Ni-P/TiO_2非晶态催化剂对α-蒎烯加氢的性能
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摘要
采用化学还原法制备Ni-P/TiO_2非晶态催化剂,以α-蒎烯加氢反应为探针反应,考察了催化剂制备条件对其催化性能的影响,得到适宜的制备条件为载体与NiCl_2·6H_2O质量比为3∶1,P/Ni摩尔比为2.5∶1,反应温度为25℃,pH为11。结果表明:该条件下制备的催化剂对α-蒎烯加氢具有较高的催化活性,α-蒎烯转化率为99.89%,顺式蒎烷选择性为98.48%,收率为98.37%,且可重复使用8次。以XRD、BET、DSC、XPS、TEM为表征手段,对催化剂失活前后的结构及形貌进行了分析,结果表明:新鲜催化剂为粒径均一的球形颗粒,粒径约为100nm,分散性较好,引入TiO2有效提高了Ni-P粒子的热稳定性,将其晶化温度分别提高了78℃、190℃和115.1℃,而失活催化剂的分散度、Ni0含量均有下降,出现了活性组分流失、氧化及团聚等现象,这可能是导致催化剂失活的主要原因。
Ni-P/TiO_2 amorphous catalyst was prepared by chemical reduction method. By taking the α-pinene hydrogenation as a probe reaction, the effects of the preparation conditions on the catalytic properties were investigated. The suitable preparation conditions were as follows: TiO_2/NiCl_2·6H_2O mass ratio 3∶1, P/Ni molar ratio 2.5∶1, reaction temperature 25℃ and pH 11. Under these conditions, the catalyst showed excellent catalytic activity in the hydrogenation of α-pinene. The conversion of α-pinene,the enantioselective of cis-pinane and were 99.89%, 98.48% and 98.37%, respectively. And the catalyst could be reused for 8 times. XRD, BET, DSC, XPS and TEM were employed to investigate the structure difference of the catalysts before and after deactivation. The results showed that the fresh catalyst was spherical and well dispersed with uniform particle size of about 100 nm. The introduction of TiO2 effectively had improved the thermal stability of the Ni-P particles. The crystallization temperature increased by 78℃, 190℃ and 115.1℃. However, the deactivated catalysts exhibited deteriorated dispersion, and reduced content of Ni~0, which was considered as the main reasons for the deactivation.
Ni-P/TiO_2 amorphous catalyst was prepared by chemical reduction method. By taking the α-pinene hydrogenation as a probe reaction, the effects of the preparation conditions on the catalytic properties were investigated. The suitable preparation conditions were as follows: TiO_2/NiCl_2·6H_2O mass ratio 3∶1, P/Ni molar ratio 2.5∶1, reaction temperature 25℃ and pH 11. Under these conditions, the catalyst showed excellent catalytic activity in the hydrogenation of α-pinene. The conversion of α-pinene,the enantioselective of cis-pinane and were 99.89%, 98.48% and 98.37%, respectively. And the catalyst could be reused for 8 times. XRD, BET, DSC, XPS and TEM were employed to investigate the structure difference of the catalysts before and after deactivation. The results showed that the fresh catalyst was spherical and well dispersed with uniform particle size of about 100 nm. The introduction of TiO2 effectively had improved the thermal stability of the Ni-P particles. The crystallization temperature increased by 78℃, 190℃ and 115.1℃. However, the deactivated catalysts exhibited deteriorated dispersion, and reduced content of Ni~0, which was considered as the main reasons for the deactivation.
引文
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[10] WANG W Y, YANG Y Q, LUO H, et al. Preparation of Ni-W-B amorphous catalysts for cyclopentanone hydrodeoxygenation[J].Catalysis Communications, 2011, 12(14):1275-1279.
[11] LI H, LIU J, XIE S H, et al. Highly active Co-B amorphous alloy catalyst with uniform nanoparticles prepared in oil-in-water microemulsion[J]. Journal of Catalysis, 2008, 259(1):104-110.
[12] ZHANG M J, LI W Z, ZU S, et al. Catalytic hydrogenation for bio-oil upgrading by a supported NiMoB amorphous alloy[J]. Chemical Engineering&Technology, 2013, 36(12):2108-2116.
