CN106564901A - Manufacturing technique for producing lime carbon pellets through pyrolytic semi-coke - Google Patents
Manufacturing technique for producing lime carbon pellets through pyrolytic semi-coke Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 239000008188 pellet Substances 0.000 title claims abstract description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 title claims abstract description 20
- 235000011941 Tilia x europaea Nutrition 0.000 title claims abstract description 20
- 239000004571 lime Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 22
- 239000000571 coke Substances 0.000 title abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000005997 Calcium carbide Substances 0.000 claims abstract description 32
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000000197 pyrolysis Methods 0.000 claims description 21
- 239000003245 coal Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000011280 coal tar Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 235000012255 calcium oxide Nutrition 0.000 abstract description 24
- 239000000292 calcium oxide Substances 0.000 abstract description 24
- 235000019738 Limestone Nutrition 0.000 abstract description 7
- 239000006028 limestone Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000010891 electric arc Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
Description
1.技术领域1. Technical field
本发明提供一种热解半焦生产石灰碳球团的生产工艺，涉及煤化工领域。The invention provides a production process for producing lime carbon pellets by pyrolyzing semi-coke and relates to the field of coal chemical industry.
2.背景技术2. Background technology
我国低阶煤约占煤炭资源的60％左右，快速热解提质是其高效清洁利用的有效途径，也是目前煤化工中投资最低、收益最大。副产的半焦，作为一种新型碳素材料，固定炭高、电阻率高含灰份低、硫和磷含量低、价格低廉，正逐步被推广应用于电石、铁合金等产品的生产，以替代价格昂贵的冶金焦。固体热载体法热质传递快、液收高、能量和资源利用合理、易于大型化，是目前最有工业化前景的粉煤快速热解提质煤工艺，但其生产的半焦均为粉焦，高效高值化利用成为制约该工艺的瓶颈。my country's low-rank coal accounts for about 60% of coal resources. Rapid pyrolysis upgrading is an effective way to use it efficiently and cleanly. It is also the lowest investment and the largest profit in coal chemical industry. The by-product semi-coke, as a new type of carbon material, has high fixed carbon, high resistivity, low ash content, low sulfur and phosphorus content, and low price. It is gradually being promoted and used in the production of calcium carbide, iron alloys and other products. Replace expensive metallurgical coke. The solid heat carrier method has fast heat and mass transfer, high liquid recovery, reasonable energy and resource utilization, and is easy to scale up. It is currently the most industrialized process for rapid pyrolysis of pulverized coal to upgrade coal, but the semi-coke it produces is all powder coke , high-efficiency and high-value utilization has become a bottleneck restricting the process.
目前乙炔主要是通过电石法大规模生产，是有机合成工业的重要原料。电石是以生石灰和碳素为原料，在电石炉中经过复杂的物理化学变化而生成的。尽管国内外电石生产工艺有电热法、旋转电弧炉法、氧热法、电热-氧热耦合法、等离子体法、催化法等，但传统的电炉加热法仍然是当前最为成熟的电石生产方法。其主要生产过程如下：块状的生石灰和焦炭首先通过配料后由电炉上端的入口或管道加入电炉内逐层升温，生石灰块在反应层内熔化成流体；在电极端部周围的大约1600℃-1700℃的高温区，具有较大活性的熔融态生石灰和焦炭块开始相互作用，发生化学反应，生成电石和富含CO的尾气；电石从电石炉底部排出，电石炉顶部排除富含CO的尾气发电或作为化工原料；电石水解生产乙炔，副产石灰浆沉降作为工业废渣亟待循环利用。电石生产过程中电石炉的尾气主要成分是CO，其处理方式有待解决。另外生石灰块和焦炭块反应过程需要经过生石灰熔融态和在焦炭块中渗入发生化学反应，反应温度高，速度慢，制约了电石业的规模化发展。At present, acetylene is mainly produced on a large scale through the calcium carbide method, and is an important raw material for the organic synthesis industry. Calcium carbide is produced from quicklime and carbon through complex physical and chemical changes in a calcium carbide furnace. Although domestic and foreign calcium carbide production processes include electrothermal method, rotary electric arc furnace method, oxygen thermal method, electrothermal-oxygen thermal coupling method, plasma method, catalytic method, etc., the traditional electric furnace heating method is still the most mature calcium carbide production method. Its main production process is as follows: First, lump quicklime and coke are added into the electric furnace through the inlet or pipe at the upper end of the furnace to raise the temperature layer by layer after batching, and the quicklime block melts into a fluid in the reaction layer; In the high temperature zone of 1700°C, the highly active molten quicklime and coke blocks begin to interact and undergo a chemical reaction to generate calcium carbide and CO-rich tail gas; the calcium carbide is discharged from the bottom of the calcium carbide furnace, and the CO-rich tail gas is discharged from the top of the calcium carbide furnace Power generation or as chemical raw materials; calcium carbide is hydrolyzed to produce acetylene, and the by-product lime slurry settles as industrial waste to be recycled urgently. The main component of the tail gas of calcium carbide furnace in the production process of calcium carbide is CO, and its treatment method needs to be solved. In addition, the reaction process of quicklime block and coke block needs to go through the molten state of quicklime and infiltrate into the coke block for chemical reaction. The reaction temperature is high and the speed is slow, which restricts the large-scale development of the calcium carbide industry.
