CN108014793B - Hydrogenation catalyst for preparing 1, 4-diacetoxybutane - Google Patents

Abstract

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

Description

Hydrogenation catalyst for preparing 1, 4-diacetoxybutane

Technical Field

The present invention relates to a hydrogenation catalyst for the preparation of 1, 4-diacetoxybutane.

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 and 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 ratio of the Asia 1,4-BDO production to the Asia 1,4-BDO production is as high as 56.6%The method takes maleic anhydride as a raw material and carries out two-step hydrogenation, the maleic anhydride is hydrogenated to generate gamma-butyrolactone and tetrahydrofuran under the action of a Ni-Re catalyst in the first step, and the gamma-butyrolactone is hydrogenated to generate Mo-Cr-K 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-butanediol and provides a novel hydrogenation catalyst for preparing 1, 4-diacetoxybutane, 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 the 1, 4-diacetoxybutane comprises a carrier and an active component, wherein the carrier is activated carbon, the active component comprises Pt element and a promoter element, and the promoter element comprises at least one metal element selected from lanthanide series 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 lanthanide metal in the hydrogenation catalyst is preferably at least one selected from La, Ce, Pr, Nd, Sm, Eu, Yb and Lu. Further comprises La and Lu. La and Lu have synergistic effect in 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 selected from group IVA metal elements, and at this time, there is a synergistic effect between the metal element in the lanthanide series and the metal element in the group IVA metal 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 lanthanum in combination with tin, lanthanum in combination with lead, and the like.

In the above technical solution, the group IVA metal in the hydrogenation catalyst is selected from at least one of Ge, Sn and Pb, and more preferably includes both Sn and Pb. Sn and Pb have a 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 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:

the method for preparing a hydrogenation 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 lanthanide metal element in step ⑤ is preferably at least one selected from lanthanum acetate, lanthanum nitrate, lanthanum chloride, lanthanum sulfate, cerium chloride, cerium nitrate, cerium acetate, praseodymium chloride, praseodymium nitrate, neodymium acetate, neodymium chloride, samarium acetate, samarium chloride, samarium nitrate, europium chloride, europium nitrate, europium acetate, ytterbium chloride, ytterbium nitrate, lutetium chloride, lutetium nitrate, and lutetium acetate, and more preferably at least one selected from lanthanum acetate and lutetium acetate.

In the above technical solution, as a non-limiting example, when the promoter element in step ⑤ includes a group IVA metal element, the specific compound corresponding to the group IVA metal element is preferably selected from at least one of tetraethylgermanium, tetraphenylgermanium, germanium tetrachloride, stannous oxalate, stannous chloride, stannous nitrate, stannous acetate, stannous oxide, lead acetate, lead stearate, basic lead carbonate, basic lead acetate, and lead nitrate, and more preferably from at least one of stannous acetate and lead 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:

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 82.49%, the selectivity reaches 94.18%, and a better technical effect is achieved. Particularly, when the active component of the hydrogenation catalyst comprises platinum, at least one metal element selected from lanthanide metals and at least one metal element selected from IVA metals, the technical effect is more prominent. 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 lanthanum acetate (La (OAc) containing 1.90g La₃·5H₂O) 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 La content was determined to be 1.90 g/L.

1, 4-diacetoxybutene hydrogenation:

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 82.49% and the selectivity was 94.18%, 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 lead acetate (Pb (OAc)) containing 1.90g of Pb₂·3H₂O) 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 Pb content was determined to be 1.90 g/L.

1, 4-diacetoxybutene hydrogenation:

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 82.35% 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.

[ 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.

1, 4-diacetoxybutene hydrogenation:

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 75.15% and the selectivity was 91.33%, 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.

Compared with the examples 1-2, the catalyst adopting hydrogenation has the advantages that the catalyst performance of the catalyst adopting hydrogenation is better than that of the catalyst only containing Pt and La as the active components, and Pt and Pb as the active components, so that the hydrogenation catalyst is beneficial to improving the activity and stability of the hydrogenation catalyst, and the yield and 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.

1, 4-diacetoxybutene hydrogenation:

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 70.10% and the selectivity was 88.03%, 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.

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 stannous acetate (Sn (OAc) containing 1.90g of Sn₂·2H₂O) 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 Pt content of the catalyst was determined by ICP to be 2.05g/L and the Sn content was determined to be 1.90 g/L.

1, 4-diacetoxybutene hydrogenation:

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 82.38% by analysis, and the selectivity was found to be 94.29%, 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 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 cerium acetate (Ce (OAc) containing 1.90g of Ce₃·6H₂O) 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 Ce content 1.90 g/L.

1, 4-diacetoxybutene hydrogenation:

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 94.14%, 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 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 praseodymium acetate (Pr (OAc) containing 1.90g of Pr₃·5H₂O) 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 is 2.05g/L and the Pr content is 1.90g/L through ICP measurement.

1, 4-diacetoxybutene hydrogenation:

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 94.17%, 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 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 Neodymium acetate (Nd (OAc) containing 1.90g of Nd₂·6H₂O) 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 Nd content was determined to be 1.90 g/L.

1, 4-diacetoxybutene hydrogenation:

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 82.47% by analysis, and the selectivity was found to be 94.14%, 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 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 lutetium acetate Lu (OAc) containing 1.90g Lu₃·6H₂O) 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 is 2.05g/L and the Lu content is 1.90g/L through ICP measurement.

1, 4-diacetoxybutene hydrogenation:

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 82.45% and the selectivity was 94.20%, 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 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 europium acetate (Eu (OAc) containing 1.00g Eu₃·6H₂O) 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 is 1.50g/L and the Eu content is 1.00g/L through ICP measurement.

