基于Py-GC/MS的中低温煤焦油催化裂解研究
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摘要
以陕北中低温煤焦油重油(CT)为原料,采用旋转薄膜精馏仪,减压200℃条件下,切取得到轻质煤焦油馏分(LCTF)和重质煤焦油馏分(HCTF).并以HZSM-5,γ-Al_2O_3,MHZSM-5和Mγ-Al_2O_3(M=w(Ni)+w(Mo),其中w(Ni)=4%,w(Mo)=20%)为催化剂,借助热裂解-气相色谱/质谱联用仪(Py-GC/MS),对CT,LCTF和HCTF进行快速(催化)裂解,考察了催化剂对裂解产物分布的影响.研究表明:催化剂对3种原料均具有催化形成轻质芳烃的改质效果,强酸性位含量丰富的HZSM-5,改质效果优于具有一定量弱酸性位的γ-Al_2O_3.随着重质组分(主要为多环芳烃)的增多,LCTF,CT和HCTF分别经同种催化剂催化改质形成轻质芳烃的转化率逐渐降低.HCTF分别经HZSM-5和MHZSM-5催化裂解后,含氧化合物百分比分别降低了63%和42%,脂肪烃百分比分别增加了39%和145%.
The light coal tar fractions(LCTF) and heavy coal tar fractions(HCTF) of low temperature coal tar heavy oil(CT) from northern Shaanxi were obtained by rotary thin-film distillation apparatus under a pressure-reducing condition at 200 ℃. HZSM-5, γ-Al_2O_3, MHZSM-5 and Mγ-Al_2O_3(M=w(Ni)+w(Mo),where w(Ni)=4%, w(Mo)=20%)were chosen as catalysts to catalyze fast(catalytic) cracking process of CT, LCTF and HCTF by pyrolysis-gas chromatograph/mass spectrometer(Py-GC/MS). The effect of catalysts on the distribution of cracking products was investigated. The results show that catalysts have effect on catalytic upgrading of three raw materials to produce light aromatics. The catalyst of HZSM-5 with rich acid contents is superior to the catalyst of γ-Al_2O_3 with weak acidity. With the increase of heavy components(mainly polycyclic aromatic hydrocarbons), the conversion rates of the formation of light aromatics obtained from the catalytic cracking of LCTF, CT and HCTF with the same catalyst gradually decrease. After the catalytic cracking of HCTF under HZSM-5 and MHZSM-5, the relative content of oxygen-containing compounds decreases by 63% and 42%, while the relative content of aliphatic hydrocarbons increases by 39% and 145%, respectively.
The light coal tar fractions(LCTF) and heavy coal tar fractions(HCTF) of low temperature coal tar heavy oil(CT) from northern Shaanxi were obtained by rotary thin-film distillation apparatus under a pressure-reducing condition at 200 ℃. HZSM-5, γ-Al_2O_3, MHZSM-5 and Mγ-Al_2O_3(M=w(Ni)+w(Mo),where w(Ni)=4%, w(Mo)=20%)were chosen as catalysts to catalyze fast(catalytic) cracking process of CT, LCTF and HCTF by pyrolysis-gas chromatograph/mass spectrometer(Py-GC/MS). The effect of catalysts on the distribution of cracking products was investigated. The results show that catalysts have effect on catalytic upgrading of three raw materials to produce light aromatics. The catalyst of HZSM-5 with rich acid contents is superior to the catalyst of γ-Al_2O_3 with weak acidity. With the increase of heavy components(mainly polycyclic aromatic hydrocarbons), the conversion rates of the formation of light aromatics obtained from the catalytic cracking of LCTF, CT and HCTF with the same catalyst gradually decrease. After the catalytic cracking of HCTF under HZSM-5 and MHZSM-5, the relative content of oxygen-containing compounds decreases by 63% and 42%, while the relative content of aliphatic hydrocarbons increases by 39% and 145%, respectively.
引文
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[2] DING L,ZHOU Z J,GUO Q H,et al.Gas evolution characteristics during pyrolysis and catalytic pyrolysis of coals by TG-MS and a high-frequency furnace[J].Fuel,2015,154:222-232.
[3] JIA X,WANG Q H,CEN K,et al.Sulfur transformation during the pyrolysis of coal mixed with coal ash in a fixed bed reactor[J].Fuel,2016,177:260-267.
[4] YANG J B,CAI N S.A TG-FTIR study on catalytic pyrolysis of coal[J].Journal of Fuel Chemistry and Technology,2006,34(6):650-654.
[5] 李爽,陈静升,冯秀燕,等.应用 TG-FTIR 技术研究黄土庙煤催化热解特性[J].燃料化学学报,2013,41(3):271-276.LI Shuang,CHEN Jingsheng,FENG Xiuyan,et al.Study on catalytic pyrolysis characteristics of Huangtumiao temple by TG-FTIR technique[J].Journal of Fuel Chemistry,2013,41(3):271-276.
