TWI788750B - Catalyst composition for hydrogenating 4,4’-methylenedianiline derivatives and method for preparing 4,4’-methylene bis(cyclohexylamine) derivatives using the same - Google Patents

Abstract

A catalyst composition for hydrogenating 4,4’-methylenedianiline derivatives is provided. The catalyst composition includes a carrier including aluminum oxide and magnesium oxide, a rhodium-ruthenium active layer loaded on the surface of the carrier, and a solvent including an organic amine. The weight percentage of magnesium oxide in the carrier is between 12% and 30%. A method for preparing 4,4’-methylene bis(cyclohexylamine) derivatives using the catalyst composition is also provided.

Description

Catalyst composition for hydrogenation of 4,4'-diaminodiphenylmethane derivative and method for preparing 4,4'-diaminodicyclohexylmethane derivative using same

The present disclosure relates to a catalyst composition, in particular to a catalyst composition for hydrogenation of 4,4'-diaminodiphenylmethane (4,4'-methylenedianiline, MDA) derivatives and its use. , The preparation method of 4'-diamino dicyclohexylmethane (4,4'-methylene bis(cyclohexylamine), PACM) derivative.

4,4'-Diaminodiphenylmethane (4,4'-methylenedianiline, referred to as MDA) is an important aromatic diamine compound, which is produced by the polymerization reaction of aniline and formaldehyde, and can be used to prepare polyurethane (polyurethane, PU) The monomer diphenylmethane diisocyanate (methylene diphenyl diisocyanate, referred to as MDI) or react with maleic anhydride to prepare N,N'-(4,4'-diphenylmethane) bismaleimide, which can also be used as Hardener for epoxy resins, used in composite materials.

MDA undergoes a hydrogenation reaction (that is, the benzene ring in the molecule is completely hydrogenated) to obtain diaminodicyclohexylmethane (4,4'-methylene bis(cyclohexylamine) or bis(para-amino cyclohexyl)methane, referred to as PACM or H12MDA ). The isocyanate (H12MDI) prepared from PACM has good optical stability (anti-yellowing), weather resistance and mechanical properties, and can be applied to the preparation of weather-resistant coatings, water-based PU fabrics and thermoplastic polyurethane (TPU), and can also be used as Epoxy resin hardener, used in high-strength, high-temperature-resistant composite materials and low-dielectric constant electronic packaging materials.

In order to improve the selectivity of synthesizing 4,4'-diaminocyclohexylmethane (bis(para-aminocyclohexyl)methane, PACM) derivatives, this disclosure provides a novel catalyst composition and 4,4 The preparation method of '-diaminodicyclohexylmethane (PACM) derivatives, by increasing the content of magnesium oxide in the catalyst system and carrying out the hydrogenation reaction with an organic amine (organic amine) solvent, on the one hand avoids the coupling of the product itself The by-products produced by the reaction, on the other hand, also greatly increase the selectivity of the synthesis of 4,4'-diaminodicyclohexylmethane (PACM) derivatives and can effectively reduce carbon monoxide (CO) and methane (CH ₄ ) in the tail gas content.

According to an embodiment of the present disclosure, a catalytic composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives is provided, including: a carrier, including alumina and magnesia, wherein the weight percentage of magnesia in the carrier is Between 12% and 30%; rhodium-ruthenium active layer, loaded on the surface of the carrier; and solvent, including organic amine.

In one embodiment, the concentration of magnesium oxide presents a gradually decreasing gradient relationship from the surface layer of the carrier to the inside. In one embodiment, the specific surface area of the carrier is between 150 m ² /g and 250 m ² /g. In one embodiment, the weight percentage of magnesium oxide in the carrier is between 14% and 25%. In one embodiment, the interior of the support is composed of alumina (Al ₂ O ₃ ), and the exterior of the support is composed of magnesium aluminum oxide (Mg(Al)O). In one embodiment, the weight ratio of magnesium oxide to aluminum oxide in magnesium aluminum oxide is between 2:1 and 1:2. In one embodiment, the weight percentage of magnesia aluminum in the carrier is between 20% and 50%.

，化學式(I)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。在一實施例中，上述溶劑更包括四氫呋喃(THF)。在一實施例中，上述溶劑不包括四氫呋喃、醇類、或醚類。在一實施例中，4,4’-二胺基二苯甲烷衍生物為取代或未取代的4,4’-二胺基二苯甲烷。In one embodiment, the weight ratio of rhodium to ruthenium in the rhodium-ruthenium active layer is between 40:60 and 10:90. In one embodiment, the weight ratio of the rhodium-ruthenium active layer to the support is between 1:24 and 1:16. In one embodiment, the organic amines include aniline, cyclohexylamine, dicyclohexylamine, o-toluidine, 2-methylaniline, 2-methylcyclohexylamine, 2,6-dimethylaniline, 2,6 -Dimethylcyclohexylamine, 2-ethyl-6-methylaniline, 2-ethyl-6-methylcyclohexylamine, 4,4'-diaminodicyclohexylmethane derivatives, or combinations thereof . In one embodiment, the 4,4'-diaminodicyclohexylmethane derivative has the formula (I):

, In chemical formula (I), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . In one embodiment, the above solvent further includes tetrahydrofuran (THF). In one embodiment, the above-mentioned solvent does not include tetrahydrofuran, alcohols, or ethers. In one embodiment, the 4,4'-diaminodiphenylmethane derivative is substituted or unsubstituted 4,4'-diaminodiphenylmethane.

