己二腈部分加氢合成氨基己腈负载型镍基催化剂的研究
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摘要
己二腈部分加氢合成氨基己腈是丁二烯氢氰化合成己内酰胺新工艺的关键步骤,研制和开发性能优良的加氢催化剂具有重要的实际意义。
本文采用等体积浸渍法制备了一系列负载型镍基催化剂,利用BET、TPR、XRD及活性评价等多种研究方法考察了载体焙烧温度、助剂、还原条件、反应条件等因素对催化剂结构和反应性能的影响,并对催化剂再生进行了初步的探索。
研究表明,由γ-Al_2O_3经1473 K焙烧获得的α-Al_2O_3载体所制备的催化剂具有较佳的己二腈部分加氢反应性能,此与其具有较大孔径及较弱酸性密切相关。K_2O助剂可以明显提高Ni/α-Al_2O_3加氢反应的稳定性及氨基己腈的选择性,而经K_2O和La_2O_3双元助剂改性的Ni/α-Al_2O_3催化剂性能更佳。
采用高压釜反应器,考察了反应条件对MgO、K_2O和La_2O_3共同改性的Ni/α-Al_2O_3催化剂己二腈部分加氢反应性能的影响。结果表明,在4.4 MPa,377 K及一定量氨存在的情况下,可以获得己二腈转化率为73.5%及氨基己腈的选择性为78.6%的结果。在保持催化剂与己二腈的质量合适的比(0.13～0.16)的情况下,通过提高己二腈的浓度可以增大反应体系处理反应物的能力。通过焙烧-还原方法再生的催化剂可以获得与新鲜催化剂基本接近的己二腈部分加氢反应性能。
The partial hydrogenation of adiponitrile to aminocapronitrile is a key step in the route of synthesis of caprolactam using butadiene as raw material, and it is practically significant to develop a new catalyst with high catalytic performance for partial hydrogenation of adiponitrile.
A series of supported nickel-based catalysts for the partial catalytic hydrogenation of adiponitrile to aminocapronitrile were prepared by the incipient impregnation method. The effects of calcinations temperature ofγ-alumina, promoters, reduction conditions and reaction conditions on the physico-chemical properties of catalysts were investigated by means of nitrogen adsorption-desorption (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR) and the performance evaluation with a fixed-bed reactor or an autoclave reactor. The catalyst deactivation and regeneration were also investigated.
The nickel catalyst supported onα-Al_2O_3 derived fromγ-Al_2O_3 calcined at 1473 K showed good catalytic performances for adiponitrile partial hydrogenation to aminocapronitrile, which was due to its large pore diameter and absence of acidic sites. Among the catalysts modified with different promoters, the catalyst supported onα-Al_2O_3 and modified with K_2O and La_2O_3 copromoter had the best performance.
The partial hydrogenation of adiponitrile to aminocapronitrile was performed on alumina supported nickel catalysts modified with potassium, lanthanum and magnesium in a high pressure stainless steel reactor. In the presence of ammonia, under the reaction conditions of 4.4 MPa and 377 K, the conversion of adiponitrile and the selectivity of aminocapronitrile reached 73.5% and 78.6% after reaction for 6h, respectively. Keeping the mass ratio of catalyst and adiponitrile as 0.13~0.16 and increasing the concentration of adiponitrile could enhance the capacity of the reactor.
The catalyst deactivation was mainly due to carbon species deposition, and the calcinations-reduction treatment was an effective regeneration method for the deactivated catalyst.
