酸碱改性ZSM-5分子筛及其噻吩烷基化性能的研究
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摘要
首先采用碱处理HZSM-5分子筛,然后采用不同浓度的柠檬酸酸洗碱处理后的HZSM-5分子筛,制备具有微孔-介孔多级孔HZSM-5分子筛。通过XRD、SEM、BET和NH3-TPD等表征手段对处理后催化剂进行表征,考察了碱处理后酸洗对HZSM-5分子筛孔结构性质的影响,结果表明:适当浓度的柠檬酸酸洗碱处理后的ZSM-5分子筛,能够清除掉残留在分子筛孔道内的杂质,增大了分子筛的孔径;在小型固定床反应器上,研究了改性前后分子筛的噻吩烷基化反应活性和稳定性,结果表明:碱处理后采用适当浓度的柠檬酸酸洗后,催化剂的初活性虽然低于碱改性的分子筛,但稳定性较好,更适合噻吩烷基化反应。
ZSM-5 zeolites were firstly treated by alkali solution. Then the HZSM-5 molecules of alkali treatment were washed by useing different concentrations of citric acid to prepare the HZSM-5 multiple microporous and mesoporous. The samples were characterized by XRD,SEM,N2 desorption,NH3-TPD and other. It has been investigated that the effect of acid washing after alkaline treatment on the structure and properties of HZSM-5 molecular sieves,It is show that: ZSM-5 molecular sieve catalyst after Alkali treatment are treated by proper concentration citric acid,which can clear the impurities remaining in the molecular sieve channel and expand the pore size of molecular sieve. The initial activity and stability of each catalyst thiophene alkylation before and after modification were studied on a small fixed bed reactor.It is show that through after alkali treatment,and washed with proper concentration of citric acid,the initial activity of the catalyst is lower than the alkali modified zeolite,but it has better stability,and which is more suitable for thiophene alkylation.
ZSM-5 zeolites were firstly treated by alkali solution. Then the HZSM-5 molecules of alkali treatment were washed by useing different concentrations of citric acid to prepare the HZSM-5 multiple microporous and mesoporous. The samples were characterized by XRD,SEM,N2 desorption,NH3-TPD and other. It has been investigated that the effect of acid washing after alkaline treatment on the structure and properties of HZSM-5 molecular sieves,It is show that: ZSM-5 molecular sieve catalyst after Alkali treatment are treated by proper concentration citric acid,which can clear the impurities remaining in the molecular sieve channel and expand the pore size of molecular sieve. The initial activity and stability of each catalyst thiophene alkylation before and after modification were studied on a small fixed bed reactor.It is show that through after alkali treatment,and washed with proper concentration of citric acid,the initial activity of the catalyst is lower than the alkali modified zeolite,but it has better stability,and which is more suitable for thiophene alkylation.
引文
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[18]刘冬梅,翟玉春,马健,等.不同碱处理制备多级孔HZSM-5催化剂及噻吩烷基化性能的研究[J].燃料化学学报,2015,43(4):462-469.
[19]刘冬梅,铁大兴,高晨义,等.混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能[J].燃料化学学报,2017,45(2):200-212.
[20]刘冬梅,王海彦,孔飞飞,等.TPAOH处理制备的微介孔催化剂物化性质与噻吩烷基化性能研究[J].燃料化学学报,2016,44(11):1370-1379.
[21]唐津莲,许友好,徐莉,等.庚烯与H2S在酸性催化剂上的反应机理Ⅱ.噻吩类化合物生成机理[J].石油学报(石油加工),2008,24(3):243-250.
[22]刘盛林,郭晓野,张泽凯,等.MCM-22分子筛介孔对汽油烷基脱硫影响[J].石油学报(石油加工),2008,24(b10):88-91.
[23]顾伯锷.工业催化过程导论[M].北京:高等教育出版社,1990,119-200.
[2]Belliere V,Geantet C,Vriant M,et al.Alkylation of 3-Methyl-thiophene with 2-Methyl-2-butene Over a Zeolitic Catalyst[J].Energy Fuels,2004,18(6):1806-1813.
