Hydrogenation catalyst, preparation method and its application in the preparation of 1,3-butanediol

Abstract

This invention provides a hydrogenation catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol. The hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum. By weight percentage, the nickel content is 40-60 wt%, the aluminum content is 20-40 wt%, the silicon content is 5-15 wt%, and the molybdenum content is 0.1-6 wt%. The hydrogenation catalyst has a particulate structure with a porous surface. This invention uses nickel as the active component and aluminum and silicon as a eutectic, resulting in a metal alloy catalyst with a porous surface, high strength, and low powder loss during manufacturing, thus improving the yield and exhibiting highly efficient hydrogenation activity. This invention also provides a method for preparing the hydrogenation catalyst and its application in the preparation of 1,3-butanediol.

Description

Technical Field

[0001] This invention relates to the field of catalysis, and more particularly to a hydrogenation catalyst, its preparation method, and its application in the preparation of 1,3-butanediol. Background Technology

[0002] 1,3-Butanediol (1,3-BDO) is a colorless, viscous liquid with good water solubility. It is readily soluble in organic solvents such as ethanol and acetone, but almost insoluble in aliphatic hydrocarbons, aromatic hydrocarbons, and carbon tetrachloride. Due to the presence of two hydroxyl groups, it is chemically reactive, has low toxicity, good hygroscopicity, and is odorless, making it widely used in chemical, pharmaceutical, and cosmetic fields.

[0003] Currently, research on the synthesis of 1,3-butanediol mainly focuses on two processes: biosynthesis and chemical synthesis. While biosynthesis is green, safe, and produces fewer emissions, its low yield makes industrial-scale production difficult. The mainstream chemical synthesis process involves the condensation reaction of acetaldehyde under alkaline conditions to produce 3-hydroxybutyraldehyde, followed by hydrogenation to obtain 1,3-butanediol.

[0004] Chinese patent applications with publication numbers CN109422624A and CN109422635A disclose a method for preparing 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde in a fixed-bed reactor. The catalyst is a supported nickel catalyst, and an ionic liquid catalyst is used for acetaldehyde condensation. 10-20% of the acetaldehyde in the crude product is recovered and recycled through a flash tank. The yield of 1,3-butanediol after hydrogenation is 83%, and the acetaldehyde conversion rate is 98%.

[0005] Chinese patent application CN111744486A discloses a method for preparing a supported catalyst and a method for preparing 1,3-butanediol. The concentration of the 3-hydroxybutyraldehyde solution is 20-30%. After hydrogenation to prepare 1,3-butanediol, the conversion rate of 3-hydroxybutyraldehyde is 100% and the selectivity is as high as 99.2%.

[0006] Chinese patent application CN111574325A discloses a method and system for highly selective preparation of 1,3-butanediol, which uses a conventional powdered Raney nickel catalyst and produces 1,3-butanediol in a two-stage or multi-stage series reactor manner.

[0007] In existing production technologies, acetaldehyde is commonly condensed to obtain 3-hydroxybutyraldehyde, which is then hydrogenated to obtain 1,3-butanediol. However, the recovery of acetaldehyde after condensation increases energy consumption. The hydrogenation process typically employs either a batch reactor or a fixed-bed reactor. Batch reactors generally use powdered Raney nickel or supported catalysts. Batch hydrogenation requires the addition of fresh catalyst to maintain reaction activity, increasing safety risks. Furthermore, the product needs to be filtered and separated from the catalyst, making the operation complex and increasing labor costs. Fixed-bed reactors typically use supported catalysts, whose preparation process generally includes carrier treatment, impregnation, calcination, and reduction. This catalyst preparation is complex and has high production costs.

[0008] Therefore, it is necessary to provide a novel hydrogenation catalyst, its preparation method, and its application in the preparation of 1,3-butanediol to solve the aforementioned problems existing in the prior art. Summary of the Invention

[0009] The purpose of this invention is to provide a hydrogenation catalyst, a preparation method, and its application in the preparation of 1,3-butanediol, so as to obtain the hydrogenation catalyst with high strength, low powder loss rate during preparation, improved yield of the hydrogenation catalyst, and high hydrogenation activity.