本文采用等体积浸渍法制备了一系列负载型镍基催化剂,利用BET、TPR、XRD及活性评价等多种研究方法考察了载体焙烧温度、助剂、还原条件、反应条件等因素对催化剂结构和反应性能的影响,并对催化剂再生进行了初步的探索。
研究表明,由γ-Al_2O_3经1473 K焙烧获得的α-Al_2O_3载体所制备的催化剂具有较佳的己二腈部分加氢反应性能,此与其具有较大孔径及较弱酸性密切相关。K_2O助剂可以明显提高Ni/α-Al_2O_3加氢反应的稳定性及氨基己腈的选择性,而经K_2O和La_2O_3双元助剂改性的Ni/α-Al_2O_3催化剂性能更佳。
采用高压釜反应器,考察了反应条件对MgO、K_2O和La_2O_3共同改性的Ni/α-Al_2O_3催化剂己二腈部分加氢反应性能的影响。结果表明,在4.4 MPa,377 K及一定量氨存在的情况下,可以获得己二腈转化率为73.5%及氨基己腈的选择性为78.6%的结果。在保持催化剂与己二腈的质量合适的比(0.13～0.16)的情况下,通过提高己二腈的浓度可以增大反应体系处理反应物的能力。通过焙烧-还原方法再生的催化剂可以获得与新鲜催化剂基本接近的己二腈部分加氢反应性能。
The partial hydrogenation of adiponitrile to aminocapronitrile is a key step in the route of synthesis of caprolactam using butadiene as raw material, and it is practically significant to develop a new catalyst with high catalytic performance for partial hydrogenation of adiponitrile.
A series of supported nickel-based catalysts for the partial catalytic hydrogenation of adiponitrile to aminocapronitrile were prepared by the incipient impregnation method. The effects of calcinations temperature ofγ-alumina, promoters, reduction conditions and reaction conditions on the physico-chemical properties of catalysts were investigated by means of nitrogen adsorption-desorption (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR) and the performance evaluation with a fixed-bed reactor or an autoclave reactor. The catalyst deactivation and regeneration were also investigated.
The nickel catalyst supported onα-Al_2O_3 derived fromγ-Al_2O_3 calcined at 1473 K showed good catalytic performances for adiponitrile partial hydrogenation to aminocapronitrile, which was due to its large pore diameter and absence of acidic sites. Among the catalysts modified with different promoters, the catalyst supported onα-Al_2O_3 and modified with K_2O and La_2O_3 copromoter had the best performance.
The partial hydrogenation of adiponitrile to aminocapronitrile was performed on alumina supported nickel catalysts modified with potassium, lanthanum and magnesium in a high pressure stainless steel reactor. In the presence of ammonia, under the reaction conditions of 4.4 MPa and 377 K, the conversion of adiponitrile and the selectivity of aminocapronitrile reached 73.5% and 78.6% after reaction for 6h, respectively. Keeping the mass ratio of catalyst and adiponitrile as 0.13~0.16 and increasing the concentration of adiponitrile could enhance the capacity of the reactor.
The catalyst deactivation was mainly due to carbon species deposition, and the calcinations-reduction treatment was an effective regeneration method for the deactivated catalyst.
引文
[1] 伍桂松,己内酰胺市场分析及发展建议,化工技术经济,2006,1:21~24
[2] 章文,己内酰胺的市场分析,上海化工,2005,5:44~46
[3] 张丛敏,己内酰胺发展前景广阔,化工中间体,2004,2:30~32
[4] 杨学萍,国内外己内酰胺行业发展趋势,化工技术经济,2005,11:1~5
[5] 程立泉,己内酰胺市场分析及技术发展概况,精细化工中间体,2005,35(2):17~21
[6] 聂颖,世界己内酰胺生产技术研究新进展,化工文摘,2005,6:50~52
[7] 王雪梅,己内酰胺生产技术及应用,河北化工,2005,5:28~30
[8] 张从容,己内酰胺生产技术及进展,化学工业与工程技术,2000,21(3):33~36
[9] 杨华,国外己内酰胺工艺进展,精细化工原料及中间体(化纤园地),2003,6:34~35
[10] 徐兆瑜,己内酰胺生产工艺技术新进展,精细化工原料及中间体(中间体),2006,3:25~29
[11] 陈百军,己内酰胺生产技术进展,合成纤维工业,2001,24(5):37~41
[12] Agterberg, Frank P W, Sielvken, et al, Process for the carbonylation of butadiene or a butadiene derivative[P].US, 5672732, 1997-09-30
