氧热法电石生产技术研发进展
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摘要
电石是一种重要的由煤生产纯化学品的中间产物,一百多年来由电弧法生产,耗电量很大,从燃煤发电算起,能耗很高。为了降低能耗,国内外很早就开始研发以含碳原料与氧气反应供热的氧热法技术。简要介绍了过去中试研发的几个氧热法技术及其存在问题,较为详细地介绍了近年来我国在电石生产反应器开发、基本化学反应和反应工程规律认识等方面的进展,重点展示了对电石生成反应机理的认识以及原料性质、形貌、传质、灰分等对反应的影响,整体工艺能效衡算等方面的特征。
Calcium carbide is an important platform chemical for production of pure chemicals and polymers from coal. Production of calcium carbide adopted in the past century relies on electric-arc heating, which is energy intensive particularly when power is generated from combustion of coal. To avoid energy loss in power generation, auto-thermal calcium carbide production processes have been developed and tested at scale up to pilot plant or industrial demonstration. This paper introduces features of these processes and shows recent developments in China in terms of fundamental aspects of the process, including reactors, reaction mechanism and kinetics, effects of feeds properties, mass transfer and phase change on the reaction, as well as system integration and analysis.
Calcium carbide is an important platform chemical for production of pure chemicals and polymers from coal. Production of calcium carbide adopted in the past century relies on electric-arc heating, which is energy intensive particularly when power is generated from combustion of coal. To avoid energy loss in power generation, auto-thermal calcium carbide production processes have been developed and tested at scale up to pilot plant or industrial demonstration. This paper introduces features of these processes and shows recent developments in China in terms of fundamental aspects of the process, including reactors, reaction mechanism and kinetics, effects of feeds properties, mass transfer and phase change on the reaction, as well as system integration and analysis.
引文
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[2]Liao Yuqing(廖玉清).Development trends of calcium carbide production technology[J].Coal Chemical Industry(煤化工),1990,3:48-52
[3]Xiong Moyuan(熊谟远).Production and Utilization of Calcium Carbide for Fine Chemicals(电石生产及其深加工产品)[M].Beijing:Chemical Industry Press,1985
[4]Liu Qing(刘青),Liu Qingya(刘清雅),Wang Renxing(王仁醒),Xu Tao(徐涛),Liu Zhenyu(刘振宇).Reaction behaviors of calcium carbide with alcohols[J].CIESC Journal(化工学报),2013,64(7):2573-2579
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[6]El-Nass M H,Munz R J,Ajersch F.Solid-phase synthesis of calcium carbide in a plasma reactor[J].Plasma Chemistry and Plasma Processing,1998,18(3):409-427
[7]Peter P,Werner H,Richard M.Ullmann’s Encyclopedia of Industrial Chemistry:Acetylene[M].New York:John Wiley&Sons,Inc.,2012
[8]Liu Zhenyu,Liu Qingya,Li Guodong.Method and system for producing calcium carbide[P]:US,13/017207.2011-01-31
[9]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Li Guodong(李国栋),Tang Xubo(唐旭博).Method for producing calcium carbide[P]:CN,101327928 A.2008-12-24
[10]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Li Guodong(李国栋).System for producing calcium carbide[P]:CN,101428799 B.2011-05-11
[11]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Wang Renxing(王仁醒),Qu Yixin(屈一新),Li Chengyue(李成岳),Liu Hui(刘辉).Hybrid reactor and method of co-production of calcium carbide,CO gas and tar[P]:CN,103272536 A.2013-09-04
[12]Liu Lu(刘陆),Yang Pengyuan(杨鹏远),Liu Hui(刘辉).Thermodynamic analysis of calcium carbide synthesis and its thermal coupling with coke combustion[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2012,39(2):1-6
