分子筛纳米簇改性的NiMoW柴油加氢催化剂的制备与评价
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摘要
本论文在无碱体系中,制备出含有ZSM-5分子筛次级结构单元(或纳米簇)的溶液,系统考察了制备方法、制备温度、硅铝比、晶化温度、晶化时间等条件对分子筛纳米簇物化性质的影响;采用XRD、IR等手段对所制备的纳米簇进行表征。结果表明,在一定条件下合成的前驱体溶液中确实含有ZSM-5分子筛次级结构单元,且没有分子筛晶粒生成。
本论文利用其对γ-Al2O3载体进行表面改性,分别考察不同制备条件的纳米簇以及不同的改性手段对氧化铝物化性质的影响。其中纳米簇制备,主要考察了晶化温度、晶化时间、硅铝比等因素的影响;改性方法,主要考察了室温浸渍、超声波分散、高温晶化、稀释法浸渍、机械混合等的影响,采用XRD、IR、Py-IR、NH3-TPD、BET等手段对样品进行表征。结果表明,经过表面改性后,分子筛纳米簇均匀分布于氧化铝载体表面,并没有形成晶粒;改性载体酸性明显增强,且有B酸性位出现,但孔结构与比表面积没有明显的变化。
以分子筛纳米簇改性后的氧化铝作为载体,制备负载型Ni-Mo-W加氢催化剂,以4,6-DMDBT作为模型化合物,利用高压微反对催化剂的HDS活性进行评价,并利用气相色谱与质谱对脱硫反应产物进行定性与定量分析。其结果表明,与传统氧化铝为载体的催化剂相比,纳米簇改性后所制备的催化剂具有较高的活性,其对4,6-DMDBT的转化率提高了52.4个百分点,同时提高了对4H-4,6-DMDBT及6H-4,6-DMDBT等部分加氢产物的脱硫活性,使得脱硫率/转化率有明显的提高。表明改性后载体由于具有较强的酸性,可以促进C-S键的断裂,同时由于金属组分与载体之间的相互作用减弱,活性相的堆垛数增加,使其加氢/氢解比例增大。
In this paper, the precursor solution containing the ZSM-5 secondary structural unit(or zeolite nanocluster)was firstly synthesized in the system without alkali metal. The influences of the preparation methods, crystallizing time, crystallizing temperature and the ratio of Si/Al on properties of zeolite nanoclusters were studied. The results of XRD and IR indicated that the zeolite nanoclusters did exist in the precursor solution but the zeolite crystalline particles didn’t exist.
The effects of nanoclusters prepared at different conditions and the modify methods on the acidity ofγ-Al2O3 were investigated. The modification methods of room temperature impregnation, ultra-audible sound assistanted dispersion , crystallizing at high temperature, dilution method impregnation, mechanically blending were examinated. The characterization results of XRD, IR, Py-IR and TPD indicated that some Br?nsted acid sites formated on the surface ofγ-Al2O3 where ZSM-5 nanoclustes dispersed, and at the same time the ZSM-5 minicrystal particles didn’t form. The acidity of modified support rised remarkably but the changes of pore diameter and BET surface were unconspicuous.
The Ni-Mo-W hydrodesulfurization catalysts were prepared with the modifiedγ-Al2O3 as support. Then the performances of HDS were evaluated in high pressure micro-reactor with 4,6-DMDBT as model compound, and the products of reaction were analyzed qualitatively and quantitatively using the GC and MS. Compared to the traditional HDS catalyst supported on theγ-Al2O3, the novel catalyst supported on the carrier modified with zeolite nanocluster presented higher conversion and desulfurization of 4,6-DMDBT. The conversion ratio of 4,6-DMDBT rised by 52.4 percentages,and meanwhile the removal ratio of partly hydrogenation sulfcompounds increased. The results revealed that the catalyst supported on modifiedγ-Al2O3 had higher HYD/DDS ratio, wich attributed to the catalyst’s stronger acidity and metal compound’s higher stacking number originated from the weaker interaction between metal compound and carrier.