[13] Burke, Patrick M, Process for the manufacture of 3-pentenoic acid [P], US, 5145995,1992-09-08
[14] Burke, Patrick M, Process for the preparation of 3-pentenoic acid from butadiene [P], US, 5250726, 1993-l0-05
[15] 沈菊,己内酰胺生产技术新进展及市场供需,中国科技成果,2003,20:19~23
[16] Teunissen, Antonius, De Vries, et a1, Process for the preparation of a linear aldehyde organic compound [P], US, 58l1589, 1998-09-22
[17] B. Chen, U. Dingerdissen, J. G. E. Krauter, et al, New developments in hydrogenation catalysis particularly in synthesis of fine and intermediate chemicals, Applied Catalysis A: General , 2005, 2801: 17~46
[18] F. Medina, P. Salagre, J. E. Sueiras, Characterization of potassium-doped nickel catalysts and activity for selective hydrogenation of 1,6-hexanedinitrile, Journal of Molecular Catalysis, 1993, 81: 387~395
[19] Marie-Christine Cotting, Laurent Gilbert, Philippe Leconte, Method for partially hydrogenation dinitriles to amnionitriles. US, 5981790, 1999
[20] 陈勇男,急冷骨架镍催化剂在磁稳定床反应器中己二腈加氢的应用,石油炼制与化工,2003,34(6):47~51
[21] Xinbin Yu, Hexing Li, Jing-Fa Deng, Selective hydrogenation of adiponitrile over a skeletal Ni-P amorphous catalyst (Raney Ni-P) at 1 atm pressure, Applied Catalysis A: General, 2000, 199: 191~198
[22] Hexing Li, Yeping Xu, Hui Li, et al, Gas-phase hydrogenation of adiponitrile with high selectivity to primary amine over supported Ni-B amorphous catalysts, Applied Catalysis A: General, 2001, 216: 51~58
[23] Hexing Li,Yeping Xu, Jing-Fa Deng, Selective hydrogenation of adiponitrile over a Raney Ni-P amorphous catalyst, New J. Chem., 1999, 23: 1059~1061
[24] H.F. Zhang, A.M. Wang, H. Li, et al, Microstructure and catalytic properties of rapidly quenched Ni–Al–Cr–Fe alloy, Materials Letters, 2001, 48: 347~350
[25] F. Medina, P. Salagre, J. E. Sueiras, Structural characteristics and catalytic performance of nickel catalysts for selective hydrogenation of 1,6-hexanedinitrile, Journal of Molecular Catalysis, 1993, 81: 363~371
[26] Schnurr, Werner Wulff-Doring, Joachim Fischer, et al, Preparation of aliphatic alpha omega-aminonitriles in the gas phase, US, 5508465, 1996
[27] Marc Serra, Pilar Salagre, Yolanda Cesteros, et al, Evolution of several Ni and Ni-MgO catalysts during the hydrogenation reaction of adiponitrile, Applied Catalysis A: General, 2004, 272: 353~362
[28] Marc Serra, Pilar Salagre, Yolanda Cesteros, et al, Nickle-Magnesia Catalysts: An Alternative for the Hydrogeantion of 1,6-Hexanedinitrile, Journal of Catalysis, 2002,209: 202~209
[29] Y. Cesteros, R. Fernandez, J. Estelle, et al, Characterization and catalytic properties of several La/Ni and Sr/Ni solids, Applied Catalysis A:General, 1997, 152: 249~269
[30] F. Medina, P. Salagre, J.E. Sueiras, Characterization and catalytic properties of several potassium-doped iron-nickel catalysts, Applied Catalysis A: General, 1992, 92: 131~141
[31] F. Medina, P. Salagre, J.E. Sueiras, et al, Surface Characterization and Hydrogenation Properties of Several Nickel/α-Alumina Catalysts, J. CHEM SOC. FARADAY TRANS., 1993, 89(18): 3507~3512
[32] F. Medina, P. Salagre, J.E. Sueiras, et al, Sturctural and Catalytic Properties of Several Potassium-doped Nickel/α-Alumina Solids, J. CHEM SOC. FARADAY TRANS., 1993, 89(21): 3981~3986
