过渡金属催化剂及热解条件对新疆吉木萨尔油页岩热解的影响
|
摘要
采用过渡金属盐:Fe_2O_3、CoCl_2·6H_2O和MnSO_4·H_2O作为催化剂对新疆吉木萨尔地区油页岩进行催化热解。首先,对添加了不同类型催化剂的油页岩进行TG实验,结果表明这几种催化剂中CoCl_2·6H_2O催化效果最好;在此基础上,对添加了CoCl_2·6H_2O的样品进一步做TG-MS实验分析,结果显示,添加CoCl_2·6H_2O后热解的初始温度降低约100℃,同时热解温度范围从435～1000℃缩小至330～650℃。催化热解过程中,产量最高的产物为CO/C_2H_4和C_3H_4,我们认为,CO/C_2H_4中大部分应为C_2H_4。随着升温速率的提高,烯烃和炔烃产量增加,H_2O、烷烃以及芳香烃产量降低,CO/C_2H_4、H_2S、乙烷、丙烯、CO_2/丙烷产量基本保持不变。从分析结果可以得出:以CoCl_2·6H_2O作为催化剂,对于吉木萨尔油页岩来讲,最佳的升温速率为5℃/min。
Transition metal salts: Fe_2O_3,CoCl_2· 6H_2O and MnSO_4· H_2O were chosen to be the catalysts for Jimsar oil shale pyrolysis. The pyrolysis behaviors of samples with different catalysts were compared by using TG analyzer firstly,the best catalytic pyrolysis process was further analyzed by TGMS. Compared to Fe_2O_3 and MnSO_4·H_2O,CoCl_2·6H_2O has the best catalytic effect for Jimsar oil shale. With CoCl_2·6H_2O,the initial reaction temperature of pyrolysis process is reduced about 100 ℃,and the temperature range is reduced from 435-1000 ℃ to 330-650 ℃. The two most productive products are CO/ethene and propyne,and we think most of the CO/ethene should be ethene. With increasing heating rate,the outputs of alkene and alkyne is increased,the outputs of H_2O,methane,alkane and aromatic hydrocarbons are decreased,and the outputs of CO/ethene,H_2S,ethane,propene and CO_2/propane have little change. From the results and analysis,it can be concluded that,taking CoCl_2·6H_2O as catalyst,the best heating rate should be 5 ℃/min for Jimsar oil shale.
Transition metal salts: Fe_2O_3,CoCl_2· 6H_2O and MnSO_4· H_2O were chosen to be the catalysts for Jimsar oil shale pyrolysis. The pyrolysis behaviors of samples with different catalysts were compared by using TG analyzer firstly,the best catalytic pyrolysis process was further analyzed by TGMS. Compared to Fe_2O_3 and MnSO_4·H_2O,CoCl_2·6H_2O has the best catalytic effect for Jimsar oil shale. With CoCl_2·6H_2O,the initial reaction temperature of pyrolysis process is reduced about 100 ℃,and the temperature range is reduced from 435-1000 ℃ to 330-650 ℃. The two most productive products are CO/ethene and propyne,and we think most of the CO/ethene should be ethene. With increasing heating rate,the outputs of alkene and alkyne is increased,the outputs of H_2O,methane,alkane and aromatic hydrocarbons are decreased,and the outputs of CO/ethene,H_2S,ethane,propene and CO_2/propane have little change. From the results and analysis,it can be concluded that,taking CoCl_2·6H_2O as catalyst,the best heating rate should be 5 ℃/min for Jimsar oil shale.
引文
[1]Coetzee S,Neomagus H W J P,Bunt J R,et al.Improved reactivity of large coal particles by K2CO3addition during steam gasification[J].Fuel Processing Technology,2013,114(3):75-80.
[2]Jaffri G,Zhang J.Catalytic gasification characteristics of mixed black liquor and calcium catalyst in mixing(air/steam)atmosphere[J].Journal of Fuel Chemistry and Technology,2008,36(4):406-414.
[3]zta?N A,Yürüm Y.Pyrolysis of Turkish Zonguldak bituminous coal.Part 1.Effect of mineral matter[J].Fuel,2000,79(10):1221-1227.
[4]Ye D P,Agnew J B,Zhang D K.Gasification of a South Australian low-rank coal with carbon dioxide and steam:kinetics and reactivity studies[J].Fuel,1998,77(11):1209-1219.
[5]zta?N A,Yürüm Y.Effect of catalysts on the pyrolysis of Turkish Zonguldak bituminous coal[J].Fuel and Energy Abstracts,2002,43(1):58.
[6]Quyn D M,Wu H,Hayashi J,et al.Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal.Part IV.Catalytic effects of Na Cl and ion-exchangeable Na in coal on char reactivity[J].Fuel,2003,82(5):587-593.
[7]Wu H W,Li X J,Hayashi J,et al.Effects of volatile-char interactions on the reactivity of chars from Na Cl-loaded Loy Yang brown coal[J].Fuel,2005,84(10):1221-1228.
