邻苯基苯酚的化学合成
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摘要
邻苯基苯酚是一种重要的精细化学品，具有显著的保鲜杀菌作用，并可以用于合成抗菌聚合物、杀虫剂等，国内外对它的研究开发日益重视。在过去，OPP主要由磺化碱熔法或氯苯高压水解法生产苯酚的蒸馏残渣分离而得；然而，这两种方法工艺路线复杂，操作环境恶劣；特别是异丙苯生产苯酚工业化之后，上面两种工艺逐渐被淘汰，OPP的来源也就相应地受到了极大的限制。因此，研制、开发新的环境安全性的OPP生产工艺就成了当务之急。在所有制备OPP的可行路线中，又以环己酮缩合、脱氢工艺最具有应用前景。
论文研究了以环己酮为原料，经由缩合生成邻环己烯基环己酮二聚体、二聚体脱氢两步法合成邻苯基苯酚的工艺路线，重点研究了脱氢催化剂的制备及催化活性考察；确定了缩合、脱氢两步化学反应的优化工艺条件，并提出了工业化生产的具体工艺。利用熔点测定、元素分析、红外、质谱、气相色谱对产品及纯度进行了分析鉴定。
在环己酮的缩合反应中，研究了不同催化剂对缩合反应的影响，以及反应温度、反应时间、催化剂用量对目标产物2-(1-环己烯基)环己酮收率及选择性的影响，同时优化了反应工艺，使之更适合工业化生产。实验证明：以50％的硫酸做催化剂，H_2SO_4：环己酮=1∶5(v／v)，在90～100℃下反应45～50min，可以高选择性合成邻环己烯基环己酮。反应结束后，进行分相、稀碱中和、有机相分离，之后进行减压蒸馏来回收未反应的环己酮，以及收集目标产物二聚体。环己酮的一
次转化率可达到72%，二聚体的一次性收率达43%，选择性达93%。
回收的环己酮可直接重新进行下一批的缩合反应。分离出来的酸水经
调配酸浓度后，也可以作为催化剂进行循环使用，这样可以减少了废
酸、废水的排放量。
脱氢催化剂的选择和制备是整个工艺中的重点及难点。实验室采
用浸渍法共制备了10个规格的负载型贵金属催化剂，并对之进行了
活性考察。其中以R一KO曰Y一A12O3的脱氢活性为最佳，所得到的直
接脱氢产物中OPP含量最高达95%，使用1 77.5hi后脱氢混合产物中
OPP含量仍高于64%。同时，论文分析研究了脱氢催化剂失活的主
要影响因素，提出了改进催化剂性能的方法，确定了催化剂活化再生
的工艺条件。
二聚体在脱氢催化剂的催化作用下进行脱氢反应。论文考察了在
相同脱氢工艺条件下不同催化剂的催化性能，以及相同催化剂不同反
应条件下的脱氢反应效果，得出了优化的反应条件:反应温度340一
360℃，气体通量v。=v。=40劝田mln，加料速度309肪，直接脱氢产
物在离开反应管后迅速结晶，OPP含量最高能达95%以上，离心后
用石油醚精制，一次重结晶纯度可达97.2%。对于分离出来的不完全
脱氢产物可以与新鲜物料混合，重新进行脱氢反应。
Orthophenylphenol(hereinafter abbreviated as OPP), is an industrial chemical with a wide variety of applications as dye intermediate products, photographic chemicals, additives in rubber industry and bactericides of low toxicity.
OPP was produced chiefly as a by-product of the alkali hydrolysis of chlorobenzene, or sulfonation fusion for the syntheses of phenol. But those two process routes were complicated and operated in poor working conditions. Especially after that phenol was industrially prepared from cumene, the above two routes were superseded, consequentially the supply of OPP has gradually dried up. So it's urgent for us to research and develop new safety environmental technology. Among all the possible routes of preparing OPP, the condensation and dehydrogenation process from cyclohexanone has the most extensive applied prospect.
A method of preparing OPP in a two-stage process from cyclohexanone which comprises the steps of forming o-cyclohexenylcyclohexanone(hereinafter abbreviated as dimer) from the cyclohexanone by condensing, and then dehydrogenating the resulting dimer with dehydrogenation catalyst on which emphasis was laid, was studied. At the same time, the optimal process conditions and methods for condensation and dehydrogenation were also presented, together with the process for industrial production. The product was confirmed by m.p. measure, element analysis, IR, MS, and GC.
