过渡金属硝酸盐浸渍对和丰煤表面形貌及热解行为的影响
|
摘要
采用SEM和FTIR技术分析浸渍过渡金属硝酸盐的脱灰和丰煤样(DC)的表面结构变化特征,利用TG-MS和固定床研究煤样的热解和气体逸出行为,探讨金属组分对半焦结构和焦油组成与品质的影响。结果表明:浸渍Fe~(3+),Ni~(2+(和Co~(2+)的硝酸盐后,煤样表面疏松并重构,热解半焦产率增加,焦油产率下降,其中在Fe组分的作用下,焦油产率比DC热解焦油产率低53.71%。Fe~(3+)有利于CO和CO_2的生成。XRD结果表明:Ni盐经由分解为NiO和还原生成Ni的过程来影响煤样的热解行为,而Fe和Co的作用形态主要为Fe_2O_3和Co_3O_4。在Ni和Co组分的催化作用下,半焦的不饱和度增加。与DC热解焦油相比,Fe,Ni和Co组分均可增加焦油中的轻质组分含量,促进沸点高于300℃的长链烷烃分解,使得C≥17组分含量分别比无金属组分作用时降低23.12%,11.90%和18.59%。
The surface structure of demineralized Hefeng coal(DC)impregnated with transition metal nitrates was analyzed with SEM and FTIR.The pyrolysis performance and gas evolution behavior of coal samples were studied using thermogravimetric analyzer and fixed bed.The effects and mechanisms of metal components on the structural characteristics of char and the quality of tar were analyzed.The results show that by comparison with DC,the surfaces of coal samples loaded with nitrates become loose and reconstructed,the yield of char increases,whereas the yield of tar decreases.Especially for the effect of Fe species,the yield of tar decreases by 53.71%.Fe species facilitate the evolution of CO and CO_2.XRD results indicate that during the pyrolysis process,nickel nitrate successively decomposes to NiO and reduces to Ni.Whereas the actual form of Fe and Co species interacted with volatiles are Fe_2O_3 and Co_3O_4,respectively.Under the catalysis of Ni~(2+)and Co~(2+)nitrates,the unsaturation of pyrolysis char increases.And Fe,Ni and Co components promote the production of the light component in the tar and facilitate the cracking of long chain alkanes with the boiling point above 300 ℃,and the content of C≥17 decreases by 23.12%,11.90%and 18.59%compared to that of DC tar.
The surface structure of demineralized Hefeng coal(DC)impregnated with transition metal nitrates was analyzed with SEM and FTIR.The pyrolysis performance and gas evolution behavior of coal samples were studied using thermogravimetric analyzer and fixed bed.The effects and mechanisms of metal components on the structural characteristics of char and the quality of tar were analyzed.The results show that by comparison with DC,the surfaces of coal samples loaded with nitrates become loose and reconstructed,the yield of char increases,whereas the yield of tar decreases.Especially for the effect of Fe species,the yield of tar decreases by 53.71%.Fe species facilitate the evolution of CO and CO_2.XRD results indicate that during the pyrolysis process,nickel nitrate successively decomposes to NiO and reduces to Ni.Whereas the actual form of Fe and Co species interacted with volatiles are Fe_2O_3 and Co_3O_4,respectively.Under the catalysis of Ni~(2+)and Co~(2+)nitrates,the unsaturation of pyrolysis char increases.And Fe,Ni and Co components promote the production of the light component in the tar and facilitate the cracking of long chain alkanes with the boiling point above 300 ℃,and the content of C≥17 decreases by 23.12%,11.90%and 18.59%compared to that of DC tar.
引文
[1]钟梅.复合流化床低阶碎煤分级热解研究[D].北京:中国科学院过程工程研究所,2012.ZHONG Mei.Fractionate Pyrolysis of Low-rank Powder Coal in Integrated Fluidized Bed[D].Beijing:Institute of Process Engineering,Chinese Academy of Sciences,2012.
[2]CHAREONPANICH M,BOONFUENG T,LIMTRAKUL J.Production of Aromatic Hydrocarbons from Mae-Moh Lignite[J].Fuel Processing Technology,2002,79(2):171-179.
[3]LIU Longlong,KUMAR S,WANG Zhihua,et al.Catalytic Effect of Metal Chlorides on Coal Pyrolysis and Gasification(Part I):Combined TG-FTIR Study for Coal Pyrolysis[J].Thermochimica Acta,2017,655:331-336.
