CN108014796B - Catalyst for producing 1, 4-diacetyl oxy butane from butadiene - Google Patents

Abstract

The invention relates to a catalyst for producing 1, 4-diacetoxybutane by using butadiene, which mainly solves the problems of low yield and low selectivity of 1, 4-diacetoxybutane in the prior art, and adopts the catalyst for producing 1, 4-diacetoxybutane by using butadiene; the technical scheme that the catalyst comprises a carrier and an active component, wherein the carrier is activated carbon, the active component comprises a Pt element and a cocatalyst element, and the cocatalyst element comprises at least one metal element selected from VIB group metals, so that the technical problem is well solved, and the catalyst can be used in the industrial production of 1, 4-diacetoxybutane.

Description

Catalyst for producing 1, 4-diacetyl oxy butane from butadiene

Technical Field

The present invention relates to a catalyst for producing 1, 4-diacetyloxybutane from butadiene.

Background

1,4-butanediol (1,4-BDO) is an important organic and fine chemical raw material and is widely applied to the fields of medicine, chemical industry, textile, papermaking, automobile, daily chemical industry and the like. It can derive a series of fine chemical products with high added value. For example, Tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma-butyrolactone (GBL) and polyurethane resins (PU Resin) can be produced from 1,4-BDO, and have received extensive attention from research institutes, particularly as a basic raw material for the production of PBT engineering plastics and PBT fibers.

The industrial production method of the 1,4-butanediol mainly comprises ① acetylenic aldehyde method (Reppe method), wherein acetylene and formaldehyde are used as raw materials, butynediol is generated by using methanol copper as a catalyst, and is subjected to two-stage hydrogenation to obtain the 1,4-BDO, the process mainly comprises the BASF company, the Reppe method developed by DuPont in the U.S. and an improved Reppe method, ② maleic anhydride method, wherein the cis-butenediol is used as the raw material and is subjected to hydrogenation to obtain the 1,4-BDO, the gamma-butyrolactone and the gamma-Cr-tetrahydrofuran-anhydride are generated by using Ni-Re as catalysts in the first step, and the gamma-butyrolactone and the gamma-Cr-tetrahydrofuran are generated by using Ni-Re as catalysts in the second step, and the gamma-Cr-tetrahydrofuran in the second step₂Hydrogenating under the action of O catalyst to generate 1, 4-BDO. The main stream process is that Japanese dittany is used③ propylene method mainly includes allyl acetate method, acrolein method and allyl alcohol method, the allyl alcohol method developed by the company of Japan Coly is used industrially at present, it is under the action of rhodium catalyst, allyl alcohol liquid phase hydroformylation gets 4-hydroxy butyraldehyde, then hydrogenate to get 1,4-butanediol ④ butadiene method, the method for producing 1,4-BDO with butadiene as raw materials, mainly include butadiene acetoxylation method and butadiene chlorination method, its mainstream technology is developed by the company of Japan Trichosporon formation and Caoda in 80 years of 20 century, it breaks the technical barrier and obstacle of Reppe method successfully.

As is well known, the butadiene acetoxylation method is a three-step process, namely firstly, butadiene is subjected to acetylation reaction with acetic acid and oxygen to generate 1, 4-diacetoxybutene and a byproduct of 3, 4-diacetoxybutene; then the 1, 4-diacetoxybutene is catalyzed and hydrogenated to generate the 1, 4-diene acetoxy butane, and finally hydrolysis reaction is carried out to obtain the 1, 4-BDO. In a 1, 4-butadiene to 1,4-butanediol process route in which 1, 4-diacetoxybutene is catalytically hydrogenated to 1, 4-diene acetoxybutane as one of the steps, the yield and selectivity of the hydrogenated product directly affects the yield and selectivity of 1,4-butanediol relative to 1, 4-butadiene.