[3]Dupuy B,Laforge S,Morais C,et al.Alkylation of 3-methylthiophene by 2-methyl-1-pentene over HY,HBEA and HMCM-22 Acidic Zeolites[J].Appl Catal A:Gen,2012,413-414(31):192-204.
[4]Dupuy B,Laforge S,Bachamant C,et al.Desulfurization of Model FCC Feedstocks by Alkylation:Transformation of Thiophenic Compounds in Presence of 2-methyl-1-pentene Over Acidic Zeolites[J].J.Mol.Catal.A:Chem.,2012,363-364.
[5]Hu L Y,Zhang Z K,Xie S J,et al.Effect of Grain Size of Zeolite Y on its Catalytic Performance in Olefin Alkylation Thiophenic Sulfur Process[J].Catal.Commun.,2009,10(6):900-904.
[6]Zhang Z K,Niu X L,Liu S L,et al.The Performance of HMCM-22 Zeolite Catalyst on the Olefin Alkylation Thiophenic Sulfur in Gasoline[J].Catal.Commun.,2008,9(1):60-64.
[7]罗国华,徐新,佟泽民,等.分子筛催化噻吩类硫化物与烯烃烷基化脱硫研究[J].化学反应工程与工艺,2005,21(2):132-137.
[8]王素珍,罗国华,徐新,等.介孔分子筛MCM-41的合成及其催化噻吩与异丁烯烷基化反应性能[J].石油化工,2004,33(2):113-117.
[9]魏书梅,徐亚荣,徐新良,等.HY分子筛催化噻吩类硫化物的烷基化反应动力学[J].化学反应工程与工艺,2012,28(2):159-163.
[10]郭晓野,张泽凯,刘盛林,等.汽油在钾修饰MCM-41分子筛上的烷基化脱硫[J].工业催化,2008,16(6):31-34.
[11]Zheng X D,Dong H J,Wang X,et al.Study on Olefin Alkylation of Thiophenic Sulfur in FCC Gasoline Using La2O3-Modified HY Zeolite[J].Catal.Lett.,2009,127(1-2):70-74.
[12]Bharat K.Modhera,Mousumi Chakraborty,Hari C.Influences of Mesoporosity Generation in ZSM-5 and Zeolite Beta on Catalytic Performance During n-Hexane Isomerization[J].Catal.Lett.,2011,141(10):1182-1190.
[13]赵岑,刘冬梅,魏民,等.多级孔ZSM-5分子筛的制备及催化噻吩烷基化性能研究[J].燃料化学学报,2013,41(10):1256-1261.
[14]Ogura M,Shinomiya S Y,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.
[15]张贵泉,白婷,屈文婷,等.甲醇芳构化的研究Ⅱ.Na OH处理HZSM-5分子筛催化剂的性能[J].石油化工,2013,42(3):265-270.
[16]赵文平,郭洪臣.用偏铝酸钠溶液改性纳米ZSM-5沸石的研究[C].全国分子筛学术大会会议论文集,2013.
[17]单程楠,唐见,赵海涛,等.不同改性方法对沸石吸附对硝基苯酚能力的影响[J].农业环境科学学报,2010,29(11):2214-2220.
[18]刘冬梅,翟玉春,马健,等.不同碱处理制备多级孔HZSM-5催化剂及噻吩烷基化性能的研究[J].燃料化学学报,2015,43(4):462-469.
[19]刘冬梅,铁大兴,高晨义,等.混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能[J].燃料化学学报,2017,45(2):200-212.
[20]刘冬梅,王海彦,孔飞飞,等.TPAOH处理制备的微介孔催化剂物化性质与噻吩烷基化性能研究[J].燃料化学学报,2016,44(11):1370-1379.
[21]唐津莲,许友好,徐莉,等.庚烯与H2S在酸性催化剂上的反应机理Ⅱ.噻吩类化合物生成机理[J].石油学报(石油加工),2008,24(3):243-250.
[22]刘盛林,郭晓野,张泽凯,等.MCM-22分子筛介孔对汽油烷基脱硫影响[J].石油学报(石油加工),2008,24(b10):88-91.
[23]顾伯锷.工业催化过程导论[M].北京:高等教育出版社,1990,119-200.