辛醇液相加氢精制催化剂的研究
|
摘要
针对工业上两步法加氢辛醇合成过程中的第二步液相加氢反应工艺，研制开发了新型镍系液相加氢催化剂。试验研究了两个系列的液相加氢催化剂，Ni/SiO2系列和Ni/Al2O 3系列催化剂。
研究的Ni/SiO2系列液相加氢催化剂，采用共沉淀法制备。考察了催化剂的各种物性参数。在小型加压评价装置上，考察了催化剂中活性组分镍含量、助剂铝的加入、助剂镁的加入、载体硅的不同加入方式以及还原温度对催化剂加氢性能的影响。在此基础上，进行了500小时的评价运转试验。试验结果表明，催化剂中活性组份镍的质量分数在55.0％左右时，催化剂的加氢活性最佳；在催化剂中加入助剂铝有利于提高加氢活性，铝的质量分数在4.5(6.5%左右为最佳；在催化剂中加入助剂镁有利于提高加氢活性，镁的质量分数在4.5(5.5%左右为最佳；载体硅以干混和共沉+干混的方式加入到催化剂中有利于提高加氢活性，而以共沉+干混的加入方式为最佳；催化剂的还原温度不宜超过600℃。在小试研究中，开发的Ni/SiO2系列催化剂用于辛醇液相加氢精制反应时，具有良好的加氢活性、选择性和稳定性，性能达到进口同类催化剂LPH-86的水平，并且催化剂的物相结构稳定，活性组份分布均匀且颗粒度较细。
研究的Ni/Al2O 3系列液相加氢催化剂，采用浸渍法制备。考察了催化剂的各物性参数。在小型加压评价装置上，考察了催化剂中的活性组分镍含量、助剂镁的加入、助剂钙的加入以及还原温度对催化剂加氢性能的影响。在此基础上，进行了500小时的评价运转试验。试验结果表明，催化剂中活性组分镍的质量分数在20.0％左右时，催化剂的加氢活性最佳；在催化剂中加入少量的助剂镁有利于提高加氢活性，镁的质量分数在2.0%左右为最佳；在催化剂中加入少量的助剂钙有利于提高加氢活性，钙的质量分数在1.8%左右为最佳；催化剂的还原温度不易超过600℃。小试研究中，开发的Ni/Al2O3系催化剂用于辛醇液相加氢精制反应，具有良好的加氢活性、选择性和稳定性，性能达到进口同类催化剂LPH-86的水平，并且催化剂的物相结构稳定，活性组份分布均匀且颗粒度较细。
在小试研究的基础上，综合考虑液相加氢催化剂的机械强度、耐磨性能和加氢性能，确定以Ni/Al2O3系列催化剂F-2进行放大，放大制备催化剂3Kg。对催
化剂的各物性参数进行考察。在1升级加压评价装置上，原颗粒装填催化剂，考察了催化剂的加氢性能。试验结果表明，催化剂的制备重复性良好，用于液相加氢反应时，具有良好的加氢活性、选择性和活性稳定性，并且催化剂的物相结构稳定，活性组份镍的颗粒度较细且均匀分布在催化剂体系中。
放大研究催化剂的各项指标，达到了小试样品的水平。并且所开发的新型镍系液相加氢催化剂与同类进口催化剂相比较，具有机械强度高、比表面积大、比孔容积大、耐磨性能好的特点，该催化剂具有良好的加氢活性、选择性和活性稳定性，综合性能良好，具备工业化条件，可以实现辛醇液相加氢精制催化剂的国产化。
As a very important chemical product, 2-ethylhexanol was applied broadly in domestic economy. Industrial 2-ethylhexanol was made usually by hydrogenation of 2-ethylhexanal. According to the liquid phase hydrogenation technology in the production of 2-ethylhexanol, we exploited a new series of Ni catalysts for liquid phase hydrogenation. The experiment researched two series of catalysts, Ni/SiO2 catalysts and Ni/Al2O3 catalysts.
