四氢糠醇经复合催化剂合成吡啶的研究
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摘要
作为一种重要的精细化工原料,吡啶及其衍生物广泛地应用于染料,医药,农药等各个领域。
本论文主要对四氢糠醇合成吡啶的催化剂、载体以及工艺进行了研究。四氢糠醇和氨气在管式固定床中,经复合金属氧化物催化剂高温催化合成吡啶。针对前期工作采用的催化剂载体难以批量化生产的问题,筛选研究了小三叶草状等5种γ- Al2O3载体,筛选出几种效果较好的载体替代原有载体。其中小三叶草状γ- Al2O3负载的10% MoO3/ Al2O3作用下,吡啶的收率为71.15%。还以小三叶草状、细条状以及前期使用的三叶草状γ- Al2O3为载体对主催化剂进行了研究,并通过向主催化剂中添加助催化剂,进一步改善了催化效果。在反应温度550℃,四氢糠醇流量0.1mL/min,n(THFA):n(NH3)=1:4条件下,采用小三叶草状γ-Al2O3载体上所负载的5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3催化剂,吡啶收率达到88.83%。
还从原料掺水比例、温度等方面对反应工艺的影响因素进行了研究,并对粗产物进行了精馏分离。当原料中体积掺水比例V(四氢糠醇):V(水)=4:1时,吡啶收率较高。当反应温度500℃,四氢糠醇流量0.1mL/min,n(THFA):n(NH3) =1:4时,5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3催化剂作用下,吡啶收率达到89.11%。粗产品经精馏塔分离提纯,吡啶含量达到94.71%。
As finechemical raw material, pyridine and its derivatives are widely used in fields such as dyes, medicinal chemicals and pesticides.
The catalysts, the carriers and the process for the synthesis of pyridine from tetrahydrofurfuryl alcohol(THFA)were studied in this article. Pyridine was prepared by THFA and ammonia in a tubular fixed bed reactor under effects of multicomponent metallic oxide catalysts and high temperature. In order to solve the batch production problems of catalyst carriers applied in previous works, five new catalystγ-Al2O3 carriers were screened and several good carriers were adopted to replace the previous carrier. The reaction yield of pyridine was 71.15% with 10%MoO3/γ-Al2O3 loaded on diminutive trifoliateγ-Al2O3. Different major catalysts were studied with diminutive trifoliate, thin strip and trifoliateγ-Al2O3 carriers, the catalytic effects of catalysts were further improved by the addition of cocatalyst into major catalyst. The reaction yield of pyridine was 88.83% with 5%MoO3-5%V2O5-3%Ce2O3-2%MgO/γ-Al2O3 as the catalyst, when reaction temperature was 550℃, the flow rate of THFA was 0.1mL/min and n(THFA):n(NH3)=1:4.
The influence of proportion of water and temperature was studied. The crude product was separated and purified by rectification. The yield of pyridine was good when water proportion V(THFA):V(H2O) =4:1 in raw material. The reaction yield of pyridine was 89.11% with 5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3 as the catalyst, when reacting temperature was 500℃, the flow rate of THFA was 0.1mL/min and n(THFA):n(NH3)=1:4. The pyridine purity was 94.71%.
