestone in the reactor to generate clinker, and at the same time co-produce gas rich in CO/ H2 .
基于上述方案，优选地，所述热等离子体包括电弧放电等离子体和电感耦合等离子体中的一种或两种的结合。Based on the above solution, preferably, the thermal plasma includes one or a combination of arc discharge plasma and inductively coupled plasma.
基于上述方案，优选地，所述热等离子体的功率为0.1kW-100MW；所述热等离子体采用直流电，电流为10-10000A、电压10-10000V。Based on the above solution, preferably, the power of the thermal plasma is 0.1kW-100MW; the thermal plasma uses direct current, with a current of 10-10000A and a voltage of 10-10000V.
基于上述方案，优选地，利用热等离子体工质气将还原气体的一种或两种的混合物带入反应器催化还原分解石灰石；所述热等离子体的工质气体载气为Ar、He、CH4、 CO2、CO、H2中的一种或两种以上的组合。Based on the above scheme, it is preferable to use thermal plasma working gas to bring one or a mixture of two reducing gases into the reactor for catalytic reduction and decomposition of limestone; the working gas carrier gas of the thermal plasma is Ar, He, One or a combination of two or more of CH 4 , CO 2 , CO, and H 2 .
基于上述方案，优选地，所述热等离子体的工质气体为部分待转化的天然气和CO2，将待转化的天然气和CO2与等离子体射流快速混合，全部待转化的天然气和CO2总焓值ΔH15℃＜160kJ/mol。Based on the above solution, preferably, the working fluid gas of the thermal plasma is part of the natural gas to be converted and CO 2 , and the natural gas and CO 2 to be converted are quickly mixed with the plasma jet, and the total natural gas and CO 2 to be converted are Enthalpy value ΔH 15℃ <160kJ/mol.
基于上述方案，优选地，所述热等离子体的工质气体为转化后的合成气，将待转化的天然气和CO2与等离子体射流快速混合，全部待转化的天然气和CO2总焓值ΔH15℃＜160kJ/mol。Based on the above solution, preferably, the working gas of the thermal plasma is converted synthesis gas, and the natural gas and CO 2 to be converted are quickly mixed with the plasma jet. The total enthalpy value of all the natural gas and CO 2 to be converted is ΔH 15℃ <160kJ/mol.
基于上述方案，优选地，所述的电弧放电等离子体的电极保护气为Ar、He、CO、 H2中的一种或两种以上的组合。Based on the above solution, preferably, the electrode protective gas of the arc discharge plasma is one or a combination of two or more of Ar, He, CO, and H2 .
基于上述方案，优选地，所述热等离子体的阴、阳极材质为铜，钨，银，铪，合金、石墨中的一种或两种以上的组合。Based on the above solution, preferably, the cathode and anode materials of the thermal plasma are one or a combination of two or more of copper, tungsten, silver, hafnium, alloy, and graphite.
基于上述方案，优选地，所述方法采用金属和/或金属氧化物作为催化剂，所述金属为Fe、Mn、Cr、Ni、Cu、Co、合金钢中的一种或两种以上；所述金属氧化物为Fe2O3、 Fe3O4、Mn3O4、MnO2、Cr2O3、NiO、CuO、Co3O4、CaO、MgO、SiO2、Al2O3、ZrO2、铁矿石、锰矿石中的一种或两种以上。进一步优选地，所述催化剂为Fe、Fe2O3、Fe3O4、 CaO、铁矿石、锰矿石、合金钢中的一种或两种以上。Based on the above solution, preferably, the method uses metal and/or metal oxide as a catalyst, and the metal is one or more of Fe, Mn, Cr, Ni, Cu, Co, and alloy steel; Metal oxides are 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, manganese ore, one or more of them. Further preferably, the catalyst is one or more of Fe, Fe 2 O 3 , Fe 3 O 4 , CaO, iron ore, manganese ore, and alloy steel.
基于上述方案，优选地，所述氢气来自化石资源的氢气、可再生电电解水得到的氢气、光解水得到的氢气；所述富含甲烷气包括纯甲烷气、甲烷与低碳烷烃混合气、天然气、页岩气、水合物提取甲烷中的一种或两种以上混合气；氢气、富含甲烷气、氨气中的一种或两种以上的混合气作为有效还原剂，与惰性气氛气体氮气、氦气、氩气中的一种或二种以上进行混合，其中有效还原剂在反应原料气中体积含量为 5～100％，惰性气体的体积含量为0～95％。Based on the above solution, preferably, the hydrogen comes from hydrogen from fossil resources, hydrogen obtained by renewable electrolysis of water, and hydrogen obtained by photolysis of water; the methane-rich gas includes pure methane gas, a mixture of methane and low-carbon alkanes , natural gas, shale gas, hydrate extracted methane, one or more than two mixed gases; hydrogen, methane-rich gas, ammonia gas, one or more mixed gases as an effective reducing agent, and inert atmosphere One or more of nitrogen, helium, and argon are mixed, in which the volume content of the effective reducing agent in the reaction raw material gas is 5 to 100%, and the volume content of the inert gas is 0 to 95%.
基于上述方案，优选地，所述反应器为所述反应器为流化床式、移动床式、旋流式、喷腾式、沸腾式分解炉，带预热室分解炉，固定床式反应器，气氛平窑的一种或两种以上的组合；所述流化床式分解炉反应器包括下行并行流化床式和提升管反应器。进一步优选地，所述反应器为旋流式、喷腾式、沸腾式分解炉或提升管反应器。Based on the above solution, preferably, the reactor is a fluidized bed type, moving bed type, cyclone type, spray type, boiling type decomposition furnace, decomposition furnace with preheating chamber, fixed bed type reactor reactor, one or a combination of two or more atmosphere flat kilns; the fluidized bed decomposition furnace reactor includes a downward parallel fluidized bed reactor and a riser reactor. Further preferably, the reactor is a cyclone, spray, boiling decomposition furnace or riser reactor.
