3-蒈烯催化转化反应及应用研究
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摘要
以建立3-蒈烯的高效利用途径为目的,对其催化转化进行了深入研究,结果表明:金属类催化剂对促进3-蒈烯发生三元环开环脱氢具有很高的活性,尤其是在铂催化下脱氢产物伞花烃的选择性超过90%,其中,间伞花烃与对伞花烃的质量比约为7∶2;分子筛催化同样会导致3-蒈烯发生三元环开环并脱氢,随着反应温度升高,脱氢产物对伞花烃进一步裂解生成甲苯等芳烃化合物,ZSM-5型分子筛在促进裂解反应方面能力突出。在此基础上,建立了以金属铂与ZSM-5型分子筛为复合催化剂,3-蒈烯经连续催化转化制备甲苯与间伞花烃的工艺路线,在V(Pt/Al_2O_3)∶V(ZSM-5)1∶1,280℃的条件下,原料转化率接近100%,产品总得率大于85%,最终产物甲苯得率约25%,纯度大于99%;间伞花烃得率约46%,纯度大于95%。
With the purpose of establishing an application method,studies on the catalytic transformation of 3-carene were carried out. The results indicated that metal catalysts,especially the platinum,had excellent ability to promote the ring opening and dehydrogenation of three-membered ring in 3-carene. With platinum-catalysis,the selectivity of dehydrogenation product cymene exceeded 90% and the mass ratio of m-cymene to p-cymene was nearly 7 ∶ 2. The ring opening and dehydrogenation of 3-carene could be similarly catalyzed by molecular sieves. However,with the rising of temperature,the dehydrogenation product p-cymene would further be cracked to aromatics like toluene. Molecular sieves ZSM-5 showed a prominent activity in promoting this reaction. On the basis of these results,a continuous process of preparation of toluene and m-cymene from 3-carene was established by using platinum and ZSM-5 as a kind of composite catalyst. The conversion rate of raw material was nearly 100%and the yield of all products was more than 85%. The yield and purity of one of the final products toluene were 25% and 99%,respectively. While m-cymene were 46% and 95%,respectively,with reaction conditions at the volume ratio of Pt / Al_2O_3 to ZSM-5 1 ∶ 1 and 280 ℃.
With the purpose of establishing an application method,studies on the catalytic transformation of 3-carene were carried out. The results indicated that metal catalysts,especially the platinum,had excellent ability to promote the ring opening and dehydrogenation of three-membered ring in 3-carene. With platinum-catalysis,the selectivity of dehydrogenation product cymene exceeded 90% and the mass ratio of m-cymene to p-cymene was nearly 7 ∶ 2. The ring opening and dehydrogenation of 3-carene could be similarly catalyzed by molecular sieves. However,with the rising of temperature,the dehydrogenation product p-cymene would further be cracked to aromatics like toluene. Molecular sieves ZSM-5 showed a prominent activity in promoting this reaction. On the basis of these results,a continuous process of preparation of toluene and m-cymene from 3-carene was established by using platinum and ZSM-5 as a kind of composite catalyst. The conversion rate of raw material was nearly 100%and the yield of all products was more than 85%. The yield and purity of one of the final products toluene were 25% and 99%,respectively. While m-cymene were 46% and 95%,respectively,with reaction conditions at the volume ratio of Pt / Al_2O_3 to ZSM-5 1 ∶ 1 and 280 ℃.
引文
[1]耿树香,尹晓兵,郑畹,等.云南3-蒈烯资源的调查研究[J].林产化学与工业,2006,26(4):57-60.GENG S X,YIN X B,ZHENG W,et al.Investigation on oleoresin resource of 3-carene in Yunnan province[J].Chemistry and Industty of Forest Products,2006,26(4):57-60.
[2]耿树香,尹晓兵,马慧芬,等.高3-蒈烯思茅松松脂的化学特征[J].南京林业大学学报:自然科学版,2005,29(5):85-87.GENG S X,YIN X B,MA H F,et al.Chemical characteristics of high content 3-carene oleoresin from Pinus kesiya var.langbianensis[J].Journal of Nanjing Forestry University:Natural Sciences Edition,2005,29(5):85-87.
[3]SIMAKOVA I L,SOLKINA Y S,MOROZ B L,et al.Selective vapour-phaseα-pinene isomerization to camphene over gold-on-alumina catalyst[J].Applied Catalysis A:General,2010,385(1):136-143.
[4]RACHWALIK R,OLEJNICZAK Z,JIAO J,et al.Isomerization ofα-pinene over dealuminated ferrierite-type zeolites[J].Journal of Catalysis,2007,252(2):161-170.
[5]吴义辉,田福平,贺民,等.固载化Al Cl3催化剂上α-蒎烯异构化反应[J].催化学报,2011,32(7):1138-1142.WU Y H,TIAN F P,HE M,et al.Isomerization ofα-pinene over immobilized Al Cl3catalysts[J].Chinese Journal of Catalysis,2011,32(7):1138-1142.
