CN117582996A

CN117582996A - Amination hydrogenation catalyst, preparation method thereof and application of amination hydrogenation catalyst in preparation process of m-xylylenediamine

Info

Publication number: CN117582996A
Application number: CN202311532329.8A
Authority: CN
Inventors: 吴炳辉; 赵立伟; 苏凯民; 刘方园; 任东成
Original assignee: Shandong Haike Innovation Research Institute Co Ltd
Current assignee: Shandong Haike Innovation Research Institute Co Ltd
Priority date: 2023-11-16
Filing date: 2023-11-16
Publication date: 2024-02-23

Abstract

The invention provides an amination hydrogenation catalyst, a preparation method thereof and application thereof in a m-xylylenediamine preparation process, and belongs to the technical field of catalysts. The amination hydrogenation catalyst provided by the invention takes nickel and cobalt bimetal as catalytic active components, the directional catalysis effect of the catalyst is improved by adding the catalyst adjusting auxiliary agent, the desorption effect of byproducts on the surface of the catalyst is improved by adding a small amount of desorption auxiliary agent, the phenomenon that the catalyst is easy to coke is reduced, the wear resistance is better, the active sites are distributed more uniformly, the phenomenon of coking deactivation of the catalyst can be effectively avoided, and the catalyst can be used in the m-xylylenediamine fixed bed continuous hydrogenation process, so that the cost of industrial production of m-xylylenediamine is reduced, and the yield of m-xylylenediamine and the conversion rate of m-xylylenediamine are also effectively improved.

Description

Amination hydrogenation catalyst, preparation method thereof and application of amination hydrogenation catalyst in preparation process of m-xylylenediamine

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to an amination hydrogenation catalyst, a preparation method thereof and application thereof in a m-xylylenediamine preparation process.

Background

The epoxy resin is an oligomer which contains 2 or more than 2 epoxy groups in the molecule, takes aliphatic, alicyclic and aromatic carbon bonds as a framework and can form thermosetting resin through epoxy group reaction. Through researches of various scholars worldwide, varieties with hundreds of specifications have been developed, and the varieties can be divided into the following components: bisphenol a type, bisphenol F type, bisphenol S type, alicyclic, aliphatic, novolac epoxy and the like.

When the epoxy resin is used, a curing agent is added to exert the performance of the epoxy resin, and the excellent curing agent ensures that the cured product of the epoxy resin has excellent performance. The curing agents can be classified into alkaline curing agents and acidic curing agents according to the acidity and alkalinity, and alkaline curing agents: aliphatic diamines, polyamines, aromatic polyamines, dicyandiamide, imidazole amines, modified amines, and the like; acid curing agent: organic acids, anhydrides, boron trifluoride and complexes thereof.

The m-xylylenediamine can be regarded as an aliphatic diamine containing aromatic rings, is structurally similar to aromatic polyamine, is cured at room temperature and is similar to aliphatic polyamine, and has two properties of aromatic amine and aliphatic amine. Therefore, the meta-xylylenediamine and the structural modification or hydrogenation modified product thereof are widely used as the epoxy resin curing agent.

However, in the synthesis process of m-xylylenediamine, a catalyst is required to be added, and the catalyst used in the prior art is extremely easy to pulverize under high pressure, so that the catalyst needs to be continuously added and the catalytic conversion effect is general, thus the catalyst deactivation phenomenon is serious, and the production cost is increased. In addition, in the existing production process of m-xylylenediamine, a kettle type batch hydrogenation process is often used, which also causes stability problems between batches of m-xylylenediamine. Therefore, a method for continuously producing m-xylylenediamine is developed while preparing a highly efficient catalyst to greatly increase the yield of m-xylylenediamine, which is essential for the future use of m-xylylenediamine.

Disclosure of Invention

The invention provides an amination hydrogenation catalyst, a preparation method and application thereof in a m-xylylenediamine preparation process, wherein the amination hydrogenation catalyst reduces the phenomenon that the catalyst is easy to coke, so that the catalyst has better wear resistance, the active sites are distributed more uniformly, the phenomenon of coking inactivation of the catalyst can be effectively avoided, and the amination hydrogenation catalyst is used in a m-xylylenediamine fixed bed continuous hydrogenation process, so that the cost of industrially producing m-xylylenediamine can be reduced, and the yield of m-xylylenediamine and the conversion rate of m-xylylenediamine can be effectively improved.