[0010] To achieve the above objectives, the hydrogenation catalyst of the present invention is applied to the hydrogenation reaction of 3-hydroxybutyraldehyde to prepare 1,3-butanediol, wherein the hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum;

[0011] The content of nickel is 40-60 wt%, the content of aluminum is 20-40 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt%, based on the weight percentage of the hydrogenation catalyst.

[0012] The hydrogenation catalyst has a particulate structure with a porous surface.

[0013] The beneficial effects of the hydrogenation catalyst of the present invention are as follows: the hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; the hydrogenation catalyst has a particulate structure with a porous surface, wherein nickel is the active component, and aluminum and silicon are a eutectic, making the obtained hydrogenation catalyst a metal alloy catalyst with a porous surface structure and high strength; molybdenum, as an active promoter, improves the hydrogenation activity and selectivity of the catalyst, resulting in high catalyst strength, low powder loss during production, improved yield of the hydrogenation catalyst, and high hydrogenation activity; by weight percentage, the content of nickel is 40-60 wt%, the content of aluminum is 20-40 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt%, that is, by adding an appropriate amount of silicon, the binding force between the metals is enhanced, and the appropriate amount of nickel not only makes the catalyst surface have a certain proportion of highly active nickel, but the remaining aluminum and silicon provide a strong core for the catalyst, making the catalyst strength higher than that of supported catalysts.

[0014] Optionally, in the hydrogenation catalyst, the content of nickel is 45-60 wt%, the content of aluminum is 30-40 wt%, the content of silicon is 8-13 wt%, and the content of molybdenum is 0.5-5 wt%, based on the weight percentage of the hydrogenation catalyst. The beneficial effects are: by adding an appropriate amount of silicon, the bonding force between the metals is enhanced; the suitable content of nickel not only gives the catalyst surface a certain proportion of highly active nickel, but the remaining aluminum and silicon provide a strong core for the catalyst, making the catalyst stronger than supported catalysts.

[0015] The application of the hydrogenation catalyst of the present invention in the preparation of 1,3-butanediol includes the following steps:

[0016] S100: Acetaldehyde is condensed under the action of an alkaline catalyst to obtain a condensation solution, wherein the condensation solution includes acetaldehyde, butenal and 3-hydroxybutanal.

[0017] S200: The condensate is heat-treated under stirring to obtain a 3-hydroxybutyraldehyde mixed solution;

[0018] S300: The gas-liquid mixture consisting of the 3-hydroxybutyraldehyde mixed solution and hydrogen is passed through the hydrogenation catalyst to carry out a hydrogenation reaction to obtain 1,3-butanediol.

[0019] The beneficial effects of the hydrogenation catalyst of the present invention in the preparation of 1,3-butanediol are as follows: By heat-treating the condensate under stirring in step S200, the utilization rate of the raw material acetaldehyde can be significantly improved, making the reaction of the raw material acetaldehyde more complete, reducing its recovery energy consumption, and further improving the yield of 3-hydroxybutyraldehyde. This solves the problem of low acetaldehyde utilization in the prior art and achieves the goal of higher yield of the target product 1,3-butanediol. Furthermore, by passing a gas-liquid mixture consisting of a 3-hydroxybutyraldehyde mixed solution and hydrogen through the hydrogenation catalyst in step S300 to carry out the hydrogenation reaction, the hydrogenation catalyst has high hydrogenation activity. While maintaining the quality of the 1,3-butanediol, it can reduce hydrogenation costs and energy consumption, making it suitable for industrial production.

[0020] Optionally, the reaction temperature of the heat treatment in step S200 is 30-100℃, and the reaction time is 1-5 hours. Its beneficial effects are: it helps to improve the utilization rate of the raw material acetaldehyde, making the reaction of the raw material acetaldehyde more complete, reducing its recovery energy consumption, further improving the yield of 3-hydroxybutyraldehyde, achieving the goal of achieving a higher yield of the target compound 1,3-butanediol, and solving the problem of low acetaldehyde utilization rate in the prior art.

[0021] Optionally, the hydrogenation reaction in step S300 is carried out in a fixed-bed reactor, the reaction temperature is 50-140℃, the reaction pressure is 2-10 MPa, and the volume hourly space velocity of the 3-hydroxybutyraldehyde mixed solution is 0.1-6 h⁻¹. -1 Its beneficial effects are that it enables the hydrogenation catalyst to maintain high hydrogenation activity, reduces hydrogenation costs and energy consumption while maintaining the quality of 1,3-butanediol, and is suitable for industrial production.

