CN107913706B - Hydrogenation catalyst for preparing 1, 4-diacetoxybutane from butadiene - Google Patents

Abstract

The invention relates to a hydrogenation catalyst for preparing 1, 4-diacetoxybutane from butadiene, which mainly solves the problem of low yield and selectivity of 1, 4-diacetoxybutane in the prior art, and the hydrogenation catalyst for synthesizing 1, 4-diacetoxybutane from butadiene 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 is selected from at least one metal element of a metalloid group metal.

Description

Hydrogenation catalyst for preparing 1, 4-diacetoxybutane from butadiene

Technical Field

The invention relates to a hydrogenation catalyst for preparing 1, 4-diacetoxybutane 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 technical barriers are high, the raw material sources are limited, the global 1,4-BDO production is relatively centralized, 2011, the global 1,4-BDO production is mainly distributed in Asia, America and Europe, wherein the occupation ratio of the Asia 1,4-BDO production is as high as 56.6 percent, and the current industrial production method of the 1,4-BDO mainly comprises a ① acetylenic aldehyde method (Reppe method) which takes acetylene and formaldehyde as raw materials and methanol copper as a catalyst to generate butynediol and butynediolThe main processes for obtaining 1,4-BDO by two-stage hydrogenation of alcohol mainly include a Reppe method developed by BASF company in Germany and DuPont in America and an improved Reppe method ② cis-butenedioic anhydride method, wherein cis-butenedioic anhydride is taken as a raw material and subjected to two-step hydrogenation to generate gamma-butyrolactone and tetrahydrofuran under the action of a Ni-Re catalyst in the first step, and the gamma-butyrolactone is subjected to Mo-Cr-K hydrogenation in the second step₂The main process of the method is mainly a two-stage hydrogenation process developed by using a Japanese dittany oil method and a Mitsubishi formation method, ③ a propylene method mainly comprises an allyl acetate method, an acrolein method and an allyl alcohol method, the allyl alcohol method developed by the Japanese Coly company is industrially applied at present, the method comprises the steps of performing liquid-phase hydroformylation on allyl alcohol to generate 4-hydroxybutyraldehyde under the action of a rhodium catalyst, and then performing hydrogenation to generate 1,4-butanediol ④ a butadiene method, and the method for producing the 1,4-BDO by using butadiene as a raw material mainly comprises a butadiene acetoxylation method and a butadiene chlorination method, the main process of the method is developed by the Japanese mitsubishi formation and Caoda company in 80 years of the 20 th century, the technical barrier and obstacle of the Reppe method are successfully broken, particularly the advantages and the prospects of the butadiene acetoxylation method, and the favor of research institutions at home and abroad is obtained.

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

The invention aims to solve the technical problem of low yield and selectivity of 1, 4-diacetoxybutane and provides a novel hydrogenation catalyst for preparing 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 hydrogenation catalyst.

The invention also provides a synthesis method of 1, 4-diacetoxybutane by using the hydrogenation catalyst.

In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: the hydrogenation catalyst for preparing 1, 4-diacetoxybutane from butadiene 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 is at least one metal element selected from metalloid 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 cm²The preferred adsorption pore volume is 0.60-1.00 cm/g³/g。

In the above technical solution, the metalloid group metal in the hydrogenation catalyst is preferably at least one selected from B, Si, Se and Te, and more preferably includes both B and Te. B and Te have synergistic effect in increasing the yield of 1, 4-diacetoxybutane and the space-time yield and selectivity of 1, 4-diacetoxybutane.

In the above technical scheme, the cocatalyst may further comprise at least one metal element in the group VIIB metal, and at this time, a synergistic effect is provided between the metal element in the metalloid group and the metal element in the group VIIB metal in the improvement of the space-time yield and selectivity of the 1, 4-diacetoxybutylene hydrogenation catalyst. By way of non-limiting example, such as but not limited to tellurium in conjunction with manganese, boron in conjunction with manganese, and the like.

In the above technical solution, the VIIB metal in the hydrogenation catalyst is preferably at least one of Mn and Re. Further comprising both Mn and Re. Mn and Re have a synergistic effect in increasing the yield of 1, 4-diacetoxybutane and the space-time yield and selectivity of 1, 4-diacetoxybutane.

