超临界水浸渍法制备炭基负载金属氧化物中温脱硫用吸附剂的研究
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摘要
以煤气化为基础的煤基多联产将能源转化与化工产品合成相结合可以实现煤炭资源价值的梯级利用,是煤炭高效清洁经济利用的途径之一。中高温煤气脱硫是解决该技术过程中污染物危害的关键技术之一。在250-500℃的温度范围内,进行煤气中含硫(H2S, COS)气体高效脱除的研究是目前关注的重点,主要解决吸附剂在上述温区反应活性低和容易失活的问题。因此,探索新型制备方法以改善吸附剂的中温活性并保持其循环稳定性具有重要的理论意义和研究价值。
超临界水(SCW, Supercritical Water)具有很多独特的物理和化学特性快速的化学反应速率和金属氧化物的低溶解性可促进金属氧化物的成核；超临界水极强的传质特性和几乎为零的比表面张力,有利于金属或金属氧化物微粒进入到多孔材料的内部形成复合结构材料。
本论文利用超临界水浸渍法(SCWI, Supercritical Water Impregnation)制备了系列负载型中温煤气吸附剂。考察了载体、前驱体种类和浓度、温度、浸渍时间、浸泡时间、金属活性组分等过程参数对吸附剂脱硫性能的影响,并与常规等体积浸渍法制备的吸附剂进行比较；结合XRD、孔结构分析仪等表征结果,对吸附剂的脱硫活性与活性组分的上载量、晶型、分布状态、以及载体的孔结构等因素进行关联,揭示制备方法影响吸附剂脱硫活性的主要规律。
得出如下主要结论：1.载体对SCWI制备吸附剂的影响
1)以Mn(NO3)2为前驱体溶液,以疏水性活性炭为载体SCWI制备的吸附剂脱硫性能优于以亲水性γ-Al2O3为载体制备的吸附剂。
2)炭基吸附剂的硫容和金属利用率的大小与载体的比表面积具有较高的相关性,较高比表面积的载体担载的氧化锰呈高分散状态,具有较多的反应活性位；载体的低比表面积使氧化锰在其表面发生多层覆盖,甚至聚集使部分孔堵塞,使锰利用率下降。
3)超临界水浸渍法制备吸附剂的过程可同时对载体进行二次活化、提高比表面积,使吸附剂的脱硫活性提高。2. SCW]制备吸附剂过程参数的影响
1) SCW]制备过程中,通过改变前驱体浓度、制备温度、浸渍时间等参数,可以调控吸附剂的比表面积、孔容、活性组分的颗粒大小及分散性。实验考察的范围内,MnOx/AC最佳的SCW]制备条件为：以0.46mol/L硝酸锰溶液为前驱体,制备温度为380℃,浸渍时间为30min,此时吸附剂具有较高的脱硫精度和硫容,而且对AC载体的物理结构影响较小
2)以Mn(NO3)2为前驱体,SCW]制备的吸附剂中Mn呈Mn3O4晶相,常规等体积浸渍法(PVI)制备的吸附剂中Mn呈MnO晶相。当前驱体浓度较低时,SCWI制备的吸附剂中活性组分分散性较好,粒径较小,脱硫活性优于负载相同量锰PVI制备的吸附剂；当前驱体浓度较大时,吸附剂中·活性组分出现严重聚集现象,脱硫活性较PVI制备的吸附剂差。
3)以Mn(Ac)2为前驱体SCWI制备吸附剂过程中,Mn与活性炭中的Si发生反应生成Mn2SiO4, Mn2SiO4具有极低的脱硫活性；Mn活性组分分散性较差,颗粒聚集现象严重,脱硫活性差于以Mn(NO3)2为前驱体制备的吸附剂。
3.SCWI制备的单一及复合金属氧化物吸附剂的硫化性能
1)超临界水浸渍法制备的Zr、MN、Cu三种吸附剂的硫容和脱硫精度的大小顺序为CuOx/AC>ZnOx/AC。
2)锰铜复合吸附剂有效提高了脱硫精度和硫容。吸附剂的硫容随着铜所占比例的增加而增大,锰铜摩尔比为3:7时吸附剂具有最佳的脱硫能力,其穿透时间和硫容分别为1185mmin和7.34 g S/100g。
3)活性组分铜的添加促进了氧化锰的分散,提高了吸附剂中活性组分锰的利用率；硫化后Cu的衍射峰消失或强度减弱,也显示了锰的存在提高了吸附剂中活性组分铜的利用率。
Coal-based poly-generation technology based on coal gasification is the inevitable trend of the efficient, clean and economical use of coal, which can combine the the energy conversion and chemical products to achieve the step utilization of coal resources. In this process, hot coal gas desulfurization is one of the key technology to abate the hazard of pollutants. Nowdays scholars at home and abroad are focused on development The effective remove of H2S and COS in the middle temperature range of 250-500℃is the focal point to be concerned. The main problems needed to be overcome are the low reactivity and easy deactivation of sorbents. So it has very important significance to explore a new preparation method to improve the active of sorbent at middle temperature and keep the cycle stability.
