1,4-butynediol hydrogenation catalyst, its preparation method and application

Abstract

The application discloses a 1,4-butynediol hydrogenation catalyst and a preparation method and application thereof. The catalyst structure is represented as Ni-CuO / X-Al2O3, wherein X is at least one of bismuth, arsenic and antimony, and the catalyst has the advantages of high active component loading, good catalytic activity, long service life and the like. The preparation method of the catalyst takes waste Raney nickel catalyst as a nickel source and an aluminum source, realizes recycling of the waste Raney nickel catalyst, solves the problem of poor recovery effect of the current deactivated Raney nickel catalyst, and simultaneously, the preparation method utilizes the interaction between quaternary ammonium salt and nickel to make the active metal deeply penetrate into the catalyst channel and be fixed, further disperses the active metal nickel through vacancies generated by decomposition of the basic copper carbonate, forms a CuO coating structure, and prolongs the service life of the catalyst by adding the protective additive X.

Description

Technical Field

[0001] This invention belongs to the field of catalytic hydrogenation, specifically relating to a 1,4-butynediol hydrogenation catalyst and preparation method produced by recycling waste Raney nickel catalyst, as well as a method for preparing 1,4-butanediol by hydrogenation using the catalyst. Background Technology

[0002] 1,4-Butanediol (BDO) is an important organic chemical product. Its downstream applications include common products or intermediates such as polybutylene terephthalate (PBT), gamma-butyrolactone (GBL), polyurethane (PU), and tetrahydrofuran (THF). It is also widely used in industries such as engineering plastics, elastic fibers, elastomers, organic solvents, and adhesives.

[0003] Currently, my country mainly produces BDO using the acetylene-aldehyde process. First, formaldehyde and acetylene are reacted to produce the intermediate 1,4-butynediol, which is then hydrogenated using a hydrogenation catalyst to produce BDO. The industry currently favors Raney nickel as the hydrogenation catalyst; however, Raney nickel catalysts typically contain 40-50% nickel, resulting in relatively high costs. Furthermore, Raney nickel catalysts currently have a lifespan of only 6-8 months. Deactivated catalysts are treated with sodium nitrate aqueous solution to oxidize the elemental nickel in the Raney nickel catalyst to nickel oxide, eliminating its flammability. Ultimately, the spent catalyst is sold as aluminum and nickel oxide scrap, undoubtedly increasing operating costs.

[0004] Patent CN113262794A discloses a nickel-type hydrogenation catalyst supported on germanium and copper-modified alumina. However, this catalyst contains multiple metals and has a complex preparation process, which is not conducive to mass production. Patent CN114797892A discloses a supported hydrogenation catalyst with Pd, Ru, Pt, or Au as the active metal. However, the production cost of this catalyst is relatively high, and examples show that its selectivity for 1,4-butanediol is only 96%, resulting in unsatisfactory hydrogenation performance.

[0005] Patent CN105217669B recovers nickel from Raney nickel catalysts into nickel sulfate through acid leaching and alum precipitation, but this process involves ball milling, acid leaching, precipitation, and crystallization, making it relatively complex and resulting in poor aluminum recovery. Patent CN111549226A recovers metallic nickel from waste Raney nickel catalysts through roasting, leaching, acid washing, calcination, and reduction, but this method generates a large amount of wastewater, posing environmental hazards and incurring relatively high purification costs.

[0006] In summary, Raney nickel catalysts currently exhibit good hydrogenation performance in the acetylacetonate-aldehyde process for BDO production. However, the process for recovering nickel and aluminum metals from deactivated catalysts suffers from problems such as long process time, incomplete metal recovery, and environmental pollution. Therefore, it is still necessary to develop new 1,4-butynediol hydrogenation catalysts to address the aforementioned issues associated with Raney nickel catalysts. Summary of the Invention

[0007] To address the aforementioned problems in the existing technology, one of the objectives of this invention is to provide a 1,4-butynediol hydrogenation catalyst with the structure represented as Ni-CuO / X-Al2O3, where X is a promoter (bismuth, arsenic, antimony). The catalyst has advantages such as high loading of active components, good catalytic activity, and long service life.

[0008] The second objective of this invention is to provide a method for preparing the above-mentioned 1,4-butynediol hydrogenation catalyst. The method uses waste Raney nickel catalyst as the nickel and aluminum source, realizing the resource recycling of waste Raney nickel catalyst and solving the problem of poor recovery efficiency of deactivated Raney nickel catalyst. At the same time, the preparation method of this invention utilizes the interaction between quaternary ammonium salt and nickel to allow the active metal to penetrate deep into the catalyst channel and be fixed. The active metal nickel is further dispersed by the vacancies generated by the decomposition of basic copper carbonate to form a CuO coating structure. The catalyst life is extended by adding a protective promoter X.

[0009] A third objective of this invention is to provide the application of the above-mentioned catalyst in the hydrogenation of 1,4-butynediol to 1,4-butanediol, which has high conversion rate and high selectivity.

[0010] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0011] The first aspect of the present invention provides a 1,4-butynediol hydrogenation catalyst with the structure represented as Ni-CuO / X-Al2O3, wherein X is at least one of bismuth (Bi), arsenic (As), and antimony (Sb).

[0012] In some preferred examples, the catalyst comprises an alumina support, and supported active components nickel, copper oxide, and additive X;

[0013] Preferably, the copper oxide coating is used to coat the active component nickel. The specific form of the copper oxide coating of the active component nickel in this invention is not limited; it can be any proportion of coating, such as full coating, half coating, or partial coating. This type of coating can be full coating or island-like coating, meaning that a portion of the surface has a coating layer while other parts of the surface are uncoated. The coating thickness can also vary in different areas; this invention does not impose specific limitations.

[0014] In some preferred examples, the catalyst composition by mass percentage includes:

[0015] Nickel content is 20-40%, for example, 20%, 25%, 30%, 35%, or 40%, preferably 25-35%.