[33] F. Medina, P. Salagre, J.E.Sueiras, et al, Characterization of several γ-Alumina-supported Nickel Catalysts and activity for selective hydrogenation of Hexanedinitrile, J.CHEM.SOC.FARADAY TRANS., 1994, 90(10): 1455~1459
[34] F. Medina, P. Salagre, J.E.Sueiras, et al, Surface characterization and catalytic properties of several graphite supported potassium-free and potassium-doped nickel catalysts, Applied Catalysis A: General, 1993, 99: 115~129
[35] J. L. Fierro, F. Medina, P. Salagre, et al, Activity and surface characteristics of several alkali-doped iron catalysts for nitrile hydrogenation, Journal of Molecular Catalysis, 1990, 61: 197～205
[36] G.沃特,K.弗里克,H.鲁伊肯等,6-氨基己腈和六亚甲基二胺的同时制备方法. CN,1113854C,2003
[37] Didier Tichit, Robert Durand, Alice Rolland, et al. Selective Half-Hydrogenation of Adiponitrile to Aminocapronitrile on Ni-based Catalysts Elaborated from Lamellar Double Hydroxide Precursors, J Catal, 2002, 211: 511~520
[38] S. Alini, A. Bottino, G. Capannelli, et al, The catalytic hydrogenation of adiponitrile to hexamethylenediamine over a rhodium/alumina catalyst in a three phase slurry reactor, J Mol Catal A, 2003, 206: 363~370
[39] 季亚英,李文钊,徐恒泳等,流化床甲烷部分氧化制合成气 Ni 催化剂及助剂 La 的作用分子催化,2001, 15 (1):37~41
[40] Y. Cesteros, R. Fernandez, J. Estelle, et al, Characterization and Catalytic Properties of Several La/Ni and Sr/Ni Solids,Applied Catalysis A:General, 1997, 152: 249~269
[41] 刘迎新,陈吉祥,张继炎等,氧化镧助剂对镍/二氧化硅催化剂结构和加氢性能的影响. 化工学报,2005,56(11):2115~2118
[42] 黄传敬,郑小明,费金华,甲烷二氧化碳重整制合成气镍-钴双金属催化剂,应用化学,2001,18(9):741~744
[43] M. Kathryn , Sanchez, Preparation of 6-aminocapronitrile. US, 5296628, 1994
[44] K. Weissermel , H. J. Arpe , Industrial Organic Chemistry, 2nd Edition, VCH, Weinheim,1993
[45] B. Stanislaw, Ziemecki, Selective low pressure hydrogenation of a dinitrile to an aminonitrile, US, 5151543, 1992
[46] Marie-Christine Cotting, Laurent Gilbert, Philippe Leconte, Method for partially hydrogenation dinitriles to amnionitriles, US, 5981790, 1999
[47] F. Mares, J. E. Galle, S. E. Diamond, et al, Preparation and Characterization of a Novel Catalyst for the Hydrogenation of Dinitriles to Aminonitriles, Journal of Catalysis,1988,112:145~156
[48] S. Alini, A. Bottino, G. Capannelli, et al, The Catalytic Hydrogenation of Adiponitrile to Hexamethylenediamine over a Rhodium/Alumina Catalyst in a Three Phase Slurry Reactor, Journal of Molecular Catalysis A:Chemical, 2003, 206: 363~370
[49] 张玉红, 熊国兴, 盛世善等, Ni/γ-Al2O3催化剂中NiO与γ-Al2O3间的相互作用,物理化学学报,1999,15(8):735~741
[50] 王军科,胡云行,翁维正等,Ni基催化剂上CH4部分氧化反应的研究,化学学报,1996,54(9):869~873
[51] 李卫,黄星亮,低温选择性加氢镍催化剂的研究,石油化工,2001,30(9):26~29
[52] M. J. F. M. Verhaak, A. J. Van Dillen, J. W. Geust, The Deactivation of Nickel Catalysts in the Hydrogenation of Acetonitrile, Journal of Catalysis, 1993,143: 187~200(1993)
[53] Yinyan Huang, Valeria Adeeva, Wolfgang M. H. Sachtler, Stability of supported transition metal catalysts in the hydrogenation of nitriles, Applied Catalysis A: General, 2000, 196: 73~85
[2] 章文,己内酰胺的市场分析,上海化工,2005,5:44~46
[3] 张丛敏,己内酰胺发展前景广阔,化工中间体,2004,2:30~32
[4] 杨学萍,国内外己内酰胺行业发展趋势,化工技术经济,2005,11:1~5