[13]Yu Yang(于洋),Li Wentao(李文涛),Dou Yaling(窦雅玲),Liu Hui(刘辉).Simulation of the reaction performance of a fluid bed reactor for oxygen-heated calcium carbide production[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2013,40(3):27-31
[14]Li Wentao(李文涛),Yu Yang(于洋),Dou Yaling(窦雅玲),Liu Hui(刘辉).Design of the preheated area in a combined bed reactor for oxygen-heating production of calcium carbide[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2014,41(1):24-28
[15]Guo Jing,Zheng Danxing.Thermodynamic analysis of low-rank-coal based oxygen-thermal acetylene manufacture process system[J].Industrial&Engineering Chemistry Research,2012,51(41):13414-13422
[16]Guo Jing,Zheng Danxing,Chen Xiaohui,Mi Yue,Liu Zhenyu.Chemical reaction equilibrium behaviors of oxy-thermal carbide furnace reaction system[J].Industrial&Engineering Chemistry Research,2013,52(50):17773-17780
[17]Mi Yue,Zheng Danxing,Guo Jing,Chen Xiaohui,Ji Peijun.Assessment of energy use and carbon footprint for low-rank coal based oxygen-thermal and electro-thermal calcium carbide manufacturing processes[J].Fuel Processing Technology,2014,119:305-315
[18]van Loon Willem,Koopal Sieds.Preparation of calcium carbide[P]:US,2738256.1956-03-13
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[20]Koopal Sieds,Moison Joannes H C.Preparation of calcium carbide[P]:US,2749219.1956-06-05
[21]Sage Bruce H.Calcium carbide process[P]:US,3044858.1962-07-17
[22]Atwell Harold V.Oxygen-thermal process[P]:US,3017244.1962-01-16
[23]Kersting Hans-Joachim,Wolfrum Erhard,Portz Willi,Strauss Georg.Production of calcium carbide[P]:US,4391786.1983-7-5
[24]Fujishige M,Yokogawa H,Ujiie S,Tokiya M.Production of calcium carbide by blast furnace process[P]:JP,61-178412.1986
[25]Yang Fumin(杨福民).Method and equipment for calcium carbide production[P]:CN,85107784 A.1987-05-13
[26]Yang Fumin(杨福民).Method for calcium carbide production[P]:CN,1047065 A.1990-11-21
[27]Yang Chaojie(杨朝杰).Method and equipment for melting calcium carbide production[P]:CN,1038798 A.1990-01-17
[28]Yue Shucai(岳书才).Calcium carbide melting technology and equipment in oil-spraying furnace[P]:CN,1191845 A.1998-09-02
[29]Yue Shucai(岳书才).Method and apparatus for preparing calcium carbide by oxygen-fuel blowing in shaft furnace[P]:CN,100513310C.2009-07-15
[30]Du Wenguang(杜文广),Liu Shoujun(刘守军),Cheng Jialin(程加林),He Xiaogang(何小刚),Zhang Zhicong(张智聪).Method for simultaneously producing acetylene stones,ferrosilicium and high-purity CO gas[P]:CN,101362599 B.2011-02-09
[31]Liu Hongjian(刘宏建),Jiang Fengzhang(姜逢章),Zhang Xiuquan(张秀全),Xu Caifu(徐才福),Li Wucheng(李伍成),Yang Weiwei(杨威威),Yang Xiaoxin(杨晓新),Yin Weiyu(殷为玉),Chen Fengjing(陈凤敬),Chen Xuefeng(陈雪枫).Reactor for oxygen thermal production of calcium carbide and synthesis gas[P]:CN,201907973 U.2011-07-27
[32]Xu Caifu(徐才福),Chen Xuefeng(陈雪枫),Xu Jianmin(徐建民),Li Wucheng(李伍成),Yang Jianguo(杨建国),Zhang Xiuquan(张秀全),Zhang Zongfei(张宗飞),Liu Hongjian(刘宏建),Zhang Zhihua(张志华),Yang Xiaolin(杨小林).Methods for oxygen thermal production of calcium carbide and synthesis gas and reactor for calcium carbide[P]:CN,102153085 B.2013-10-16
[33]Latta William,Vierstra Scott,Targett Matthew,et al.Cyclone reactor and method for producing usable by-products using cyclone reactor[P]:US,20120263640.2012-10-18
[34]Jia Huiping(贾会平).Device for oxygen thermal production of calcium carbide[P]:CN,103303923 A.2013-09-18
[35]Tagawa H,Sugawara H.The kinetics of the formation of calcium carbide in a solid-solid reaction[J].J.Chem.Soc.Jpn.,1962,35:1276-1279
[36]Müller M B.Structure,properties and reactions of CaO in burnt lime(Ⅲ):Composite reactions of CaO and C in solid and liquid state[J].Scand.J.Metall.,1990,19:210-217