According to an embodiment of the present disclosure, a method for preparing 4,4'-diaminodicyclohexylmethane derivatives is provided, comprising: combining the above-mentioned catalysts for hydrogenating 4,4'-diaminodiphenylmethane derivatives The material is configured in the reactor; and 4,4'-diaminodiphenylmethane (MDA) derivatives and hydrogen are introduced into the reactor for hydrogenation reaction to prepare 4,4'-diaminodicyclohexylmethane (PACM) derivatives.

In one embodiment, the reactor comprises a continuous reactor. In one embodiment, the reactor includes a trickle-bed reactor, a bubble column reactor, or a loop reactor.

In one embodiment, the hydrogen pressure of the hydrogenation reaction is between 60 bar and 80 bar. In one embodiment, the temperature of the hydrogenation reaction is between 100°C and 160°C.

，化學式(II)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。In one embodiment, the 4,4'-diaminodiphenylmethane derivative has the formula (II):

, In chemical formula (II), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ .

This disclosure adopts a novel catalyst hydrogenation process, by increasing the content of magnesium oxide in the catalyst system and matching organic amine solvents, and in a continuous reactor, under relatively low pressure conditions (within 80bar), the diamine base Continuous hydrogenation of diphenylmethane (MDA) derivatives to produce liquid 4,4'-diaminodicyclohexylmethane (PACM) derivatives with a yield of over 90%, and 4,4'-diamine The ratio of trans-trans isomers of dicyclohexylmethane (PACM) derivatives is less than 30%. When the solvent does not use tetrahydrofuran, alcohols, or ethers, the tail gas contains only a small amount of carbon monoxide (CO) Catalyst poisoning gas. The present disclosure uses a ruthenium (Ru)-rhodium (Rh) bimetallic catalyst supported on a carrier comprising magnesia and alumina, while utilizing liquid organic amines such as cyclohexylamine, aniline or its own product 4,4'-di Aminodicyclohexylmethane (PACM) derivatives are used as the base source in the system and simultaneously as the solvent. The disclosed hydrogenation process is not easy to generate self-coupling by-products and gaseous by-products such as carbon monoxide (CO) or methane (CH ₄ ), which greatly reduces raw material consumption and eliminates (gas, liquid) purification process to improve economy. And the hydrogen introduced in the process can be directly recovered and recycled, reducing investment costs and increasing competitiveness.

According to an embodiment of the present disclosure, there is provided a catalytic composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives, comprising: a carrier comprising alumina and magnesia, the weight percentage of magnesia in the carrier between 12% and 30%; a rhodium-ruthenium active layer loaded on the surface of the above-mentioned carrier; and a solvent including organic amine. The content of magnesium oxide has a certain relationship with the characteristics (pH) of the carrier. Generally speaking, the basicity of the carrier will increase with the increase of magnesium oxide content, and a proper proportion of magnesium oxide content can obtain better reactivity, product selectivity and mechanical strength of the catalyst. In the present disclosure, the 4,4'-diaminodiphenylmethane derivative refers to substituted or unsubstituted 4,4'-diaminodiphenylmethane.

In one embodiment, the specific surface area of the carrier is about 150 m ² /g to 250 m ² /g. In one embodiment, the weight percentage of magnesium oxide in the above carrier is about 14% to 25%. In one embodiment, the concentration of magnesium oxide presents a gradually decreasing gradient relationship from the surface layer of the carrier to the inside. In one embodiment, the interior of the above-mentioned carrier is mainly composed of alumina (Al ₂ O ₃ ), and the exterior of the above-mentioned carrier is mainly composed of magnesium aluminum oxide (Mg(Al)O), wherein the concentration distribution of magnesium oxide is given by The surface layer of the carrier presents a gradually decreasing gradient relationship inward. The "magnesia aluminum oxide" mentioned in this disclosure refers to the composite oxide of aluminum oxide and magnesium oxide. In one embodiment, the weight ratio of magnesium oxide to aluminum oxide in magnesium aluminum oxide (Mg(Al)O) is about 2:1 to 1:2. In one embodiment, the weight percentage of magnesia aluminum in the above-mentioned carrier is about 20% to 50%.

，化學式(I)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。在一實施例中，本揭露觸媒組合物的溶劑更包括四氫呋喃(THF)。在一實施例中，有機胺於溶劑中的重量比大約介於2.5wt%至100wt%。在一實施例中，本揭露觸媒組合物的溶劑不含四氫呋喃(THF)、醇類、醚類、或其他有機溶劑，可以有效降低尾氣中一氧化碳(CO)或甲烷(CH₄ )等氣體副產物的含量。In one embodiment, the weight ratio of rhodium to ruthenium in the rhodium-ruthenium active layer is about 40:60 to 10:90. In one embodiment, the weight ratio of the rhodium-ruthenium active layer to the carrier is about 1:24 to 1:16. In one embodiment, the above-mentioned organic amines may include aniline, cyclohexylamine, dicyclohexylamine, o-toluidine, 2-methylaniline, 2-methylcyclohexylamine, 2,6-dimethylaniline, 2 ,6-Dimethylcyclohexylamine, 2-ethyl-6-methylaniline, 2-ethyl-6-methylcyclohexylamine, 4,4'-diaminodicyclohexylmethane derivatives, or its combination. In one embodiment, the 4,4'-diaminodicyclohexylmethane derivative has the formula (I):