[13] WEI S, CUI H, WANG J, et al. Preparation and activity evaluation of NiMoB/γ-Al2O3catalyst by liquid-phase furfural hydrogenation[J].Particuology, 2011, 9(1):69-74.
[14] LI H, LI H, DAI W L, et al. XPS studies on surface electronic characteristicsofNi–BandNi–Pamorphousalloyanditscorrelationto their catalytic properties[J]. Applied Surface Science, 1999, 152(1/2):25-34.
[15] LEE S P, CHEN Y W. Nitrobenzene hydrogenation on Ni-P, Ni-B and Ni-P-B ultrafine materials[J]. Journal of Molecular Catalysis A:Chemical, 2000, 152(1/2):213-223.
[16]王秋霞,徐强,赵璧英,等. V2O5在载体表面的分散状态与表面酸性[J].催化学报, 1993, 14(6):437-442.WANG Q X, XU Q, ZHAO B Y, et al. Dispersion of V2O5on supports and consequent surface acidity[J]. Journal of Catalysis, 1993, 14(6):437-442.
[17] KOSH,CHOUTC,YANGTJ.Selectivehydrogenationof(-)-.alphaPinene over nickel catalysts prepared by electroless deposition[J].Industrial&Engineering Chemistry Research, 1995, 34(2):457-467.
[18]李凝,马庆丰,刘伟,等.负载型NiB非晶态合金上α-蒎烯催化加氢性能研究[J].精细化工,2010,27(11):1073-1077.LI N, MA Q F, LIU W, et al. Study on catalytical performance of supported NiB amorphous alloy on hydrogenation ofα-pinene[J]. Fine Chemicals,2010,27(11):1073-1077.
[19]程庆彦,李伟,吴隽,等. TiO2负载非晶态合金NiB催化剂的制备、表征及HDS动力学研究[J].燃料化学学报, 2000, 28(3):249-252.CHEN Q Y, LI W, WU J, et al. Study on preparation, characterization and HDS reaction kinetics of NiB amorphous alloy catalysts supported on TiO2[J]. Journal of Fuel Chemistry and Technology, 2000, 28(3):249-252.
[20] CHEN Y, JIANG L H, WANG H, et al. Process optimization for selective hydrogenation ofα-pinene over Ni/AlPO4[J]. Korean Journal of Chemical Engineering, 2018, 35(2):409-420.
[21]张家华,蒋丽红,伍水生,等.非晶态镍硼/石墨烯复合材料的制备及其蒎烯催化加氢活性[J].化工学报, 2016, 67(6):2363-2370.ZHANG J H, JIANG L H, WU S S, et al. Preparation of amorphous NiB/graphene composites for catalytic hydrogenation of pinene[J]. CIESC Journal, 2016, 67(6):2363-2370.
[22]潘登,王亚明,钟申洁,等.响应面法优化Ni-P/APO-11非晶态催化剂催化松节油加氢反应[J].化工学报, 2017, 68(6):2376-2385.PAN D, WANG Y M, ZHONG S H, et al. Optimization of Ni-P/APO-11 amorphous catalyst for catalytic hydrogenation of turpentine using response surface methodology[J]. CIESC Journal, 2017, 68(6):2376-2385.
[23]刘自力,秦祖赠,张健杰,等.非晶态Ni-Mo-P催化剂上硝基苯加氢为苯胺及催化剂失活机理[J].化工学报, 2012, 63(1):121-126.LIU Z L, QIN Z Z, ZHANG J J, et al, Hydrogenation of nitrobenzene to aniline on amorphous Ni-Mo-P catalyst and mechanism of catalyst deactivation[J]. CIESC Journal, 2012, 63(1):121-126.
[24]王威燕,杨运泉,罗和安,等. Co对非晶态催化剂Ni-Mo-B加氢脱氧性能的影响[J].化工学报, 2010, 61(1):73-79.WANG W Y, YANG Y Q, LUO H A, et al. Effect of Co on Ni-Mo-B amorphous catalyst in hydrodeoxygenation[J]. CIESC Journal, 2010, 61(1):73-79.
