CN102010340A - Method of catalytic preparation of 4-aminodiphenylamine by Ni-B amorphous alloy-loaded catalyst - Google Patents

Abstract

The invention discloses a method for catalytically producing 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst, comprising the following steps: (1) mixing aniline and an aqueous alkali solution to distill aniline-water azeotrope; (2) ) add nitrobenzene, react; (3) add water and load Ni-B amorphous alloy catalyst, pass into hydrogen; (4) solid-liquid separation, separate out load Ni-B amorphous alloy catalyst and liquid phase Load Ni-B amorphous alloy catalyst returns to step (3); Liquid phase is carried out phase separation, separates organic phase and aqueous alkali solution, organic phase is rectified, obtains product 4-aminodiphenylamine and reclaims aniline simultaneously, will The aqueous alkali solution returns to step (1). The method of the present invention uses a catalyst lower in price than noble metal catalysts, and simultaneously azobenzene/azobenzene oxide and/or hydrogenated azobenzene are directly hydrogenated into aniline in the hydrogenation reaction step, so that the production process is shortened and the production Reduce costs.

Description

Catalytic production method of 4-aminodiphenylamine with supported Ni-B amorphous alloy catalyst

technical field

The invention relates to a method for producing 4-aminodiphenylamine, in particular to a method for catalytically producing 4-aminodiphenylamine with a Ni-B amorphous alloy catalyst loaded on it.

Background technique

4-aminodiphenylamine (4-aminodiphenylamine) is an important fine chemical intermediate, which can be used in rubber additives, dyes, textiles, printing and pharmaceutical industries, etc. It is mainly used in the production of p-phenylenediamine rubber antioxidants 4010NA, 4020, etc.

There are four main production processes for 4-aminodiphenylamine: aniline method, diphenylamine method, formanilide method and nitrobenzene method. Each of the four routes has its own characteristics. The aniline method is simple in process and low in cost, but has high reaction temperature, many side reactions, and poor product quality. The diphenylamine method mainly uses diphenylamine as a raw material. In the presence of inorganic acids, nitrosation is carried out with nitrite in an organic solvent to obtain N-nitrosodiphenylamine, which is then rearranged into 4-nitrosodiphenylamine with anhydrous hydrogen chloride. Nitrodiphenylamine hydrochloride can be neutralized with alkali to generate 4-nitrosodiphenylamine, and finally reduced to obtain 4-aminodiphenylamine. The process of this method is simple, and the reaction conditions are mild, but there is a large amount of waste water that is difficult to treat, and the cost of raw materials is relatively high. In the formanilide method, aniline first reacts with formic acid to form formanilide, and in the presence of potassium carbonate, directly condenses with p-nitrochlorobenzene to obtain N-formyl diphenylamine, and then decarbonylates to generate 4-nitrodiphenylamine. Then reduce to get 4-aminodiphenylamine. In this method, due to the addition of the acid-binding agent potassium carbonate, a considerable amount of saline waste water is produced, and formic acid is consumed in addition, which not only increases the production cost, but also seriously pollutes the three wastes. The nitrobenzene method uses nitrobenzene to replace p-nitrochlorobenzene and aniline to condense to prepare p-4-aminodiphenylamine. Since nitrobenzene has no chlorine group, hydrogen chloride will not be generated during the condensation process, and a large amount of potassium chloride The waste liquid has disappeared, and its three wastes are reduced by 99% compared with the traditional formanilide route. It is a clean and green process that has developed rapidly in recent years.

