A water-resistant catalyst for hydrogenation of aqueous sec-butyl acetate and its preparation method and application

Abstract

The present invention relates to a water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, and a preparation method and application thereof, which mainly solves the problem that aqueous sec-butyl acetate materials in the prior art are difficult to be directly used for hydrogenation to produce sec-butyl alcohol and ethanol. The present invention adopts a water-resistant catalyst, comprising copper oxide, a cerium dioxide carrier and a praseodymium oxide promoter, wherein the copper oxide mass content in the catalyst is 5-20%, the cerium dioxide carrier mass content is 75-95%, and the praseodymium oxide promoter mass content is 0.1-5%, and the technical scheme of its preparation method and application solves the above problems well, and can be used for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, and can also be used for further hydrogenation of crude sec-butyl acetate obtained by reacting liquefied petroleum gas containing butene with acetic acid to produce sec-butyl alcohol and ethanol.

Description

Technical Field

[0001] The invention relates to a water-resistant catalyst for hydrogenating aqueous sec-butyl acetate and a preparation method and application thereof. Background Art

[0002] Isobutyl acetate can be prepared by the addition esterification of acetic acid and butene. This method does not require pure butene as raw material, and can directly use liquefied petroleum gas containing more than 25% butene. After the industrialization of this "acid-ene addition method" technology, the national isobutyl acetate production capacity has increased sharply, with the highest annual output reaching millions of tons. As isobutyl acetate has become a bulk chemical product, the development of its downstream products has attracted widespread attention from academia and industry.

[0003] 2-Butanol is an important chemical product with a wide range of uses, of which 90% is used to produce methyl ethyl ketone. Methyl ethyl ketone is an excellent organic solvent with a moderate boiling point and good solubility. It is widely used in industries such as oil refining, coatings, dyes and medicines; it is also an important raw material for organic synthesis.

[0004] The production of sec-butyl acetate by the acid-olefin addition method and the direct production of sec-butyl alcohol by hydrogenation of sec-butyl acetate have received increasing attention, and the development of such hydrogenation catalysts has become increasingly mature.

[0005] CN102146019B discloses a method for preparing alcohol from olefins, which includes two processes: esterification and hydrogenation. Under the action of a solid acid catalyst, olefins and acetic acid react to form acetate; then, under the action of a copper-containing hydrogenation catalyst, the acetate is hydrogenated to obtain ethanol and a secondary alcohol corresponding to the corresponding olefin. In this method, the hydrogenation raw material is a finished product of sec-butyl acetate, the ester conversion rate is 93.5%, and the alcohol selectivity is 100%.

[0006] CN103172492A discloses a method for preparing sec-butyl alcohol and ethanol by esterification and hydrogenation of mixed C4 and acetic acid, wherein the copper-based catalyst used for hydrogenation of sec-butyl acetate includes a Cu / Al2O3 catalyst prepared by an impregnation method, a commercial Cu-Cr catalyst, and a commercial Cu-Zn catalyst. In the method, the hydrogenation raw material is a finished sec-butyl acetate, and a sec-butyl acetate conversion rate greater than 96% can only be obtained at a low liquid hourly space velocity or a reaction pressure greater than 6.0 MPa, and the product contains 1-3wt% of isobutanol, which is not conducive to subsequent product separation and production.

[0007] In the actual production process of sec-butyl acetate, acetic acid is generally excessive. The method for separating sec-butyl acetate from the reaction solution generally adopts the method of azeotropic separation by adding water, so it is easier to obtain aqueous sec-butyl acetate. CN101168506A discloses a method for preparing sec-butyl acetate with a product separation process. The product mixture after the reaction of acetic acid and butene is sent to an azeotropic distillation tower, water is added as an entrainer, and sec-butyl acetate is distilled from the top of the tower. The sec-butyl acetate carrying water enters the next refining tower for further purification to obtain a high-purity sec-butyl acetate product. If aqueous sec-butyl acetate can be directly used as a hydrogenation raw material, the final refining tower is not required.

