A resin catalyst for MIBK production, preparation method and application thereof

Abstract

The present invention provides a resin catalyst for MIBK production, a preparation method and application thereof, wherein the preparation method of the catalyst comprises the steps of preparing a chloromethylstyrene-divinylbenzene-styrene copolymer through amination / quaternization, alkali washing and loading metal palladium. The catalyst prepared by the method of the present invention has the technical advantages of firm palladium loading, better stability, high activity, long service life, high acetone single-pass conversion rate and high MIBK selectivity.

Description

Technical Field

[0001] The invention relates to the technical field of resin catalysts, and in particular to a resin catalyst for MIBK production, a preparation method and application thereof. Background Art

[0002] Methyl isobutyl ketone, referred to as MIBK, is an organic solvent with excellent performance. It is mainly used as a solvent for spray paint, nitrocellulose, grease and rubber. It is also used in the synthesis of rubber antioxidants.

[0003] In the early stage of MIBK production, a three-step method was used. However, due to technical problems such as complex process routes, high costs, and low yields, it has been gradually eliminated. The current production processes all use a one-step method, using palladium catalysts, which are divided into Pd / Al2O3, Pd molecular sieve, and Pd resin catalysts according to different carriers. The water produced during the preparation of MIBK causes the strength of the carrier to drop rapidly, making it impossible to use them stably for a long period of time; palladium resin catalysts have high conversion rates, good selectivity, and long life, but because this type of catalyst is sulfonated on the benzene ring, the sulfonate group is easy to fall off and lose, causing non-negligible corrosion to the preparation equipment, and palladium is introduced into the resin through ion exchange, and its stability is poor, and there will also be a certain amount of loss, affecting the activity and service life of the catalyst.

[0004] Therefore, it is still necessary to provide a new resin catalyst for MIBK production to improve the firmness and stability of the catalyst-supported palladium, thereby improving the catalytic activity and conversion rate. Summary of the invention

[0005] One object of the present invention is to provide a method for preparing a resin catalyst for synthesizing MIBK, thereby improving the firmness and stability of palladium supported on the catalyst, while improving its catalytic activity and conversion rate, and maintaining a high catalytic conversion rate and selectivity after long-term operation.

[0006] Another object of the present invention is to provide a catalyst prepared by the preparation method.

[0007] Another object of the present invention is to provide the application of the catalyst.

[0008] In order to achieve the above invention object, the present invention adopts the following technical solution:

[0009] A method for preparing a resin catalyst for MIBK production comprises the steps of reacting chloromethylstyrene-divinylbenzene-styrene copolymer with amine, then neutralizing by alkali washing, filtering by water washing, adding an aqueous solution of palladium salt for impregnation loading, then solidifying by palladium reduction, filtering, washing, and drying to prepare the resin catalyst.

[0010] In a specific embodiment, the amine is selected from tertiary amines and / or ethyleneamines; preferably, the tertiary amine is selected from at least any one of C1-C12 tertiary amines, preferably triethylamine; the ethyleneamine is selected from at least any one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or cyclic amines, preferably diethylenetriamine, and the cyclic amines are selected from at least any one of piperazine, aminoethylpiperazine, and hydroxyethylpiperazine; more preferably, the amine is selected from tertiary amines and ethyleneamines, and the mass ratio of the two amines is 1:1-1:5.

[0011] In a specific embodiment, the reaction mass ratio of the chloromethylstyrene-divinylbenzene-styrene copolymer to the amine is (1-10):1; preferably, the reaction temperature is 50-110°C, the reaction gauge pressure is 0-2Mpa, and the reaction time is 0.5-2h.

[0012] In a specific embodiment, the alkali used for alkali washing neutralization is selected from alkali metal or alkaline earth metal hydroxides, preferably sodium hydroxide; preferably, the mass ratio of the alkali to the chloromethylstyrene-divinylbenzene-styrene copolymer is 0.1:1-1:1, the alkali washing neutralization temperature is 0-100°C, and the alkali washing neutralization time is 0.5-4h.

[0013] In a specific embodiment, deionized water is used for washing until the total amount of sodium ions, chloride ions, and hydroxide ions in the water is less than 100 ppm.

[0014] In a specific embodiment, the palladium salt used is one or more of palladium chloride, palladium acetate, palladium nitrate, and palladium acetylacetonate.

[0015] In a specific embodiment, the palladium salt solution is measured and loaded by impregnation according to the palladium loading amount being 0.1-0.5 wt % of the mass of the chloromethylstyrene-divinylbenzene-styrene copolymer; preferably, the impregnation time is 0.5-1 hour.

[0016] In a specific embodiment, hydrazine hydrate with a mass concentration of 5-10% is used for reduction and solidification until no bubbles emerge, and then washed and dried for use; preferably, the drying temperature is 80-120° C. and the drying time is 12-48 hours.