, In chemical formula (I), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . In one embodiment, the solvent of the catalyst composition of the present disclosure further includes tetrahydrofuran (THF). In one embodiment, the weight ratio of the organic amine in the solvent is about 2.5 wt % to 100 wt %. In one embodiment, the solvent of the catalyst composition of the present disclosure does not contain tetrahydrofuran (THF), alcohols, ethers, or other organic solvents, which can effectively reduce gas by-products such as carbon monoxide (CO) or methane (CH ₄ ) in the tail gas. product content.

According to an embodiment of the present disclosure, there is provided a method for preparing 4,4'-diaminodicyclohexylmethane derivatives, comprising: a catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives Configured in a reactor; and introducing 4,4'-diaminodiphenylmethane (MDA) derivatives and hydrogen into the above reactor for hydrogenation reaction to prepare 4,4'-diaminodicyclohexylmethane (PACM) derivatives.

In one embodiment, the catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives may include a carrier, a rhodium-ruthenium active layer, and a solvent containing an organic amine. The above-mentioned carrier may include alumina and magnesia, and the weight percentage of magnesia in the above-mentioned carrier is about 12% to 30%. The rhodium-ruthenium active layer is supported on the surface of the carrier.

In one embodiment, the specific surface area of the carrier is about 150 m ² /g to 250 m ² /g. In one embodiment, the weight percentage of magnesium oxide in the above carrier is about 14% to 25%. In one embodiment, the concentration of magnesium oxide presents a gradually decreasing gradient relationship from the surface layer of the carrier to the inside. In one embodiment, the interior of the above-mentioned carrier is mainly composed of alumina (Al ₂ O ₃ ), and the exterior of the above-mentioned carrier is mainly composed of magnesium aluminum oxide (Mg(Al)O), wherein the concentration distribution of magnesium oxide is given by The surface layer of the carrier presents a gradually decreasing gradient relationship inward. In one embodiment, the weight ratio of magnesium oxide to aluminum oxide in magnesium aluminum oxide (Mg(Al)O) is about 2:1 to 1:2. In one embodiment, the weight percentage of magnesia aluminum in the above-mentioned carrier is about 20% to 50%.

，化學式(I)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。在一實施例中，本揭露觸媒組合物的溶劑更包括四氫呋喃(THF)。在一實施例中，有機胺於溶劑中的重量比大約介於2.5wt%至100wt%。在一實施例中，本揭露觸媒組合物的溶劑不含四氫呋喃(THF)、醇類、醚類、或其他有機溶劑。In one embodiment, the weight ratio of rhodium to ruthenium in the rhodium-ruthenium active layer is about 40:60 to 10:90. In one embodiment, the weight ratio of the rhodium-ruthenium active layer to the carrier is about 1:24 to 1:16. In one embodiment, the above-mentioned organic amines may include aniline, cyclohexylamine, dicyclohexylamine, o-toluidine, 2-methylaniline, 2-methylcyclohexylamine, 2,6-dimethylaniline, 2 ,6-Dimethylcyclohexylamine, 2-ethyl-6-methylaniline, 2-ethyl-6-methylcyclohexylamine, 4,4'-diaminodicyclohexylmethane derivatives, or its combination. In one embodiment, the 4,4'-diaminodicyclohexylmethane derivative has the formula (I):

, In chemical formula (I), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . In one embodiment, the solvent of the catalyst composition of the present disclosure further includes tetrahydrofuran (THF). In one embodiment, the weight ratio of the organic amine in the solvent is about 2.5 wt % to 100 wt %. In one embodiment, the solvent of the catalyst composition of the present disclosure does not contain tetrahydrofuran (THF), alcohols, ethers, or other organic solvents.

In one embodiment, the above-mentioned reactor may include a continuous reactor. In one embodiment, the above-mentioned reactor may include a trickle-bed reactor, a bubble column reactor, or a loop reactor. In one embodiment, the hydrogen pressure of the hydrogenation reaction is approximately between 60 bar and 80 bar. In one embodiment, the temperature of the hydrogenation reaction is approximately between 100°C and 160°C. If the reaction temperature is too high, the trans-trans isomer ratio of the product may be too high.