The Ni/SiO2 catalysts were prepared by co-precipitation method. First, the physical properties of Ni/SiO2 catalysts were investigated by the various analysis measures. In laboratory pressurized system, effects of the active component Ni content、the addition of promoter Al、the addition of promoter Mg、incorporating ways of support SiO2 and reduction temperature on hydrogenating property of catalysts were studied. On the basis of these studies, an investigating test of 500 hours was carried out. The results showed that (1) the best hydrogenation activity was obtained on catalyst with a mass fraction of Ni about 55.0%; (2) the incorporation of promoter aluminum into Ni/SiO2 catalysts can improve the hydrogenation activity and the best mass fraction of Al in catalyst system was about 4.5~6.5%; (3) the addition of promoter magnesium into Ni/SiO2 catalysts can promote the hydrogenating activity of catalysts and the best mass fraction of Mg in catalyst system was about 4.5~5.5%; (4) the support SiO2 with the dried mixture way or the co-precipitation + dried mixture way adding into catalyst system was favorable to improve hydrogenation activity of catalysts; and (5) the reduction temperature of Ni/SiO2 catalysts should not be higher than 600℃. The studied Ni/SiO2 catalysts showed very good activity for liquid phase hydrogenation of 2-ethylhexanol processing. Proved that the Ni/SiO2 catalysts have excellent hydrogenating activity、selectivity and stability, as well the catalysts have the stable substance structure and the active component Ni crystalline was well fine scattering into the catalyst system.
The Ni/Al2O3 catalysts were prepared by the impregnation method. First, the physical properties of Ni/Al2O3 catalysts were investigated by the various analysis
measures. On the laboratory small pressurized apparatus, effects of the active component Ni content、the addition of promoter Mg、the addition of promoter Ca and reduction temperature on hydrogenating property of catalysts were studied. On the basis of these studies, an investigating test of 500 hours was carried out. The results showed that (1) the best hydrogenation activity was obtained on catalyst with a mass fraction of Ni about 20.0%; (2) the addition of promoter magnesium into Ni/Al2O3 catalysts can improve the hydrogenation activity and the best mass fraction of Mg in Ni/Al2O3 catalyst system was about 2.0%; (3) the addition of promoter calcium into Ni/Al2O3 catalysts can promote the hydrogenating activity of catalyst and the best mass fraction of Ca in catalyst system was about 1.8%; and (4) the reduction temperature of Ni/Al2O3 catalysts should not be higher than 600℃. Studies indicated that Ni/Al2O3 catalysts for liquid phase hydrogenation have excellent hydrogenating activity、selectivity and stability, moreover Ni/Al2O3 catalysts have the stable substance structure and the active component Ni crystalline was well fine to scatter into the catalyst system.
On the basis of laboratory studies, comprehensively considering mechanical strength、wear-resisting property and hydrogenation property of catalysts, Ni/Al2O3 catalyst F-2 was defined to prepare enlarged 3Kg. And in the 1L pressurized investigating system, the hydrogenating performance of original-particular-loading catalysts was inspected. The results showed that the prepared catalysts took better repetition, and exploited catalysts for liquid phase hydrogenation have excellent hydrogenating activity、selectivity and stability. While the new liquid phase hydrogenation catalysts have the stable substance structure and the active component Ni crystalline was well fine
