Aminated hydrogenation catalyst, process for its preparation and its use in the preparation of m-xylylenediamine

Abstract

The application provides an amination hydrogenation catalyst, a preparation method thereof and application thereof in a preparation process of m-xylylenediamine, and belongs to the technical field of catalysts. The amination hydrogenation catalyst provided by the application takes nickel and cobalt bimetal as a catalytic active component, adds a catalyst adjusting additive to improve the directional catalysis effect of the catalyst, adds a small amount of a desorption additive to improve the desorption effect of by-products on the surface of the catalyst, reduces the phenomenon of easy coking of the catalyst, makes the catalyst have good wear resistance and more uniform active site distribution, effectively avoids the coking and deactivation of the catalyst, and when the catalyst is used in a fixed-bed continuous hydrogenation process of m-xylylenediamine, not only can the cost of industrial production of m-xylylenediamine be reduced, but also the yield of m-xylylenediamine and the conversion rate of m-xylylene cyanide can be effectively improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to an amination hydrogenation catalyst, a preparation method thereof, and application of the amination hydrogenation catalyst in a preparation process of m-xylylenediamine. BACKGROUND

[0002] Epoxy resin is a kind of oligomer containing two or more than two epoxy groups in the molecule, taking aliphatic, alicyclic, aromatic carbon bond as the skeleton and being able to form a thermosetting resin through the reaction of the epoxy groups. After the research of scholars all over the world, more than one hundred specifications of varieties have been developed, which can be divided into the following types according to their composition: bisphenol A type, bisphenol F type, bisphenol S type, alicyclic type, aliphatic type, phenolic aldehyde epoxy and the like.

[0003] When the epoxy resin is used, a curing agent must be added to play its performance, and an excellent curing agent enables the epoxy resin curing product to have excellent performance. According to the acid-base property, the curing agent can be divided into two types of basic curing agent and acidic curing agent, the basic curing agent including aliphatic diamine, polyamine, aromatic polyamine, dicyandiamide, imidazole amine and modified amine, and the acidic curing agent including organic acid, acid anhydride, boron trifluoride and its complex.

[0004] M-xylylenediamine can be regarded as a kind of aliphatic diamine containing aromatic ring, which is close to aromatic polyamine in structure, and is similar to aliphatic polyamine in room temperature curing, and has both the performance of aromatic amine and aliphatic amine. Therefore, m-xylylenediamine and its structure modified or hydrogenated modified product are widely used as the curing agent of epoxy resin.

[0005] However, a catalyst needs to be added in the synthesis process of m-xylylenediamine, and the catalyst used in the field at present is easy to be pulverized under high pressure, which leads to the need of continuous addition of the catalyst and the general catalytic conversion effect, so that not only the catalyst deactivation phenomenon is serious, but also the production cost is increased. Moreover, the existing preparation process of m-xylylenediamine mostly adopts the kettle type batch hydrogenation process, which also leads to the stability problem between batches of m-xylylenediamine. Therefore, it is very important for the future application of m-xylylenediamine to prepare a high-efficiency catalyst and develop a method for continuously producing m-xylylenediamine, so as to greatly improve the yield of m-xylylenediamine and inhibit the generation of by-products. SUMMARY

[0006] The present application provides an amination hydrogenation catalyst, a preparation method thereof and application of the amination hydrogenation catalyst in a preparation process of m-xylylenediamine. The amination hydrogenation catalyst reduces the phenomenon of easy coking of the catalyst, has good wear resistance and more uniform active site distribution, and can effectively avoid the catalyst coking deactivation phenomenon. When the catalyst is used in the m-xylylenediamine fixed bed continuous hydrogenation process, not only the cost of industrial production of m-xylylenediamine can be reduced, but also the yield of m-xylylenediamine and the conversion rate of m-xylylene nitrile can be effectively improved.

[0007] In order to achieve the above-mentioned purpose, the present application provides an amination hydrogenation catalyst, which is prepared by a granulation and molding process, and uses at least one of silica, silica sol and diatomite as a carrier, and at least contains a nickel-based compound, a cobalt-based compound, a molybdenum-based compound, a potassium-based compound, and at least one compound selected from 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 active components.

[0008] In the above-mentioned scheme, it can be understood that each component functions as follows: the nickel-based compound and the cobalt-based compound are effective components of the catalyst, the silica is a carrier of the catalyst, the molybdenum-based compound is a desorption aid for secondary amines, tertiary amines or cyclic compounds, the potassium-based compound is an adjusting aid for the acid-base degree of the catalyst, and the other components are the rhodium-based compound and the palladium-based compound, which provide a channel for hydrogen adsorption and mass transfer of the catalyst, and the aluminum-based compound and the magnesium-based compound provide an alkaline environment for the catalyst. The scheme uses nickel and cobalt bimetal as the catalytically active components, adds catalyst adjusting aids, improves the directional catalytic effect of the catalyst, and adds a small amount of desorption aids to improve the desorption effect of by-products on the surface of the catalyst, thereby reducing the phenomenon of easy coking of the catalyst, improving the wear resistance, and making the active sites more uniformly distributed. It can also be understood that at least one method selected from the group consisting of an impregnation method, a drying method, a sol-gel method, a drying method, and a tabletting method can be used when the catalyst is granulated.

