MDA催化加氢制备含低反—反异构PACM的实验研究
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摘要
4，4’-二氨基-二环己基甲烷(简称PACM)是聚氨酯和聚酰胺生产中重要的有机中间体，一般由4，4’-二氨基二苯基甲烷(简称MDA)液相催化加氢制备。
PACM存在着反-反、顺-反、顺-顺三种热力学性质不同的立体异构体，异构体的组成决定了其及其后续产品的性质及用途，而且难于通过分离手段获得单一或者特定异构体组成的PACM，因此工业上PACM产品均为各种立体异构的混合物且习惯用反-反异构体含量定义PACM的规格与用途，反-反异构体含量20％以下称为PACM-20，主要用于制备脂肪族聚氨酯，反-反异构体含量50％左右称为PACM-50，主要用于制备聚酰胺树脂。
上世纪90年代以来，环境友好且透明的脂肪族异氰酸酯的应用前景看好，PACM-20的需求加大，因此开发合成稳定的含低反-反立体异构的PACM-20的生产技术成为关键。本文以此为背景，研究并开发了MDA液相催化加氢合成PACM-20的催化剂及其合成工艺，为PACM-20的进一步工业开发提供了依据。研究结果具体体现在：
1．由γ-三氧化二铝为载体、采用混合浸渍法制得的合适比例组成的钌铑负载型催化剂可以用于MDA催化加氢，可制备出符合要求的PACM—20。
2．使用氢氧化锂对催化剂进行碱处理，效果良好。
3．温度的变化对收率的影响最大，钌／铑比例次之，压力和催化剂用量的改变对收率影响最小。
4．反应时间对反-反异构体含量的影响十分显著，延长反应时间将使反-反异构体含量增加。
5．有效控制反应温度和反应时间是获得低反-反异构体含量PACM的关键。
6．较佳的工艺条件为：反应温度180℃，反应压力8.0MPa，催化剂需经过碱处理，其用量为2.5 wt％。
7．在较佳工艺条件下，催化剂经三次连续套用后仍可以满足PACM-20产品的要求，主产物PACM的收率能达到95％～97％以上。
8．进一步提出了MDA催化加氢制备PACM的反应网络，并且得出了控制副反应产生的关键，为将来生产工艺的改善提供了依据。
As for the industries of Polyurethane (PU) and Polyamines, bis(para-aminocyclohexyl)methane(PACM) is an important intermediate. In general, PACM could be synthesized by hydrogenating 4,4'-Methylene-dianiline (MDA) with catalyst in high temperature and pressure environment.
In term of thermal properties of PACM, its stereo-isomers could be grouped into three categories: trans-trans, cis-trans, cis-cis. The properties and future uses of PACM and its derivatives are determined by the proportions of the three stereo-isomers. And it is difficult to produce pure stereoisomer or the ratio given PACM. In the industry, the products of PACM are named according to the percentage of tans-trans stereo-isomer. For example, the PACM containing 20% trans-trans isomer is named as PACM-20, which is mainly used to prepare the corresponding isocyanate, and analogously, the PACM with 50% trans-trans isomer is called as PACM-50, which is mainly used to prepare alicyclic polyamines.
In the last decade, a promising prospect of alicyclic isocyanate, which is transparent and hurtless to the environment, begins to emerge, and the need of PACM-20 turns to be growing. And thus, the methods for steadily synthesizing PACM-20 become the key technology for producing PACM-20. Under this background, the thesis emphasizes on the studies and production of the catalysts which can be used to the catalytic hydrogenation of MDA to prepare PACM-20, and establishes the reliable process for the further industrial production of PACM-20. The detailed content and results were given as following:
1. One kind of catalyst was prepared which could be used for the catalytic hydrogenation of MDA to prepare the target PACM-20. This catalyst mainly made up of Ruthenium and Rhodium with proper ratio, and its carrier was y-A12O3.
2. The catalyst which was post-processed by LiOH is steadier than that without post-process.
3. The most significant factor to the yield was the temperature, and the secondly important factor was the ratio between ruthenium and rhodium. The alteration of pressure and dosage of catalysts had the least effects on the yield.
4. The reaction time has a remarkable effect on the content of trans-trans isomer. And prolonging the reaction time could lead to the increase of the content of trans-trans isomer.
5. The efficient control of the reaction temperature and time were crucial to prepare the PACM containing low trans-trans isomer.
6. The optimal reaction process derived by experiments was listed as following: 180 ,8.0Mpa, 2.5% catalytic dosage which was post-processed by alkali.
7. Under the optimized reaction conditions, the improved catalyst could still meet the requirements of preparing PACM-20 after re-use three times and the yield of PACM could still reach 95%-97%.
8. The reaction network for synthesizing PACM from MDA was proposed. Moreover, the key steps for control side reactions were pointed out, which could provide guidance for further optimization of the reaction process.
