丁腈橡胶非均相加氢催化剂失活原因及再生性能研究
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摘要
对丁腈橡胶非均相催化加氢制备高附加值氢化丁腈橡胶过程中催化剂失活的原因进行了探究,发现造成催化剂活性下降的原因并不是贵金属纳米颗粒的流失、团聚或中毒,而是催化剂表面的活性位被聚合物覆盖而无法与反应物接触,因此将覆盖在活性位上的聚合物进行脱除才是催化剂再生和重复利用的关键。根据相似相容原理选择单溶剂或者混合溶剂对反应后催化剂进行处理,结果表明经过乙酸乙酯、丁酮、N,N-二甲基甲酰胺以及N-甲基吡咯烷酮这四种有机溶剂处理后,其催化加氢活性可以恢复至新鲜催化剂活性的90%;当用混合溶剂处理后,其催化活性可以提高至新鲜催化剂活性的95%,且循环利用4次其催化活性仍能保持不变。
The reason for the deactivation of catalysts in the process of preparing high value-added hydrogenated nitrile rubber by heterogeneous catalytic hydrogenation of nitrile rubber was investigated. It was found that the cause of the decrease in catalyst activity was not the loss, agglomeration or poisoning of noble metal nanoparticles.The reactants could not contact with the active sites, which was the real reason for the reduced activity. Therefore,the effective removal of the polymers from the active sites was the key to catalyst regeneration and reuse. Secondly,based on the similarity-intermiscibility theory, the recycled catalyst was treated with a single or a mixed solvent to elute the polymers and recover its activity. The results showed that the catalyst activity could be restored to 90% of the fresh catalyst activity by washing with ethyl acetate, butanone, N,N-dimethylfirmamide or N-methylpyrrolidone.When treated with a mixed solvent, its catalyst activity could be increased to 95% of the fresh catalyst activity, and could remain steady after recycling 4 times. SEM and TG characterization results showed that after the organic solvent regeneration, Pd active sites on the surface of the catalyst were exposed, thus its hydrogenation activity was remarkably improved.
The reason for the deactivation of catalysts in the process of preparing high value-added hydrogenated nitrile rubber by heterogeneous catalytic hydrogenation of nitrile rubber was investigated. It was found that the cause of the decrease in catalyst activity was not the loss, agglomeration or poisoning of noble metal nanoparticles.The reactants could not contact with the active sites, which was the real reason for the reduced activity. Therefore,the effective removal of the polymers from the active sites was the key to catalyst regeneration and reuse. Secondly,based on the similarity-intermiscibility theory, the recycled catalyst was treated with a single or a mixed solvent to elute the polymers and recover its activity. The results showed that the catalyst activity could be restored to 90% of the fresh catalyst activity by washing with ethyl acetate, butanone, N,N-dimethylfirmamide or N-methylpyrrolidone.When treated with a mixed solvent, its catalyst activity could be increased to 95% of the fresh catalyst activity, and could remain steady after recycling 4 times. SEM and TG characterization results showed that after the organic solvent regeneration, Pd active sites on the surface of the catalyst were exposed, thus its hydrogenation activity was remarkably improved.
引文
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[2]Parent J S,Mcmanus N T,Rempel G L.RhCl(PPh3)3and RhH(PPh3)4catalyzed hydrogenation of acrylonitrile-butadiene copolymers[J].Industrial&Engineering Chemistry Research,1996,35(12):4417-4423.
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[4]Mcmanus N,Rempel G.Improvements in the hydrogenation of nitrile rubber using Wilkinson.s catalyst[J].Rubber Chemistry and Technology,2008,81(2):227-243.
[5]Bhattacharjee S,Bhowmick A K,Avasthi B N.Preparation of hydrogenated nitrile rubber using palladium acetate catalyst its characterization and kinetics[J].Journal of Polymer Science Part A-Polymer Chemistry,1992,30(3):471-484.
[6]Bhattacharjee S,Rajagopalan P,Bhowmick A K,et al.Selective hydrogenation of olefinic bonds in styrene-isoprene-styrene triblock copolymer by palladium acetate catalyst[J].Journal of Applied Polymer Science,1993,49(11):1971-1977.
