溶剂热浸渍法制备高稳定性Zn(OAc)_2/SiO_2催化剂及其催化合成苯氨基甲酸甲酯
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摘要
Zn(OAc)_2对由碳酸二甲酯(DMC)和苯胺合成苯氨基甲酸甲酯(MPC)的反应具有优异的催化性能,但存在易失活、不能重复使用的缺点。为此,以DMC为溶剂,利用溶剂热浸渍法制备Zn(OAc)_2/SiO_2催化剂,并对其催化性能进行了研究。利用XRD、FTIR和TG-DTA等方法对其进行了表征,结果表明,Zn(OAc)_2/SiO_2催化剂表面存在Zn(OAc)_2和ZnO,且其在SiO_2表面分散较好;优化了Zn(OAc)_2/SiO_2催化剂的反应条件,当反应温度为190℃、反应时间为5h、苯胺与DMC的摩尔比为1∶20、催化剂与苯胺质量比为0.2时,苯胺的转化率为97.2%,MPC的选择性为89.4%。和等体积浸渍法制备的催化剂相比,溶剂热浸渍法制备的Zn(OAc)_2/SiO_2催化剂具有较好的稳定性,重复使用7次,苯胺的转化率下降至79.1%,MPC的选择性下降至79.2%。Zn(OAc)_2/SiO_2活性下降的原因是由于ZnO的生成,并对其进行了再生,再生后的催化剂活性与新鲜催化剂接近。
Zn(OAc)_2 exhibits excellent catalytic performance in the methyl N-phenyl carbamate(MPC)synthesis using aniline and dimethyl carbonate(DMC), but it cannot be reused. Zn(OAc)_2/SiO_2 catalyst was prepared by solvothermal impregnation with DMC as the solvent in this paper. Zn(OAc)_2/SiO_2 was characterized by XRD、 FTIR and TG-DTA. The results suggested that Zn(OAc)_2 and ZnO were well dispersed on SiO_2 surface. At reaction temperature of 190℃, reaction time of 5 h, nDMC∶nanilineof 20∶1 and maniline: mZn( OAc)2/SiO_2 of 0.2, Zn(OAc)_2/SiO_2 showed the best catalytic performance, giving an aniline conversion of 97.2% and a MPC selectivity of 89.4%. The obtained Zn(OAc)_2/SiO_2 showed better stability than that prepared by incipient impregnation. After the Zn(OAc)_2/SiO_2 was used for the seventh time,aniline conversion and MPC selectivity were found to be 79.1% and 79.2%, respectively and the catalytic activity decrease is attributed to the formation of ZnO. The deactivated Zn(OAc)_2/SiO_2 can be regenerated with the catalytic activity almost the same as that of the fresh catalyst.
Zn(OAc)_2 exhibits excellent catalytic performance in the methyl N-phenyl carbamate(MPC)synthesis using aniline and dimethyl carbonate(DMC), but it cannot be reused. Zn(OAc)_2/SiO_2 catalyst was prepared by solvothermal impregnation with DMC as the solvent in this paper. Zn(OAc)_2/SiO_2 was characterized by XRD、 FTIR and TG-DTA. The results suggested that Zn(OAc)_2 and ZnO were well dispersed on SiO_2 surface. At reaction temperature of 190℃, reaction time of 5 h, nDMC∶nanilineof 20∶1 and maniline: mZn( OAc)2/SiO_2 of 0.2, Zn(OAc)_2/SiO_2 showed the best catalytic performance, giving an aniline conversion of 97.2% and a MPC selectivity of 89.4%. The obtained Zn(OAc)_2/SiO_2 showed better stability than that prepared by incipient impregnation. After the Zn(OAc)_2/SiO_2 was used for the seventh time,aniline conversion and MPC selectivity were found to be 79.1% and 79.2%, respectively and the catalytic activity decrease is attributed to the formation of ZnO. The deactivated Zn(OAc)_2/SiO_2 can be regenerated with the catalytic activity almost the same as that of the fresh catalyst.
引文
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[21]LI F,WANG Y J,XUE W,et al.Clean synthesis of methyl N-phenyl carbamate over ZnO-TiO2catalyst[J].Journal of Chemical Technology&Biotechnology,2009,84(1):48-53.
[22]ZHURAVLEV L T.The surface chemistry of amorphous silica.Zhuravlev model[J].Colloids&Surfaces A:Physicochemical&Engineering Aspects,2000,173(1):1-38.
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[25]BISWICK T,JONES W,PACULA A,et al.Evidence for the formation of anhydrous zinc acetate and acetic anhydride during the thermal degradation of zinc hydroxy acetate,Zn(OH)(CHCO)·4HO to ZnO[J].Solid State Sciences,2009,11(2):330-335.
[2]FU Z H,ONO Y.Synthesis of methyl N-phenyl carbamate by methoxycarbonylation of aniline with dimethyl carbonate using Pb compounds as catalysts[J].Journal of Molecular Catalysis,1994,91(3):399-405.
[3]WANG S P,ZHANG G L,MA X B,et al.Investigations of catalytic activity,deactivation,and regeneration of Pb(OAc)2for methoxycarbonylation of 2,4-toluene diamine with dimethyl carbonate[J].Industrial&Engineering Chemistry Research,2007,46(21):6858-6864.