[4]AMIN M N,LI Yi,LU Xingmei.In Situ Catalytic Pyrolysis of Low-rank Coal for the Conversion of Heavy Oils into Light Oils[J].Advances in Materials Science and Engineering,2017,2017:1-8.
[5]CUI Xin,QI Cong,LI Liang,et al.Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process[J].International Journal of Thermophysics,2017,38(8):116-133.
[6]LI Shuang,CHEN Jingsheng,HAO Ting,et al.Pyrolysis of Huangtumiao Coal over Faujasite Zeolite and Supported Transition Metal Catalysts[J].Journal of Analytical and Applied Pyrolysis,2013,102(7):161-169.
[7]AMIN M N,LI Yi,RAZZAQ R,et al.Pyrolysis of Low Rank Coal by Nickel Based Zeolite Catalysts in the Two-staged Bed Reactor[J].Journal of Analytical and Applied Pyrolysis,2016,118:54-62.
[8]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic Upgrading of Gaseous Tar from Coal Pyrolysis over Mo and Nimodified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.
[9]LIU Tianlong,CAO Jingpei,ZHAO Xiaoyan,et al.In Situ Upgrading of Shengli Lignite Pyrolysis Vapors over Metal-loaded HZSM-5Catalyst[J].Fuel Processing Technology,2017,160:19-26.
[10]REN Xueyu,CAO Jingpei,ZHAO Xiaoyan,et al.Catalytic Upgrading of Pyrolysis Vapors from Lignite over Mono/Bimetalloaded Mesoporous HZSM-5[J].Fuel,2018,218:33-40.
[11]REN Xueyu,CAO Jingpei,ZHAO Xiaoyan,et al.Increasing Light Aromatic Products During Upgrading of Lignite Pyrolysis Vapor over Co-modified HZSM-5[J].Journal of Analytical and Applied Pyrolysis,2018,130:190-197.
[12]LIU Jiahe,HU Haoquan,JIN Lijun,et al.Integrated Coal Pyrolysis with CO2Reforming of Methane over Ni/MgO Catalyst for Improving Tar Yield[J].Fuel Processing Technology,2010,91(4):419-423.
[13]ZHU Ping,YU Zhengpeng,ZHANG Jinli,et al.Catalytic Pyrolysis of Bituminous Coal Under Pyrolysis Gas over a Ni/MgOCatalyst[J].Chemical Engineering and Technology,2017,40(9):1605-1610.
[14]SHEN Yafei,ZHAO Peitao,SHAO Qinfu,et al.In Situ Catalytic Conversion of Tar Using Rice Husk Char/Ash Supported Nickel-iron Catalysts for Biomass Pyrolysis/Gasification[J].Applied Catalysis B:Environmental,2014,152/153:140-151.
[15]LIANG Litong,HUAI Juntian,ZHANG Qian,et al.Catalytic Depolymerization of a Typical Lignite for Improving Tar Yield by Co and Zn Catalyst[J].Scientific Reports,2017.DOI:10.1038/s41598-017-14869-w.
[16]LIANG Litong,HUANG Wei,GAO Fuxing,et al.Mild Catalytic Depolymerization of Low Rank Coals:a Novel Way to Increase Tar Yield[J].RSC Advances,2015,5:2493-2503.
[17]CAHYONO R B,ROZHAN A N,YASUDA N.Integrated Coal-pyrolysis Tar Reforming Using Steelmaking Slag for Carbon Composite and Hydrogen Production[J].Fuel,2013,109:439-444.
[18]CAHYONO R B,YASUDA N,NOMURA T,et al.Optimum Temperatures for Carbon Deposition During Integrated Coal Pyrolysis-tar Decomposition over Low-grade Iron Ore for Ironmaking Applications[J].Fuel Processing Technology,2014,119:272-277.
[19]鲍卫仁,常丽萍,谢克昌.酸洗脱灰对原煤样品性能的影响研究[J].太原理工大学学报,2000,31(4):354-357.BAO Weiren,CHANG Liping,XIE Kechang.Effects of Acid Washing Methods on the Characteristics of Raw Coal[J].Journal of Taiyuan University of Technology,2000,31(4):354-357.
[20]ROETS L,STRYDOM C,BUNT J R,et al.The Effect of Acid Washing on the Pyrolysis Products Derived from a Vitriniterich Bituminous Coal[J].Journal of Analytical and Applied Pyrolysis,2015,116:142-151.
