CN114011421B

CN114011421B - Preparation method of hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and preparation method of succinic anhydride

Info

Publication number: CN114011421B
Application number: CN202111495668.4A
Authority: CN
Inventors: 丁可; 王磊; 曾伟; 付松; 刘运海; 蒋玉鑫; 史意胜; 赵欣; 杨洋; 陈永; 宋延方
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2021-12-09
Filing date: 2021-12-09
Publication date: 2023-03-31
Anticipated expiration: 2041-12-09
Also published as: CN114011421A

Abstract

The invention discloses a preparation method of a hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and relates to a preparation method of succinic anhydride. The hydrogenation catalyst adopts basic salt modified supported nickel or supported cobalt catalyst, and further hydrogenation reaction of succinic anhydride can be inhibited by adding a modifier, so that the selectivity of the succinic anhydride is improved. The method can inhibit the generation of byproducts while improving the conversion rate of maleic anhydride, and realize the continuous production of succinic anhydride with high selectivity and high yield.

Description

Preparation method of hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and preparation method of succinic anhydride

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a hydrogenation catalyst and a method for preparing succinic anhydride by hydrogenation of maleic anhydride.

Background

Succinic anhydride is an important organic synthesis intermediate and fine chemical raw material, and is widely applied to the fields of food, surfactants, coatings, medicines, agriculture, plastics and the like. In the food industry, succinic anhydride is mainly used as a flavoring agent, and the sodium salt of succinic anhydride can improve the quality of soy sauce and salted products and the color of liquid, and is used for pickles, hams, pickles, meat products, fruit cans and the like. In addition, the succinic anhydride can also be used as a milk enhancer, such as a flavoring agent of milk powder, candies and biscuits, so as to effectively promote the development of human bones. Derivatives of succinic anhydride are important components of detergents, soaps and demulsifiers in the surfactant industry. In the coating industry, succinic anhydride can be used in synthetic resin paints and water-based paints, such as polyester, paint, alkyd and maleate paint products. In the pharmaceutical industry, succinic anhydride can be used for preparing drugs such as sulfa drugs, vitamin A and B6, hemostatics, cortisone derivatives and the like. In the agricultural industry, succinic anhydride can be used to produce a plant growth regulator, N-dimethylamino succinamide, for controlling plant growth, regulating plant nutrients, and increasing waterlogging and freezing resistance. In the plastic industry, the hydrolysis product of succinic anhydride and the polycondensation of butanediol can be used for preparing biodegradable plastic poly (butylene succinate) (PBS) with excellent performance. With the increasing severity of the white pollution problem, the market prospect of PBS is very wide, thereby greatly stimulating and driving the market demand of upstream succinic anhydride products. Along with the development of the industries such as pesticide, medicine, petrochemical industry and the like in China, the demand of succinic anhydride is increased year by year.

The maleic anhydride hydrogenation method is to prepare succinic anhydride by taking maleic anhydride as a raw material and adopting a direct hydrogenation method. The method has the advantages of simple process flow, convenient operation, high equipment utilization rate, low operation cost and high product purity, and is the most efficient process for producing the succinic anhydride at present.

Patent CN1063484a discloses a method for preparing succinic anhydride by hydrogenation of maleic anhydride in molten state with raney nickel catalyst under solvent-free condition. The patent adopts a kettle type reactor, a catalyst and maleic anhydride are added into the reaction kettle according to a certain proportion, the pressure of the system is kept constant, the yield of the succinic anhydride is 96 percent at most, the method can only adopt an intermittent production method, the manual operation is more, the yield of the succinic anhydride is lower, and the method also has the defects of large process investment and the like.

Patent EP0691335 discloses a method for preparing succinic anhydride by maleic anhydride hydrogenation in the presence of a solvent, noble metal Pd is adopted, the metal content is as high as 2-10wt%, the catalyst cost is high, in addition, by adopting the patent process, the yield of succinic anhydride is only 95%, and the yield of succinic acid is low.