基于上述方案，优选地，所述金属或金属氧化物催化剂包括一定粒度的颗粒、超细粉末、整体柱形式；所述金属或金属氧化物催化剂可采用不同方式填装在反应器中，包括整体柱形式、涂覆在反应器壁、与石灰石原料直接混合、粉末单独进料于反应器中；所述反应器的材质，包括石英、碳化硅、氧化锆、刚玉和合金钢中的一种或两种以上的组合。Based on the above solution, preferably, the metal or metal oxide catalyst includes particles of a certain size, ultrafine powder, and monolithic column form; the metal or metal oxide catalyst can be filled in the reactor in different ways, including monolithic Column form, coated on the reactor wall, directly mixed with limestone raw materials, and the powder is separately fed into the reactor; the material of the reactor includes one of quartz, silicon carbide, zirconia, corundum and alloy steel, or A combination of two or more.
基于上述方案，优选地，反应压力为常压～3MPa；反应温度为300～1000℃。进一步优选为反应压力为常压～1MPa，反应温度为300～500℃；最优选为反应压力为0.2～0.5MPa；反应温度为300～600℃。Based on the above scheme, preferably, the reaction pressure is normal pressure ~ 3MPa; the reaction temperature is 300 ~ 1000°C. It is further preferred that the reaction pressure is normal pressure to 1MPa and the reaction temperature is 300-500°C; the most preferred reaction pressure is 0.2-0.5MPa and the reaction temperature is 300-600°C.
基于上述方案，优选地，以固定床为反应器，反应条件为：气固比为2-2000L/L；堆密度为0.5-5g/ml；固体流量为0.05kg-100t/h；气体流量为0.01～200m3/h；颗粒粒径为0.1-10mm；颗粒密度为100-5000kg/m3；停留时间0.01-10h；气体流向分为逆流和并流；Based on the above scheme, preferably, a fixed bed is used as the reactor, and the reaction conditions are: gas-to-solid ratio is 2-2000L/L; bulk density is 0.5-5g/ml; solid flow rate is 0.05kg-100t/h; gas flow rate is 0.01～200m 3 /h; particle size is 0.1-10mm; particle density is 100-5000kg/m 3 ; residence time is 0.01-10h; gas flow direction is divided into counter-current and co-current;
以移动床为反应器，反应条件为：气固比为2-2000L/L；堆密度为0.5-10g/ml；固体流量为0.05kg-100t/h；气体流量为0.01～200m3/h；颗粒粒径为0.1-10mm；颗粒密度为100-5000kg/m3；停留时间0.01-10h；气体流向分为逆流和并流；Using the moving bed as the reactor, the reaction conditions are: gas-solid ratio 2-2000L/L; bulk density 0.5-10g/ml; solid flow rate 0.05kg-100t/h; gas flow rate 0.01-200m3 /h; The particle size is 0.1-10mm; the particle density is 100-5000kg/m 3 ; the residence time is 0.01-10h; the gas flow direction is divided into countercurrent and cocurrent flow;
以提升管为反应器，反应条件为：气固比为5-2000L/L；堆密度为0.5-10g/ml；固体流量为0.05kg-100t/h；气体流量为0.01～500m3/h；颗粒粒径为0.1-5mm；颗粒密度为1000-10000kg/m3；停留时间1s-5min；气体流向为逆流；Using the riser as the reactor, the reaction conditions are: gas-solid ratio 5-2000L/L; bulk density 0.5-10g/ml; solid flow rate 0.05kg-100t/h; gas flow rate 0.01~ 500m3 /h; The particle size is 0.1-5mm; the particle density is 1000-10000kg/m 3 ; the residence time is 1s-5min; the gas flow direction is countercurrent;
以流化床或下行并行流化床为反应器，反应条件为：气固比为10-2000L/L；堆密度为0.5-10g/ml；固体流量为0.05kg-100t/h；气体流量为0.01～300m3/h；颗粒粒径为 0.1-10mm；颗粒密度为500-10000kg/m3；停留时间1s-10s；气体流向为并流；Using a fluidized bed or a downward parallel fluidized bed as the reactor, the reaction conditions are: gas-solid ratio 10-2000L/L; bulk density 0.5-10g/ml; solid flow rate 0.05kg-100t/h; gas flow rate: 0.01～300m 3 /h; particle size is 0.1-10mm; particle density is 500-10000kg/m 3 ; residence time is 1s-10s; gas flow direction is co-current;
以气氛平窑为反应器，反应条件为：气固比为10-2000L/L；堆密度为0.5-10g/ml；固体流量为0.05kg-200t/h；气体流量为0.01～500m3/h；颗粒粒径为0.1-10mm；颗粒密度为500-10000kg/m3；停留时间0.1-200h；气体流向为逆流、并流、鼓泡。Using an atmosphere flat kiln as the reactor, the reaction conditions are: gas-solid ratio 10-2000L/L; bulk density 0.5-10g/ml; solid flow rate 0.05kg-200t/h; gas flow rate 0.01~ 500m3 /h ; Particle size is 0.1-10mm; Particle density is 500-10000kg/m 3 ; Residence time is 0.1-200h; Gas flow direction is countercurrent, cocurrent, and bubbling.