[37]Wang J,Morishita K,Takarada T.High-temperature interactions between coal char and mixtures of calcium oxide,quartz,and kaolinite[J].Energy Fuel,2001,15:1145-1152
[38]Li Guodong(李国栋).Fundamental study on a novel technology of CaC2 production from fine coke and fine CaO[D].Beijing:Beijing University of Chemical Technology,2011
[39]Li Guodong,Liu Qingya,Liu Zhenyu.CaC2 production from pulverized coke and CaO at low temperatures reaction mechanisms[J].Industrial&Engineering Chemistry Research,2012,51(33):10742-10747
[40]Chen Weiliang(陈为亮).Study on preparing lithium from Li2CO3 by vacuum carbothermic reduction[D].Kunming:Kunming University of Science and Technology,2000
[41]Yu Jiaqing,Wu Weitao,Wang Maocai.Interfacial reactions between glass coatings and steel substrates induced by laser cladding[J].Surface Coating Technology,1995,72:112-119
[42]Ji Leiming,Liu Qingya,Liu Zhenyu.Thermodynamic analysis of calcium carbide production[J].Industrial&Engineering Chemistry Research,2014,53(6):2537-2543
[43]Li Guodong,Liu Qingya,Liu Zhenyu.Production of calcium carbide from fine biochars[J].Angewandte Chemie International Edition,2010,49(45):8480-8483
[44]Li Guodong,Liu Qingya,Liu Zhenyu.Kinetic behaviors of CaC2production from coke and CaO[J].Industrial&Engineering Chemistry Research,2013,52(16):5587-5592
[45]Brookes C,Gall C E,Hudgins R R.A model for the formation of calcium carbide in solid pellets[J].Canadian J.Chem.Eng.,1975,53:527-535
[46]Torikai Naochika,Nagaishi Takashi,Saito Sadao,Miyamoto Gen.Reaction between calcium oxide and graphite[J].Bull.Fac.Eng.Yokohama Nat.Univ.,1967,16:21-28
[47]Steven Lee Rowan,Ismail Celik,Jose Escobar Vargas,Suryanarayana Raju Pakalapati,Matt Targett.Reaction kinetics modeling of CaC2formation from coal and lime[J].Industrial&Engineering Chemistry Research,2014,53(8):2963-2975
[48]Li Guodong,Liu Qingya,Liu Zhenyu.CaC2 production from pulverized coke and CaO at low temperatures-influence of minerals in coal-derived coke[J].Industrial&Engineering Chemistry Research,2012,51(33):10748-10754
[49]Schwerdtfeger K,Schubert H G.Solubility of nitrogen and carbon in ESR type slag[J].Metall.Trans.B,1977,8B:689-691
[50]Mitchell A.The CaF2-CaC2 system,and its relation to electroslag remelting practice[J].Trans.Metall.Soc.AIME,1968,242:2507-2511
[51]Tang Xubo(唐旭博),Ma Caixia(马彩霞),Liu Qingya(刘清雅),Li Guodong(李国栋),Liu Zhenyu(刘振宇).Reactions of calcium compounds and coke for preparation of calcium carbide[J].Journal of Fuel Chemistry and Technology(燃料化学学报),2010,38(5):539-543
[2]Liao Yuqing(廖玉清).Development trends of calcium carbide production technology[J].Coal Chemical Industry(煤化工),1990,3:48-52
[3]Xiong Moyuan(熊谟远).Production and Utilization of Calcium Carbide for Fine Chemicals(电石生产及其深加工产品)[M].Beijing:Chemical Industry Press,1985
[4]Liu Qing(刘青),Liu Qingya(刘清雅),Wang Renxing(王仁醒),Xu Tao(徐涛),Liu Zhenyu(刘振宇).Reaction behaviors of calcium carbide with alcohols[J].CIESC Journal(化工学报),2013,64(7):2573-2579
[5]National Bureau of Statistics of China(中华人民共和国国家统计局).National data[OL].Beijing:National Bureau of Statistics of China.[2014-01-29].http://data.stats.gov.cn/workspace/advm=hgnd&x=index&y=time&z=region&time=-1,2003&selectId=000000
[6]El-Nass M H,Munz R J,Ajersch F.Solid-phase synthesis of calcium carbide in a plasma reactor[J].Plasma Chemistry and Plasma Processing,1998,18(3):409-427
[7]Peter P,Werner H,Richard M.Ullmann’s Encyclopedia of Industrial Chemistry:Acetylene[M].New York:John Wiley&Sons,Inc.,2012
