基于复合微反应器催化氧化脱硫研究
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摘要
近年来,环保问题受到人们越来越多的关注,燃料油的深度脱硫问题就是其中之一。2006年柴油中的硫含量将限制到16ppm之内,然而传统的加氢脱硫法(HDS)已远远不能满足人们的要求。而且,加氢脱硫法反应条件苛刻,设备投资大,使燃料油的成本显著提高。因此,寻找一种能够补充或替代加氢脱硫法的脱硫工艺,是石油工业领域所关注的焦点。目前,吸附脱硫、萃取脱硫、氧化脱硫和生物脱硫等脱硫技术曾被用于燃料油脱硫。其中与液液萃取技术相结合的催化氧化脱硫法是最具潜力的深度脱硫法之一。该方法以对有机硫化物进行氧化为核心技术,选择性的将燃料油中的噻吩及其衍生物转化为相应的砜,然后利用砜较强的极性,通过萃取、吸附等分离技术将砜除去,达到深度脱硫的目的。
以高分子水凝胶为模板制备具有特殊结构和性能的复合微球材料是当今材料科学领域研究热点之一,其优势在于模板的空间限域和调控作用可实现对复合材料的表面形貌及结构的控制,获得各种具有特异表面结构的无机—有机复合材料,从而实现纳米尺寸微粒与大尺度模板间的有效复合。本研究首次将负载有过氧杂多酸季胺盐的有机—无机复合微球催化剂用于燃料油的深度脱硫。该研究的优势在于:一方面,由于复合微球较大的尺寸可以实现催化剂与反应体系的简易分离;另一方面,由于微球具有核壳型结构,而且亲水性内核为过氧化氢的储存提供了可能,外壳负载相转移催化剂使两相反应易于界面发生。
本论文主要对负载过氧磷钨杂多酸季胺盐(PW-HPA)的有机—无机复合微球制备、表征及其在燃料油深度脱硫中的应用进行了研究,其研究工作包括以下两个方面:
(一)采用反相悬浮聚合法合成了PAM微凝胶微球,以此微球为模板,用磷钨酸(HPA)为溶胀液,分别在正庚烷、过氧化氢两种体系中,通过两相界面反应使过氧磷钨杂多酸季胺盐沉积于微凝胶表面,制得具有核/壳结构的PAM/PW-HPA复合微球材料。利用扫描电子显微镜(SEM)、傅立叶变换红外光谱(FTIR)和热重分析仪(TGA)对复合微球的形貌、组分和无机沉积物PW-HPA的负载量等进行了表征。
实验结果表明:微凝胶的模板作用使得所得复合物整体上呈现球状结构,且具有微米级尺寸;PAM/PW-HPA复合微球具有一定特征的表面图案化和可逆的溶胀性;复合微球表面结构可通过改变模板溶胀度、调整无机物的沉积量等方式进行有效地调控。微米级尺寸和纳米级表面图案是这类复合微球材料最大的特点。这种特点使其同时具有易于分离和极大比表面等特性。因此,该复合材料制备方法对于构筑两相催化微反应器具有普遍的借鉴意义。
(二)在十氢化萘、四氢化萘和正戊烷混合溶剂中,以30%H_2O_2为氧化剂,
Recently, people put a lot of attentions to the environmental problems becoming more and more serious. Deep desulfurization of fuel oil has become an environmentally urgent subject worldwide. Very stringent environmental regulations limit the sulfur levels in diesel fuels to less than 15 ppm by the year 2006. However, it is very difficult to decrease the sulfur content from several hundred ppm to a few ppm with traditional hydrodesulphurization (HDS) method. At the same time, strict operation condition and huge instrument investment make cost of oil very high. So alternation and perfection of desulfurization processes are absolutely necessary for producing clean fuels. Possible strategies to realize deep desulfurization currently include adsorption, extraction, oxidation and bioprocesses. Selective catalytic oxidation combined with extraction is one of the most promising deep desulfurization methods. Catalytic oxidation desulfurization may oxide sulfides of fuel oil into sulfones. Then the efficiency of deep desulfurization, by using either extraction or adsorption, can be completed due to the greater polarity and the higher solubility of sulfones in a polar solution than that of corresponding sulfides.Microgel template approaches on the preparation of composite materials with special structure and properties have increased interest in materials science. The main advantage of composite materials is that employing the effect of space confinement of template for guest can easily control the hybridization between template materials and guest with large difference in size as well as the surface morphology of composite microspheres. This research firstly applies the composite microspheres loaded with peroxide phosphotungsten heteropolyacid quarter ammonium salt (PW-HPA) as catalyst to deep desulfurization of fuel oil. The advantages include two aspects. One side, the micrometer size of composite microspheres makes its easy separation from the system possible. The other side, the composite microspheres have hydrophilic core and hydrophobic shell, which can store hydrogen peroxide inside and perform catalysis at the interface.This research mainly focuses on the preparation and characteristic of composite microspheres, and application to deep desulfurization of fuel oil. Based on the idea mentioned above, the research in this thesis includes the following two parts.(1) PAM microgels microspheres were prepared by reverse suspension polymerization technique. The microspheres thus prepared were employed as