进一步优选为，More preferably,
以固定床为反应器，反应条件为：气固比为10-500L/L；堆密度为0.5-3g/ml；固体流量为0.5kg-50t/h；气体流量为0.1～100m3/h；颗粒粒径为0.01-5mm；颗粒密度为 200-2000kg/m3；停留时间为0.01-10h；Using a fixed bed as the reactor, the reaction conditions are: gas-solid ratio 10-500L/L; bulk density 0.5-3g/ml; solid flow rate 0.5kg-50t/h; gas flow rate 0.1-100m3 /h; The particle size is 0.01-5mm; the particle density is 200-2000kg/m 3 ; the residence time is 0.01-10h;
以移动床为反应器，反应条件为：气固比为10-500L/L；堆密度为0.5-3g/ml；固体流量为0.5kg-50t/h；气体流量为0.1～100m3/h；颗粒粒径为0.01-1mm；颗粒密度为 200-2000kg/m3；停留时间为0.01-2h；Using the moving bed as the reactor, the reaction conditions are: gas-solid ratio 10-500L/L; bulk density 0.5-3g/ml; solid flow rate 0.5kg-50t/h; gas flow rate 0.1-100m 3 /h; The particle size is 0.01-1mm; the particle density is 200-2000kg/m 3 ; the residence time is 0.01-2h;
以提升管为反应器，反应条件为：气固比为5-500L/L；堆密度为0.5-5g/ml；固体流量为0.5kg-50t/h；气体流量为0.1～150m3/h；颗粒粒径为0.05-1mm；颗粒密度为 2000-5000kg/m3；停留时间为1s-60s；Using the riser as the reactor, the reaction conditions are: gas-solid ratio 5-500L/L; bulk density 0.5-5g/ml; solid flow rate 0.5kg-50t/h; gas flow rate 0.1-150m3 /h; The particle size is 0.05-1mm; the particle density is 2000-5000kg/m 3 ; the residence time is 1s-60s;
以流化床或下行流化床为反应器，反应条件为：气固比为10-800L/L；堆密度为0.5-5g/ml；固体流量为0.5kg-50t/h；气体流量为0.1～100m3/h；颗粒粒径为0.01-2mm；颗粒密度为500-5000kg/m3；停留时间为1s-30s；Using a fluidized bed or a downflow fluidized bed as the reactor, the reaction conditions are: gas-solid ratio 10-800L/L; bulk density 0.5-5g/ml; solid flow rate 0.5kg-50t/h; gas flow rate 0.1 ~100m 3 /h; particle size is 0.01-2mm; particle density is 500-5000kg/m 3 ; residence time is 1s-30s;
以气氛平窑为反应器，反应条件为：气固比为10-500L/L；堆密度为0.5-5g/ml；固体流量为0.5kg-50t/h；气体流量为0.1～150m3/h；颗粒粒径为0.01-3mm；颗粒密度为500-5000kg/m3；停留时间为0.1-50h。Using an atmosphere flat kiln as the reactor, the reaction conditions are: gas-solid ratio 10-500L/L; bulk density 0.5-5g/ml; solid flow rate 0.5kg-50t/h; gas flow rate 0.1~ 150m3 /h ; The particle size is 0.01-3mm; the particle density is 500-5000kg/m 3 ; the residence time is 0.1-50h.
本发明的原理为：热等离子体作用于工质气体，除提供石灰石分解(强吸热过程)所需能量外，同时一步将石灰石分解产生的CO2还原为CO，等离子体炬内高温将工质气体部分转化为离子、自由基等，这些离子、自由基将催化加速与CO2的反应和还原过程，形成了等离子强化耦合石灰石还原分解过程。本发明的有益效果为：The principle of the invention is: thermal plasma acts on the working fluid gas. In addition to providing the energy required for limestone decomposition (strong endothermic process), it also reduces the CO2 generated by the decomposition of limestone into CO in one step. The high temperature in the plasma torch converts the working gas into CO2. The mass gas is partially converted into ions, free radicals, etc. These ions and free radicals will catalytically accelerate the reaction and reduction process with CO 2 , forming a plasma-enhanced coupled limestone reduction and decomposition process. The beneficial effects of the present invention are:
(1)本发明热等离子体，可以进一步将气体还原剂热解离成自由基、带电离子，除携带大量热量外，同时提高了还原效率。(1) The thermal plasma of the present invention can further thermally dissociate the gas reducing agent into free radicals and charged ions, which not only carries a large amount of heat, but also improves the reduction efficiency.
(2)本发明提供的热等离子体耦合一步还原分解石灰石制熟料并联产CO方法，同时联产富含CO/H2的气体，气体产品组成为CO含量20-60％、H2含量10-50％，CO2含量<20％，CH4含量<10％，可作为主要成分供给城市煤气，或作为烯烃、油品、芳烃等高值化学品的合成原料气，本发明技术可实现水泥工业、熟石灰工业二氧化碳减排60％，具有广阔的工业应用前景。(2) The thermal plasma coupling one-step reduction and decomposition of limestone clinker and co-production of CO method provided by the invention simultaneously co-produces gas rich in CO/H 2. The gas product composition is CO content 20-60% and H 2 content. 10-50%, CO 2 content < 20%, CH 4 content < 10%, which can be supplied as the main component to city gas, or used as synthetic raw material gas for high-value chemicals such as olefins, oils, aromatics, etc. The technology of the present invention can achieve The cement industry and slaked lime industry can reduce carbon dioxide emissions by 60% and have broad industrial application prospects.
(3)本发明可在流化床式、移动床式、旋流式、喷腾式、沸腾式等分解炉，带预热室分解炉，提升管反应器，固定床式反应器或气氛平窑中实现，具有过程简单、产品附加值高、工业化难度小、产物易于分离、过程重复性好、操作安全可靠等特点。(3) The present invention can be used in fluidized bed type, moving bed type, cyclone type, spray type, boiling type and other decomposition furnaces, decomposition furnaces with preheating chambers, riser reactors, fixed bed reactors or atmosphere level reactors. Realized in a kiln, it has the characteristics of simple process, high product added value, low industrialization difficulty, easy product separation, good process repeatability, safe and reliable operation, etc.
(4)本发明催化剂的使用可以进一步加快反应速率，降低反应温度，有利于降低能耗，提高反应效率。(4) The use of the catalyst of the present invention can further accelerate the reaction rate and reduce the reaction temperature, which is beneficial to reducing energy consumption and improving reaction efficiency.
具体实施方式Detailed ways
以下的实施例仅限于解释本发明，本发明的保护范围应包括权利要求的全部内容，不仅仅限于本实施例。以下实施例中各产物均为质谱检测到的产物，并且依据反应前后的碳平衡，故H2不做计算。The following examples are limited to explaining the present invention, and the protection scope of the present invention should include the entire content of the claims and is not limited to this embodiment. Each product in the following examples is a product detected by mass spectrometry, and is based on the carbon balance before and after the reaction, so H 2 is not calculated.
对比例1Comparative example 1
准确称量1g重质碳酸钙(0.05mm)和10mg Fe2O3催化剂(0.05mm)置于石英固定床反应器中，堆密度为0.8g/ml，气固比为50L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.3 kW，Ar保护气0.5L/min；Ar工质气2.5L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙完全反应分解结束，产物为CO2。Accurately weigh 1g heavy calcium carbonate (0.05mm) and 10mg Fe 2 O 3 catalyst (0.05mm) and place them in a quartz fixed bed reactor. The bulk density is 0.8g/ml, the gas-solid ratio is 50L/L, and the coupled arc In the discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.3 kW, Ar protective gas 0.5L/min; Ar working gas 2.5L/min ; After a 30-minute hold, online analysis begins, during which mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1 hour, and the analysis results show that the complete reaction and decomposition of heavy calcium carbonate is completed, and the product is CO 2 .