[0016] Copper oxide content of 10-40%, for example 10, 15, 20, 25, 30, 35, 40%, preferably 10-20%;

[0017] Additive X 0.1-2%, for example 0.1, 0.5, 1.0, 1.5, 2.0%, preferably 0.1-1.5%;

[0018] Aluminum oxide 20-70%, for example 20, 30, 40, 50, 60, 70%, preferably 45-65%;

[0019] The total content of all components is 100%.

[0020] A second aspect of the present invention provides a method for preparing the 1,4-butynediol hydrogenation catalyst as described above, comprising the following steps:

[0021] (1) The Raney nickel catalyst treated with sodium nitrate was mixed with water, heated and alkali was added under stirring to adjust the pH to alkaline, and then filtered to obtain nickel oxide solid and a solution containing aluminate ions respectively.

[0022] (2) The nickel oxide solid obtained in step (1) is mixed with water, then heated and acid is added under stirring until the solid is completely dissolved. The temperature is lowered, and then alkali is added to adjust the pH to neutral. Then, a methanol solution of quaternary ammonium salt, basic copper carbonate, and a compound containing auxiliary agent X are added to react. After separation, washing, and drying, the solid is obtained.

[0023] (3) Add the solid from step (2) to the solution containing aluminate from step (1), remove the water, and then calcine to obtain the precursor (structure represented as NiO-CuO / X-Al2O3).

[0024] (4) The precursor obtained in step (3) is subjected to hydrogenation reduction reaction to obtain the 1,4-butynediol hydrogenation catalyst (i.e., Ni-CuO / X-Al2O3).

[0025] In some specific examples, the mass ratio of water to deactivated Raney nickel treated with sodium nitrate in step (1) is (10-100):1, for example (10, 20, 40, 60, 80, 100):1, preferably (15-40):1.

[0026] Raney nickel is a solid heterogeneous catalyst composed of fine grains of a nickel-aluminum alloy with a porous structure. It is commonly used as a hydrogenation catalyst. Existing technologies document the quenching of Raney nickel with sodium nitrate solution, and deactivating Raney nickel catalysts are also typically treated with an aqueous sodium nitrate solution. The sodium nitrate-treated Raney nickel described in this invention is preferably a sodium nitrate-treated deactivated Raney nickel, which can be a deactivated Raney nickel catalyst from any catalytic production process, preferably a deactivated Raney nickel catalyst from the hydrogenation of 1,4-butynediol to 1,4-butanediol. The Raney nickel can be any existing Raney nickel product, such as Xunkai hydrogenation catalyst 5508, Grace hydrogenation catalyst, etc.

[0027] Specifically, the source of the Raney nickel treated with sodium nitrate is not limited. It can be purchased directly or deactivated Raney nickel catalyst can be treated with sodium nitrate itself. This treatment method is a conventional operation in the field. For example, the treatment method can be to add the Raney nickel catalyst to an aqueous sodium nitrate solution for passivation treatment for a certain period of time. This process will release ammonia gas, which needs to be discharged in a closed system. Passivation is completed after no more bubbles are generated.

[0028] Preferably, the concentration of the sodium nitrate aqueous solution is 2-20 wt%, for example 2, 5, 10, 15, 20 wt%, the treatment temperature is 25-60℃, for example 25, 30, 40, 50, 60℃, and the treatment time is 1-8h, for example 1, 2, 4, 6, 8h.

[0029] In some specific examples, the heating in step (1) is at a temperature of 20 to 95°C, for example, 20, 30, 40, 50, 60, 70, 80, 90, or 95°C, preferably 50 to 75°C.

[0030] In some specific examples, the stirring in step (1) takes 1 to 4 hours, for example 1, 2, 3, or 4 hours, preferably 2 to 3 hours.

[0031] In some specific examples, the alkali in step (1) is selected from metal hydroxides, preferably at least one of sodium hydroxide, potassium hydroxide, and calcium hydroxide, and more preferably sodium hydroxide;

[0032] In some specific examples, step (1) involves adding alkali to adjust the pH to alkaline, preferably 10 to 14, such as 10, 11, 12, 13, 14, and more preferably 13 to 13.5.

[0033] In some specific examples, the mass ratio of nickel oxide solid to water in step (2) is 1:(1-40), for example 1:(1, 5, 10, 15, 20, 25, 30, 35, 40), preferably 1:(2.5-10);

[0034] Preferably, the nickel oxide solid is washed with water before being mixed with water. The washing temperature is 20-60°C, for example, 20, 40, or 60°C, preferably 20-30°C, and the washing time is 10-60 min, for example, 10, 20, 40, or 60 min, preferably 10-20 min.

[0035] Preferably, the washing is performed under ultrasonic conditions.

[0036] In some specific examples, the heating in step (2) is at a temperature of 30 to 100°C, for example, 30, 50, 70, 90, or 100°C, preferably 60 to 85°C.

[0037] In some specific examples, the stirring in step (2) takes 1 to 4 hours, for example 1, 2, 3, or 4 hours, preferably 2 to 3 hours.

[0038] In some specific examples, the acid in step (2) is selected from at least one of perchloric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, sulfuric acid, and nitric acid, preferably sulfuric acid;

[0039] Preferably, the acid is a dilute acid with a concentration of 0.5 to 1 mol / L, for example, 0.5, 0.7, 0.9, or 1.0 mol / L.

[0040] In some specific examples, the cooling in step (2) is to reduce the temperature to room temperature, for example, 10, 20, 30, or 40°C, preferably 20 to 30°C.

[0041] In some specific examples, the alkali mentioned in step (2) is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia water, preferably sodium hydroxide;

[0042] Preferably, the alkali is prepared as an aqueous solution with a concentration of 0.5 to 1 wt%, for example, 0.5, 0.7, 0.9, or 1.0 wt%.