U.S. Pat. No. 4032458(production of 1,4-butane diol) teaches the production of 1,4-butanediol using furan in the presence of a catalyst under certain conditions of temperature and pressure. Patent CN94108094.3 (process for preparing 1,4-butanediol) describes the preparation of 1,4-butanediol by gas phase catalytic hydrogenation reaction using maleic anhydride as raw material in the presence of a specifically designed catalyst. Patent CN104326871A (a preparation method of butanediol) describes that 2-butene with a content of more than 99% is mixed with acetic acid, nitrogen, oxygen and water vapor at a high temperature and then introduced into a fixed bed by using a fixed bed catalytic technology, and 1,4-butanediol is prepared under the conditions of a catalyst, a certain temperature and a certain pressure, and the like. However, the methods have the problems of low yield and low selectivity of the 1,4-BDO in the process of preparing the 1, 4-BDO.

Disclosure of Invention

One of the technical problems to be solved by the invention is the problem that the yield and the selectivity of 1, 4-diacetoxybutane are low, and the invention provides a novel catalyst for the process of producing 1, 4-diacetoxybutane from butadiene, wherein the catalyst has the characteristics of high yield and high selectivity of 1, 4-diacetoxybutane.

The second technical problem to be solved by the invention is the preparation method of the catalyst.

The invention also provides a method for synthesizing 1, 4-diacetoxybutane by using the catalyst.

In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a catalyst for the production of 1, 4-diacetoxybutane from butadiene; the catalyst comprises a carrier and an active component, wherein the carrier is activated carbon, the active component comprises a Pt element and a promoter element, and the promoter element comprises at least one metal element selected from VIB group metals.

In the technical scheme, the activated carbon is preferably at least one of coal columnar carbon, coconut shell activated carbon, apricot shell activated carbon and bamboo activated carbon.

In the technical scheme, the specific surface area of the activated carbon is preferably 1000-1500 cm2/g, and the adsorption pore volume is preferably 0.60-1.00 cm 3/g.

In the above technical scheme, the group VIB metal in the catalyst is preferably at least one selected from Cr, Mo and W. Further comprises Cr and W. Cr and W have synergistic effect on improving the yield of 1, 4-diacetoxybutane and the selectivity of 1, 4-diacetoxybutane.

In the above technical solution, the promoter element may further include at least one metal element selected from alkaline earth metals, and at this time, a synergistic effect is achieved between the metal element in the alkaline earth metals and the metal element in the group VIB metals in the aspect of improving the yield of 1, 4-diacetoxybutane and the selectivity of 1, 4-diacetoxybutane. By way of non-limiting example, such as but not limited to strontium in conjunction with chromium, strontium in conjunction with tungsten, and the like.

In the above technical solution, the alkaline earth metal in the catalyst is preferably at least one selected from Be, Mg, Ca, Sr and Ba, and more preferably includes both Ba and Sr. Ba and Sr have synergistic effect in increasing the yield of 1, 4-diacetoxybutane and the selectivity of 1, 4-diacetoxybutane.

In the technical scheme, the content of Pt in the catalyst is preferably 1.00-8.50 g/L, and more preferably 1.50-5.00 g/L.

In the technical scheme, the content of the promoter element in the catalyst is preferably 0.50-10.00 g/L, and more preferably 1.00-6.00 g/L.

To solve the second technical problem, the technical solution of the present invention is as follows:

the method for preparing a catalyst according to any of the preceding technical solutions, comprising the steps of:

① mixing the solution containing platinum element with the carrier according to the composition of the catalyst to obtain a catalyst precursor I;

② aging the catalyst precursor I to obtain a catalyst precursor II;

③ reducing the combined platinum element in the catalyst precursor II into simple substance platinum to obtain a catalyst precursor III;

④ washing with water, drying to obtain catalyst precursor IV;

⑤ according to the composition of the catalyst, the solution containing the promoter element is loaded on the catalyst precursor IV by adopting an impregnation method, and the catalyst is obtained by drying.

