半焦催化裂解煤焦油试验研究Experimental study on catalytic cracking of coal tar by semi-coke
刘思源,张军,蔡锦羽,陆柒安
LIU Siyuan,ZHANG Jun,CAI Jinyu,LU Qi'an
摘要(Abstract):
为了提高褐煤热解制得半焦对焦油的催化裂解效果,采用煤热解制备的半焦催化裂解煤热解过程中产生的煤焦油。采用两段式固定床反应器,在反应器上段放置煤样热解,下段放置半焦催化剂催化裂解上段产生的焦油。研究了制焦温度、半焦用量、经O_2活化后半焦对焦油催化裂解效果的影响。结果表明,增加褐煤的制焦温度,焦油产率明显下降,褐煤900℃制备的活化半焦1 g时的焦油产率仅6.3%,提高半焦制焦温度有利于焦油中的大分子芳香类物质催化裂解成少环物质和小分子气体组分;增加半焦用量对焦油脱除效果作用不明显,焦油产率缓慢减少。与未活化半焦相比,O_2活化后的半焦对焦油的脱除效果更好。半焦的比表面积及孔隙分析(BET)表明,活化后半焦的比表面积更大,且孔隙更丰富;能谱分析(EDS)发现,活化后半焦表面金属元素总量高于未活化半焦。
In order to improve the catalytic cracking effect of semi-coke from lignite pyrolysis on tar,the semi-coke prepared by coal pyrolysis was used to catalyze the pyrolysis of coal tar.Two-stage fixed bed reactor was used to study the effects of coking temperature,char consumption and oxygen activation on the catalytic cracking of tar.Coal samples were placed in the upper section of the reactor for pyrolysis,and semi-coke catalyst was placed in the lower section to catalyze the pyrolysis of tar produced in the upper section.The results show that the yield of tar decreases obviously with the increase of coking temperature of lignite.The yield of tar is only 6.3% when the activated semi-coke prepared from lignite at 900 ℃ is 1 g.Increasing the coking temperature is beneficial to the catalytic cracking of macromolecular aromatics in tar into less-loop substances and small-molecule components.Increasing the char consumption has no obvious effect on tar removal,the tar yield decreases slowly.Compared with the unactivated char,the char activated by O_2 has better removal effect on tar.Specific surface area and pore analysis of semi-coke( BET) show that the activated char has larger specific surface area and more pore space.Energy spectrum analysis( EDS) shows that the total amount of metal elements on the surface of activated char is higher than that of unactivated char.
关键词(KeyWords):
半焦;催化裂解;煤焦油;热解
semi-coke;catalytic cracking;coal tar;pyrolysis
基金项目(Foundation): 国家重点研发计划资助项目(2017YFB0602900)
作者(Author):
刘思源,张军,蔡锦羽,陆柒安
LIU Siyuan,ZHANG Jun,CAI Jinyu,LU Qi'an
DOI: 10.13226/j.issn.1006-6772.19041202
参考文献(References):
- [1]刘殊远,汪印,武荣成,等.热态半焦和冷态半焦催化裂解煤焦油研究[J].燃料化学学报,2013,41(9):1041-1049.LIU Shuyuan,WANG Yin,WU Rongcheng,et al.Research on coal tar catalytic cracking over hot in-situ chars[J]. Journal of Fuel Chemistry,2013,41(9):1041-1049.
- [2] SHEN Y,YOSHIKAWA K.Recent progresses in catalytic tar elimination during biomass gasification or pyrolysis—A review[J]. Renewable and Sustainable Energy Reviews,2013,21:371-392.
- [3] LIU S,WANG Y,WU R,et al.Fundamentals of catalytic tar removal over in situ and ex situ chars in two-stage gasification of coal[J].Energy&Fuels,2013,28(1):58-66.
- [4] MIN Z,YIMSIRI P,ASADULLAH M,et al.Catalytic reforming of tar during gasification. Part II. Char as a catalyst or as a catalyst support for tar reforming[J].Fuel,2011,90(7):2545-2552.