[0043] Preferably, an alkaline solution is added to adjust the pH to neutral, with a pH range of 6 to 7.

[0044] In some specific examples, the quaternary ammonium salt in step (2) is one or more of single-chain quaternary ammonium salts, double-chain quaternary ammonium salts, and pyridine quaternary ammonium salts, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, octadecyldimethyltertiary amine, trimethylalkylammonium bromide, and trimethylalkylammonium chloride, more preferably hexadecyltrimethylammonium bromide;

[0045] Preferably, the amount of the quaternary ammonium salt added is 0.1 to 1% of the mass of the nickel oxide solid, for example, 0.1, 0.3, 0.5, 0.7, or 0.9%, and more preferably 0.1 to 0.5%.

[0046] Preferably, the alcoholic solution of the quaternary ammonium salt has a concentration of 2 to 200 g / L; preferably, the alcohol is selected from short-chain alcohols of C1-C4, and more preferably methanol or ethanol.

[0047] In some specific examples, the mass ratio of nickel oxide solid to basic copper carbonate in step (2) is (0.4 to 10):1, for example (0.4, 0.8, 1, 3, 5, 7, 9):1, preferably (0.5 to 5):1.

[0048] In some specific examples, the compound containing auxiliary agent X in step (2) is selected from at least one of compounds containing bismuth, arsenic, and antimony, preferably at least one of BiCO3, SbF3, SbCl3, SbBr3, AsCl3, and AsCl5, with BiCO3 being the most preferred;

[0049] Preferably, the amount of the compound containing auxiliary agent X is 0.1% to 4% of the mass of the nickel oxide solid, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, and more preferably 2% to 3.6%.

[0050] In some specific examples, the reaction in step (2) takes 1 to 6 hours, for example 1, 2, 3, 4, 5, 6 hours, preferably 2 to 4 hours, and the temperature is 20 to 80°C, for example 20, 30, 40, 50, 60, 70, 80°C, preferably 40 to 50°C;

[0051] Preferably, the reaction is carried out under stirring conditions.

[0052] The separation, washing, and drying in step (2) of this invention are conventional operations in the field. In some specific examples, the separation is carried out by filtration; the washing is carried out with water as the medium, preferably washing more than twice; the drying medium is air or nitrogen, preferably air, and the drying temperature is 25-90°C, for example 25, 50, 75, 90°C, preferably 30-50°C.

[0053] In some specific examples, the mass ratio of the solid in step (3) to the solution containing aluminate is (0.01 to 1):1, for example (0.01, 0.03, 0.05, 0.1, 0.5, 1):1, preferably (0.02 to 0.05):1.

[0054] In some specific examples, the removal of moisture in step (3) is carried out by rotary evaporation, and the rotary evaporation pressure is 5 to 100 kPaA, for example 5, 10, 50, 100 kPaA, preferably 30 to 60 kPaA;

[0055] Preferably, the rotary evaporation temperature is 20–80°C, for example, 20, 50, or 80°C, and more preferably 30–50°C.

[0056] In some specific examples, the roasting in step (3) is carried out at a temperature of 500 to 750°C, for example, 500, 550, 600, 650, 700, 750°C, preferably 600 to 700°C, and for a time of 1 to 5 hours, for example, 1, 2, 3, 4, 5 hours, preferably 2 to 3 hours.

[0057] In some specific examples, the hydrogenation reduction reaction in step (4) is carried out at a temperature of 600-800°C, for example, 600, 650, 700, 750, 800°C, preferably 600-700°C, and for a time of 1-4 hours, for example, 1, 2, 3, 4 hours, preferably 2-3 hours.

[0058] The hydrogenation reduction reaction does not have any special requirements for the amount of hydrogen used; simply maintaining a hydrogen environment is sufficient, and the pressure should be atmospheric pressure.

[0059] In this invention, the 1,4-butynediol hydrogenation catalyst prepared by the above method has a specific surface area of ​​90–450 m². 2 / g.

[0060] The catalyst preparation method described in this invention can simultaneously recycle deactivated Raney nickel, allowing the nickel oxide and aluminum in the deactivated Raney nickel to be recovered and reused, which has significant economic value.

[0061] It should be noted that the methods disclosed in this invention are merely illustrative examples of one preparation method used to achieve the 1,4-butynediol hydrogenation catalyst described in this invention. The 1,4-butynediol hydrogenation catalyst described in this invention should not be limited to the steps and parameters in the above methods. In actual operation, other auxiliaries and additives may be added during the preparation process, and the type and content ratio of Raney nickel catalyst, temperature, time, and other operating parameters may not be limited to the examples above. Those skilled in the art can make corresponding non-substantial adjustments as needed.

[0062] The third aspect of the present invention provides the application of the 1,4-butynediol hydrogenation catalyst, the catalyst prepared by the present invention being suitable for the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0063] This invention provides a method for preparing 1,4-butynediol by hydrogenation, comprising the following steps: in the presence of the catalyst described in this invention, using 1,4-butynediol and water as reaction substrates and hydrogen as the hydrogen source, a hydrogenation reaction is carried out.

[0064] Preferably, the mass ratio of 1,4-butynediol to water is 1:(0.2-2), for example, 1:(0.2, 0.5, 1.0, 1.5, 2.0).

[0065] The amount of catalyst used is 0.5 to 10% of the mass of 1,4-butynediol, for example 0.5, 1, 3, 5, 7, 9, 10%, preferably 1 to 3%.

[0066] The hydrogen feed is 2 to 12 times the molar amount of 1,4-butynediol, for example, 2, 4, 6, 8, 10, or 12 times, preferably 3 to 6 times.

[0067] Preferably, the hydrogenation reaction is carried out at a temperature of 100–250°C, for example, 100, 150, 200, or 250°C, more preferably 100–130°C, and the residence time is 0.5–4 h, for example, 0.5, 1, 2, 3, or 4 h, more preferably 0.5–2 h.