[0008] CN106554251A discloses a method for preparing sec-butyl alcohol and ethanol using a post-etherification C4 fraction. The method comprises the following steps: i) reacting the post-etherification C4 fraction and acetic acid under the action of a first catalyst to obtain a crude product of sec-butyl acetate containing acetic acid; ii) reacting hydrogen and the crude product of sec-butyl acetate containing acetic acid under the action of a second catalyst to separate a liquid mixture from the mixture obtained by the reaction; iii) rectifying the liquid mixture to obtain ethanol and sec-butyl alcohol products, respectively. In the method, excess acetic acid directly enters a hydrogenation reactor together with sec-butyl acetate, and the catalyst used is Cu-NiO / Al2O3 or NiO / Al2O3 or Cu-ZnO / Al2O3. It can be seen from the principle of chemical reaction that Ni, NiO, Zn or ZnO are not tolerant to acetic acid, and the catalyst life of the method cannot be effectively guaranteed. Summary of the invention

[0009] One of the technical problems to be solved by the present invention is that there is no water-resistant catalyst that can use aqueous sec-butyl acetate as a hydrogenation raw material in the prior art, and a new water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol is provided. The second technical problem to be solved by the present invention is to provide a preparation method of a water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol corresponding to the first technical problem. The third technical problem to be solved by the present invention is to provide a catalyst application corresponding to the first technical problem, which is used for a method for directly hydrogenating aqueous sec-butyl acetate to obtain ethanol and sec-butyl alcohol. The fourth technical problem to be solved by the present invention is to provide a catalyst application corresponding to the first technical problem, which is a method for directly hydrogenating aqueous sec-butyl acetate obtained by reacting butene-containing petroleum liquefied gas and acetic acid to obtain ethanol and sec-butyl alcohol.

[0010] To solve one of the above problems, the technical solution adopted by the present invention is as follows: a water-resistant catalyst for the hydrogenation of aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, comprising copper oxide, a cerium dioxide carrier and a praseodymium oxide promoter, the mass content of copper oxide in the catalyst is 5-20%, preferably 6-18%, preferably 8-16%, preferably 10-15%, the mass content of the cerium dioxide carrier is 75-95%, preferably 75-93%, preferably 77-90%, preferably 80-88%, and the mass content of the praseodymium oxide promoter is 0.1-5%, preferably 0.2-4%, preferably 0.5-3%, preferably 1-2%, based on the total weight of the catalyst.

[0011] To solve the second problem above, the technical solution adopted by the present invention is as follows: a method for preparing a water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, comprising the following steps:

[0012] 1) preparing a metal salt solution of copper and praseodymium, wherein the solution contains copper ions and praseodymium ions;

[0013] 2) adding cerium dioxide powder to the metal salt solution under stirring until a uniform paste-like mixture is formed;

[0014] 3) drying and calcining the paste mixture;

[0015] 4) The calcined catalyst is reduced with hydrogen.

[0016] In the above method, the amounts of copper and praseodymium metal salts and cerium dioxide used should be such that in the final catalyst, the mass content of copper oxide is 5-20%, preferably 6-18%, preferably 8-16%, preferably 10-15%, the mass content of the cerium dioxide carrier is 75-95%, preferably 75-93%, preferably 77-90%, preferably 80-88%, and the mass content of the praseodymium oxide additive is 0.1-5%, preferably 0.2-4%, preferably 0.5-3%, preferably 1-2%, based on the total weight of the catalyst.

[0017] Preferably, drying comprises placing the paste mixture into an oven, heating the mixture to 90-110°C, preferably about 100°C, at a rate of 2-10°C / min, further at a rate of about 5°C / min, and maintaining the temperature for 1-4h, preferably about 2h to obtain a dry mixture.

[0018] Preferably, calcination comprises placing the dry mixture into a muffle furnace, heating to 550-650°C, preferably about 600°C, at a rate of 10-30°C / min, preferably about 20°C / min, and maintaining for 1-4h, preferably about 2h, to obtain a catalyst precursor.

[0019] Preferably, hydrogen reduction includes molding the obtained catalyst precursor, for example, into a cylindrical shape, for example, with a diameter of 1-5mm, such as 2mm, and a length of 4-10mm, such as 5mm, and then placing it in a reaction tube, first purging with nitrogen; then switching hydrogen, pressure 2-8MPa, preferably about 5MPa, heating rate 30-60℃ / h, preferably about 50℃ / h, 180-220℃, preferably about 200℃ constant temperature 1-4h, preferably about 2h; heating rate 15-35℃ / h, preferably about 25℃ / h, 380-420℃, preferably about 400℃ constant temperature 1-4h, preferably about 2h; heating rate 5-15℃ / h, preferably about 10℃ / h, 450-550℃, preferably about 500℃ constant temperature 1-4h, preferably about 2h to obtain the catalyst, cool to the reaction temperature and use directly. The present invention is not limited to the above hydrogen reduction method.