The production of 4-aminodiphenylamine by the nitrobenzene method was first developed by Monsanto, and the application date of its core patent (US 5,117,063) was June 21, 1991. The consortium of Monsanto and Akzo Nobel - Flexsyth has established a large-scale production facility of 10,000 tons in Antwerp, Belgium, and won the US President's Green Chemistry Challenge Award in 1998. Many research institutes in China are developing this process, and some enterprises have adopted this route to produce 4-aminodiphenylamine. The typical processing conditions (US6140538, Chinese Patent Application No. 99807892.1) of this method are as follows:

(1) Condensation: Nitrobenzene and aniline undergo condensation reaction at 20-80°C in the presence of tetramethylammonium hydroxide;

(2) Hydrogenation: the condensation reaction mixture is hydrogenated in the presence of noble metal catalysts such as platinum/carbon or palladium/carbon. In the two steps (1) and (2), azobenzene oxide/azobenzene and/or hydrazobenzene will be produced as the main impurity, with a content of about 1-25% (based on nitrobenzene);

(3) Separation and removal of the hydrogenation catalyst, the mixture is layered to obtain two phases, and the water phase (containing tetramethylammonium hydroxide) can be recycled to the condensation reaction;

(4) organic phase rectification under reduced pressure, separate and remove aniline and impurity azobenzene and hydroazobenzene etc., obtain the target product;

(5) The azobenzene or hydroazobenzene obtained in step (4) is hydrogenated and reduced to aniline in the presence of a noble metal catalyst and a cocatalyst, and is recovered and applied to the condensation reaction.

The main deficiency of this method is that, use precious metal catalyst; After hydrogenation reduction product removes tetramethylammonium hydroxide, aniline and finished product 4-aminodiphenylamine, the separated azobenzene/hydroazobenzene etc. need to be separated in an independent In the reactor, it is hydrogenated and reduced to aniline in the presence of a noble metal catalyst and a co-catalyst, and then recycled and applied to the condensation reaction. Although this method can reclaim azobenzene and improve the yield, it will increase equipment, the process route will be long, and investment and production costs will be increased.

Contents of the invention

The purpose of the invention is to overcome the deficiencies in the prior art and provide a method for catalytically producing 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst.

Technical scheme of the present invention is summarized as follows:

The method for catalyzing the production of 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst may further comprise the steps:

(1) Aniline and an aqueous alkali solution of 5% to 40% by mass are mixed in a reactor, and the aniline-water azeotrope is distilled out so that the molar ratio of water and alkali in the reactor is 0.6 to 4 : 1; the alkali is tetramethyl ammonium hydroxide, alkali metal hydroxide and tetramethyl quaternary ammonium salt with a molar ratio of 1: 0～0.5: 0～0.5;

(2) At 20-100°C and a gauge pressure of 0.005-0.1MPa, add nitrobenzene to the reaction kettle within 0.5-5 hours, so that the molar ratio of aniline in the reaction kettle to the added nitrobenzene 3 to 10:1, react for 0 to 1 hour, and generate a mixed solution containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or their salts, azobenzene oxide and azobenzene; alkali The molar ratio with nitrobenzene is 0.7～4:1;

(3) add water, make the mass percent composition of alkali in water be 5%～40%, add the Ni-B amorphous alloy catalyst of loading, pass into hydrogen, make 4-nitrodiphenylamine and 4-nitroso Diphenylamine and/or their salts are hydrogenated to 4-aminodiphenylamine, and azobenzene oxide and azobenzene are hydrogenated to aniline;

(4) The mixture obtained in step (3) is subjected to solid-liquid separation, and the supported Ni-B amorphous alloy catalyst and liquid phase are separated; the supported Ni-B amorphous alloy catalyst returns to step (3) or After regeneration, return to step (3); the liquid phase is phase-separated, the organic phase and the aqueous alkali solution are separated, and the organic phase is rectified to obtain the product 4-aminodiphenylamine while reclaiming aniline, and the aniline Return to step (1), and return the aqueous alkali solution to step (1).

The regeneration of the supported Ni-B amorphous alloy catalyst in the step (4) refers to washing with sodium hydroxide solution.

The alkali metal hydroxide is sodium hydroxide or potassium hydroxide.

The tetramethyl quaternary ammonium salt is tetramethyl ammonium chloride or tetramethyl ammonium bromide.