[6]ROBERGE D M,BUHL D,NIEDERER J P M,et al.Catalytic aspects in the transformation of pinenes to p-cymene[J].Applied Catalysis A:General,2001,215(1):111-124.
[7]SWIFT K A D.Catalytic transformations of the major terpene feedstocks[J].Topics in Catalysis,2004,27(1):143-155.
[8]WANG J,HUA W M,YUE Y H,et al.MSU-S mesoporous materials:An efficient catalyst for isomerization ofα-pinene[J].Bioresource Technology,2010,101:7224-7230.
[9]李桂珍,刘雄民,马丽,等.用分子筛催化异构化α-蒎烯和β-蒎烯及其混合体系的研究[J].应用化工,2007,36(2):120-123.LI G Z,LIU X M,MA L,et al.Study on isomerization ofα-pinene andβ-pinene and their mixed system catalyzed by molecular sieves[J].Applied Chemical Industry,2007,36(2):120-123.
[10]元丽.甲酚生产工艺技术研究进展[J].化工技术与开发,2012,41(9):21-23.YUAN L.Technology research progress of cresol production process[J].Technology&Development of Chemical Industry,2012,41(9):21-23.
[11]李书纹,郭洪臣,王桂茹.甲苯与丙烯在ZSM-5上合成对、间位混合异丙基甲苯的研究[J].石油学报:石油加工,1995,11(2):24-31.LI S W,GUO H C,WANG G R.Study on synthesis of para-,meta-mixed cymene from toluene and propylene over ZSM-5 zeolites[J].Acta Petrolei Sinica:Petroleum Processing Section,1995,11(2):24-31.
[12]张旖旎,余倩,何伟盛,等.间甲酚烷基化合成麝香草酚的研究进展[J].材料研究与应用,2008,2(4):377-379.ZHANG Q N,YU Q,HE W S,et al.Research process of synthesis of thymol by isopropylation of m-cresol[J].Materials Research and Application,2008,2(4):377-379.
[2]耿树香,尹晓兵,马慧芬,等.高3-蒈烯思茅松松脂的化学特征[J].南京林业大学学报:自然科学版,2005,29(5):85-87.GENG S X,YIN X B,MA H F,et al.Chemical characteristics of high content 3-carene oleoresin from Pinus kesiya var.langbianensis[J].Journal of Nanjing Forestry University:Natural Sciences Edition,2005,29(5):85-87.
[3]SIMAKOVA I L,SOLKINA Y S,MOROZ B L,et al.Selective vapour-phaseα-pinene isomerization to camphene over gold-on-alumina catalyst[J].Applied Catalysis A:General,2010,385(1):136-143.
[4]RACHWALIK R,OLEJNICZAK Z,JIAO J,et al.Isomerization ofα-pinene over dealuminated ferrierite-type zeolites[J].Journal of Catalysis,2007,252(2):161-170.
[5]吴义辉,田福平,贺民,等.固载化Al Cl3催化剂上α-蒎烯异构化反应[J].催化学报,2011,32(7):1138-1142.WU Y H,TIAN F P,HE M,et al.Isomerization ofα-pinene over immobilized Al Cl3catalysts[J].Chinese Journal of Catalysis,2011,32(7):1138-1142.
[6]ROBERGE D M,BUHL D,NIEDERER J P M,et al.Catalytic aspects in the transformation of pinenes to p-cymene[J].Applied Catalysis A:General,2001,215(1):111-124.
[7]SWIFT K A D.Catalytic transformations of the major terpene feedstocks[J].Topics in Catalysis,2004,27(1):143-155.
[8]WANG J,HUA W M,YUE Y H,et al.MSU-S mesoporous materials:An efficient catalyst for isomerization ofα-pinene[J].Bioresource Technology,2010,101:7224-7230.
[9]李桂珍,刘雄民,马丽,等.用分子筛催化异构化α-蒎烯和β-蒎烯及其混合体系的研究[J].应用化工,2007,36(2):120-123.LI G Z,LIU X M,MA L,et al.Study on isomerization ofα-pinene andβ-pinene and their mixed system catalyzed by molecular sieves[J].Applied Chemical Industry,2007,36(2):120-123.
[10]元丽.甲酚生产工艺技术研究进展[J].化工技术与开发,2012,41(9):21-23.YUAN L.Technology research progress of cresol production process[J].Technology&Development of Chemical Industry,2012,41(9):21-23.
[11]李书纹,郭洪臣,王桂茹.甲苯与丙烯在ZSM-5上合成对、间位混合异丙基甲苯的研究[J].石油学报:石油加工,1995,11(2):24-31.LI S W,GUO H C,WANG G R.Study on synthesis of para-,meta-mixed cymene from toluene and propylene over ZSM-5 zeolites[J].Acta Petrolei Sinica:Petroleum Processing Section,1995,11(2):24-31.
[12]张旖旎,余倩,何伟盛,等.间甲酚烷基化合成麝香草酚的研究进展[J].材料研究与应用,2008,2(4):377-379.ZHANG Q N,YU Q,HE W S,et al.Research process of synthesis of thymol by isopropylation of m-cresol[J].Materials Research and Application,2008,2(4):377-379.