温和条件下改性骨架镍催化二甲基硝基苯加氢
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摘要
本文采用骤冷法制备了Ni-Al-Mo合金薄条,经粉碎、碱活化后得到改性的骨架镍,采用XRD对其进行了表征。将改性骨架镍催化剂用于催化2,4-二甲基硝基苯和3,4-二甲基硝基苯加氢制备相应的芳胺。系统地研究了溶剂种类、反应温度、反应压力、底物浓度、催化剂用量等条件对2,4-二甲基硝基苯和3,4-二甲基硝基苯加氢反应的影响。结果表明,改性骨架镍对以上反应具有优异的催化性能,与文献报道相比,反应条件更加温和,产品收率更高,具有潜在的工业化价值。
将改性骨架镍用于催化2,4-二甲基硝基苯加氢制备2,4-二甲基苯胺,催化剂显示出极高的活性和选择性。以乙醇为溶剂,原料初始浓度为2.5mol·L~(-1),催化剂的用量为原料质量的6%,在40℃,1.0MPa的下反应130min,2,4-二甲基硝基苯的转化率为100%,2,4-二甲基苯胺选择性可达100%。改性骨架镍催化剂具有良好的稳定性,催化剂连续套用16釜后仍具有很高的活性。
将改性骨架镍用于3,4-二甲基硝基苯的液相催化加氢,结合GC跟踪反应过程,探讨了可能的反应历程。得到了优化的反应条件:以甲醇为溶剂,原料初始浓度1.0mol·L~(-1),催化剂质量为原料质量的7%,在60℃、0.5MPa下反应40min,3,4-二甲基硝基苯的转化率和3,4-二甲基苯胺的选择性均达到100%。对催化剂进行寿命实验考察,结果表明该催化剂具有很高的稳定性。反应得到的产品纯度高,色相好,市场竞争力强。
In this thesis, the rapid quenching technique was introduced into the production of Ni-Al-Mo alloy ribbon. After crushing, ball milling and extracting Al by alkali, modified skeletal Ni was obtained. The catalyst was characterized by XRD and employed for the hydrogenation of 2,4-dimethylnitrobenzene and 3,4-dimethylnitrobenzene. The effects of reaction parameters including solvent type, temperature, pressure, initial concentration of the substrate and amount of the catalyst were investigated in the above two substrates' reaction system. Modified skeletal Ni catalyst showed excellent catalytic properties. Compared with that in literatures, the yield of the products was higher while the conditions were milder. So the crafts have great potential value in industry.
The modified skeletal Ni was proved to be very active and selective for the hydrogenation of 2,4-dimethylnitrobenzene to 2,4-dimethylaniline. Under the optimized conditions of m(catalyst)/m(substrate) = 6% in ethanol, initial concentration of the substrate = 2.5mol·L~(-1), 1.0MPa and 40℃, the conversion of 2,4-dimethylnitrobenzene in 130min was up to 100%, and the selectivity of 2,4-dimethylaniline was as high as 100%. The modified skeletal Ni exhibited good stability, and it maintained high activity even after 16 times batch-running.
The modified skeletal Ni was also used for liquid phase hydrogenation of 3,4-dimethylnitrobenzene. The reaction process was monitored by gas chromatography, and the hydrogenation pathway was discussed. Under the optimized conditions〔m(catalyst)/ m(substrate) = 7% in methanol, initial concentration of the substrate = 1.0mol·L~(-1), 60℃and 0.5MPa〕, both the conversion of 3,4-dimethylnitrobenzene and the selectivity of 3,4-dimethylaniline were up to 100% in 40 minutes. The life of catalyst was investigated and the catalyst showed good stability. Meanwhile, the product exhibited excellent hue with high purity, which enhances its market competitiveness.