[0022] Optionally, in the condensation solution, the content of acetaldehyde is 5-10 wt%, the content of butenal is 0.5-3 wt%, and the content of 3-hydroxybutyraldehyde is 60-80 wt%, based on the weight percentage of the condensation solution. The beneficial effects are: a higher concentration of 3-hydroxybutyraldehyde can increase the yield of the target product 1,3-butanediol, increase production capacity, reduce subsequent distillation energy consumption, and lower production costs.

[0023] The method for preparing the hydrogenation catalyst of the present invention includes the following steps:

[0024] S0: Provide a metal raw material, the metal raw material including nickel, aluminum, silicon and molybdenum, wherein the content of nickel is 35-60 wt%, the content of aluminum is 30-50 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt% by weight percentage of the metal raw material;

[0025] S1: The metal raw material is melted at high temperature into an alloy block, and then the alloy block is crushed into metal alloy particles;

[0026] S2: The metal alloy particles are subjected to cyclic activation treatment with alkaline solution to obtain alkaline-activated alloy particles;

[0027] S3: The alloy particles activated by alkali are washed with first deionized water until the pH of the collected waste liquid after washing is 7-9, so as to obtain the hydrogenation catalyst.

[0028] The beneficial effects of the preparation method of the hydrogenation catalyst of the present invention are as follows: by using alkaline solution to perform cyclic activation treatment on the metal alloy particles in step S2, the alkaline solution can be recycled, greatly reducing the required alkaline solution, reducing input costs, and producing less waste liquid, which is more environmentally friendly; by using first deionized water to wash the alkaline-activated alloy particles, deionized water is inexpensive and readily available, reducing input costs, producing less waste liquid, which is more environmentally friendly; moreover, the preparation method of the hydrogenation catalyst is convenient to operate, has a simple process, and significantly reduces raw material costs compared with the prior art.

[0029] Optionally, the average particle size of the metal alloy particles is 2-8 mm.

[0030] Further optionally, the average particle size of the metal alloy particles is 3-7 mm.

[0031] Optionally, in step S2, the activation treatment time is 1-6 hours, the activation treatment temperature is greater than or equal to room temperature and less than or equal to 60°C, and the alkaline solution is a mixture of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.

[0032] Optionally, in step S3, the temperature of the washing process is greater than or equal to room temperature and less than or equal to 80°C.

[0033] Optionally, step S2, which involves cyclically activating the metal alloy particles with an alkaline solution, includes:

[0034] S21: Provide an intermediate storage tank containing second deionized water, and inject the second deionized water into a reactor containing the metal alloy particles through a circulation pump. After the second deionized water flows through the metal alloy particles, it returns to the intermediate storage tank to form a circulation loop.

[0035] S22: Liquid alkali is added to the intermediate storage tank by an alkali pump, and the liquid alkali is mixed with the second deionized water to obtain the diluted alkali solution;

[0036] S23: The alkaline solution is injected into the reactor through the circulating pump, and the alkaline solution flows through the metal alloy particles to activate the metal alloy particles, and then returns to the intermediate storage tank.

[0037] S24: Repeat steps S22 and S23 until all the liquid alkali of the preset amount has been added to the intermediate storage tank. Then, continue with step S23 to activate the metal alloy particles with the alkali solution for 1-6 hours. The beneficial effects are: by cyclically repeating step S22, the concentration of the alkali solution reacting with the metal alloy particles gradually increases, making the activation treatment of the metal alloy particles by the alkali solution more stable during the cyclical repetition of step S23. Furthermore, it allows for the recycling of the second deionized water and the alkali solution, reducing input and recovery costs, and is more environmentally friendly.

[0038] Optionally, the weight of the second deionized water in the intermediate storage tank is 5-20 times the weight of the metal alloy particles, and the total weight of the liquid alkali added to the intermediate storage tank is 1-4 times the weight of the metal alloy particles. The advantages are: by using a recycling method, the amount of alkali used is reduced, the generation of waste alkali water is reduced, production costs are lowered, and environmental pollution is reduced.