[0020] In the above technical solution, preferably, the metal salt is one or more of metal nitrates, acetates, oxalates, etc., which can be calcined to form oxides.

[0021] To solve the third problem, the technical solution adopted by the present invention is as follows: the application of a water-resistant catalyst for hydrogenation of aqueous sec-butyl acetate to co-produce sec-butyl alcohol and ethanol, and the use of the catalyst for hydrogenation of aqueous sec-butyl acetate to co-produce sec-butyl alcohol and ethanol. Usually, the water content of aqueous sec-butyl acetate is 0.01-3%, the acetic acid content is 0.001-0.05%, the sec-butyl alcohol content is 0.01-50%, the C8 hydrocarbon content is 0.01-1%, and the rest is sec-butyl acetate; the reaction pressure is 2-8MPa, the reaction temperature is 150-300°C, and the total liquid hourly space velocity of aqueous sec-butyl acetate is 0.5-2h -1 , the molar ratio of hydrogen to sec-butyl acetate is 10-50.

[0022] In the above technical solution, preferably, the water content of the aqueous sec-butyl acetate is 0.01-2%.

[0023] In the above technical solution, preferably, the acetic acid content of the aqueous sec-butyl acetate is 0.001-0.01%.

[0024] In the above technical solution, preferably, the sec-butyl alcohol content of the aqueous sec-butyl acetate is 0.01-10%.

[0025] In the above technical solution, preferably, the C8 hydrocarbon content of the aqueous sec-butyl acetate is 0.01-2%.

[0026] The aqueous sec-butyl acetate can come from a crude product in the production process of sec-butyl acetate, that is, a product mixture obtained by reacting acetic acid with liquefied petroleum gas containing butene.

[0027] In the above technical solution, preferably, the reaction pressure is 3.0-4.0 MPa, the reaction temperature is 180-200°C; the liquid hourly space velocity of sec-butyl acetate is 0.5-2h -1 , the molar ratio of hydrogen to sec-butyl acetate is 15-30.

[0028] To solve the fourth problem above, the technical solution adopted by the present invention is as follows: a method for directly hydrogenating crude aqueous sec-butyl acetate to obtain ethanol and sec-butyl alcohol, especially a method for directly hydrogenating crude aqueous sec-butyl acetate obtained by reacting butene-containing petroleum liquefied gas and acetic acid to obtain ethanol and sec-butyl alcohol, the method comprising using the above-mentioned water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to co-produce sec-butyl alcohol and ethanol.

[0029] In a specific embodiment, the method comprises:

[0030] 1) Liquefied petroleum gas containing butene and acetic acid are introduced into a fixed bed catalytic reactor to obtain a mixture containing sec-butyl acetate, wherein the butene content in the liquefied petroleum gas is greater than 25%; the catalyst is an acidic cation exchange resin; the reaction temperature is 50-120° C., the reaction pressure is 2-5 MPa, the acid-olefin ratio is 1.1-3, and the total liquid hourly space velocity is 1-10 h -1 ;

[0031] 2) the product of step (1) is passed into a flash tower to remove the remaining liquefied petroleum gas, the tower pressure is controlled to be 1-4 MPa, the tower bottom temperature is controlled to be 120-200° C., and the tower top temperature is controlled to be 35-100° C.;

[0032] 3) The product of step (2) is passed into an azeotropic tower, water is added as an entrainer, and the azeotropic substance is collected at the top of the tower. After stratification, the upper layer is taken to obtain a crude product of hydrous sec-butyl acetate, and the water content of the crude product is 1.4-1.7%. After the azeotropic substance at the top of the tower is stratified, the lower layer is the water layer, and total reflux is performed, and the amount of entrainer water added is controlled to be 1-5% of the total amount of sec-butyl acetate, the tower bottom temperature is controlled to be 101-135°C, and the tower top temperature is controlled to be 35-60°C;

[0033] 4) The crude sec-butyl acetate containing water is passed into a fixed bed reactor filled with the water-resistant catalyst for hydrogenation of sec-butyl acetate to produce sec-butyl alcohol and ethanol, and hydrogenated to obtain a mixture of sec-butyl alcohol and ethanol. The reaction pressure is 2-8 MPa, the reaction temperature is 150-300°C, and the total liquid hourly space velocity of sec-butyl acetate containing water is 0.5-2h -1 , the molar ratio of hydrogen to sec-butyl acetate is 10-50;

[0034] 5) The hydrogenated mixture is passed into an ethanol separation tower, and industrial ethanol is collected at the top of the tower, and industrial sec-butyl alcohol is obtained in the bottom of the tower. The bottom temperature is controlled at 80-98° C., and the top temperature is controlled at 75-85° C.