In the above embodiment, the specific compound corresponding to the platinum element in step ① is preferably at least one compound selected from the group consisting of platinum acetate, platinum chloride, ammonium chloroplatinate, dinitrosoplatinate, chloroplatinic acid and tetraammineplatinate, and more preferably ammonium chloroplatinate, by way of non-limiting example.

In the above technical solution, as a non-limiting example, the specific compound corresponding to the group VIB metal element in step ⑤ is preferably at least one selected from chromium acetate, chromium nitrate, chromium chloride, ammonium molybdate, molybdenum pentachloride, molybdenum carbonyl, molybdic acid, tungsten chloride, tungsten carbonyl, ammonium paratungstate and ammonium tungstate, and more preferably at least one selected from chromium acetate and ammonium tungstate.

In the above technical solution, as a non-limiting example, when the promoter element in the step ⑤ includes an alkaline earth metal element, a specific compound corresponding to the alkaline earth metal element is preferably at least one selected from an alkaline earth metal oxide, an alkaline earth metal chloride, an alkaline earth metal sulfate, an alkaline earth metal nitrate and an alkaline earth metal acetate, more preferably at least one selected from an alkaline earth metal acetate, and most preferably at least one selected from barium acetate and strontium acetate.

In the technical scheme, based on the understanding of a person skilled in the art that the reducing agent in the step ③ is not particularly required, the reducing agent can be gas or liquid, the reducing agent is preferably at least one of hydrogen and hydrazine hydrate, the drying temperature in the step ④ is preferably 30-120 ℃, the drying time is preferably 1-5 hours, and the drying temperature in the step ⑤ is preferably 80-120 ℃, and more preferably 100-120 ℃.

To solve the third technical problem, the technical scheme of the invention is as follows:

1, 4-diacetoxybutane is obtained by reacting hydrogen with 1, 4-diacetoxybutene in the presence of a catalyst according to any of the preceding technical claims.

The key to the invention is the selection of the catalyst, and the skilled person knows how to determine the appropriate hydrogenation process conditions such as reaction temperature, reaction time, reaction pressure and feed ratio according to actual needs. However:

in the technical scheme, the temperature of the hydrogenation reaction is preferably 20-120 ℃.

In the above technical scheme, the pressure of the hydrogenation reaction is preferably 1.0-10.0 MPa, and more preferably 1.0-6.0 MPa.

In the technical scheme, the time of the hydrogenation reaction is preferably 0.5-5.0 h, and more preferably 0.5-2.0 h.

1, 4-diacetoxybutene is commercially available or can be synthesized by butadiene oxyacetylation. The butadiene oxyacetylation method can select Pd-Te/C as butadiene oxyacetylation catalyst. The content of palladium element in the suitable Pd-Te/C catalyst is preferably 2.50-5.00 g/L, and more preferably 3.00-4.50 g/L; the content of tellurium is preferably 0.50 to 3.00g/L, more preferably 1.00 to 2.50 g/L. The suitable temperature of the oxyacetylation reaction is preferably 40-150 ℃; the pressure of the oxyacetylation reaction is preferably 1.0-10.0 MPa; the preferred time of the oxyacetylation reaction is 0.5-5 h; the molar ratio of butadiene to acetic acid is preferably 0.010-2.0. After the butadiene is subjected to the butadiene oxyacetylation reaction, the mixture of the butadiene oxyacetylation reaction can be separated to obtain the target product 1, 4-diacetoxybutene, and then the hydrogenation reaction is carried out, or the hydrogenation reaction can be directly carried out without separating. However, in order to eliminate other impurities to cause system complexity and facilitate the same proportion, the section of the embodiment of the invention adopts pure 1, 4-diacetyloxybutene as the hydrogenation reaction raw material.

The product mixture of the hydrogenation reaction can be separated to obtain the target product 1, 4-diacetyloxybutane.