[7]Schulz G A,Comin E,Souza R F.Catalytic hydrogenation of nitrile rubber using palladium and ruthenium complexes[J].Journal of Applied Polymer Science,2007,106(1):659-663.
[8]Liu Q,Wei Z.Catalyst compositions and their use for hydrogenation of nitrile rubber:US9605088[P].2017-03-28.
[9]Hallett J P,Ford J W,Jones R S,et al.Hydroformylation catalyst recycle with gas-expanded liquids[J].Industrial&Engineering Chemistry Research,2008,47(8):2585-2589.
[10]Yang L,Pan Q,Rempel G L.Recovery of Wilkinson.s catalyst from polymer based matrix using carbon dioxide expanded methanol[J].Journal of Supercritical Fluids,2012,68:104-112.
[11]Yang L,Pan Q,Rempel G L.Development of a green separation technique for recovery of Wilkinson.s catalysts from bulk hydrogenated nitrile butadiene rubber[J].Catalysis Today,2013,207(207):153-161.
[12]Hutchings G J.Heterogeneous catalysts-discovery and design[J].Journal of Materials Chemistry,2009,19(9):1222-1235.
[13]Almusaiteer K A.Effect of supports on the catalytic hydrogenation of polystyrene[J].Topics in Catalysis,2012,55(7/8/9/10):498-504.
[14]Buding H,Konigshofen H,Szentivanyi Z,et al.Production of hydrogenated nitrile rubbers:US4581417A[P].1986-04-08.
[15]Kubo Y.Hydrogenation of conjugated diene polymer:JP62218403[P].1987.
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[17]Albers P,Pietsch P,Parker S F.Poisoning and deactivation of palladium catalysts[J].Journal of Molecular Catalysis A Chemical,2001,173(1):275-286.
[18]Argyle M D,Bartholomew C H.Heterogeneous catalyst deactivation and regeneration:a review[J].Catalysts,2015,5(1):145-269.
[19]陈筱金.Pd/C催化剂失活原因分析与改进措施[J].化学反应工程与工艺,2002,18(3):275-278.Chen X J.Analysis of Pd/C catalyst deactivation mechanisms and improvement measures for CTA hydrogenation process[J].Chemical Reaction Engineering and Technology,2002,18(3):275-278.
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[21]Escandon L S,Ordonez S,Vega A,et al.Sulphur poisoning of palladium catalysts used for methane combustion:effect of the support[J].Journal of Hazardous Materials,2008,153(1/2):742-750.
[22]Ahn I Y,Lee J H,Kim S K,et al.Three-stage deactivation of Pd/SiO2and Pd-Ag/SiO2catalysts during the selective hydrogenation of acetylene[J].Applied Catalysis A-General,2009,360(1):38-42.
[23]Abate S,Perathoner S,Centi G.Deactivation mechanism of Pd supported on ordered and non-ordered mesoporous silica in the direct H2O2synthesis using CO2-expanded methanol[J].Catalysis Today,2012,179(1):170-177.
[24]Jiang D,Mao J,Fang Z,et al.Deactivation of Pd/SiO2catalyst in the continuous liquid-phase selective hydrogenation of an unsaturated ketone[J].Reaction Kinetics Mechanisms and Catalysis,2015,116(2):451-466.
[25]Zou R,Li C,Zhang L,et al.Selective hydrogenation of nitrile butadiene rubber(NBR)with rhodium nanoparticles supported on carbon nanotubes at room temperature[J].Catalysis Communications,2016,81(4-9):1566-7367.
[26]Cao P,Ni Y,Zou R,et al.Enhanced catalytic properties of rhodium nanoparticles deposited on chemically modified SiO2for hydrogenation of nitrile butadiene rubber[J].RSC Advances,2015,5(5):3417-3424.
[27]Cao P,Su N,Li C,et al.Highly active and reusable rhodium catalyst for selective hydrogenation of nitrile-butadiene rubber[J].Rubber Chemistry and Technology,2015,88(4):150623072814001.
[28]Chen J,Ma L,Cheng T,et al.Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with microporous shells for enhanced catalytic hydrogenation of NBR[J].Journal of Materials Science,2018,53(21):15064-15080.