研究的Ni/SiO2系列液相加氢催化剂，采用共沉淀法制备。考察了催化剂的各种物性参数。在小型加压评价装置上，考察了催化剂中活性组分镍含量、助剂铝的加入、助剂镁的加入、载体硅的不同加入方式以及还原温度对催化剂加氢性能的影响。在此基础上，进行了500小时的评价运转试验。试验结果表明，催化剂中活性组份镍的质量分数在55.0％左右时，催化剂的加氢活性最佳；在催化剂中加入助剂铝有利于提高加氢活性，铝的质量分数在4.5(6.5%左右为最佳；在催化剂中加入助剂镁有利于提高加氢活性，镁的质量分数在4.5(5.5%左右为最佳；载体硅以干混和共沉+干混的方式加入到催化剂中有利于提高加氢活性，而以共沉+干混的加入方式为最佳；催化剂的还原温度不宜超过600℃。在小试研究中，开发的Ni/SiO2系列催化剂用于辛醇液相加氢精制反应时，具有良好的加氢活性、选择性和稳定性，性能达到进口同类催化剂LPH-86的水平，并且催化剂的物相结构稳定，活性组份分布均匀且颗粒度较细。
研究的Ni/Al2O 3系列液相加氢催化剂，采用浸渍法制备。考察了催化剂的各物性参数。在小型加压评价装置上，考察了催化剂中的活性组分镍含量、助剂镁的加入、助剂钙的加入以及还原温度对催化剂加氢性能的影响。在此基础上，进行了500小时的评价运转试验。试验结果表明，催化剂中活性组分镍的质量分数在20.0％左右时，催化剂的加氢活性最佳；在催化剂中加入少量的助剂镁有利于提高加氢活性，镁的质量分数在2.0%左右为最佳；在催化剂中加入少量的助剂钙有利于提高加氢活性，钙的质量分数在1.8%左右为最佳；催化剂的还原温度不易超过600℃。小试研究中，开发的Ni/Al2O3系催化剂用于辛醇液相加氢精制反应，具有良好的加氢活性、选择性和稳定性，性能达到进口同类催化剂LPH-86的水平，并且催化剂的物相结构稳定，活性组份分布均匀且颗粒度较细。
在小试研究的基础上，综合考虑液相加氢催化剂的机械强度、耐磨性能和加氢性能，确定以Ni/Al2O3系列催化剂F-2进行放大，放大制备催化剂3Kg。对催
化剂的各物性参数进行考察。在1升级加压评价装置上，原颗粒装填催化剂，考察了催化剂的加氢性能。试验结果表明，催化剂的制备重复性良好，用于液相加氢反应时，具有良好的加氢活性、选择性和活性稳定性，并且催化剂的物相结构稳定，活性组份镍的颗粒度较细且均匀分布在催化剂体系中。
放大研究催化剂的各项指标，达到了小试样品的水平。并且所开发的新型镍系液相加氢催化剂与同类进口催化剂相比较，具有机械强度高、比表面积大、比孔容积大、耐磨性能好的特点，该催化剂具有良好的加氢活性、选择性和活性稳定性，综合性能良好，具备工业化条件，可以实现辛醇液相加氢精制催化剂的国产化。
As a very important chemical product, 2-ethylhexanol was applied broadly in domestic economy. Industrial 2-ethylhexanol was made usually by hydrogenation of 2-ethylhexanal. According to the liquid phase hydrogenation technology in the production of 2-ethylhexanol, we exploited a new series of Ni catalysts for liquid phase hydrogenation. The experiment researched two series of catalysts, Ni/SiO2 catalysts and Ni/Al2O3 catalysts.
The Ni/SiO2 catalysts were prepared by co-precipitation method. First, the physical properties of Ni/SiO2 catalysts were investigated by the various analysis measures. In laboratory pressurized system, effects of the active component Ni content、the addition of promoter Al、the addition of promoter Mg、incorporating ways of support SiO2 and reduction temperature on hydrogenating property of catalysts were studied. On the basis of these studies, an investigating test of 500 hours was carried out. The results showed that (1) the best hydrogenation activity was obtained on catalyst with a mass fraction of Ni about 55.0%; (2) the incorporation of promoter aluminum into Ni/SiO2 catalysts can improve the hydrogenation activity and the best mass fraction of Al in catalyst system was about 4.5~6.5%; (3) the addition of promoter magnesium into Ni/SiO2 catalysts can promote the hydrogenating activity of catalysts and the best mass fraction of Mg in catalyst system was about 4.5~5.5%; (4) the support SiO2 with the dried mixture way or the co-precipitation + dried mixture way adding into catalyst system was favorable to improve hydrogenation activity of catalysts; and (5) the reduction temperature of Ni/SiO2 catalysts should not be higher than 600℃. The studied Ni/SiO2 catalysts showed very good activity for liquid phase hydrogenation of 2-ethylhexanol processing. Proved that the Ni/SiO2 catalysts have excellent hydrogenating activity、selectivity and stability, as well the catalysts have the stable substance structure and the active component Ni crystalline was well fine scattering into the catalyst system.