目前的电炉加热法工艺过程中生石灰添加过程繁琐、复杂，且在石灰石在整个生产和使用过程中，始终伴随着固体破碎、固体筛分和固体运输等工序，这些工序均会产生大量小于6mm的粉状生石灰，亟待利用。另外由于优质石灰石资源较为紧张，开采对山体环境破坏严重，各地对石灰石开采量控制越来越严，成为国内生石灰生产的瓶颈，亟待提高石灰石的循环利用率。The process of adding quicklime in the current electric furnace heating process is cumbersome and complicated, and in the whole production and use of limestone, it is always accompanied by solid crushing, solid screening and solid transportation, etc. These processes will produce a large number of particles less than 6mm Powdered quicklime needs to be utilized urgently. In addition, due to the shortage of high-quality limestone resources, the mining has seriously damaged the mountain environment, and the control of limestone mining in various places has become more and more strict, which has become the bottleneck of domestic quicklime production. It is urgent to improve the recycling rate of limestone.
因此急需开发能够利用生石灰粉和粉焦生产电石的新工艺，消除粉煤热解提质的瓶颈，提高石灰石的循环利用率，降低反应温度，加快反应速度，降低生产能耗和成本，提高电石炉的处理能力，消除二次污染。Therefore, there is an urgent need to develop a new process that can use quicklime powder and powder coke to produce calcium carbide, eliminate the bottleneck of pyrolysis and upgrading of pulverized coal, improve the recycling rate of limestone, reduce the reaction temperature, speed up the reaction speed, reduce production energy consumption and cost, and increase the production of calcium carbide. The processing capacity of the furnace can eliminate secondary pollution.
3.发明内容3. Contents of the invention
本发明的目的是为了克服现有电炉加热法生产电石需要生石灰块和焦块的不足而发明的一种热解半焦生产石灰碳球团的生产工艺，既解决了生石灰粉和快速热解焦粉的利用难题，又降低反应温度、加快反应速度、降低生产能耗和成本、提高了电石炉的处理能力。The purpose of the present invention is to overcome the shortage of quicklime and coke in the production of calcium carbide by the existing electric furnace heating method, and to invent a production process for producing lime carbon pellets by pyrolysis of semi-coke, which not only solves the problem of quicklime powder and rapid pyrolysis of coke It solves the problem of powder utilization, reduces the reaction temperature, accelerates the reaction speed, reduces production energy consumption and cost, and improves the processing capacity of the calcium carbide furnace.
本发明的技术方案：Technical scheme of the present invention:
本发明的目的是通过将生石灰粉和热解焦粉通过粘合剂挤压成球团，在电石生产过程中生石灰和碳粉原位熔融反应，降低生产能耗和成本，提高电石炉处理能力。其特征是将生石灰粉和粘合剂按重量比4-8:1的配比，在密闭干燥条件下混合粉碎到1mm以下，制取改性生石灰粉；快速热解装置排出的高温焦粉换热冷却到70℃～550℃，将改性生石灰粉和热解焦粉按重量比1.3-1.8:1快速混合，保温30秒到40分钟，然后送入压力成型机热压成型生产石灰碳球团；压力成型机用惰性干燥气体密封，石灰碳球团同样使用惰性干燥气体冷却降温，作为产品送入电石炉原位反应生产电石。The purpose of the present invention is to reduce production energy consumption and cost and improve the processing capacity of calcium carbide furnace by extruding quicklime powder and pyrolysis coke powder into pellets through a binder, and in situ melting reaction of quicklime and carbon powder in the production process of calcium carbide . It is characterized in that quicklime powder and binder are mixed and pulverized to less than 1mm under airtight and dry conditions in a weight ratio of 4-8:1 to produce modified quicklime powder; the high-temperature coke powder discharged from the rapid pyrolysis device is replaced Heat and cool to 70 ℃ ~ 550 ℃, quickly mix the modified quicklime powder and pyrolysis coke powder according to the weight ratio of 1.3-1.8:1, keep it warm for 30 seconds to 40 minutes, and then send it to the pressure molding machine for hot pressing to produce lime carbon spheres The pressure molding machine is sealed with an inert dry gas, and the lime carbon pellets are also cooled with an inert dry gas, and sent as a product into the calcium carbide furnace for in-situ reaction to produce calcium carbide.