将改性骨架镍用于催化2,4-二甲基硝基苯加氢制备2,4-二甲基苯胺,催化剂显示出极高的活性和选择性。以乙醇为溶剂,原料初始浓度为2.5mol·L~(-1),催化剂的用量为原料质量的6%,在40℃,1.0MPa的下反应130min,2,4-二甲基硝基苯的转化率为100%,2,4-二甲基苯胺选择性可达100%。改性骨架镍催化剂具有良好的稳定性,催化剂连续套用16釜后仍具有很高的活性。
将改性骨架镍用于3,4-二甲基硝基苯的液相催化加氢,结合GC跟踪反应过程,探讨了可能的反应历程。得到了优化的反应条件:以甲醇为溶剂,原料初始浓度1.0mol·L~(-1),催化剂质量为原料质量的7%,在60℃、0.5MPa下反应40min,3,4-二甲基硝基苯的转化率和3,4-二甲基苯胺的选择性均达到100%。对催化剂进行寿命实验考察,结果表明该催化剂具有很高的稳定性。反应得到的产品纯度高,色相好,市场竞争力强。
In this thesis, the rapid quenching technique was introduced into the production of Ni-Al-Mo alloy ribbon. After crushing, ball milling and extracting Al by alkali, modified skeletal Ni was obtained. The catalyst was characterized by XRD and employed for the hydrogenation of 2,4-dimethylnitrobenzene and 3,4-dimethylnitrobenzene. The effects of reaction parameters including solvent type, temperature, pressure, initial concentration of the substrate and amount of the catalyst were investigated in the above two substrates' reaction system. Modified skeletal Ni catalyst showed excellent catalytic properties. Compared with that in literatures, the yield of the products was higher while the conditions were milder. So the crafts have great potential value in industry.
The modified skeletal Ni was proved to be very active and selective for the hydrogenation of 2,4-dimethylnitrobenzene to 2,4-dimethylaniline. Under the optimized conditions of m(catalyst)/m(substrate) = 6% in ethanol, initial concentration of the substrate = 2.5mol·L~(-1), 1.0MPa and 40℃, the conversion of 2,4-dimethylnitrobenzene in 130min was up to 100%, and the selectivity of 2,4-dimethylaniline was as high as 100%. The modified skeletal Ni exhibited good stability, and it maintained high activity even after 16 times batch-running.
The modified skeletal Ni was also used for liquid phase hydrogenation of 3,4-dimethylnitrobenzene. The reaction process was monitored by gas chromatography, and the hydrogenation pathway was discussed. Under the optimized conditions〔m(catalyst)/ m(substrate) = 7% in methanol, initial concentration of the substrate = 1.0mol·L~(-1), 60℃and 0.5MPa〕, both the conversion of 3,4-dimethylnitrobenzene and the selectivity of 3,4-dimethylaniline were up to 100% in 40 minutes. The life of catalyst was investigated and the catalyst showed good stability. Meanwhile, the product exhibited excellent hue with high purity, which enhances its market competitiveness.
引文
[1]姚正蒙,程侣柏,王家儒.精细化工产品合成原理[M].北京:中国石化出版社,2000.
[2]姜麟忠.催化氢化在有机合成中的应用[M].北京:化学工业出版社,1987:
[3]Dovell F S,Ferguson W E,Greenfield H,et al.Kinetic study of hydrogenation of dinitrotoluene and m-dinitrobenzene[J].I&EC product research and development,1970,9(2):224-229.
[4]Raney M.Method of preparing catalytic material:US,1563587[P],1925-12-10.
[5]Raney M.Method of producing finely divided nickel:US,1628190[P],1927-05-10.
[6]Covert L W,Adkins H.Nickel by the raney process as a catalyst-of hydrogenation [J].Journal of the American Chemical Society,1932,54(10):4116-4117.
[7]Adkins H,Pavlic A A.Preparation of a raney nickel catalyst[J].Journal of the American Chemical Society,1946,68(8):1471-1471.
[8]Adkins H,Billica H R.The preparation of raney nickel catalysts and their use under conditions comparable with those for platinum and palladium catalysts[J].Journal of the American Chemical Society,1948,70(2):695-698.
[9]陈江,沈德隆,章海燕.Raney-Ni催化剂的制备[J].浙江化工,2004,35(4):21-22.
[10]李大东译.催化剂的制备:Ⅱ制备非均相催化剂的科学基础[M].北京:化学工业出版社,1988.
[11]Nishimura S,Urushibara Y.Method for the preparation of Raney nickel catalyst with greater activity[J].Bulletin of the Chemical Society of Japan,1957,30:199.
[12]Choudhary V R,Chaudhari S K.Adsorption of reaction species on Raney nickel for slurry-phase hydrogenation of p-nitrotoluene[J].Journal of Chemical Technology and Biotechnology,Chemical Technology,1983,33A(8):428-434.