[0068] The reaction pressure is 0.5 to 20 MPa, for example, 0.5, 2, 4, 6, 10, 15, or 20 MPa, preferably 2 to 5 MPa.

[0069] The method for preparing 1,4-butanediol by hydrogenation of 1,4-butynediol using the catalyst described in this invention has a conversion rate and selectivity of over 99%.

[0070] In the 1,4-butanediol product, the content of methyl-1,4-butanediol is less than 55 ppm, preferably less than 30 ppm; the content of 2-(4-hydroxybutoxy)-tetrahydrofuran is less than 100 ppm, preferably less than 50 ppm.

[0071] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0072] 1. A novel 1,4-butynediol hydrogenation catalyst with advantages such as high loading of active components, good catalytic activity, and long service life is provided.

[0073] 2. A catalyst preparation method using deactivated Raney nickel catalyst as the main raw material is provided, realizing the resource recycling of spent Raney nickel catalyst and reducing production costs. In this preparation method, the interaction between quaternary ammonium salt and nickel ions allows the active metal to penetrate deep into the catalyst channels, increasing the catalyst loading per unit area, which is beneficial for the diffusion of reaction molecules and products, improving catalyst activity, and reducing the generation of impurities such as butanol and 4-hydroxybutyraldehyde during hydrogenation. By adding basic copper carbonate, which decomposes into copper oxide and forms vacancies inside, these vacancies are filled by nickel metal, dispersing it within the copper oxide to form a copper-coated structure. This enhances the copper-nickel metal interaction, facilitating hydrogen adsorption to the catalyst surface and promoting unsaturated bond addition. The addition of promoter X effectively prevents the influence of impurities such as sulfur, aldehydes, and unsaturated bonds, making the active nickel metal less prone to deactivation and greatly extending the catalyst's lifespan. Detailed Implementation

[0074] The present invention will be described in more detail below with reference to specific examples. However, it should be noted that the following embodiments are not limiting examples of the scope of the present invention.

[0075] The main sources of raw materials used in the following embodiments are as follows:

[0076] The Raney nickel catalyst deactivated by sodium nitrate: It was obtained from the Raney nickel catalyst discharged during the shutdown of the BDO hydrogenation unit of Wanhua Chemical (Sichuan) Co., Ltd. The Raney nickel hydrogenation catalyst used in this unit is Grace hydrogenation catalyst. The specific treatment method is to add the waste Raney nickel catalyst into a 2wt% sodium nitrate aqueous solution and passivate it at 60℃ for 8 hours.

[0077] Unless otherwise specified, all other chemical reagents were obtained through ordinary commercial channels and were of analytical grade.

[0078] Catalyst characterization: The pore structure of the catalyst was characterized using a Tristar 3020 instrument manufactured by Micron Technology, USA. Specifically, the sample was dried, degassed under vacuum at 300℃ for 8 hours, and then subjected to liquid nitrogen adsorption and desorption processes for measurement. Finally, the specific surface area of ​​the catalyst was obtained using the BET method.

[0079] The following examples demonstrate the detailed determination and quantitative analysis of 1,4-butanediol, butanol, and other substances in the products using an Agilent Technologies 7890A gas chromatograph. An FID detector and a DB-5 column were employed, with an injection port temperature of 280°C, a detector temperature of 280°C, a carrier gas (nitrogen) flow rate of 3 ml / min, an air flow rate of 400 ml / min, and a hydrogen flow rate of 40 ml / min.

[0080] Example 1

[0081] 1) Preparation of 1,4-butynediol hydrogenation catalyst, the steps are as follows:

[0082] Take 30g of Raney nickel catalyst solid deactivated by sodium nitrate and add it to 300g of deionized water and mix well. Heat to 50℃, add sodium hydroxide to adjust the pH to 13 while stirring, stir for 2h, filter to obtain 19.8g of nickel oxide solid and 311g of solution containing aluminate ions.

[0083] After ultrasonically cleaning 19.8g of the above nickel oxide solid with water at 20℃ for 10min, it was added to 80g of deionized water and mixed evenly. The mixture was heated to 40℃, and 1mol / L dilute sulfuric acid was added with stirring until the solid was completely dissolved. After stirring for 2h, the temperature was lowered to 20℃, and then 1wt% sodium hydroxide aqueous solution was added to adjust the pH to 6-7. Then, 50ml of 2g / L hexadecyltrimethylammonium bromide methanol solution was added, followed by 5g of basic copper carbonate and 0.5g of bismuth carbonate. The mixture was stirred at 40℃ for 2h, filtered, and dried at 50℃ to obtain 23g of dry solid.

[0084] Then, 23g of the above-mentioned dry solid was added to 311g of a solution containing aluminate, and the water was evaporated to dryness using a rotary evaporator at 30kPaA and 50℃. The solution was then calcined at 600℃ for 2h to obtain the precursor (structure NiO-CuO / Bi-Al2O3).

[0085] The precursor was reduced at 700℃ for 2 h under hydrogen conditions to obtain a 1,4-butynediol hydrogenation catalyst, the structure of which is represented as Ni-CuO / Bi-Al2O3.

[0086] The catalyst, by mass percentage, comprises: 36% nickel, 17% copper oxide, 1.1% Bi additive, and 45.9% aluminum oxide; its specific surface area, determined by the BET method, is 100 m² / g. 2 / g.

[0087] The recovery rate of nickel oxide in deactivated Raney nickel was 94 wt%, and the recovery rate of aluminum was 97 wt%.

