多层流化床低阶煤分级热解提高焦油品质研究
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- 英文论文题名：Study on improving tar quality from staged pyrolysis of low rank coal in multistage fluidized bed
- 论文作者：周琦
- 英文论文作者：Zhou Qi ; National Key Laboratory of Multi-phase Complex Systems ; Institute of Process Engineering ; CAS ; Beijing Research Institute of Coal Chemistry ; Coal Science and Technology Research Institute Co. ; Ltd. ; State Key Laboratory of Coal Mining and Clean Utilization ; National Energy Technology and Equipment Laboratory of Coal Utilization and Emission Control
- 年：2016
- 作者机构：中国科学院过程工程研究所多相复杂系统国家重点实验室;煤炭科学技术研究院有限公司煤化工分院;煤炭资源高效开采与洁净利用国家重点实验室;国家能源煤炭高效利用与节能减排技术装备重点实验室;
- 论文关键词：低阶煤 ; 分级热解 ; 多层流化床 ; 煤气化 ; 焦油品质
- 英文论文关键词：low rank coal ; staged pyrolysis ; multistage fluidized bed ; coal gasification ; tar quality
- 会议召开时间：2016-11-29
- 会议录名称：第三届煤炭科技创新高峰论坛——煤炭绿色开发与清洁利用技术与装备论文集
- 语种：中文
- 分类号：TQ530.2
- 学会代码：ZGMT
- 会议名称：第三届煤炭科技创新高峰论坛——煤炭绿色开发与清洁利用技术与装备
- 会议地点：中国北京
- 主办单位：中国煤炭工业协会、中国煤炭科工集团有限公司、中国煤炭学会、煤炭科学研究总院
- 学会名称：中国煤炭学会
- 页数：8
- 文件大小：1237k
- 原文格式：O
- 会议级别：全国
摘要
为提高低阶煤热解焦油品质,提出了上部煤分级热解和下部半焦气化耦合的多层流化床低阶煤热解新工艺,在实验室多层溢流管式流化床中研究了操作模式(流化床层数分别为单层、双层、三层)、过量氧气系数、水蒸气煤比(质量比)等因素对热解产物产率和焦油品质的影响。结果表明:氧气和水蒸气作为气化剂可促进多环芳烃的裂解;高温区产生的重质焦油在经过上部床层时与热态半焦接触,在半焦催化作用下发生催化重整反应可提高焦油品质;随着流化床层数从单层增加到三层,热解气体和焦油产率增加,半焦产率下降,焦油的组分明显减少,焦油中轻油的产率逐渐增加,而酚油和洗油产率下降:轻油与酚油质量分数之和在流化床层数为三层时达到了99.49%。因此,通过多层流化床热解低阶煤可以获得轻质组分含量较高的焦油。
In order to improve tar quality from pyrolysis of low rank coal,the new technique of low rank coal pyrolysis in multistage fluidized bed with coal staged pyrolysis in the upper stage and char gasification in the lower stage was proposed.The effects on products distribution and tar quality were investigated under the conditon of different operation mode(the numbers of fluidized bed stages was single,double and three respectively),excessive oxygen ratio and steam and coal mass ratio.The results showed that the oxygen and steam as gasifying agent could promote cracking of poly cyclic aromatic hydrocarbon.The heavy tar species formed in the high temperature region was contacted with hot char when they passed the upper bed,which could be furtherly cracked and reformed under the catalysis of char to improve the tar quality.With increasing the number of stages from single to three,the yield of pyrolysis gas and tar,and the content of light oil increased,whereas the char yield,the amount of component of tar,the content of phenol oil and wash oil decreased.The content of both the light oil and phenol oil of tar obtained from the three-stage fluidized bed pyrolysis reached 99.49%.Therefore,the tar with high content of light oil could obtained by staged pyrolysis of low rank coal in multistage fluidized bed.