1, 4-diacetoxybutene hydrogenation:

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 80.62% and the selectivity was 93.92%, 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 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 ytterbium acetate (Yb (OAc) containing 6.00g Yb₃·6H₂O) 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 Yb content was determined to be 6.00 g/L.

1, 4-diacetoxybutene hydrogenation:

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 analytically calculated to be 82.54% and the selectivity was 93.89%, 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 lanthanum acetate (La (OAc) containing 1.20g of La and 0.70g of Lu₃·5H₂O) and lutetium acetate (Lu (OAc)₃·6H₂O) 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 is 2.05g/L, the La content is 1.20g/L and the Lu content is 0.70g/L through ICP determination.

1, 4-diacetoxybutene hydrogenation:

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, and the selectivity was found to be 94.35%, 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.

From example 10, which is comparable to examples 1 and 7, it can be seen that the hydrogenation catalyst used in the present invention has a better synergistic effect of the metal element La and the metal element Lu in the lanthanide metals in terms of the improvement of 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 lead acetate (Pb (OAc)) containing 0.90g of Pb and 1.00g of Sn₂·3H₂O) and stannous acetate (Sn (OAc)₂·2H₂O) 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 Pb content of 0.90g/L and a Sn content of 1.00g/L as determined by ICP.

1, 4-diacetoxybutene hydrogenation:

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 83.31% by analysis and the selectivity to 94.46%, 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 can be seen from example 11 in comparison with examples 2 and 3, the hydrogenation catalyst used in the present invention has a good synergistic effect of the metal element Pb and Sn in the group IVA metal in terms of 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 lanthanum acetate (La (OAc) containing 1.09g of La and 0.81g of Pb₃·5H₂O) and lead acetate (Pb (OAc)₂·3H₂O) was immersed in 180ml of an aqueous solution of 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, the La content was 1.09g/L, and the Pb content was 0.81 g/L.

1, 4-diacetoxybutene hydrogenation:

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 84.39% and the selectivity was 95.03%, 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 example 12, which is comparable to examples 1 and 2, the hydrogenation catalyst used in the present invention has a better synergistic effect of La, which is a metal of the lanthanide series, and Pb, which is a metal of the IVA group, 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 lanthanum acetate (La (OAc) containing 1.09g of La and 0.81g of Sn₃·5H₂O) and stannous acetate (Sn (OAc)₂·2H₂O) 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 La content of 1.09g/L and a Sn content of 0.81g/L as determined by ICP.

1, 4-diacetoxybutene hydrogenation:

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 84.33% by analysis and the selectivity was found to be 95.11%, 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.

From example 13, which is compared with examples 1 and 3, it can be seen that the hydrogenation catalyst used in the present invention has a better synergistic effect of La, which is a metal element in lanthanide series, and Sn, which is a metal element in group IVA, 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 lanthanum acetate (La (OAc) containing 1.09g of La, 0.35g of Pb and 0.46g of Sn₃·5H₂O), lead acetate (Pb (OAc)₂·3H₂O) and acetylideneTin (Sn (OAc)₂·2H₂O) 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 La content of 1.09g/L, a Pb content of 0.35g/L and a Sn content of 0.46g/L as determined by ICP.

1, 4-diacetoxybutene hydrogenation:

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 85.27% by analysis, and the selectivity was found to be 95.44%, 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 between La, which is a metal element in the lanthanoid group, and Pb and Sn, which are metal elements in the IVA group, in terms of improvement in the yield and selectivity of 1, 4-diacetoxybutane.

[ example 15 ]

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 waterHydrazine 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 lutetium acetate (Lu (OAc) containing 1.09g of Lu, 0.35g of Pb and 0.46g of Sn₃·6H₂O), lead acetate (Pb (OAc)₂·3H₂O) and stannous acetate (Sn (OAc)₂·2H₂O) 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 Lu content of 1.09g/L, a Pb content of 0.35g/L and a Sn content of 0.46g/L as measured by ICP.

1, 4-diacetoxybutene hydrogenation:

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 95.48%, 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 concentrationIs 8% (in 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 lanthanum acetate (La (OAc) containing 0.69g of La, 0.40g of Lu, 0.35g of Pb and 0.46g of Sn₃·5H₂O), lutetium acetate (Lu (OAc)₃·6H₂O), lead acetate (Pb (OAc)₂·3H₂O) and stannous acetate (Sn (OAc)₂·2H₂O) 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 La content of 0.69g/L, a Lu content of 0.40g/L, a Pb content of 0.35g/L and a Sn content of 0.46g/L through ICP determination.

1, 4-diacetoxybutene hydrogenation:

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 86.37% and the selectivity 95.59%, 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.

As can be seen from the comparison between example 16 and examples 14 and 15, the hydrogenation catalyst used in the present invention has a better synergistic effect of the metal elements La, Lu in the lanthanide series metals and the metal elements Pb and Sn in the group IVA metals in terms of improving the yield and selectivity of 1, 4-diacetoxybutane.

TABLE 1

TABLE 2

Claims (6)

1. A method for producing 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 Pt element and a promoter element, and the promoter element comprises at least one metal element selected from lanthanide metals;

wherein the lanthanide metal is selected from at least one of La, Ce, Pr, Nd, Sm, Eu, Yb and Lu;

wherein, the content of Pt element in the hydrogenation catalyst is 0.90-8.00 g/L, and the content of promoter element is 0.50-10.00 g/L.

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

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