[5] 程立泉,己内酰胺市场分析及技术发展概况,精细化工中间体,2005,35(2):17~21
[6] 聂颖,世界己内酰胺生产技术研究新进展,化工文摘,2005,6:50~52
[7] 王雪梅,己内酰胺生产技术及应用,河北化工,2005,5:28~30
[8] 张从容,己内酰胺生产技术及进展,化学工业与工程技术,2000,21(3):33~36
[9] 杨华,国外己内酰胺工艺进展,精细化工原料及中间体(化纤园地),2003,6:34~35
[10] 徐兆瑜,己内酰胺生产工艺技术新进展,精细化工原料及中间体(中间体),2006,3:25~29
[11] 陈百军,己内酰胺生产技术进展,合成纤维工业,2001,24(5):37~41
[12] Agterberg, Frank P W, Sielvken, et al, Process for the carbonylation of butadiene or a butadiene derivative[P].US, 5672732, 1997-09-30
[13] Burke, Patrick M, Process for the manufacture of 3-pentenoic acid [P], US, 5145995,1992-09-08
[14] Burke, Patrick M, Process for the preparation of 3-pentenoic acid from butadiene [P], US, 5250726, 1993-l0-05
[15] 沈菊,己内酰胺生产技术新进展及市场供需,中国科技成果,2003,20:19~23
[16] Teunissen, Antonius, De Vries, et a1, Process for the preparation of a linear aldehyde organic compound [P], US, 58l1589, 1998-09-22
[17] B. Chen, U. Dingerdissen, J. G. E. Krauter, et al, New developments in hydrogenation catalysis particularly in synthesis of fine and intermediate chemicals, Applied Catalysis A: General , 2005, 2801: 17~46
[18] F. Medina, P. Salagre, J. E. Sueiras, Characterization of potassium-doped nickel catalysts and activity for selective hydrogenation of 1,6-hexanedinitrile, Journal of Molecular Catalysis, 1993, 81: 387~395
[19] Marie-Christine Cotting, Laurent Gilbert, Philippe Leconte, Method for partially hydrogenation dinitriles to amnionitriles. US, 5981790, 1999
[20] 陈勇男,急冷骨架镍催化剂在磁稳定床反应器中己二腈加氢的应用,石油炼制与化工,2003,34(6):47~51
[21] Xinbin Yu, Hexing Li, Jing-Fa Deng, Selective hydrogenation of adiponitrile over a skeletal Ni-P amorphous catalyst (Raney Ni-P) at 1 atm pressure, Applied Catalysis A: General, 2000, 199: 191~198
[22] Hexing Li, Yeping Xu, Hui Li, et al, Gas-phase hydrogenation of adiponitrile with high selectivity to primary amine over supported Ni-B amorphous catalysts, Applied Catalysis A: General, 2001, 216: 51~58
[23] Hexing Li,Yeping Xu, Jing-Fa Deng, Selective hydrogenation of adiponitrile over a Raney Ni-P amorphous catalyst, New J. Chem., 1999, 23: 1059~1061
[24] H.F. Zhang, A.M. Wang, H. Li, et al, Microstructure and catalytic properties of rapidly quenched Ni–Al–Cr–Fe alloy, Materials Letters, 2001, 48: 347~350
[25] F. Medina, P. Salagre, J. E. Sueiras, Structural characteristics and catalytic performance of nickel catalysts for selective hydrogenation of 1,6-hexanedinitrile, Journal of Molecular Catalysis, 1993, 81: 363~371
[26] Schnurr, Werner Wulff-Doring, Joachim Fischer, et al, Preparation of aliphatic alpha omega-aminonitriles in the gas phase, US, 5508465, 1996
[27] Marc Serra, Pilar Salagre, Yolanda Cesteros, et al, Evolution of several Ni and Ni-MgO catalysts during the hydrogenation reaction of adiponitrile, Applied Catalysis A: General, 2004, 272: 353~362
[28] Marc Serra, Pilar Salagre, Yolanda Cesteros, et al, Nickle-Magnesia Catalysts: An Alternative for the Hydrogeantion of 1,6-Hexanedinitrile, Journal of Catalysis, 2002,209: 202~209
[29] Y. Cesteros, R. Fernandez, J. Estelle, et al, Characterization and catalytic properties of several La/Ni and Sr/Ni solids, Applied Catalysis A:General, 1997, 152: 249~269