[13]施玉葵,顾其威.沥滤法制备骨架镍催化剂的过程动力学[J].化学反应工程与工艺,1991,7(4):345-350.
[14]Nakabayashi I,Nagao E,Miyata K,et al.Spectroscopic study on plate-and sponge-type Raney nickel electrodes for fuel cells[J].Journal of Materials Chemistry,1995,5(5):737-742.
[15]Sane S,Bonnier J M,Damon J P,et al.Raney metal catalysts.I.Comparative properties of Raney nickel proceeding from nickel-aluminum intermetallic phases [J].Applied Catalysis,1984,9(1):69-83.
[16]Bakker M L,Young D J,Wainwright M S.Selective leaching of nickel-aluminum(NiAl3and Ni2Al3) intermetallics to form Raney nickels[J].Journal of Materials Science,1988,23(11):3921-3926.
[17]江志东,瑞芳,金渠.雷尼镍催化剂[J].化学工业与工程,997,4(2):23-32.
[18] Freel J, Pieters W J M, Anderson R B. The structure of Raney nickel: I Pore structure [J].Journal of Catalysis, 1969, 14:247-256.
[19] Freel J, Pieters W J M. The structure of Raney nickel : II Electron microprobe studies [J].Journal of Catalysis, 1970, 16:281-291.
[20] Khaidar M, Allibert C, Driole J, et al. Composition, structure and crystallite size of Raney catalysts proceeding from several Ni-Al and Fe-Al intermetallic phases [J]. Materials Research Buttetin, 1982,17:329-337.
[21] Fouilloux P, Martin G A, Renouprez A J, et al. Texture and structure of Raney nickel [J]. Journal of Catalysis, 1972, 25(2):212-222.
[22] Freel J, Robertson S D, Anderson R B. Structure of Raney nickel. III. Chemisorption of hydrogen and carbon monoxide [J].Journal of Catalysis, 1970, 18(3):243-248.
[23] Birkenstock U., Holm R, Reinfandt B, et al. Surface analysis of Raney catalysts [J].Journal of Catalysis,1985,93(1):55-67.
[24] Fouilloux P. The nature of Raney nickel, its adsorbed hydrogen and its catalytic activity for hydrogenation reactions (review) [J]. Applied Catalysis, 1983,8(1):1-42.
[25] Robertson S D, Anderson R B. Structure of Raney nickel. IV. X-ray diffraction studies [J].Journal of Catalysis, 1971, 23(2):286-294.
[26] Yoshino T, Abe T, Abe S, et al. Surface characteristics and activities of plate-type Raney nickel catalyst [J].Journal of Catalysis, 1989,118(2):436-442.
[27] Gallezot P, Cerino P J, Blanc B, et al. Glucose hydrogenation on promoted Raney-nickel catalysts [J].Journal of Catalysis, 1994, 146(1):93-102.
[28] 赵纯洁,夏少武.骨架镍催化剂活性原因的分析[J].青岛化工学院学报,2002,23(3):12-15.
[29] Macnab J I, Anderson R B. Structure of Raney nickel. VIII. Magnetic properties related to particle size and hydrogen evolution [J]. Journal of Catalysis,1973,29(2): 338-345.
[30] Renouprez A J, Fouilloux P, Coudurier G, et al. Different species of hydrogen chemisorbed on Raney nickel studied by neutron inelastic spectroscopy [J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1977, 73(1): 1-10.
[31] Nicolau I, Anderson R B. Hydrogen in a commercial Raney nickel [J].Journal of Catalysis, 1981,68(2):339-348.
[32] Augustine R L. Catalytic Hydrogenation: Technique and application in Organic Synthesis [M]. NewYork: Marcel Dekker Inc, 1965.
[33]Bonnier J M,Damon J P,Masson J.New approach to skeletal nickel catalysts:catalytic properties of the nickel-chromium system[J].Applied Catalysis,1988,42(2):285-297.
[34]于甦生,吴指南,薛立我等.在改性骨架镍催化剂上丁炔二醇加氢制1,4-丁二醇[J].石油化工,1989,18(3):148-153.
[35]Pardillos-Guindet J,Metais S,Vidal S,et al.Electrode potential of a dispersed Raney nickel electrode during acetone hydrogenation:Influence of the promoters [J].Applied Catalysis,A:General,1995,132(1):61-75.