，化學式(II)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。在一實施例中，4,4’-二胺基二苯甲烷衍生物包括二胺基二苯甲烷(MDA)、3,3’-二甲基-4,4’-二氨基二苯甲烷(MDT)、或4,4’-亞甲基雙(2-甲基-6-乙基苯胺)(MED)。在一實施例中，4,4’-二胺基二環己基甲烷衍生物(氫化反應的產物)具有化學式(I)：

，化學式(I)中，R1、R2、R3與R4獨立地包括H、CH₃ 、C₂ H₅ 、或C₃ H₇ 。在一實施例中，4,4’-二胺基二環己基甲烷衍生物包括4,4’-二胺基二環己基甲烷(PACM)、3,3’-二甲基-4,4-二氨基二環己基甲烷(DMDC)或氫化4,4’-亞甲基雙(2-甲基-6-乙基苯胺)(H-MED)。In one embodiment, the 4,4'-diaminodiphenylmethane derivative (reactant of the hydrogenation reaction) has the formula (II):

, In chemical formula (II), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . In one embodiment, 4,4'-diaminodiphenylmethane derivatives include diaminodiphenylmethane (MDA), 3,3'-dimethyl-4,4'-diaminodiphenylmethane ( MDT), or 4,4'-methylenebis(2-methyl-6-ethylaniline) (MED). In one embodiment, the 4,4'-diaminodicyclohexylmethane derivative (product of the hydrogenation reaction) has the formula (I):

, In chemical formula (I), R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . In one embodiment, 4,4'-diaminodicyclohexylmethane derivatives include 4,4'-diaminodicyclohexylmethane (PACM), 3,3'-dimethyl-4,4- Diaminodicyclohexylmethane (DMDC) or hydrogenated 4,4'-methylenebis(2-methyl-6-ethylaniline) (H-MED).

This disclosure adopts a novel catalyst hydrogenation process, by increasing the content of magnesium oxide in the catalyst system and matching organic amine solvents, and in a continuous reactor, under relatively low pressure conditions (within 80bar), the diamine base Continuous hydrogenation of diphenylmethane (MDA) derivatives to produce liquid 4,4'-diaminodicyclohexylmethane (PACM) derivatives with a yield of over 90%, and 4,4'-diamine The ratio of trans-trans isomers of dicyclohexylmethane (PACM) derivatives is less than 30%, and at the same time, the tail gas contains only a very small amount of catalyst poisoning gases such as carbon monoxide (CO). The present disclosure uses a ruthenium (Ru)-rhodium (Rh) bimetallic catalyst supported on a carrier comprising magnesia and alumina, while utilizing liquid organic amines such as cyclohexylamine, aniline or its own product 4,4'-di Aminodicyclohexylmethane (PACM) derivatives are used as the base source in the system and simultaneously as the solvent. The disclosed hydrogenation process is not easy to generate self-coupling by-products and gaseous by-products such as carbon monoxide (CO) or methane (CH ₄ ), which greatly reduces raw material consumption and eliminates (gas, liquid) purification process to improve economy. And the hydrogen introduced in the process can be directly recovered and recycled, reducing investment costs and increasing competitiveness.

Preparation Example 1

catalyst A preparation of

First, 2.6L deionized aqueous solution containing 258g of magnesium nitrate and 377g of aluminum nitrate was added to 2L deionized aqueous solution containing 118g of sodium hydroxide and 256g of sodium carbonate, stirred at room temperature and matured (aging) for 18 hours to form Magnesium-aluminum gel (Mg-Al sol-gel). Afterwards, 255 g of alumina (purchased from UOP, with a specific surface area of 188 m ² /g and a pore volume of 0.87 ml/g) was added to the gel, stirred continuously for 1 hour and then filtered. Gained filter cake is dried in 110 ℃ after washing three times. The dried filter cake is crushed to less than 100 mesh to obtain modified alumina powder. Next, the modified alumina powder, adhesive and water are mixed uniformly, extruded into strips, dried at 110°C, and calcined at 450°C. After pelletizing, the carrier can be obtained. The magnesium oxide content of the support is about 9.6%.

Weigh 15-20g of the carrier, and add 4 times the amount of impregnation solution (ie 60-80g) to impregnate for 40 minutes. _The preparation _{of the} impregnating solution was prepared with specific _metal concentration (4%Ru, 1% Rh) impregnation solution. The impregnated catalyst was filtered, dried, and calcined at 450° C. for 4 hours to obtain the catalyst A prepared in this preparation example.

Preparation example 2

catalyst B preparation of

First, 2.6L deionized aqueous solution containing 310g of magnesium nitrate and 301g of aluminum nitrate was added to 2L deionized aqueous solution containing 118g of sodium hydroxide and 256g of sodium carbonate, stirred at room temperature and matured (aging) for 18 hours to form Magnesium-aluminum gel (Mg-Al sol-gel). Afterwards, 205 g of alumina (purchased from UOP, with a specific surface area of 188 m ² /g and a pore volume of 0.87 ml/g) was added to the gel, stirred continuously for 1 hour and then filtered. Gained filter cake is dried in 110 ℃ after washing three times. The dried filter cake is crushed to less than 100 mesh to obtain modified alumina powder. Next, the modified alumina powder, adhesive and water are mixed uniformly, extruded into strips, dried at 110°C, and calcined at 450°C. After pelletizing, the carrier can be obtained. The magnesium oxide content of the support is about 14.2%.

Weigh 15-20g of the carrier, and add 4 times the amount of impregnation solution (ie 60-80g) to impregnate for 40 minutes. _The preparation _{of the} impregnating solution was prepared with specific _metal concentration (4%Ru, 1% Rh) impregnation solution. The impregnated catalyst was filtered, dried, and calcined at 450° C. for 4 hours to obtain the catalyst B prepared in this preparation example.