The Ni/Al2O3 catalysts were prepared by the impregnation method. First, the physical properties of Ni/Al2O3 catalysts were investigated by the various analysis
measures. On the laboratory small pressurized apparatus, effects of the active component Ni content、the addition of promoter Mg、the addition of promoter Ca and reduction temperature on hydrogenating property of catalysts were studied. On the basis of these studies, an investigating test of 500 hours was carried out. The results showed that (1) the best hydrogenation activity was obtained on catalyst with a mass fraction of Ni about 20.0%; (2) the addition of promoter magnesium into Ni/Al2O3 catalysts can improve the hydrogenation activity and the best mass fraction of Mg in Ni/Al2O3 catalyst system was about 2.0%; (3) the addition of promoter calcium into Ni/Al2O3 catalysts can promote the hydrogenating activity of catalyst and the best mass fraction of Ca in catalyst system was about 1.8%; and (4) the reduction temperature of Ni/Al2O3 catalysts should not be higher than 600℃. Studies indicated that Ni/Al2O3 catalysts for liquid phase hydrogenation have excellent hydrogenating activity、selectivity and stability, moreover Ni/Al2O3 catalysts have the stable substance structure and the active component Ni crystalline was well fine to scatter into the catalyst system.
On the basis of laboratory studies, comprehensively considering mechanical strength、wear-resisting property and hydrogenation property of catalysts, Ni/Al2O3 catalyst F-2 was defined to prepare enlarged 3Kg. And in the 1L pressurized investigating system, the hydrogenating performance of original-particular-loading catalysts was inspected. The results showed that the prepared catalysts took better repetition, and exploited catalysts for liquid phase hydrogenation have excellent hydrogenating activity、selectivity and stability. While the new liquid phase hydrogenation catalysts have the stable substance structure and the active component Ni crystalline was well fine
引文
[1] 章思规. 精细有机化学品技术手册下册[M].北京：科学出版社, 1992.997.
[2] 中国化工产品大全（上卷）[M].北京：化学工业出版社，1994.479.
[3] 姚蒙正. 精细化工产品合成原理[M].北京：中国石化出版社, 2000.187(189.
[4] 何素珍，李省歧，卞允庆，等.[J].化工技术经济，2003，21（1）：24(28.
[5] 玄恩锋. [J].齐鲁石油化工，1999，27（1）：76(78.
[6] Ludwig Gerhard, Fischer Lothar, Hess Dieter, et al.(Huels A.-G., Germany).Process for The Preparation of Saturated Alcohols by Gas-phase Hydrogenation of Aldehydes over Alkaline Copper Catalysts and Acidic Nickel Catalysts[P].EP 470344 A2，1992-02-12.
[7] Kelly Donald G, Nebesh Eugene (Harshaw/Filtrol Partnership, USA).Extruded Copper Chromite-Alumina Hydrogenation Catalyst [P].US 4666879 A, 1987-05-19.
[8] Gurevich G S. [J]. Khim. Prom-st.(Moscow), 1987，10:581(583.
[9] Florea Delia Dana，Georgescu Lucica，Vasilescu Florin，et al.(Intreprinderea Rafinaria Vega, Ploiesti, Rom.) Manufacture of Copper-Chromium-Nickel Catalysts for Hydrogenation of 2-Ethylhex-2-enal to 2-Ethylhexanol [P]. RO 94520 B1，1988-06-30.
[10] Florea Delia D，Georgescu Lucica，Vasilescu Florin，et al.(Rafinaria Vega, Ploiesti, Rom.) Silica Supports for Aldehyde Hydrogenation Catalysts [P]. RO 94237 B1，1988-03-30.
[11] Mori Tomoyuki，Fujita Kouichi，Hinoishi Hiroki(Mitsubishi Chemical Corp.,Japan).Vapor-Phase Hydrogenation Process and Catalysts for The Preparation of Saturated Alcohols from Unsaturated Aldehydes[P]. JP 94-53532，1994-03-24.
[12] 荀彤，张文成，于宏伟. [J].炼油与化工，2002，13：18，22.
[13] 宋艳丽，孙发民，郭立艳，等.[J]. 天津化工，2002，7:4(6.
[14] Ludwig G H. (Katalysatorenwerke Huels GmbH, Marl, Germany) [J]. Hydrocarbon Processing，1993，72(3)：67(70，72，74.
[15] Horn Gerhardt，Deckers Gregor(Hoechst A.-G., Germany).
Cooper-Zinc-Aluminum Hydrogenation Catalyst P]. DE 4244273 A1,1994-06-30.