本论文利用其对γ-Al2O3载体进行表面改性,分别考察不同制备条件的纳米簇以及不同的改性手段对氧化铝物化性质的影响。其中纳米簇制备,主要考察了晶化温度、晶化时间、硅铝比等因素的影响;改性方法,主要考察了室温浸渍、超声波分散、高温晶化、稀释法浸渍、机械混合等的影响,采用XRD、IR、Py-IR、NH3-TPD、BET等手段对样品进行表征。结果表明,经过表面改性后,分子筛纳米簇均匀分布于氧化铝载体表面,并没有形成晶粒;改性载体酸性明显增强,且有B酸性位出现,但孔结构与比表面积没有明显的变化。
以分子筛纳米簇改性后的氧化铝作为载体,制备负载型Ni-Mo-W加氢催化剂,以4,6-DMDBT作为模型化合物,利用高压微反对催化剂的HDS活性进行评价,并利用气相色谱与质谱对脱硫反应产物进行定性与定量分析。其结果表明,与传统氧化铝为载体的催化剂相比,纳米簇改性后所制备的催化剂具有较高的活性,其对4,6-DMDBT的转化率提高了52.4个百分点,同时提高了对4H-4,6-DMDBT及6H-4,6-DMDBT等部分加氢产物的脱硫活性,使得脱硫率/转化率有明显的提高。表明改性后载体由于具有较强的酸性,可以促进C-S键的断裂,同时由于金属组分与载体之间的相互作用减弱,活性相的堆垛数增加,使其加氢/氢解比例增大。
In this paper, the precursor solution containing the ZSM-5 secondary structural unit(or zeolite nanocluster)was firstly synthesized in the system without alkali metal. The influences of the preparation methods, crystallizing time, crystallizing temperature and the ratio of Si/Al on properties of zeolite nanoclusters were studied. The results of XRD and IR indicated that the zeolite nanoclusters did exist in the precursor solution but the zeolite crystalline particles didn’t exist.
The effects of nanoclusters prepared at different conditions and the modify methods on the acidity ofγ-Al2O3 were investigated. The modification methods of room temperature impregnation, ultra-audible sound assistanted dispersion , crystallizing at high temperature, dilution method impregnation, mechanically blending were examinated. The characterization results of XRD, IR, Py-IR and TPD indicated that some Br?nsted acid sites formated on the surface ofγ-Al2O3 where ZSM-5 nanoclustes dispersed, and at the same time the ZSM-5 minicrystal particles didn’t form. The acidity of modified support rised remarkably but the changes of pore diameter and BET surface were unconspicuous.
The Ni-Mo-W hydrodesulfurization catalysts were prepared with the modifiedγ-Al2O3 as support. Then the performances of HDS were evaluated in high pressure micro-reactor with 4,6-DMDBT as model compound, and the products of reaction were analyzed qualitatively and quantitatively using the GC and MS. Compared to the traditional HDS catalyst supported on theγ-Al2O3, the novel catalyst supported on the carrier modified with zeolite nanocluster presented higher conversion and desulfurization of 4,6-DMDBT. The conversion ratio of 4,6-DMDBT rised by 52.4 percentages,and meanwhile the removal ratio of partly hydrogenation sulfcompounds increased. The results revealed that the catalyst supported on modifiedγ-Al2O3 had higher HYD/DDS ratio, wich attributed to the catalyst’s stronger acidity and metal compound’s higher stacking number originated from the weaker interaction between metal compound and carrier.
引文
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[3]王倩.氮化物、H2S和芳烃对深度加氢脱硫的影响.石化技术与应用,2004,24(1): 60-64
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[5] Ma XL, Sun L, Song C Sh. A new approach to deep desulfurization of gasoline ,diesel fuel and jet fuel by selective ad-sorption for ultra - clean fuels and for fuel cell. Applications Catalysis Today, 2002 , 77: 107-116
[6] Mille V, Schulz E, Variant M, Loamier M. A new route towards deep desulphurization: selective charge transfer complex formation J. Chemical Communication , 1998(12): 305-306
[7]赵延飞,晏乃强,吴旦,等.石油的非加氢脱硫技术研究进展(J).石油与天然气化工, 1998(33): 305-311
[8]王雪松,钟雄辉,王志良,等.柴油加氢脱硫催化剂的研究进展.当代化工2006 , 35(3): 198-201
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[10]万国赋,段爱军,赵震,等.柴油超深度脱硫技术进展.黑龙江大学自然科学学报,2006,10(12): 30-32
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