Effect on condensation of cyclohexanone catalyzed by several catalysts were
discussed, together with selectivity and yield of dimer caused by reaction time and temperature, catalyst amount. The experiments indicated that, the process of cyclohexanone condensation carried out at the temperature of 90 to 100#, for 45 to 50 minutes catalyzed by 50% sulphuric acid, was a simple and effective one. At the end of reaction the phases were separated and the upper organic phase was neutralized with a solution of sodium bicarbonate, then the product was separated by distillation into dimer and cyclohexanone for recycle. The aqueous phase at the end of the reaction contained sulphuric acid and a substantial amount of organic material, which was therefore made up with fresh sulphuric acid and used in the preparation of the next batch.
The preparation of dehydrogenation catalyst was the most difficult work among the whole experiments. Ten different lands of supported noble metal catalyst were prepared by the soaking method, and dehydrogenation was conducted with those 10 catalysts, respectively. It was found the Pt-KOH/ Y -Al_(2)O_(3) catalyst was the most effective one, Investigation of changes in composition of the resulting liquid product with the lapse of reaction time revealed that the content of OPP was at least 95% at the beginning and 64% after the lapse of 177.5 hours. And at the same time, the reasons that caused the catalyst deactivation were also investigated, based which the catalyst was improved. The method of reactivation was proved, too.
The dehydrogenation was carried out in present of several catalysts at different reaction conditions, respectively, from which it was found that, if the dimer was fed at a flow rate of 30g/hr in a maintained at 340~360#, together with hydrogen and nitrogen supplied at a flow rate of 40ml/min respectively, ideal dehydrogenation products, which were able to crystallize immediately after they left the catalyst bed, were obtained. The content of OPP was 95% and could reach 97.2% after it was recrystallized by petrolic ether. And the fraction-dehydrogenation products were mixed with fresh dimmer, recycling to dehydrogenate.
论文研究了以环己酮为原料，经由缩合生成邻环己烯基环己酮二聚体、二聚体脱氢两步法合成邻苯基苯酚的工艺路线，重点研究了脱氢催化剂的制备及催化活性考察；确定了缩合、脱氢两步化学反应的优化工艺条件，并提出了工业化生产的具体工艺。利用熔点测定、元素分析、红外、质谱、气相色谱对产品及纯度进行了分析鉴定。
在环己酮的缩合反应中，研究了不同催化剂对缩合反应的影响，以及反应温度、反应时间、催化剂用量对目标产物2-(1-环己烯基)环己酮收率及选择性的影响，同时优化了反应工艺，使之更适合工业化生产。实验证明：以50％的硫酸做催化剂，H_2SO_4：环己酮=1∶5(v／v)，在90～100℃下反应45～50min，可以高选择性合成邻环己烯基环己酮。反应结束后，进行分相、稀碱中和、有机相分离，之后进行减压蒸馏来回收未反应的环己酮，以及收集目标产物二聚体。环己酮的一
次转化率可达到72%，二聚体的一次性收率达43%，选择性达93%。
回收的环己酮可直接重新进行下一批的缩合反应。分离出来的酸水经
调配酸浓度后，也可以作为催化剂进行循环使用，这样可以减少了废
酸、废水的排放量。
脱氢催化剂的选择和制备是整个工艺中的重点及难点。实验室采
用浸渍法共制备了10个规格的负载型贵金属催化剂，并对之进行了
活性考察。其中以R一KO曰Y一A12O3的脱氢活性为最佳，所得到的直
接脱氢产物中OPP含量最高达95%，使用1 77.5hi后脱氢混合产物中
OPP含量仍高于64%。同时，论文分析研究了脱氢催化剂失活的主
要影响因素，提出了改进催化剂性能的方法，确定了催化剂活化再生
的工艺条件。
二聚体在脱氢催化剂的催化作用下进行脱氢反应。论文考察了在
相同脱氢工艺条件下不同催化剂的催化性能，以及相同催化剂不同反
应条件下的脱氢反应效果，得出了优化的反应条件:反应温度340一
360℃，气体通量v。=v。=40劝田mln，加料速度309肪，直接脱氢产
物在离开反应管后迅速结晶，OPP含量最高能达95%以上，离心后
用石油醚精制，一次重结晶纯度可达97.2%。对于分离出来的不完全
脱氢产物可以与新鲜物料混合，重新进行脱氢反应。
Orthophenylphenol(hereinafter abbreviated as OPP), is an industrial chemical with a wide variety of applications as dye intermediate products, photographic chemicals, additives in rubber industry and bactericides of low toxicity.