[25] SONG Hua, YU Hongkun, LIU Quanfu, et al. Advances in modification of Ni-B and Ni-P amorphous alloy catalysts[J]. Industrial catalysis, 2009,17(3):1-5.
[26] WANG L, LI W, ZHANG M, et al. The interactions between the NiB amorphous alloy and TiO2support in the NiB/TiO2amorphous catalysts[J]. Applied Catalysis A:General, 2004, 259(2):185-190.
[27] WANG M, LI F, ZHANG R. Study on catalytic hydrogenation properties and thermal stability of amorphous NiB alloy supported on carbon nanotubes[J]. Catalysis Today, 2004, 93:603-606.
[28] PARK J I, LEE J K, MIYAWAKI J, et al. Hydro-conversion of 1-methyl naphthalene into(alkyl)benzenes over alumina-coated USY zeolite-supported NiMoS catalysts[J]. Fuel, 2011, 90(1):182-189.
[29] BATTEZ A H, GONZáLEZ R, VIESCA J L, et al. Tribological behaviour of two imidazolium ionic liquids as lubricant additives for steel/steel contacts[J]. Wear, 2009, 266(11):1224-1228.
[30] REN S B, QIU J H, WANG C Y, et al. Influence of nickel salt precursors on the hydrogenation activity of Ni/Al2O3catalyst[J].Industrial Catalysis, 2007, 28(7):651-656.
[31]陈小鹏,王琳琳,阳承利,等.α-蒎烯催化加氢反应的研究[J].天然气化工:C1化学与化工, 2002, 27(6):55-58.CHEN X P, WANG L L, YANG C L, et al. Study on catalytic hydrogenation ofα-pinene[J]. Natural Gas Chemical Industry, 2002,27(6):55-58.
[32]谢晖,杨圣军,张志杰.纳米镍催化α-蒎烯加氢合成顺式蒎烷的研究[J].林产化学与工业, 2005, 25(4):56-58.XIE H, YANG S J, ZHANG Z J. Study on hydrogenation ofα-pinene to cis-pinane catalyzed by nanometer nickel[J]. Chemistry and Industry of Forest Products, 2005, 25(4):56-58.
[33]邢宏大,肖树德,张晓东.蒎烯合成香料二氢月桂烯醇及其甲酸酯[J].化学通讯, 1983, 9(1):21-27.XING H D, XIAO S D, ZHANG X D. Synthesis of perfume dihydromyrcenol and its formate from pinene[J]. Chemical Newsletter,1983, 9(1):21-27.
[34]郭慧青.废FCC触媒改性再生及其催化松节油单萜烯加氢反应研究[D].南宁:广西大学, 2015.GUO H Q. Study of the catalytic hydrogenation of turpentine monoterpene over the modified regeneration of spent fluid catalytic cracking catalyst[D]. Nanning:Guangxi University, 2015.
[2] ISHIDA T, ASAKAWA Y, TAKEMOTO T, et al. Terpenoids biotransformation in mammals III:biotransformation ofα-pinene,β-pinene, pinane, 3-carene, carane, myrcene, and p-cymene in rabbits[J]. Journal of Pharmaceutical Sciences, 1981, 70(4):406-415.
[3] SHELDON R A, DOWNING R S. Heterogeneous catalytic transformations for environmentally friendly production[J]. Applied Catalysis A:General, 1999, 189(2):163-183.
[4] DELLA P C, FALLETTA E, ROSSI M. Update on selective oxidation using gold[J]. Chemical Society Reviews, 2012, 41(1):350-369.
[5] JPSEPH P B. Preparation of 2,6-dimethyl-2,7-octadiene:US3277206[P]. 1966-10-04.
[6] IRINA L S, YULIA S, IRINA D. Modeling of kinetics and stereoselectivity in liquid-phaseα-pinene hydrogenation over Pd/C[J].Applied Catalysis A:General, 2009, 356(2):216-224.
[7] KO S H, CHOU T C. Kinetics of the liquid-phase hydrogenation of(-)-. alpha.-pinene over electrolessly deposited nickel-phosphorus/.gamma.-alumina catalyst[J]. Industrial&Engineering Chemistry Research, 1993, 32(8):1579-1587.