Preparation example 3

catalyst C preparation of

First, 2.6L deionized aqueous solution containing 258g of magnesium nitrate and 377g of aluminum nitrate was added to 2L deionized aqueous solution containing 118g of sodium hydroxide and 256g of sodium carbonate, stirred at room temperature and matured (aging) for 18 hours to form Magnesium-aluminum gel (Mg-Al sol-gel). Afterwards, 102 g of alumina (purchased from UOP, with a specific surface area of 188 m ² /g and a pore volume of 0.87 ml/g) was added to the gel, stirred continuously for 1 hour and then filtered. Gained filter cake is dried in 110 ℃ after washing three times. The dried filter cake is crushed to less than 100 mesh to obtain modified alumina powder. Next, the modified alumina powder, adhesive and water are mixed uniformly, extruded into strips, dried at 110°C, and calcined at 450°C. After pelletizing, the carrier can be obtained. The magnesium oxide content of this support is about 18.9%.

Weigh 15-20g of the carrier, and add 4 times the amount of impregnation solution (ie 60-80g) to impregnate for 40 minutes. _{The preparation of the} impregnating solution was prepared with specific metal concentration (4%Ru, 1% Rh) impregnation solution. The impregnated catalyst was filtered, dried, and calcined at 450° C. for 4 hours to obtain the catalyst C prepared in this preparation example.

Preparation Example 4

catalyst D. preparation of

First, 2.6L deionized aqueous solution containing 281g of magnesium nitrate and 206g of aluminum nitrate was added to 2L deionized aqueous solution containing 118g of sodium hydroxide and 256g of sodium carbonate, stirred at room temperature and matured (aging) for 18 hours to form Magnesium-aluminum gel (Mg-Al sol-gel). Afterwards, 100 g of alumina (purchased from UOP, with a specific surface area of 218 m ² /g and a pore volume of 0.51 ml/g) was added to the gel, stirred continuously for 1 hour and then filtered. Gained filter cake is dried in 110 ℃ after washing three times. The dried filter cake is crushed to less than 100 mesh to obtain modified alumina powder. Next, the modified alumina powder, adhesive and water are mixed uniformly, extruded into strips, dried at 110°C, and calcined at 450°C. After pelletizing, the carrier can be obtained. The magnesium oxide content of this support is about 23.8%.

Weigh 15-20g of the carrier, and add 4 times the amount of impregnation solution (ie 60-80g) to impregnate for 40 minutes. _{The preparation of the} impregnating solution was prepared with specific metal concentration (4%Ru, 1% Rh) impregnation solution. The impregnated catalyst was filtered, dried, and calcined at 450° C. for 4 hours to obtain the catalyst D prepared in this preparation example.

Example 1

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst B (20-30 mesh) prepared in Preparation Example 2, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with cyclohexylamine (cyclohexylamine, CHA) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was 92-94%, and the proportion of (trans, trans)-PACM was about 25%. The ratio of self-coupling by-products was 0% (GC retention time at 40 minutes), and the ratio of product and cyclohexylamine coupling by-products was 3-5% (GC retention time at 25 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example is 86-90%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 2ppm, methane gas (CH ₄ ) is about 0.03%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1.

Example 2

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst C (20-30 mesh) prepared in Preparation Example 3, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with cyclohexylamine (cyclohexylamine, CHA) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 94%, and the proportion of (trans, trans)-PACM was about 25%. The ratio of self-coupling by-products was 0% (GC retention time at 40 minutes), and the ratio of product and cyclohexylamine coupling by-products was 2-3% (GC retention time at 25 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example is greater than 90%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 2ppm, methane gas (CH ₄ ) is about 0.03%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1.

Example 3

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with cyclohexylamine (cyclohexylamine, CHA) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 95%, and the proportion of (trans, trans)-PACM was about 25%. The ratio of self-coupling by-products was 0% (GC retention time at 40 min), and the ratio of product to cyclohexylamine coupling by-product was about 2% (GC retention time at 25 min). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example is greater than 90%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 2ppm, methane gas (CH ₄ ) is about 0.03%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1.

Example 4

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst C (20-30 mesh) prepared in Preparation Example 3, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: using 4,4'-diaminodicyclohexylmethane (PACM) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 96-98%, and the proportion of (trans, trans)-PACM was about 27%. The ratio of self-coupling by-products was 0% (GC retention time at 40 minutes), and the ratio of product to cyclohexylamine coupling by-products was 0% (GC retention time at 25 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example is greater than 95%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 2ppm, methane gas (CH ₄ ) is about 0.03%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1.

Comparative example 1

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst A (20-30 mesh) prepared in Preparation Example 1, which contains 4.0% Ru and 1.0% Rh (weight ratio relative to the carrier). Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with cyclohexylamine (cyclohexylamine, CHA) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was 75-80%, and the proportion of (trans, trans)-PACM was about 25%. The ratio of self-coupling by-products was 0% (GC retention time at 40 minutes), and the ratio of product to cyclohexylamine coupling by-products was 10-16% (GC retention time at 25 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this comparative example is 70-80%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 2ppm, methane gas (CH ₄ ) is about 0.03%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1.