[0088] 2) The preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol involves the following steps:

[0089] 160g of a 50% (w / w) aqueous solution of 1,4-butynediol and 2g of the above-mentioned Ni-CuO / Bi-Al2O3 catalyst were added to a high-pressure reactor. Nitrogen gas was introduced to replace the air in the reactor four times, followed by H2 until the pressure inside the reactor reached 5 MPaA. The pressure inside the reactor was stabilized at 5 MPaA by controlling the back pressure valve. Stirring was started at 800 r / min, and then heating was started. After reaching the reaction temperature of 110℃, continuous feeding was started. The feed rate of the 1,4-butynediol aqueous solution was 4.0 g / min, and the feed rate of hydrogen gas was 0.279 g / min (the molar ratio of hydrogen gas to 1,4-butynediol was 6:1). The residence time of the 1,4-butynediol aqueous solution was 40 min. The composition of the reaction solution was analyzed every hour.

[0090] The results of sampling and testing after 1 hour of reaction were as follows: 1,4-butynediol conversion rate was 99.998%, 1,4-butanediol selectivity was 99.98%, methyl-1,4-butanediol content was about 20 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 40 ppm.

[0091] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.99%, 1,4-butanediol selectivity was 99.96%, methyl-1,4-butanediol content was about 22 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 42 ppm.

[0092] Example 2

[0093] 1) Preparation of 1,4-butynediol hydrogenation catalyst, the steps are as follows:

[0094] Take 30g of Raney nickel catalyst solid deactivated by sodium nitrate and add it to 400g of deionized water and mix well. Heat to 70℃, add sodium hydroxide while stirring to adjust the pH to 12.5, stir for 2h, filter to obtain 19.4g of nickel oxide solid and 410g of solution containing aluminate ions.

[0095] After ultrasonically cleaning 19.4g of the above nickel oxide solid with water at 30℃ for 20min, it was added to 50g of deionized water and mixed evenly. The mixture was heated to 65℃, and 0.5mol / L dilute sulfuric acid was added with stirring until the solid was completely dissolved. After stirring for 2h, the temperature was lowered to 25℃, and then 0.7wt% sodium hydroxide aqueous solution was added to adjust the pH to 6-7. Then 60ml of 2g / L hexadecyltrimethylammonium bromide methanol solution was added, followed by 7g of basic copper carbonate and 0.7g of AsCl3 solid. The mixture was stirred at 45℃ for 3h, filtered, and dried at 50℃ to obtain 30g of dry solid.

[0096] Then, 30g of the above-mentioned dried solid was added to 410g of a solution containing aluminate, and the water was evaporated to dryness using a rotary evaporator at 30kPaA and 50℃. The solution was then calcined at 700℃ for 2.5h to obtain the precursor (structure NiO-CuO / As-Al2O3).

[0097] The precursor was reduced at 700℃ for 3 h under hydrogen conditions to obtain a 1,4-butynediol hydrogenation catalyst, with the structure represented as Ni-CuO / As-Al2O3.

[0098] The catalyst, by mass percentage, comprises: 33% nickel, 22% copper oxide, 1.5% As (an auxiliary agent), and 43.5% aluminum oxide; its specific surface area, determined by the BET method, is 120 m² / g. 2 / g.

[0099] The recovery rate of nickel oxide in deactivated Raney nickel was 93 wt%, and the recovery rate of aluminum was 96 wt%.

[0100] 2) The preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol involves the following steps:

[0101] 160g of a 50% (w / w) aqueous solution of 1,4-butynediol and 2g of the above-mentioned Ni-CuO / As-Al2O3 catalyst were added to a high-pressure reactor. Nitrogen gas was introduced to purge the air in the reactor four times, followed by H2 until the pressure inside the reactor reached 8 MPaA. The pressure inside the reactor was stabilized at 8 MPaA by controlling the back pressure valve. Stirring was started at 800 r / min, and then heating was started. After reaching the reaction temperature of 100℃, continuous feeding was started. The feed rate of the 1,4-butynediol aqueous solution was 4.0 g / min, and the feed rate of hydrogen gas was 0.5581 g / min (the molar ratio of hydrogen gas to 1,4-butynediol was 12:1). The residence time of the 1,4-butynediol aqueous solution was 40 min. The composition of the reaction solution was analyzed every hour.

[0102] The results of the 1-hour reaction sampling test were as follows: 1,4-butynediol conversion rate was 99.995%, 1,4-butanediol selectivity was 99.90%, methyl-1,4-butanediol content was about 30 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 47 ppm.

[0103] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.994%, 1,4-butanediol selectivity was 99.82%, methyl-1,4-butanediol content was about 32 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 60 ppm.

[0104] Example 3

[0105] 1) Preparation of 1,4-butynediol hydrogenation catalyst, the steps are as follows:

[0106] Take 30g of Raney nickel catalyst solid deactivated by sodium nitrate and add it to 1200g of deionized water and mix well. Heat to 50℃, add sodium hydroxide under stirring to adjust the pH to 14, stir for 4h, filter to obtain 19.4g of nickel oxide solid and 1210g of solution containing aluminate ions.

[0107] After ultrasonically cleaning 19.4g of the above nickel oxide solid with water at 60℃ for 20min, it was added to 200g of deionized water and mixed evenly. The mixture was heated to 85℃, and 0.75mol / L dilute hydrochloric acid was added with stirring until the solid was completely dissolved. After stirring for 2h, the temperature was lowered to 25℃, and then 0.7wt% sodium hydroxide aqueous solution was added to adjust the pH to 6-7. Then 100ml of 10g / L hexadecyltrimethylammonium bromide methanol solution was added, followed by 10g of basic copper carbonate and 0.4g of SbCl3 solid. The mixture was stirred and reacted at 45℃ for 3h, filtered, and dried at 50℃ to obtain 34g of dry solid.

[0108] Then, 34g of the above-mentioned dried solid was added to 1200g of a solution containing aluminate, and the water was evaporated to dryness using a rotary evaporator at 10 kPaA and 80°C. The solution was then calcined at 700°C for 2.5h to obtain the precursor (structure NiO-CuO / Sb-Al2O3).