Patent CN101502802B provides a catalyst for continuously producing succinic anhydride by maleic anhydride hydrogenation, a supported nickel catalyst is adopted, but transition metals such as noble metals or lanthanide series metals are required to be added as an accelerator, and the yield of succinic anhydride also has a space for improving.

Patent CN111841551A provides a catalyst for preparing succinic anhydride by maleic anhydride hydrogenation, the catalyst adopts a hydrotalcite-like layered structure as a precursor, ni-M is a metal active component, and M is selected from one or two of Cu, ag, au, pd, pt, fe, co, ru, rh and Ir. The catalyst is prepared by using alkaline (selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, potassium hydroxide, potassium carbonate or potassium bicarbonate) water solution as precipitant, adjusting pH to 6-10, precipitating to obtain slurry, and washing with water for several times to remove alkali metal ions. The selectivity of the succinic anhydride of the catalyst can reach 99 percent, and by-products and selectivity information thereof are not given, and service life data of the catalyst are also not given. The catalyst in the patent has the defects of complex preparation process, large metal loading capacity and the like.

Disclosure of Invention

The invention provides a preparation method of a hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and relates to a preparation method of succinic anhydride. The hydrogenation catalyst can improve the conversion rate of maleic anhydride and inhibit the generation of byproducts at the same time under the relatively mild condition, thereby realizing the continuous preparation of succinic anhydride with high selectivity and high yield.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

a preparation method of a hydrogenation catalyst for preparing succinic anhydride from maleic anhydride comprises the following steps: dissolving soluble salt of active metal and modifier in water, adding carrier, soaking in the same volume, forming, drying and roasting to obtain the hydrogenation catalyst.

The soluble salt of the active metal in the invention is selected from nitrate, hydrochloride, sulfate or phosphate of nickel or cobalt, preferably nitrate.

The modifier is selected from one or more of basic carbonate, basic sulfate, basic phosphate and basic hydrochloride, preferably one or more of basic copper carbonate, basic magnesium chloride, basic magnesium sulfate, basic copper sulfate and magnesium ammonium phosphate, and more preferably basic magnesium carbonate and/or magnesium ammonium phosphate.

The modifier is used in 1-20 mol%, preferably 2-8 mol% of active metal element. The surface area of the catalyst can be obviously reduced and the activity of the catalyst is influenced if the addition amount of the modifier is too large; the addition amount of the catalyst is small, and the function of improving the selectivity of the succinic anhydride cannot be achieved.

The hydrogenation catalyst, wherein the amount of the active metal components Ni or/and Co, as metal oxides, is 5-40wt%, preferably 10-20 wt%, of the support.

The carrier of the present invention may be one or more of alumina, silica, titania, magnesia and activated carbon, preferably alumina.

The time for equal-volume impregnation is 20-30h.

Preferably, the particle size range of the formed catalyst is 2-3mm, the shape is not limited, and the catalyst is preferably clover-shaped.

Preferably, the drying is preferably carried out at a temperature of 110-120 ℃ for 1.5-2.0h.

Preferably, the roasting temperature is 550-600 ℃ and the roasting time is 5.5-6.0h.

The hydrogenation catalyst has reaction activity after being reduced and activated by hydrogen. As a preferred embodiment, the method of activation comprises the following steps:

(1) In a per m ratio ³ Catalyst 200-300m ³ The velocity of/h is passed into N ₂ Simultaneously heating the reactor to 120 ℃ at the heating rate of 20-30 ℃/h, and keeping the temperature for 2-4 hours to dry the catalyst;

(2) Raising the temperature of the catalyst bed to 400 ℃ at a temperature raising rate of 20-30 ℃/H, and introducing H into the reaction device ₂ At about 5% of the total gas flow, H is gradually added ₂ To the introduction of pure H ₂ Keeping the temperature at 400 ℃ for 10-12 hours, and cooling.

A preparation method of succinic anhydride comprises the following steps: in the presence of hydrogen and the catalyst of the invention, maleic anhydride is subjected to selective hydrogenation reaction to prepare succinic anhydride.

As a preferable embodiment, in the method for preparing succinic anhydride according to the present invention, the catalyst is preferably modified supported nickel.