PACM存在着反-反、顺-反、顺-顺三种热力学性质不同的立体异构体，异构体的组成决定了其及其后续产品的性质及用途，而且难于通过分离手段获得单一或者特定异构体组成的PACM，因此工业上PACM产品均为各种立体异构的混合物且习惯用反-反异构体含量定义PACM的规格与用途，反-反异构体含量20％以下称为PACM-20，主要用于制备脂肪族聚氨酯，反-反异构体含量50％左右称为PACM-50，主要用于制备聚酰胺树脂。
上世纪90年代以来，环境友好且透明的脂肪族异氰酸酯的应用前景看好，PACM-20的需求加大，因此开发合成稳定的含低反-反立体异构的PACM-20的生产技术成为关键。本文以此为背景，研究并开发了MDA液相催化加氢合成PACM-20的催化剂及其合成工艺，为PACM-20的进一步工业开发提供了依据。研究结果具体体现在：
1．由γ-三氧化二铝为载体、采用混合浸渍法制得的合适比例组成的钌铑负载型催化剂可以用于MDA催化加氢，可制备出符合要求的PACM—20。
2．使用氢氧化锂对催化剂进行碱处理，效果良好。
3．温度的变化对收率的影响最大，钌／铑比例次之，压力和催化剂用量的改变对收率影响最小。
4．反应时间对反-反异构体含量的影响十分显著，延长反应时间将使反-反异构体含量增加。
5．有效控制反应温度和反应时间是获得低反-反异构体含量PACM的关键。
6．较佳的工艺条件为：反应温度180℃，反应压力8.0MPa，催化剂需经过碱处理，其用量为2.5 wt％。
7．在较佳工艺条件下，催化剂经三次连续套用后仍可以满足PACM-20产品的要求，主产物PACM的收率能达到95％～97％以上。
8．进一步提出了MDA催化加氢制备PACM的反应网络，并且得出了控制副反应产生的关键，为将来生产工艺的改善提供了依据。
As for the industries of Polyurethane (PU) and Polyamines, bis(para-aminocyclohexyl)methane(PACM) is an important intermediate. In general, PACM could be synthesized by hydrogenating 4,4'-Methylene-dianiline (MDA) with catalyst in high temperature and pressure environment.
In term of thermal properties of PACM, its stereo-isomers could be grouped into three categories: trans-trans, cis-trans, cis-cis. The properties and future uses of PACM and its derivatives are determined by the proportions of the three stereo-isomers. And it is difficult to produce pure stereoisomer or the ratio given PACM. In the industry, the products of PACM are named according to the percentage of tans-trans stereo-isomer. For example, the PACM containing 20% trans-trans isomer is named as PACM-20, which is mainly used to prepare the corresponding isocyanate, and analogously, the PACM with 50% trans-trans isomer is called as PACM-50, which is mainly used to prepare alicyclic polyamines.
In the last decade, a promising prospect of alicyclic isocyanate, which is transparent and hurtless to the environment, begins to emerge, and the need of PACM-20 turns to be growing. And thus, the methods for steadily synthesizing PACM-20 become the key technology for producing PACM-20. Under this background, the thesis emphasizes on the studies and production of the catalysts which can be used to the catalytic hydrogenation of MDA to prepare PACM-20, and establishes the reliable process for the further industrial production of PACM-20. The detailed content and results were given as following:
1. One kind of catalyst was prepared which could be used for the catalytic hydrogenation of MDA to prepare the target PACM-20. This catalyst mainly made up of Ruthenium and Rhodium with proper ratio, and its carrier was y-A12O3.
2. The catalyst which was post-processed by LiOH is steadier than that without post-process.
3. The most significant factor to the yield was the temperature, and the secondly important factor was the ratio between ruthenium and rhodium. The alteration of pressure and dosage of catalysts had the least effects on the yield.
4. The reaction time has a remarkable effect on the content of trans-trans isomer. And prolonging the reaction time could lead to the increase of the content of trans-trans isomer.
5. The efficient control of the reaction temperature and time were crucial to prepare the PACM containing low trans-trans isomer.
6. The optimal reaction process derived by experiments was listed as following: 180 ,8.0Mpa, 2.5% catalytic dosage which was post-processed by alkali.
7. Under the optimized reaction conditions, the improved catalyst could still meet the requirements of preparing PACM-20 after re-use three times and the yield of PACM could still reach 95%-97%.
8. The reaction network for synthesizing PACM from MDA was proposed. Moreover, the key steps for control side reactions were pointed out, which could provide guidance for further optimization of the reaction process.
引文
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[41]. Gary F. Alien. Catalytic hydrogenation of di(4-aminophenyl)methane. 1983-07-19. US4394522. (MDA催化加氢)
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[46]. Takahata Hiroyuki; others .Production of bis(4-aminocyclohexyl)methane. 1988-08-30. JP63208555. (PACM 的制备)
[47]. Gary F. Allen; Bub Gunther Dr; Otte Werner Dr; Schmelzer Hans-georg. Process for the production of 4,4'-diamino-dicyclohexylmethane with a low trans-trans isomer content by the
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[56]. Peter J. Whitman. Method of increasing hydrogenation rate of aromatic amines. 1996-08-27.
US5550294(=WO9608462)．(提高芳香胺加氢速率的方法)
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[67]． Michael J．Girgis．etc．刘晨光，王芳珠，译。曹重远，校。高压催化加氢过程的反应性、反应网络和动力学(综述)。世界石油科学。1994年第5期(总第64期)：1995年第1期(总第66期)；1995年第2期(总第67期)；1995年第3期(总第68期)：1995年
第4期(总第69期)：(《Ind．Eng．Chem．Res．》，Vol．30，No．9，1991)
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[69]. A. E. Barkdoll; H. W. Gray; W. Kirk, JR. Alicyclic diamines: The geometric Isomers of Bis-(4-aminocyclohexyl)-methane. Vol. 73. Feb. 1951. (脂环二胺: 二-(4-氨基环己基)-甲烷的几何异构体)