锌钴钼复合脱硫剂中温脱硫与加氢催化耦合  

Coupling of medium temperature desulfurization and hydrogenation catalysis of Zinc-Cobalt-Molybdenum composite desulfurizer

作　　者：宋昕芮 赵玉 王玉晓 苏哲林 寇佳伟 杨超 樊惠玲[2] SONG Xinrui;ZHAO Yu;WANG Yuxiao;SU Zhelin;KOU Jiawei;YANG Chao;FAN Huiling(College of Chemistry,Taiyuan University of Technology,Taiyuan 030024,China;College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,China;College of Environmental Science and Engineering,Taiyuan University of Technology,Taiyuan 030024,China)

机构地区：[1]太原理工大学化学学院,山西太原030024 [2]太原理工大学化学工程与技术学院,山西太原030024 [3]太原理工大学环境科学与工程学院,山西太原030024

出　　处：《煤炭学报》2025年第3期1760-1768,共9页Journal of China Coal Society

基　　金：国家自然科学基金资助项目(22078223)。

摘　　要：在当前的工业脱硫领域,处理脱硫剂产生的固废正面临巨大的挑战。为了缓解这一压力,实现固废资源化再利用已成为一项亟待解决的研究课题。为了更好地应对这一挑战,研究者们正致力于改进和优化脱硫剂。其中,钼元素因其独特的理化性质受到了广泛关注。采用溶胶凝胶法制备了钼改性的锌钴复合脱硫剂,以期提高其脱硫性能以及硫化后对噻吩的加氢催化性能。通过XRD、XPS和氮气吸附/脱附等表征手段分析了新鲜脱硫剂和硫化样的物相组成和结构并与其脱硫和加氢性能相关联。结果表明:钼物种通过影响比表面积、物相组成以及形成特定活性相前驱体等方式,增强了锌钴脱硫剂的脱硫及后续加氢性能。钼物种的引入与钴相互作用形成了与H_(2)S更具反应性的CoMoO_(4)物种,同时该物种也是CoMoS活性相的前驱体,这将对脱硫及后续加氢性能产生积极影响。此外钼改性提高了脱硫剂的比表面积,有利于活性位点的暴露,从而提高脱硫性能。在350℃的条件下,钼物质的量分数为20%的锌钴钼复合脱硫剂穿透硫容为223.6mg/g。钼改性后MoS_(2)和CoMoS活性相的形成是加氢活性提高的关键。当温度为250℃、压力为0.1MPa、C_(4)H_(4)S质量浓度为(150±10)mg/m^(3)、H_(2)的体积分数为10%和体积空速为7800h-1的条件下,钼物质的量分数为20%的加氢活性是未改性的2.46倍,这表明钼改性显著提高了加氢脱硫性能。通过钼改性使脱硫剂的脱硫能力提高,同时使其硫化产物可作为噻吩加氢的高效催化剂,实现脱硫和加氢过程耦合,为废脱硫剂的再利用提供了新的途径。In the current field of industrial desulphurization,the treatment of solid waste generated by desulphurization agents is facing great challenges.In order to alleviate this pressure,the realization of solid waste resource reuse has be-come an urgent research topic.In order to better meet this challenge,researchers are working on improving and optimiz-ing desulfurizers.Among them,molybdenum has been widely concerned because of its unique physical and chemical properties.Molybdenum modified Zinc-Cobalt compound desulfurizer was prepared by sol-gel method in order to im-prove its desulfurization performance and hydrogenation catalytic performance for thiophene after vulcanization.The phase composition and structure of the fresh desulfurizer and vulcanized sample were analyzed by XRD,XPS and nitro-gen adsorption/desorption,and correlated with their desulfurization and hydrogenation properties.The results showed that molybdenum species enhanced the desulfurization and subsequent hydrogenation performance of Zinc-Cobalt desulfurizer by influencing the specific surface area,phase composition and forming specific active phase precursor.The introduction of molybdenum species interacts with cobalt to form CoMoO_(4) species,which is more reactive to H_(2)S,and is also a pre-cursor of CoMoS active phase,which will have a positive impact on desulfurization and subsequent hydrogenation per-formance.In addition,molybdenum modification improves the specific surface area of the desulfurizer,which is condu-cive to the exposure of the active site,thus improving the desulfurization performance.Under a condition of 350℃,the zinc-cobalt-molybdenum composite desulfurizer with a molybdenum molar fraction of 20%exhibits a breakthrough sulfur capacity of 223.6 mg/g.The formation of active phases of MoS_(2) and CoMoS after molybdenum modification is the key to the improvement of hydrogenation activity.Under the conditions of 250℃,0.1 MPa pressure,C_(4)H_(4)S mass concentration of(150±10)mg/m^(3),H_(2) volume fraction of 10%,and a space

关 键 词：钼改性 锌钴钼复合脱硫剂 硫化氢 中温脱硫 噻吩 加氢脱硫 

分 类 号：TQ546.6[化学工程—煤化学工程]