[29]Pan D,Shi G,Zhang T,et al.New understanding and controllable synthesis of silica hollow microspheres with size-tunable penetrating macroporous shells as a superior support for polystyrene hydrogenation catalysts[J].Journal of Materials Chemistry A,2013,1(34):9597-9602.
[30]Leeuwen P W N M V.Homogeneous Catalysis:Understanding the Art[M].Boston:Kluwer Academic Publishers,2004:6-9.
[31]Brück D.IR-spectrometric determination of the proportions of acrylonitrile,butadiene and hydrogenated butadiene in hydrogenated acrylonitrile-butadiene rubbers(HNBR)(Ⅱ):Residual double bonds in commercial HNBR products[J].Kautschuk Gummi Kunststoffe,1989,42(3):194-197.
[32]Bhattacharjee S,Bhowmick A K,Avasthi B N.High-pressure hydrogenation of nitrile rubber:thermodynamics and kinetics[J].Industrial&Engineering Chemistry Research,1991,30(6):1086-1092.
[33]Wang H,Yang L,Rempel G L.Homogeneous hydrogenation art of nitrile butadiene rubber:a review[J].Polymer Reviews,2013,53(2):192-239.
[2]Parent J S,Mcmanus N T,Rempel G L.RhCl(PPh3)3and RhH(PPh3)4catalyzed hydrogenation of acrylonitrile-butadiene copolymers[J].Industrial&Engineering Chemistry Research,1996,35(12):4417-4423.
[3]Rempel G L,Mcmanus N T,Guo X Y.Catalytic solution hydrogenation of nitrile rubber:US5258467[P].1993-11-02.
[4]Mcmanus N,Rempel G.Improvements in the hydrogenation of nitrile rubber using Wilkinson.s catalyst[J].Rubber Chemistry and Technology,2008,81(2):227-243.
[5]Bhattacharjee S,Bhowmick A K,Avasthi B N.Preparation of hydrogenated nitrile rubber using palladium acetate catalyst its characterization and kinetics[J].Journal of Polymer Science Part A-Polymer Chemistry,1992,30(3):471-484.
[6]Bhattacharjee S,Rajagopalan P,Bhowmick A K,et al.Selective hydrogenation of olefinic bonds in styrene-isoprene-styrene triblock copolymer by palladium acetate catalyst[J].Journal of Applied Polymer Science,1993,49(11):1971-1977.
[7]Schulz G A,Comin E,Souza R F.Catalytic hydrogenation of nitrile rubber using palladium and ruthenium complexes[J].Journal of Applied Polymer Science,2007,106(1):659-663.
[8]Liu Q,Wei Z.Catalyst compositions and their use for hydrogenation of nitrile rubber:US9605088[P].2017-03-28.
[9]Hallett J P,Ford J W,Jones R S,et al.Hydroformylation catalyst recycle with gas-expanded liquids[J].Industrial&Engineering Chemistry Research,2008,47(8):2585-2589.
[10]Yang L,Pan Q,Rempel G L.Recovery of Wilkinson.s catalyst from polymer based matrix using carbon dioxide expanded methanol[J].Journal of Supercritical Fluids,2012,68:104-112.
[11]Yang L,Pan Q,Rempel G L.Development of a green separation technique for recovery of Wilkinson.s catalysts from bulk hydrogenated nitrile butadiene rubber[J].Catalysis Today,2013,207(207):153-161.
[12]Hutchings G J.Heterogeneous catalysts-discovery and design[J].Journal of Materials Chemistry,2009,19(9):1222-1235.
[13]Almusaiteer K A.Effect of supports on the catalytic hydrogenation of polystyrene[J].Topics in Catalysis,2012,55(7/8/9/10):498-504.
[14]Buding H,Konigshofen H,Szentivanyi Z,et al.Production of hydrogenated nitrile rubbers:US4581417A[P].1986-04-08.
[15]Kubo Y.Hydrogenation of conjugated diene polymer:JP62218403[P].1987.
[16]Kubo Y,Ohura K.Process for hydrogenation of conjugated diene polymers:US4337329[P].1982-06-29.