[36]石川重三郎.日本化学会志,1961,82(1):135
[37]许丹倩胡智燕,严新焕等.改性骨架镍催化加氢合成2,4-二氯-5-异丙氧基苯胺[J].农药,2003,42(10):20-21.
[38]Hamar-Thibault S,Koscielski T,Damon J P,et al.Structure of Raney nickel catalysts modified by chromium hydroxide deposition[J].Applied Catalysis,1989,56(1):57-71.
[39]Hamar-Thibault S,Masson J,Fouilloux P,et al.Selective hydrogenation of acetophenone on chromium promoted raney nickel catalysts:Ⅰ.Characterization of the catalysts[J].Applied Catalysis A:General,1993,99(2):131-145.
[40]Liu B J,Lu L H,Wang B C,et al.Liquid phase selective hydrogenation of furfural on Raney nickel modified by impregnation of salts of heteropolyacids[J].Applied Catalysis A:General,1998,171(1):117-122.
[41]刘百军,蔡天锡等.杂多酸盐修饰骨架镍催化剂上肉桂醛的选择加氢[J].分子催化,2003,17(4):270-273.
[42]Chen H N,Li R,Wang H L,et al.Highly efficient enantioselective hydrogenation of methyl acetoacetate over chirally modified Raney nickel catalytic system[J].Journal of Molecular Catalysis A:Chemical,2007,269(1-2):125-132.
[43]Koscielski T,Bonnier J M,Damon J P,et al.Catalytic hydrogenation on Raney nickel catalyst modified by chromium hydroxide deposition[J].Applied Catalysis,1989,49(1):91-99.
[44]Mikhailenko S D,Fasman A B,Maksimova N A,et al.Influence of preparation conditions on structure and physicochemical properties of multicomponent Raney nickel catalysts[J].Applied Catalysis,1984,12(2):141-150.
[45]Klein J C.Surface analysis by x-ray photoelectron spectroscopy and Auger electron spectroscopy of molybdenum-doped Raney nickel catalysts[J].Analytical Chemistry,1984,56:685-689.
[46]Koscielski T,Bonnier J M,Damon J P,et al.Catalytic hydrogenation on Raney nickel catalyst modified by chromium hydroxide deposition[J].Applied catalysis,1989,49:91-99.
[47]吴慧军,沈刚,杨俊杰,等.非晶态合金催化剂的制备与SR-NA-4催化剂的加氢性能[J].石油化工,2003,32(11),986.
[48]Liu B,Qiao M H,Deng J F,et al.Skeletal Ni Catalyst Prepared from a Rapidly Quenehed Ni-Al Alloys and Its High Selectivity in 2-Ethylanthraquinone Hydrogenation[J].Journal of Catalysis,2001,204:512-515.
[49]Hu H R,Xie F Z,Pei Y,et al.Skeletal Ni catalysts prepared from Ni-Al alloys rapidly quenched at different rates:Texture,structure and catalytic performance in chemoselective hydrogenation of 2-ethylanthraquinone[J].Journal of Catalysis,2006,237(1):143-151.
[50]Zhang H F,Wang A M,Li H,et al.Microstructure and catalytic properties of rapidly quenched Ni-Al-Cr-Fe alloy[J].Material Letters,2001,48(6):347-350.
[51]Li H X,Wang W J,Zong BN,et al.Skeletal Ni-P amorphous alloy(R-Ni-P) as a hydrogenation catalyst[J].Chemistry Letter,1998,27(4):371-372.
[52]Lei H,Song Z,Tan D L,et al.Preparation of novel Raney-Ni catalysts and characterization by XRD,SEM and XPS[J].Applied Catalysis A,2001,214(1):69-76.
[53]Hu H R,Qiao M H,Yan P,et al.Kinetics of hydrogen evolution in alkali leaching of rapidly quenched Ni-Al alloy[J].Applied Catalysis A,2003,252(1):173-183.
[54]胡华荣,方敬,乔明华等.猝冷速度对骨架Ni催化剂结构和催化性能的影响[J].高等学校化学学报,2005,26(7):1317-1320.
[55]汪颖,慕旭宏,宗保宁.非晶态合金催化剂在己内酰胺生产中的应用[J].石油化工,2001,30(8):631-634.
