金属/炭复合材料制备及羰基硫催化转化研究
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摘要
整体煤气化联合发电(IGCC)技术由于高效率、低污染特点成为当前最有前景的洁净燃煤发电技术之一,其中煤气脱硫净化是关键环节。煤气中含硫化合物主要是无机硫H_2S(90%以上)和有机硫COS、CS_2和极少量的硫醇、噻吩等,前者通过金属氧化物可以实现精脱除,而有机硫脱除还面临困难,致使总硫脱除率不高,难以达到工艺过程对脱硫精度的要求。因此煤气化过程中有机硫(COS)的脱除成了当今关注的热点。加氢转化法脱除有机硫精度高、操作简单,而且可以直接利用煤气中的H_2而无需外加气源,是加氢脱除煤气中COS最适宜方法。
过渡金属镍、钼是很好的加氢脱除有机硫活性组分,载体多用γ-Al_2O_3,但是γ-Al_2O_3与金属氧化物间作用力强,易形成Al-O-M相,使预硫化不完全,从而降低COS催化转化率,以活性炭做载体便能克服以上缺陷,目前炭基Ni/Mo催化剂用于加氢脱除COS的报道较少。传统催化剂通常采用浸渍金属盐溶液、干燥、高温焙烧和预硫化处理得到。该法制备的催化剂一方面并不能得到人们想要的金属活性组分高度分散的催化剂;另一方面预硫化程序操作复杂、反应条件苛刻、能耗大,而且预硫化不一定完全。基于存在的这三方面问题,本文从两方面开展:
(1)利用成本低廉的水溶性酚醛树脂为炭原料,水溶性金属盐类为催化剂前驱体,采用前驱体均相混合法制备不同金属种类和不同担载量的Mo/酚醛树脂基活性炭,标记为(M/PAC),并将其应用于COS的加氢催化转化研究,主要解决传统催化剂中载体和金属分散性的问题;
(2)选择商业椰壳活性炭为载体,采用自制硫化态前驱体四硫代钼酸铵(ATTM)和硝酸镍溶液对活性炭进行等体积浸渍改性,焙烧后得到催化剂,标记为(M/AC),并将其应用于COS的加氢催化转化研究,解决载体和预硫化操作过程中存在的一系列问题。
研究结果表明,MoS_2是主要的活性组分,硫化镍主要是促进Mo在活性炭载体表面的分散,并使Ni-Mo复合基催化剂生成更多的活性中心;实验所选条件下,担载Mo和Ni-Mo的催化剂对COS都有很高的转化率;在反应过程中,M/AC催化剂最佳反应温度范围在200℃-300℃,M/PAC最佳反应温度为240℃-300℃;M/AC催化剂对COS的脱除中既存在吸附又存在转化,而M/PAC催化剂是单纯转化过程;由于催化剂活性组分是硫化物,因此有失硫现象发生,但M/AC的失硫时间比M/PAC要长,反应稳定后,前者对COS的转化率比后者高。
The removal of sulfur specises is crucial in Integrated Gasification Combined Cycle (IGCC) technology which is regarded to be the most promising technology due to the high efficiency and low pollution features. The sulfur-containing compounds in the coal gas include mainly hydrogen sulfide and organic sulfur, such as carbonyl sulfides, carbon bisulfide and neglectable thiol, thiophene. Hydrogen sulfide can be removed successfully using metal oxide. However, organic sulfur removal is not so easy, which is difficult to reach the requirements of fine desulfurization. Therefore, the removal of organic sulfur (COS) in hot coal gas become an important topic today. Hydrodesulfurization is thought of the most appropriate method on removal of carbonyl sulfide because it not only has high desulfurization precision, simple operation, but also H_2 in the gas can be used directly without additional gas source.
