碱处理HZSM-5分子筛对神东煤热解产物分布的影响
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摘要
使用NaOH溶液对HZSM-5分子筛进行处理,利用粉-粒流化床快速热解实验装置,考察了经过不同时间碱处理的HZSM-5分子筛对神东煤热解产物分布的影响。结果表明:适当的碱处理能够在不破坏HZSM-5分子筛晶相结构的情况下在晶体内部引入介孔,且随着碱处理时间的延长,分子筛的介孔孔容、介孔比表面积增加,孔径分布变宽,总酸量先增大后减小。碱处理0.5h的HZSM-5分子筛催化时焦油中苯、甲苯含量最大,较原煤热解分别增加了268%、296%;碱处理2h的HZSM-5分子筛催化下热解气体总含量达到最大,较原煤热解增加了24.8%;碱处理4h的HZSM-5催化时焦油中萘及萘的同系物、多环芳烃(除萘类)含量最大,分别较原煤增加了92%、192%。
HZSM-5 zeolites were treated with NaOH solutions. Powder-particle fluidized bed reactor was used to investigate the effect of alkali-treated HZSM-5 zeolites with different treatment time on product distribution of Shendong coal pyrolysis. The results showed that a proper alkali treatment can introduce mesopores into the crystal without destroying its phase structure. The amount of mesopore volume and the specific surface area enhanced with increasing alkali treatment time. In addition, the pore size distribution became broader and the acidity reached a peak followed by a continuous decrease. The content of the benzene and toluene in tar derived from pyrolysis in the presence of 0.5 h alkali-treated zeolite increased up to 268% and 296% compared to that of raw coal, respectively. In the case of 2 h alkali-treated HZSM-5 used in pyrolysis, the total amount of the pyrolysis gas was the highest, which was 24.8% higher than that of raw coal. The highest content of naphthalene, naphthalenederivates and polycyclic aromatic hydrocarbon(excluding naphthalenes) in tar could be obtained from pyrolysis when 4 h alkali-treated zeolite was exploited, which was about 92% and 192% higher than that of raw coal, respectively.
HZSM-5 zeolites were treated with NaOH solutions. Powder-particle fluidized bed reactor was used to investigate the effect of alkali-treated HZSM-5 zeolites with different treatment time on product distribution of Shendong coal pyrolysis. The results showed that a proper alkali treatment can introduce mesopores into the crystal without destroying its phase structure. The amount of mesopore volume and the specific surface area enhanced with increasing alkali treatment time. In addition, the pore size distribution became broader and the acidity reached a peak followed by a continuous decrease. The content of the benzene and toluene in tar derived from pyrolysis in the presence of 0.5 h alkali-treated zeolite increased up to 268% and 296% compared to that of raw coal, respectively. In the case of 2 h alkali-treated HZSM-5 used in pyrolysis, the total amount of the pyrolysis gas was the highest, which was 24.8% higher than that of raw coal. The highest content of naphthalene, naphthalenederivates and polycyclic aromatic hydrocarbon(excluding naphthalenes) in tar could be obtained from pyrolysis when 4 h alkali-treated zeolite was exploited, which was about 92% and 192% higher than that of raw coal, respectively.
引文
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[17]GROEN J C,JANSEN J C,MOULIJN J A,et al.Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication[J].The Journal of Physical Chemistry B,2004,108(35):13062-13065.
[18]李莎,李玉平,狄春雨,等.TPAOH/Na OH混合碱体系对ZSM-5沸石的改性及其催化性能研究[J].燃料化学学报,2012,40(5):583-588.LI Sha,LI Yuping,DI Chunyu,et al.Modification and catalyst performance of ZSM-5 zeolite by treatment with TPAOH/Na OHmixed alkali[J].Journal of Fuel Chemistry and Technology,2012,40(5):583-588.
[19]孙超,杨依苏,杜俊明,等.碱处理法制备微介孔ZSM-5催化剂及其在甲醇制丙烯(MTP)反应中的应用[J].复旦学报(自然科学版),2012,51(5):559-565.SUN Chao,YANG Yisu,DU Junming,et al.Preparation of mesopore containing zeolite ZSM-5 and its application in methanol to propylene reaction[J].Journal of Fudan University(Natural Science),2012,51(5):559-565.
[20]卢信清,许春慧,张富民,等.碱处理制备介孔-微孔沸石分子筛的影响因素及其应用研究进展[J].化工进展,2014,33(8):2038-2043.LU Xinqing,XU Chunhui,ZHANG Fumin,et al.Influence factors for preparation of meso-microporous zeolites by alkali-treatment and their research progress[J].Chemical Industry and Engineering Progress,2014,33(8):2038-2043.
[21]LIU T L,CAO J P,ZHAO X Y,et al.In situ,upgrading of Shengli lignite pyrolysis vapors over metal-loaded HZSM-5 catalyst[J].Fuel Processing Technology,2017,160:19-26.
[22]LI Y,AMIN M N,LU X,et al.Pyrolysisand catalytic upgrading of low-rank coal using a NiO/MgO-Al2O3,catalyst[J].Chemical Engineering Science,2016,155:194-200.
[2]张晶,张生军,周凡,等.煤催化热解研究现状[J].煤炭技术,2014,33(4):238-241.ZHANG Jing,ZHANG Shengjun,ZHOU Fan,et al.Research advancement on coal catalytic pyrolysis[J].Coal Technology,2014,33(4):238-241.
[3]TAKARADA T,ONOYAMA Y,TAKAYAMA K,et al.Hydropyrolysis of coal in a pressurized powder-particle fluidized bed using several catalysts[J].Catalysis Today,1997,39:127-136.