In order to achieve the aim, the invention provides an amination hydrogenation catalyst which is prepared by taking at least one of silicon dioxide, silica sol and diatomite as a carrier, taking at least one compound selected from a nickel-based compound, a cobalt-based compound, a molybdenum-based compound, a potassium-based compound and a silver-based compound, a rhodium-based compound, a palladium-based compound, a gold-based compound, a sodium-based compound, an iron-based compound, an aluminum-based compound and a magnesium-based compound as an active component, and adopting a granulating and molding process.

In the above scheme, it can be understood that the components function as follows: the nickel-based compound and the cobalt-based compound are used as active ingredients of the catalyst, the silicon dioxide is used as a catalyst carrier, the molybdenum-based compound is used as a desorption auxiliary agent of secondary amine, tertiary amine or cyclic compound, the potassium-based compound is used as an auxiliary agent for regulating the pH value of the catalyst, the other components are used as channels for adsorbing hydrogen and transferring mass of the catalyst, and the aluminum-based compound and the magnesium-based compound are used as alkaline environments for the catalyst. According to the scheme, the nickel and cobalt bimetal is used as a catalytic active component, the catalyst adjusting auxiliary agent is added, the directional catalytic effect of the catalyst is improved, and the desorption effect of byproducts on the surface of the catalyst is improved by adding a small amount of desorption auxiliary agent, so that the phenomenon that the catalyst is easy to coke is reduced, the wear resistance is better, and the active sites are distributed more uniformly. It is also understood that the catalyst may be pelletized by at least one method selected from the group consisting of impregnation, drying, sol-gel, baking and pelleting.

Preferably, the active component contains at least 40 to 60mol% of nickel-based compound, 20 to 30mol% of cobalt-based compound, 1 to 5mol% of molybdenum-based compound, 0.5 to 1mol% of potassium-based compound, and 0.01 to 0.05mol% of at least one selected from the group consisting of silver-based compound, rhodium-based compound, palladium-based compound, gold-based compound, sodium-based compound, iron-based compound, aluminum-based compound, and magnesium-based compound, in terms of molar content.

Preferably, the active component further comprises at least one inorganic component selected from diatomite, aluminum oxide, magnesium oxide and magnesium aluminum oxide as a carrier in a molar content of 10-50%. It will be appreciated that the active component may also include an inorganic component which acts to provide a uniform attachment point for the active component to the catalyst support.

Preferably, the nickel-based compound is at least one of nickel nitrate, nickel carbonate and nickel nitrite, the cobalt-based compound is at least one of cobalt nitrate, cobalt nitrite and cobalt carbonate, the molybdenum-based compound is at least one of ammonium molybdate, the potassium-based compound is at least one of potassium acetate and potassium nitrate, the silver-based compound is silver nitrate, the rhodium-based compound is rhodium acetylacetonate, the palladium-based compound is palladium acetate, the gold-based compound is at least one of gold oxide and gold hydroxide, the sodium-based compound is at least one of sodium nitrate, sodium carbonate and sodium nitrite, the iron-based compound is at least one of iron oxide, ferrous oxide and iron hydroxide, the aluminum-based compound is at least one of aluminum oxide and aluminum hydroxide, and the magnesium-based compound is at least one of magnesium oxide, magnesium nitrate and magnesium carbonate.

Preferably, it is prepared by the following method:

uniformly mixing a weighed nickel-based compound, cobalt-based compound, molybdenum-based compound, potassium-based compound, silica sol and at least one compound selected from silver-based compound, rhodium-based compound, palladium-based compound, gold-based compound, sodium-based compound, iron-based compound, aluminum-based compound and magnesium-based compound, stirring and curing, evaporating and concentrating, spraying and granulating, and drying to obtain the catalyst;

mixing polyvinyl alcohol with the catalyst, extruding, forming, and calcining in a muffle furnace to obtain the fixed bed hydrogenation catalyst.

Preferably, the curing time is between 4 and 8 hours at the temperature of between 70 and 90 ℃;

the evaporating concentration temperature is 80-100 ℃, and the evaporating concentration time is 6-10 h;

the drying temperature is 100-120 ℃, and the drying time is 10-16 h;

the calcination temperature is 100 to 1000 ℃, preferably 300 to 600 ℃, more preferably 400 to 500 ℃ and the calcination time is 12 to 24 hours. It is understood that if the aging time is less than 4 hours, the deposition of the active ingredient is not uniform, and if it is more than 8 hours, the crystal form of the active ingredient grows, and the catalytic area is reduced.

The invention also provides an application of the amination hydrogenation catalyst in the preparation process of m-xylylenediamine according to any one of the technical schemes.