Transition metal nickel and molybdenum are both effective active components for carbonyl sulfide hydrodesulfurization reaction andγ-Al_2O_3 exclusively act as carrier. Because there is strong intercation betweenγ-Al_2O_3 and metal oxides, it is easy to form Al-O-Mo phase which is not propitious to presulfurize and. reduces the conversion of COS. This problem can be solved using activated carbon as carrier. However, the reports on research for catalytic conversion of carbonyl sulfides using (Ni)Mo/AC catalysts are few. Furthermore, traditional catalysts are prepared by incipient-wetness impregnation, dryness, calcined and presulfuration treatment using metal salts solution as modifiers. The catalysts using impregnation method have two aspects weakness. On one hand, the metal active component in the catalysts cannot be highly dispersed. On the other hand, presulfuration process is complicated to operate due to harsh conditions and energy-consuming. Moreover, the active components may not become entirely metal sulfide. The present work has been conducted focusing on three aspect problems refered.
(1) Phenolic resin-based activated carbon desulfurized (M/PAC) containing the different kinds of metal and Mo with different loading are prepared using the mixture of low-cost water-soluble phenolic resin and metal salts as precursors and applied to the COS hydrogenation catalytic reaction to solve the problems of carrier and metal dispersing;
(2) MAC desulfurizers are prepared by incipient-wetness impregnation method using ammonium tetrathiomolybdate (ATTM) as modifiers and commercial coconut shell activated carbon as catalyst carrier and applied to hydro-conversion behaviors study of carbonyl sulfide (COS) in hot coal gas to figure out the problems of carriers and presulfuration.
The results show that M0S2 is the main active component. Ni sulfide specises are mainly responsible for better dispersion of Mo specises on actived carbon surface, as a result, more active centres can be formed. The catalysts with Mo and Ni-Mo both have high removal ability to COS under the experiment conditions. During reaction process, the optimal reaction temperature for M/AC and M/PAC is in the range of 200°C-300°C and 240°C-300°C, respectively. The removal of the COS includes both absorption and hydro-conversion courses using M/AC catalysts, whereas the catalytic conversion of COS is exclusively responsible for the removal of COS in M/PAC. Metal sulfide serves as active components in these catalysts, therefore both of them suffer from sulfur loss with low sulfur species in the gas system during reaction process. However, the sulfur loss time of M/AC catalysts is longer than that of M/PAC. The results also show COS conversion rate of M/AC is higher than that of M/PAC when the reaction approaches the state of equilibrium.
过渡金属镍、钼是很好的加氢脱除有机硫活性组分,载体多用γ-Al_2O_3,但是γ-Al_2O_3与金属氧化物间作用力强,易形成Al-O-M相,使预硫化不完全,从而降低COS催化转化率,以活性炭做载体便能克服以上缺陷,目前炭基Ni/Mo催化剂用于加氢脱除COS的报道较少。传统催化剂通常采用浸渍金属盐溶液、干燥、高温焙烧和预硫化处理得到。该法制备的催化剂一方面并不能得到人们想要的金属活性组分高度分散的催化剂;另一方面预硫化程序操作复杂、反应条件苛刻、能耗大,而且预硫化不一定完全。基于存在的这三方面问题,本文从两方面开展:
(1)利用成本低廉的水溶性酚醛树脂为炭原料,水溶性金属盐类为催化剂前驱体,采用前驱体均相混合法制备不同金属种类和不同担载量的Mo/酚醛树脂基活性炭,标记为(M/PAC),并将其应用于COS的加氢催化转化研究,主要解决传统催化剂中载体和金属分散性的问题;
(2)选择商业椰壳活性炭为载体,采用自制硫化态前驱体四硫代钼酸铵(ATTM)和硝酸镍溶液对活性炭进行等体积浸渍改性,焙烧后得到催化剂,标记为(M/AC),并将其应用于COS的加氢催化转化研究,解决载体和预硫化操作过程中存在的一系列问题。
研究结果表明,MoS_2是主要的活性组分,硫化镍主要是促进Mo在活性炭载体表面的分散,并使Ni-Mo复合基催化剂生成更多的活性中心;实验所选条件下,担载Mo和Ni-Mo的催化剂对COS都有很高的转化率;在反应过程中,M/AC催化剂最佳反应温度范围在200℃-300℃,M/PAC最佳反应温度为240℃-300℃;M/AC催化剂对COS的脱除中既存在吸附又存在转化,而M/PAC催化剂是单纯转化过程;由于催化剂活性组分是硫化物,因此有失硫现象发生,但M/AC的失硫时间比M/PAC要长,反应稳定后,前者对COS的转化率比后者高。