[0009] As a preferred embodiment, the active components at least contain 40-60 mol% of the nickel-based compound, 20-30 mol% of the cobalt-based compound, 1-5 mol% of the molybdenum-based compound, 0.5-1 mol% of the potassium-based compound, and 0.01-0.05 mol% of at least one compound selected from the group consisting of 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.

[0010] As a preferred embodiment, the active components further include at least one inorganic component selected from diatomite, alumina, magnesium oxide and magnesium-aluminum oxide as a carrier, and the molar content of the inorganic component is 10%-50%. It can be understood that the active components can further include inorganic components, which function as a carrier of the catalyst and provide uniform attachment points for the active components.

[0011] As preferred, the nickel-based compound is at least one of nickel nitrate, nickel carbonate, nickel nitrite, the cobalt-based compound is at least one of cobalt nitrate, cobalt nitrite, cobalt carbonate, the molybdenum-based compound is ammonium molybdate, the potassium-based compound is at least one of potassium acetate, 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, gold hydroxide, the sodium-based compound is at least one of sodium nitrate, sodium carbonate, sodium nitrite, the iron-based compound is at least one of iron oxide, ferrous oxide, iron hydroxide, the aluminum-based compound is at least one of aluminum oxide, aluminum hydroxide, and the magnesium-based compound is at least one of magnesium oxide, magnesium nitrate, magnesium carbonate.

[0012] As preferred, it is prepared by the following method:

[0013] The weighed nickel-based compound, cobalt-based compound, molybdenum-based compound, potassium-based compound, silica sol, and at least one compound 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 are uniformly mixed, and after aging with stirring, evaporation concentration, spray granulation, and drying, a catalyst is obtained;

[0014] The polyvinyl alcohol is mixed with the obtained catalyst, extruded, calcined in a muffle furnace, and a fixed-bed hydrogenation catalyst is obtained.

[0015] As preferred, the aging temperature is 70-90℃, and the aging time is 4-8h;

[0016] The evaporation concentration temperature is 80-100℃, and the evaporation concentration time is 6-10h;

[0017] The drying temperature is 100-120℃, and the drying time is 10-16h;

[0018] The calcination temperature is 100-1000℃, preferably 300-600℃, more preferably 400-500℃, and the calcination time is 12-24h. It can be understood that if the aging time is less than 4h, the active component will be unevenly deposited, and if the aging time is more than 8h, the active component will grow in crystal form, and the catalytic area will be reduced.

[0019] The application also provides an application of the amination hydrogenation catalyst in a preparation process of m-xylylenediamine.

[0020] The application also provides a preparation process of m-xylylenediamine, which uses the amination hydrogenation catalyst according to any one of the above technical solutions as a catalyst.

[0021] As preferred, the isophthalonitrile is dissolved in a mixture of organic solvent and base, and then is introduced into a hydrogenation reactor, and a continuous reaction is carried out in the hydrogenation reactor under the action of ammonia and hydrogen, wherein the hydrogenation reactor is filled with the amine hydrogenation catalyst subjected to a reduction treatment in advance according to any one of the technical solutions described above.

[0022] As preferred, the temperature of the fixed-bed continuous reaction is 50-120℃, preferably 80-120℃, and more preferably 80-100℃.

[0023] The reaction pressure is 4-8MPa, preferably 4-6MPa, and more preferably 4-5MPa.

[0024] As preferred, the hydrogenation reactor is a stainless steel tubular reactor with a diameter of 20mm and a length of 1000mm.

[0025] The amine hydrogenation catalyst is added in an amount of 12-30ml.

[0026] The reduction treatment is to reduce the amine hydrogenation catalyst under a flowing hydrogen atmosphere at 500-700℃ for 8-12h before use.

[0027] As preferred, the organic solvent is at least one selected from the group consisting of methanol, toluene, ethanol, m-xylylenediamine, NMP, DMF, dimethylbenzene, ethylene glycol, propyl formate, ethyl acetate, ethyl propionate, propyl propionate, butyl formate, butyl acetate, butyl propionate, butyl butyrate, diethyl oxalate.

[0028] The base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia water, liquid ammonia, triethylamine, ethylenediamine, sodium carbonate, sodium bicarbonate, potassium bicarbonate.