本论文主要对四氢糠醇合成吡啶的催化剂、载体以及工艺进行了研究。四氢糠醇和氨气在管式固定床中,经复合金属氧化物催化剂高温催化合成吡啶。针对前期工作采用的催化剂载体难以批量化生产的问题,筛选研究了小三叶草状等5种γ- Al2O3载体,筛选出几种效果较好的载体替代原有载体。其中小三叶草状γ- Al2O3负载的10% MoO3/ Al2O3作用下,吡啶的收率为71.15%。还以小三叶草状、细条状以及前期使用的三叶草状γ- Al2O3为载体对主催化剂进行了研究,并通过向主催化剂中添加助催化剂,进一步改善了催化效果。在反应温度550℃,四氢糠醇流量0.1mL/min,n(THFA):n(NH3)=1:4条件下,采用小三叶草状γ-Al2O3载体上所负载的5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3催化剂,吡啶收率达到88.83%。
还从原料掺水比例、温度等方面对反应工艺的影响因素进行了研究,并对粗产物进行了精馏分离。当原料中体积掺水比例V(四氢糠醇):V(水)=4:1时,吡啶收率较高。当反应温度500℃,四氢糠醇流量0.1mL/min,n(THFA):n(NH3) =1:4时,5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3催化剂作用下,吡啶收率达到89.11%。粗产品经精馏塔分离提纯,吡啶含量达到94.71%。
As finechemical raw material, pyridine and its derivatives are widely used in fields such as dyes, medicinal chemicals and pesticides.
The catalysts, the carriers and the process for the synthesis of pyridine from tetrahydrofurfuryl alcohol(THFA)were studied in this article. Pyridine was prepared by THFA and ammonia in a tubular fixed bed reactor under effects of multicomponent metallic oxide catalysts and high temperature. In order to solve the batch production problems of catalyst carriers applied in previous works, five new catalystγ-Al2O3 carriers were screened and several good carriers were adopted to replace the previous carrier. The reaction yield of pyridine was 71.15% with 10%MoO3/γ-Al2O3 loaded on diminutive trifoliateγ-Al2O3. Different major catalysts were studied with diminutive trifoliate, thin strip and trifoliateγ-Al2O3 carriers, the catalytic effects of catalysts were further improved by the addition of cocatalyst into major catalyst. The reaction yield of pyridine was 88.83% with 5%MoO3-5%V2O5-3%Ce2O3-2%MgO/γ-Al2O3 as the catalyst, when reaction temperature was 550℃, the flow rate of THFA was 0.1mL/min and n(THFA):n(NH3)=1:4.
The influence of proportion of water and temperature was studied. The crude product was separated and purified by rectification. The yield of pyridine was good when water proportion V(THFA):V(H2O) =4:1 in raw material. The reaction yield of pyridine was 89.11% with 5%MoO3-5%V2O5-3%Ce2O3-2%MgO /γ-Al2O3 as the catalyst, when reacting temperature was 500℃, the flow rate of THFA was 0.1mL/min and n(THFA):n(NH3)=1:4. The pyridine purity was 94.71%.