OPP was produced chiefly as a by-product of the alkali hydrolysis of chlorobenzene, or sulfonation fusion for the syntheses of phenol. But those two process routes were complicated and operated in poor working conditions. Especially after that phenol was industrially prepared from cumene, the above two routes were superseded, consequentially the supply of OPP has gradually dried up. So it's urgent for us to research and develop new safety environmental technology. Among all the possible routes of preparing OPP, the condensation and dehydrogenation process from cyclohexanone has the most extensive applied prospect.
A method of preparing OPP in a two-stage process from cyclohexanone which comprises the steps of forming o-cyclohexenylcyclohexanone(hereinafter abbreviated as dimer) from the cyclohexanone by condensing, and then dehydrogenating the resulting dimer with dehydrogenation catalyst on which emphasis was laid, was studied. At the same time, the optimal process conditions and methods for condensation and dehydrogenation were also presented, together with the process for industrial production. The product was confirmed by m.p. measure, element analysis, IR, MS, and GC.
Effect on condensation of cyclohexanone catalyzed by several catalysts were
discussed, together with selectivity and yield of dimer caused by reaction time and temperature, catalyst amount. The experiments indicated that, the process of cyclohexanone condensation carried out at the temperature of 90 to 100#, for 45 to 50 minutes catalyzed by 50% sulphuric acid, was a simple and effective one. At the end of reaction the phases were separated and the upper organic phase was neutralized with a solution of sodium bicarbonate, then the product was separated by distillation into dimer and cyclohexanone for recycle. The aqueous phase at the end of the reaction contained sulphuric acid and a substantial amount of organic material, which was therefore made up with fresh sulphuric acid and used in the preparation of the next batch.
The preparation of dehydrogenation catalyst was the most difficult work among the whole experiments. Ten different lands of supported noble metal catalyst were prepared by the soaking method, and dehydrogenation was conducted with those 10 catalysts, respectively. It was found the Pt-KOH/ Y -Al_(2)O_(3) catalyst was the most effective one, Investigation of changes in composition of the resulting liquid product with the lapse of reaction time revealed that the content of OPP was at least 95% at the beginning and 64% after the lapse of 177.5 hours. And at the same time, the reasons that caused the catalyst deactivation were also investigated, based which the catalyst was improved. The method of reactivation was proved, too.
The dehydrogenation was carried out in present of several catalysts at different reaction conditions, respectively, from which it was found that, if the dimer was fed at a flow rate of 30g/hr in a maintained at 340~360#, together with hydrogen and nitrogen supplied at a flow rate of 40ml/min respectively, ideal dehydrogenation products, which were able to crystallize immediately after they left the catalyst bed, were obtained. The content of OPP was 95% and could reach 97.2% after it was recrystallized by petrolic ether. And the fraction-dehydrogenation products were mixed with fresh dimmer, recycling to dehydrogenate.
引文
[1] http://www.sanko-inet.cojp/o-pp.html.
[2] 迪安JA主编．兰氏化学手册[M]．科学出版社，1991：7—244-245．
[3] 王大全．精细化工辞典[M]．化学工业出版社．1998．
[4] Gartner, Charles D. Suspension formulations of ortho-phenylphenol[P]. US: 5629350,1997-5-13.
[5] K Shimzu, M Ando, I Juichi. 合成[J].J. Japan. Petrol. Inst., 1984, 27(1): 45-52.
[6] Lee, Guo-shuh J., Garces, et al. Method to prepare ortho substituted phenol[P]. US: 5583268,1996-12-10.
[7] Fishel, Norman A., Gross, et al. Process for production of ortho- phenylphenol[P]. US: 4035428, 1977-7-12.
[8] 李瑞硕，王心葵．环己酮双聚合成环己烯环己酮新型催化剂的研究[J]．石油化工，1995，24：95．
[9] 冯月兰，张亮枚，孙晓金等．从环己酮一步合成邻苯基苯酚[J]．精细化工，1994，11：42—45．
[10] 蔡春，吕春绪．邻苯基苯酚的合成[J]．南京理工大学学报，2001，25(4)：436—439．
[11] 冯望烟，陈诩，缪雪茹．环己酮二聚物脱氢制邻苯基苯酚反应及催化剂研究[J]．石油化工，1990，19：238．
[12] 蔡春，吕春绪．载钯ZSM-5分子筛催化脱氢合成邻苯基苯酚[J]．应用化学，2001，18(2)：167—138
[13] Andrzej KAIM, Jaroslaw KAMINSKI, Waclaw KOLODZlEJSKI. Thermal self-condensation of cyclohexanone[J]. Acta Chim. Hung., 1988, 125(1): 141-145.