[8]Liu Zhenyu,Liu Qingya,Li Guodong.Method and system for producing calcium carbide[P]:US,13/017207.2011-01-31
[9]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Li Guodong(李国栋),Tang Xubo(唐旭博).Method for producing calcium carbide[P]:CN,101327928 A.2008-12-24
[10]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Li Guodong(李国栋).System for producing calcium carbide[P]:CN,101428799 B.2011-05-11
[11]Liu Zhenyu(刘振宇),Liu Qingya(刘清雅),Wang Renxing(王仁醒),Qu Yixin(屈一新),Li Chengyue(李成岳),Liu Hui(刘辉).Hybrid reactor and method of co-production of calcium carbide,CO gas and tar[P]:CN,103272536 A.2013-09-04
[12]Liu Lu(刘陆),Yang Pengyuan(杨鹏远),Liu Hui(刘辉).Thermodynamic analysis of calcium carbide synthesis and its thermal coupling with coke combustion[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2012,39(2):1-6
[13]Yu Yang(于洋),Li Wentao(李文涛),Dou Yaling(窦雅玲),Liu Hui(刘辉).Simulation of the reaction performance of a fluid bed reactor for oxygen-heated calcium carbide production[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2013,40(3):27-31
[14]Li Wentao(李文涛),Yu Yang(于洋),Dou Yaling(窦雅玲),Liu Hui(刘辉).Design of the preheated area in a combined bed reactor for oxygen-heating production of calcium carbide[J].Journal of Beijing University of Chemical Technology:Natural Science Edition(北京化工大学学报:自然科学版),2014,41(1):24-28
[15]Guo Jing,Zheng Danxing.Thermodynamic analysis of low-rank-coal based oxygen-thermal acetylene manufacture process system[J].Industrial&Engineering Chemistry Research,2012,51(41):13414-13422
[16]Guo Jing,Zheng Danxing,Chen Xiaohui,Mi Yue,Liu Zhenyu.Chemical reaction equilibrium behaviors of oxy-thermal carbide furnace reaction system[J].Industrial&Engineering Chemistry Research,2013,52(50):17773-17780
[17]Mi Yue,Zheng Danxing,Guo Jing,Chen Xiaohui,Ji Peijun.Assessment of energy use and carbon footprint for low-rank coal based oxygen-thermal and electro-thermal calcium carbide manufacturing processes[J].Fuel Processing Technology,2014,119:305-315
[18]van Loon Willem,Koopal Sieds.Preparation of calcium carbide[P]:US,2738256.1956-03-13
[19]van Loon Willem,Koopal Sieds.Preparation of calcium carbide[P]:US,2794706.1957-06-04
[20]Koopal Sieds,Moison Joannes H C.Preparation of calcium carbide[P]:US,2749219.1956-06-05
[21]Sage Bruce H.Calcium carbide process[P]:US,3044858.1962-07-17
[22]Atwell Harold V.Oxygen-thermal process[P]:US,3017244.1962-01-16
[23]Kersting Hans-Joachim,Wolfrum Erhard,Portz Willi,Strauss Georg.Production of calcium carbide[P]:US,4391786.1983-7-5
[24]Fujishige M,Yokogawa H,Ujiie S,Tokiya M.Production of calcium carbide by blast furnace process[P]:JP,61-178412.1986
[25]Yang Fumin(杨福民).Method and equipment for calcium carbide production[P]:CN,85107784 A.1987-05-13
[26]Yang Fumin(杨福民).Method for calcium carbide production[P]:CN,1047065 A.1990-11-21
[27]Yang Chaojie(杨朝杰).Method and equipment for melting calcium carbide production[P]:CN,1038798 A.1990-01-17
[28]Yue Shucai(岳书才).Calcium carbide melting technology and equipment in oil-spraying furnace[P]:CN,1191845 A.1998-09-02
[29]Yue Shucai(岳书才).Method and apparatus for preparing calcium carbide by oxygen-fuel blowing in shaft furnace[P]:CN,100513310C.2009-07-15
[30]Du Wenguang(杜文广),Liu Shoujun(刘守军),Cheng Jialin(程加林),He Xiaogang(何小刚),Zhang Zhicong(张智聪).Method for simultaneously producing acetylene stones,ferrosilicium and high-purity CO gas[P]:CN,101362599 B.2011-02-09
[31]Liu Hongjian(刘宏建),Jiang Fengzhang(姜逢章),Zhang Xiuquan(张秀全),Xu Caifu(徐才福),Li Wucheng(李伍成),Yang Weiwei(杨威威),Yang Xiaoxin(杨晓新),Yin Weiyu(殷为玉),Chen Fengjing(陈凤敬),Chen Xuefeng(陈雪枫).Reactor for oxygen thermal production of calcium carbide and synthesis gas[P]:CN,201907973 U.2011-07-27
