【作者】 卫延安；

【导师】 吕春绪；

【作者基本信息】 南京理工大学 ， 应用化学， 2004， 博士

【摘要】 以环己酮为原料，制备出环己酮二聚物（环己烯基环己酮）。以贵金属Pd、和Pt为活性组分，选择了HZSM-5，γ-Al₂O₃及覆炭γ-Al₂O₃（CCA）为载体，制备出脱氢催化剂用于环己烯基环己酮为原料的脱氢，合成邻苯基苯酚（OPP），对影响催化剂性能的诸多因素进行了较为系统的研究。 以离子交换方式制备的Pd／HZSM-5催化剂，经过还原后，Pd有较好的分散度，w（Pd）=0.9％的Pd／HZSM-5催化剂对环己酮二聚物的脱氢活性为95％，OPP的选择性为90％。采用浸渍法制备出Pt／γ-Al₂O₃催化剂，通过添加助催化剂K₂SO₄和K₂O对其进行改性，使催化剂的性能得到了提高。当w（Pt）=0.3％～0.5％时，Pt／γ-Al₂O₃对环己酮二聚物的脱氢活性达到95％以上，OPP的选择性也大于90％。催化剂的组成为[w（Pt）=0.3％，w（K₂SO₄）=2％]的Pt／γ-Al₂O₃催化剂，在温度350℃、控制氢气流速为50mL／min，二聚物的滴料速度为7mL／h，催化剂的起始脱氢活性可达到96.4％，OPP的收率超过90％。 以环己烯作裂解原料，制备出新型的覆炭载体CCA。在温度一定的情况下，γ-Al₂O₃上覆炭量与时间呈线性关系。在400℃～650℃范围内，随反应温度的升高，覆炭量呈指数增高，覆炭量随时间而增加。通过表面结构分析，CCA载体比表面积有所增加，微孔孔径分布趋于均匀。[w（Pt）=0.5％、w（K₂O）=1％]的Pt／CCA催化剂，连续使用100h后对环己酮二聚物的脱氢活性仍可达到95％，OPP的选择性保持相对稳定。以m（CS₂）：m（Pt）=1∶100对催化剂预中毒后，连续使用200h，OPP的收率仍在90％以上。XPS的分析结果表明，在催化剂表面上的S的2P₃电子的结合能由165ev升高至169ev，S可能参与抑制了脱氢过程中的H的转移，降低了氢解反应，提高了OPP的选择性。 采用精馏、重结晶工艺精制OPP，OPP的质量纯度为99.8％以上。采用一锅合成法，将OPP与过量的PCl₃反应，合成9，10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide（DOPO）and 2’-hydroxydiphenyl-2-phosphinic acid（HPPA）混合物，产品收率为96.9％（以OPP为基准）。不需真空精馏等操作，无需分离中间产物。更多还原

【Abstract】 Cyclohexenylcyclohexanone was prepared from cyclohexanone. o-Phenylphenol was made from cyclohexenyl cyclohexanone by dehydrogenation reaction. The noble metal (Pd or Pt) supported on HZSM-5 and r -Al2O3 or CCA respectively using as dehydrogenation catalysts were prepared. The factors that could influence catalysts’ properties were studied by the numbers.Pd/HZSM-5 was prepared by method of iron-exchanged reaction, Pd could be dispersed better on the catalyst after deoxidizing. The cyclohexenylcyclohexanone conversion rate and the selectivity of OPP were more 95% and 90% respectively, while Pd/HZSM-5 catalyst in an amount of w(Pd) = 0.9%. K2SO4 or K2O as assistant agent were used for Pt supported by Y -Al2O3 catalyst. The results showed that: catalyst consist as [w(Pt)=0.3% w(K.2SO4)=2%], the initiative conversion rate of cyclohexenylcyclohexanone is more 96% and the yield of OPP is as high as 90% in a certain reaction condition ,which temperature is 350 C and flux of H2 is 50mL/min,adding rate is 7mL/h.CCA carrier was prepared by cyclohexene cracked to carbon compound over the r -Al2O3 under higher temperature 400C-650C. The amount of carbon-covered has linear relation with time when temperature is determined. With temperature rising, the total amounts of carbon-covered has exponential relation with temperature. Through BET surface structure analysis ,CCA has more SSA than that of Y -AI2O3 and it’s pore diameter distributing is tend to equality. When the catalyst Pt/CCA [w(Pt)=0.5% w(K2O)=l%] was lasted used 100h,the dehydrogenation convert of rate for cyclohexenylcyclohexanone is 95%,and the selectivity of OPP keep stabilization. When the catalyst was pre-poisoned by CS2 which amount of CS2 be controlled under [m(CS2): m(Pt)=1:10] the yield of OPP is more 90% after lasted using 200h. The results of XPS analysis showed that the S 2P3 electron bring energy rose to 169ev from normal 165ev, it is possible that S has play participate to restrain H transfer in the process of dehydrogenation so as to reduce hydrogenolysis and promoteselectivity of OPP.OPP was refined by rectify and recrystal technology and purity add to 99.8%. DOPO and HPPA are synthesized with phosphorous trichloride and o-phenylphenol by an "one-pot" method without isolating intermediate products and avoiding a distillation step.更多还原