[8]Yu J L,Tian F J,Chow M C,et al.Effect of iron on the gasification of Victorian brown coal with steam:enhancement of hydrogen production[J].Fuel,2006,85(2):127-133.
[9]Jiang H F,Song L H,Cheng Z Q,et al.Influence of pyrolysis condition and transition metal salt on the product yield and characterization via Huadian oil shale pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2015,112:230-236.
[10]Zou X W,Yao J Z,Yang X M,et al.Catalytic effects of metal chlorides on the pyrolysis of lignite[J].Energy and Fuels,2007,21(2):619-624.
[11]Williams P T,Chishti H M.Two stage pyrolysis of oil shale using a zeolite catalyst[J].Journal of Analytical and Applied Pyrolysis,2000,55(2):217-234.
[12]Gai R H,Jin L J,Zhang J B,et al.Effect of inherent and additional pyrite on the pyrolysis behavior of oil shale[J].Journal of Analytical and Applied Pyrolysis,2014,105:342-347.
[13]Bakr M Y,Yokono T,Sanada Y,et al.Role of pyrite during the thermal degradation of kerogen using in situ high-temperature ESR technique[J].Energy and Fuels,1991,5(3):441-444.
[14]MetecanⅰH,Sa4lam M,Yan1k J,et al.The effect of pyrite catalyst on the hydroliquefaction of G9ynük(Turkey)oil shale in the presence of toluene[J].Fuel,1999,78(5):619-622.
[15]Vucelic D,Markovic V,Vucelic V,et al.Investigation of catalytic effects of indigenous minerals in the pyrolysis of Aleksinac oil shale organic matter[J].Organic Geochemistry,1992,19(4):445-453.
[16]Brendow D K,Council W E,Geneva.Global oil shale issues and perspectives[J].Oil Shale,2003,20(1):81-92.
[17]Bunger J W,Crawford P M,Johnson H R.Is oil shale America answer to peak-oil challenge[J].Oil and Gas Journal,2004,102:16-24.
[18]Pan L W,Dai F Q,Huang J Z,et al.Investigation of the gas flow distribution and pressure drop in Xinjiang oil shale retort[J].Oil Shale,2015,32(2):172-185.
[19]Pan L W,Dai F Q,Li G Q,et al.A TGA/DTA-MS investigation to the influence of process conditions on the pyrolysis of Jimsar oil shale[J].Energy,2015,86:749-757.
[20]Pan L W,Dai F Q,Tian Y Q,et al.Experimental investigation of the sphericity of irregularly shaped oil shale particle groups[J].Advanced Powder Technology,2015,26(1):66-72.
[21]Pan L W,Dai F Q,Huang J Z,et al.Study of a new gas inlet structure designed for Xinjiang oil shale retort[J].Oil Shale,2016,33(1):67-79.
[22]Pan L W,Dai F Q,Huang J Z,et al.Study of the effect of mineral matters on the thermal decomposition of Jimsar oil shale using TG-MS[J].Thermochimica Acta.,2016,627:31-38.
[23]Liu L L,Kumar S,Wang Z H,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.
[24]Tiwari P,Deo M.Compositional and kinetic analysis of oil shale pyrolysis using TGA-MS[J].Fuel,2012,94:333-341.
[25]Haddadin R A,Mizyed F A.Thermogravimetric analysis kinetics of Jordan shale[J].Industrial and Engineering Chemistry Process Design and Development,1974,13(4):332-336.
[26]Williams P F V.Thermogravimetry and decomposition kinetics of British Kimmeridge clay oil shale[J].Fuel,1985,64(4):540-545.
[27]Thakur D S,Nuttall H E.Kinetics of pyrolysis of Moroccan oil shale by thermogravimetry[J].Industrial and Engineering Chemistry Research,1987,26(7):1351-1356.
[28]谢欣馨,罗进成,葛启明,等.催化剂对煤热解特性的影响[J].煤化工,2015,43(4):38-42.
[29]Mango F D.Transition metal catalysis in the generation of petroleum and natural gas[J].Geochimica et Cosmochimica Acta.,1992,56(1):553-555.
[30]罗文国,温朗友,俞芳,等.Ziegler-Natta型催化剂上异辛烯加氢制异辛烷的研究[J].石油学报(石油加工),2007,23(6):86-90.
[2]Jaffri G,Zhang J.Catalytic gasification characteristics of mixed black liquor and calcium catalyst in mixing(air/steam)atmosphere[J].Journal of Fuel Chemistry and Technology,2008,36(4):406-414.
[3]zta?N A,Yürüm Y.Pyrolysis of Turkish Zonguldak bituminous coal.Part 1.Effect of mineral matter[J].Fuel,2000,79(10):1221-1227.
[4]Ye D P,Agnew J B,Zhang D K.Gasification of a South Australian low-rank coal with carbon dioxide and steam:kinetics and reactivity studies[J].Fuel,1998,77(11):1209-1219.