[0035] In the above technical scheme, in step 1), preferably, the butene content in the liquefied petroleum gas is greater than 40%; the catalyst used is an A15 type acidic cation exchange resin catalyst; the reaction temperature is 60-80°C, the reaction pressure is 2-3MPa, the acid-olefin ratio is 1.5-2, and the total liquid hourly space velocity is 2-4h -1 .

[0036] In step 2) of the above technical solution, preferably, the tower pressure is controlled to be 1-1.2 MPa, the tower bottom temperature is controlled to be 140-160°C, and the tower top temperature is controlled to be 40-50°C.

[0037] In step 3) of the above technical solution, preferably, the amount of entrainer water added is controlled to be 1.5-1.8% of the total amount of sec-butyl acetate, the bottom temperature is controlled to be 101-105°C, and the top temperature is controlled to be 40-45°C.

[0038] In step 4) of the above technical solution, preferably, the reaction pressure is 3.0-4.0 MPa, the reaction temperature is 180-200°C; the liquid hourly space velocity of sec-butyl acetate is 0.5-2h -1 , the molar ratio of hydrogen to sec-butyl acetate is 15-30.

[0039] In step 5) of the above technical solution, preferably, the temperature of the tower bottom is controlled at 90-95°C, and the temperature of the tower top is controlled at 75-78°C.

[0040] The present invention provides a water-resistant catalyst for hydrogenating aqueous sec-butyl acetate to sec-butyl alcohol and ethanol, and a preparation method and application thereof. Under optimized reaction conditions, the sec-butyl acetate conversion rate on the catalyst is greater than 99%, the sec-butyl alcohol selectivity is greater than 99.5%, and the ethanol selectivity is greater than 99.6%; the service life of the catalyst exceeds 1 year. The preparation method of the catalyst is simple, the application range is wide, and it has good market prospects.

[0041] The present invention will be further described below by way of examples, but is not limited thereto. DETAILED DESCRIPTION

[0042] The present invention is further illustrated by the following examples.

[0043] Example 1

[0044] Place 1kg of Cu(NO3)2 and 200g of Pr(NO3)3 in a beaker, and add 2kg of distilled water to completely dissolve them. Add 8kg of commercially available cerium dioxide powder to the solution under stirring until it becomes a uniform paste mixture. Put the paste mixture into an oven, heat it to 100℃ at a rate of 5℃ / min, and keep it for 2h to obtain a dry mixture; put the dry mixture into a muffle furnace, heat it to 600℃ at a rate of 20℃ / min, and keep it for 2h to obtain a catalyst precursor. The obtained catalyst precursor is made into a cylindrical shape with a diameter of 2mm and a length of 5mm, and then placed in a reaction tube. First purge with nitrogen; then switch to hydrogen, the hydrogen flow rate is 100L / h, and the pressure is 5MPa; the heating rate is 50℃ / h, and the temperature is kept at 200℃ for 2h; the heating rate is 25℃ / h, and the temperature is kept at 400℃ for 2h; the heating rate is 10℃ / h, and the temperature is kept at 500℃ for 2h to obtain catalyst 1. Cool down to reaction temperature and use directly.

[0045] Using sec-butyl acetate (purity 99.54%, also containing 0.005% acetic acid, 0.1% sec-butyl alcohol, 0.31% C8 hydrocarbon content) containing 0.05% water as raw material, the reaction pressure is 3.2MPa, the reaction temperature is 200℃; the liquid hourly space velocity of sec-butyl acetate is 0.8h -1 , the molar ratio of hydrogen to sec-butyl acetate is 40. The solution after the reaction was tested by gas chromatography, and the conversion rate of sec-butyl acetate was 99.5%, the selectivity of ethanol was 99.7%, and the selectivity of sec-butyl alcohol was 99.5% by area normalization method.

