Ni-P/TiO2非晶态催化剂对α-蒎烯加氢的性能

doi:10.16085/j.issn.1000-6613.2018-1684

摘要/Abstract

摘要：

采用化学还原法制备Ni-P/TiO₂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NiCl₂?6H₂O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。

关键词: 非晶态催化剂, Ni-P/TiO₂, α-蒎烯, 加氢, 选择性, 失活

Abstract:

Ni-P/TiO₂ 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: TiO₂/NiCl₂?6H₂O 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 100nm. 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 Ni⁰, which was considered as the main reasons for the deactivation.

Key words: amorphous catalyst, Ni-P/TiO₂, α-pinene, hydrogenation, selectivity, deactivation

中图分类号:

TQ333

蒋丽红, 宋爽爽, 潘登, 王亚明, 刘坤, 郑燕娥. Ni-P/TiO₂非晶态催化剂对α-蒎烯加氢的性能[J]. 化工进展, 2019, 38(06): 2768-2775.

Lihong JIANG, Shuangshuang SONG, Deng PAN, Yaming WANG, Kun LIU, Yan’e ZHENG. Study on the properties of amorphous catalyst Ni-P/TiO₂ for hydrogenation of α-pinene[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2768-2775.

图/表 10

参考文献 34

1	王琳琳, 徐徐, 陈小鹏, 等 . 松节油催化异构-分子间氢转移反应的研究[J]. 高校化学工程学报, 2008, 22(5): 809-815.
	WANG L L , XU X , CHEN X P , et al . Catalytic isomerization-intermolecular hydrogen transfer of turpentine[J]. Journal of Chemical Engineering of Chinese Universities, 2008, 22(5): 809-815.
2	ISHIDA T , ASAKAWA Y , TAKEMOTO T , et al . Terpenoids biotransformation in mammals III: biotransformation of α-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-phase α-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 on γ-Al₂O₃ and catalytic activity of derived nickel catalysts for hydrogenation of α-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-Al₂O₃ catalyst 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 characteristics of Ni–B and Ni–P amorphous alloy and its correlation to 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 V₂O₅ on supports and consequent surface acidity[J]. Journal of Catalysis, 1993, 14(6):437-442.
17	KO S H, CHOU T C , YANG T J . Selective hydrogenation of (-)-. alpha-Pinene 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 of α-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 of α-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 Ni-B/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 , al et , 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/TiO₂ amorphous 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/Al₂O₃ catalyst[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 of α-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 of α-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.

催化剂	S _BET/m²·g^-1	转化率/%	选择性/%
TiO₂	34	—	—
Ni-P	21	81%	94%
Ni-P/TiO₂	29	99%	98%

催化剂	S _BET/m²·g^-1	转化率/%	选择性/%
TiO₂	34	—	—
Ni-P	21	81%	94%
Ni-P/TiO₂	29	99%	98%

样品	原子量/%
样品	Ni	P	其他
新鲜催化剂	18.80	5.79	75.41
失活催化剂	4.25	5.53	90.22

样品	原子量/%
样品	Ni	P	其他
新鲜催化剂	18.80	5.79	75.41
失活催化剂	4.25	5.53	90.22

序号	催化剂	反应条件	活性			参考文献
序号	催化剂	反应条件	转化率/%		选择性/%	参考文献
1	Ni-P/TiO₂	130℃, 4MPa, 4h	99.0	98.0		本研究
2	Ni/γ-A1₂O₃	170℃, 0.1MPa, 6.5h	97.7	83.1		[30]
3	Raney Ni	160℃, 6MPa,4h	98.2	92.7		[31]
4	纳米镍	90℃,4MPa, 1.5h	100.0	94.3		[32]
5	氧化铝、丝光沸石、金属镍沸石分子筛催化剂	180~230℃, 2.0MPa, 连续140h	95.0	75.0		[33]
6	Ni/FCC催化剂	120℃, 3MPa,2h	99.4	94.41		[34]

Ni-P/TiO₂非晶态催化剂对α-蒎烯加氢的性能

Study on the properties of amorphous catalyst Ni-P/TiO₂ for hydrogenation of α-pinene

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价

[1]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[2]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[3]	李化全, 王明华, 邱贵宝. 硫酸酸解钙钛矿相精矿的行为[J]. 化工进展, 2023, 42(S1): 536-541.
[4]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[5]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[6]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[7]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[8]	毛善俊, 王哲, 王勇. 基团辨识加氢：从概念到应用[J]. 化工进展, 2023, 42(8): 3917-3922.
[9]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[10]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[11]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[12]	王兰江, 梁瑜, 汤琼, 唐明兴, 李学宽, 刘雷, 董晋湘. 快速热解铂前体合成高分散的Pt/HY催化剂及其萘深度加氢性能[J]. 化工进展, 2023, 42(8): 4159-4166.
[13]	王晓晗, 周亚松, 于志庆, 魏强, 孙劲晓, 姜鹏. 不同晶粒尺寸Y分子筛的合成及其加氢裂化反应性能[J]. 化工进展, 2023, 42(8): 4283-4295.
[14]	李佳, 樊星, 陈莉, 李坚. 硝酸生产尾气中NO _x 和N₂O联合脱除技术研究进展[J]. 化工进展, 2023, 42(7): 3770-3779.
[15]	汪嘉欣, 潘勇, 熊欣怡, 万晓月, 王建超. 甲苯一步催化硝化制备二硝基甲苯反应过程及危险性[J]. 化工进展, 2023, 42(7): 3420-3430.