[5]zta?N A,Yürüm Y.Effect of catalysts on the pyrolysis of Turkish Zonguldak bituminous coal[J].Fuel and Energy Abstracts,2002,43(1):58.
[6]Quyn D M,Wu H,Hayashi J,et al.Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal.Part IV.Catalytic effects of Na Cl and ion-exchangeable Na in coal on char reactivity[J].Fuel,2003,82(5):587-593.
[7]Wu H W,Li X J,Hayashi J,et al.Effects of volatile-char interactions on the reactivity of chars from Na Cl-loaded Loy Yang brown coal[J].Fuel,2005,84(10):1221-1228.
[8]Yu J L,Tian F J,Chow M C,et al.Effect of iron on the gasification of Victorian brown coal with steam:enhancement of hydrogen production[J].Fuel,2006,85(2):127-133.
[9]Jiang H F,Song L H,Cheng Z Q,et al.Influence of pyrolysis condition and transition metal salt on the product yield and characterization via Huadian oil shale pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2015,112:230-236.
[10]Zou X W,Yao J Z,Yang X M,et al.Catalytic effects of metal chlorides on the pyrolysis of lignite[J].Energy and Fuels,2007,21(2):619-624.
[11]Williams P T,Chishti H M.Two stage pyrolysis of oil shale using a zeolite catalyst[J].Journal of Analytical and Applied Pyrolysis,2000,55(2):217-234.
[12]Gai R H,Jin L J,Zhang J B,et al.Effect of inherent and additional pyrite on the pyrolysis behavior of oil shale[J].Journal of Analytical and Applied Pyrolysis,2014,105:342-347.
[13]Bakr M Y,Yokono T,Sanada Y,et al.Role of pyrite during the thermal degradation of kerogen using in situ high-temperature ESR technique[J].Energy and Fuels,1991,5(3):441-444.
[14]MetecanⅰH,Sa4lam M,Yan1k J,et al.The effect of pyrite catalyst on the hydroliquefaction of G9ynük(Turkey)oil shale in the presence of toluene[J].Fuel,1999,78(5):619-622.
[15]Vucelic D,Markovic V,Vucelic V,et al.Investigation of catalytic effects of indigenous minerals in the pyrolysis of Aleksinac oil shale organic matter[J].Organic Geochemistry,1992,19(4):445-453.
[16]Brendow D K,Council W E,Geneva.Global oil shale issues and perspectives[J].Oil Shale,2003,20(1):81-92.
[17]Bunger J W,Crawford P M,Johnson H R.Is oil shale America answer to peak-oil challenge[J].Oil and Gas Journal,2004,102:16-24.
[18]Pan L W,Dai F Q,Huang J Z,et al.Investigation of the gas flow distribution and pressure drop in Xinjiang oil shale retort[J].Oil Shale,2015,32(2):172-185.
[19]Pan L W,Dai F Q,Li G Q,et al.A TGA/DTA-MS investigation to the influence of process conditions on the pyrolysis of Jimsar oil shale[J].Energy,2015,86:749-757.
[20]Pan L W,Dai F Q,Tian Y Q,et al.Experimental investigation of the sphericity of irregularly shaped oil shale particle groups[J].Advanced Powder Technology,2015,26(1):66-72.
[21]Pan L W,Dai F Q,Huang J Z,et al.Study of a new gas inlet structure designed for Xinjiang oil shale retort[J].Oil Shale,2016,33(1):67-79.
[22]Pan L W,Dai F Q,Huang J Z,et al.Study of the effect of mineral matters on the thermal decomposition of Jimsar oil shale using TG-MS[J].Thermochimica Acta.,2016,627:31-38.
[23]Liu L L,Kumar S,Wang Z H,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.
[24]Tiwari P,Deo M.Compositional and kinetic analysis of oil shale pyrolysis using TGA-MS[J].Fuel,2012,94:333-341.
[25]Haddadin R A,Mizyed F A.Thermogravimetric analysis kinetics of Jordan shale[J].Industrial and Engineering Chemistry Process Design and Development,1974,13(4):332-336.
[26]Williams P F V.Thermogravimetry and decomposition kinetics of British Kimmeridge clay oil shale[J].Fuel,1985,64(4):540-545.
[27]Thakur D S,Nuttall H E.Kinetics of pyrolysis of Moroccan oil shale by thermogravimetry[J].Industrial and Engineering Chemistry Research,1987,26(7):1351-1356.
[28]谢欣馨,罗进成,葛启明,等.催化剂对煤热解特性的影响[J].煤化工,2015,43(4):38-42.
[29]Mango F D.Transition metal catalysis in the generation of petroleum and natural gas[J].Geochimica et Cosmochimica Acta.,1992,56(1):553-555.
[30]罗文国,温朗友,俞芳,等.Ziegler-Natta型催化剂上异辛烯加氢制异辛烷的研究[J].石油学报(石油加工),2007,23(6):86-90.