[21]DING Lu,ZHOU Zhijie,GUO Qinghua,et al.Catalytic Effects of Na2CO3 Additive on Coal Pyrolysis and Gasification[J].Fuel,2015,142:134-144.
[22]ZHOU Qi,ZOU Tao,ZHONG Mei,et al.Lignite Upgrading by Multi-stage Fluidized Bed Pyrolysis[J].Fuel Processing Technology,2013,116:35-43.
[23]MIN Zhenhua,YIMSIRI P,ASADULLAH M,et al.Catalytic Reforming of Tar During Gasification(PartⅡ):Char as a Catalyst or as a Catalyst Support for Tar Reforming[J].Fuel,2011,90(7):2545-2552.
[24]王桂茹.催化剂与催化作用[M].大连:大连理工大学出版社,2015:114.WANG Guiru.Catalyst and Catalysis[M].Dalian:Dalian University of Technology Press,2015:114.
[25]GYUL’MALIEV A M,GOLOVIN G S,GAGARIN S G.Classification of Fossil Fuels According to Structural-chemical Characteristics[J].Solid Fuel Chemistry,2007,41(5):257-266.
[26]SHENG Changdong.Char Structure Characterised by Raman Spectroscopy and Its Correlations with Combustion Reactivity[J].Fuel,2007,86(15):2316-2324.
[27]HAN Jiangze,LIU Xiaoxing,YUE Junrong,et al.Catalytic Upgrading of In Situ Coal Pyrolysis Tar over Ni-char Catalyst with Different Additives[J].Energy and Fuels,2014,28(8):4934-4941.
[28]OMAE I.Agostic Bonds in Cyclometalation[J].Journal of Organometallic Chemistry,2011,696(6):1128-1145.
[2]CHAREONPANICH M,BOONFUENG T,LIMTRAKUL J.Production of Aromatic Hydrocarbons from Mae-Moh Lignite[J].Fuel Processing Technology,2002,79(2):171-179.
[3]LIU Longlong,KUMAR S,WANG Zhihua,et al.Catalytic Effect of Metal Chlorides on Coal Pyrolysis and Gasification(Part I):Combined TG-FTIR Study for Coal Pyrolysis[J].Thermochimica Acta,2017,655:331-336.
[4]AMIN M N,LI Yi,LU Xingmei.In Situ Catalytic Pyrolysis of Low-rank Coal for the Conversion of Heavy Oils into Light Oils[J].Advances in Materials Science and Engineering,2017,2017:1-8.
[5]CUI Xin,QI Cong,LI Liang,et al.Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process[J].International Journal of Thermophysics,2017,38(8):116-133.
[6]LI Shuang,CHEN Jingsheng,HAO Ting,et al.Pyrolysis of Huangtumiao Coal over Faujasite Zeolite and Supported Transition Metal Catalysts[J].Journal of Analytical and Applied Pyrolysis,2013,102(7):161-169.
[7]AMIN M N,LI Yi,RAZZAQ R,et al.Pyrolysis of Low Rank Coal by Nickel Based Zeolite Catalysts in the Two-staged Bed Reactor[J].Journal of Analytical and Applied Pyrolysis,2016,118:54-62.
[8]闫伦靖,孔晓俊,白永辉,等.Mo和Ni改性的HZSM-5催化剂对煤热解焦油的改质[J].燃料化学学报,2016,44(1):30-36.YAN Lunjing,KONG Xiaojun,BAI Yonghui,et al.Catalytic Upgrading of Gaseous Tar from Coal Pyrolysis over Mo and Nimodified HZSM-5[J].Journal of Fuel Chemistry and Technology,2016,44(1):30-36.
[9]LIU Tianlong,CAO Jingpei,ZHAO Xiaoyan,et al.In Situ Upgrading of Shengli Lignite Pyrolysis Vapors over Metal-loaded HZSM-5Catalyst[J].Fuel Processing Technology,2017,160:19-26.
[10]REN Xueyu,CAO Jingpei,ZHAO Xiaoyan,et al.Catalytic Upgrading of Pyrolysis Vapors from Lignite over Mono/Bimetalloaded Mesoporous HZSM-5[J].Fuel,2018,218:33-40.
[11]REN Xueyu,CAO Jingpei,ZHAO Xiaoyan,et al.Increasing Light Aromatic Products During Upgrading of Lignite Pyrolysis Vapor over Co-modified HZSM-5[J].Journal of Analytical and Applied Pyrolysis,2018,130:190-197.