In the preparation method of the succinic anhydride, the hydrogenation reaction pressure is 0.1-10MPa (gauge pressure), preferably 1-2MPa; the reaction temperature is 30 to 150 ℃, preferably 60 to 100 ℃.

The reaction temperature is required to be controlled in the reaction process, the reaction temperature is not too high, the reaction temperature is high, the hydrogenation reduction of carbon-oxygen double bonds is easy to cause, and the selectivity of succinic anhydride is reduced; the reaction temperature is low, the catalytic hydrogenation activity is low, and the maleic anhydride is difficult to effectively convert.

In the preparation method of succinic anhydride, the hydrogenation reaction can be carried out in a batch or continuous mode, and is preferably a continuous reaction; the hydrogenation reactor is selected from a reaction kettle, a fixed bed or a slurry bed, and preferably the fixed bed.

The modified supported nickel catalyst has strong hydrogenation activity, so that succinic anhydride is often catalyzed to be further converted into gamma-butyrolactone, even tetrahydrofuran.

Without being bound by any theory, the effect of the basic salt modifier added in the present invention may be:

1) The metal ions in the basic salt and the active metal form amorphous lamellar aggregates to promote the active metal Ni on the surface of the catalyst ²⁺ Or Co ²⁺ The concentration of active metal on the surface of the catalyst is reduced due to the distribution of ions, the content of Ni or Co on the surface of the catalyst is reduced after the catalyst is reduced by using hydrogen, the reducibility of the catalyst is weakened, and the selectivity of succinic anhydride is improved;

2) The modifier is added to influence the electron cloud density around the active metal, so that the electron binding energy is reduced, and the active metal Ni or Co is easier to adsorb with carbon-carbon double bonds rather than carbon-oxygen double bonds which are relatively electron-deficient, thereby being more beneficial to hydrogenation with the carbon-carbon double bonds;

3) The basic salt contains certain alkalinity, and can reduce the surface acidity of the catalyst by doping in the catalyst, accelerate the desorption of succinic anhydride and avoid further hydrogenation of the succinic anhydride; and the reduction of the acidity of the surface of the catalyst is beneficial to avoiding the generation of polymers, thereby reducing the carbon deposition rate and improving the stability of the catalyst.

According to the preparation method, the conversion rate of maleic anhydride can reach more than 99.9%, the selectivity of succinic anhydride can reach more than 99.5%, and the selectivity of a byproduct gamma-butyrolactone is lower than 0.2%. The method can inhibit the generation of byproducts while improving the conversion rate of maleic anhydride, improve the stability of the catalyst and realize the continuous production of succinic anhydride with high selectivity and high yield.

Detailed Description

In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

In the following examples, the chemical composition was determined by gas phase analysis of Shimadzu GC-2010 plus. The conditions for gas chromatography were: and (3) chromatographic column: 30m DB-WAX, ID 0.32mm, FD 0.25 μm;50-230 ℃,3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400mL/min; sample introduction amount: 0.2. Mu.L. Conversion and selectivity were calculated using area normalization.

Example 1

38.9gNi (NO) was prepared by an isovolumetric impregnation method ₃ ) ₂ ·6H ₂ Adding O and 0.05g of tetrahydrate type magnesium carbonate into water under stirring, adding water until the volume of the solution is 100ml after salt is completely dissolved, stirring, adding 100g of alumina serving as a carrier in batches, soaking at room temperature for 24 hours, forming into 2-3mm clover shapes, and drying at 120 ℃ for 2 hours; then roasting for 6h at 600 ℃ to obtain the catalyst 1. The loading of Ni is 10wt% of the carrier calculated by NiO, and the amount of the modifier calculated by Mg element is 2% of the molar amount of Ni.

Example 2

By adopting an equal volume impregnation method, 77.8gNi (NO) is added ₃ ) ₂ ·6H ₂ Adding O and 0.25g of tetrahydrate type magnesium carbonate into water under stirring, adding water until the volume of the solution is 100ml after all the salt is dissolved, adding 100g of alumina serving as a carrier by stirring in batches, soaking at room temperature for 24 hours, forming into a 2-3mm clover shape, and drying at 120 ℃ for 2 hours; then roasting at 600 DEG CCatalyst 2 was obtained after 6 h. The loading of Ni is 20wt% of the carrier calculated by NiO, and the amount of the modifier calculated by Mg element is 5% of the molar amount of Ni.