[6] DING L,ZHOU Z J,GUO Q H,et al.Catalytic effects of Na2CO3 additive on coal pyrolysis and gasification[J].Fuel,2015,142:134-144.
[7] HAN J Z,WANG X D,YUE J R,et al.Catalytic upgrading of coal pyrolysis tar over char based catalysts[J].Fuel Processing Technology,2014,122:98-106.
[8] JIN L J,BAI X Y,LI Y,et al.In-situ catalytic upgrading of coal pyrolysis tar on carbon-based catalysts in a fixed bed reactor[J].Fuel Processing Technology,2016,147:41-46.
[9] AMIN M N,LI Y,RAZZAQ R,et al.Pyrolysis of low rank coal by nickel based zeolite in the two-staged bed reactor[J].Journal of Analytical and Applied Pyrolysis,2016,118:54-62.
[10] YAN L J,KONG X J,ZHAO R F,et al.Catalytic upgrading of gaseous tars over zeolite catalysts during coal pyrolysis[J].Fuel Processing Technology,2015,138:424-429.
[11] ZHANG M,RESENDE FLP,MOUTSOGLOU A.Catalytic fast pyrolysis of aspen lignin via Py-GC/MS[J].Fuel,2014,116:358-369.
[12] 陆强,李志文,张栋,等.锯末快速热解气的在线催化裂解[J].化工学报,2009,60(2):351-357.LU Qiang,LI Zhiwen,ZHANG Dong,et al.In situ catalytic cracking of sawdust fast pyrolysis vapors[J].CIESC Journal,2009,60(2):351-357.
[13] VICHAPHUND S,AHTONG D,SRICHAROENCHAIKUL V,et al.Catalytic upgrading pyrolysis vapors of Jatropha waste using metal promoted ZSM-5 catalysts:An analytical Py-GC/MS[J].Renewable Energy,2014,65:70-77.
[14] ZHENG Y,CHEN D Y,ZHU X F.Aromatic hydrocarbon production by the online catalytic cracking of lignin fast pyrolysis vapors using Mo2N/γ-Al2O3[J].Journal of Analytical and Applied Pyrolysis,2013,104:514-520.
[15] 张智博,董长青,叶小宁,等.利用固体磷酸催化热解纤维素制备左旋葡萄糖酮[J].化工学报,2014,65(3):912-920.ZHANG Zhibo,DONG Changqing,YE Xiaoning,et al.Preparation of levoglucosenone by catalytic pyrolysis of cellulose over solid phosphoric acid[J].CIESC Journal,2014,65(3):912-920.
[16] 李攀,李缔,隋海清,等.纤维素快速热解反应气体的在线催化裂解[J].化工学报,2015,66(10):4131-4137.LI Pan,LI Di,SUI Haiqing,et al.On-line catalytic cracking of vapors from cellulose fast pyrolysis[J].CIESC Journal,2015,66(10):4131-4137.
[17] LI G L,YAN L J,ZHAO R F,et al.Improving aromatic hydrocarbons yield from coal pyrolysis volatile products over HZSM-5 and Mo-modified HZSM-5[J].Fuel,2014,130:154-159.
[18] CHAREONPANICH M,TAKEDA T,YAMASHITA H,et al.Catalytic hydrocracking reaction of nascent coal volatile matter under high pressure[J].Fuel,1994,73(5):666-670.
[19] 李冠龙.煤热解挥发分催化转化生成BTEXN的研究[D].太原:太原理工大学,2014:18-19.LI Guanlong.Improving BTEXN yield from coal pyrolysis volatile products through catalytic conversion[D].Taiyuan:Taiyuan University of Technology,2014:18-19.
[20] LIU Y J,YAN L J,BAI Y H,et al.Catalytic upgrading of volatile form coal pyrolysis over faujasite zeolites[J].Journal of Analytical and Applied Pyrolysis,2018,132:184-189.
[21] ZHOU X,LIU Y,MENG X,et al.Synthesis and catalytic cracking performance of Fe/Ti-ZSM-5 zeolite from attapulgite mineral[J].Chinese Journal of Catalysis,2013,34(8):1504-1512.
[22] LI J,MA H,SUN Q,et al.Effect of iron and phosphorus on HZSM-5 in catalytic cracking of 1-butene[J].Fuel Processing Technology,2015,134:32-38.
[23] ZHU X,LIU S,SONG Y,et al.Catalytic cracking of C4 alkenes to propene and ethene:Influences of zeolites pore structures and Si/Al2 ratios[J].Applied Catalysis A General,2005,288(1/2):134-142.
[24] CHAREONPANICH M,BOONFHENG T,LIMTRAKUL J.Production of aromatic hydrocarbons from Mae-Moh lignite[J].Fuel Processing Technology,2002,79(2):171-179.