[30] F. Medina, P. Salagre, J.E. Sueiras, Characterization and catalytic properties of several potassium-doped iron-nickel catalysts, Applied Catalysis A: General, 1992, 92: 131~141
[31] F. Medina, P. Salagre, J.E. Sueiras, et al, Surface Characterization and Hydrogenation Properties of Several Nickel/α-Alumina Catalysts, J. CHEM SOC. FARADAY TRANS., 1993, 89(18): 3507~3512
[32] F. Medina, P. Salagre, J.E. Sueiras, et al, Sturctural and Catalytic Properties of Several Potassium-doped Nickel/α-Alumina Solids, J. CHEM SOC. FARADAY TRANS., 1993, 89(21): 3981~3986
[33] F. Medina, P. Salagre, J.E.Sueiras, et al, Characterization of several γ-Alumina-supported Nickel Catalysts and activity for selective hydrogenation of Hexanedinitrile, J.CHEM.SOC.FARADAY TRANS., 1994, 90(10): 1455~1459
[34] F. Medina, P. Salagre, J.E.Sueiras, et al, Surface characterization and catalytic properties of several graphite supported potassium-free and potassium-doped nickel catalysts, Applied Catalysis A: General, 1993, 99: 115~129
[35] J. L. Fierro, F. Medina, P. Salagre, et al, Activity and surface characteristics of several alkali-doped iron catalysts for nitrile hydrogenation, Journal of Molecular Catalysis, 1990, 61: 197～205
[36] G.沃特,K.弗里克,H.鲁伊肯等,6-氨基己腈和六亚甲基二胺的同时制备方法. CN,1113854C,2003
[37] Didier Tichit, Robert Durand, Alice Rolland, et al. Selective Half-Hydrogenation of Adiponitrile to Aminocapronitrile on Ni-based Catalysts Elaborated from Lamellar Double Hydroxide Precursors, J Catal, 2002, 211: 511~520
[38] S. Alini, A. Bottino, G. Capannelli, et al, The catalytic hydrogenation of adiponitrile to hexamethylenediamine over a rhodium/alumina catalyst in a three phase slurry reactor, J Mol Catal A, 2003, 206: 363~370
[39] 季亚英,李文钊,徐恒泳等,流化床甲烷部分氧化制合成气 Ni 催化剂及助剂 La 的作用分子催化,2001, 15 (1):37~41
[40] Y. Cesteros, R. Fernandez, J. Estelle, et al, Characterization and Catalytic Properties of Several La/Ni and Sr/Ni Solids,Applied Catalysis A:General, 1997, 152: 249~269
[41] 刘迎新,陈吉祥,张继炎等,氧化镧助剂对镍/二氧化硅催化剂结构和加氢性能的影响. 化工学报,2005,56(11):2115~2118
[42] 黄传敬,郑小明,费金华,甲烷二氧化碳重整制合成气镍-钴双金属催化剂,应用化学,2001,18(9):741~744
[43] M. Kathryn , Sanchez, Preparation of 6-aminocapronitrile. US, 5296628, 1994
[44] K. Weissermel , H. J. Arpe , Industrial Organic Chemistry, 2nd Edition, VCH, Weinheim,1993
[45] B. Stanislaw, Ziemecki, Selective low pressure hydrogenation of a dinitrile to an aminonitrile, US, 5151543, 1992
[46] Marie-Christine Cotting, Laurent Gilbert, Philippe Leconte, Method for partially hydrogenation dinitriles to amnionitriles, US, 5981790, 1999
[47] F. Mares, J. E. Galle, S. E. Diamond, et al, Preparation and Characterization of a Novel Catalyst for the Hydrogenation of Dinitriles to Aminonitriles, Journal of Catalysis,1988,112:145~156
[48] S. Alini, A. Bottino, G. Capannelli, et al, The Catalytic Hydrogenation of Adiponitrile to Hexamethylenediamine over a Rhodium/Alumina Catalyst in a Three Phase Slurry Reactor, Journal of Molecular Catalysis A:Chemical, 2003, 206: 363~370
[49] 张玉红, 熊国兴, 盛世善等, Ni/γ-Al2O3催化剂中NiO与γ-Al2O3间的相互作用,物理化学学报,1999,15(8):735~741
[50] 王军科,胡云行,翁维正等,Ni基催化剂上CH4部分氧化反应的研究,化学学报,1996,54(9):869~873
[51] 李卫,黄星亮,低温选择性加氢镍催化剂的研究,石油化工,2001,30(9):26~29
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