[17]Albers P,Pietsch P,Parker S F.Poisoning and deactivation of palladium catalysts[J].Journal of Molecular Catalysis A Chemical,2001,173(1):275-286.
[18]Argyle M D,Bartholomew C H.Heterogeneous catalyst deactivation and regeneration:a review[J].Catalysts,2015,5(1):145-269.
[19]陈筱金.Pd/C催化剂失活原因分析与改进措施[J].化学反应工程与工艺,2002,18(3):275-278.Chen X J.Analysis of Pd/C catalyst deactivation mechanisms and improvement measures for CTA hydrogenation process[J].Chemical Reaction Engineering and Technology,2002,18(3):275-278.
[20]张建远,康保安.脂肪腈加氢胺化过程中Pd/C催化剂失活原因探讨[J].化学通报,2006,69(9):696-700.Zhang J Y,Kang B A.Study on Pd/C catalysts deactivation during the process of fatty nitrile hydroamination[J].Chemistry Bulletin,2006,69(9):696-700.
[21]Escandon L S,Ordonez S,Vega A,et al.Sulphur poisoning of palladium catalysts used for methane combustion:effect of the support[J].Journal of Hazardous Materials,2008,153(1/2):742-750.
[22]Ahn I Y,Lee J H,Kim S K,et al.Three-stage deactivation of Pd/SiO2and Pd-Ag/SiO2catalysts during the selective hydrogenation of acetylene[J].Applied Catalysis A-General,2009,360(1):38-42.
[23]Abate S,Perathoner S,Centi G.Deactivation mechanism of Pd supported on ordered and non-ordered mesoporous silica in the direct H2O2synthesis using CO2-expanded methanol[J].Catalysis Today,2012,179(1):170-177.
[24]Jiang D,Mao J,Fang Z,et al.Deactivation of Pd/SiO2catalyst in the continuous liquid-phase selective hydrogenation of an unsaturated ketone[J].Reaction Kinetics Mechanisms and Catalysis,2015,116(2):451-466.
[25]Zou R,Li C,Zhang L,et al.Selective hydrogenation of nitrile butadiene rubber(NBR)with rhodium nanoparticles supported on carbon nanotubes at room temperature[J].Catalysis Communications,2016,81(4-9):1566-7367.
[26]Cao P,Ni Y,Zou R,et al.Enhanced catalytic properties of rhodium nanoparticles deposited on chemically modified SiO2for hydrogenation of nitrile butadiene rubber[J].RSC Advances,2015,5(5):3417-3424.
[27]Cao P,Su N,Li C,et al.Highly active and reusable rhodium catalyst for selective hydrogenation of nitrile-butadiene rubber[J].Rubber Chemistry and Technology,2015,88(4):150623072814001.
[28]Chen J,Ma L,Cheng T,et al.Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with microporous shells for enhanced catalytic hydrogenation of NBR[J].Journal of Materials Science,2018,53(21):15064-15080.
[29]Pan D,Shi G,Zhang T,et al.New understanding and controllable synthesis of silica hollow microspheres with size-tunable penetrating macroporous shells as a superior support for polystyrene hydrogenation catalysts[J].Journal of Materials Chemistry A,2013,1(34):9597-9602.
[30]Leeuwen P W N M V.Homogeneous Catalysis:Understanding the Art[M].Boston:Kluwer Academic Publishers,2004:6-9.
[31]Brück D.IR-spectrometric determination of the proportions of acrylonitrile,butadiene and hydrogenated butadiene in hydrogenated acrylonitrile-butadiene rubbers(HNBR)(Ⅱ):Residual double bonds in commercial HNBR products[J].Kautschuk Gummi Kunststoffe,1989,42(3):194-197.
[32]Bhattacharjee S,Bhowmick A K,Avasthi B N.High-pressure hydrogenation of nitrile rubber:thermodynamics and kinetics[J].Industrial&Engineering Chemistry Research,1991,30(6):1086-1092.
[33]Wang H,Yang L,Rempel G L.Homogeneous hydrogenation art of nitrile butadiene rubber:a review[J].Polymer Reviews,2013,53(2):192-239.