The 1, 4-diacetoxybutane can be further used to obtain 1,4-butanediol by a hydrolysis process. The selection of an appropriate hydrolysis catalyst and the determination of an appropriate hydrolysis reaction temperature, time and feed ratio are well known to those skilled in the art. The hydrolysis catalysts which are commonly used may be inorganic acids, inorganic bases, organic acids and organic bases. Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, benzenesulfonic acid, and ion exchange resins. The appropriate hydrolysis reaction temperature is preferably 30-100 ℃; the hydrolysis reaction pressure is preferably 0-2.0 MPa; the solvent is preferably water.

The product mixture after hydrogenation reaction is analyzed by a gas chromatography-MASS spectrometer (GC-MASS), and the yield and selectivity of 1, 4-diacetoxybutane are calculated according to the following formula:

compared with the prior art, the catalyst used in the invention improves the yield and selectivity of the 1, 4-diacetoxybutane.

The experimental result shows that when the method is adopted, the yield of the 1, 4-diacetoxybutane reaches 82.36 percent, the selectivity reaches 94.26 percent, and a better technical effect is achieved. Especially, when the active component of the hydrogenation catalyst simultaneously comprises platinum, at least one metal element selected from alkaline earth metals and at least one metal element selected from VIB group metals, more outstanding technical effects are obtained. The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 1.88g Sr₂·0.5H₂O) was impregnated on the catalyst precursor IV in 180ml of an aqueous solution and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the Sr content was 1.88 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was analytically calculated to be 82.36% and the selectivity 94.26%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

[ example 2 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium tungstate containing 1.88g W ((NH)₄)₁₀W₁₂O₄₁·4H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the W content 1.88 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 82.44% by analysis, the selectivity was found to be 94.12%, and the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively, for ease of illustration and comparison.

[ COMPARATIVE EXAMPLE 1 ]

Are comparative examples of [ example 1 ] and [ example 2 ].

Preparation of hydrogenation catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying for 4 hours at 50 ℃ to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 75.21% with selectivity to 91.27%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

Compared with the examples 1-2, the catalyst adopted by the invention has the advantages that the catalyst performance of the catalyst containing Pt and Sr as active components and Pt and W as active components is better than that of the catalyst containing Pt only as active components, and the active components of the hydrogenation catalyst simultaneously contain Pt and at least one metal element selected from alkaline earth metals and VIB group metals, so that the activity and stability of the catalyst are improved, and the yield and selectivity of the 1, 4-diacetoxybutane are high.

[ COMPARATIVE EXAMPLE 2 ]

Comparative example [ comparative example 1 ].

Preparation of the catalyst:

① ammonium chloropalladite containing 2.05gPd ((NH)₄)₂PdCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying for 4 hours at 50 ℃ to obtain the catalyst.

The Pd content of the catalyst was determined by ICP to be 2.05 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was analytically calculated to be 70.14% and the selectivity was 88.09%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield and selectivity of 1, 4-diacetoxybutane are shown in tables 1 and 2, respectively.

As can be seen from comparison with comparative example 1, the catalyst using hydrogenation of the present invention has better performance than the catalyst containing Pd active component, which indicates that the use of Pt as the active component of the catalyst is favorable for hydrogenation of 1, 4-diacetoxybutene and that the yield and selectivity of 1, 4-diacetoxybutane are high.

[ example 3 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ chromium acetate (Cr (OAc)) containing 1.88g of Cr₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst is 2.05g/L and the Cr content is 1.88g/L through ICP measurement.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 82.41% by analysis, the selectivity was found to be 94.14%, and the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively, for ease of illustration and comparison.

[ example 4 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.60cm³Per g, specific surface area 1000cm²Soaking a coconut shell cylindrical activated carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ beryllium acetate (Be (OAc) containing 1.88g Be₂·H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 100 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to Be 2.05g/L and the Be content was 1.88 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was analytically calculated to be 82.31% and the selectivity 94.24%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield and selectivity of 1, 4-diacetoxybutane are shown in tables 1 and 2, respectively.