[0029] As preferred, the yield of the obtained m-xylylenediamine is ≥92.1%, and the conversion rate of the isophthalonitrile is ≥99.2%.

[0030] Compared with the prior art, the present application has the following advantages and positive effects:

[0031] 1. The present application provides an amine hydrogenation catalyst, which uses nickel and cobalt bimetal as catalytic active components, adds catalyst adjusting additives to improve the directional catalytic effect of the catalyst, and adds a small amount of desorption additives to improve the desorption effect of by-products on the surface of the catalyst, thereby reducing the phenomenon of easy coking of the catalyst, improving the wear resistance, and making the active sites more uniformly distributed.

[0032] 2. The amination hydrogenation catalyst provided by this invention can effectively avoid catalyst coking and deactivation, and therefore can be used in the fixed-bed continuous hydrogenation process of m-phenylenediamine. This not only reduces the cost of industrial production of m-phenylenediamine, but also effectively improves the yield of m-phenylenediamine and the conversion rate of isophthalonitrile. The yield of m-phenylenediamine is ≥92.1%, and the conversion rate of isophthalonitrile is ≥99.2%. Attached Figure Description

[0033] Figure 1 This is an EDS characterization diagram of the catalyst elemental distribution obtained in Example 1 of the present invention. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1

[0036] 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) were weighed out and stirred at 70℃ for 8 hours. The mixture was then evaporated and concentrated to 660g at 80℃, spray-dried, and dried in a 100℃ oven for 10 hours. 10g of the resulting polyvinyl alcohol mixture was then weighed out and extruded (cylindrical shape: 1mm diameter, 2mm length). The mixture was calcined in a muffle furnace at 500℃ to obtain catalyst 1. The elemental distribution of the catalyst is shown in the EDS characterization diagram below. Figure 1 As shown. Figure 1 As shown, the metal elements are uniformly distributed on the surface of the catalyst support without any aggregation, indicating that the catalyst preparation is qualified.

[0037] Example 2

[0038] 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) were weighed out and stirred at 72℃ for 6.5h. Then, the mixture was evaporated and concentrated to 660g at 80℃. The mixture was spray-dried and granulated using a spray dryer, and then dried in an oven at 100℃ for 10h. 10g of the catalyst obtained by mixing with polyvinyl alcohol was weighed out and extruded into cylindrical shape (1mm in diameter and 2mm in length). The mixture was then calcined in a muffle furnace at 500℃ to obtain catalyst 2.

[0039] Example 3

[0040] 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) were weighed out and stirred at 75℃ for 6.2h. Then, the mixture was evaporated and concentrated to 660g at 85℃. The mixture was spray-dried and granulated using a spray dryer, and then dried in an oven at 100℃ for 10h. 10g of the catalyst obtained by mixing with polyvinyl alcohol was weighed out and extruded into cylindrical shape (1mm in diameter and 2mm in length). The mixture was then calcined in a muffle furnace at 500℃ to obtain catalyst 3.

[0041] Example 4

[0042] 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 alumina (20% aqueous solution) were weighed out and matured at 80℃ for 6 hours. Then, the mixture was evaporated and concentrated to 660g at 90℃. The mixture was spray-dried and granulated using a spray dryer, and then dried in an oven at 100℃ for 10 hours. 10g of the catalyst obtained by mixing with polyvinyl alcohol was weighed out and extruded into cylindrical shape (1mm in diameter and 2mm in length). The mixture was then calcined in a muffle furnace at 500℃ to obtain catalyst 4.

[0043] Example 5

[0044] 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) were weighed out and stirred at 85℃ for 5 hours. Then, the mixture was evaporated and concentrated to 660g at 100℃. The mixture was spray-dried and granulated using a spray dryer, and then dried in an oven at 100℃ for 12 hours. 10g of the catalyst obtained by mixing with polyvinyl alcohol was weighed out and extruded into cylindrical shape (1mm in diameter and 2mm in length). The mixture was then calcined in a muffle furnace at 700℃ to obtain catalyst 5.

[0045] Example 6

[0046] 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) were weighed out and stirred at 90℃ for 4 hours. Then, the mixture was evaporated and concentrated to 660g at 80℃. The mixture was spray-dried and granulated using a spray dryer, and then dried in an oven at 100℃ for 10 hours. 10g of the catalyst obtained by mixing with polyvinyl alcohol was weighed out and extruded into cylindrical shape (1mm in diameter and 2mm in length). The mixture was then calcined in a muffle furnace at 700℃ to obtain catalyst 6.

[0047] Comparative Example 1

[0048] The comparative catalyst used was commercially available Raney nickel.

[0049] Comparative Example 2

[0050] The comparative catalyst used was SNCAT-6210P from Xunkai.