[0017] On the other hand, the resin catalyst prepared by the aforementioned preparation method is used for MIBK production.

[0018] In another aspect, the resin catalyst for MIBK production is used in the preparation of MIBK.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] (1) The active group of the palladium resin catalyst of the present invention for catalyzing the condensation of acetone is a quaternary ammonium base group. By changing the catalytic active group from an acidic group to a strong base group, the activity of catalyzing the condensation of acetone is better and the by-products are reduced. This method of using a strong base to catalyze the condensation of acetone has higher selectivity and conversion rate.

[0021] (2) The resin catalyst of the present invention uses a ligand containing multiple nitrogen atoms to chelate palladium, which has a stronger binding force, is less likely to cause palladium loss, and has a more stable catalyst activity. DETAILED DESCRIPTION

[0022] The following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0023] A method for preparing a resin catalyst for synthesizing MIBK comprises the following steps: reacting a chloromethylstyrene-divinylbenzene-styrene copolymer with an amine, then neutralizing the reaction with alkali, washing with water, filtering, adding an aqueous solution of a palladium salt for impregnation and loading, then solidifying the reaction with palladium reduction, filtering and washing, and preparing the catalyst.

[0024] The amine used is selected from one or more of the following two types of amines, one is selected from tertiary amines, preferably any one of trimethylamine and triethylamine, and the other is selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and cyclic amines such as piperazine, aminoethylpiperazine, hydroxyethylpiperazine, preferably diethylenetriamine. Wherein, the mass ratio of the chloromethylstyrene-divinylbenzene-styrene copolymer to the amine is (1-10):1, for example including but not limited to 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1. When the amine is selected from two amines, the mass ratio of the two amines is 1:1-1:5, for example, including but not limited to 1:1, 1:2, 1:3, 1:4, 1:5; the reaction temperature is 50-110°C, for example, including but not limited to 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, the reaction gauge pressure is 0-2Mpa, for example, including but not limited to 0Mpa, 0.5Mpa, 1Mpa, 1.5Mpa, 2Mpa, and the reaction time is 0.5-2h, for example, including but not limited to 0.5h, 1h, 1.5h, 2h.

[0025] After the chloromethylstyrene-divinylbenzene-styrene copolymer reacts with the amine, it is neutralized by alkali washing, and the alkali used is selected from common alkali metal or alkaline earth metal hydroxides, for example, sodium hydroxide solution is used, wherein the mass ratio of the amount of sodium hydroxide to the amount of the chloromethylstyrene-divinylbenzene-styrene copolymer is 0.1:1-1:1, for example, including but not limited to 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, the temperature of alkali washing neutralization is controlled to be 0-100°C, for example, including but not limited to 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, and the alkali washing time is 0.5-4h, for example, including but not limited to 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h. After alkali washing, deionized water is used for washing until the total amount of sodium ions, chloride ions and hydroxide ions in the washed water is less than 100 ppm.

[0026] After washing with water, the filter cake is filtered, and an aqueous solution of a palladium salt is added to the filter cake for impregnation loading. The palladium salt used for loading is one or more of palladium chloride, palladium acetate, palladium nitrate, and palladium acetylacetonate. The palladium salt solution is calculated according to the palladium loading amount of 0.1-0.5wt% of the mass of the chloromethylstyrene-divinylbenzene-styrene copolymer, and the impregnation loading is carried out for 0.5-1 hour, and then reduced and solidified by hydrazine hydrate with a concentration of 5-10% until no bubbles emerge, and then washed and dried for standby use. The drying temperature is, for example, 80-120° C. and the drying time is 12-48 hours.

[0027] Taking trimethylamine and diethylenetriamine as raw materials and palladium chloride solution as loading example, the reaction process equation is as follows:

[0028]

[0029] As shown in the above equation, chloromethylstyrene-divinylbenzene-styrene copolymer undergoes amination and quaternization reaction with amines. After neutralization with sodium hydroxide, a part of it generates a quaternary ammonium base, and the other part generates a chelated ligand containing multiple nitrogen atoms. After adding palladium salt, the nitrogen-containing ligand and metallic palladium undergo chelation coordination, and the palladium metal is loaded on the resin.

[0030] The active group of the palladium resin catalyst used in the current industrial production of MIBK to catalyze the condensation of acetone is a sulfonic acid group, while the active group of the palladium resin catalyst in the present invention to catalyze the condensation of acetone is a quaternary ammonium base group. The catalytic active group is changed from an acidic group to a strong base group, and the activity of catalyzing the condensation of acetone is better, and the by-products are reduced, and the selectivity becomes higher. In addition, the loading mode of palladium is different. The loading mode of the palladium resin catalyst used in the current industrial production of MIBK is that palladium is loaded on the sulfonic acid group through ion exchange, and the sulfonic acid group is easy to fall off in a water environment, resulting in palladium loss. Different from it, the present invention adopts a chelating ligand containing multiple nitrogen atoms and palladium coordination loading, and the binding force is stronger, palladium loss is not easy to occur, and the catalyst activity is more stable.