[ example 5 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm and pore volume of 1.00cm³Per g, specific surface area 1500cm²Soaking the apricot shell cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ magnesium acetate (Mg (OAc) containing 1.88g Mg₂·4H₂O) 180ml of an aqueous solution was impregnated on the catalyst precursor IV, and dried at 120 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the Mg content 1.88 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was analytically calculated to be 82.31% and the selectivity 94.24%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield and selectivity of 1, 4-diacetoxybutane are shown in tables 1 and 2, respectively.

[ example 6 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a bamboo cylindrical activated carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ calcium acetate (Ca (OAc) containing 1.88g Ca₂·H₂O) 180ml of an aqueous solution was impregnated on the catalyst precursor IV, and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the Ca content 1.88 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 82.32% with selectivity to 94.28%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

[ example 7 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolved in 8 wt% saltAdding 1L of aqueous acid solution to obtain 200ml of impregnation solution, wherein the impregnation solution has a diameter of 3mm, a length of 2cm and a pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ barium acetate containing 1.88g Ba (OAc)₂·H₂O) 180ml of an aqueous solution, was impregnated on the catalyst precursor IV, and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst had a Pt content of 2.05g/L and a Ba content of 1.88g/L as determined by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 50 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 82.37% by analysis, the selectivity was found to be 94.27%, and the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively, for ease of illustration and comparison.

[ example 8 ]

Preparation of the catalyst:

① ammonium chloroplatinite (NH) containing 1.50gPt₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Coal cylindrical activated carbon carrier in gImmersing the catalyst precursor in the immersion liquid to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 1.00g Sr₂·0.5H₂O) 180ml of an aqueous solution, was impregnated on the catalyst precursor IV, and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was 1.50g/L and the Sr content was 1.00g/L as determined by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 0.5MPa, introducing hydrogen until the pressure is 1.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 20 ℃, continuously reacting for 30min, and stopping the reaction. Cooling the reaction kettle to room temperature, and purifying to remove impurities to obtain the 1, 4-diacetyloxy butane.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 80.71% with a selectivity of 93.88%, and the catalyst preparation, reaction conditions, feed rates, yield and selectivity of 1, 4-diacetoxybutane were shown in tables 1 and 2, respectively, for ease of illustration and comparison.

[ example 9 ]

Preparation of the catalyst:

① ammonium chloroplatinite (NH) containing 5.00gPt₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 6.00g Sr₂·0.5H₂O) 180ml of an aqueous solution, was impregnated on the catalyst precursor IV, and dried at 110 ℃ for 4 hours to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 5.00g/L and the Sr content was determined to be 6.00 g/L.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 6.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 120 ℃, continuously reacting for 120min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 82.61% by analysis and the selectivity was found to be 93.92%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

[ example 10 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 1.22g of Sr and 0.66g of Ba₂·0.5H₂O) and barium acetate (Ba (OAc)₂·H₂O) was impregnated on the catalyst precursor IV in 180ml of an aqueous solution and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has a Pt content of 2.05g/L, a Sr content of 1.22g/L and a Ba content of 0.66g/L as determined by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 83.29% by analysis, and the selectivity was found to be 94.50%, and the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively, for ease of illustration and comparison.

As can be seen from the comparison between example 10 and examples 1 and 7, in the catalyst used in the present invention, in terms of improvement in the yield and selectivity of 1, 4-diacetoxybutane, the metal element Sr and the metal element Ba in the alkaline earth metal have a good synergistic effect.

[ example 11 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²The coal-based cylindrical activated carbon carrier is impregnated in the impregnation solution to obtain a catalyst precursorI；

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium tungstate containing 0.98g of 0.98g W and 0.90g of Cr ((NH)₄)₁₀W₁₂O₄₁·4H₂O) and chromium acetate (Cr (OAc)₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has a Pt content of 2.05g/L, a W content of 0.98g/L and a Cr content of 0.90g/L as measured by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 83.43% by analysis, the selectivity was found to be 94.33%, and the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively, for ease of illustration and comparison.