对比例2Comparative example 2
准确称量1g重质碳酸钙(0.08mm)和10mg铁矿石催化剂(0.08mm)置于石英固定床反应器中，堆密度为0.78g/ml，气固比为80L/L，将反应装置升温至900℃(提供分解所需的热量)，使用0.5L/min Ar气置换反应器中的空气约30分钟后，通入1.25 L/min Ar+.25L/min NH3的混合气；并保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1.5h，分析结果显示重质碳酸钙完全反应分解结束，产物为CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为78％，CO2的选择性为21％，CH4的选择性为1％。Accurately weigh 1g heavy calcium carbonate (0.08mm) and 10mg iron ore catalyst (0.08mm) and place them in a quartz fixed bed reactor. The bulk density is 0.78g/ml and the gas-to-solid ratio is 80L/L. Place the reaction device Raise the temperature to 900°C (to provide the heat required for decomposition), use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, and then introduce a mixed gas of 1.25 L/min Ar+.25L/min NH 3 ; and keep Online analysis began after 30 minutes, during which mass spectrometry was used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate is completed. The products are CO, H 2 O, CH 4 , and CO 2. H 2 O can be removed by condensation, and the selectivity of CO is 78%. The selectivity for CO2 is 21% and the selectivity for CH4 is 1%.
实施例1Example 1
准确称量1g重质碳酸钙(0.08mm)和10mg铁矿石催化剂(0.08mm)置于石英固定床反应器中，堆密度为0.78g/ml，气固比为80L/L，耦合电弧放电等离子体装置，使用0.5L/minAr气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为 0.3kW，Ar保护气0.5L/min；通入Ar工质气1.25L/min、NH3还原剂1.25L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1.5h，分析结果显示重质碳酸钙在580℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 88％，CO2的选择性为11.5％，CH4的选择性为0.5％。Accurately weigh 1g heavy calcium carbonate (0.08mm) and 10mg iron ore catalyst (0.08mm) and place them in a quartz fixed bed reactor. The bulk density is 0.78g/ml and the gas-to-solid ratio is 80L/L. Couple arc discharge For the plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes. Then adjust the plasma parameters to: power 0.3kW, Ar protective gas 0.5L/min; introduce Ar working gas 1.25L/min. , NH 3 reducing agent 1.25L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 580°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 88%, with a CO2 selectivity of 11.5% and a CH4 selectivity of 0.5%.
实施例2Example 2
准确称量1g重质碳酸钙(0.1mm)和10mg Fe3O4/Fe2O3负载型催化剂(0.1mm) 置于石英固定床反应器中，堆密度为0.75g/ml，气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.38kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为2h，分析结果显示重质碳酸钙在490℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 92％，CO2的选择性为7％，CH4的选择性为1％。Accurately weigh 1g heavy calcium carbonate (0.1mm) and 10mg Fe 3 O 4 /Fe 2 O 3 supported catalyst (0.1mm) and place them in a quartz fixed bed reactor with a bulk density of 0.75g/ml and a gas-to-solid ratio 100L/L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.38kW, Ar protective gas 0.5L/min; pass Add H 2 2.5L/min as the working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 2h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 490°C. The products are H 2 , CO, H 2 O, CH 4 , CO 2 , among which H 2 O can be removed by condensation, and the selection of CO The selectivity is 92%, CO2 selectivity is 7%, and CH4 selectivity is 1%.
实施例3Example 3
准确称量1g重质碳酸钙(0.12mm)和10mg铁矿石粉末催化剂(0.12mm)置于石英固定床反应器中，堆密度为0.74g/ml，气固比为110L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.42kW，Ar保护气0.5L/min；通入Ar工质气1.5L/min，NH3还原剂2.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为2.5h，分析结果显示重质碳酸钙在510℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去其中CO的选择性为86％， CO2的选择性为14％。Accurately weigh 1g heavy calcium carbonate (0.12mm) and 10mg iron ore powder catalyst (0.12mm) and place them in a quartz fixed bed reactor. The bulk density is 0.74g/ml, the gas-to-solid ratio is 110L/L, and the coupled arc In the discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.42kW, Ar protective gas 0.5L/min; introduce 1.5L Ar working gas /min, NH 3 reducing agent 2.0L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 2.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 510°C. The products are H 2 , CO, H 2 O, and CO 2 . H 2 O can be removed by condensation, and the selectivity of CO is 86. %, CO2 selectivity is 14%.
实施例4Example 4
准确称量1g重质碳酸钙(0.25mm)和20mg Fe粉末催化剂(0.25mm)置于石英固定床反应器中，堆密度为0.72g/ml，气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.5kW，Ar保护气0.5L/min；通入H2工质气1.75L/min，Ar还原剂0.25L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙在595℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中CO的选择性为89％，CO2的选择性为11％。Accurately weigh 1g heavy calcium carbonate (0.25mm) and 20mg Fe powder catalyst (0.25mm) and place them in a quartz fixed bed reactor with a bulk density of 0.72g/ml and a gas-to-solid ratio of 100L/L. Couple arc discharge plasma Plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.5kW, Ar protective gas 0.5L/min; pass in H 2 working gas 1.75L/min min, Ar reducing agent 0.25L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1 hour. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 595°C. The products are H 2 , CO, H 2 O, and CO 2 . The selectivity of CO is 89% and the selectivity of CO 2 is 11. %.
实施例5Example 5
准确称量1g重质碳酸钙(0.33mm)和10mg铁矿石粉末催化剂(0.33mm)置于石英固定床反应器中，堆密度为0.72g/ml，气固比为140L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.38kW，Ar保护气0.5L/min；通入H2工质气1.2L/min，Ar还原剂0.8L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在480℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 91％，CO2的选择性为9.8％，CH4的选择性为0.2％。Accurately weigh 1g heavy calcium carbonate (0.33mm) and 10mg iron ore powder catalyst (0.33mm) and place them in a quartz fixed bed reactor. The bulk density is 0.72g/ml, the gas-to-solid ratio is 140L/L, and the coupled arc In the discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.38kW, Ar protective gas 0.5L/min; pass in H 2 working gas 1.2 L/min, Ar reducing agent 0.8L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 480°C. The products are H 2 , CO, H 2 O, CH 4 , CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 91%, CO2 selectivity is 9.8%, and CH4 selectivity is 0.2%.