[12]LIU Jiahe,HU Haoquan,JIN Lijun,et al.Integrated Coal Pyrolysis with CO2Reforming of Methane over Ni/MgO Catalyst for Improving Tar Yield[J].Fuel Processing Technology,2010,91(4):419-423.
[13]ZHU Ping,YU Zhengpeng,ZHANG Jinli,et al.Catalytic Pyrolysis of Bituminous Coal Under Pyrolysis Gas over a Ni/MgOCatalyst[J].Chemical Engineering and Technology,2017,40(9):1605-1610.
[14]SHEN Yafei,ZHAO Peitao,SHAO Qinfu,et al.In Situ Catalytic Conversion of Tar Using Rice Husk Char/Ash Supported Nickel-iron Catalysts for Biomass Pyrolysis/Gasification[J].Applied Catalysis B:Environmental,2014,152/153:140-151.
[15]LIANG Litong,HUAI Juntian,ZHANG Qian,et al.Catalytic Depolymerization of a Typical Lignite for Improving Tar Yield by Co and Zn Catalyst[J].Scientific Reports,2017.DOI:10.1038/s41598-017-14869-w.
[16]LIANG Litong,HUANG Wei,GAO Fuxing,et al.Mild Catalytic Depolymerization of Low Rank Coals:a Novel Way to Increase Tar Yield[J].RSC Advances,2015,5:2493-2503.
[17]CAHYONO R B,ROZHAN A N,YASUDA N.Integrated Coal-pyrolysis Tar Reforming Using Steelmaking Slag for Carbon Composite and Hydrogen Production[J].Fuel,2013,109:439-444.
[18]CAHYONO R B,YASUDA N,NOMURA T,et al.Optimum Temperatures for Carbon Deposition During Integrated Coal Pyrolysis-tar Decomposition over Low-grade Iron Ore for Ironmaking Applications[J].Fuel Processing Technology,2014,119:272-277.
[19]鲍卫仁,常丽萍,谢克昌.酸洗脱灰对原煤样品性能的影响研究[J].太原理工大学学报,2000,31(4):354-357.BAO Weiren,CHANG Liping,XIE Kechang.Effects of Acid Washing Methods on the Characteristics of Raw Coal[J].Journal of Taiyuan University of Technology,2000,31(4):354-357.
[20]ROETS L,STRYDOM C,BUNT J R,et al.The Effect of Acid Washing on the Pyrolysis Products Derived from a Vitriniterich Bituminous Coal[J].Journal of Analytical and Applied Pyrolysis,2015,116:142-151.
[21]DING Lu,ZHOU Zhijie,GUO Qinghua,et al.Catalytic Effects of Na2CO3 Additive on Coal Pyrolysis and Gasification[J].Fuel,2015,142:134-144.
[22]ZHOU Qi,ZOU Tao,ZHONG Mei,et al.Lignite Upgrading by Multi-stage Fluidized Bed Pyrolysis[J].Fuel Processing Technology,2013,116:35-43.
[23]MIN Zhenhua,YIMSIRI P,ASADULLAH M,et al.Catalytic Reforming of Tar During Gasification(PartⅡ):Char as a Catalyst or as a Catalyst Support for Tar Reforming[J].Fuel,2011,90(7):2545-2552.
[24]王桂茹.催化剂与催化作用[M].大连:大连理工大学出版社,2015:114.WANG Guiru.Catalyst and Catalysis[M].Dalian:Dalian University of Technology Press,2015:114.
[25]GYUL’MALIEV A M,GOLOVIN G S,GAGARIN S G.Classification of Fossil Fuels According to Structural-chemical Characteristics[J].Solid Fuel Chemistry,2007,41(5):257-266.
[26]SHENG Changdong.Char Structure Characterised by Raman Spectroscopy and Its Correlations with Combustion Reactivity[J].Fuel,2007,86(15):2316-2324.
[27]HAN Jiangze,LIU Xiaoxing,YUE Junrong,et al.Catalytic Upgrading of In Situ Coal Pyrolysis Tar over Ni-char Catalyst with Different Additives[J].Energy and Fuels,2014,28(8):4934-4941.
[28]OMAE I.Agostic Bonds in Cyclometalation[J].Journal of Organometallic Chemistry,2011,696(6):1128-1145.