[8] REN S B, QIU J H, WANG C Y, et al. Dispersion state of nickel ions onγ-Al2O3and catalytic activity of derived nickel catalysts for hydrogenation ofα-pinene[J]. Chinese Journal of Inorganic Chemistry,2007, 23(6):1021-1028.
[9] LIU P, CHANG W T, LIANG X Y, et al. Small amorphous and crystalline Ni-P particles synthesized in glycol for catalytic hydrogenation of nitrobenzene[J]. Catalysis Communications, 2016, 76:42-45.
[10] WANG W Y, YANG Y Q, LUO H, et al. Preparation of Ni-W-B amorphous catalysts for cyclopentanone hydrodeoxygenation[J].Catalysis Communications, 2011, 12(14):1275-1279.
[11] LI H, LIU J, XIE S H, et al. Highly active Co-B amorphous alloy catalyst with uniform nanoparticles prepared in oil-in-water microemulsion[J]. Journal of Catalysis, 2008, 259(1):104-110.
[12] ZHANG M J, LI W Z, ZU S, et al. Catalytic hydrogenation for bio-oil upgrading by a supported NiMoB amorphous alloy[J]. Chemical Engineering&Technology, 2013, 36(12):2108-2116.
[13] WEI S, CUI H, WANG J, et al. Preparation and activity evaluation of NiMoB/γ-Al2O3catalyst by liquid-phase furfural hydrogenation[J].Particuology, 2011, 9(1):69-74.
[14] LI H, LI H, DAI W L, et al. XPS studies on surface electronic characteristicsofNi–BandNi–Pamorphousalloyanditscorrelationto their catalytic properties[J]. Applied Surface Science, 1999, 152(1/2):25-34.
[15] LEE S P, CHEN Y W. Nitrobenzene hydrogenation on Ni-P, Ni-B and Ni-P-B ultrafine materials[J]. Journal of Molecular Catalysis A:Chemical, 2000, 152(1/2):213-223.
[16]王秋霞,徐强,赵璧英,等. V2O5在载体表面的分散状态与表面酸性[J].催化学报, 1993, 14(6):437-442.WANG Q X, XU Q, ZHAO B Y, et al. Dispersion of V2O5on supports and consequent surface acidity[J]. Journal of Catalysis, 1993, 14(6):437-442.
[17] KOSH,CHOUTC,YANGTJ.Selectivehydrogenationof(-)-.alphaPinene over nickel catalysts prepared by electroless deposition[J].Industrial&Engineering Chemistry Research, 1995, 34(2):457-467.
[18]李凝,马庆丰,刘伟,等.负载型NiB非晶态合金上α-蒎烯催化加氢性能研究[J].精细化工,2010,27(11):1073-1077.LI N, MA Q F, LIU W, et al. Study on catalytical performance of supported NiB amorphous alloy on hydrogenation ofα-pinene[J]. Fine Chemicals,2010,27(11):1073-1077.
[19]程庆彦,李伟,吴隽,等. TiO2负载非晶态合金NiB催化剂的制备、表征及HDS动力学研究[J].燃料化学学报, 2000, 28(3):249-252.CHEN Q Y, LI W, WU J, et al. Study on preparation, characterization and HDS reaction kinetics of NiB amorphous alloy catalysts supported on TiO2[J]. Journal of Fuel Chemistry and Technology, 2000, 28(3):249-252.
[20] CHEN Y, JIANG L H, WANG H, et al. Process optimization for selective hydrogenation ofα-pinene over Ni/AlPO4[J]. Korean Journal of Chemical Engineering, 2018, 35(2):409-420.
[21]张家华,蒋丽红,伍水生,等.非晶态镍硼/石墨烯复合材料的制备及其蒎烯催化加氢活性[J].化工学报, 2016, 67(6):2363-2370.ZHANG J H, JIANG L H, WU S S, et al. Preparation of amorphous NiB/graphene composites for catalytic hydrogenation of pinene[J]. CIESC Journal, 2016, 67(6):2363-2370.