The mass ratio of Ni-B amorphous alloy catalyst loaded in step (3) to the liquid after adding water in step (3) is 1～6:100, preferably 2～5:100, and the temperature of hydrogenation reaction is 50～200 °C, preferably 60-100 °C, the gauge pressure of the hydrogenation reaction is 1-8.0 MPa, preferably 2-6.0 MPa, and the hydrogenation reaction time is 2-7 hours, preferably 3-5 hours.

The supported Ni-B amorphous alloy catalyst is preferably made by the following method: the nickel chloride aqueous solution is adsorbed on the carrier to make a loaded nickel chloride with a nickel chloride mass content of 5% to 50%, and then adding Ni The aqueous solution of potassium borohydride or sodium borohydride with a molar ratio of : B of 1: 1 to 20 is filtered, washed with water, and washed with ethanol to obtain a loaded Ni-B amorphous alloy catalyst, which is stored in ethanol. The carrier is activated carbon or Al ₂ O ₃ . The Ni:B molar ratio is preferably 1:1.5-2.

In the method for catalytic production of 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst of the present invention, a noble metal catalyst is not used in the hydrogenation step, and azobenzene/azobenzene oxide and/or hydrogenated azobenzene are simultaneously Direct hydrogenation into aniline in the hydrogenation reaction step avoids the need in the prior art to separate the azobenzene/azobenzene oxide and/or hydrogenated azobenzene and make the process complicated by hydrogenation alone. The technological process is shortened and the production cost is reduced.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited thereby.

Example 1

Preparation of supported Ni-B amorphous alloy catalyst:

The aqueous solution of nickel chloride is adsorbed on Al ₂ O ₃ to make nickel chloride with a mass content of 50% loaded nickel chloride, then add Ni:B mol ratio of potassium borohydride aqueous solution of 1:2, filter, wash with water until pH = 10, and then washed twice with ethanol, and the obtained supported Ni-B amorphous alloy catalyst was stored in ethanol.

Example 2

Preparation of supported Ni-B amorphous alloy catalyst:

The aqueous solution of nickel chloride is adsorbed on Al ₂ O ₃ to make nickel chloride with a mass content of 50% loaded nickel chloride, then add Ni:B mol ratio of potassium borohydride aqueous solution of 1:20, filter, wash with water until pH = 10, and then washed twice with ethanol, and the obtained supported Ni-B amorphous alloy catalyst was stored in ethanol.

Example 3

Preparation of supported Ni-B amorphous alloy catalyst:

The aqueous solution of nickel chloride is adsorbed on Al ₂ O ₃ to make nickel chloride with a mass content of 5% loaded nickel chloride, then add Ni:B molar ratio of 1:1 sodium borohydride aqueous solution, filter, wash to pH = 10, and then washed twice with ethanol, and the obtained supported Ni-B amorphous alloy catalyst was stored in ethanol.

Example 4

Preparation of supported Ni-B amorphous alloy catalyst:

The aqueous solution of nickel chloride is adsorbed on activated carbon to make a loaded nickel chloride with a mass content of nickel chloride of 25%, and then an aqueous sodium borohydride solution with a Ni:B molar ratio of 1:1.5 is added, filtered and washed with water until pH=10 , and then washed twice with ethanol, and the obtained supported Ni-B amorphous alloy catalyst was stored in ethanol.

Example 5

70 grams of 40% (weight) tetramethylammonium hydroxide aqueous solution is put into the reactor, and the temperature is raised to 60 DEG C under gauge pressure 0.009MPa gram of 25% alkali aqueous solution, under gauge pressure 0.009MPa, be warming up to 60 ℃, be concentrated into 40% (weight) solution], then add 142 grams of aniline to mix, under gauge pressure 0.009MPa, be warming up to 80 ℃, aniline Azeotropic distillation and dehydration with water until the molar ratio of water/tetramethylammonium hydroxide is 3:1, add 35 grams of nitrobenzene to carry out condensation reaction within 3 hours, continue to stir and maintain for 0.5 hours to obtain the coupled product; The weight percent composition of organic matter is: 48.9% of aniline, 30.1% of 4-nitrosodiphenylamine, 7.0% of 4-nitrodiphenylamine, 0.35% of phenazine, 7.6% of azobenzene, and 6.5% of tetramethylammonium hydroxide.