[0039] Optionally, the feed mass hourly space velocity of the circulating pump is 10-80 h⁻¹. -1 The feed mass hourly space velocity (HHSV) of the liquid alkali is 0.3-4 h⁻¹. -1 Its beneficial effects are: by using a suitable circulating feed space velocity, the exothermic reaction can be quickly removed, and at the same time, a high space velocity will make the catalyst activation more uniform, resulting in a smaller difference in the activation depth of the particles in the upper and lower parts of the reactor.

[0040] Optionally, the liquid alkali is a liquid alkali with a mass concentration of 32 wt%.

[0041] Optionally, the liquid alkali is a liquid alkali with a mass concentration of 32 wt%, prepared by mixing one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and sodium bicarbonate. Attached Figure Description

[0042] Figure 1 This is a schematic diagram of the structure of the hydrogenation catalyst according to an embodiment of the present invention;

[0043] Figure 2 This is a schematic flowchart of the preparation method of the hydrogenation catalyst according to an embodiment of the present invention;

[0044] Figure 3 This is a schematic diagram illustrating the application of the hydrogenation catalyst in the preparation of 1,3-butanediol according to an embodiment of the present invention. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, the technical or scientific terms used herein should have the ordinary meaning understood by those skilled in the art. The terms "comprising" and similar expressions used herein mean that the element or object preceding the word covers the element or object listed after the word and its equivalents, but does not exclude other elements or objects.

[0046] To overcome the problems existing in the prior art, the present invention provides a hydrogenation catalyst, a preparation method, and its application in the preparation of 1,3-butanediol, so as to obtain the hydrogenation catalyst with high strength, low powder loss rate during the preparation of the hydrogenation catalyst, improve the yield of the hydrogenation catalyst, and have high hydrogenation activity.

[0047] In some embodiments of the present invention, the hydrogenation catalyst is applied to the hydrogenation of 3-hydroxybutyraldehyde to prepare 1,3-butanediol. The hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum. The content of nickel is 40-60 wt%, the content of aluminum is 20-40 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt% by weight of the hydrogenation catalyst. The hydrogenation catalyst has a particulate structure with a porous surface.

[0048] Specifically, the hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; the hydrogenation catalyst has a particulate structure with a porous surface, wherein nickel is the active component, and aluminum and silicon are a eutectic, making the resulting hydrogenation catalyst a metal alloy catalyst with a porous surface structure and high strength. Molybdenum, as an active promoter, improves the hydrogenation activity and selectivity of the catalyst, resulting in high catalyst strength, low powder loss during production, improved yield of the hydrogenation catalyst, and high hydrogenation activity; by using a percentage by weight of the hydrogenation catalyst... The nickel content is 40-60 wt%, the aluminum content is 20-40 wt%, the silicon content is 5-15 wt%, and the molybdenum content is 0.1-6 wt%. This means that adding an appropriate amount of silicon enhances the bonding between the metals. The suitable amount of nickel not only gives the catalyst surface a certain proportion of highly active nickel, but also means that approximately 90% of the surface depth (about 1 mm) of the hydrogenation catalyst particle is active nickel. The remaining aluminum and silicon provide a strong core for the catalyst, making its strength higher than that of supported catalysts.

[0049] In this process, because nickel-aluminum, nickel-silicon, or nickel-aluminum-molybdenum, nickel-silicon-molybdenum crystals in the metal raw materials can form crystals of different phases, and the metals are in a very uniform state rather than simply dispersed, aluminum and silicon can act as a eutectic, making the resulting hydrogenation catalyst a metal alloy catalyst with a porous surface structure, and at the same time giving the hydrogenation catalyst high strength.

[0050] Figure 1 This is a schematic diagram of the structure of the hydrogenation catalyst in an embodiment of the present invention.

[0051] In some embodiments of the present invention, the hydrogenation catalyst has a particulate structure with a porous surface, meaning that the surface of the hydrogenation catalyst has a porous structure while the interior is solid. This structure gives the surface of the hydrogenation catalyst high activity, while the internal structure is very robust, thus making the hydrogenation catalyst less prone to collapse and pulverization. Specifically, as shown... Figure 1 As shown, the hydrogenation catalyst includes a semi-through-hole portion 10 and a solid portion 20. The semi-through-hole portion 10 includes a plurality of pore structures and is disposed on the surface of the solid portion 20.