In order to improve tar quality from pyrolysis of low rank coal,the new technique of low rank coal pyrolysis in multistage fluidized bed with coal staged pyrolysis in the upper stage and char gasification in the lower stage was proposed.The effects on products distribution and tar quality were investigated under the conditon of different operation mode(the numbers of fluidized bed stages was single,double and three respectively),excessive oxygen ratio and steam and coal mass ratio.The results showed that the oxygen and steam as gasifying agent could promote cracking of poly cyclic aromatic hydrocarbon.The heavy tar species formed in the high temperature region was contacted with hot char when they passed the upper bed,which could be furtherly cracked and reformed under the catalysis of char to improve the tar quality.With increasing the number of stages from single to three,the yield of pyrolysis gas and tar,and the content of light oil increased,whereas the char yield,the amount of component of tar,the content of phenol oil and wash oil decreased.The content of both the light oil and phenol oil of tar obtained from the three-stage fluidized bed pyrolysis reached 99.49%.Therefore,the tar with high content of light oil could obtained by staged pyrolysis of low rank coal in multistage fluidized bed.
引文
[1]Li C,Suzuki K.Resources,properties and utilization of tar[J].Resources Conservation&Recycling,2010,54(11):905-915.
[2]Atwood M T,Schulman B L.The toscoal process pyrolysis of western coals and lignites for char and oil production[J].Preprints of Papers-American Chemical Society,Division of Fuel Chemical,1977,22(2):233-252.
[3]White L C.Frederick J P.ENCOAL mild coal gasification project[J].Fuel&Energy Abstracts,1995(2):76.
[4]Strom A H,Eddinger R T.COED plant for coal conversion[J].Chemical Engineering Progress,1971,67(3):75-80.
[5]Rammler R W,Luigi K.Synthetic fuels from Lurgi coal pyrolysis[J].Energy Progress,1982,2(2):121-129.
[6]戴秋菊,唐道武,常万林.采用多段回转炉热解工艺综合利用年青煤[J].煤炭加工与综合利用,1999(3):22-23.Dai Qiuju,Tang Daowu,Chang Wanlin.Comprehensive utilization of low rank coal in multistage rotary furnace pyrolysis technology[J].Coal Processing and Comprehensive Utilization,1999(3):22-23.
[7]Guo S C,Luo C Q,Zhang D J,et al.Experiment in pilot plant of new technology for lignite retorting using solid heat carrier[J].Journal of Dalian University of Technology,1995,35(1):46-50.
[8]Wang J G,Lu X S,Yao J Z,et al.Experimental study of coal topping process in a downer reactor[J].Industrial&Engineering Chemistry Research,2005,44:463-470.
[9]Qu X,Liang P,Wang Z F,et al.Pilot development of a polygeneration process of circulating fluidized bed combustion combined with coal pyrolysis[J].Chemical Engineering&Technology,2011,34:61-68.
[10]Velegol D,Gautam M,Shamsi A.Catalytic cracking of a coal tar in a fluid bed reactor[J].Powder Technology,1997,93:93-100.
[11]Kimura T,Miyazawa T,Nishikawa J,et al.Development of Ni catalysts for tar removal by steam gasification of biomass[J].Applied Catalysis B:Environmental,2006,68:160-170.
[12]Edwards J H,Schluter K,Tyler R J.Upgrading of flash pyrolysis tars to synthetic crude oil:1.First stage hydrotreatment using a disposable catalyst[J].Fuel,1985,64(5):594-599.
[13]Kouichi Miura.Mild conversion of coal for producing valuable chemicals[J].Fuel Processing Technology,2000,62(2):119-135.
[14]Graff R A,Brandes S D.Modification of coal by subcritical steam:pyrolysis and extraction yields[J].Energy&Fuels,1987,1(1):84-88.
[15]Serio M A,Kroo E,Charpenay S,et al.Improved liquefaction of low rank coals by reduction of retrogressive reactions[J].Preprints of Papers-American Chemical Society,Division Fuel Chemistry,1993,38:1021-1027.
[16]Ishaq M,Ahmad I,Shakirullah M,et al.Pyrolysis of some whole plastics and plastics-coal mixtures[J].Energy Conversion Management,2006,47:3216-3223.