[22]潘登,王亚明,钟申洁,等.响应面法优化Ni-P/APO-11非晶态催化剂催化松节油加氢反应[J].化工学报, 2017, 68(6):2376-2385.PAN D, WANG Y M, ZHONG S H, et al. Optimization of Ni-P/APO-11 amorphous catalyst for catalytic hydrogenation of turpentine using response surface methodology[J]. CIESC Journal, 2017, 68(6):2376-2385.
[23]刘自力,秦祖赠,张健杰,等.非晶态Ni-Mo-P催化剂上硝基苯加氢为苯胺及催化剂失活机理[J].化工学报, 2012, 63(1):121-126.LIU Z L, QIN Z Z, ZHANG J J, et al, Hydrogenation of nitrobenzene to aniline on amorphous Ni-Mo-P catalyst and mechanism of catalyst deactivation[J]. CIESC Journal, 2012, 63(1):121-126.
[24]王威燕,杨运泉,罗和安,等. Co对非晶态催化剂Ni-Mo-B加氢脱氧性能的影响[J].化工学报, 2010, 61(1):73-79.WANG W Y, YANG Y Q, LUO H A, et al. Effect of Co on Ni-Mo-B amorphous catalyst in hydrodeoxygenation[J]. CIESC Journal, 2010, 61(1):73-79.
[25] SONG Hua, YU Hongkun, LIU Quanfu, et al. Advances in modification of Ni-B and Ni-P amorphous alloy catalysts[J]. Industrial catalysis, 2009,17(3):1-5.
[26] WANG L, LI W, ZHANG M, et al. The interactions between the NiB amorphous alloy and TiO2support in the NiB/TiO2amorphous catalysts[J]. Applied Catalysis A:General, 2004, 259(2):185-190.
[27] WANG M, LI F, ZHANG R. Study on catalytic hydrogenation properties and thermal stability of amorphous NiB alloy supported on carbon nanotubes[J]. Catalysis Today, 2004, 93:603-606.
[28] PARK J I, LEE J K, MIYAWAKI J, et al. Hydro-conversion of 1-methyl naphthalene into(alkyl)benzenes over alumina-coated USY zeolite-supported NiMoS catalysts[J]. Fuel, 2011, 90(1):182-189.
[29] BATTEZ A H, GONZáLEZ R, VIESCA J L, et al. Tribological behaviour of two imidazolium ionic liquids as lubricant additives for steel/steel contacts[J]. Wear, 2009, 266(11):1224-1228.
[30] REN S B, QIU J H, WANG C Y, et al. Influence of nickel salt precursors on the hydrogenation activity of Ni/Al2O3catalyst[J].Industrial Catalysis, 2007, 28(7):651-656.
[31]陈小鹏,王琳琳,阳承利,等.α-蒎烯催化加氢反应的研究[J].天然气化工:C1化学与化工, 2002, 27(6):55-58.CHEN X P, WANG L L, YANG C L, et al. Study on catalytic hydrogenation ofα-pinene[J]. Natural Gas Chemical Industry, 2002,27(6):55-58.
[32]谢晖,杨圣军,张志杰.纳米镍催化α-蒎烯加氢合成顺式蒎烷的研究[J].林产化学与工业, 2005, 25(4):56-58.XIE H, YANG S J, ZHANG Z J. Study on hydrogenation ofα-pinene to cis-pinane catalyzed by nanometer nickel[J]. Chemistry and Industry of Forest Products, 2005, 25(4):56-58.
[33]邢宏大,肖树德,张晓东.蒎烯合成香料二氢月桂烯醇及其甲酸酯[J].化学通讯, 1983, 9(1):21-27.XING H D, XIAO S D, ZHANG X D. Synthesis of perfume dihydromyrcenol and its formate from pinene[J]. Chemical Newsletter,1983, 9(1):21-27.
[34]郭慧青.废FCC触媒改性再生及其催化松节油单萜烯加氢反应研究[D].南宁:广西大学, 2015.GUO H Q. Study of the catalytic hydrogenation of turpentine monoterpene over the modified regeneration of spent fluid catalytic cracking catalyst[D]. Nanning:Guangxi University, 2015.
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