[56]杨克勇,汪颖,赵成军等.一种非晶态合金催化剂加氢精制己内酰胺水溶液新工艺的开发[J].石油炼制与化工,2001,32(7):21-24.
[57]吴浩,潘智勇,宗保宁等.非晶态Ni合金催化剂用于低温甲烷化反应的研究[J].化工进展,2005,24(3):299-302.
[58]杨从新.非晶态合金催化剂的表征与应用研究综述[J].山东化工,2007,36:10-12
[59]幕旭宏,王宣,宗保宁,等.非晶态合金催化剂用于葡萄糖加氢制山梨醇的研究[J].精细化工,1999,16(5):41-43.
[60]张国辉,付桂云,何旭,等.钯碳催化还原制备2,4-二甲基苯胺的研究[J].江西化工,2008(3):95-96
[61]BAHRMANNH,CORNILS B,DIERDORF S,HABER S.Hydrogenation of nitro-aromatics to anilines in high yield and selectivity-uses aq.soln.of rhodium tri-sodium tri-phenylphosphine-tri-sulphonate as homogeneous catalyst system:DE,529874Al[P].1997-02-20
[62]王纪康,王桂林,严魏,等.2,4-二甲基苯胺和2,6-二甲基苯胺的制备方法:中国,1055922A[P].1991,01,6.
[63]费炳新,李有明.用液相催化加氢法制备二甲基苯胺[J].陕西化工,1997(2):19-23.
[64]吴崖迪,王桂林.3,4-二甲基苯胺合成进展[J].浙江化工,2003,34(5):22-24.
[65]陈颖,靳惠娟.3,4-二甲基苯胺的合成[J].河北化工,2006,(2):30-33.
[66]Knifton J F,Suggitt R M.Homogeneous Ruthenium catalysts useful in the reduction of nitroaromatics to amines:US,3832401[P],1974-08-24.
[67]Knifton J F,Suggitt R M.Homogeneous Ruthenium catalysts useful in the selective reduction of nitroaromatics to amines:US,3906045[P],1975-09-16.
[68]Saha C R,Somnath B.Reduction of nitroaromatics with poly(vinylpyridine)complexes of Palladium(Ⅱ) and Platinum[J].J.Chem.Tech.Biotechno,1987,37,233-245.
[69]Lu L H,Rong Z M,Du W Q,et al.Selective hydrogenation of single benzene ring in biphenyl catalyzed by skeletal Ni[J].ChemCatChem,2009,1(3):369-371.
[70]杜文强,王越,吕连海.非晶态NiMoAl合金催化葡萄糖加氢制备山梨醇[J].精细化工,2007,24(12):1204-1206.
[71]张鹏,王越,吕连海.高活性骨架镍温和条件下催化间苯二甲腈加氢制备间苯二甲胺[J].精细化工,2008,25(2):201-204.
[72]马荣华,胡爽,辛俊娜,等.3-硝基-4-甲氧基乙酰苯胺的选择性催化加氢[J].精细化工,2006,23(11):1138-1141.
[73]Blaser H U.A Golden Boost to an Old Reaction[J].Science,2006,313(5785):312-313.
[74]唐培堃.中间体化学及工艺学[M].北京:化学工业出版社,1984.
[75]Holler V,Wegricht D,Yuranov I,et al.Three-phase nitrobenzene hydrogenation over supported glass fiber catalysts:reaction kinetics study[J].Chemical Engineering & Technology,2000,23(3):251-255.
[2]姜麟忠.催化氢化在有机合成中的应用[M].北京:化学工业出版社,1987:
[3]Dovell F S,Ferguson W E,Greenfield H,et al.Kinetic study of hydrogenation of dinitrotoluene and m-dinitrobenzene[J].I&EC product research and development,1970,9(2):224-229.
[4]Raney M.Method of preparing catalytic material:US,1563587[P],1925-12-10.
[5]Raney M.Method of producing finely divided nickel:US,1628190[P],1927-05-10.
[6]Covert L W,Adkins H.Nickel by the raney process as a catalyst-of hydrogenation [J].Journal of the American Chemical Society,1932,54(10):4116-4117.
[7]Adkins H,Pavlic A A.Preparation of a raney nickel catalyst[J].Journal of the American Chemical Society,1946,68(8):1471-1471.