[17]董美玉,朱子彬,何亦华,等.烟煤快速加氢热解研究Ⅲ.焦油组成考察[J].燃料化学学报,2000,28(1):55-58.Dong Meiyu,Zhu Zibin,He Yihua,et al.Flash hydropyrolysis of bituminous coalⅢ:Research on flash hydropyrolysis tar[J]Journal of Fuel Chemistry and Technology,2000,28(1):55-58.
[18]Fidalgo B,Niekerk D V,Millan M.The effect of syngas on tar quality and quantity in pyrolysis of a typical South African inertinite-rich coal[J].Fuel,2014,134(90):90-96.
[19]Sharma D K,Sulimma A,Van Heek KH.Hydropyrolysis of coal in the presence of steam[J].Fuel,1986,65(11):1571-1574.
[20]Zhang L X,Malsuhara T,Kudo S,et al.Rapid pyrolysis of brown coal in a drop-lube reactor with co-feeding of char as a promoter of in situ tar reforming[J].Fuel.2013,112(3):681-686.
[21]Liu S,Wang Y,Wu R,et al.Research on coal tar catalytic cracking over hot in-situ chars[J].Journal of Fuel Chemistry&Technology,2013,41(9):1041-1049.
[22]许徐飞,周琦,邹涛,等.溢流管式多层气固流化床稳定操作气速范围的影响因素[J].过程工程学报,2012,12(3):361-368.Xu Xufei,Zhou Qi,Zou Tao,et al.Gas velocity range of stable operation in a gas solid multistage fluidized bed with overflow standpipes[J].The Chinese Journal of Process Engineering,2012,12(3):361-368.
[23]Zhou Q,Zou T,Zhong M,et al.Lignite upgrading by multi-stage fluidized bed pyrolysis[J].Fuel Processing Technology,2013,116:35-43.
[24]周琦,邹涛,初茉,等.多层流化床褐煤热解半焦特性与自燃倾向性抑制[J].煤炭学报,2014,39(S2):531-537.Zhou Qi,Zou Tao,Chu Mo,et al.Characterization and suppression of spontaneous combustion propensity of lignite char by multi-stage fluidized bed pyrolysis[J].Journal of China Coal Society,2014,39(S2):531-537.
[25]Anthony D B.Howard J B.Coal devolatilization and hydrogasification[J].American Institute of Chemical Engineers,1976,22(4):625-656.
[26]Chen Y,Luo Y,Wu W,et al.Experimental investigation on tar formation and destruction in a lab-scale two-stage reactor[J].Energy&Fuels,2009,23(9):4659-4667.
[27]吴仕生,曾玺,任明威,等.含氧/蒸汽气氛中煤高温分解产物分布及反应性[J].燃料化学学报,2015,40(6):660-665.Wu Shisheng,Zeng Xi,Ren Mingwei,et al.Product distribution and reactivity of coal pyrolysis at high temperature and in atmospheres containing O_2/steam[J].Journal of Fuel Chemical and Technology,2015,40(6):660-665.
[28]Zhang C,Wu R,Xu G.Coal pyrolysis for high-quality tar in a fixed-bed pyrolyzer enhanced with internals[J].Energy&Fuels,2013,28(1):236-244.
[29]Zhang C,Wu R,Hu E,et al.Coal pyrolysis for high-quality tar and gas in 100 kg fixed bed enhanced with internals[J].Energy&Fuels,2014,28(11):7294-7302.
[30]王兴栋,韩江则,陆江银,等.半焦基催化剂裂解煤热解产物提高油气品质[J].化工学报,2013,63(12):3897-3905.Wang Xingdong,Han Jiangze,Lu Jiangyin,et al.Catalytic cracking of coal pyrolysis product for oil and gas upgrading over char-based catalysts[J].CIESC Journal,2013,63(12):3897-3905.
[31]钟梅,马风云.不同气氛下煤连续热解产物的分配规律及产品品质分析[J].燃料化学学报,2013,41(12):1427-1436.Zhong Mei,Ma Fengyun.Analysis of product distribution and quality for continuous pyrolysis of coal in different atmospheres[J].Journal of Fuel Chemistry and Technology,2013,41(12):1427-1436.