After the condensation reaction finishes, add 42 grams of water, 12 grams of loaded Ni-B amorphous alloy catalyst (dry base) prepared by embodiment 1, feed hydrogen, carry out reduction reaction, when reaction temperature is 80 ℃, hydrogen gauge pressure 2.5 MPa, hydrogenation time 2 hours; Cool after reaction finishes, filter (solid-liquid separation) reclaim catalyst, liquid phase static layering, organic phase obtains following result with high-performance liquid chromatography analysis: 4-nitrosodiphenylamine and 4- The conversion rate of nitrodiphenylamine is 100%, and there is no azobenzene and hydroazobenzene in the product. The organic phase is rectified to obtain the target product 4-aminodiphenylamine. The yield of 4-aminodiphenylamine is 95.2% (for nitrobenzene), and the fractional distillation of 4-aminodiphenylamine has a product purity of 99.5%.

Example 6

The method for catalyzing the production of 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst may further comprise the steps:

(1) aniline and mass percentage composition are 5% alkali aqueous solution (alkali is the mixture of tetramethylammonium hydroxide, sodium hydroxide and tetramethylammonium bromide that the molar ratio is 1: 0.2: 0.3) in reaction Mix in the still, distill out aniline-water azeotrope, make the mol ratio of water and alkali in the reaction still be 0.6: 1;

(2) At 20°C and a gauge pressure of 0.005MPa, add nitrobenzene to the reactor within 5 hours so that the molar ratio of aniline in the reactor to the added nitrobenzene is 10:1; react for 1 hour to obtain Containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or their salts, and a mixed solution of azobenzene oxide and azobenzene; the molar ratio of base to nitrobenzene is 0.7:1;

(3) add water, make the mass percent composition of alkali in water be 5%, add the supported Ni-B amorphous alloy catalyst prepared by embodiment 2, load the quality of Ni-B amorphous alloy catalyst and reaction liquid Ratio is 1: 100, feed hydrogen, when reaction temperature is 50 ℃, hydrogen gauge pressure is 8MPa, hydrogenation time is 7 hours, carry out hydrogenation reduction reaction, make 4-nitrodiphenylamine and 4-nitrosodiphenylamine and /or their salts are hydrogenated to 4-aminodiphenylamine, and azobenzene oxide and azobenzene are hydrogenated to aniline at the same time, and cooled after the hydrogenation reaction is completed;

(4) carry out solid-liquid separation to the mixture that step (3) obtains, separate loaded Ni-B amorphous alloy catalyst and liquid phase; Load Ni-B amorphous alloy catalyst returns to step (3); Liquid The phases are separated, the organic phase and the aqueous alkali solution are separated, the organic phase is rectified, and the product 4-aminodiphenylamine is recovered while aniline is recovered, the aniline is returned to step (1), and the aqueous alkali solution is returned to step (1).

The conversion rates of 4-nitrosodiphenylamine and 4-nitrodiphenylamine are both 100%, and there is no azobenzene and hydroazobenzene in the product. The yield of 4-aminodiphenylamine was 94.9% (for nitrobenzene).

Example 7

The method for catalyzing the production of 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst may further comprise the steps:

(1) Aniline and 40% aqueous alkali solution (alkali is a mixture of tetramethylammonium hydroxide and potassium hydroxide with a molar ratio of 1:0.2) are mixed in a reaction kettle to distill out aniline-water Azeotrope, making the mol ratio of water and alkali in the reactor be 4: 1;

(2) At 100° C. and a gauge pressure of 0.1 MPa, add nitrobenzene to the reactor within 0.5 hours, so that the molar ratio of aniline in the reactor to the added nitrobenzene is 3: 1; 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or their salts, and azobenzene oxide, a mixed solution of azobenzene; the molar ratio of alkali to nitrobenzene is 4:1;