引文
[1]蒋劼，毛东森，杨为民，卢冠忠，吡啶碱的合成及应用前景[J].应用化工,2003,32(1):15～17
[2]江镇海,烷基吡啶应用前景广阔[J].化工中间体,2002,2:18
[3]李涛,吡啶的生产应用及市场前景分析[J].化工科技市场,2005,7:12～15
[4]周焕文,于世钧,徐杰,朱丹,吡啶及其衍生物催化合成进展及应用前景[J].工业催化,2001,9(3):26～32
[5]蒋劼，卢冠忠，毛东森，杨为民，吡啶碱类化合物合成进展[J].精细石油化工,2002,3(12):25～28
[6] Girish K., Jocelyn A, John P.. Pyridine/picoline production process [P]. US5994550, 1999-11-30
[7]孙南怡,烷基吡啶的生产与应用[J].化工中间体,2002,16:9～10
[8]孙华林,烷基吡啶[J].精细石油化工,2002,6:59～61
[9]吡啶系列原料国内市场分析[J].精细与专用化学品,2001,1:6～8
[10]胡斌,吡啶衍生物产品开发方兴未艾[J].化工开发与设计,2001,12: 38～39
[11]吡啶类化合物市场前景广阔[J].医药化工,2005,10:40
[12]蒋劼，毛东森，杨为民，卢冠忠，吡啶碱的生产、应用及市场[J].化工中间体,2003,2:14～17
[13] Zhang J., Xiao G. M., Liang H. H., Study on catalyst for pyridine synthesis [J].Journal of Southeast University(English Edition), 2004, 20(1): 62～64
[14]赵云,吡啶碱类化合物的应用与合成[J].四川化工与腐蚀控制,1998,3(1):33～35
[15]孙荫辉,吡啶类化合物的合成与应用[J].江苏化工,1996,24(5):9～14
[16]欧阳南,詹晓力,陈丰秋,合成吡啶类化合物用催化剂的再生行为研究[J].精细石油化工,2002,6:22～25
[17]卫双绍,合成吡啶碱的现状与开发建议[J].中氮肥,1994,6:1～8
[18]梁诚,吡啶及其衍生物生产与应用[J].化工文摘,2003,8:21～22
[19] Choi J. H., Lee W. Y., Pyridine synthesis from tetrahydrofurfuryl clcohol over a Pd/γ-Al2O3 catalystⅡ. Effect of supports and palladium loading[J].Applied catalysis A: General, 1993, 98(1):21～31
[20]周丹,冯亚青,孟舒献,傅雪晶,钯/氧化铝催化剂对四氢糠醇合成吡啶的研究[J].高校化学工程学报,2006,20(2):250～253
[21]周丹,冯亚青,傅雪晶,张家欣,MoO3/Al2O3在四氢糠醇合成吡啶中的应用[J].精细化工,2005,22(10):795～797
[22]魏优昌,吡啶衍生物及其催化闭环法合成[J].精细与专用化学品,2006,14(17):1～9
[23]崔英德,黎新明,烟酸的应用与生产方法[J].广州化工,2000,28(4):97～98
[24]徐兆瑜,医药中间体中的吡啶化合物[J].农化市场十日讯,2006,429:13
[25]孙玉泉,张丽华,3-甲基吡啶的合成与应用[J].天津化工,2006,20(4):50～52
[26]徐兆瑜,医药中间体中的吡啶化合物[J].医药化工,2005,7:21～24
[27]陈瑞战,李晓莉,伍辛军,王晓菊,赵伦,聚(苯乙烯-丙烯酸)钕配合物催化苯乙烯与4-乙烯基吡啶共聚的研究[J].中国稀土学报,2005,23(6): 663～667
[28]肖国民,张进,烷基吡啶的合成及应用前景[J].化工技术经济,2001,4:7～9
[29]岳涛,孔祥峰,曹社会,刘辉,绿色饲料添加剂――二氢吡啶在动物生产中的研究与应用[J].饲料工业,2006,27(4):11～14
[30]令海,郑立金,周壮,2-氯吡啶的合成与应用[J].中国氯碱,2006,6:16～18
[31]张伟,徐杰,孙志强,杜中田,卤代吡啶类化合物的合成及应用[J].精细化工中间体,2006,36(4):1～6
[32]徐兆瑜,医药中间体中的一些重要杂环化合物[J].精细化工原料及中间体,2006,2:27～33
[33]周丹,冯亚青,傅雪晶,高活性,高选择性骨架镍在糠醇加氢中的应用研究[J].精细化工,2005,22(2):113～115