[32]陈宗定,张书,王芳杰,等.活化前后半焦原位催化重整褐煤热解焦油研究[J].煤炭科学技术,2014,42(11):105-110.Chen Zongding,Zhang Shu,Wang Fangjie,et al.Study on in-situ catalytic reforming of coal tar from pyrolysis of brown coal by activated and inactivated char[J].Coal Science and Technology,2014,42(11):105-110.
[33]Liao H Q,Li B Q,Zhang B J.Co-pyrolysis of coal with hydrogen-rich gases[J].Fuel,1998,77(8):847-851.
[2]Atwood M T,Schulman B L.The toscoal process pyrolysis of western coals and lignites for char and oil production[J].Preprints of Papers-American Chemical Society,Division of Fuel Chemical,1977,22(2):233-252.
[3]White L C.Frederick J P.ENCOAL mild coal gasification project[J].Fuel&Energy Abstracts,1995(2):76.
[4]Strom A H,Eddinger R T.COED plant for coal conversion[J].Chemical Engineering Progress,1971,67(3):75-80.
[5]Rammler R W,Luigi K.Synthetic fuels from Lurgi coal pyrolysis[J].Energy Progress,1982,2(2):121-129.
[6]戴秋菊,唐道武,常万林.采用多段回转炉热解工艺综合利用年青煤[J].煤炭加工与综合利用,1999(3):22-23.Dai Qiuju,Tang Daowu,Chang Wanlin.Comprehensive utilization of low rank coal in multistage rotary furnace pyrolysis technology[J].Coal Processing and Comprehensive Utilization,1999(3):22-23.
[7]Guo S C,Luo C Q,Zhang D J,et al.Experiment in pilot plant of new technology for lignite retorting using solid heat carrier[J].Journal of Dalian University of Technology,1995,35(1):46-50.
[8]Wang J G,Lu X S,Yao J Z,et al.Experimental study of coal topping process in a downer reactor[J].Industrial&Engineering Chemistry Research,2005,44:463-470.
[9]Qu X,Liang P,Wang Z F,et al.Pilot development of a polygeneration process of circulating fluidized bed combustion combined with coal pyrolysis[J].Chemical Engineering&Technology,2011,34:61-68.
[10]Velegol D,Gautam M,Shamsi A.Catalytic cracking of a coal tar in a fluid bed reactor[J].Powder Technology,1997,93:93-100.
[11]Kimura T,Miyazawa T,Nishikawa J,et al.Development of Ni catalysts for tar removal by steam gasification of biomass[J].Applied Catalysis B:Environmental,2006,68:160-170.
[12]Edwards J H,Schluter K,Tyler R J.Upgrading of flash pyrolysis tars to synthetic crude oil:1.First stage hydrotreatment using a disposable catalyst[J].Fuel,1985,64(5):594-599.
[13]Kouichi Miura.Mild conversion of coal for producing valuable chemicals[J].Fuel Processing Technology,2000,62(2):119-135.
[14]Graff R A,Brandes S D.Modification of coal by subcritical steam:pyrolysis and extraction yields[J].Energy&Fuels,1987,1(1):84-88.
[15]Serio M A,Kroo E,Charpenay S,et al.Improved liquefaction of low rank coals by reduction of retrogressive reactions[J].Preprints of Papers-American Chemical Society,Division Fuel Chemistry,1993,38:1021-1027.
[16]Ishaq M,Ahmad I,Shakirullah M,et al.Pyrolysis of some whole plastics and plastics-coal mixtures[J].Energy Conversion Management,2006,47:3216-3223.
[17]董美玉,朱子彬,何亦华,等.烟煤快速加氢热解研究Ⅲ.焦油组成考察[J].燃料化学学报,2000,28(1):55-58.Dong Meiyu,Zhu Zibin,He Yihua,et al.Flash hydropyrolysis of bituminous coalⅢ:Research on flash hydropyrolysis tar[J]Journal of Fuel Chemistry and Technology,2000,28(1):55-58.
[18]Fidalgo B,Niekerk D V,Millan M.The effect of syngas on tar quality and quantity in pyrolysis of a typical South African inertinite-rich coal[J].Fuel,2014,134(90):90-96.