[16] Horn Gerhard，Rohning Carl Dieter(Hoechst A.-G., Germany). Copper-Zinc Oxide-Aluminum Oxide-Containing Catalysts，Their Preparation and Their Use[P]. DE 4127318 A1，1993-02-18.
[17] Roberts Brian D，Carrick William J，Thakur Deepak S.(Engelhard Corporation，USA). Shaped Hdrogenation Catalysts Containing Metals，Calcium Silicate and Clay，Their Preparation and Use[P]. WO 9700131 A1，1997-01-03.
[18] Logsdon John E，Loke Richard A，Merriam Jay S，et al.（Union Carbide Corporation）Aldehyde Hydrogenation Catalyst[P]. US 4762817，1988-08-09.
[19] Logsdon John E，Loke Richard A，Merriam Jay S，et al.（Union Carbide Chemicals and Plastics Company Inc）Improved Aldehyde Hydrogenation Process [P]. US 4876402，1989-10-24.
[20] Hiles Andrew G，Logsdon John E.(Davy McKee London Ltd.) Multistage Hydrogenation of Aldehydes [P]. US 4626604 A，198612-02.
[21] Khvorov Aleksandr Petrovich. Manufacture of 2-Ethylhexanol by Hydrogenation of 2-Ethylhexanal Using Manganese Oxide and Chromium Trioxide-Activated Charcoal-Promoted Catalyst Containing Graphite and Copper，Zinc，Calcium，and Aluminum Oxides[P]. RU 2052445 C1，1996-01-20.
[22] 李东立，戴伟，朱洪法，等.[J]. 石油化工，2000，29（11），835(840.
[23] 赵胤. [J]. 化工科技，1999，7（3）：22(27.
[24] 邓德胜，张兴福. 化工科技，2002，10（6）：34(37.
[25] Horn Gerhardt，Frohning Carl Dieter.(Hoechst A.-G., Fed. Rep. Ger.). Preparation of Alcohols by Hydrogenation of Carbonyl Compounds over Nickel and Aluminum Oxide and Zirconium Dioxide-Containing Catalyst[P]. EP 421196 A1，1991-01-10.
[26] Deckers Gregor，Diekhaus Gerhard，Dorsch Bernd，et al.（Hoechst Aktiengesellschaft ) Hydrogenation Catalyst，A Process for Its Preparation and Use Thereof[P].DE 43100538，1993-03-27
[27] Toussaint Herbert，Schossig Juergen，Graefje Heinz，et al.(BASF A.-G.) Catalyst for The Hydrogenation of Unsaturated Aliphatic Compounds [P]. EP 394842
A1，1990-10-31.
[28] Lueken Hans Gerd，Tanger Uwe，Droste Wilhelm，et al.(Huels A.-G., Fed. Rep. Ger.) Process for The Preparation of 2-Ethylhexanol by Liquid Phase Hydrogenation of 2-Ethylhexenal and Catalyst for This Preparation [P]. EP 326674 A2，1989-08-09.
[29] Akiyama Tsunekazu，Sugiyama Hitoshi，Kameo Hiroshi，et al.(Mitsubishi Chemical Industries Co., Ltd., Japan). Hydrogenation of Higher Aldehydes [P]. JP 61172838 A2， 1986-08-04.
[30] Bednar Zdenek，Cirova Alena，Grosser Vojtech，et al.(Chemopetrol a.s., Czech Rep.) Supported Ni-Cr Catalyst for Producing n-Butanol，Isobutanol, and 2-Ethylhexanol by Hydrogenation of Corresponding Aldehydes [P]. CZ 280125 B6，1995-11-15.
[31] Bucur Victor，Goidea Dumitru，Florea Delia，etal.(Institutul de Cercetari Inginerie Tehnologica si Proiectare pentru Rafinarii, ploiesti, Rom.). Catalyst for Hydrogenation of Unsaturated Organic Compounds[P]. RO 100615 B1，1991-11-11.
[32] Ruhl Thomas，Breitscheidel Boris，Henkelmann Jochen，et al. (BASF A.-G., Germany). Supported Ruthenium Catalyst and Conversion of Organic Compounds in Its Presence[P]. EP 813906 A2，1997-12-29.