Example 3

Using an isovolumetric impregnation method, 58.4gNi (NO) is added ₃ ) ₂ ·6H ₂ Adding O and 0.13g of magnesium ammonium phosphate hexahydrate into water under stirring, adding water until the volume of the solution is 100ml after all the salt is dissolved, stirring, adding 100g of alumina serving as a carrier in batches, soaking at room temperature for 24 hours, forming into a 2-3mm clover shape, and drying at 120 ℃ for 2 hours; then roasting for 6h at 600 ℃ to obtain the catalyst 3. The loading of Ni is 15wt% of the carrier calculated by NiO, and the amount of the modifier calculated by Mg element is 2% of the molar amount of Ni.

Example 4

Catalyst 4 was obtained in the same manner as in example 3 except that 0.52g of magnesium ammonium phosphate hexahydrate was used instead of 0.13g of magnesium ammonium phosphate hexahydrate. The loading amount of Ni calculated by NiO is 15wt% of the carrier, and the amount of the modifier calculated by Mg element is 8% of the molar amount of Ni.

Comparative example 1

Comparative catalyst 1 was obtained in the same manner as in example 3 except that magnesium ammonium phosphate hexahydrate was not added. The loading of Ni was 15wt% of the support based on NiO.

Comparative example 2

Comparative catalyst 2 was prepared in the same manner as in example 2 except that 0.85g of sodium carbonate as a precipitant in CN111841551A was used in place of the tetrahydrate basic magnesium carbonate. Based on NiO, the loading amount of Ni is 20wt% of the carrier, and the amount of Na is 6% of the molar amount of Ni.

Comparative example 3

Comparative catalyst 3 was obtained in the same manner as in example 3 except that 0.13g of magnesium carbonate was used instead of magnesium ammonium phosphate hexahydrate. The loading of Ni is 15wt% of the carrier based on NiO.

Comparative example 4

Comparative catalyst 4 was obtained in the same manner as in example 3 except that 0.13g of magnesium phosphate was used instead of magnesium ammonium phosphate hexahydrate. The loading of Ni is 15wt% of the carrier based on NiO.

Examples 5 to 9

100ml of catalyst 1 are charged in a fixed bed reactorBefore hydrogenation reaction, hydrogen is adopted for reduction activation, and the reduction conditions are as follows: reducing for 8h at the temperature of 270 ℃ under the pressure of 2 MPa. Then cooling to the reaction temperature, the reaction pressure is 1-2MPa, and the maleic anhydride is continuously pumped in with the space velocity of 0.2-1h ^-1 The ratio of the hydrogen anhydride is 20-50, and the reaction outlet material is analyzed.

The results of the different examples are shown in table 1 below:

TABLE 1 EXAMPLES 5-9 reaction conditions and analysis of results

In the above embodiment, the catalyst is taken out after running for 1000h, and subjected to thermogravimetric analysis after being washed and dried by butyrolactone, the weight loss of the catalyst is less than 1%, and no obvious polymer is attached to the surface of the catalyst.

Comparative example 5

The other conditions were the same as in example 7 except that the catalyst was changed to comparative catalyst 1, the conversion of maleic anhydride was 99.9%, the selectivity of succinic anhydride was 78.5%, and the selectivity of butyrolactone was 15.3%, and after 100 hours of reaction, the conversion of maleic anhydride was 89.9%, the selectivity of succinic anhydride was 68.9%, and the selectivity of butyrolactone was 24.3%. The catalyst which reacts for 100h adopts thermal weight loss analysis after washing and drying of butyrolactone, the thermal weight loss rate of the catalyst is 7.8%, and the surface of the catalyst has obvious polymer accumulation.