[19]Sharma D K,Sulimma A,Van Heek KH.Hydropyrolysis of coal in the presence of steam[J].Fuel,1986,65(11):1571-1574.
[20]Zhang L X,Malsuhara T,Kudo S,et al.Rapid pyrolysis of brown coal in a drop-lube reactor with co-feeding of char as a promoter of in situ tar reforming[J].Fuel.2013,112(3):681-686.
[21]Liu S,Wang Y,Wu R,et al.Research on coal tar catalytic cracking over hot in-situ chars[J].Journal of Fuel Chemistry&Technology,2013,41(9):1041-1049.
[22]许徐飞,周琦,邹涛,等.溢流管式多层气固流化床稳定操作气速范围的影响因素[J].过程工程学报,2012,12(3):361-368.Xu Xufei,Zhou Qi,Zou Tao,et al.Gas velocity range of stable operation in a gas solid multistage fluidized bed with overflow standpipes[J].The Chinese Journal of Process Engineering,2012,12(3):361-368.
[23]Zhou Q,Zou T,Zhong M,et al.Lignite upgrading by multi-stage fluidized bed pyrolysis[J].Fuel Processing Technology,2013,116:35-43.
[24]周琦,邹涛,初茉,等.多层流化床褐煤热解半焦特性与自燃倾向性抑制[J].煤炭学报,2014,39(S2):531-537.Zhou Qi,Zou Tao,Chu Mo,et al.Characterization and suppression of spontaneous combustion propensity of lignite char by multi-stage fluidized bed pyrolysis[J].Journal of China Coal Society,2014,39(S2):531-537.
[25]Anthony D B.Howard J B.Coal devolatilization and hydrogasification[J].American Institute of Chemical Engineers,1976,22(4):625-656.
[26]Chen Y,Luo Y,Wu W,et al.Experimental investigation on tar formation and destruction in a lab-scale two-stage reactor[J].Energy&Fuels,2009,23(9):4659-4667.
[27]吴仕生,曾玺,任明威,等.含氧/蒸汽气氛中煤高温分解产物分布及反应性[J].燃料化学学报,2015,40(6):660-665.Wu Shisheng,Zeng Xi,Ren Mingwei,et al.Product distribution and reactivity of coal pyrolysis at high temperature and in atmospheres containing O_2/steam[J].Journal of Fuel Chemical and Technology,2015,40(6):660-665.
[28]Zhang C,Wu R,Xu G.Coal pyrolysis for high-quality tar in a fixed-bed pyrolyzer enhanced with internals[J].Energy&Fuels,2013,28(1):236-244.
[29]Zhang C,Wu R,Hu E,et al.Coal pyrolysis for high-quality tar and gas in 100 kg fixed bed enhanced with internals[J].Energy&Fuels,2014,28(11):7294-7302.
[30]王兴栋,韩江则,陆江银,等.半焦基催化剂裂解煤热解产物提高油气品质[J].化工学报,2013,63(12):3897-3905.Wang Xingdong,Han Jiangze,Lu Jiangyin,et al.Catalytic cracking of coal pyrolysis product for oil and gas upgrading over char-based catalysts[J].CIESC Journal,2013,63(12):3897-3905.
[31]钟梅,马风云.不同气氛下煤连续热解产物的分配规律及产品品质分析[J].燃料化学学报,2013,41(12):1427-1436.Zhong Mei,Ma Fengyun.Analysis of product distribution and quality for continuous pyrolysis of coal in different atmospheres[J].Journal of Fuel Chemistry and Technology,2013,41(12):1427-1436.
[32]陈宗定,张书,王芳杰,等.活化前后半焦原位催化重整褐煤热解焦油研究[J].煤炭科学技术,2014,42(11):105-110.Chen Zongding,Zhang Shu,Wang Fangjie,et al.Study on in-situ catalytic reforming of coal tar from pyrolysis of brown coal by activated and inactivated char[J].Coal Science and Technology,2014,42(11):105-110.
[33]Liao H Q,Li B Q,Zhang B J.Co-pyrolysis of coal with hydrogen-rich gases[J].Fuel,1998,77(8):847-851.