[4]PEI Y X,LI H Q,LIU H T,et al.Kinetic study of methoxycarbonylation of methylene dianiline with dimethyl carbonate using lead acetate catalyst[J].Industrial&Engineering Chemistry Research,2011,50(4):1955-1961.
[5]GURGIOLO A E,LAKE J.Preparation of carbamates from aromatic amines and organic carbonates:US4268683[P].1981-05-19.
[6]王延吉,张文会.二苯甲烷二异氰酸酯清洁合成过程研究[J].石油学报(石油加工),1999,15(6):9-14.WANG Y J,ZHANG W H.Study on the clean synthesis of diphenyl methane diisocyanate[J].Acta Petrolei Sinica(Petroleum Processing Section),1999,15(6):9-14.
[7]LI F,LI W B,LI J,et al.Investigation of supported Zn(OAc)2 catalyst and its stability in N-phenyl carbamate synthesis[J].Applied Catalysis A:General,2014,475(5):355-362.
[8]ZHAO X Q,WANG Y J,WANG S F,et al.Synthesis of MDI from dimethyl carbonate over solid catalysts[J].Industrial&Engineering Chemistry Research,2002,41(21):5139-5144.
[9]ZHAO X Q,KANG L J,WANG N,et al.Synthesis of methyl N?phenyl carbamate catalyzed by ionic liquid-promoted zinc zcetate[J].Industrial&Engineering Chemistry Research,2012,51(35):11335-11340.
[10]WANG Y,LIU B.Efficient and recyclable heterogeneous zinc alkyl carboxylate catalyst for the synthesis of N-phenyl carbamate from aniline and dimethyl carbonate[J].Catalysis Science&Technology,2014,5(1):109-113.
[11]BOSETTI A,CESTI P,CALDERAZZO F.Process for the production of aromatic carbamates:US5698731[P].1997-12-16.
[12]BABA T,KOBAYASHI A,YAMAUCHI T,et al.Catalytic methoxycarbonylation of aromatic diamines with dimethyl carbonate to their dicarbamates using zinc acetate[J].Catalysis Letters,2002,82(3/4):193-197.
[13]BABA T,KOBAYASHI A,KAWANAMI Y,et al.Characteristics of methoxycarbonylation of aromatic diamine with dimethyl carbonate to dicarbamate using a zinc acetate catalyst[J].Green Chemistry,2005,7(3):159-165.
[14]GUO X C,QIN Z F,FAN W B,et al.Zinc carboxylate functionalized mesoporous SBA-15 catalyst for selective synthesis of methyl-4,4′-di(phenylcarbamate)[J].Catalysis Letters,2009,128(3/4):405-412.
[15]REIXACH E,BONET N,RIUS-RUIZ F X,et al.Zinc acetates as efficient catalysts for the synthesis of bis-isocyanate precursors[J].Industrial&Engineering Chemistry Research,2010,49(14):6362-6366.
[16]REIXACH E,HAAK R M,WERSHOFEN S,et al.Alkoxycarbonylation of industrially relevant anilines using Zn4O(O2CCH3)6as catalyst[J].Industrial&Engineering Chemistry Research,2012,51(50):16165-16170.
[17]KATADA N,FUJINAGA H,NAKAMURA Y,et al.Catalytic activity of mesoporous silica for synthesis of methyl N-phenyl carbamate from dimethyl carbonate and aniline[J].Catalysis Letters,2002,80(1/2):47-51.
[18]KANG W K,KANG T,MA F,et al.Catalytic performance of supported PbO catalysts for synthesis of methyl N-phenyl carbamate from aniline and dimethyl carbonate[J].Chinese Journal of Catalysis,2007,28(1):5-9.
[19]LI Q F,WANG J W,DONG W S,et al.Synthesis of methyl N-phenyl carbamate by methoxycarbonylation of aniline with dimethyl carbonate[J].Chinese Journal of Catalysis,2003,24(8):639-642.
[20]LI F,MIAO J,WANG Y J,et al.Synthesis of methyl N-phenyl carbamate from aniline and dimethyl carbonate over supported zirconia catalyst[J].Industrial&Engineering Chemistry Research,2006,45(14):4892-4897.
[21]LI F,WANG Y J,XUE W,et al.Clean synthesis of methyl N-phenyl carbamate over ZnO-TiO2catalyst[J].Journal of Chemical Technology&Biotechnology,2009,84(1):48-53.
[22]ZHURAVLEV L T.The surface chemistry of amorphous silica.Zhuravlev model[J].Colloids&Surfaces A:Physicochemical&Engineering Aspects,2000,173(1):1-38.
[23]XIE Y C,TANG Y Q.Spontaneous monolayer dispersion of oxides and salts onto surfaces of supports:applications to heterogeneous catalysis[J].Advan.Catal.,1990,37:1-43.
[24]KORETSKY C M,SVERJENSKY D A,SALISBURY J W,et al.Detection of surface hydroxyl species on quartz,γ-alumina,and feldspars using diffuse reflectance infrared spectroscopy[J].Geochimica et Cosmochimica Acta,1997,61(11):2193-2210.
[25]BISWICK T,JONES W,PACULA A,et al.Evidence for the formation of anhydrous zinc acetate and acetic anhydride during the thermal degradation of zinc hydroxy acetate,Zn(OH)(CHCO)·4HO to ZnO[J].Solid State Sciences,2009,11(2):330-335.