[8]Adkins H,Billica H R.The preparation of raney nickel catalysts and their use under conditions comparable with those for platinum and palladium catalysts[J].Journal of the American Chemical Society,1948,70(2):695-698.
[9]陈江,沈德隆,章海燕.Raney-Ni催化剂的制备[J].浙江化工,2004,35(4):21-22.
[10]李大东译.催化剂的制备:Ⅱ制备非均相催化剂的科学基础[M].北京:化学工业出版社,1988.
[11]Nishimura S,Urushibara Y.Method for the preparation of Raney nickel catalyst with greater activity[J].Bulletin of the Chemical Society of Japan,1957,30:199.
[12]Choudhary V R,Chaudhari S K.Adsorption of reaction species on Raney nickel for slurry-phase hydrogenation of p-nitrotoluene[J].Journal of Chemical Technology and Biotechnology,Chemical Technology,1983,33A(8):428-434.
[13]施玉葵,顾其威.沥滤法制备骨架镍催化剂的过程动力学[J].化学反应工程与工艺,1991,7(4):345-350.
[14]Nakabayashi I,Nagao E,Miyata K,et al.Spectroscopic study on plate-and sponge-type Raney nickel electrodes for fuel cells[J].Journal of Materials Chemistry,1995,5(5):737-742.
[15]Sane S,Bonnier J M,Damon J P,et al.Raney metal catalysts.I.Comparative properties of Raney nickel proceeding from nickel-aluminum intermetallic phases [J].Applied Catalysis,1984,9(1):69-83.
[16]Bakker M L,Young D J,Wainwright M S.Selective leaching of nickel-aluminum(NiAl3and Ni2Al3) intermetallics to form Raney nickels[J].Journal of Materials Science,1988,23(11):3921-3926.
[17]江志东,瑞芳,金渠.雷尼镍催化剂[J].化学工业与工程,997,4(2):23-32.
[18] Freel J, Pieters W J M, Anderson R B. The structure of Raney nickel: I Pore structure [J].Journal of Catalysis, 1969, 14:247-256.
[19] Freel J, Pieters W J M. The structure of Raney nickel : II Electron microprobe studies [J].Journal of Catalysis, 1970, 16:281-291.
[20] Khaidar M, Allibert C, Driole J, et al. Composition, structure and crystallite size of Raney catalysts proceeding from several Ni-Al and Fe-Al intermetallic phases [J]. Materials Research Buttetin, 1982,17:329-337.
[21] Fouilloux P, Martin G A, Renouprez A J, et al. Texture and structure of Raney nickel [J]. Journal of Catalysis, 1972, 25(2):212-222.
[22] Freel J, Robertson S D, Anderson R B. Structure of Raney nickel. III. Chemisorption of hydrogen and carbon monoxide [J].Journal of Catalysis, 1970, 18(3):243-248.
[23] Birkenstock U., Holm R, Reinfandt B, et al. Surface analysis of Raney catalysts [J].Journal of Catalysis,1985,93(1):55-67.
[24] Fouilloux P. The nature of Raney nickel, its adsorbed hydrogen and its catalytic activity for hydrogenation reactions (review) [J]. Applied Catalysis, 1983,8(1):1-42.
[25] Robertson S D, Anderson R B. Structure of Raney nickel. IV. X-ray diffraction studies [J].Journal of Catalysis, 1971, 23(2):286-294.
[26] Yoshino T, Abe T, Abe S, et al. Surface characteristics and activities of plate-type Raney nickel catalyst [J].Journal of Catalysis, 1989,118(2):436-442.
[27] Gallezot P, Cerino P J, Blanc B, et al. Glucose hydrogenation on promoted Raney-nickel catalysts [J].Journal of Catalysis, 1994, 146(1):93-102.
[28] 赵纯洁,夏少武.骨架镍催化剂活性原因的分析[J].青岛化工学院学报,2002,23(3):12-15.
[29] Macnab J I, Anderson R B. Structure of Raney nickel. VIII. Magnetic properties related to particle size and hydrogen evolution [J]. Journal of Catalysis,1973,29(2): 338-345.
[30] Renouprez A J, Fouilloux P, Coudurier G, et al. Different species of hydrogen chemisorbed on Raney nickel studied by neutron inelastic spectroscopy [J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1977, 73(1): 1-10.