The invention also provides a preparation process of m-xylylenediamine, which adopts the amination hydrogenation catalyst according to any one of the technical schemes as a catalyst.

Preferably, isophthalonitrile is dissolved in a mixture of an organic solution and an alkaline substance and is introduced into a hydrogenation reactor, and continuous reaction is carried out in the hydrogenation reactor under the action of ammonia and hydrogen, wherein the hydrogenation reactor is filled with the amination hydrogenation catalyst which is subjected to reduction treatment in advance and adopts any one of the technical schemes.

Preferably, the temperature of the fixed bed continuous reaction is 50 to 120 ℃, preferably 80 to 120 ℃, more preferably 80 to 100 ℃;

the reaction pressure is 4 to 8MPa, preferably 4 to 6MPa, more preferably 4 to 5MPa.

Preferably, the hydrogenation reactor is a stainless steel tube reactor with phi 20mm multiplied by 1000 mm;

the addition amount of the amination hydrogenation catalyst is 12-30 ml;

the reduction treatment is to reduce the amination hydrogenation catalyst for 8-12 h in a flowing hydrogen atmosphere at 500-700 ℃ before use.

Preferably, the organic solvent is at least one selected from methanol, toluene, ethanol, m-xylylenediamine, NMP, DMF, xylene, ethylene glycol, propyl formate, ethyl acetate, ethyl propionate, propyl propionate, butyl formate, butyl acetate, butyl propionate, butyl butyrate and diethyl oxalate;

the alkaline matter is at least one selected from sodium hydroxide, potassium hydroxide, ammonia water, liquid ammonia, triethylamine, ethylenediamine, sodium carbonate, sodium bicarbonate and potassium bicarbonate.

Preferably, the yield of the obtained m-xylylenediamine is more than or equal to 92.1%, and the conversion rate of the m-phthalonitrile is more than or equal to 99.2%.

Compared with the prior art, the invention has the advantages and positive effects that:

1. the invention provides an amination hydrogenation catalyst, which takes nickel and cobalt bimetal as catalytic active components, improves the directional catalysis effect of the catalyst by adding catalyst adjusting auxiliary agents, improves the desorption effect of byproducts on the surface of the catalyst by adding a small amount of desorption auxiliary agents, reduces the phenomenon of easy coking of the catalyst, and ensures that the catalyst has better wear resistance and more uniform active site distribution.

2. The amination hydrogenation catalyst provided by the invention can effectively avoid the coking deactivation phenomenon of the catalyst, so that the amination hydrogenation catalyst can be used in a m-xylylenediamine fixed bed continuous hydrogenation process, the cost of industrially producing m-xylylenediamine can be reduced, the yield of m-xylylenediamine and the conversion rate of m-xylylenediamine can be effectively improved, the yield of m-xylylenediamine is more than or equal to 92.1%, and the conversion rate of m-xylylenediamine is more than or equal to 99.2%.

Drawings

FIG. 1 is a graph showing the EDS characterization of the catalyst element distribution obtained in example 1 of the present invention.

Detailed Description

The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

200g of nickel nitrate, 180g of cobalt nitrate, 0.1g of palladium acetate, 5g of ammonium molybdate, 1.2g of potassium acetate and 502g of silica sol (20% aqueous solution) are respectively weighed, stirred and cured for 8 hours at 70 ℃, then evaporated and concentrated to 660g at 80 ℃, spray-granulated by a spray dryer, dried for 10 hours by a 100 ℃ oven, and then extruded into a shape (cylindrical shape: diameter 1mm and length 2 mm) by weighing 10g of a catalyst obtained by mixing polyvinyl alcohol, and calcined in a muffle furnace at 500 ℃ to obtain a catalyst 1, wherein the EDS characterization diagram of the catalyst element distribution is shown in figure 1. As shown in FIG. 1, the metal elements are uniformly distributed on the surface of the catalyst carrier, the aggregation distribution condition does not occur, and the catalyst is qualified in preparation.

Example 2

Respectively weighing 250g of nickel nitrate, 130g of cobalt nitrate, 0.1g of palladium acetate, 5g of ammonium molybdate, 1.2g of potassium acetate and 502g of silica sol (20% aqueous solution), stirring and curing for 6.5h at 72 ℃, evaporating and concentrating to 660g at 80 ℃, carrying out spray granulation by a spray dryer, putting into a 100 ℃ oven for drying for 10h, weighing 10g of catalyst obtained by mixing polyvinyl alcohol, carrying out extrusion molding (cylindrical shape: diameter 1mm and length 2 mm), and putting into a muffle furnace for calcining at 500 ℃ to obtain the catalyst 2.