The Supercritical Water (SCW) possesses the specific chemical and physical properties. At the supercritical region, a fast reaction rate and low metal oxide solubility led to an extremely high nucleation rate, which allow for the formation of nano-sized particles. The gas-liquid transport properties and very low surface tension of supercritical water have the great contribution in the effective impregnation of metal oxides on porous solid materials and the enhanced dispersion of the particles deep inside the pores.
The SCWI (Supercritical Water Impregnation) method is used to prepare supported sorbent for removing H2S from hot coal gas in this study. The effects of the supports, precursors and loading amounts, supercritical water temperature, impregnation time, soak time and metal active component during sorbent preparation on the removal of H2S in simulated coal-derived gas were investigated. And the desulfurization experiments of sorbents prepared from the pore volume impregnation (PVI) were also comparatively carried out. The characterization results from XRD, nitrogen sorption measurements and so on were correlated the loading amounts of metal oxide, crystal form and disperse of metal oxide, pore with desulfurization activity of sorbent to explore the effects of the operation parameters in SCWI preparation on the activity of sorbent desulfurization. The main conclusions are shown in the following:
1. Effects of support on the sorbents prepared by SCWI
1) The sulfidation properties of sorbents prepared using hydrophobicity AC support are better than hydrophilicγ-Al2O3 by SCWI and manganese nitrate precursor.
2) The sulfur capacity and the use rate of active component are closely correlated with the surface area of support. AC have the highest surface area which can promote the disperse of metal oxides. The lower surface areas of AC-1 and CC cause the metal oxide aggregated seriously. The sequence of desulfurization activity of three sorbents was AC> AC-2> CC.
3) During sorbent preparation by SCWI, the carbonization carbon support can be activated and the surface area is enhanced, which will cause the improving of desulfurization activity.
2. Effect of the main operation factors in SCWI preparation on the sorbents
1) The micropore volume and surface area of sorbents, the particle sizes of metal oxide particles and its dispersion on the support can be adjusted by changing the precursor concentration, preparation temperature and impregnation time during SCWI. The optima] SCWI conditions for preparing Mn-based sorbents are 0.46 mol/L precursor solution concentration,380℃preparing temperature, and 30 min impregnation time.
2) The Mn3O4 is existed in the sorbent prepared by SCWI, the MnO is existed in the sorbent preparing by PVI. The manganese oxide particles are well dispersed on the sorbents prepared by SCWI with the low precursor solution concentration, the sulfidation properties of these sorbents are also better than those obtained by PV. However, when the concentration of precursor solution is high, the metal oxide particles on AC supports is aggregated seriously and metal utilization is remarkably decreased.
3) The sulfidation properties of sorbents prepared by SCWI in the solution of manganese nitrate precursor are better than that of manganese acetate precursor. This is because Mn2SiO4 formed from reaction of Mn in Mn(Ac)2 and Si in AC support has the very low desulfurization activity, the manganese oxide particles are seriously agglomerated and poorly dispersed on the AC support with the precursor solution of Mn(Ac)2.
3. The single-metal and bi-metal sorbents prepared by SCWI
1) The sequence of sulfur capacity and desulfurization precision of Zn, Mn and Cu active component sorbents prepared by SCWI was MnOx/AC CuOx/AC> ZnOx/AC
2) The bi-metal oxides active component of copper and manganese in the sorbent can promote the removal of H2S from hot coal gas, The sulfur capacity of sorbent increases with the increase of Cu content in the sorbent. The sorbent with the 3:7 molar ratio of manganese/copper has the optimum desulfurization capacity of 1185min and 7.34 g S/100g.