As can be seen from the comparison between example 11 and examples 2 and 3, the catalyst used in the present invention has a good synergistic effect of W and Cr, which are metal elements in the group VIB, in increasing the yield and selectivity of 1, 4-diacetoxybutane.

[ example 12 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) DissolutionAdding into 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ contains Sr (1.04 g) and Sr acetate (Sr (OAc)) 0.84g W₂·0.5H₂O) and ammonium tungstate ((NH)₄)₁₀W₁₂O₄₁·4H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst had a Pt content of 2.05g/L, a Sr content of 1.04g/L and a W content of 0.84g/L as determined by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 84.32% by analysis and the selectivity was found to be 95.11%, and for convenience of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity were shown in tables 1 and 2, respectively.

From example 12 in comparison with examples 1 and 2, it can be seen that the catalyst used in the present invention has a better synergistic effect of the metal element Sr in the alkaline earth metal and the metal element W in the group VIB metal in terms of improving the yield and selectivity of 1, 4-diacetoxybutane.

[ example 13 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 1.04g of Sr and 0.84g of Cr₂·0.5H₂O) and chromium acetate (Cr (OAc)₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has a Pt content of 2.05g/L, a Sr content of 1.04g/L and a Cr content of 0.84g/L as determined by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 84.28% with a selectivity of 95.08%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

From example 13, which is compared with examples 1 and 3, it can be seen that the catalyst used in the present invention has a better synergistic effect of the metal element Sr in the alkaline earth metal and the metal element Cr in the group VIB metal in terms of improving the yield and selectivity of 1, 4-diacetoxybutane.

[ example 14 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 1.04g of Sr, 0.58g W and 0.26g of Cr₂·0.5H₂O), ammonium tungstate ((NH)₄)₁₀W₁₂O₄₁·4H₂O) and chromium acetate (Cr (OAc)₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has a Pt content of 2.05g/L, a Sr content of 1.04g/L, a W content of 0.58g/L and a Cr content of 0.26g/L as measured by ICP.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 85.22% with selectivity to 95.31%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

From example 14 in comparison with examples 12 and 13, it can be seen that the catalyst used in the present invention has a better synergistic effect of the metal element Sr in the alkaline earth metal and the metal element W, Cr in the group VIB metal in improving the yield and selectivity of 1, 4-diacetoxybutane.

[ example 15 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ barium acetate (Ba (OAc)) containing 1.04g Ba, 0.58g W and 0.26g Cr₂·H₂O), ammonium tungstate ((NH)₄)₁₀W₁₂O₄₁·4H₂O) and chromium acetate (Cr (OAc)₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has a Pt content of 2.05g/L, a Ba content of 1.04g/L, a W content of 0.58g/L and a Cr content of 0.26g/L through ICP determination.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was found to be 85.17% by analysis and the selectivity was found to be 95.35%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

[ example 16 ]

Preparation of the catalyst:

① ammonium chloroplatinite 2.05gPt in (NH)₄)₂PtCl₄) Dissolving in 8 wt% hydrochloric acid aqueous solution to obtain 200ml of impregnation solution, and mixing 1L of solution with diameter of 3mm, length of 2cm, and pore volume of 0.80cm³A specific surface area of 1200 cm/g²Soaking a coal cylindrical active carbon carrier in the soaking solution to obtain a catalyst precursor I;

② standing and aging for 24h to obtain a catalyst precursor II;

③ the concentration is 8% (by N)₂H₄·H₂O weight ratio) of 500ml of hydrazine hydrate is used for reducing the catalyst precursor II for 3h to obtain a catalyst precursor III;

④, washing with water until no chloride ion exists, and drying at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ strontium acetate (Sr (OAc)) containing 0.65g of Sr, 0.39g of Ba, 0.58g W and 0.26g of Cr₂·0.5H₂O), barium acetate (Ba (OAc)₂·H₂O), ammonium tungstate ((NH)₄)₁₀W₁₂O₄₁·4H₂O) and chromium acetate (Cr (OAc)₃·6H₂O) was dissolved in hot water to obtain 180ml of an impregnation solution, which was impregnated on the catalyst precursor IV and dried at 110 ℃ for 4 hours to obtain the catalyst.