[34]李春林,伏义路,孟明,卞国柱,水蒸气对Ni/CeO2-ZrO2-Al2O3催化剂上CO2+CH4重整反应的影响[J].化学物理学报,2004,17(1):95～99
[2]江镇海,烷基吡啶应用前景广阔[J].化工中间体,2002,2:18
[3]李涛,吡啶的生产应用及市场前景分析[J].化工科技市场,2005,7:12～15
[4]周焕文,于世钧,徐杰,朱丹,吡啶及其衍生物催化合成进展及应用前景[J].工业催化,2001,9(3):26～32
[5]蒋劼，卢冠忠，毛东森，杨为民，吡啶碱类化合物合成进展[J].精细石油化工,2002,3(12):25～28
[6] Girish K., Jocelyn A, John P.. Pyridine/picoline production process [P]. US5994550, 1999-11-30
[7]孙南怡,烷基吡啶的生产与应用[J].化工中间体,2002,16:9～10
[8]孙华林,烷基吡啶[J].精细石油化工,2002,6:59～61
[9]吡啶系列原料国内市场分析[J].精细与专用化学品,2001,1:6～8
[10]胡斌,吡啶衍生物产品开发方兴未艾[J].化工开发与设计,2001,12: 38～39
[11]吡啶类化合物市场前景广阔[J].医药化工,2005,10:40
[12]蒋劼，毛东森，杨为民，卢冠忠，吡啶碱的生产、应用及市场[J].化工中间体,2003,2:14～17
[13] Zhang J., Xiao G. M., Liang H. H., Study on catalyst for pyridine synthesis [J].Journal of Southeast University(English Edition), 2004, 20(1): 62～64
[14]赵云,吡啶碱类化合物的应用与合成[J].四川化工与腐蚀控制,1998,3(1):33～35
[15]孙荫辉,吡啶类化合物的合成与应用[J].江苏化工,1996,24(5):9～14
[16]欧阳南,詹晓力,陈丰秋,合成吡啶类化合物用催化剂的再生行为研究[J].精细石油化工,2002,6:22～25
[17]卫双绍,合成吡啶碱的现状与开发建议[J].中氮肥,1994,6:1～8
[18]梁诚,吡啶及其衍生物生产与应用[J].化工文摘,2003,8:21～22
[19] Choi J. H., Lee W. Y., Pyridine synthesis from tetrahydrofurfuryl clcohol over a Pd/γ-Al2O3 catalystⅡ. Effect of supports and palladium loading[J].Applied catalysis A: General, 1993, 98(1):21～31
[20]周丹,冯亚青,孟舒献,傅雪晶,钯/氧化铝催化剂对四氢糠醇合成吡啶的研究[J].高校化学工程学报,2006,20(2):250～253
[21]周丹,冯亚青,傅雪晶,张家欣,MoO3/Al2O3在四氢糠醇合成吡啶中的应用[J].精细化工,2005,22(10):795～797
[22]魏优昌,吡啶衍生物及其催化闭环法合成[J].精细与专用化学品,2006,14(17):1～9
[23]崔英德,黎新明,烟酸的应用与生产方法[J].广州化工,2000,28(4):97～98
[24]徐兆瑜,医药中间体中的吡啶化合物[J].农化市场十日讯,2006,429:13
[25]孙玉泉,张丽华,3-甲基吡啶的合成与应用[J].天津化工,2006,20(4):50～52
[26]徐兆瑜,医药中间体中的吡啶化合物[J].医药化工,2005,7:21～24
[27]陈瑞战,李晓莉,伍辛军,王晓菊,赵伦,聚(苯乙烯-丙烯酸)钕配合物催化苯乙烯与4-乙烯基吡啶共聚的研究[J].中国稀土学报,2005,23(6): 663～667
[28]肖国民,张进,烷基吡啶的合成及应用前景[J].化工技术经济,2001,4:7～9
[29]岳涛,孔祥峰,曹社会,刘辉,绿色饲料添加剂――二氢吡啶在动物生产中的研究与应用[J].饲料工业,2006,27(4):11～14
[30]令海,郑立金,周壮,2-氯吡啶的合成与应用[J].中国氯碱,2006,6:16～18
[31]张伟,徐杰,孙志强,杜中田,卤代吡啶类化合物的合成及应用[J].精细化工中间体,2006,36(4):1～6
[32]徐兆瑜,医药中间体中的一些重要杂环化合物[J].精细化工原料及中间体,2006,2:27～33
[33]周丹,冯亚青,傅雪晶,高活性,高选择性骨架镍在糠醇加氢中的应用研究[J].精细化工,2005,22(2):113～115
[34]李春林,伏义路,孟明,卞国柱,水蒸气对Ni/CeO2-ZrO2-Al2O3催化剂上CO2+CH4重整反应的影响[J].化学物理学报,2004,17(1):95～99