3) The addition of copper component can effectively promote the dispersion of manganese oxide on AC support and improve the sulfidation capacity of the sorbent. The peak intensity of Cu is weaken or disappeared to improve the utilization rate of Cu-active component.
超临界水(SCW, Supercritical Water)具有很多独特的物理和化学特性快速的化学反应速率和金属氧化物的低溶解性可促进金属氧化物的成核；超临界水极强的传质特性和几乎为零的比表面张力,有利于金属或金属氧化物微粒进入到多孔材料的内部形成复合结构材料。
本论文利用超临界水浸渍法(SCWI, Supercritical Water Impregnation)制备了系列负载型中温煤气吸附剂。考察了载体、前驱体种类和浓度、温度、浸渍时间、浸泡时间、金属活性组分等过程参数对吸附剂脱硫性能的影响,并与常规等体积浸渍法制备的吸附剂进行比较；结合XRD、孔结构分析仪等表征结果,对吸附剂的脱硫活性与活性组分的上载量、晶型、分布状态、以及载体的孔结构等因素进行关联,揭示制备方法影响吸附剂脱硫活性的主要规律。
得出如下主要结论：1.载体对SCWI制备吸附剂的影响
1)以Mn(NO3)2为前驱体溶液,以疏水性活性炭为载体SCWI制备的吸附剂脱硫性能优于以亲水性γ-Al2O3为载体制备的吸附剂。
2)炭基吸附剂的硫容和金属利用率的大小与载体的比表面积具有较高的相关性,较高比表面积的载体担载的氧化锰呈高分散状态,具有较多的反应活性位；载体的低比表面积使氧化锰在其表面发生多层覆盖,甚至聚集使部分孔堵塞,使锰利用率下降。
3)超临界水浸渍法制备吸附剂的过程可同时对载体进行二次活化、提高比表面积,使吸附剂的脱硫活性提高。2. SCW]制备吸附剂过程参数的影响
1) SCW]制备过程中,通过改变前驱体浓度、制备温度、浸渍时间等参数,可以调控吸附剂的比表面积、孔容、活性组分的颗粒大小及分散性。实验考察的范围内,MnOx/AC最佳的SCW]制备条件为：以0.46mol/L硝酸锰溶液为前驱体,制备温度为380℃,浸渍时间为30min,此时吸附剂具有较高的脱硫精度和硫容,而且对AC载体的物理结构影响较小
2)以Mn(NO3)2为前驱体,SCW]制备的吸附剂中Mn呈Mn3O4晶相,常规等体积浸渍法(PVI)制备的吸附剂中Mn呈MnO晶相。当前驱体浓度较低时,SCWI制备的吸附剂中活性组分分散性较好,粒径较小,脱硫活性优于负载相同量锰PVI制备的吸附剂；当前驱体浓度较大时,吸附剂中·活性组分出现严重聚集现象,脱硫活性较PVI制备的吸附剂差。
3)以Mn(Ac)2为前驱体SCWI制备吸附剂过程中,Mn与活性炭中的Si发生反应生成Mn2SiO4, Mn2SiO4具有极低的脱硫活性；Mn活性组分分散性较差,颗粒聚集现象严重,脱硫活性差于以Mn(NO3)2为前驱体制备的吸附剂。
3.SCWI制备的单一及复合金属氧化物吸附剂的硫化性能
1)超临界水浸渍法制备的Zr、MN、Cu三种吸附剂的硫容和脱硫精度的大小顺序为CuOx/AC>ZnOx/AC。
2)锰铜复合吸附剂有效提高了脱硫精度和硫容。吸附剂的硫容随着铜所占比例的增加而增大,锰铜摩尔比为3:7时吸附剂具有最佳的脱硫能力,其穿透时间和硫容分别为1185mmin和7.34 g S/100g。
3)活性组分铜的添加促进了氧化锰的分散,提高了吸附剂中活性组分锰的利用率；硫化后Cu的衍射峰消失或强度减弱,也显示了锰的存在提高了吸附剂中活性组分铜的利用率。
Coal-based poly-generation technology based on coal gasification is the inevitable trend of the efficient, clean and economical use of coal, which can combine the the energy conversion and chemical products to achieve the step utilization of coal resources. In this process, hot coal gas desulfurization is one of the key technology to abate the hazard of pollutants. Nowdays scholars at home and abroad are focused on development The effective remove of H2S and COS in the middle temperature range of 250-500℃is the focal point to be concerned. The main problems needed to be overcome are the low reactivity and easy deactivation of sorbents. So it has very important significance to explore a new preparation method to improve the active of sorbent at middle temperature and keep the cycle stability.