Example 3

Respectively weighing 200g of nickel nitrate, 180g of cobalt nitrate, 0.1g of rhodium acetylacetonate, 5g of ammonium molybdate, 1.2g of potassium acetate and 502g of silica sol (20% aqueous solution), stirring and curing for 6.2h at 75 ℃, evaporating and concentrating to 660g at 85 ℃, carrying out spray granulation by a spray dryer, putting into a 100 ℃ oven for drying for 10h, weighing 10g of catalyst obtained by mixing polyvinyl alcohol, carrying out extrusion molding (cylindrical shape: diameter 1mm and length 2 mm), and putting into a muffle furnace for calcining at 500 ℃ to obtain the catalyst 3.

Example 4

Respectively weighing 200g of nickel nitrate, 180g of cobalt nitrate, 0.1g of rhodium acetylacetonate, 5g of ammonium molybdate, 1.2g of potassium acetate and 502g of aluminum oxide (20% aqueous solution), stirring and curing for 6 hours at 80 ℃, evaporating and concentrating to 660g at 90 ℃, carrying out spray granulation by a spray dryer, putting into a 100 ℃ oven for drying for 10 hours, weighing 10g of a catalyst obtained by mixing polyvinyl alcohol, carrying out extrusion molding (cylindrical shape: diameter 1mm and length 2 mm), and putting into a muffle furnace for calcining at 500 ℃ to obtain the catalyst 4.

Example 5

Respectively weighing 200g of nickel nitrate, 180g of cobalt nitrate, 0.1g of rhodium acetylacetonate, 5.5g of ammonium molybdate, 1.5g of potassium acetate and 502g of alumina (20% aqueous solution), stirring and curing for 5 hours at 85 ℃, evaporating and concentrating to 660g at 100 ℃, carrying out spray granulation by a spray dryer, putting into a 100 ℃ oven for drying for 12 hours, weighing 10g of catalyst obtained by mixing polyvinyl alcohol, carrying out extrusion molding (cylindrical shape: diameter 1mm and length 2 mm), and putting into a muffle furnace for calcination at 700 ℃ to obtain the catalyst 5.

Example 6

Respectively weighing 200g of nickel nitrate, 180g of cobalt nitrate, 0.1g of silver nitrate, 5g of ammonium molybdate, 1.2g of potassium acetate and 502g of silica sol (20% aqueous solution), stirring and curing for 4 hours at 90 ℃, evaporating and concentrating to 660g at 80 ℃, carrying out spray granulation by a spray dryer, putting into a 100 ℃ oven for drying for 10 hours, weighing 10g of a catalyst obtained by mixing polyvinyl alcohol, carrying out extrusion molding (cylindrical shape: diameter 1mm and length 2 mm), and putting into a muffle furnace for calcining at 700 ℃ to obtain the catalyst 6.

Comparative example 1

The comparative catalyst was commercially available Raney nickel.

Comparative example 2

The comparative catalyst was selected from the XueKai catalyst SNCAT-6210P.

Performance testing

1000ml (volume ratio of 4:6) of a mixture of isophthalonitrile (200 g) and methanol with DMF is fed into a hydrogenation reactor from the bottom at a set speed, ammonia and hydrogen are fed into the hydrogenation reactor from the other pipeline together, the reaction pressure is 4MPa, the reaction temperature is 85 ℃, the liquid flow rate is 2ml/min, the reaction evaluation is 100h, and the results are shown in Table 1.

Wherein, the hydrogenation reactor is 1 stainless steel tube reactor with phi 20mm multiplied by 1000mm, quartz cotton is arranged at the bottom and the upper part of the catalyst, and the catalyst is respectively filled with 20ml of catalyst 1-6. The catalysts 1-6 were reduced for 10h in a flowing hydrogen atmosphere at 700 ℃ before use.

TABLE 1

As shown in Table 1, in the case of fine adjustment of the auxiliary agent, the carrier, the aging time and the like, the dispersion of the catalyst active metal of the microstructure was more uniform, and the result of higher yield in the test evaluation of m-xylylenediamine was found to be higher in the conversion of m-xylylenediamine (. Gtoreq.99.2%) and higher in the yield of m-xylylenediamine (. Gtoreq.92.1%) than the two catalysts commercially available.