[32]Xu Caifu(徐才福),Chen Xuefeng(陈雪枫),Xu Jianmin(徐建民),Li Wucheng(李伍成),Yang Jianguo(杨建国),Zhang Xiuquan(张秀全),Zhang Zongfei(张宗飞),Liu Hongjian(刘宏建),Zhang Zhihua(张志华),Yang Xiaolin(杨小林).Methods for oxygen thermal production of calcium carbide and synthesis gas and reactor for calcium carbide[P]:CN,102153085 B.2013-10-16
[33]Latta William,Vierstra Scott,Targett Matthew,et al.Cyclone reactor and method for producing usable by-products using cyclone reactor[P]:US,20120263640.2012-10-18
[34]Jia Huiping(贾会平).Device for oxygen thermal production of calcium carbide[P]:CN,103303923 A.2013-09-18
[35]Tagawa H,Sugawara H.The kinetics of the formation of calcium carbide in a solid-solid reaction[J].J.Chem.Soc.Jpn.,1962,35:1276-1279
[36]Müller M B.Structure,properties and reactions of CaO in burnt lime(Ⅲ):Composite reactions of CaO and C in solid and liquid state[J].Scand.J.Metall.,1990,19:210-217
[37]Wang J,Morishita K,Takarada T.High-temperature interactions between coal char and mixtures of calcium oxide,quartz,and kaolinite[J].Energy Fuel,2001,15:1145-1152
[38]Li Guodong(李国栋).Fundamental study on a novel technology of CaC2 production from fine coke and fine CaO[D].Beijing:Beijing University of Chemical Technology,2011
[39]Li Guodong,Liu Qingya,Liu Zhenyu.CaC2 production from pulverized coke and CaO at low temperatures reaction mechanisms[J].Industrial&Engineering Chemistry Research,2012,51(33):10742-10747
[40]Chen Weiliang(陈为亮).Study on preparing lithium from Li2CO3 by vacuum carbothermic reduction[D].Kunming:Kunming University of Science and Technology,2000
[41]Yu Jiaqing,Wu Weitao,Wang Maocai.Interfacial reactions between glass coatings and steel substrates induced by laser cladding[J].Surface Coating Technology,1995,72:112-119
[42]Ji Leiming,Liu Qingya,Liu Zhenyu.Thermodynamic analysis of calcium carbide production[J].Industrial&Engineering Chemistry Research,2014,53(6):2537-2543
[43]Li Guodong,Liu Qingya,Liu Zhenyu.Production of calcium carbide from fine biochars[J].Angewandte Chemie International Edition,2010,49(45):8480-8483
[44]Li Guodong,Liu Qingya,Liu Zhenyu.Kinetic behaviors of CaC2production from coke and CaO[J].Industrial&Engineering Chemistry Research,2013,52(16):5587-5592
[45]Brookes C,Gall C E,Hudgins R R.A model for the formation of calcium carbide in solid pellets[J].Canadian J.Chem.Eng.,1975,53:527-535
[46]Torikai Naochika,Nagaishi Takashi,Saito Sadao,Miyamoto Gen.Reaction between calcium oxide and graphite[J].Bull.Fac.Eng.Yokohama Nat.Univ.,1967,16:21-28
[47]Steven Lee Rowan,Ismail Celik,Jose Escobar Vargas,Suryanarayana Raju Pakalapati,Matt Targett.Reaction kinetics modeling of CaC2formation from coal and lime[J].Industrial&Engineering Chemistry Research,2014,53(8):2963-2975
[48]Li Guodong,Liu Qingya,Liu Zhenyu.CaC2 production from pulverized coke and CaO at low temperatures-influence of minerals in coal-derived coke[J].Industrial&Engineering Chemistry Research,2012,51(33):10748-10754
[49]Schwerdtfeger K,Schubert H G.Solubility of nitrogen and carbon in ESR type slag[J].Metall.Trans.B,1977,8B:689-691
[50]Mitchell A.The CaF2-CaC2 system,and its relation to electroslag remelting practice[J].Trans.Metall.Soc.AIME,1968,242:2507-2511
[51]Tang Xubo(唐旭博),Ma Caixia(马彩霞),Liu Qingya(刘清雅),Li Guodong(李国栋),Liu Zhenyu(刘振宇).Reactions of calcium compounds and coke for preparation of calcium carbide[J].Journal of Fuel Chemistry and Technology(燃料化学学报),2010,38(5):539-543