- [5] LI C Z.Some recent advances in the understanding of the pyrolysis and gasification behaviour of Victorian brown coal[J].Fuel,2007,86(12/13):1664-1683.
- [6] HAYASHI J I,IWATSUKI M,MORISHITA K,et al.Roles of inherent metallic species in secondary reactions of tar and char during rapid pyrolysis of brown coals in a drop-tube reactor[J]. Fuel,2002,81(15):1977-1987.
- [7] MATSUHARA T,HOSOKAI S,NORINAGA K,et al.In-situ reforming of tar from the rapid pyrolysis of a brown coal over char[J].Energy&Fuels,2009,24(1):76-83.
- [8] WANG F J,ZHANG S,CHEN Z D,et al.Tar reforming using char as catalyst during pyrolysis and gasification of Shengli brown coal[J]. Journal of Analytical and Applied Pyrolysis,2014,105:269-275.
- [9] NESTLER F,BURHENNE L,AMTENBRINK M J,et al.Catalytic decomposition of biomass tars:The impact of wood char surface characteristics on the catalytic performance for naphthalene removal[J].Fuel Processing Technology,2016,145:31-41.
- [10] ZHANG K,LI Y,WANG Z,et al.Pyrolysis behavior of a typical Chinese sub-bituminous Zhundong coal from moderate to high temperatures[J].Fuel,2016,185:701-708.
- [11] WANG F J,ZHANG S,CHEN Z D,et al.Tar reforming using char as catalyst during pyrolysis and gasification of Shengli brown coal[J]. Journal of analytical and applied pyrolysis,2014,105:269-275.
- [12]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,2012,40(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 O2/steam[J]. Journal of Fuel Chemistry,2012,40(6):660-665.
- [13] SHEN Y.Chars as carbonaceous adsorbents/catalysts for tar elimination during biomass pyrolysis or gasification[J]. Renewable and Sustainable Energy Reviews,2015,43:281-295.
- [14]陈昭睿.煤热解过程中热解气停留时间对热解产物的影响[D].杭州:浙江大学,2015:27-39.CHEN Zhaorui.Influence of gas residence time on product distribution of coal pyrolysis[D]. Hangzhou:Zhejiang University,2015:27-39.
- [15]张睿.烟煤热解半焦气化特性的研究[D].杭州:浙江大学,2014:106-116.ZHANG Rui. Study on gasification characteristics of bituminous coal pyrolysis semi-coke[D]. Hangzhou:Zhejiang University,2014:106-116.
- [16]史磊.半焦的活化及脱灰研究[D].大连:大连理工大学,2008.SHI Lei. The study on activating and deashing coal char[D].Dalian:Dalian University of Technology,2008.
- [17]王芳,曾玺,孙延林,等.两段流化床中半焦催化脱除焦油特性[J].化工学报,2017,68(10):3762-3769.WANG Fang,ZENG Xi,SUN Yanlin,et al. Characteristics of char catalytic reforming of tar in two-stage fluidized bed[J].Journal of Chemical Engineering,2017,68(10):3762-3769.
- [18] HOSOKAI S,KUMABE K,OHSHITA M,et al.Mechanism of decomposition of aromatics over charcoal and necessary condition for maintaining its activity[J]. Fuel,2008,87(13/14):2914-2922.
- [19] LU L,SAHAJWALLA V,HARRIS D.Characteristics of chars prepared from various pulverized coals at different temperatures using drop-tube furnace[J].Energy&Fuels,2000,14(4):869-876.
- [20] ZENG X,WANG Y,YU J,et al. Gas upgrading in a downdraft fixed-bed reactor downstream of a fluidized-bed coal pyrolyzer[J].Energy&Fuels,2011,25(11):5242-5249.
- [21] JIN L,BAI X,LI Y,et al.In-situ catalytic upgrading of coal pyrolysis tar on carbon-based catalyst in a fixed-bed reactor[J].Fuel Processing Technology,2016,147:41-46.