The Supercritical Water (SCW) possesses the specific chemical and physical properties. At the supercritical region, a fast reaction rate and low metal oxide solubility led to an extremely high nucleation rate, which allow for the formation of nano-sized particles. The gas-liquid transport properties and very low surface tension of supercritical water have the great contribution in the effective impregnation of metal oxides on porous solid materials and the enhanced dispersion of the particles deep inside the pores.
The SCWI (Supercritical Water Impregnation) method is used to prepare supported sorbent for removing H2S from hot coal gas in this study. The effects of the supports, precursors and loading amounts, supercritical water temperature, impregnation time, soak time and metal active component during sorbent preparation on the removal of H2S in simulated coal-derived gas were investigated. And the desulfurization experiments of sorbents prepared from the pore volume impregnation (PVI) were also comparatively carried out. The characterization results from XRD, nitrogen sorption measurements and so on were correlated the loading amounts of metal oxide, crystal form and disperse of metal oxide, pore with desulfurization activity of sorbent to explore the effects of the operation parameters in SCWI preparation on the activity of sorbent desulfurization. The main conclusions are shown in the following:
1. Effects of support on the sorbents prepared by SCWI
1) The sulfidation properties of sorbents prepared using hydrophobicity AC support are better than hydrophilicγ-Al2O3 by SCWI and manganese nitrate precursor.
2) The sulfur capacity and the use rate of active component are closely correlated with the surface area of support. AC have the highest surface area which can promote the disperse of metal oxides. The lower surface areas of AC-1 and CC cause the metal oxide aggregated seriously. The sequence of desulfurization activity of three sorbents was AC> AC-2> CC.
3) During sorbent preparation by SCWI, the carbonization carbon support can be activated and the surface area is enhanced, which will cause the improving of desulfurization activity.
2. Effect of the main operation factors in SCWI preparation on the sorbents
1) The micropore volume and surface area of sorbents, the particle sizes of metal oxide particles and its dispersion on the support can be adjusted by changing the precursor concentration, preparation temperature and impregnation time during SCWI. The optima] SCWI conditions for preparing Mn-based sorbents are 0.46 mol/L precursor solution concentration,380℃preparing temperature, and 30 min impregnation time.
2) The Mn3O4 is existed in the sorbent prepared by SCWI, the MnO is existed in the sorbent preparing by PVI. The manganese oxide particles are well dispersed on the sorbents prepared by SCWI with the low precursor solution concentration, the sulfidation properties of these sorbents are also better than those obtained by PV. However, when the concentration of precursor solution is high, the metal oxide particles on AC supports is aggregated seriously and metal utilization is remarkably decreased.
3) The sulfidation properties of sorbents prepared by SCWI in the solution of manganese nitrate precursor are better than that of manganese acetate precursor. This is because Mn2SiO4 formed from reaction of Mn in Mn(Ac)2 and Si in AC support has the very low desulfurization activity, the manganese oxide particles are seriously agglomerated and poorly dispersed on the AC support with the precursor solution of Mn(Ac)2.
3. The single-metal and bi-metal sorbents prepared by SCWI
1) The sequence of sulfur capacity and desulfurization precision of Zn, Mn and Cu active component sorbents prepared by SCWI was MnOx/AC CuOx/AC> ZnOx/AC
2) The bi-metal oxides active component of copper and manganese in the sorbent can promote the removal of H2S from hot coal gas, The sulfur capacity of sorbent increases with the increase of Cu content in the sorbent. The sorbent with the 3:7 molar ratio of manganese/copper has the optimum desulfurization capacity of 1185min and 7.34 g S/100g.
3) The addition of copper component can effectively promote the dispersion of manganese oxide on AC support and improve the sulfidation capacity of the sorbent. The peak intensity of Cu is weaken or disappeared to improve the utilization rate of Cu-active component.
引文
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