Claims

1. The amination hydrogenation catalyst is characterized in that at least one of silicon dioxide, silica sol and diatomite is used as a carrier, at least one compound selected from nickel-based compounds, cobalt-based compounds, molybdenum-based compounds, potassium-based compounds and silver-based compounds, rhodium-based compounds, palladium-based compounds, gold-based compounds, sodium-based compounds, iron-based compounds, aluminum-based compounds and magnesium-based compounds are used as an active component, and the amination hydrogenation catalyst is prepared through a granulating and molding process.

2. The aminated hydrogenation catalyst according to claim 1, wherein the active component comprises at least 40 to 60mol% of nickel-based compound, 20 to 30mol% of cobalt-based compound, 1 to 5mol% of molybdenum-based compound, 0.5 to 1mol% of potassium-based compound and 0.01 to 0.05mol% of at least one selected from the group consisting of silver-based compound, rhodium-based compound, palladium-based compound, gold-based compound, sodium-based compound, iron-based compound, aluminum-based compound and aluminum-based compound, based on a molar content;

the active component can further comprise at least one inorganic component selected from diatomite, aluminum oxide, magnesium oxide and magnesium aluminum oxide as a carrier, wherein the molar content of the inorganic component is 10-50 percent.

3. The amination hydrogenation catalyst according to claim 1 or 2, wherein the nickel-based compound is at least one of nickel nitrate, nickel carbonate and nickel nitrite, the cobalt-based compound is at least one of cobalt nitrate, cobalt nitrite and cobalt carbonate, the molybdenum-based compound is ammonium molybdate, the potassium-based compound is at least one of potassium acetate and potassium nitrate, the silver-based compound is silver nitrate, the rhodium-based compound is rhodium acetylacetonate, the palladium-based compound is palladium acetate, the gold-based compound is at least one of gold oxide and gold hydroxide, the sodium-based compound is at least one of sodium nitrate, sodium carbonate and sodium nitrite, the iron-based compound is at least one of iron oxide, ferrous oxide and iron hydroxide, the aluminum-based compound is at least one of aluminum oxide and aluminum hydroxide, and the magnesium-based compound is at least one of magnesium oxide, magnesium nitrate and magnesium carbonate.

4. An aminated hydrogenation catalyst according to any one of claims 1-3, characterized in that it is prepared by the following process:

mixing 1-5% by mass of polyvinyl alcohol with the catalyst, extruding, forming, and calcining in a muffle furnace to obtain the fixed bed hydrogenation catalyst.

5. The amination hydrogenation catalyst according to claim 4, wherein the curing temperature is 70-90 ℃ and the curing time is 4-8 hours;

the drying temperature is 100-120 ℃, and the drying time is 10-16 h;

the calcination temperature is 100 to 1000 ℃, preferably 300 to 600 ℃, more preferably 400 to 500 ℃ and the calcination time is 12 to 24 hours.

6. Use of the aminated hydrogenation catalyst according to any one of claims 1 to 5 in a process for preparing m-xylylenediamine.

7. A process for producing m-xylylenediamine, which comprises using the amination hydrogenation catalyst according to any one of claims 1 to 5 as a catalyst.

8. The process according to claim 7, wherein isophthalonitrile is dissolved in a mixture of an organic solution and an alkaline substance and introduced into a hydrogenation reactor, and a fixed bed continuous reaction is carried out under the action of ammonia gas and hydrogen gas, wherein the hydrogenation reactor is filled with the amination hydrogenation catalyst according to any one of claims 1 to 5, which is subjected to a reduction treatment in advance.

9. The preparation process according to claim 8, characterized in that the temperature of the fixed bed continuous reaction is 50-120 ℃, preferably 80-120 ℃, more preferably 80-100 ℃;

the reaction pressure is 4-8 MPa, preferably 4-6 MPa, more preferably 4-5 MPa;

the hydrogenation reactor is a stainless steel tube reactor with phi of 20mm multiplied by 1000 mm;

the addition amount of the amination hydrogenation catalyst is 12-30 ml;

the reduction treatment is to reduce the amination hydrogenation catalyst for 8 to 12 hours in a flowing hydrogen atmosphere at 500 to 700 ℃ before use;

the organic solvent is at least one selected from methanol, toluene, ethanol, m-xylylenediamine, NMP, DMF, xylene, ethylene glycol, propyl formate, ethyl acetate, ethyl propionate, propyl propionate, butyl formate, butyl acetate, butyl propionate, butyl butyrate and diethyl oxalate;

10. The process according to any one of claims 7 to 9, wherein the yield of m-xylylenediamine obtained is not less than 92.1% and the conversion of isophthalonitrile is not less than 99.2%.