[0051] Performance testing

[0052] 1000 ml of a mixture of isophthalonitrile (200 g) and methanol and DMF (volume ratio 4:6) was fed into the hydrogenation reactor from the bottom at a set rate. Ammonia and hydrogen were fed into the reaction from another pipeline. The reaction pressure was 4 MPa, the reaction temperature was 85 °C, the liquid flow rate was 2 ml / min, and the reaction was evaluated after 100 h. The results are shown in Table 1.

[0053] The hydrogenation reactor is a single stainless steel tubular reactor with a diameter of 20mm and a diameter of 1000mm. Quartz wool is placed at the bottom and top of the catalyst, and 20ml of catalyst 1-6 is loaded into each reactor. Catalysts 1-6 are reduced for 10 hours at 700℃ under a flowing hydrogen atmosphere before use.

[0054] Table 1

[0055]

[0056] As shown in Table 1, with fine-tuning of additives, supports, aging time, etc., the active metal of the catalyst with microstructure is more uniformly dispersed, and a higher yield was obtained in the m-phenylenediamine test. Compared with the two commercially available catalysts, the conversion rate of isophthalonitrile is higher (≥99.2%) and the yield of m-phenylenediamine is higher (≥92.1%).

Claims

1. An amination hydrogenation catalyst, characterized in that, The product is prepared by granulation and molding processes using at least one of silica sol and alumina as a carrier and at least one of nickel-based compounds, cobalt-based compounds, molybdenum-based compounds, potassium-based compounds, and at least one compound selected from 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 as active components. Based on molar content, the active component comprises at least 40-60 mol% of a nickel-based compound, 20-30 mol% of a cobalt-based compound, 1-5 mol% of a molybdenum-based compound, 0.5-1 mol% of a potassium-based compound, and 0.01-0.05 mol% of at least one selected from 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.

2. The amination hydrogenation catalyst according to claim 1, characterized in that, 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.

3. The amination hydrogenation catalyst according to claim 1 or 2, characterized in that, It is prepared by the following method: The 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 are mixed evenly, stirred and matured, then evaporated and concentrated, spray-granulated, and dried to obtain the catalyst. The catalyst obtained above was mixed with 1%-5% by weight of polyvinyl alcohol, extruded and calcined in a muffle furnace to obtain a fixed-bed hydrogenation catalyst.

4. The amination hydrogenation catalyst according to claim 3, characterized in that, The curing temperature is 70~90℃, and the curing time is 4~8h; The evaporation and concentration temperature is 80~100℃, and the evaporation and concentration time is 6~10h; The drying temperature is 100~120℃, and the drying time is 10~16h; The calcination temperature is 100~1000℃, and the calcination time is 12~24h.

5. The amination hydrogenation catalyst according to claim 4, characterized in that, The calcination temperature is 300~600℃.

6. The amination hydrogenation catalyst according to claim 5, characterized in that, The calcination temperature is 400~500℃.

7. The application of the amination hydrogenation catalyst according to any one of claims 1-6 in the preparation process of m-phenylenediamine.

8. A process for preparing m-phenylenediamine, characterized in that, The amination hydrogenation catalyst according to any one of claims 1-4 is used as the catalyst.

9. The preparation process according to claim 8, characterized in that, Isophthalonitrile is dissolved in a mixture of organic solution and alkaline substance and passed into a hydrogenation reactor, where a fixed-bed continuous reaction is carried out under the action of ammonia and hydrogen. The hydrogenation reactor is filled with an amination hydrogenation catalyst according to any one of claims 1-6 that has been pre-reduced.

10. The preparation process according to claim 9, characterized in that, The temperature of the continuous reaction in the fixed bed is 50~120℃; The reaction pressure is 4~8 MPa; The hydrogenation reactor is a stainless steel tubular reactor with a diameter of 20mm and a diameter of 1000mm. The amount of the amination hydrogenation catalyst added is 12~30 ml; The reduction treatment involves reducing the amination hydrogenation catalyst at 500-700°C under a flowing hydrogen atmosphere for 8-12 hours before use. The organic solvent is selected from at least one of methanol, toluene, ethanol, m-phenylenediamine, 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 substance is selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, liquid ammonia, triethylamine, ethylenediamine, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

11. The preparation process according to claim 10, characterized in that, The temperature of the continuous reaction in the fixed bed is 80~120℃; the reaction pressure is 4~6MPa.

12. The preparation process according to claim 11, characterized in that, The temperature of the continuous reaction in the fixed bed is 80~100℃; the reaction pressure is 4~5MPa.

13. The preparation process according to any one of claims 8-12, characterized in that, The yield of m-phenylenediamine was ≥92.1%, and the conversion rate of isophthalonitrile was ≥99.2%.

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