[33] Adam Karl，Haarer Erich. Production of 2-Ethylhexanol by Hydrogenation of 2-Ethylhexenal[P]. US 4021497，1977-05-03.
[34] Ando Chie. [J] Appl. Catal.，1999，185(2)：181(183.
[35] Lee Richard J，Meyer Delbert H，Senneke Darrell M.（Standard Oil Company ，Indiana） Rhodium-Catalyzed Hydrogenation of Unsaturated Aldehydes to Unsaturated Alcohols [P]. US 4292452，1981-09-29.
[36] Ichikawa Yataro，Suzuki Nobuo，Sawaki Toru.（Teijin, Limited ，Osaka，JP) Process for Hydrogenating Unsaturated Aldehydes to Unsaturated Alcohols [P].US 4100180，1978-07-11.
[2] 中国化工产品大全（上卷）[M].北京：化学工业出版社，1994.479.
[3] 姚蒙正. 精细化工产品合成原理[M].北京：中国石化出版社, 2000.187(189.
[4] 何素珍，李省歧，卞允庆，等.[J].化工技术经济，2003，21（1）：24(28.
[5] 玄恩锋. [J].齐鲁石油化工，1999，27（1）：76(78.
[6] Ludwig Gerhard, Fischer Lothar, Hess Dieter, et al.(Huels A.-G., Germany).Process for The Preparation of Saturated Alcohols by Gas-phase Hydrogenation of Aldehydes over Alkaline Copper Catalysts and Acidic Nickel Catalysts[P].EP 470344 A2，1992-02-12.
[7] Kelly Donald G, Nebesh Eugene (Harshaw/Filtrol Partnership, USA).Extruded Copper Chromite-Alumina Hydrogenation Catalyst [P].US 4666879 A, 1987-05-19.
[8] Gurevich G S. [J]. Khim. Prom-st.(Moscow), 1987，10:581(583.
[9] Florea Delia Dana，Georgescu Lucica，Vasilescu Florin，et al.(Intreprinderea Rafinaria Vega, Ploiesti, Rom.) Manufacture of Copper-Chromium-Nickel Catalysts for Hydrogenation of 2-Ethylhex-2-enal to 2-Ethylhexanol [P]. RO 94520 B1，1988-06-30.
[10] Florea Delia D，Georgescu Lucica，Vasilescu Florin，et al.(Rafinaria Vega, Ploiesti, Rom.) Silica Supports for Aldehyde Hydrogenation Catalysts [P]. RO 94237 B1，1988-03-30.
[11] Mori Tomoyuki，Fujita Kouichi，Hinoishi Hiroki(Mitsubishi Chemical Corp.,Japan).Vapor-Phase Hydrogenation Process and Catalysts for The Preparation of Saturated Alcohols from Unsaturated Aldehydes[P]. JP 94-53532，1994-03-24.
[12] 荀彤，张文成，于宏伟. [J].炼油与化工，2002，13：18，22.
[13] 宋艳丽，孙发民，郭立艳，等.[J]. 天津化工，2002，7:4(6.
[14] Ludwig G H. (Katalysatorenwerke Huels GmbH, Marl, Germany) [J]. Hydrocarbon Processing，1993，72(3)：67(70，72，74.
[15] Horn Gerhardt，Deckers Gregor(Hoechst A.-G., Germany).
Cooper-Zinc-Aluminum Hydrogenation Catalyst P]. DE 4244273 A1,1994-06-30.
[16] Horn Gerhard，Rohning Carl Dieter(Hoechst A.-G., Germany). Copper-Zinc Oxide-Aluminum Oxide-Containing Catalysts，Their Preparation and Their Use[P]. DE 4127318 A1，1993-02-18.
[17] Roberts Brian D，Carrick William J，Thakur Deepak S.(Engelhard Corporation，USA). Shaped Hdrogenation Catalysts Containing Metals，Calcium Silicate and Clay，Their Preparation and Use[P]. WO 9700131 A1，1997-01-03.
[18] Logsdon John E，Loke Richard A，Merriam Jay S，et al.（Union Carbide Corporation）Aldehyde Hydrogenation Catalyst[P]. US 4762817，1988-08-09.