template for the deposition of PW-HPA in the n-heptane and hydrogen peroxide systems, respectively. Then the morphology ^ composition and loading amount of the composite microspheres materials PAM/PW-HPA have been characterized by the SEML FT IR and TGA, respectively.It was demonstrated that the composite materials in shape were generally microspheres with different surface morphology. The surface structures of the composite microspheres could be tailored to certain extent by varying the swelling degree of the PAM template and the amount of PW-HPA deposited. The composite microspheres have micrometer size and nanometer morphology. This characteristic makes its easy separation and big surface possible. So, the preparation method of the composite microspheres is significant in conducting the biphase catalytic microreactor.(2) For a model reaction run, dibenzothiophene (DBT) was dissolved in a mixture of decahydronaphthalene, tetrahydronaphthalene and n-pentane. 30% H2O2 as oxidant and composite microspheres as catalyst oxide the DBT into the corresponding sulfones. Then the mixture is extracted by acetonitrile. Comparing the catalytic performance of PW-HPA and PAM/PW-HPA, the results show that catalytic efficiency of PAM/PW-HPA was almost the same to that of PW-HPA. Under the best condition, the conversion of DBT is about 95%. But the PAM/PW-HPA is separated more easily than PW-HPA from the mixture and can be recycled after dehydrogenization by acetone.
以高分子水凝胶为模板制备具有特殊结构和性能的复合微球材料是当今材料科学领域研究热点之一,其优势在于模板的空间限域和调控作用可实现对复合材料的表面形貌及结构的控制,获得各种具有特异表面结构的无机—有机复合材料,从而实现纳米尺寸微粒与大尺度模板间的有效复合。本研究首次将负载有过氧杂多酸季胺盐的有机—无机复合微球催化剂用于燃料油的深度脱硫。该研究的优势在于:一方面,由于复合微球较大的尺寸可以实现催化剂与反应体系的简易分离;另一方面,由于微球具有核壳型结构,而且亲水性内核为过氧化氢的储存提供了可能,外壳负载相转移催化剂使两相反应易于界面发生。
本论文主要对负载过氧磷钨杂多酸季胺盐(PW-HPA)的有机—无机复合微球制备、表征及其在燃料油深度脱硫中的应用进行了研究,其研究工作包括以下两个方面:
(一)采用反相悬浮聚合法合成了PAM微凝胶微球,以此微球为模板,用磷钨酸(HPA)为溶胀液,分别在正庚烷、过氧化氢两种体系中,通过两相界面反应使过氧磷钨杂多酸季胺盐沉积于微凝胶表面,制得具有核/壳结构的PAM/PW-HPA复合微球材料。利用扫描电子显微镜(SEM)、傅立叶变换红外光谱(FTIR)和热重分析仪(TGA)对复合微球的形貌、组分和无机沉积物PW-HPA的负载量等进行了表征。
实验结果表明:微凝胶的模板作用使得所得复合物整体上呈现球状结构,且具有微米级尺寸;PAM/PW-HPA复合微球具有一定特征的表面图案化和可逆的溶胀性;复合微球表面结构可通过改变模板溶胀度、调整无机物的沉积量等方式进行有效地调控。微米级尺寸和纳米级表面图案是这类复合微球材料最大的特点。这种特点使其同时具有易于分离和极大比表面等特性。因此,该复合材料制备方法对于构筑两相催化微反应器具有普遍的借鉴意义。
(二)在十氢化萘、四氢化萘和正戊烷混合溶剂中,以30%H_2O_2为氧化剂,
Recently, people put a lot of attentions to the environmental problems becoming more and more serious. Deep desulfurization of fuel oil has become an environmentally urgent subject worldwide. Very stringent environmental regulations limit the sulfur levels in diesel fuels to less than 15 ppm by the year 2006. However, it is very difficult to decrease the sulfur content from several hundred ppm to a few ppm with traditional hydrodesulphurization (HDS) method. At the same time, strict operation condition and huge instrument investment make cost of oil very high. So alternation and perfection of desulfurization processes are absolutely necessary for producing clean fuels. Possible strategies to realize deep desulfurization currently include adsorption, extraction, oxidation and bioprocesses. Selective catalytic oxidation combined with extraction is one of the most promising deep desulfurization methods. Catalytic oxidation desulfurization may oxide sulfides of fuel oil into sulfones. Then the efficiency of deep desulfurization, by using either extraction or adsorption, can be completed due to the greater polarity and the higher solubility of sulfones in a polar solution than that of corresponding sulfides.Microgel template approaches on the preparation of composite materials with special structure and properties have increased interest in materials science. The main advantage of composite materials is that employing the effect of space confinement of template for guest can easily control the hybridization between template materials and guest with large difference in size as well as the surface morphology of composite microspheres. This research firstly applies the composite microspheres loaded with peroxide phosphotungsten heteropolyacid quarter ammonium salt (PW-HPA) as catalyst to deep desulfurization of fuel oil. The advantages include two aspects. One side, the micrometer size of composite microspheres makes its easy separation from the system possible. The other side, the composite microspheres have hydrophilic core and hydrophobic shell, which can store hydrogen peroxide inside and perform catalysis at the interface.This research mainly focuses on the preparation and characteristic of composite microspheres, and application to deep desulfurization of fuel oil. Based on the idea mentioned above, the research in this thesis includes the following two parts.(1) PAM microgels microspheres were prepared by reverse suspension polymerization technique. The microspheres thus prepared were employed as
template for the deposition of PW-HPA in the n-heptane and hydrogen peroxide systems, respectively. Then the morphology ^ composition and loading amount of the composite microspheres materials PAM/PW-HPA have been characterized by the SEML FT IR and TGA, respectively.It was demonstrated that the composite materials in shape were generally microspheres with different surface morphology. The surface structures of the composite microspheres could be tailored to certain extent by varying the swelling degree of the PAM template and the amount of PW-HPA deposited. The composite microspheres have micrometer size and nanometer morphology. This characteristic makes its easy separation and big surface possible. So, the preparation method of the composite microspheres is significant in conducting the biphase catalytic microreactor.(2) For a model reaction run, dibenzothiophene (DBT) was dissolved in a mixture of decahydronaphthalene, tetrahydronaphthalene and n-pentane. 30% H2O2 as oxidant and composite microspheres as catalyst oxide the DBT into the corresponding sulfones. Then the mixture is extracted by acetonitrile. Comparing the catalytic performance of PW-HPA and PAM/PW-HPA, the results show that catalytic efficiency of PAM/PW-HPA was almost the same to that of PW-HPA. Under the best condition, the conversion of DBT is about 95%. But the PAM/PW-HPA is separated more easily than PW-HPA from the mixture and can be recycled after dehydrogenization by acetone.
引文
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