In the technical scheme, the content of Pt in the hydrogenation catalyst is preferably 0.90-8.00 g/L, and more preferably 1.50-5.00 g/L.

In the technical scheme, the content of the promoter element in the hydrogenation 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:

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, when the promoter element in step ⑤ includes a metalloid element, a specific compound corresponding to the metalloid element is preferably at least one selected from boric acid, ammonium pentaborate, dimethylaminoborane, silicic acid, silicon tetrachloride, ammonium silicate, selenic acid, selenium citrate, ammonium tellurate, tellurium dioxide and telluric acid, and more preferably at least one selected from ammonium pentaborate and ammonium tellurate.

In the above embodiment, by way of non-limiting example, when the promoter element in step ⑤ includes a group VIIB metal element, the specific compound corresponding to the group VIIB metal element is preferably at least one selected from manganese acetate, manganese nitrate, manganese chloride, manganese sulfate, manganese citrate, manganese tartrate, methyl rhenium trioxide, perrhenic acid, rhenium oxide, and ammonium perrhenate, and more preferably at least one selected from manganese acetate and ammonium perrhenate.

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:

a method for synthesizing 1, 4-diacetoxybutane, wherein hydrogen and 1, 4-diacetoxybutene are reacted in the presence of a hydrogenation catalyst according to any one of the technical schemes of the technical problems to obtain 1, 4-diacetoxybutane.

The key of the invention is the selection of hydrogenation catalyst, and the skilled person knows how to determine suitable 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 hydrogenation catalyst improves the yield and the selectivity of the 1, 4-diacetoxybutane.

Experimental results show that when the method is adopted, the yield of the 1, 4-diacetoxybutane reaches 82.47%, the selectivity reaches 94.06%, 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 metalloid group metals and at least one metal element selected from VIIB group metals, more outstanding technical effects are obtained. The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 1.95g Mn₂·4H₂O) 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 Mn content was 1.95 g/L.

Hydrogenation- -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 82.47% and the selectivity was 94.06%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amounts, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ 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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium tellurate containing 1.95g Te ((NH)₄)₂TeO₄) Fully dissolved in 10 wt% acetic acid water solution to obtain 180ml impregnation liquid impregnated in the catalyst precursor IV, 110 degrees C drying for 4 hours, get the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the Te content was determined to be 1.95 g/L.

Hydrogenation- -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 82.34% and the selectivity to be 94.12%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity to be shown in tables 1 and 2, respectively.

[ 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.

Hydrogenation- -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 75.32% and the selectivity was 91.16%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

Compared with the examples 1-2, the catalyst adopting hydrogenation has the advantages that the performance of the catalyst containing Pt and Mn as active components and Pt and Te as active components is better than that of the catalyst containing Pt only as active components, and the catalyst containing Pt and at least one metal element compound selected from metalloid group metals and VIIB group metals is used as the active component of the hydrogenation catalyst, so that the activity and the stability of the hydrogenation catalyst are improved, and the yield and the selectivity of the 1, 4-diacetoxybutane are high.

[ COMPARATIVE EXAMPLE 2 ]

Comparative example [ comparative example 1 ].

Preparation of hydrogenation 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.

Hydrogenation- -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 70.21% and the selectivity was 88.11%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

Compared with the comparative example 1, the catalyst adopting hydrogenation has better performance than the catalyst containing Pd active component, which shows that the hydrogenation catalyst uses Pt as the active component to favor the hydrogenation of 1, 4-diacetoxybutene and the yield and the selectivity of 1, 4-diacetoxybutane are high.

[ example 3 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium perrhenate (NH) containing 1.95g Re₄ReO₄) Dissolving in 10 wt% acetic acid water solution to obtain 180ml impregnation solution, impregnating on catalyst precursor IV, and drying at 110 deg.C for 4 hr to obtain the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L and the Re content was 1.95 g/L.

Hydrogenation- -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 82.41% and the selectivity was 94.04%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amounts, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 4 ]

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 0.60cm³Per 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 manganese nitrate (Mn (NO) containing 1.95g Mn₃)₂·4H₂O) 180ml of an aqueous solution 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 Mn content was 1.95 g/L.