[14] 2—(1合成用触媒. 公开特许公报[P]. 昭62-221451.
[15] Kimiaki IMAFUKU, Junko ODA, Kenshi ITOH, et al. Dehydrogenation of 2-(1-cyclohexenyl) cyclohexanone with palladium catalyst[J]. Bull. Chem. Soc. Japan., 1974, 47(5): 1201-1202.
[16] Hisashi MATSUMURA, Kimiaki IMAFUKU, Izumi TAKANO, et al. Rearrangements in the palladium-catalyzed dedydrogenation of cyclohexylphenols to phenylphenols[J]. Bull. Chem. Soc. Japan., 1971, 44: 567.
[17] Goto, Hideo, Shibamoto, et al. Process for preparing o-phenylphenol[P]. US: 4060559,1977-11-29.
[18] Goto, Hideo, Shibamoto, et al. Process for preparing o-phenylphenol[P]. US: 4088702,1978-5-9.
[19] Imamura, Juichi. Process for the production of o-phenylphenol[P]. US: 4080390, 1978-3-21.
[20] Weissel, Oskar, Schwar-z, et al. Process for preparing hydroxydiphenyl[P]. US: 3932536,1976-1-13.
[21] Weissel, Oskar, Koller, et al. Process for preparing hydroxydiphenyl[P]. US: 3933924,1976-1-20.
[2] 迪安JA主编．兰氏化学手册[M]．科学出版社，1991：7—244-245．
[3] 王大全．精细化工辞典[M]．化学工业出版社．1998．
[4] Gartner, Charles D. Suspension formulations of ortho-phenylphenol[P]. US: 5629350,1997-5-13.
[5] K Shimzu, M Ando, I Juichi. 合成[J].J. Japan. Petrol. Inst., 1984, 27(1): 45-52.
[6] Lee, Guo-shuh J., Garces, et al. Method to prepare ortho substituted phenol[P]. US: 5583268,1996-12-10.
[7] Fishel, Norman A., Gross, et al. Process for production of ortho- phenylphenol[P]. US: 4035428, 1977-7-12.
[8] 李瑞硕，王心葵．环己酮双聚合成环己烯环己酮新型催化剂的研究[J]．石油化工，1995，24：95．
[9] 冯月兰，张亮枚，孙晓金等．从环己酮一步合成邻苯基苯酚[J]．精细化工，1994，11：42—45．
[10] 蔡春，吕春绪．邻苯基苯酚的合成[J]．南京理工大学学报，2001，25(4)：436—439．
[11] 冯望烟，陈诩，缪雪茹．环己酮二聚物脱氢制邻苯基苯酚反应及催化剂研究[J]．石油化工，1990，19：238．
[12] 蔡春，吕春绪．载钯ZSM-5分子筛催化脱氢合成邻苯基苯酚[J]．应用化学，2001，18(2)：167—138
[13] Andrzej KAIM, Jaroslaw KAMINSKI, Waclaw KOLODZlEJSKI. Thermal self-condensation of cyclohexanone[J]. Acta Chim. Hung., 1988, 125(1): 141-145.
[14] 2—(1合成用触媒. 公开特许公报[P]. 昭62-221451.
[15] Kimiaki IMAFUKU, Junko ODA, Kenshi ITOH, et al. Dehydrogenation of 2-(1-cyclohexenyl) cyclohexanone with palladium catalyst[J]. Bull. Chem. Soc. Japan., 1974, 47(5): 1201-1202.
[16] Hisashi MATSUMURA, Kimiaki IMAFUKU, Izumi TAKANO, et al. Rearrangements in the palladium-catalyzed dedydrogenation of cyclohexylphenols to phenylphenols[J]. Bull. Chem. Soc. Japan., 1971, 44: 567.
[17] Goto, Hideo, Shibamoto, et al. Process for preparing o-phenylphenol[P]. US: 4060559,1977-11-29.
[18] Goto, Hideo, Shibamoto, et al. Process for preparing o-phenylphenol[P]. US: 4088702,1978-5-9.
[19] Imamura, Juichi. Process for the production of o-phenylphenol[P]. US: 4080390, 1978-3-21.
[20] Weissel, Oskar, Schwar-z, et al. Process for preparing hydroxydiphenyl[P]. US: 3932536,1976-1-13.
[21] Weissel, Oskar, Koller, et al. Process for preparing hydroxydiphenyl[P]. US: 3933924,1976-1-20.