实施例6Example 6
准确称量1g重质碳酸钙(0.38mm)和10mg Ni粉末催化剂(0.38mm)置于石英固定床反应器中，堆密度为0.71g/ml，气固比为140L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.44kW，Ar保护气0.5L/min；通入Ar工质气2.0L/min，CH4还原剂2.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.9h，分析结果显示重质碳酸钙在600℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 84％，CO2的选择性为15％，CH4的选择性为1％。Accurately weigh 1g heavy calcium carbonate (0.38mm) and 10mg Ni powder catalyst (0.38mm) and place them in a quartz fixed bed reactor with a bulk density of 0.71g/ml and a gas-to-solid ratio of 140L/L. Couple arc discharge plasma Plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.44kW, Ar protective gas 0.5L/min; pass in Ar working gas 2.0L/min , CH 4 reducing agent 2.0L/min; start online analysis after holding for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.9h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 600°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 84%, with a selectivity of 15% for CO2 and 1% for CH4 .
实施例7Example 7
准确称量1g重质碳酸钙(0.25mm)和100mg Cu粉末催化剂(0.25mm)置于碳化硅固定床反应器中，堆密度为3g/ml，气固比为85L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.42kW，Ar保护气0.5L/min；通入H2 2.0L/min作为工质气和还原剂；保持30 分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.8h，分析结果显示重质碳酸钙在580℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去，其中CO的选择性为90％，CO2的选择性为10％。Accurately weigh 1g heavy calcium carbonate (0.25mm) and 100mg Cu powder catalyst (0.25mm) and place them in a silicon carbide fixed bed reactor with a bulk density of 3g/ml and a gas-to-solid ratio of 85L/L. Couple arc discharge plasma Plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters as follows: power is 0.42kW, Ar protective gas 0.5L/min; H 2 2.0L/min is introduced as the working Mass gas and reducing agent; hold for 30 minutes before starting online analysis, during which mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.8h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 580°C. The products are H 2 , CO, H 2 O, and CO 2 , among which H 2 O can be removed by condensation, and the selectivity of CO is 90%, CO2 selectivity is 10%.
实施例8Example 8
准确称量1g重质碳酸钙(0.3mm)和10mg Fe2O3/CaO负载型催化剂(0.3mm) 置于刚玉固定床反应器中，堆密度为0.71g/ml，气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.45kW，Ar保护气0.5L/min；通入H2 2.0L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在550℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 92％，CO2的选择性为7.7％，CH4的选择性为0.3％。Accurately weigh 1g heavy calcium carbonate (0.3mm) and 10mg Fe 2 O 3 /CaO supported catalyst (0.3mm) and place them in a corundum fixed bed reactor. The bulk density is 0.71g/ml and the gas-to-solid ratio is 100L/ L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.45kW, Ar protective gas 0.5L/min; pass in H 2 2.0L/min as working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 550°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 92%, CO2 selectivity is 7.7%, and CH4 selectivity is 0.3%.
实施例9Example 9
准确称量1g重质碳酸钙(0.08mm)和10mg Fe3O4粉末催化剂(0.08mm)置于合金钢(Incoloy 800HT)固定床反应器中，堆密度为0.8g/ml，气固比为50L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.55kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙在515℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中其中H2O可通过冷凝除去，其中CO的选择性为87％，CO2的选择性为12.7％，CH4的选择性为0.3％。Accurately weigh 1g heavy calcium carbonate (0.08mm) and 10mg Fe 3 O 4 powder catalyst (0.08mm) and place them in an alloy steel (Incoloy 800HT) fixed bed reactor. The bulk density is 0.8g/ml and the gas-to-solid ratio is 50L/L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.55kW, Ar protective gas 0.5L/min; pass in H 2 2.5L/min was used as the working gas and reducing agent; online analysis was started after maintaining for 30 minutes. During this process, mass spectrometry was used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1 hour. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 515°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 87%, with a CO2 selectivity of 12.7% and a CH4 selectivity of 0.3%.
实施例10Example 10
准确称量1g重质碳酸钙(0.15mm)和10mg Co3O4/Fe2O3负载型催化剂(0.15mm) 置于石英固定床反应器中，堆密度为0.74g/ml，耦合电弧放电等离子体装置，使用0.5 L/minAr气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.59kW， Ar保护气0.5L/min；通入H2工质气2.5L/min，NH3还原剂1.5L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.8h，分析结果显示重质碳酸钙在590℃完全反应分解结束，产物为H2、 CO、H2O、CH4、N2、CO2，其中H2O可通过冷凝除去，其中CO的选择性为82％， CO2的选择性为17％，CH4的选择性为0.3％，N2的选择性为0.7％。Accurately weigh 1g heavy calcium carbonate (0.15mm) and 10mg Co 3 O 4 /Fe 2 O 3 supported catalyst (0.15mm) and place them in a quartz fixed bed reactor with a bulk density of 0.74g/ml and a coupled arc discharge For the plasma device, use 0.5 L/min Ar gas to replace the air in the reactor for about 30 minutes. Then adjust the plasma parameters to: power 0.59kW, Ar protective gas 0.5L/min; introduce H 2 working gas 2.5L/min. min, NH 3 reducing agent 1.5L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.8h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 590°C. The products are H 2 , CO, H 2 O, CH 4 , N 2 , and CO 2 , among which H 2 O can be removed by condensation. Among them, the selectivity of CO is 82%, the selectivity of CO2 is 17%, the selectivity of CH4 is 0.3%, and the selectivity of N2 is 0.7%.
实施例11Example 11
准确称量1g重质碳酸钙(0.08mm)和10mg锰矿石粉末催化剂(0.08mm)置于金属(材质为Incoloy 800HT)固定床反应器中，堆密度为0.78g/ml，气固比为60L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.59kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.3h，分析结果显示重质碳酸钙在490℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为93％，CO2的选择性为1.1％，N2的选择性为5％、CH4的选择性为 0.9％。Accurately weigh 1g heavy calcium carbonate (0.08mm) and 10mg manganese ore powder catalyst (0.08mm) and place them in a metal (made of Incoloy 800HT) fixed bed reactor. The bulk density is 0.78g/ml and the gas-to-solid ratio is 60L. /L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.59kW, Ar protective gas 0.5L/min; pass in H 2 2.5L/min as working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.3h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 490°C. The products are H 2 , CO, H 2 O, CH 4 , CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 93%, the selectivity of CO2 is 1.1%, the selectivity of N2 is 5%, and the selectivity of CH4 is 0.9%.