Hydrogenation- -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 82.46% and the selectivity was 94.04%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 5 ]

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 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 manganese citrate (Mn) containing 1.95g Mn₃C₁₂H₁₀O₁₄·4H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight to obtain 180ml of an impregnation solution, which was then 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 Mn content was 1.95 g/L.

Hydrogenation- -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 82.45% and the selectivity 94.05%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity are shown in tables 1 and 2, respectively.

[ example 6 ]

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 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 manganese tartrate (C) containing 1.95g Mn₄H₄O₆Mn·4H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight to obtain 180ml of an impregnation solution, which was then 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 Mn content was 1.95 g/L.

Hydrogenation- -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 82.47% and the selectivity was 94.07%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amounts, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 7 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium pentaborate (NH) containing 1.95g B₄)B₅O₈·8H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight to obtain 180ml of an impregnation solution, which was then 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 B content 1.95 g/L.

Hydrogenation- -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 analytically calculated to be 82.35% and the selectivity 94.24%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity are shown in tables 1 and 2, respectively.

[ example 8 ]

Preparation of hydrogenation 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/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 manganese acetate (Mn (OAc) containing 1.00g of Mn₂·4H₂O) 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 Mn content was 1.00g/L as determined by ICP.

Hydrogenation- -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 analytically calculated to be 80.81% and the selectivity was 93.90%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 9 ]

Preparation of hydrogenation 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 manganese acetate (Mn (OAc) containing 6.00g of Mn₂·4H₂O) 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 Mn content was determined to be 6.00 g/L.

Hydrogenation- -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 calculated analytically to be 82.93% and the selectivity 93.58%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 10 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 1.05g of Mn and 0.90g of Re₂·4H₂O) and ammonium perrhenate (NH)₄ReO₄) Fully dissolved in 10 wt% acetic acid water solution to obtain 180ml impregnation liquid impregnated in the catalyst precursor IV, 110 degrees C drying for 4 hours, get the catalyst.

The Pt content of the catalyst was determined by ICP to be 2.05g/L, Mn 1.05g/L, and Re 0.90 g/L.

Hydrogenation- -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 83.40% and the selectivity was 94.39%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amounts, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

As can be seen from the comparison between example 10 and examples 1 and 3, in the hydrogenation catalyst used in the present invention, the metal element Mn and the metal element Re in the VIIB group metal have a better synergistic effect in increasing the yield and selectivity of 1, 4-diacetoxybutane.

[ example 11 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ ammonium tellurate containing 1.35g Te and 0.60g B ((NH)₄)₂TeO₄) And ammonium pentaborate ((NH)₄)B₅O₈·8H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight 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 Te content of 1.35g/L and a B content of 0.60g/L as determined by ICP.

Hydrogenation- -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 83.37% by analysis and the selectivity to 94.47%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity to 1, 4-diacetoxybutane were shown in tables 1 and 2, respectively.

As is apparent from the comparison between example 11 and examples 2 and 7, in the hydrogenation catalyst used in the present invention, the metal element Te of the metalloid group metal and the metal element B are more excellent in the synergistic effect in improving the yield and selectivity of 1, 4-diacetoxybutane.

[ example 12 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 1.10g of Mn and 0.85g of Te₂·4H₂O) and ammonium tellurate ((NH)₄)₂TeO₄) Is immersed in 180ml of the aqueous solution of (A), and dried at 110 ℃ for 4 hours to obtain the catalyst。

The catalyst had a Pt content of 2.05g/L, a Mn content of 1.10g/L and a Te content of 0.85g/L as determined by ICP.

Hydrogenation- -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 84.46% by analysis, and the selectivity was found to be 95.17%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

As can be seen from the comparison between example 12 and examples 1 and 2, in the hydrogenation catalyst used in the present invention, the metal element Te in the metalloid group metal and the metal element Mn in the VIIB group metal have a good synergistic effect in increasing the yield and selectivity of 1, 4-diacetoxybutane.

[ example 13 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 1.10g of Mn and 0.85g B₂·4H₂O) and ammonium pentaborate ((NH)₄)B₅O₈·8H₂O) was dissolved in an aqueous solution of acetic acid having a concentration of 10 wt% to obtain 180ml of an impregnation solution, which was then impregnated with 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 Mn content of 1.10g/L and a B content of 0.85g/L as determined by ICP.