[0109] The precursor was reduced at 600℃ for 4 h under hydrogen conditions to obtain a 1,4-butynediol hydrogenation catalyst, the structure of which is represented as Ni-CuO / Bi-Al2O3.

[0110] The catalyst, by mass percentage, comprises: 32.2% nickel, 28% copper oxide, 0.8% Sb (an auxiliary agent), and 39% aluminum oxide; its specific surface area, determined by the BET method, is 120 m² / s. 2 / g.

[0111] The recovery rate of nickel oxide in deactivated Raney nickel was 97 wt%, and the recovery rate of aluminum was 92 wt%.

[0112] 2) The preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol involves the following steps:

[0113] 160g of a 50% (w / w) aqueous solution of 1,4-butynediol and 2g of the above-mentioned Ni-CuO / Sb-Al2O3 catalyst were added to a high-pressure reactor. Nitrogen gas was introduced to replace the air in the reactor four times, followed by H2 until the pressure inside the reactor reached 10 MPaA. The pressure inside the reactor was stabilized at 10 MPaA by controlling the back pressure valve. Stirring was started at a speed of 800 r / min, and then heating was started. After reaching the reaction temperature of 140℃, continuous feeding was started. The feed rate of the 1,4-butynediol aqueous solution was 4.0 g / min, and the feed rate of hydrogen gas was 0.139 g / min (the molar ratio of hydrogen gas to 1,4-butynediol was 3:1). The residence time of the 1,4-butynediol aqueous solution was 40 min. The composition of the reaction solution was analyzed every hour.

[0114] The results of the 1-hour reaction sampling test were as follows: 1,4-butynediol conversion rate was 99.992%, 1,4-butanediol selectivity was 99.92%, methyl-1,4-butanediol content was about 27 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 39 ppm.

[0115] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.994%, 1,4-butanediol selectivity was 99.93%, methyl-1,4-butanediol content was about 30 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 45 ppm.

[0116] Example 4

[0117] The catalyst was prepared according to the method in step 1) of Example 1, except that a methanol solution of hexadecyltrimethylammonium bromide was not added to the raw materials, and the resulting catalyst structure was represented as Ni-CuO / Bi-Al2O3.

[0118] Following the same method as step 2) of Example 1, but replacing the above-mentioned catalyst Ni-CuO / Bi-Al2O3, 1,4-butynediol was prepared by hydrogenation of 1,4-butynediol.

[0119] The results of the 1-hour reaction sampling test were as follows: 1,4-butynediol conversion rate was 99.95%, 1,4-butanediol selectivity was 99.9%, methyl-1,4-butanediol content was about 40 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 90 ppm.

[0120] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.9%, 1,4-butanediol selectivity was 99.85%, methyl-1,4-butanediol content was about 54 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 100 ppm.

[0121] Example 5

[0122] The catalyst was prepared according to the method in step 1) of Example 1, except that the methanol solution of hexadecyltrimethylammonium bromide in the raw materials was replaced with an aqueous solution of sodium dodecylbenzenesulfonate of the same concentration, and the resulting catalyst structure was represented as Ni-CuO / Bi-Al2O3.

[0123] Following the same method as step 2) of Example 1, but replacing the above-mentioned catalyst Ni-CuO / Bi-Al2O3, 1,4-butynediol was prepared by hydrogenation of 1,4-butynediol.

[0124] The results of the 1-hour reaction sampling test were as follows: 1,4-butynediol conversion rate was 99.96%, 1,4-butanediol selectivity was 99.8%, methyl-1,4-butanediol content was about 45 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 92 ppm.

[0125] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.95%, 1,4-butanediol selectivity was 99.79%, methyl-1,4-butanediol content was about 50 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 98 ppm.

[0126] Comparative Example 1

[0127] The catalyst was prepared according to the method in step 1) of Example 1, except that bismuth carbonate was not added to the raw materials, and the resulting catalyst structure was represented as Ni-CuO / Al2O3.

[0128] Following the same method as step 2) of Example 1, but replacing the above catalyst Ni-CuO / Al2O3, 1,4-butynediol was prepared by hydrogenation of 1,4-butynediol.

[0129] The results of sampling and testing after 1 hour of reaction were as follows: 1,4-butynediol conversion rate 99.8%, 1,4-butanediol selectivity 99.5%, methyl-1,4-butanediol content approximately 80 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content approximately 120 ppm.

[0130] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate 99.7%, 1,4-butanediol selectivity 99.4%, methyl-1,4-butanediol content approximately 88 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content approximately 127 ppm.

[0131] Comparative Example 2

[0132] The catalyst was prepared according to the method in step 1) of Example 1, except that bismuth carbonate in the raw materials was replaced with an equal amount of cerium carbonate, and the resulting catalyst structure was represented as Ni-CuO / Ce-Al2O3.

[0133] Following the same method as step 2) of Example 1, but replacing the above catalyst Ni-CuO / Ce-Al2O3, 1,4-butynediol was hydrogenated to prepare 1,4-butanediol.

[0134] The results of sampling and testing after 1 hour of reaction were as follows: 1,4-butynediol conversion rate 99.9%, 1,4-butanediol selectivity 99.4%, methyl-1,4-butanediol content approximately 200 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content approximately 500 ppm.

[0135] The results of sampling and testing after 1000 h of reaction were as follows: 1,4-butynediol conversion rate was 99.87%, 1,4-butanediol selectivity was 99.3%, methyl-1,4-butanediol content was about 210 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 520 ppm.

[0136] Comparative Example 3

[0137] The catalyst was prepared according to the method in step 1) of Example 1, except that basic copper carbonate was not added to the raw materials, and the resulting catalyst structure was represented as Ni-Bi-Al2O3.