[4]邹献武,姚建中,杨学民,等.喷动-载流床中Co/ZSM-5分子筛催化剂对煤热解的催化作用[J].过程工程学报,2007,7(6):1107-1113.ZOU Xianwu,YAO Jianzhong,YANG Xuemin,et al.Effect of Co/ZSM-5 zeolite catalyst on pyrolysis of coal in a spouted fluidized bed[J].The Chinese Journal of Process Engineering,2007,7(6):1107-1113.
[5]李兆飞,刘其武,王骞,等.相同晶貌不同硅铝比ZSM-5的合成及其催化裂化性能研究[J].工业催化,2014,22(3):215-220.LI Zhaofei,LIU Qiwu,WANG Qian,et al.Synthesis and catalytic cracking performance of ZSM-5 with controlled morphology and different silica-alumina ratios[J].Industrial Catalysis,2014,22(3):215-220.
[6]勾明雷.ZSM-5沸石的改性及其在氧化苯乙烯重排制备苯乙醛中的催化性能[D].天津:天津大学,2014.GOU Minglei.Modification of ZSM-5 zeolites and their catalytic performances in the isomerization of styrene oxide to phenylacetaldehyde[D].Tianjin:Tianjin University,2014.
[7]AND L T,VALTCHEV V P.Nanozeolites:?synthesis,crystallization mechanism,and applications[J].Cheminform,2005,36(29):2494.
[8]ZHANG W,BAO X,GUO X,et al.A high‐resolution solid‐state NMR study on nano‐structured HZSM‐5 zeolite[J].Catalysis Letters,1999,60(1-2):89-94.
[9]TAGO T,KONNO H,SAKAMOTO M,et al.Selective synthesis for light olefins from acetone over ZSM-5 zeolites with nano-and macro-crystal sizes[J].Applied Catalysis A:General,2011,403(1/2):183-191.
[10]魏民,孔飞飞,丁越野,等.碱处理法制备微介孔ZSM-5及其加氢脱硫性能的研究[J].石油炼制与化工,2015,46(10):61-66.WEI Min,KONG Feifei,DING Yueye,et al.Study on preparation of micro-mesoporous ZSM-5 zeolite by alkali treatment and proformance in hydrodesulfurization of FCC gasoline[J].Petroleum Processing and Petrochemicals,2015,46(10):61-66.
[11]MU X H,WANG D,WANG Y,et al.Nanosized molecular sieves as petroleum refining and petrochemical catalysts[J].Chinese Journal of Catalysis,2013,34(1):69-79.
[12]OGURA M,SHINOMIYA S,TATENO J,et al.Formation of uniform mesopores in ZSM-5 zeolite through treatment in alkaline solution[J].Chemistry Letters,2000,29(8):882-883.
[13]OGURA M,SHINOMIYA S,TATENO J,et al.Alkali-treatment technique--new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J].Applied Catalysis A:General,2001,219(1/2):33-43.
[14]PéREZ-RAMíREZ J,CHRISTENSEN C H,EGEBLAD K,et al.Hierarchical zeolites:enhanced utilisation of microporous crystals in catalysis by advances in materials design[J].Chemical Society Reviews,2008,37(11):2530-2542.
[15]GOU M L,WANG R,QIAO Q,et al.Effect of mesoporosity by desilication on acidity and performance of HZSM-5 in the isomerization of styrene oxide to phenylacetaldehyde[J].Microporous&Mesoporous Materials,2015,206:170-176.
[16]GROEN J C,PEFFER La A,MOULIJN J A,et al.Mesoporosity development in ZSM-5 zeolite upon optimized desilication conditions in alkaline medium[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2004,241(1/2/3):53-58.
[17]GROEN J C,JANSEN J C,MOULIJN J A,et al.Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication[J].The Journal of Physical Chemistry B,2004,108(35):13062-13065.
[18]李莎,李玉平,狄春雨,等.TPAOH/Na OH混合碱体系对ZSM-5沸石的改性及其催化性能研究[J].燃料化学学报,2012,40(5):583-588.LI Sha,LI Yuping,DI Chunyu,et al.Modification and catalyst performance of ZSM-5 zeolite by treatment with TPAOH/Na OHmixed alkali[J].Journal of Fuel Chemistry and Technology,2012,40(5):583-588.
[19]孙超,杨依苏,杜俊明,等.碱处理法制备微介孔ZSM-5催化剂及其在甲醇制丙烯(MTP)反应中的应用[J].复旦学报(自然科学版),2012,51(5):559-565.SUN Chao,YANG Yisu,DU Junming,et al.Preparation of mesopore containing zeolite ZSM-5 and its application in methanol to propylene reaction[J].Journal of Fudan University(Natural Science),2012,51(5):559-565.
[20]卢信清,许春慧,张富民,等.碱处理制备介孔-微孔沸石分子筛的影响因素及其应用研究进展[J].化工进展,2014,33(8):2038-2043.LU Xinqing,XU Chunhui,ZHANG Fumin,et al.Influence factors for preparation of meso-microporous zeolites by alkali-treatment and their research progress[J].Chemical Industry and Engineering Progress,2014,33(8):2038-2043.
[21]LIU T L,CAO J P,ZHAO X Y,et al.In situ,upgrading of Shengli lignite pyrolysis vapors over metal-loaded HZSM-5 catalyst[J].Fuel Processing Technology,2017,160:19-26.
[22]LI Y,AMIN M N,LU X,et al.Pyrolysisand catalytic upgrading of low-rank coal using a NiO/MgO-Al2O3,catalyst[J].Chemical Engineering Science,2016,155:194-200.