[0046] Example 2

[0047] 1.5 kg of Cu(NO3)2 and 100 g of Pr(NO3)3 were placed in a beaker, and 3 kg of distilled water was added to completely dissolve them. 8 kg of commercially available cerium dioxide powder was added to the solution under stirring until it became a uniform paste mixture. The paste mixture was placed in an oven, heated to 100°C at a rate of 5°C / min, and maintained for 2 hours to obtain a dry mixture; the dry mixture was placed in a muffle furnace, heated to 600°C at a rate of 20°C / min, and maintained for 2 hours to obtain a catalyst precursor. The obtained catalyst precursor was made into a cylindrical shape with a diameter of 2 mm and a length of 5 mm, and then placed in a reaction tube. First purge with nitrogen; then switch to hydrogen, with a hydrogen flow rate of 100 L / h and a pressure of 5 MPa; the heating rate was 50°C / h, and the temperature was kept constant at 200°C for 2 hours; the heating rate was 25°C / h, and the temperature was kept constant at 400°C for 2 hours; the heating rate was 10°C / h, and the temperature was kept constant at 500°C for 2 hours to obtain catalyst 1. Cool down to reaction temperature and use directly.

[0048] Using sec-butyl acetate (purity 97.24%, also containing 0.01% acetic acid, 1.41% sec-butyl alcohol, 0.54% C8 hydrocarbon content) containing 0.88% water as raw material, the reaction pressure is 4.0MPa, the reaction temperature is 220℃; the liquid hourly space velocity of sec-butyl acetate is 0.5h -1 , the molar ratio of hydrogen to sec-butyl acetate was 30. The solution after the reaction was tested by gas chromatography, and the conversion rate of sec-butyl acetate was 99.6%, the selectivity of ethanol was 99.8%, and the selectivity of sec-butyl alcohol was 99.7%.

[0049] Example 3

[0050] 2kg of Cu(NO3)2 and 300g of Pr(NO3)3 were placed in a beaker, and 4kg of distilled water was added to completely dissolve them. 8kg of commercially available cerium dioxide powder was added to the solution under stirring until it became a uniform paste mixture. The paste mixture was placed in an oven, heated to 100℃ at a rate of 5℃ / min, and kept for 2h to obtain a dry mixture; the dry mixture was placed in a muffle furnace, heated to 600℃ at a rate of 20℃ / min, and kept for 2h to obtain a catalyst precursor. The obtained catalyst precursor was made into a cylindrical shape with a diameter of 2mm and a length of 5mm, and then placed in a reaction tube. First purge with nitrogen; then switch to hydrogen, with a hydrogen flow rate of 100L / h and a pressure of 5MPa; the heating rate was 50℃ / h, and the temperature was kept at 200℃ for 2h; the heating rate was 25℃ / h, and the temperature was kept at 400℃ for 2h; the heating rate was 10℃ / h, and the temperature was kept at 500℃ for 2h to obtain catalyst 1. Cool down to reaction temperature and use directly.

[0051] Using sec-butyl acetate (purity 85.99%, also containing 0.02% acetic acid, 10.23% sec-butyl alcohol, 2.11% C8 hydrocarbon content) containing 1.65% water as raw material, the reaction pressure is 3.6MPa, the reaction temperature is 230℃; the liquid hourly space velocity of sec-butyl acetate is 1.2h -1 , the molar ratio of hydrogen to sec-butyl acetate was 50. The solution after the reaction was tested by gas chromatography, and the conversion rate of sec-butyl acetate was 99.7%, the selectivity of ethanol was 99.4%, and the selectivity of sec-butyl alcohol was 99.8%.

[0052] In this embodiment, after the hydrogenation reaction was continuously operated for 1000 hours, the test results showed that the conversion rate of sec-butyl acetate was 99.4%, the selectivity of ethanol was 99.5%, and the selectivity of sec-butyl alcohol was 99.8%.