(3) add water, make the mass percent composition of alkali in water be 40%, add the supported Ni-B amorphous alloy catalyst prepared by embodiment 3, load the quality of Ni-B amorphous alloy catalyst and reaction liquid The ratio is 6: 100, feed hydrogen, when the reaction temperature is 200°C, the hydrogen gauge pressure is 1MPa, the hydrogenation time is 2 hours, and the hydrogenation reduction reaction is carried out to make 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or Or their salts are hydrogenated to 4-aminodiphenylamine, and azobenzene oxide and azobenzene are hydrogenated to aniline at the same time; cool after the hydrogenation reaction;

(4) carry out solid-liquid separation to the mixture that step (3) obtains, separate loaded Ni-B amorphous alloy catalyst and liquid phase; Load Ni-B amorphous alloy catalyst returns to step (3); Liquid The phases are separated, the organic phase and the aqueous alkali solution are separated, the organic phase is rectified to obtain the product 4-aminodiphenylamine and aniline is recovered simultaneously, the aniline is returned to step (1), and the aqueous alkali solution is returned to step (1).

The conversion rates of 4-nitrosodiphenylamine and 4-nitrodiphenylamine are both 100%, and there is no azobenzene and hydroazobenzene in the product. The yield of 4-aminodiphenylamine was 94.2% (for nitrobenzene).

Example 8

The method for catalyzing the production of 4-aminodiphenylamine with a supported Ni-B amorphous alloy catalyst may further comprise the steps:

(1) Aniline and 20% aqueous alkali solution (alkali is a mixture of tetramethylammonium hydroxide and tetramethylammonium chloride with a molar ratio of 1:0.3) are mixed in a reaction kettle, distilled out Aniline-water azeotrope makes the mol ratio of water and alkali in the reactor be 2: 1;

(2) At 50°C and a gauge pressure of 0.01MPa, add nitrobenzene to the reactor within 1 hour so that the molar ratio of aniline in the reactor to the added nitrobenzene is 5:1, and react for 0.5 hours to obtain Containing 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or their salts, and a mixed solution of azobenzene oxide and azobenzene; the molar ratio of alkali to nitrobenzene is 2:1;

(3) add water, make the mass percent composition of alkali in water be 20%, add the supported Ni-B amorphous alloy catalyst prepared by embodiment 4, the mass ratio of catalyzer and reaction liquid is 4: 100, pass into Hydrogen, when reaction temperature is 80 DEG C, hydrogen gauge pressure 2.5MPa, hydrogenation time 5 hours, carry out hydrogenation reduction reaction, make 4-nitrodiphenylamine and 4-nitrosodiphenylamine and/or their salt hydrogenation be 4-Aminodiphenylamine, while azobenzene oxide and azobenzene are hydrogenated to aniline; after the hydrogenation reaction, cool down;

(4) carry out solid-liquid separation to the mixture that step (3) obtains, separate loaded Ni-B amorphous alloy catalyst and liquid phase; Load Ni-B amorphous alloy catalyst returns to step (3) after regeneration Carrying out phase separation of the liquid phase, separating the organic phase and the aqueous alkali solution, rectifying the organic phase to obtain the product 4-aminodiphenylamine while reclaiming aniline, returning the aniline to step (1), and returning the aqueous alkali solution to step (1 ).

The conversion rates of 4-nitrosodiphenylamine and 4-nitrodiphenylamine are both 100%, and there is no azobenzene and hydroazobenzene in the product. The yield of 4-aminodiphenylamine was 94.9% (for nitrobenzene).

Using the catalyst recovered from the above separation, repeated use 5 times under the same conditions as above, the conversion rate of 4-nitrosodiphenylamine and 4-nitrodiphenylamine was 100%, and there was no azobenzene and hydroazo in the product. benzene. The yield of 4-aminodiphenylamine was 93.3% (for nitrobenzene).