[19] Logsdon John E，Loke Richard A，Merriam Jay S，et al.（Union Carbide Chemicals and Plastics Company Inc）Improved Aldehyde Hydrogenation Process [P]. US 4876402，1989-10-24.
[20] Hiles Andrew G，Logsdon John E.(Davy McKee London Ltd.) Multistage Hydrogenation of Aldehydes [P]. US 4626604 A，198612-02.
[21] Khvorov Aleksandr Petrovich. Manufacture of 2-Ethylhexanol by Hydrogenation of 2-Ethylhexanal Using Manganese Oxide and Chromium Trioxide-Activated Charcoal-Promoted Catalyst Containing Graphite and Copper，Zinc，Calcium，and Aluminum Oxides[P]. RU 2052445 C1，1996-01-20.
[22] 李东立，戴伟，朱洪法，等.[J]. 石油化工，2000，29（11），835(840.
[23] 赵胤. [J]. 化工科技，1999，7（3）：22(27.
[24] 邓德胜，张兴福. 化工科技，2002，10（6）：34(37.
[25] Horn Gerhardt，Frohning Carl Dieter.(Hoechst A.-G., Fed. Rep. Ger.). Preparation of Alcohols by Hydrogenation of Carbonyl Compounds over Nickel and Aluminum Oxide and Zirconium Dioxide-Containing Catalyst[P]. EP 421196 A1，1991-01-10.
[26] Deckers Gregor，Diekhaus Gerhard，Dorsch Bernd，et al.（Hoechst Aktiengesellschaft ) Hydrogenation Catalyst，A Process for Its Preparation and Use Thereof[P].DE 43100538，1993-03-27
[27] Toussaint Herbert，Schossig Juergen，Graefje Heinz，et al.(BASF A.-G.) Catalyst for The Hydrogenation of Unsaturated Aliphatic Compounds [P]. EP 394842
A1，1990-10-31.
[28] Lueken Hans Gerd，Tanger Uwe，Droste Wilhelm，et al.(Huels A.-G., Fed. Rep. Ger.) Process for The Preparation of 2-Ethylhexanol by Liquid Phase Hydrogenation of 2-Ethylhexenal and Catalyst for This Preparation [P]. EP 326674 A2，1989-08-09.
[29] Akiyama Tsunekazu，Sugiyama Hitoshi，Kameo Hiroshi，et al.(Mitsubishi Chemical Industries Co., Ltd., Japan). Hydrogenation of Higher Aldehydes [P]. JP 61172838 A2， 1986-08-04.
[30] Bednar Zdenek，Cirova Alena，Grosser Vojtech，et al.(Chemopetrol a.s., Czech Rep.) Supported Ni-Cr Catalyst for Producing n-Butanol，Isobutanol, and 2-Ethylhexanol by Hydrogenation of Corresponding Aldehydes [P]. CZ 280125 B6，1995-11-15.
[31] Bucur Victor，Goidea Dumitru，Florea Delia，etal.(Institutul de Cercetari Inginerie Tehnologica si Proiectare pentru Rafinarii, ploiesti, Rom.). Catalyst for Hydrogenation of Unsaturated Organic Compounds[P]. RO 100615 B1，1991-11-11.
[32] Ruhl Thomas，Breitscheidel Boris，Henkelmann Jochen，et al. (BASF A.-G., Germany). Supported Ruthenium Catalyst and Conversion of Organic Compounds in Its Presence[P]. EP 813906 A2，1997-12-29.
[33] Adam Karl，Haarer Erich. Production of 2-Ethylhexanol by Hydrogenation of 2-Ethylhexenal[P]. US 4021497，1977-05-03.
[34] Ando Chie. [J] Appl. Catal.，1999，185(2)：181(183.
[35] Lee Richard J，Meyer Delbert H，Senneke Darrell M.（Standard Oil Company ，Indiana） Rhodium-Catalyzed Hydrogenation of Unsaturated Aldehydes to Unsaturated Alcohols [P]. US 4292452，1981-09-29.
[36] Ichikawa Yataro，Suzuki Nobuo，Sawaki Toru.（Teijin, Limited ，Osaka，JP) Process for Hydrogenating Unsaturated Aldehydes to Unsaturated Alcohols [P].US 4100180，1978-07-11.