[0052] In some optional embodiments of the present invention, the hydrogenation catalyst contains, by weight percentage, 45-60 wt% nickel, 30-40 wt% aluminum, 8-13 wt% silicon, and 0.5-5 wt% molybdenum. The addition of an appropriate amount of silicon enhances the bonding force between the metals, and the suitable amount of nickel not only gives the catalyst surface a certain proportion of highly active nickel, but the remaining aluminum and silicon provide a strong core for the catalyst, making the catalyst stronger than supported catalysts.

[0053] Figure 2 This is a schematic flowchart of the preparation method of the hydrogenation catalyst according to an embodiment of the present invention.

[0054] In some embodiments of the present invention, the preparation method of the hydrogenation catalyst is described in reference to... Figure 2 This includes the following steps:

[0055] S0: Provide a metal raw material, the metal raw material including nickel, aluminum, silicon and molybdenum, wherein the content of nickel is 35-60 wt%, the content of aluminum is 30-50 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt% by weight percentage of the metal raw material;

[0056] S1: The metal raw material is melted at high temperature into an alloy block, and then the alloy block is crushed into metal alloy particles;

[0057] S2: The metal alloy particles are subjected to cyclic activation treatment with alkaline solution to obtain alkaline-activated alloy particles;

[0058] S3: The alloy particles activated by alkali are washed with first deionized water until the pH of the collected waste liquid after washing is 7-9, so as to obtain the hydrogenation catalyst.

[0059] Specifically, in step S2, the metal alloy particles are cyclically activated using an alkaline solution, allowing the alkaline solution to be recycled, greatly reducing the amount of alkaline solution required, reducing input costs, and producing less waste, making it more environmentally friendly. The alkaline-activated alloy particles are then washed with a first deionized water, which is inexpensive and readily available, further reducing input costs and producing less waste, making it more environmentally friendly. Moreover, the preparation method of the hydrogenation catalyst is convenient to operate and has a simple process, significantly reducing raw material costs compared to existing technologies.

[0060] In fact, after the metal raw material is treated with the alkaline solution, the content of nickel and molybdenum in the alkaline-activated alloy particles will increase, while the content of aluminum and silicon will decrease.

[0061] In some specific embodiments of the present invention, the metal raw materials are a mixture, and the content of nickel is 40-50 wt%, the content of aluminum is 35-45 wt%, the content of silicon is 10-15 wt%, and the content of molybdenum is 0.5-5 wt%, based on the weight percentage of the metal raw materials.

[0062] In some embodiments of the present invention, the average particle size of the metal alloy particles is 2-8 mm.

[0063] In some optional embodiments of the present invention, the average particle size of the metal alloy particles is 3-7 mm.

[0064] In some embodiments of the present invention, the step of using an alkaline solution to perform cyclic activation treatment on the metal alloy particles in step S2 includes:

[0065] S21: Provide an intermediate storage tank containing second deionized water, and inject the second deionized water into a reactor containing the metal alloy particles through a circulation pump. After the second deionized water flows through the metal alloy particles, it returns to the intermediate storage tank to form a circulation loop.

[0066] S22: Liquid alkali is added to the intermediate storage tank by an alkali pump, and the liquid alkali is mixed with the second deionized water to obtain the diluted alkali solution;

[0067] S23: The alkaline solution is injected into the reactor through the circulating pump, and the alkaline solution flows through the metal alloy particles to activate the metal alloy particles, and then returns to the intermediate storage tank.

[0068] S24: Repeat steps S22 and S23 until all the liquid alkali of the preset amount has been added to the intermediate storage tank. Then, continue with step S23 to activate the metal alloy particles with the alkali solution for 1-6 hours. By repeating step S22, the concentration of the alkali solution reacting with the metal alloy particles gradually increases. This makes the activation treatment of the metal alloy particles with the alkali solution more stable during the repeated steps S23. Furthermore, it allows for the recycling of the second deionized water and the alkali solution, reducing input and recovery costs and making the process more environmentally friendly.