Comparative example 6

Under the other conditions, the catalyst was changed to comparative catalyst 2, except that the conversion of maleic anhydride was 94.9%, the selectivity of succinic anhydride was 88.3%, and the selectivity of butyrolactone was 12.7%, and after 150 hours of reaction, the conversion of maleic anhydride was 85.9%, the selectivity of succinic anhydride was 74.9%, and the selectivity of butyrolactone was 18.7%.

After the reaction is carried out for 150 hours, the catalyst is taken out, washed and dried by butyrolactone, and then thermal weight loss analysis is carried out, the thermal weight loss rate of the catalyst is 9.3%, and obvious polymer accumulation is carried out on the surface of the catalyst.

Comparative example 7

The other conditions were the same as in example 7 except that the catalyst was changed to comparative catalyst 3, the conversion of maleic anhydride was 99.9%, the selectivity of succinic anhydride was 82.5%, and the selectivity of butyrolactone was 13.6%, and after 300 hours of reaction, the conversion of maleic anhydride was 89.9%, the selectivity of succinic anhydride was 86.9%, and the selectivity of butyrolactone was 10.3%.

After the catalyst is reacted for 300h, the thermal weight loss analysis is carried out on the catalyst after washing and drying by adopting butyrolactone, the thermal weight loss rate of the catalyst is 9.1 percent, and the polymer accumulation is obvious on the surface of the catalyst.

Comparative example 8

The other conditions were the same as in example 7 except that the catalyst was changed to comparative catalyst 4, the conversion of maleic anhydride was 98.9%, the selectivity of succinic anhydride was 81.3%, and the selectivity of butyrolactone was 14.7%, and after 300 hours of reaction, the conversion of maleic anhydride was 87.8%, the selectivity of succinic anhydride was 83.9%, and the selectivity of butyrolactone was 11.7%.

After the catalyst is reacted for 300h, the thermal weight loss analysis is carried out on the catalyst after washing and drying by adopting butyrolactone, the thermal weight loss rate of the catalyst is 9.8 percent, and the polymer accumulation is obvious on the surface of the catalyst.

Comparative example 9

The other conditions were the same as in example 7 except that the reaction temperature was elevated to 130 ℃ to achieve 99.9% conversion of maleic anhydride, 86.7% selectivity for succinic anhydride and 7.7% selectivity for butyrolactone.

Claims

1. A preparation method of a hydrogenation catalyst for preparing succinic anhydride from maleic anhydride comprises the following steps: dissolving soluble salt of active metal and a modifier in water, adding a carrier for isovolumetric impregnation, molding, drying and roasting to obtain a hydrogenation catalyst; the soluble salt of the active metal is selected from nitrate, hydrochloride, sulfate or phosphate of nickel or cobalt; the modifier is selected from one or more of basic carbonate, basic sulfate, basic phosphate and basic hydrochloride.

2. The process of claim 1 wherein the modifier is selected from one or more of basic copper carbonate, basic magnesium chloride, basic magnesium sulfate, basic copper sulfate and magnesium ammonium phosphate.

3. The method of claim 1, wherein the modifier is present in an amount of 1 to 20 mole percent of the reactive metal element.

4. The process of claim 1 wherein the modifier is used in an amount of 2 to 8 mole percent of the active metal element.

5. The process according to claim 1, wherein the hydrogenation catalyst comprises Ni and/or Co as active metal components in an amount of 5 to 40wt% based on the metal oxide.

6. The process of claim 1 wherein the hydrogenation catalyst comprises Ni and/or Co as the active metal components in an amount of from 10 to 20wt% based on the metal oxide.

7. The method of claim 1, wherein the support is one or more of alumina, silica, titania, magnesia, and activated carbon.

8. A preparation method of succinic anhydride comprises the following steps: the selective hydrogenation of maleic anhydride to succinic anhydride in the presence of hydrogen and a catalyst according to any one of claims 1 to 7.

9. The process of claim 8, wherein the hydrogenation reaction pressure is from 0.1 to 10MPa; the reaction temperature is 30-150 ℃.

10. The process of claim 9, wherein the hydrogenation reaction pressure is from 1 to 2MPa; the reaction temperature is 60-100 ℃.