[0138] Following the same method as step 2) of Example 1, but replacing the above-mentioned catalyst Ni-Bi-Al2O3, 1,4-butynediol was hydrogenated to prepare 1,4-butanediol.

[0139] Results of sampling and testing after 1 hour of reaction: 1,4-butynediol conversion rate 98%, 1,4-butanediol selectivity 96%, methyl-1,4-butanediol content approximately 300 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content approximately 400 ppm.

[0140] The results of sampling and testing after 1000 hours of reaction were as follows: 1,4-butynediol conversion rate was 97%, 1,4-butanediol selectivity was 95.6%, methyl-1,4-butanediol content was about 320 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 500 ppm.

[0141] Comparative Example 4

[0142] Following the same method as step 2) of Example 1, the catalyst was replaced with the precursor (NiO-CuO / Bi-Al2O3) prepared in step 1) of Example 1, and 1,4-butynediol was prepared by hydrogenation of 1,4-butynediol.

[0143] Results of sampling and testing after 1 hour of reaction: 1,4-butynediol conversion rate 91%, 1,4-butanediol selectivity 94%, methyl-1,4-butanediol content approximately 500 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content approximately 700 ppm.

[0144] The results of sampling and testing after 1000 hours of reaction were as follows: 1,4-butynediol conversion rate was 89%, 1,4-butanediol selectivity was 90%, methyl-1,4-butanediol content was about 540 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 710 ppm.

[0145] Comparative Example 5

[0146] The catalyst was prepared according to step 1) of Example 1, except that the aluminate solution was replaced with pure water, that is, the dry solid was added to the water, and the resulting catalyst structure was represented as Ni-CuO / Bi.

[0147] Following the same method as step 2) of Example 1, but replacing the above-mentioned catalyst Ni-CuO / Bi, 1,4-butynediol was prepared by hydrogenation of 1,4-butynediol.

[0148] The results of the 1-hour reaction sampling test were as follows: 1,4-butynediol conversion rate was 99.9%, 1,4-butanediol selectivity was 98%, methyl-1,4-butanediol content was about 210 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 340 ppm.

[0149] The results of sampling and testing after 1000 hours of reaction were as follows: 1,4-butynediol conversion rate was 98%, 1,4-butanediol selectivity was 97.6%, methyl-1,4-butanediol content was about 220 ppm, and 2-(4-hydroxybutoxy)-tetrahydrofuran content was about 400 ppm.

Claims

1. A 1,4-butynediol hydrogenation catalyst characterized in that, The structure is represented as Ni-CuO / X-Al2O3, wherein X is at least one of bismuth, arsenic, and antimony; The 1,4-butynediol hydrogenation catalyst comprises a di-aluminum oxide carrier, and a supported active component of nickel, copper oxide, and an auxiliary X; The mass percentage composition of the catalyst comprises: Nickel 20-40%; Copper oxide 10-40%; Auxiliary X 0.1-2%; Di-aluminum oxide 20-70%; The total content of each component is 100%.

2. The 1,4-butyndiol hydrogenation catalyst of claim 1, wherein, The mass percentage composition of the catalyst comprises: Nickel 25-35%; Copper oxide 10-20%; Auxiliary X 0.1-1.5%; Di-aluminum oxide 45-65%; The total content of each component is 100%.

3. The 1,4-butynediol hydrogenation catalyst of claim 1, wherein, The mass percentage composition of the catalyst comprises:

4. A process for the preparation of a 1,4-butynediol hydrogenation catalyst according to any one of claims 1 to 3, characterized in that Nickel 25-35%; Copper oxide 10-20%; Auxiliary X 0.1-1.5%; Di-aluminum oxide 45-65%; The total content of each component is 100%.

5. The production method according to claim 4, characterized by, The copper oxide coats the active component of nickel. The method comprises the following steps: (1) mixing sodium nitrate-treated Raney nickel catalyst with water, heating, and adding a base under stirring to adjust the pH to alkaline, and then filtering to obtain a nickel oxide solid and a met-aluminate-containing solution, respectively; (2) mixing the nickel oxide solid obtained in step (1) with water, then heating and adding an acid under stirring until the solid is completely dissolved, cooling, adjusting the pH to neutral by adding a base, and then adding an alcohol solution of a quaternary ammonium salt, basic copper carbonate, and a compound containing auxiliary X, and performing a reaction, followed by separation, washing, and drying to obtain a solid; 6. The production method according to claim 5, wherein (3) adding the solid of step (2) to the met-aluminate-containing solution of step (1), removing water, and then calcining to obtain a precursor; 7. The preparation method according to claim 5, characterized in that, (4) performing a hydrogen reduction reaction on the precursor obtained in step (3) to obtain the 1,4-butynediol hydrogenation catalyst.

8. The preparation method according to claim 5, characterized in that, In step (1), the mass ratio of water to sodium nitrate-treated deactivated Raney nickel is (10-100):1; and / or 9. The preparation method according to claim 5, characterized in that, In step (1), the heating is performed at a temperature of 20-95°C; and / or 10. The method of claim 5, wherein, In step (1), the stirring is performed for 1-4 h; and / or 11. The method of claim 5, wherein, In step (1), the base is selected from metal hydroxides.

12. The method of claim 4, wherein, The mass ratio of water to sodium nitrate-treated deactivated Raney nickel is (15-40):

1.

13. The method of claim 12, wherein, The heating is performed at a temperature of 50-75°C.

14. The method of claim 4, wherein, The stirring is performed for 2-3 h. The base is selected from at least one of sodium hydroxide, potassium hydroxide, and calcium hydroxide. The pH is 10-14. The pH is 13-13.

5. In step (1), the sodium nitrate-treated deactivated Raney nickel is prepared by adding Raney nickel catalyst to an aqueous sodium nitrate solution for passivation treatment for a certain period of time. The concentration of the aqueous sodium nitrate solution is 2-20 wt%, the treatment temperature is 25-50°C, and the treatment time is 1-5 h.