Comparative example 2

4,4'- Preparation and Product Analysis of Diaminodicyclohexylmethane

First, weigh 7 mL of catalyst A (20-30 mesh) prepared in Preparation Example 1, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為25.0wt%，液體流速為4.5mL/h，反應溫度為130°C，反應壓力為70-75bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with tetrahydrofuran (THF) as solvent, diaminodiphenylmethane (MDA) (MDA ₁₀₀ ,

) (purchased from Shuangbang) has a concentration of 25.0wt%, a liquid flow rate of 4.5mL/h, a reaction temperature of 130°C, a reaction pressure of 70-75bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 70%, and the proportion of (trans, trans)-PACM was about 20%. The ratio of self-coupling by-products was 12-20% (GC retention time at 40 minutes), and the ratio of product to cyclohexylamine coupling by-products was 0% (GC retention time at 25 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this comparative example is 60-70%.

Tail gas analysis is as follows: carbon monoxide (CO) is about 250-300ppm, methane gas (CH ₄ ) is about 1-2%. The above hydrogenation reaction conditions, gas chromatography analysis results and tail gas analysis results are shown in Table 1. Table 1 Example/Comparative example catalyst Feed self-coupling Coupling with cyclohexylamine PACM selectivity Tail gas CO (ppm), CH ₄ (%) content Example 1 B 25%MDA/CHA na 3-5% 86-90% ≤2ppm; ≤0.03% Example 2 C 25%MDA/CHA na 2-3% ≥90% ≤2ppm; ≤0.03% Example 3 D. 25%MDA/CHA na ~2% ≥90% ≤2ppm; ≤0.03% Example 4 C 25%MDA/PACM na na ≥95% ≤2ppm; ≤0.03% Comparative example 1 A 25%MDA/CHA na 10-16% 70-80% ≤2ppm; ≤0.03% Comparative example 2 A 25%MDA/ THF 12-20% na 60-70% 250-300 ppm; 1-2%

Example 5

hydrogenation 4,4'- methylene bis (2- methyl -6- Ethylaniline )(H-MED) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, this catalyst was placed in a fixed-bed reactor, and 4,4'-methylenebis(2-methyl-6-ethylaniline) (MED ) for hydrogenation to prepare hydrogenated 4,4'-methylenebis(2-methyl-6-ethylaniline) (H-MED).

)(購自雙邦)的濃度為10.0wt%，液體流速為7.20mL/h，反應溫度為132°C，反應壓力為70bar，氫氣流速為60-100mL/m。The hydrogenation reaction conditions are as follows: use tetrahydrofuran (THF) as solvent, and add 5.0wt% of 2-ethyl-6-methylaniline (2E6M-aniline), 4,4'-methylenebis(2-methyl- 6-Ethylaniline) (MED,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 7.20mL/h, a reaction temperature of 132°C, a reaction pressure of 70bar, and a hydrogen flow rate of 60-100mL/m.

The analysis result of gas chromatography analyzer is as follows: 4,4'-methylenebis(2-methyl-6-ethylaniline) (MED) conversion rate is 100% (0.56% monocyclic hydrogenation intermediate product (H6MED)), the yield of hydrogenated 4,4'-methylenebis(2-methyl-6-ethylaniline) (H-MED) was about 99%, and the proportion of self-coupling by-products was 0% (GC retention time at 40 minutes). The selectivity of hydrogenated 4,4'-methylenebis(2-methyl-6-ethylaniline) (H-MED) prepared in this example was 98.7%, and the results are shown in Table 2.

Example 6

3,3'- Dimethyl -4,4- Diaminodicyclohexylmethane (DMDC) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst was placed in a fixed-bed reactor to treat 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) in a continuous trickle-bed mode. Hydrogenation to produce 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC).

)(購自雙邦)的濃度為10.0wt%，液體流速為7.20mL/h，反應溫度為132°C，反應壓力為70bar，氫氣流速為60-100mL/m。The hydrogenation reaction conditions are as follows: use tetrahydrofuran (THF) as solvent, and add 5.0wt% cyclohexylamine (cyclohexylamine, CHA), 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 7.20mL/h, a reaction temperature of 132°C, a reaction pressure of 70bar, and a hydrogen flow rate of 60-100mL/m.

The analysis results of the gas chromatography analyzer are as follows: the conversion rate of 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) is 100% (no monocyclic hydrogenation intermediate product (H6MDT)) , the yield of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) is about 97-98%, and the proportion of self-coupling by-products is 0% (GC retention time is 40 minutes ), the ratio of product and cyclohexylamine coupling by-product is about 0.2-0.6% (GC retention time at 26 minutes). The selectivity of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) prepared in this example was 97.8%, and the results are shown in Table 2.

Example 7

3,3'- Dimethyl -4,4- Diaminodicyclohexylmethane (DMDC) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst was placed in a fixed-bed reactor to treat 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) in a continuous trickle-bed mode. Hydrogenation to produce 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC).

)(購自雙邦)的濃度為10.0wt%，液體流速為7.20mL/h，反應溫度為132°C，反應壓力為70bar，氫氣流速為60-80mL/m。The hydrogenation reaction conditions are as follows: use tetrahydrofuran (THF) as solvent, and add 5.0wt% aniline (aniline, AN), 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 7.20mL/h, a reaction temperature of 132°C, a reaction pressure of 70bar, and a hydrogen flow rate of 60-80mL/m.