其中，粘合剂为高软化点沥青、低阶煤、焦煤、煤焦油沥青、高分子合成有机物中的一种或多种。Wherein, the binder is one or more of high softening point pitch, low-rank coal, coking coal, coal tar pitch, and polymer synthetic organic matter.
本发明将实施例来详细叙述本发明的特点。The present invention describes the characteristics of the present invention in detail with examples.
4.附图说明4. Description of drawings
附图1为本发明的工艺示意图。Accompanying drawing 1 is process schematic diagram of the present invention.
附图的图面说明如下：The descriptions of the attached drawings are as follows:
1、生石灰粉加入口 2、粘合剂加入口 3、粉碎机 4、固体换热器 5、混合器6、保温罐 7、压力成型机 8、冷却器 9、热解焦粉入口1. Lime powder inlet 2. Adhesive inlet 3. Pulverizer 4. Solid heat exchanger 5. Mixer 6. Insulation tank 7. Pressure forming machine 8. Cooler 9. Pyrolysis coke powder inlet
下面结合附图和实施例来详述本发明的工艺特点。The process characteristics of the present invention will be described in detail below in conjunction with the accompanying drawings and examples.
5.具体实施方式5. Specific implementation
实施例1，将生石灰粉和煤焦油沥青按重量比5:1的配比，分别从生石灰粉补充口(1)和粘合剂加入口(1)加入到粉碎机(3)中、在密闭干燥条件下低温混合粉碎到1mm以下，制取改性生石灰粉；快速热解装置排出的高温焦粉经固体换热器(4)换热冷却到300℃，将改性生石灰粉和热解焦粉按重量比1.6:1通过混合器(5)快速混合，在保温罐(6)保温30秒，然后送入压力成型机(7)热压成型生产石灰碳球团；压力成型机(7)用干燥N2密封，石灰碳球团同样使用冷却器(8)N2冷却降温，作为产品送入电石炉原位反应生产电石。Example 1, quicklime powder and coal tar pitch are added to the pulverizer (3) from the quicklime powder replenishment port (1) and the binder addition port (1) respectively in a proportioning ratio of 5:1 by weight. Under dry conditions, low-temperature mixing and crushing to less than 1mm is used to produce modified quicklime powder; the high-temperature coke powder discharged from the rapid pyrolysis device is cooled to 300°C through the solid heat exchanger (4), and the modified quicklime powder and pyrolysis coke The powder is quickly mixed by the mixer (5) at a weight ratio of 1.6:1, kept in the heat preservation tank (6) for 30 seconds, and then sent to the pressure forming machine (7) for hot pressing to produce lime carbon pellets; the pressure forming machine (7) Sealed with dry N 2 , the lime carbon pellets are also cooled with cooler (8) N 2 , and sent as a product into the calcium carbide furnace for in-situ reaction to produce calcium carbide.
采用MT-T925-2004工业型煤落下强度测定方法测定石灰碳球团的落下强度，落下强度大于95％。The drop strength of lime carbon pellets was measured by MT-T925-2004 industrial briquette drop strength test method, and the drop strength was greater than 95%.
实施例2，将生石灰粉和焦煤按重量比4:1的配比，分别从生石灰粉补充口(1)和粘合剂加入口(1)加入到粉碎机(3)中、在密闭干燥条件下混合粉碎到1mm以下，制取改性生石灰粉；快速热解装置排出的高温焦粉经固体换热器(4)换热冷却到550℃，将改性生石灰粉和热解焦粉按重量比1.7:1通过混合器(5)快速混合，在保温罐(6)保温15分钟，然后送入压力成型机(7)热压成型生产石灰碳球团；压力成型机(7)用热解干气密封，石灰碳球团同样使用冷却器(8)热解干气冷却降温，作为产品送入电石炉原位反应生产电石。Example 2, quicklime powder and coking coal are added to the pulverizer (3) from the quicklime powder replenishment port (1) and the binder addition port (1) respectively in a weight ratio of 4:1, under airtight and dry conditions. Mix and pulverize below 1mm to produce modified quicklime powder; the high-temperature coke powder discharged from the rapid pyrolysis device is cooled to 550°C through the solid heat exchanger (4), and the modified quicklime powder and pyrolysis coke powder are mixed by weight Ratio of 1.7:1 is quickly mixed by the mixer (5), kept in the insulation tank (6) for 15 minutes, and then sent to the pressure forming machine (7) for hot pressing to produce lime carbon pellets; the pressure forming machine (7) uses pyrolysis The dry gas is sealed, and the lime carbon pellets are also cooled and cooled by the pyrolysis dry gas of the cooler (8), and sent into the calcium carbide furnace as a product for in-situ reaction to produce calcium carbide.