实施例12Example 12
准确称量1g重质碳酸钙(0.1mm)和15mg锰矿石粉末催化剂(0.1mm)置于石英移动床反应器中，堆密度为0.75g/ml，气固比为110L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.66kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持30 分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.1h，分析结果显示重质碳酸钙在420℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为91％， CO2的选择性为8.8％，CH4的选择性为0.2％。Accurately weigh 1g heavy calcium carbonate (0.1mm) and 15mg manganese ore powder catalyst (0.1mm) and place them in a quartz moving bed reactor. The bulk density is 0.75g/ml and the gas-to-solid ratio is 110L/L. Couple arc discharge For the plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes. Then adjust the plasma parameters to: power 0.66kW, Ar protective gas 0.5L/min; introduce H 2 2.5L/min as Working gas and reducing agent; hold for 30 minutes before starting online analysis. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.1h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 420°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 91%, CO2 selectivity is 8.8%, and CH4 selectivity is 0.2%.
实施例13Example 13
准确称量1g重质碳酸钙(0.1mm)和10mg铁矿石粉末催化剂(0.1mm)置于石英移动床反应器中，堆密度为0.74g/ml，气固比为120L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.71kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持 30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在381℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为89％， CO2的选择性为10.8％，CH4的选择性为0.2％。Accurately weigh 1g heavy calcium carbonate (0.1mm) and 10mg iron ore powder catalyst (0.1mm) and place them in a quartz moving bed reactor. The bulk density is 0.74g/ml, the gas-to-solid ratio is 120L/L, and the coupled arc In the discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.71kW, Ar protective gas 0.5L/min; pass in H 2 2.5L/min As working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 381°C. The products are H 2 , CO, H 2 O, CH 4 , CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 89%, CO2 selectivity is 10.8%, and CH4 selectivity is 0.2%.
实施例14Example 14
准确称量1g重质碳酸钙(0.05mm)和12mg Ni/MgO负载型催化剂(0.05mm) 置于石英移动床反应器中，堆密度为0.8g/ml，气固比为60L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.82kW，Ar保护气0.5L/min；通入H2 3.5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在505℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为 89％，CO2的选择性为10.4％，CH4的选择性为0.6％。Accurately weigh 1g heavy calcium carbonate (0.05mm) and 12mg Ni/MgO supported catalyst (0.05mm) and place them in a quartz moving bed reactor with a bulk density of 0.8g/ml and a gas-to-solid ratio of 60L/L. In the arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.82kW, Ar protective gas 0.5L/min; pass in H 2 3.5L/ min serves as the working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 505°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 89%, CO2 selectivity is 10.4%, and CH4 selectivity is 0.6%.
实施例15Example 15
准确称量10g重质碳酸钙(0.15mm)和100mg Cr/SiO2负载型催化剂(0.15mm) 置于石英移动床反应器中，堆密度为0.76g/ml，气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.82kW，Ar保护气0.5L/min；Ar工质气2.0L/min，NH3还原剂2.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙在478℃完全反应分解结束，产物为H2、CO、H2O、N2、CO2，其中H2O可通过冷凝除去，其中CO的选择性为85％，CO2的选择性为11.4％，N2的选择性为3％，CH4的选择性为0.6％。Accurately weigh 10g heavy calcium carbonate (0.15mm) and 100mg Cr/SiO 2 supported catalyst (0.15mm) and place them in a quartz moving bed reactor. The bulk density is 0.76g/ml and the gas-to-solid ratio is 100L/L. Coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust the plasma parameters to: power 0.82kW, Ar protective gas 0.5L/min; Ar working gas 2.0L /min, NH 3 reducing agent 2.0L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1 hour. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 478°C. The products are H 2 , CO, H 2 O, N 2 , and CO 2 , among which H 2 O can be removed by condensation. The selection of CO The selectivity is 85%, the selectivity of CO2 is 11.4%, the selectivity of N2 is 3%, and the selectivity of CH4 is 0.6%.
实施例16Example 16
准确称量50g重质碳酸钙(0.15mm)和0.5g Fe/ZrO2负载型催化剂(0.15mm) 置于石英移动床反应器中，堆密度为0.75g/ml，气固比为110L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为1.2kW，Ar保护气0.5L/min；通入H2 5L/min作为工质气和还原剂；保持 30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在560℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去，其中CO的选择性为93％， CO2的选择性为6.4％，CH4的选择性为0.6％。Accurately weigh 50g heavy calcium carbonate (0.15mm) and 0.5g Fe/ZrO 2 supported catalyst (0.15mm) and place them in a quartz moving bed reactor. The bulk density is 0.75g/ml and the gas-to-solid ratio is 110L/L. , coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 1.2kW, Ar protective gas 0.5L/min; pass in H 2 5L /min as working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 560°C. The products are H 2 , CO, H 2 O, and CO 2 , among which H 2 O can be removed by condensation, and the selectivity of CO is 93%, CO2 selectivity is 6.4%, CH4 selectivity is 0.6%.
实施例17Example 17
准确称量1g重质碳酸钙(0.1mm)和11mg MnO2:Ni:Mn＝3:1:2(质量比)粉末催化剂(0.1mm)置于石英旋流式分解炉反应器中，堆密度为0.75g/ml，气固比为160L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.58kW，Ar保护气0.5L/min；通入H2 2.5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在570℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为93％，CO2的选择性为6.5％，CH4的选择性为0.5％。Accurately weigh 1g heavy calcium carbonate (0.1mm) and 11mg MnO 2 :Ni:Mn=3:1:2 (mass ratio) powder catalyst (0.1mm) and place it in the quartz cyclone decomposition furnace reactor. The bulk density is 0.75g/ml, the gas-to-solid ratio is 160L/L, and the arc discharge plasma device is coupled. After replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, adjust the plasma parameters as follows: the power is 0.58kW, Ar protective gas 0.5L/min; H 2 2.5L/min was introduced as working gas and reducing agent; online analysis started after maintaining for 30 minutes. During this process, mass spectrometry was used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. . The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 570°C. The products are H 2 , CO, H 2 O, CH 4 and CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 93%, with a CO2 selectivity of 6.5% and a CH4 selectivity of 0.5%.