The catalyst has Pt content of 2.05g/L, Sr content of 0.65g/L, Ba content of 0.39g/L, W content of 0.58g/L and Cr content of 0.26g/L through ICP determination.

Synthesis of 1, 4-diacetoxybutane:

adding 15ml of 1, 4-diacetoxybutene, 30ml of toluene and 0.01mol of hydrogenation catalyst into a 100ml titanium reaction kettle, discharging air in the kettle by using argon, pressurizing to 1.0MPa, introducing hydrogen until the pressure is 3.0MPa, increasing the stirring speed to 600rpm, stirring, heating to the reaction temperature, controlling the reaction temperature to be 60 ℃, continuously reacting for 90min, and stopping the reaction.

The yield of 1, 4-diacetoxybutane was calculated analytically to be 86.29% with a selectivity of 95.52%, and for ease of illustration and comparison, the catalyst preparation, reaction conditions, feed rates, yield of 1, 4-diacetoxybutane and selectivity are shown in tables 1 and 2, respectively.

From example 16, which is compared with examples 14 and 15, it is seen that the catalyst used in the present invention has a better synergistic effect of metal elements Sr, Ba and W, Cr in the alkaline earth metals of the group VIB metals in terms of improving the yield and selectivity of 1, 4-diacetoxybutane.

TABLE 1

TABLE 2

Claims (6)

1. A method for synthesizing 1, 4-diacetoxybutane comprises the steps of carrying out hydrogenation reaction on hydrogen and 1, 4-diacetoxybutene in the presence of a hydrogenation catalyst to obtain 1, 4-diacetoxybutane; the hydrogenation catalyst comprises a carrier and an active component, wherein the carrier is activated carbon, the active component comprises a Pt element and a promoter element, and the promoter element comprises at least one metal element selected from VIB group metals;

wherein, the VIB group metal in the hydrogenation catalyst is at least one of Cr, Mo and W;

wherein the content of Pt element in the catalyst is 1.00-8.50 g/L, and the content of promoter element is 0.50-10.00 g/L.

2. The method of synthesizing 1, 4-diacetoxybutane according to claim 1, wherein the activated carbon is at least one of coal columnar carbon, coconut shell activated carbon, apricot shell activated carbon, and bamboo activated carbon.

3. The method for synthesizing 1, 4-diacetoxybutane according to claim 1, wherein the specific surface area of the activated carbon is 1000 to 1500 m²The volume of the adsorption holes is 0.60-1.00 cm³/g。

4. The method of synthesizing 1, 4-diacetoxybutane according to any one of claims 1 to 3 wherein the hydrogenation catalyst is prepared by a process comprising the steps of:

① mixing the solution containing platinum element with the carrier according to the composition of the catalyst to obtain a catalyst precursor I;

② aging the catalyst precursor I to obtain a catalyst precursor II;

③ reducing the combined platinum element in the catalyst precursor II into simple substance platinum to obtain a catalyst precursor III;

④ washing with water, drying to obtain catalyst precursor IV;

⑤ according to the composition of the catalyst, the solution containing the promoter element is loaded on the catalyst precursor IV by adopting an impregnation method, and the catalyst is obtained by drying.

5. The method for synthesizing 1, 4-diacetoxybutane according to claim 1, wherein the temperature of the hydrogenation reaction is 20 to 120 ℃.

6. The method for synthesizing 1, 4-diacetoxybutane according to claim 1, wherein the pressure of the hydrogenation reaction is 1.0 to 10.0 MPa.