[31] Nicolau I, Anderson R B. Hydrogen in a commercial Raney nickel [J].Journal of Catalysis, 1981,68(2):339-348.
[32] Augustine R L. Catalytic Hydrogenation: Technique and application in Organic Synthesis [M]. NewYork: Marcel Dekker Inc, 1965.
[33]Bonnier J M,Damon J P,Masson J.New approach to skeletal nickel catalysts:catalytic properties of the nickel-chromium system[J].Applied Catalysis,1988,42(2):285-297.
[34]于甦生,吴指南,薛立我等.在改性骨架镍催化剂上丁炔二醇加氢制1,4-丁二醇[J].石油化工,1989,18(3):148-153.
[35]Pardillos-Guindet J,Metais S,Vidal S,et al.Electrode potential of a dispersed Raney nickel electrode during acetone hydrogenation:Influence of the promoters [J].Applied Catalysis,A:General,1995,132(1):61-75.
[36]石川重三郎.日本化学会志,1961,82(1):135
[37]许丹倩胡智燕,严新焕等.改性骨架镍催化加氢合成2,4-二氯-5-异丙氧基苯胺[J].农药,2003,42(10):20-21.
[38]Hamar-Thibault S,Koscielski T,Damon J P,et al.Structure of Raney nickel catalysts modified by chromium hydroxide deposition[J].Applied Catalysis,1989,56(1):57-71.
[39]Hamar-Thibault S,Masson J,Fouilloux P,et al.Selective hydrogenation of acetophenone on chromium promoted raney nickel catalysts:Ⅰ.Characterization of the catalysts[J].Applied Catalysis A:General,1993,99(2):131-145.
[40]Liu B J,Lu L H,Wang B C,et al.Liquid phase selective hydrogenation of furfural on Raney nickel modified by impregnation of salts of heteropolyacids[J].Applied Catalysis A:General,1998,171(1):117-122.
[41]刘百军,蔡天锡等.杂多酸盐修饰骨架镍催化剂上肉桂醛的选择加氢[J].分子催化,2003,17(4):270-273.
[42]Chen H N,Li R,Wang H L,et al.Highly efficient enantioselective hydrogenation of methyl acetoacetate over chirally modified Raney nickel catalytic system[J].Journal of Molecular Catalysis A:Chemical,2007,269(1-2):125-132.
[43]Koscielski T,Bonnier J M,Damon J P,et al.Catalytic hydrogenation on Raney nickel catalyst modified by chromium hydroxide deposition[J].Applied Catalysis,1989,49(1):91-99.
[44]Mikhailenko S D,Fasman A B,Maksimova N A,et al.Influence of preparation conditions on structure and physicochemical properties of multicomponent Raney nickel catalysts[J].Applied Catalysis,1984,12(2):141-150.
[45]Klein J C.Surface analysis by x-ray photoelectron spectroscopy and Auger electron spectroscopy of molybdenum-doped Raney nickel catalysts[J].Analytical Chemistry,1984,56:685-689.
[46]Koscielski T,Bonnier J M,Damon J P,et al.Catalytic hydrogenation on Raney nickel catalyst modified by chromium hydroxide deposition[J].Applied catalysis,1989,49:91-99.
[47]吴慧军,沈刚,杨俊杰,等.非晶态合金催化剂的制备与SR-NA-4催化剂的加氢性能[J].石油化工,2003,32(11),986.
[48]Liu B,Qiao M H,Deng J F,et al.Skeletal Ni Catalyst Prepared from a Rapidly Quenehed Ni-Al Alloys and Its High Selectivity in 2-Ethylanthraquinone Hydrogenation[J].Journal of Catalysis,2001,204:512-515.
[49]Hu H R,Xie F Z,Pei Y,et al.Skeletal Ni catalysts prepared from Ni-Al alloys rapidly quenched at different rates:Texture,structure and catalytic performance in chemoselective hydrogenation of 2-ethylanthraquinone[J].Journal of Catalysis,2006,237(1):143-151.
[50]Zhang H F,Wang A M,Li H,et al.Microstructure and catalytic properties of rapidly quenched Ni-Al-Cr-Fe alloy[J].Material Letters,2001,48(6):347-350.
[51]Li H X,Wang W J,Zong BN,et al.Skeletal Ni-P amorphous alloy(R-Ni-P) as a hydrogenation catalyst[J].Chemistry Letter,1998,27(4):371-372.