15. The preparation method according to claim 14, characterized in that, In step (2), the mixing mass ratio of the nickel oxide solid to water is 1:(1-40); and / or In step (2), the heating is performed at a temperature of 30-100°C; and / or In step (2), the stirring is performed for 1-4 h; and / or In step (2), the acid is selected from at least one of perchloric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, sulfuric acid, and nitric acid; and / or In step (2), the cooling is to room temperature; and / or In step (2), the base is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia water. The mixing mass ratio of the nickel oxide solid to water is 1:(2.5-10).

16. The method of claim 14, wherein, The heating is at a temperature of 60-85℃.

17. The method of claim 14, wherein, The stirring is for 2-3h.

18. The method of claim 14, wherein, The cooling is to a temperature of 20-30℃.

19. The method of claim 4, wherein, The acid in step (2) is a dilute acid with a concentration of 0.5-1mol / L.

20. The method of claim 4, wherein, The base in step (2) is prepared as an aqueous solution with a concentration of 0.5-1wt%.

21. The method of claim 4, wherein, The base solution in step (2) is added to adjust the pH to neutral, and the pH range is 6-7.

22. The method of claim 4, wherein, The quaternary ammonium salt in step (2) is one or more of a single-chain quaternary ammonium salt, a double-chain quaternary ammonium salt, and a pyridine quaternary ammonium salt; and / or The mass ratio of the nickel oxide solid to the basic copper carbonate in step (2) is (0.4-10):1; and / or The compound containing the auxiliary X in step (2) is at least one of a bismuth-containing compound, an arsenic-containing compound, and an antimony-containing compound; and / or The reaction in step (2) is carried out for 1-6h at a temperature of 20-80℃.

23. The preparation method according to claim 22, characterized in that, The quaternary ammonium salt is at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyl dimethyl tertiary amine, trimethylalkyl bromide, and trimethylalkyl chloride.

24. The method of claim 22, wherein, The mass ratio of the nickel oxide solid to the basic copper carbonate is (0.5-5):

1.

25. The preparation method according to claim 22, characterized in that, The compound containing the auxiliary X is at least one of BiCO3, SbF3, SbCl3, SbBr3, AsCl3, and AsCl5.

26. The method of claim 22, wherein, The reaction is carried out for 2-4h at a temperature of 40-50℃.

27. The method of claim 4, wherein, The quaternary ammonium salt in step (2) is added in an amount of 0.1-1% of the mass of the nickel oxide solid.

28. The method of claim 27, wherein, The quaternary ammonium salt is added in an amount of 0.1-0.5% of the mass of the nickel oxide solid.

29. The method of claim 4, wherein, The alcohol solution of the quaternary ammonium salt in step (2) has a concentration of 2-200g / L.

30. The method of claim 29, wherein, The alcohol is a short-chain alcohol with 1-4 carbon atoms.

31. The preparation method according to claim 29, characterized in that, The alcohol is methanol or ethanol.

32. The method of claim 4, wherein, The compound containing the auxiliary X in step (2) is added in an amount of 0.1-4% of the mass of the nickel oxide solid.

33. The method of claim 32, wherein, The compound containing the auxiliary X is added in an amount of 2-3.6% of the mass of the nickel oxide solid.

34. The method of claim 4, wherein, The mass ratio of the solid to the solution containing the metaliate in step (3) is (0.01-1):1; and / or The water removal in step (3) is carried out by rotary evaporation at an evaporation pressure of 5-100kPaA; and / or The calcination in step (3) is carried out at a temperature of 500-750℃ for 1-5h.

35. The preparation method according to claim 34, characterized in that, The mass ratio of the solid to the solution containing the metaliate is (0.02-0.05):

1.

36. The preparation method according to claim 34, characterized in that, The rotary evaporation is carried out at an evaporation pressure of 30-60kPaA.

37. The preparation method according to claim 34, characterized in that, The rotary evaporation is carried out at an evaporation temperature of 20-80℃.

38. The method of claim 37, wherein the method is carried out at a temperature of about 20 °C to about 30 °C. The rotary evaporation is carried out at an evaporation temperature of 30-50℃.

39. The method of claim 34, wherein, The calcination is carried out at a temperature of 600-700℃ for 2-3h.

40. The method of claim 4, wherein, The hydrogen reduction reaction in step (4) is carried out at a temperature of 600-800℃ for 1-4h.

41. The method of claim 40, wherein, The hydrogen reduction reaction is carried out at a temperature of 600-700℃ for 2-3h.

42. A process for the production of 1,4-butanediol by the hydrogenation of 1,4-butynediol, characterized in that, The method comprises the following steps: The hydrogenation reaction is carried out in the presence of the 1,4-butynediol hydrogenation catalyst according to any one of claims 1-3 or the 1,4-butynediol hydrogenation catalyst prepared by the method according to any one of claims 4-41, with 1,4-butynediol and water as the reaction substrates, and hydrogen as the hydrogen source.

43. The method of claim 42, wherein, 1,4-butynediol and water in a mass ratio of 1:(0.2-2); and / or The amount of the catalyst is 0.5-10% of the mass of 1,4-butynediol; and / or The hydrogen feed is 2-12 times the molar amount of 1,4-butynediol; and / or The hydrogenation reaction is carried out at a temperature of 100-250°C, a residence time of 0.5-4h, and a reaction pressure of 0.5-20MPaA.

44. The method of claim 43, wherein, The amount of the catalyst is 1-3% of the mass of 1,4-butynediol.

45. The method of claim 43, wherein, The hydrogen feed is 3-6 times the molar amount of 1,4-butynediol.

46. The method of claim 43, wherein, The hydrogenation reaction is carried out at a temperature of 100-130°C, a residence time of 0.5-2h, and a reaction pressure of 2-5MPaA.