兼具加氢和脱硫活性的富含Ni^(δ+)非晶态NiP@γ-Al_(2)O_(3)催化剂的构筑及其用于石油树脂加氢的性能研究  

Construction of amorphous NiP@γ-Al_(2)O_(3)catalyst rich in Ni^(δ+)for petroleum resin hydrogenation with enhanced hydrogenation and desulfurization activity

作　　者：胡德政 王榕[1] 王世栋 杨文菲 张宏伟 袁珮 HU Dezheng;WANG Rong;WANG Shidong;YANG Wenfei;ZHANG Hongwei;YUAN Pei(College of Chemical Engineering,Fuzhou University,Fuzhou 350116,Fujian,China;Qingyuan Innovation Laboratory,Quanzhou 362801,Fujian,China)

机构地区：[1]福州大学化工学院,福建福州350116 [2]福建省清源创新实验室,福建泉州362801

出　　处：《化工学报》2024年第9期3152-3162,共11页CIESC Journal

基　　金：国家自然科学基金项目(22078064,22378062);福建省自然科学基金项目(2021J02009,2021J05137);福建省清源创新实验室项目(00121002)。

摘　　要：C_(9)石油树脂(C9PR)是由乙烯裂解副产物C_(9)馏分聚合而成的热塑性树脂,经加氢改性后可以制得色度浅、抗氧化稳定性高、相容性好的高附加值氢化石油树脂(HC9PR)。但C9PR分子量大、空间位阻高且原料中含有硫化物等杂质易使催化剂中毒失活,因此加氢难度极大。为了同时实现C9PR的加氢和脱杂,采用化学还原法结合球磨法制备了非晶态NiP@γ-Al_(2)O_(3)催化剂。表征结果显示,该催化剂具有较大的比表面积、富含Ni^(δ+)活性物种、较多的活性位数量,并对C==C键具有较强的吸附能力。对其进行C9PR加氢性能评价,结果显示非晶态Ni P@γ-Al_(2)O_(3)催化剂表现出优异的加氢活性(加氢度98.35%)和脱硫活性(硫含量从122.80μg/g降低至8.00μg/g),明显优于利用程序升温还原法结合球磨法制备的不同晶型磷化镍催化剂。此外,经过连续100 h的反应,该催化剂仍能保持较高的加氢度,表明其具有良好的稳定性。C_(9) petroleum resin(C9PR)is a thermoplastic resin polymerized from the C_(9) fraction of ethylene cracking byproduct.After hydrogenation modification,it can be used to obtain high-value-added hydrogenated petroleum resin(HC9PR)with light color,high antioxidant stability and good compatibility.However,C9PR has high molecular weight,high steric hindrance and impurities such as sulfide in the raw materials which are easy to poison and deactivate the catalyst,making hydrogenation extremely difficult.Herein,in order to achieve simultaneous hydrogenation and desulfurization of C9PR,we have successfully prepared the amorphous NiP@γ-Al_(2)O_(3)catalyst by using chemical reduction method combined with ball milling method.The results showed that the catalyst has large specific surface area,high-content Ni^(δ+)active species,high number of active sites and strong adsorption capacity for C==C bond.The obtained amorphous NiP@γ-Al_(2)O_(3)catalyst showed an enhanced hydrogenation activity(hydrogenation degree of 98.35%)and desulfurization activity(sulfur content reduced from 122.80μg/g to 8.00μg/g)for C9PR hydrogenation,which is obviously superior to different crystalline nickel phosphide catalysts(the nickel phosphide was prepared by temperature programmed reduction method and loaded onγ-alumina carrier by ball milling).In addition,the amorphous NiP@γ-Al_(2)O_(3)catalyst exhibited high hydrogenation degree after 100 h of continuous reaction,indicating that the catalyst had good stability.

关 键 词：石油树脂 非晶态磷化镍 加氢 脱硫 球磨法 

分 类 号：TQ326.8[化学工程—合成树脂塑料工业]