[52]Lei H,Song Z,Tan D L,et al.Preparation of novel Raney-Ni catalysts and characterization by XRD,SEM and XPS[J].Applied Catalysis A,2001,214(1):69-76.
[53]Hu H R,Qiao M H,Yan P,et al.Kinetics of hydrogen evolution in alkali leaching of rapidly quenched Ni-Al alloy[J].Applied Catalysis A,2003,252(1):173-183.
[54]胡华荣,方敬,乔明华等.猝冷速度对骨架Ni催化剂结构和催化性能的影响[J].高等学校化学学报,2005,26(7):1317-1320.
[55]汪颖,慕旭宏,宗保宁.非晶态合金催化剂在己内酰胺生产中的应用[J].石油化工,2001,30(8):631-634.
[56]杨克勇,汪颖,赵成军等.一种非晶态合金催化剂加氢精制己内酰胺水溶液新工艺的开发[J].石油炼制与化工,2001,32(7):21-24.
[57]吴浩,潘智勇,宗保宁等.非晶态Ni合金催化剂用于低温甲烷化反应的研究[J].化工进展,2005,24(3):299-302.
[58]杨从新.非晶态合金催化剂的表征与应用研究综述[J].山东化工,2007,36:10-12
[59]幕旭宏,王宣,宗保宁,等.非晶态合金催化剂用于葡萄糖加氢制山梨醇的研究[J].精细化工,1999,16(5):41-43.
[60]张国辉,付桂云,何旭,等.钯碳催化还原制备2,4-二甲基苯胺的研究[J].江西化工,2008(3):95-96
[61]BAHRMANNH,CORNILS B,DIERDORF S,HABER S.Hydrogenation of nitro-aromatics to anilines in high yield and selectivity-uses aq.soln.of rhodium tri-sodium tri-phenylphosphine-tri-sulphonate as homogeneous catalyst system:DE,529874Al[P].1997-02-20
[62]王纪康,王桂林,严魏,等.2,4-二甲基苯胺和2,6-二甲基苯胺的制备方法:中国,1055922A[P].1991,01,6.
[63]费炳新,李有明.用液相催化加氢法制备二甲基苯胺[J].陕西化工,1997(2):19-23.
[64]吴崖迪,王桂林.3,4-二甲基苯胺合成进展[J].浙江化工,2003,34(5):22-24.
[65]陈颖,靳惠娟.3,4-二甲基苯胺的合成[J].河北化工,2006,(2):30-33.
[66]Knifton J F,Suggitt R M.Homogeneous Ruthenium catalysts useful in the reduction of nitroaromatics to amines:US,3832401[P],1974-08-24.
[67]Knifton J F,Suggitt R M.Homogeneous Ruthenium catalysts useful in the selective reduction of nitroaromatics to amines:US,3906045[P],1975-09-16.
[68]Saha C R,Somnath B.Reduction of nitroaromatics with poly(vinylpyridine)complexes of Palladium(Ⅱ) and Platinum[J].J.Chem.Tech.Biotechno,1987,37,233-245.
[69]Lu L H,Rong Z M,Du W Q,et al.Selective hydrogenation of single benzene ring in biphenyl catalyzed by skeletal Ni[J].ChemCatChem,2009,1(3):369-371.
[70]杜文强,王越,吕连海.非晶态NiMoAl合金催化葡萄糖加氢制备山梨醇[J].精细化工,2007,24(12):1204-1206.
[71]张鹏,王越,吕连海.高活性骨架镍温和条件下催化间苯二甲腈加氢制备间苯二甲胺[J].精细化工,2008,25(2):201-204.
[72]马荣华,胡爽,辛俊娜,等.3-硝基-4-甲氧基乙酰苯胺的选择性催化加氢[J].精细化工,2006,23(11):1138-1141.
[73]Blaser H U.A Golden Boost to an Old Reaction[J].Science,2006,313(5785):312-313.
[74]唐培堃.中间体化学及工艺学[M].北京:化学工业出版社,1984.
[75]Holler V,Wegricht D,Yuranov I,et al.Three-phase nitrobenzene hydrogenation over supported glass fiber catalysts:reaction kinetics study[J].Chemical Engineering & Technology,2000,23(3):251-255.