[0053] Example 4

[0054] 1) 2.0 kg / h of liquefied petroleum gas containing 41.4% of linear butene (specifically 35.1% of isobutane, 23.2% of normal butane, 16.0% of trans-butene, 15.1% of normal butene, 0.2% of isobutene, 10.3% of cis-butene and 0.1% of butadiene) and 2.0 kg / h of acetic acid are introduced into a fixed bed catalytic reactor through a horizontal flow pump to obtain a mixture containing sec-butyl acetate. The loading catalyst is 2 liters of A15 type acidic cation exchange resin; the middle reaction temperature is 78°C, the reaction pressure is 3.5 MPa, the acid-olefin ratio is 2.0, and the total liquid hourly space velocity is 2h -1 .

[0055] 2) Pass into the flash tower to remove the remaining liquefied petroleum gas. Control the tower pressure to 1.2MPa, the tower bottom temperature to 140-145℃, and the tower top temperature to 40-45℃.

[0056] 3) Pass into the azeotropic tower and add water as an entrainer. Collect the azeotrope at the top of the tower, and after stratification, take the upper layer to obtain 1.4 kg / h of crude water-containing sec-butyl acetate, and the water content in the crude product is 1.7%. After the azeotropic substance at the top of the tower is stratified, the lower layer is the water layer, and full reflux is performed. The amount of entrainer water added is controlled to be 30 g / h, the tower kettle temperature is controlled to be 105-110°C, and the tower top temperature is controlled to be 40-45°C.

[0057] 4) Place 300g of Cu(NO3)2 and 20g of Pr(NO3)3 in a beaker, and add 600g of distilled water to completely dissolve them. Add 800g of commercially available cerium dioxide powder to the solution under stirring until it becomes a uniform paste mixture. Put the paste mixture into an oven, heat it to 100℃ at a rate of 5℃ / min, and keep it for 2h to obtain a dry mixture; put the dry mixture into a muffle furnace, heat it to 600℃ at a rate of 20℃ / min, and keep it for 2h to obtain a catalyst precursor. The obtained catalyst precursor is made into a cylindrical shape with a diameter of 2mm and a length of 5mm, and then placed in a reaction tube. First purge with nitrogen; then switch to hydrogen, the hydrogen flow rate is 10L / h, and the pressure is 5MPa; the heating rate is 50℃ / h, and the temperature is kept at 200℃ for 2h; the heating rate is 25℃ / h, and the temperature is kept at 400℃ for 2h; the heating rate is 10℃ / h, and the temperature is kept at 500℃ for 2h to obtain catalyst 1. The crude product of aqueous sec-butyl acetate in step 3 (purity 96.42%, also containing 1.7% water, 0.01% acetic acid, 0.35% sec-butyl alcohol, 1.52% C8 hydrocarbon content) was introduced into a reaction tube for hydrogenation reaction at a reaction pressure of 4.3 MPa, a reaction temperature of 205°C, and a liquid hourly space velocity of sec-butyl acetate of about 1.3 h -1 , the molar ratio of hydrogen to sec-butyl acetate is 36.

[0058] 5) The hydrogenation mixture is passed into an ethanol separation tower, and the tower bottom temperature is controlled at 88-90°C and the tower top temperature is controlled at 76-78°C. 563 g / h of 96.3% industrial ethanol is collected from the tower top, and 880 g / h of 99.5% industrial sec-butyl alcohol is collected from the tower bottom. Calculations show that the conversion rate of sec-butyl acetate is 99.7%, the selectivity of sec-butyl alcohol is 99.8%, and the selectivity of ethanol is 99.4%.

[0059] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any changes, equivalent substitutions and improvements made within the principles and ideas of the present invention should be included in the protection scope of the present invention.

Claims

1. Application of a water-resistant catalyst for hydrogenation of aqueous sec-butyl acetate to co-production of sec-butyl alcohol and ethanol, characterized in that: The water-resistant catalyst comprises copper oxide, a cerium dioxide carrier and a praseodymium oxide additive. The copper oxide content of the water-resistant catalyst is 5-20% by weight, the cerium dioxide carrier content is 75-95% by weight, and the praseodymium oxide additive content is 0.1-5% by weight, based on the total weight of the water-resistant catalyst.

2. The use according to claim 1, characterized in that: The mass content of copper oxide in the water-resistant catalyst is 6-18%, the mass content of the cerium dioxide carrier is 75-93%, and the mass content of the praseodymium oxide additive is 0.2-4%.

3. The use according to claim 2, characterized in that: The mass content of copper oxide in the water-resistant catalyst is 8-16%, the mass content of the cerium dioxide carrier is 77-90%, and the mass content of the praseodymium oxide additive is 0.5-3%.