The removal of sulfur specises is crucial in Integrated Gasification Combined Cycle (IGCC) technology which is regarded to be the most promising technology due to the high efficiency and low pollution features. The sulfur-containing compounds in the coal gas include mainly hydrogen sulfide and organic sulfur, such as carbonyl sulfides, carbon bisulfide and neglectable thiol, thiophene. Hydrogen sulfide can be removed successfully using metal oxide. However, organic sulfur removal is not so easy, which is difficult to reach the requirements of fine desulfurization. Therefore, the removal of organic sulfur (COS) in hot coal gas become an important topic today. Hydrodesulfurization is thought of the most appropriate method on removal of carbonyl sulfide because it not only has high desulfurization precision, simple operation, but also H_2 in the gas can be used directly without additional gas source.
Transition metal nickel and molybdenum are both effective active components for carbonyl sulfide hydrodesulfurization reaction andγ-Al_2O_3 exclusively act as carrier. Because there is strong intercation betweenγ-Al_2O_3 and metal oxides, it is easy to form Al-O-Mo phase which is not propitious to presulfurize and. reduces the conversion of COS. This problem can be solved using activated carbon as carrier. However, the reports on research for catalytic conversion of carbonyl sulfides using (Ni)Mo/AC catalysts are few. Furthermore, traditional catalysts are prepared by incipient-wetness impregnation, dryness, calcined and presulfuration treatment using metal salts solution as modifiers. The catalysts using impregnation method have two aspects weakness. On one hand, the metal active component in the catalysts cannot be highly dispersed. On the other hand, presulfuration process is complicated to operate due to harsh conditions and energy-consuming. Moreover, the active components may not become entirely metal sulfide. The present work has been conducted focusing on three aspect problems refered.
(1) Phenolic resin-based activated carbon desulfurized (M/PAC) containing the different kinds of metal and Mo with different loading are prepared using the mixture of low-cost water-soluble phenolic resin and metal salts as precursors and applied to the COS hydrogenation catalytic reaction to solve the problems of carrier and metal dispersing;
(2) MAC desulfurizers are prepared by incipient-wetness impregnation method using ammonium tetrathiomolybdate (ATTM) as modifiers and commercial coconut shell activated carbon as catalyst carrier and applied to hydro-conversion behaviors study of carbonyl sulfide (COS) in hot coal gas to figure out the problems of carriers and presulfuration.
The results show that M0S2 is the main active component. Ni sulfide specises are mainly responsible for better dispersion of Mo specises on actived carbon surface, as a result, more active centres can be formed. The catalysts with Mo and Ni-Mo both have high removal ability to COS under the experiment conditions. During reaction process, the optimal reaction temperature for M/AC and M/PAC is in the range of 200°C-300°C and 240°C-300°C, respectively. The removal of the COS includes both absorption and hydro-conversion courses using M/AC catalysts, whereas the catalytic conversion of COS is exclusively responsible for the removal of COS in M/PAC. Metal sulfide serves as active components in these catalysts, therefore both of them suffer from sulfur loss with low sulfur species in the gas system during reaction process. However, the sulfur loss time of M/AC catalysts is longer than that of M/PAC. The results also show COS conversion rate of M/AC is higher than that of M/PAC when the reaction approaches the state of equilibrium.
引文
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