[0031] The present invention will be further described in detail below in conjunction with more specific embodiments, but shall not be construed as limiting in any way.

[0032] The main raw material sources used in the embodiments are as follows:

[0033] Chloromethylstyrene-divinylbenzene-styrene copolymer was purchased from TCI (Tianjin Cihe Chemical Industry Development Co., Ltd.); amine, base and palladium were purchased from Aladdin Reagent Company.

[0034] The analytical instruments and methods used in the embodiments are as follows:

[0035] Gas chromatograph: Agilent-7820;

[0036] Gas chromatography column: 0.25mm×30m DB-5 capillary column, detector FID, vaporization chamber temperature 280℃, column box temperature 280℃, FID detector temperature 300℃, argon flow rate 2.1mL / min, hydrogen flow rate 30mL / min, air flow rate 400mL / min, injection volume 1.0μL. The conversion rate of olefins and the selectivity of products were calculated using the area normalization method. Heating program: preheat to column temperature 40℃, maintain for 5min, increase from 40℃ to 280℃ at a rate of 15℃ / min, and maintain for 2min.

[0037] All conversion and selectivity statistics below are from chromatographic analysis.

[0038] Example 1

[0039] Add 100g of chloromethylstyrene-divinylbenzene-styrene copolymer to the reactor, pass 100g of trimethylamine gas, heat to 50°C, normal pressure, stir and react for 0.5h, then add 10% potassium hydroxide solution 100g, stir and react at 0°C for 0.5h, filter, wash with deionized water for multiple times, detect and wash until the sodium ion, chloride ion, and hydroxide ion content in the water, and stop washing when the total amount is less than 100ppm. Add the resin to 100g of palladium chloride solution (palladium concentration 0.1wt%), soak for 0.5h, filter, add 5% hydrazine hydrate solution 100ml, stir until no bubbles are generated, wash with deionized water, filter, and dry at 110°C for 12h for standby use.

[0040] Example 2

[0041] 120g of chloromethylstyrene-divinylbenzene-styrene copolymer was added to the reactor, 2g of triethylamine and 10g of triethylenetetramine gas were introduced, the temperature was raised to 110°C, and the reaction was stirred at 2Mpa pressure for 2h, followed by the addition of 1200g of 10% cesium hydroxide solution, and the reaction was stirred at 100°C for 4h, filtered, washed with deionized water for multiple times, and the sodium ion, chloride ion, and hydroxide ion content in the water were detected and washed when the total amount was <100ppm. The resin was added to 120g of palladium chloride solution (palladium concentration 0.5wt%), immersed for 1h, filtered, 100ml of 10% hydrazine hydrate solution was added, stirred until no bubbles were generated, washed with deionized water, filtered, and dried at 80°C for 48h for standby use.

[0042] Example 3

[0043] 80g of chloromethylstyrene-divinylbenzene-styrene copolymer was added to the reactor, 5g of trihexylamine and 15g of piperazine were introduced, the temperature was raised to 70°C, and the reaction was stirred at 1Mpa pressure for 1h, followed by the addition of 400g of 10% barium hydroxide solution, and the reaction was stirred at 50°C for 1h, filtered, and washed with deionized water for multiple times, and the sodium ion, chloride ion, and hydroxide ion content in the water were detected and washed when the total amount was <100ppm. The resin was added to 80g of palladium nitrate solution (palladium concentration 0.4wt%), and after impregnation for 1h, filtered, 100ml of 10% hydrazine hydrate solution was added, and stirred until no bubbles were generated, washed with deionized water, filtered, and dried at 120°C for 12h for standby use.

[0044] Example 4

[0045] Add 100g of chloromethylstyrene-divinylbenzene-styrene copolymer to the reactor, pass 5g of tri-n-dodecylamine and 20g of pentaethylenehexamine gas, heat to 90°C, stir and react at 0.5Mpa pressure for 0.5h, then add 200g of 10% sodium hydroxide solution, stir and react at 80°C for 2h, filter, wash with deionized water for multiple times, detect the content of sodium ions, chloride ions and hydroxide ions in the water, and stop washing when the total amount is less than 100ppm. Add the resin to 100g of acetylacetone palladium solution (palladium concentration 0.5wt%), soak for 1h, filter, add 100ml of 8% hydrazine hydrate solution, stir until no bubbles are generated, wash with deionized water, filter, and dry at 110°C for 24h for standby use.