4. The use according to claim 3, characterized in that: The mass content of copper oxide in the water-resistant catalyst is 10-15%, the mass content of the cerium dioxide carrier is 80-88%, and the mass content of the praseodymium oxide additive is 1-2%.

5. The use according to claim 1, characterized in that: The water-resistant catalyst is prepared by the following steps: 1) Prepare a metal salt solution containing copper ions and praseodymium ions; 2) adding cerium dioxide powder to the metal salt solution under stirring until a uniform paste-like mixture is formed; 3) drying and calcining the paste mixture to obtain a catalyst precursor; 4) Reducing the obtained catalyst precursor with hydrogen.

6. The use according to claim 5, characterized in that: The metal salt is selected from one or more of nitrates, acetates and oxalates of metals that can be calcined to oxides.

7. The use according to claim 5, characterized in that: Drying includes placing the paste mixture in an oven, heating it to 100°C at a rate of 5°C / min, and maintaining it for 2 hours to obtain a dry mixture; The calcination includes placing the dry mixture into a muffle furnace, heating it to 600° C. at a rate of 20° C. / min, and maintaining it for 2 hours to obtain a catalyst precursor.

8. The use according to any one of claims 5 to 7, characterized in that: Hydrogen reduction includes shaping the obtained catalyst precursor, placing it in a reaction tube, and purging it with nitrogen first; then switching to hydrogen, pressure 2-8MPa, heating rate 30-60℃ / h, 180-220℃, constant temperature 1-4h; heating rate 15-35℃ / h, 380-420℃ constant temperature 1-4h; heating rate 5-15℃ / h, 450-550℃ constant temperature 1-4h, to obtain a water-resistant catalyst, which can be directly used after cooling to the reaction temperature.

9. The use according to claim 8, characterized in that: The obtained catalyst precursor was formed into a cylindrical shape.

10. The use according to claim 8, characterized in that: After nitrogen purging, switch to hydrogen, with a pressure of 5 MPa, a heating rate of 50°C / h, and a constant temperature of 200°C for 2h; a heating rate of 25°C / h, and a constant temperature of 400°C for 2h; a heating rate of 10°C / h, and a constant temperature of 500°C for 2h, to obtain a water-resistant catalyst.

11. The use according to claim 1, characterized in that: In the reaction of hydrogenation of aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, the reaction pressure is 2-8MPa, the reaction temperature is 150-300℃, and the total liquid hourly space velocity of aqueous sec-butyl acetate is 0.5-2h -1 , the molar ratio of hydrogen to sec-butyl acetate is 10-50.

12. The use according to claim 1, characterized in that: The water content of the aqueous sec-butyl acetate is 0.01-3wt%.

13. The use according to claim 12, characterized in that: The aqueous sec-butyl acetate comes from the crude product in the production process of sec-butyl acetate, that is, the product mixture after the reaction of acetic acid and petroleum liquefied gas containing butene, which is first sent to a flash tower to remove the remaining liquefied gas, and then passed into an azeotropic distillation tower, water is added as an azeotropic agent, and sec-butyl acetate is distilled from the top of the tower to obtain aqueous sec-butyl acetate.

14. A method for hydrogenating aqueous sec-butyl acetate to produce sec-butyl alcohol and ethanol, characterized in that: A water-resistant catalyst is used, which comprises copper oxide, a cerium dioxide carrier and a praseodymium oxide additive. The mass content of copper oxide in the water-resistant catalyst is 5-20%, the mass content of the cerium dioxide carrier is 75-95%, and the mass content of the praseodymium oxide additive is 0.1-5%, based on the total weight of the water-resistant catalyst.

15. The method according to claim 14, characterized in that The mass content of copper oxide in the water-resistant catalyst is 6-18%, the mass content of the cerium dioxide carrier is 75-93%, and the mass content of the praseodymium oxide additive is 0.2-4%.

16. The method according to claim 15, characterized in that The mass content of copper oxide in the water-resistant catalyst is 8-16%, the mass content of the cerium dioxide carrier is 77-90%, and the mass content of the praseodymium oxide additive is 0.5-3%.

17. The method according to claim 16, characterized in that The mass content of copper oxide in the water-resistant catalyst is 10-15%, the mass content of the cerium dioxide carrier is 80-88%, and the mass content of the praseodymium oxide additive is 1-2%.