The analysis results of the gas chromatography analyzer are as follows: the conversion rate of 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) is 100% (no monocyclic hydrogenation intermediate product (H6MDT)) , the yield of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) is about 98%, and the proportion of self-coupling by-products is 0% (GC retention time is 40 minutes), The ratio of product to cyclohexylamine coupling by-product was about 0.3-0.5% (GC retention time at 26 minutes). The selectivity of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) prepared in this example was 98.1%, and the results are shown in Table 2.

Example 8

3,3'- Dimethyl -4,4- Diaminodicyclohexylmethane (DMDC) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst was placed in a fixed-bed reactor to treat 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) in a continuous trickle-bed mode. Hydrogenation to produce 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC).

)(購自雙邦)的濃度為10.0wt%，液體流速為7.20mL/h，反應溫度為132°C，反應壓力為70bar，氫氣流速為60-100mL/m。The hydrogenation reaction conditions are as follows: use tetrahydrofuran (THF) as solvent, and add 5.0wt% o-toluidine (o-toluidine), 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 7.20mL/h, a reaction temperature of 132°C, a reaction pressure of 70bar, and a hydrogen flow rate of 60-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MDT) conversion rate of 100% (0.09% monocyclic hydrogenation intermediate product (H6MDT )), the yield of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) was about 97-98%, and the proportion of self-coupling by-products was 0% (GC retention time in 40 minutes), the ratio of product and o-toluidine coupling by-product is about 0.4 ~ 0.5% (GC retention time at 26 minutes). The selectivity of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane (DMDC) prepared in this example was 97.5%, and the results are shown in Table 2.

Example 9

4,4'- Diaminodicyclohexylmethane (PACM) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為10.0wt%，液體流速為6.3mL/h，反應溫度為115°C，反應壓力為70bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: use tetrahydrofuran (THF) as solvent, and add 5.0wt% aniline (aniline, AN), diaminodiphenylmethane (MDA) (MDA ₉₆ ,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 6.3mL/h, a reaction temperature of 115°C, a reaction pressure of 70bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 93-95%, and the proportion of (trans, trans)-PACM was about 20-22%. The ratio of self-coupling by-products was 0% (GC retention time at 40 min), and the ratio of product to cyclohexylamine coupling by-product was about 3.3-3.5% (GC retention time at 25 min). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example was 95%.

Comparative example 3

4,4'- Diaminodicyclohexylmethane (PACM) Preparation and product analysis

First, weigh 7 mL of catalyst D (20-30 mesh) prepared in Preparation Example 4, which contains 4.0% Ru and 1.0% Rh. Afterwards, the catalyst is placed in a fixed-bed reactor to hydrogenate diaminodiphenylmethane (MDA) in a continuous trickle-bed mode to produce 4,4'-diamino Dicyclohexylmethane (PACM).

)(購自雙邦)的濃度為10.0wt%，液體流速為6.3mL/h，反應溫度為110-115°C，反應壓力為65-70bar，氫氣流速為80-100mL/m。The hydrogenation reaction conditions are as follows: with tetrahydrofuran (THF) as solvent, diaminodiphenylmethane (MDA) (MDA ₉₆ ,

) (purchased from Shuangbang) has a concentration of 10.0wt%, a liquid flow rate of 6.3mL/h, a reaction temperature of 110-115°C, a reaction pressure of 65-70bar, and a hydrogen flow rate of 80-100mL/m.

The analytical results of the gas chromatography analyzer are as follows: the conversion rate of diaminodiphenylmethane (MDA) is 100% (no monocyclic hydrogenation intermediate product (H6MDA)), 4,4'-diaminodicyclohexylmethane The yield of (PACM) was about 90%, and the proportion of (trans, trans)-PACM was about 21%. The proportion of self-coupling by-products was 8% (GC retention time at 40 minutes). The selectivity of 4,4'-diaminodicyclohexylmethane (PACM) prepared in this example was 90%. Table 2 Example/Comparative example catalyst Feed Selection rate (%) mid product(%) Conversion rate(%) Yield(%) Example 5 D. 10% MED/5% 2E6M-aniline/ THF 98.7 0.56 100 99.29 Example 6 D. 10%MDT/5%CHA/THF 97.8 0 100 97.87 Example 7 D. 10% MDT/5% aniline/THF 98.1 0 100 98.09 Example 8 D. 10% MDT/5% o-toluidine/THF 97.5 0.09 100 97.54 Example 9 D. 10% MDA/5% aniline/THF 95 0 100 95 Comparative example 3 D. 10% MDA/THF 90 0 100 90

As can be seen from the results in Table 1, when only non-amine solvents (such as tetrahydrofuran (THF)) are added in the hydrogenation catalyst system or the magnesium oxide content in the carrier is less than 10% (comparative examples 1, 2), there will be relatively Too many coupling by-products, low product selectivity, or high content of carbon monoxide and methane gas in the tail gas (poisoned catalyst activity), resulting in difficulties in hydrogen recovery and process complexity, increasing investment and solvent costs. However, when the solvent added in the hydrogenation catalyst system is an organic amine solvent (such as cyclohexylamine or 4,4'-diaminodicyclohexylmethane) or when the magnesium oxide content in the carrier is increased (more than 12%) ( Embodiment 1-4), not only its own coupling by-products and the coupling by-products of the product and cyclohexylamine can be greatly reduced, but also only contain a very low proportion of carbon monoxide and methane gas in the tail gas, and can effectively improve the 4,4' - The selectivity of diaminodicyclohexylmethane is over 95%.