Hydrogenation- -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 84.43% and the selectivity was 95.15%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amounts, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

From the comparison between example 13 and examples 1 and 7, it is seen that in the hydrogenation catalyst used in the present invention, the metal element B in the metalloid group metal and the metal element Mn in the VIIB group metal have a better synergistic effect in increasing the yield and selectivity of 1, 4-diacetoxybutane.

[ example 14 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 1.10g of Mn, 0.60g of Te and 0.25g of B₂·4H₂O), ammonium tellurate ((NH)₄)₂TeO₄) And ammonium pentaborate ((NH)₄)B₅O₈·8H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight 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 Mn content of 1.10g/L, a Te content of 0.60g/L and a B content of 0.25g/L as measured by ICP.

Hydrogenation- -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 85.25% by analysis and the selectivity was found to be 95.38%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

As can be seen from the comparison between example 14 and examples 12 and 13, the hydrogenation catalyst used in the present invention has a good synergistic effect of Mn, which is a metal element in the VIIB group, and B, Te, which is a metal element in the metalloid group, in increasing the yield and selectivity of 1, 4-diacetoxybutane.

[ example 15 ]

Preparation of hydrogenation catalyst:

① will contain2.05gPt ammonium chloroplatinite ((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 perrhenate (NH) with 1.10g Re, 0.60g Te and 0.25g B₄ReO₄) Telluric acid ammonium ((NH)₄)₂TeO₄) And ammonium pentaborate ((NH)₄)B₅O₈·8H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight 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 Re content of 1.10g/L, a Te content of 0.60g/L and a B content of 0.25g/L as determined by ICP.

Hydrogenation- -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 85.10% by analysis, and the selectivity was found to be 95.41%, and for convenience of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed amount, the yield of 1, 4-diacetoxybutane and the selectivity were shown in tables 1 and 2, respectively.

[ example 16 ]

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 at 50 ℃ for 4 hours to obtain a catalyst precursor IV;

⑤ manganese acetate (Mn (OAc) containing 0.75g of Mn, 0.35g of Re, 0.60g of Te and 0.25g B₂·4H₂O), ammonium perrhenate (NH)₄ReO₄) Telluric acid ammonium ((NH)₄)₂TeO₄) And ammonium pentaborate ((NH)₄)B₅O₈·8H₂O) was sufficiently dissolved in an aqueous solution of acetic acid having a concentration of 10% by weight 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 Mn content of 0.75g/L, a Re content of 0.35g/L, a Te content of 0.60g/L and a B content of 0.25g/L, which are measured by ICP.

Hydrogenation- -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 86.49% and the selectivity to be 95.63%, and for ease of illustration and comparison, the preparation of the hydrogenation catalyst, the reaction conditions, the feed rates, the yield of 1, 4-diacetoxybutane and the selectivity to be shown in tables 1 and 2, respectively.

As can be seen from the comparison between example 16 and examples 14 and 15, in the hydrogenation catalyst used in the present invention, the metal elements Te, B and VIIB of the metalloid group metals, Mn and Re of the metal elements, are more synergistic in improving the yield and selectivity of 1, 4-diacetoxybutane.

TABLE 1

TABLE 2

Claims (6)

1. A production method of 1, 4-diacetoxybutane is characterized in that in the presence of a hydrogenation catalyst, hydrogen and 1, 4-diacetoxybutene are subjected to hydrogenation reaction to obtain the 1, 4-diacetoxybutane, wherein the hydrogenation catalyst comprises a carrier and an active component, the carrier is activated carbon, the active component comprises Pt element and a promoter element, and the promoter element is at least one selected from metalloid elements B, Si, Se and Te; the content of Pt element in the hydrogenation catalyst is 0.90-8.00 g/L; the content of the promoter element is 0.50-10.00 g/L.

2. The production method according to claim 1, characterized in that 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 production method according to claim 1, wherein the activated carbon has a specific surface area of 1000 to 1500m²The volume of the adsorption holes is 0.60-1.00 cm³/g。

4. The production process according to claim 1, characterized in that the preparation process of the hydrogenation catalyst comprises 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 production process according to claim 1, wherein the hydrogenation reaction is carried out at a temperature of 20 to 120 ℃.

6. The production process according to claim 1, wherein the pressure of the hydrogenation reaction is 1.0 to 10.0 MPa.