实施例18Example 18
准确称量1g重质碳酸钙(0.1mm)和11mg CuNi/ZrO2负载型催化剂(0.1mm) 置于石英旋流式分解炉反应器中，堆密度为0.79g/ml，气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.62kW，Ar保护气0.5L/min；Ar+H2(摩尔比1：5)工质气2.5L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。分析结果显示重质碳酸钙在660℃完全反应分解结束，产物为H2、CO、 H2O、CH4、CO2，其中H2O可通过冷凝除去，其中CO的选择性为86％，CO2的选择性为13.5％，CH4的选择性为0.5％。Accurately weigh 1g heavy calcium carbonate (0.1mm) and 11mg CuNi/ZrO 2 supported catalyst (0.1mm) and place them in a quartz cyclone decomposition furnace reactor with a bulk density of 0.79g/ml and a gas-to-solid ratio of 100L /L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.62kW, Ar protective gas 0.5L/min; Ar+H 2 (molar ratio 1:5) working gas 2.5L/min; maintain for 30 minutes before starting online analysis. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 660°C, and the products are H 2 , CO, H 2 O, CH 4 , and CO 2 , among which H 2 O can be removed by condensation, and the selectivity of CO is 86%. The selectivity for CO2 is 13.5% and the selectivity for CH4 is 0.5%.
实施例19Example 19
准确称量50g重质碳酸钙(1mm)和200mg铁矿石粉末催化剂(1mm)置于金属(材质为Incoloy800HT)喷腾式分解炉反应器中，堆密度为0.69g/ml，气固比为300 L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.8kW，Ar保护气0.5L/min；通入H2 3.5L/min 作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在 660℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去，其中CO的选择性为92％，CO2的选择性为8％。Accurately weigh 50g heavy calcium carbonate (1mm) and 200mg iron ore powder catalyst (1mm) and place them in a metal (made of Incoloy800HT) penetrating decomposition furnace reactor. The bulk density is 0.69g/ml and the gas-to-solid ratio is 300 L/L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.8kW, Ar protective gas 0.5L/min; pass Add H 2 3.5L/min as the working gas and reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 660°C. The products are H 2 , CO, H 2 O, and CO 2 , among which H 2 O can be removed by condensation, and the selectivity of CO is 92%, CO2 selectivity is 8%.
实施例20Example 20
准确称量12g重质碳酸钙(0.45mm)和200mg NiO/SiO2负载型催化剂(0.15mm) 置于刚玉喷腾式分解炉反应器中，堆密度为0.74g/ml，气固比为210L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.58kW，Ar保护气0.5L/min；通入Ar工质气2.5L/min，NH3还原剂2.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.5h，分析结果显示重质碳酸钙在605℃完全反应分解结束，产物为H2、CO、H2O、N2、CO2，其中H2O可通过冷凝除去，其中CO的选择性为90％，CO2的选择性为5％，N2的选择性为5％。Accurately weigh 12g heavy calcium carbonate (0.45mm) and 200mg NiO/SiO 2 supported catalyst (0.15mm) and place them in the corundum penetrating decomposition furnace reactor. The bulk density is 0.74g/ml and the gas-to-solid ratio is 210L. /L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.58kW, Ar protective gas 0.5L/min; introduce Ar Working gas 2.5L/min, NH 3 reducing agent 2.0L/min; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.5h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 605°C. The products are H 2 , CO, H 2 O, N 2 , CO 2 , among which H 2 O can be removed by condensation, among which CO The selectivity is 90%, CO2 selectivity is 5%, N2 selectivity is 5%.
实施例21Example 21
准确称量1g重质碳酸钙(0.25mm)和10mg Mn2O3/Fe2O3-Al2O3负载型催化剂(0.15mm)置于石英带预热室分解炉反应器中，堆密度为0.76g/ml，气固比为180L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.92kW，Ar保护气0.5L/min；通入H2工质气2.5L/min， CH4还原剂2.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.8h，分析结果显示重质碳酸钙在 640℃完全反应分解结束，产物为CO、H2O、CO2，其中H2O可通过冷凝除去，其中 CO的选择性为93％，CO2的选择性为7％。Accurately weigh 1g heavy calcium carbonate (0.25mm) and 10mg Mn 2 O 3 /Fe 2 O 3 -Al 2 O 3 supported catalyst (0.15mm) and place it in the quartz preheating chamber decomposition furnace reactor. The bulk density is 0.76g/ml, the gas-to-solid ratio is 180L/L, and the arc discharge plasma device is coupled. After replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, adjust the plasma parameters as follows: the power is 0.92kW, Ar protective gas 0.5L/min; pass in H 2 working gas 2.5L/min, CH 4 reducing agent 2.0L/min; start online analysis after maintaining for 30 minutes. During this process, use mass spectrometry to monitor the decomposition products at the beginning and end of the reaction. The relative proportions at the end. The residence time is 0.8h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 640°C. The products are CO, H 2 O, and CO 2. H 2 O can be removed by condensation, and the selectivity of CO is 93%. CO2 selectivity is 7%.
实施例22Example 22
准确称量1g石灰石钙(1mm)和10mg Mn3O4:NiO＝1:7催化剂(质量比)(1mm) 置于石英带预热室分解炉反应器中，堆密度为0.69g/ml，气固比为140L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.92kW，Ar保护气0.5L/min；通入H2工质气2.5L/min，CH4还原剂3.0L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为0.3h，分析结果显示重质碳酸钙在590℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去，其中 CO的选择性为94％，CO2的选择性为6％。Accurately weigh 1g limestone calcium (1mm) and 10mg Mn 3 O 4 : NiO = 1:7 catalyst (mass ratio) (1mm) and place them in a quartz preheating chamber decomposition furnace reactor with a bulk density of 0.69g/ml. The gas-solid ratio is 140L/L, and the coupled arc discharge plasma device is used. After replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, adjust the plasma parameters to: power 0.92kW, Ar protective gas 0.5L/ min; pass in 2.5L/min of H 2 working gas and 3.0L/min of CH 4 reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 0.3h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 590°C. The products are H 2 , CO, H 2 O, and CO 2 , among which H 2 O can be removed by condensation, and the selectivity of CO is 94%, CO2 selectivity is 6%.
实施例23Example 23
准确称量1g重质碳酸钙(0.08mm)和10mg铁矿石:NiO:CuO:Fe＝1:2:6:2(质量比)催化剂(0.08mm)置于金属(材质为Incoloy 800HT)提升管反应器中，堆密度为 0.81g/ml，20大气压下气固比为80L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.92kW，Ar 保护气0.5L/min；通入H25L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为30s，分析结果显示重质碳酸钙在480℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中H2O可通过冷凝除去，其中CO的选择性为98％，CO2的选择性为2％。Accurately weigh 1g heavy calcium carbonate (0.08mm) and 10mg iron ore: NiO:CuO:Fe=1:2:6:2 (mass ratio) catalyst (0.08mm) and place it on the metal (material is Incoloy 800HT) to lift In the tube reactor, the bulk density is 0.81g/ml, the gas-to-solid ratio at 20 atmospheres is 80L/L, coupled to the arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, then adjust The plasma parameters are: power is 0.92kW, Ar protective gas 0.5L/min; H 2 5L/min is introduced as the working gas and reducing agent; online analysis starts after maintaining for 30 minutes, and mass spectrometry is used to monitor the decomposition products during the process Relative proportions at the beginning and end of a reaction. The residence time is 30s. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 480°C. The products are H 2 , CO, H 2 O, and CO 2 . H 2 O can be removed by condensation, and the selectivity of CO is 98. %, CO2 selectivity is 2%.
实施例24Example 24
准确称量1g石灰石(0.15mm)和10mg Ni:Fe:Co＝1:2:9催化剂(质量比)(0.15mm)置于金属(金属材质为Inconel 601)提升管反应器中，堆密度为0.78g/ml，2个大气气固比为100L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.92kW，Ar保护气0.5L/min；通入 Ar工质气1L/min，H2还原剂1L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为35s，分析结果显示重质碳酸钙在460℃完全反应分解结束，产物为H2、CO、H2O、CH4、CO2，其中 H2O可通过冷凝除去，其中CO的选择性为93％，CO2的选择性为6％，CH4的选择性为0.3％。Accurately weigh 1g limestone (0.15mm) and 10mg Ni:Fe:Co=1:2:9 catalyst (mass ratio) (0.15mm) and place them in a metal (metal material is Inconel 601) riser reactor. The bulk density is 0.78g/ml, gas-to-solid ratio of 2 atmospheres is 100L/L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: the power is 0.92 kW, Ar protective gas 0.5L/min; pass in Ar working gas 1L/min, H 2 reducing agent 1L/min; start online analysis after maintaining for 30 minutes, during this process, use mass spectrometry to monitor the decomposition products at the beginning and end of the reaction relative proportions. The residence time is 35s. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 460°C. The products are H 2 , CO, H 2 O, CH 4 , and CO 2 , among which H 2 O can be removed by condensation. The selection of CO The selectivity is 93%, CO2 selectivity is 6%, and CH4 selectivity is 0.3%.
实施例25Example 25
准确称量1g重质碳酸钙(0.15mm)和10mg铁矿石:Fe＝1:2(质量比)粉末催化剂(0.15mm)置于金属(材质为Incoloy800HT)气氛平窑反应器中，堆密度为0.79g/ml， 30个大气压气固比为160L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为1.1kW，Ar保护气 0.5L/min；通入H2 5L/min作为工质气和还原剂；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙在530℃完全反应分解结束，产物为H2、CO、H2O、CO2，其中 H2O可通过冷凝除去，其中CO的选择性为95％，CO2的选择性为5％。Accurately weigh 1g heavy calcium carbonate (0.15mm) and 10mg iron ore: Fe = 1:2 (mass ratio) powder catalyst (0.15mm) and place it in a metal (material: Incoloy800HT) atmosphere flat kiln reactor. The bulk density is 0.79g/ml, the gas-to-solid ratio at 30 atmospheres is 160L/L, and the arc discharge plasma device is coupled. After replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, adjust the plasma parameters to: The power is 1.1kW, Ar protective gas 0.5L/min; H 2 5L/min was introduced as the working gas and reducing agent; online analysis started after maintaining for 30 minutes. During this process, mass spectrometry was used to monitor the decomposition products at the beginning and end of the reaction. relative proportions. The residence time is 1 hour. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 530°C. The products are H 2 , CO, H 2 O, and CO 2 . H 2 O can be removed by condensation, and the selectivity of CO is 95. %, CO2 selectivity is 5%.
实施例26Example 26
准确称量1g重质碳酸钙(0.25mm)和10mg NiFe/MgO-Al2O3负载型催化剂(0.25 mm)置于石英气氛平窑反应器中，堆密度为0.76g/ml，气固比为150L/L，耦合电弧放电等离子体装置，使用0.5L/min Ar气置换反应器中的空气约30分钟后，调节等离子体参数为：功率为0.56kW，Ar保护气0.5L/min；通入H2工质气5L/min，NH3还原剂1.5L/min；保持30分钟后开始在线分析，在此过程中使用质谱监测分解产物在反应开始和结束时的相对比例。停留时间为1h，分析结果显示重质碳酸钙在590℃完全反应分解结束，产物为H2、CO、H2O、N2、CO2，其中H2O可通过冷凝除去，其中CO 的选择性为93％，CO2的选择性为4％，N2的选择性为3％。Accurately weigh 1g heavy calcium carbonate (0.25mm) and 10mg NiFe/MgO-Al 2 O 3 supported catalyst (0.25 mm) and place them in a quartz atmosphere flat kiln reactor. The bulk density is 0.76g/ml and the gas-to-solid ratio 150L/L, coupled arc discharge plasma device, use 0.5L/min Ar gas to replace the air in the reactor for about 30 minutes, adjust the plasma parameters to: power 0.56kW, Ar protective gas 0.5L/min; pass Add 5L/min of H 2 working gas and 1.5L/min of NH 3 reducing agent; start online analysis after maintaining for 30 minutes. During this process, mass spectrometry is used to monitor the relative proportions of decomposition products at the beginning and end of the reaction. The residence time is 1h. The analysis results show that the complete reaction and decomposition of heavy calcium carbonate ends at 590°C. The products are H 2 , CO, H 2 O, N 2 , and CO 2 , among which H 2 O can be removed by condensation, and the selection of CO The selectivity is 93%, CO2 selectivity is 4%, and N2 selectivity is 3%.
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