[0046] Example 5

[0047] The same method as in Example 1 was used, except that trimethylamine was replaced by diethylenetriamine, and the other conditions remained unchanged.

[0048] Comparative Example 1

[0049] A commercial CH28 MIBK resin catalyst from Dow was used to conduct a comparative test with the catalysts of the above four examples, including an initial activity evaluation and a 2000-hour long-cycle evaluation test.

[0050] 100 ml of each example and Dow MIBK resin catalyst were loaded into a fixed bed reactor to carry out a test of synthesizing MIBK. The synthesis reaction pressure was 3.0 MPa and the space velocity was 0.5 h -1 , reaction temperature 100 ° C, hydrogen and acetone volume ratio of 300:1, the results are as follows:

[0051]

[0052] From the data in the table, it can be seen that the catalyst of the present invention has significantly better indicators such as acetone single-pass conversion rate and MIBK selectivity than the existing catalyst, and has excellent pore structure. After long-term operation, the catalyst conversion rate and selectivity in the embodiment are significantly higher than the catalyst in the comparative example, indicating that the catalyst palladium loading of the present invention is firm and has better stability.

[0053] Although the above embodiments have described the technical solutions of the present invention in detail, the technical solutions of the present invention are not limited to the above embodiments. Without departing from the idea and purpose of the present invention, any changes made to the technical solutions of the present invention will fall within the scope defined by the claims of the present invention.

Claims

1. A method for preparing a resin catalyst for MIBK production, characterized in that: The method comprises the steps of reacting chloromethylstyrene-divinylbenzene-styrene copolymer with amine, then neutralizing by alkali washing, filtering by water washing, adding an aqueous solution of palladium salt for impregnation and loading, then solidifying by palladium reduction, filtering, washing and drying to prepare the resin catalyst.

2. The preparation method according to claim 1, characterized in that: The amine is selected from tertiary amines and / or ethylene amines.

3. The preparation method according to claim 2, characterized in that: The tertiary amine is selected from at least any one of C1-C12 tertiary amines; the ethyleneamine is selected from at least any one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or cyclic amines, and the cyclic amines are selected from at least any one of piperazine, aminoethylpiperazine and hydroxyethylpiperazine.

4. The preparation method according to claim 3, characterized in that: The tertiary amine is selected from triethylamine; and the ethyleneamine is selected from diethylenetriamine.

5. The preparation method according to claim 3, characterized in that: The amine is selected from tertiary amine and ethylene amine, and the mass ratio of the two amines is 1:1-1:

5.

6. The preparation method according to claim 1, characterized in that: The reaction mass ratio of the chloromethylstyrene-divinylbenzene-styrene copolymer to the amine is (1-10):

1.

7. The preparation method according to claim 6, characterized in that: The reaction temperature is 50-110°C, the reaction gauge pressure is 0-2Mpa, and the reaction time is 0.5-2h.

8. The preparation method according to claim 1, characterized in that: The alkali used for alkali washing and neutralization is selected from hydroxides of alkali metals or alkaline earth metals.

9. The preparation method according to claim 8, characterized in that: The alkali used for alkali washing and neutralization is selected from sodium hydroxide.

10. The preparation method according to claim 8, characterized in that: The reaction mass ratio of the alkali to the chloromethylstyrene-divinylbenzene-styrene copolymer is 0.1:1-1:1, the alkali washing neutralization temperature is 0-100°C, and the alkali washing neutralization time is 0.5-4h.

11. The preparation method according to claim 1, characterized in that: Use deionized water to wash until the total amount of sodium ions, chloride ions, and hydroxide ions in the water is less than 100 ppm.

12. The preparation method according to claim 1, characterized in that: The palladium salt used is one or more of palladium chloride, palladium acetate, palladium nitrate and palladium acetylacetonate.

13. The preparation method according to claim 1, characterized in that: According to the calculation that the palladium loading amount is 0.1-0.5wt% of the mass of the chloromethylstyrene-divinylbenzene-styrene copolymer, a palladium salt solution is measured and loaded by immersion.

14. The preparation method according to claim 13, characterized in that: The impregnation time for the impregnated load is 0.5-1 hour.

15. The preparation method according to claim 1, characterized in that: Use hydrazine hydrate with a mass concentration of 5-10% to reduce and solidify until no bubbles emerge, wash and dry for later use.

16. The preparation method according to claim 15, characterized in that: The drying temperature is 80-120℃ and the drying time is 12-48h.

17. A resin catalyst for MIBK production obtained by the preparation method according to any one of claims 1 to 16.

18. Use of the resin catalyst for MIBK production according to claim 17 in the preparation of MIBK.

Images