采用MT-T925-2004工业型煤落下强度测定方法测定石灰碳球团的落下强度，落下强度大于85％。The drop strength of lime carbon pellets was measured by MT-T925-2004 industrial briquette drop strength test method, and the drop strength was greater than 85%.
实施例3，利用热解装置的低阶煤粉代替焦煤，其他过程与实施例2相同。In Example 3, low-rank pulverized coal from a pyrolysis device is used instead of coking coal, and the other processes are the same as in Example 2.
本发明所提供的热解半焦生产石灰碳球团的生产工艺，采用分步混合，既有利于粘合剂、生石灰粉和焦粉混合均匀，减少粘合剂的使用量，减少石灰碳球团挥发分，提高固碳量；又通过粘合剂包覆生石灰粉表面，减少生石灰粉吸潮，降低了生石灰粉的储存和运输难度；同时以生石灰粉和焦粉为原料，扩大了电石原料的来源，提高了半焦粉的附加值，降低了生产成本；石灰碳球团用于电炉法生产电石，原位发生化学反应降低了电耗，大大简化了电石生产工艺，提高了电石炉的处理能力，避免了电石渣的固废污染，实现了优质石灰石资源的循环利用。The production process for producing lime carbon pellets by pyrolysis of semi-coke provided by the present invention adopts step-by-step mixing, which is beneficial to uniform mixing of binder, quicklime powder and coke powder, reduces the amount of binder used, and reduces lime carbon pellets Volatile matter can be collected to increase the amount of carbon fixation; the surface of quicklime powder is coated with adhesives to reduce the moisture absorption of quicklime powder and reduce the difficulty of storage and transportation of quicklime powder; The source of semi-coke powder improves the added value of semi-coke powder and reduces production costs; lime carbon pellets are used in the production of calcium carbide by electric furnace method, and the chemical reaction occurs in situ to reduce power consumption, greatly simplify the production process of calcium carbide, and improve the production efficiency of calcium carbide furnace. The processing capacity avoids the solid waste pollution of carbide slag and realizes the recycling of high-quality limestone resources.
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| CN (1) | CN106564901A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107117618A (en) * | 2017-06-16 | 2017-09-01 | 中国石油大学(华东) | A kind of hot method of calcium focal sphere group classification oxygen produces the device of calcium carbide |
| CN108525608A (en) * | 2018-03-23 | 2018-09-14 | 宁夏宝塔化工中心实验室(有限公司) | A method of producing calcium carbide coke powder mix and convert calcium lime powder pressure ball molding |
| CN109133063A (en) * | 2018-10-29 | 2019-01-04 | 北京科技大学 | The method of electrothermal way generation calcium carbide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105668568A (en) * | 2016-01-04 | 2016-06-15 | 神雾环保技术股份有限公司 | System and method for production of calcium carbide |
| CN105907436A (en) * | 2016-06-08 | 2016-08-31 | 北京神雾环境能源科技集团股份有限公司 | System and method for preparing calcium carbide raw material |
| CN106008133A (en) * | 2016-07-01 | 2016-10-12 | 神雾环保技术股份有限公司 | Method and system for preparing acetylene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668568A (en) * | 2016-01-04 | 2016-06-15 | 神雾环保技术股份有限公司 | System and method for production of calcium carbide |
| CN105907436A (en) * | 2016-06-08 | 2016-08-31 | 北京神雾环境能源科技集团股份有限公司 | System and method for preparing calcium carbide raw material |
| CN106008133A (en) * | 2016-07-01 | 2016-10-12 | 神雾环保技术股份有限公司 | Method and system for preparing acetylene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117618A (en) * | 2017-06-16 | 2017-09-01 | 中国石油大学(华东) | A kind of hot method of calcium focal sphere group classification oxygen produces the device of calcium carbide |
| CN107117618B (en) * | 2017-06-16 | 2023-11-24 | 中国石油大学(华东) | A device for producing calcium carbide using the graded oxythermal method of calcium coke pellets |
| CN108525608A (en) * | 2018-03-23 | 2018-09-14 | 宁夏宝塔化工中心实验室(有限公司) | A method of producing calcium carbide coke powder mix and convert calcium lime powder pressure ball molding |
| CN109133063A (en) * | 2018-10-29 | 2019-01-04 | 北京科技大学 | The method of electrothermal way generation calcium carbide |
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