It can be seen from the results in Table 2 that when only non-amine solvents (such as tetrahydrofuran (THF)) are added to the hydrogenation catalyst system (comparative example 3), the product selectivity drops significantly. However, when an organic amine solvent (such as aniline, cyclohexylamine or o-toluidine) is added in addition to tetrahydrofuran to the hydrogenation catalyst system (Example 5-9), not only the by-product itself but also the product and cyclo The coupling by-products of hexylamine can be reduced, and the selectivity of 4,4'-diaminodicyclohexylmethane derivatives can be effectively increased to close to 99%.

The features of the above-mentioned embodiments are helpful for those skilled in the art to understand the present invention. Those skilled in the art should understand that the present invention can be used as a basis to design and change other processes and structures to achieve the same purpose and/or the same advantages of the above-mentioned embodiments. Those skilled in the art should also understand that these equivalent replacements do not depart from the spirit and scope of the present invention, and can be changed, replaced, or modified without departing from the spirit and scope of the present invention.

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Claims (18)

A catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives, comprising: a carrier comprising alumina and magnesia, wherein the weight percentage of the magnesia in the carrier is between 14% and 25% between; rhodium-ruthenium active layer, loaded on the surface of the carrier; and solvents, including organic amines, wherein the organic amines include aniline, cyclohexylamine, dicyclohexylamine, o-toluidine, 2-methylaniline, 2 -Methylcyclohexylamine, 2,6-dimethylaniline, 2,6-dimethylcyclohexylamine, 2-ethyl-6-methylaniline, 2-ethyl-6-methylcyclohexylamine , 4,4'-diaminodicyclohexylmethane derivatives, or a combination thereof. The catalyst composition for the hydrogenation of 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the concentration of the magnesium oxide presents a gradually decreasing gradient relationship from the surface layer of the carrier to the inside. The catalyst composition for hydrogenation of 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the specific surface area of the carrier is between 150m ² /g and 250m ² /g. The catalyst composition for hydrogenation of 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the interior of the carrier is made of the alumina, and the exterior of the carrier is made of magnesium aluminum oxide constitute. The catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives as described in item 4 of the claim, wherein the weight ratio of magnesium oxide to aluminum oxide in the magnesium aluminum oxide is between 2:1 and 1 : Between 2. The catalyst composition for hydrogenation of 4,4'-diaminodiphenylmethane derivatives as described in item 4 of the claim, wherein the weight percentage of the magnesium aluminum oxide in the carrier is between 20% and 50% . The catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the weight ratio of rhodium to ruthenium in the rhodium-ruthenium active layer is between 40:60 to 10 : Between 90. The catalyst composition for the hydrogenation of 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the weight ratio of the rhodium-ruthenium active layer to the support is between 1:24 and 1: Between 16. The catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the 4,4'-diaminodicyclohexylmethane derivatives have the chemical formula (I) :

Wherein R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ . The catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the solvent further includes tetrahydrofuran (THF). The catalyst composition for hydrogenating 4,4'-diaminodiphenylmethane derivatives as described in item 1 of the claim, wherein the solvent does not include tetrahydrofuran, alcohols, or ethers. Hydrogenated 4,4'-diaminodiphenylmethane as described in claim item 1 A catalytic composition of derivatives, wherein the 4,4'-diaminodiphenylmethane derivative is substituted or unsubstituted 4,4'-diaminodiphenylmethane. A method for preparing 4,4'-diaminodicyclohexylmethane derivatives, comprising: hydrogenating 4,4'-diaminodiphenyl as described in any one of claim items 1 to 12 The catalyst composition of methane derivatives is arranged in a reactor; and 4,4'-diaminodiphenylmethane derivatives and hydrogen are introduced into the reactor for hydrogenation reaction to prepare 4,4'-diamine dicyclohexylmethane derivatives. The method for preparing 4,4'-diaminodicyclohexylmethane derivatives as described in claim item 13, wherein the reactor comprises a continuous reactor. The preparation method of 4,4'-diaminodicyclohexylmethane derivatives as described in claim item 13, wherein the reactor comprises a trickle bed reactor, a bubble column reactor, or a loop reactor. The method for preparing 4,4'-diaminodicyclohexylmethane derivatives as described in item 13 of the claim, wherein the hydrogen pressure of the hydrogenation reaction is between 60bar and 80bar. The method for preparing 4,4'-diaminodicyclohexylmethane derivatives as described in item 13 of the claim, wherein the temperature of the hydrogenation reaction is between 100°C and 160°C. The preparation method of 4,4'-diaminodicyclohexylmethane derivatives as described in item 13 of the claim, wherein the 4,4'-diaminodiphenylmethane derivatives have the chemical formula (II):

Wherein R1, R2, R3 and R4 independently include H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇ .