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邻苯二甲酸二(2-乙基己基)酯合成反应的多相催化剂研究
其他题名Study on multi-phase catalysts for dioctyl phthalate synthesis
周华锋
学位类型博士
导师张劲松
2009-02-14
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料加工工程
关键词Mcm-41介孔分子筛 整体催化剂 邻苯二甲酸二(2-乙基己基)酯 增塑剂 酯化反应
摘要邻苯二甲酸二(2-乙基己基)酯(Dioctyl phthalate,简写为DOP)是国内外塑料助剂行业中工业化产量最大的一种主增塑剂,具有优良的综合性能,因此被广泛的应用于塑料和橡胶制品、儿童玩具、医疗器械等各个领域。本文制备了三类多相催化剂,研究了制备条件对其结构和性能的影响,考查了所制备的多相催化剂在DOP合成反应中的催化活性、选择性和寿命。 采用水热合成法,一步合成了杂原子(Al,Zn,Ni,Fe,Cu,Ce)掺杂的MCM-41介孔分子筛(T-MCM-41),研究了杂原子的掺杂量、溶液的pH值、不同原子的掺杂对MCM-41分子筛结构和性能的影响。结果表明:(1)合成Al-MCM-41分子筛最佳Si/Al比为40,最佳pH值为10.5;(2)合成的T-MCM-41(40) 分子筛都具有六方有序排列结构,并且由于杂原子的引入使得MCM-41分子筛的总酸量和催化活性均有不同程度的提高。其中,以Al-MCM-41(40)分子筛的催化活性最高。以它为催化剂(用量为反应物总量的2.2 wt.%),当反应进行4h时,苯酐的转化率可以达到 98.45%,DOP的选择性达到99.13%。 以泡沫镍为载体制备了活性组分为SnO和Sn的SnO(Sn)/泡沫镍整体催化剂,研究了它们对DOP合成反应的催化活性;考查了电镀电流密度、电镀温度对电镀速率的影响,以及热氧化处理和镀锡量对催化剂性能的影响。结果表明:(1)电镀时的最佳电流密度为0.6 A∙dm-2、最佳电镀温度为70℃;(2)经300℃热氧化处理,一部分金属锡被氧化成了高活性的氧化亚锡,从而提高了泡沫镍整体催化剂的催化活性;(3)随着镀锡量的增加,整体催化剂的活性也不断增加。所制备的Sn/Ni-3(300)整体催化剂对DOP的合成有很好的催化活性和选择性。用它做催化剂时,反应进行2.5h时,苯酐的转化率达到98.02%,产物中DOP的选择性达到97.7%。 采用SiC泡沫陶瓷做载体制备了几种整体催化剂,研究了它们对DOP合成反应的催化活性。考查了热氧化处理、镍涂层的添加、电镀时间等对催化剂性能的影响,结果表明:(1)采用热氧化处理使得低熔点的金属锡氧化成了具有较高熔点的氧化亚锡,消除了由于金属锡熔化造成的脱落问题,同时也由于SnO的生成提高了催化剂的催化活性;(2)镍涂层的添加进一步缓解了所制备的整体催化剂的涂层的脱落;(3)所制备的整体催化剂对DOP的合成有很好的催化活性和选择性。以Sn/Ni/SiC-1 (300)作催化剂时,反应在2.5h时苯酐的转化率达到96.06%,DOP的选择性达到97.1%。 所制备的这三类多相催化剂(尤其是后两类整体催化剂)在使用后很容易与反应体系分离,且无需任何处理即可重复使用多次.
其他摘要Dioctyl phthalate (DOP) is a kind of main plasticizers in plastic assistant industry whose output is the highest. It is widely used in plastic and rubber prouducts, toys, medical apparatus and instruments due to its excellent characteristics. In this paper, three kinds of multi-phase catalysts were prepared. The effects of preparation condition on structures and properties of the catalysts were investigated. The catalytic performance, selectivity and life of the catalysts in DOP synthesis were also studied. MCM-41 mesoporous molecular sieves containing heteroatoms (Al, Zn, Ni, Cu, Ce, Fe) (T-MCM-41) were synthesized by direct hydrothermal process. The effects of Si/Al mole ratio, pH value and different heteroatoms incorporation on structures and properties of T-MCM-41 were investigated. The results show that (1) the optimal Si/Al mole ratio is 40 and the optimal pH value is 10.5. (2) T-MCM-41(40) still remains the well-ordered hexagonal mesostructure of MCM-41. Meanwhile, they have high catalytic activity and selectivity in DOP synthesis because heteroatoms incorporation can produce acid centers. Among them, Al-MCM-41(40) shows the highest catalytic activity. When Al-MCM-41(40) was used as the catalyst, whose weight was 2.2 wt.% of the total reaction mixture, the conversion of phthalic anhydride (PA) reaches 98.45% and DOP selectivity reaches 99.13% in 4h. A series of monolithic catalysts which Sn and SnO are active components, were prepared and and their catalytic performance in synthesis of DOP were studied when nickel foams used as the supports. The effects of current density and electroplating temperature on the electroplating rate were investigated, and the influence of the calcination process and the amount of Sn on the catalytic activities of the catalysts were also studied. The results show that (1) the optimal current density and the temperature is 0.6 A∙dm-2 and 70℃, respectively. (2) the catalytic activity of the catalyst increases after oxidation treatment at 300℃, which attributes to some Sn was oxidized to SnO with higher catalytic activity. (3) the catalytic activities of the monolithic catalysts increase with the amount of Sn increasing. When Sn/Ni-3(300) was used as the catalyst, the conversion of PA reaches 98.02% and DOP selectivity reaches 97.7% in 2.5h. A series of monolithic catalysts, which SiC foams were used as the supports, were prepared and their catalytic performance in the synthesis of dioctyl phthalate were studied. The effects of calcination process, Ni washcoat and electroplating time on the properties of the catalysts were investigated. The results show that (1) the catalytic activities of the catalysts increase after oxidation, due to the formation of SnO oxidized by Sn. Moreover, the slough caused by Sn melting was avoided because the melting point of SnO is higher than Sn. (2) the addition of Ni washcoat further slows the sloughing speed. (3) these monolithic catalysts have good catalytic activities and selectivities in DOP synthesis. When Sn/Ni/SiC-1(300) was used as the catalyst, the conversion of PA reaches 96.06% and DOP selectivity reaches 97.1% in 2.5h. The multi-phase catalysts (especially two kinds of monolithic catalysts) prepared in this paper can be easily separated from the reaction mixture and be reused without any treatment.
页数133
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/16966
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
周华锋. 邻苯二甲酸二(2-乙基己基)酯合成反应的多相催化剂研究[D]. 金属研究所. 中国科学院金属研究所,2009.
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