The catalyzer separated and recovered for the 5th time was washed 3 times with 10% sodium hydroxide aqueous solution by mass content, and the reaction result of using the 6th time was: the transformation rate of 4-nitrosodiphenylamine and 4-nitrodiphenylamine were both It is 100%, and there is no azobenzene and hydroazobenzene in the product. The yield of 4-aminodiphenylamine was 94.1% (for nitrobenzene).

Example 8 shows that the hydrogenation performance of the supported Ni-B amorphous alloy catalyst decreases somewhat after being used for many times, and the catalytic performance is restored after being treated with sodium hydroxide solution.

Claims (8)

1. with the method for load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine, it is characterized in that comprising the steps:

(1) is that 5%～40% alkali aqueous solution mixes in reactor with aniline and quality percentage composition, distills out aniline-water azeotrope, make that the mol ratio of water and alkali is 0.6～4: 1 in the described reactor; Described alkali is that mol ratio is 1: 0～0.5: 0～0.5 Tetramethylammonium hydroxide, alkali metal hydroxide and tetramethyl-quaternary ammonium salt;

(2) be under 0.005～0.1MPa at 20～100 ℃, gauge pressure, in 0.5～5 hour, in described reactor, add oil of mirbane, making the mol ratio of the oil of mirbane of aniline and adding in the described reactor is 3～10: 1, reacted 0～1 hour, generation contains 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt, and the mixed solution of zinin, nitrogen benzide; The mol ratio of described alkali and oil of mirbane is 0.7～4: 1;

(3) add entry, making the quality percentage composition of alkali in water is 5%～40%, add load Ni-B amorphous alloy catalyst, feed hydrogen, make 4 nitrodiphenyl amine and 4-nitrosodiphenylamine and/or their salt be hydrogenated to the 4-aminodiphenylamine, simultaneous oxidation nitrogen benzide and nitrogen benzide are hydrogenated to aniline;

(4) mixture that step (3) is obtained carries out the solid-liquid separation, isolates load Ni-B amorphous alloy catalyst and liquid phase; Described load Ni-B amorphous alloy catalyst turns back to step (3) or turn back to step (3) after regeneration; Described liquid phase is separated, isolates organic phase and alkali aqueous solution,, obtain product 4-aminodiphenylamine and reclaim aniline simultaneously, described aniline is returned step (1), described alkali aqueous solution is returned step (1) described organic phase rectifying.

2. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 1 is characterized in that described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.

3. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 1 is characterized in that described tetramethyl-quaternary ammonium salt is tetramethyl ammonium chloride or 4 bromide.

4. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 1, it is characterized in that the mass ratio that described load Ni-B amorphous alloy catalyst and step (3) add the liquid after the entry is 1～6: 100, the temperature of hydrogenation reaction is 50～200 ℃, the gauge pressure of hydrogenation reaction is 1～8.0MPa, and the time of hydrogenation reaction is 2～7 hours.

5. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 4, it is characterized in that the mass ratio that described load Ni-B amorphous alloy catalyst and step (3) add the liquid after the entry is 2～5: 100, the temperature of described hydrogenation reaction is 60～100 ℃, the gauge pressure of described hydrogenation reaction is 2～6.0MPa, and the time of described hydrogenation reaction is 3～5 hours.

6. according to claim 1,4 or 5 described methods with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine, it is characterized in that described load Ni-B amorphous alloy catalyst is to make with following method: nickel chloride aqueous solution is adsorbed on the carrier, make the nickelous chloride mass content and be 5%～50% load nickelous chloride, add Ni then: the B mol ratio is 1: 1～20 the POTASSIUM BOROHYDRIDE or the aqueous solution of sodium borohydride, filter, wash, use washing with alcohol again, promptly obtain load Ni-B amorphous alloy catalyst, be kept in the ethanol.

7. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 6 is characterized in that described carrier is gac or Al ₂O ₃

8. the method with load Ni-B amorphous alloy catalyst catalytic production 4-aminodiphenylamine according to claim 6, it is characterized in that described Ni: the B mol ratio is 1: 1.5～2.