[0069] In some specific embodiments of the present invention, in steps S21 and S22, both the second deionized water and the alkaline solution enter the reactor from the bottom of the reactor, flow through the metal alloy particles, and finally exit from the top of the reactor and return to the intermediate storage tank. This allows the alkaline solution to carry away the heat generated during the activation process, thereby preventing the temperature from becoming too high and facilitating a more stable activation process.

[0070] In some embodiments of the present invention, the weight of the second deionized water in the intermediate storage tank is 5-20 times the weight of the metal alloy particles. The total weight of the liquid alkali added to the intermediate storage tank is 1-4 times the weight of the metal alloy particles, and the total weight of the liquid alkali is the weight of the liquid alkali continuously added to the intermediate storage tank in step S22. By adopting a recycling method, the amount of alkali used is reduced, the generation of waste alkali water is reduced, production costs are lowered, and environmental pollution is reduced.

[0071] In some optional embodiments of the present invention, the weight of the second deionized water contained in the intermediate storage tank is 5-15 times the weight of the metal alloy particles, and the total weight of the liquid alkali added to the intermediate storage tank is 1.5-3 times the weight of the metal alloy particles.

[0072] In some embodiments of the present invention, the feed mass hourly space velocity of the circulating pump is 10-80 h⁻¹. -1 That is, the alkaline solution is prepared over 10-80 hours. -1 The mass hourly space velocity (MHSV) passes through the metal alloy particles. The feed MHSV of the liquid alkali is 0.3-4 h⁻¹. -1 That is, the liquid alkali is applied at a concentration of 0.3-4 hours. -1 The mass hourly space velocity (MHV) is introduced into the intermediate storage tank. By using a suitable circulating feed MHV, the exothermic reaction can be quickly removed, and the high MHV also makes the catalyst activation more uniform, resulting in a smaller difference in the activation depth of the particles in the upper and lower parts of the reactor.

[0073] In the embodiments of the present invention, the feed mass hourly space velocity (MHSV) of the circulating pump refers to the mass of alkali solution passing through a unit mass of metal alloy particles per hour. The feed MHSV of the liquid alkali refers to the mass of liquid passing through a unit mass of metal alloy particles per hour.

[0074] In some optional embodiments of the present invention, the feed mass hourly space velocity of the circulating pump is 20-60 h⁻¹. -1 The feed mass hourly space velocity (HHSV) of the liquid alkali is 0.3-3 h⁻¹. -1 .

[0075] In some embodiments of the present invention, the liquid alkali is a liquid alkali with a mass concentration of 32 wt%.

[0076] In some other embodiments of the present invention, the liquid alkali is a liquid alkali with a mass concentration of 32 wt%, prepared by mixing one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.

[0077] In some embodiments of the present invention, in step S2, the activation treatment time is 1-6 hours, the activation treatment temperature is greater than or equal to room temperature and less than or equal to 60°C, and the alkaline solution is a mixture of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.

[0078] Specifically, the total weight of the liquid alkali is gradually injected into the intermediate storage tank, and then the alkali solution is injected into the reactor through the circulation pump. The alkali solution is used to activate the metal alloy particles for 1-6 hours to obtain alkali-activated alloy particles.

[0079] In some optional embodiments of the present invention, in step S2, the activation treatment time is 1-4 hours, the activation treatment temperature is 30-60°C, and the alkaline solution is a mixture of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and sodium bicarbonate.

[0080] In some embodiments of the present invention, in step S3, the temperature of the washing process is greater than or equal to room temperature and less than or equal to 80°C.

[0081] In some optional embodiments of the present invention, the temperature of the washing process in step S3 is 30-60°C.

[0082] In some specific embodiments of the present invention, the preparation method of the hydrogenation catalyst includes the following steps:

[0083] S0, providing metal raw materials;

[0084] S1. Preparation of metal alloy particles: The metal raw material is melted into an alloy block using high-temperature melting technology, and then the alloy block is crushed into metal alloy particles. The metal alloy particles of the required size are obtained after crushing and screening.

[0085] S2. Alkali activation treatment: The metal alloy particles are loaded into the reactor and activated by circulating the alkali solution at a preset flow rate to obtain alkali-activated alloy particles.

[0086] S3. Water washing treatment: The alkaline solution is switched to the first deionized water, and the first deionized water is used to wash the alkaline-activated alloy particles under preset conditions until the pH value of the outlet washing solution is 7-9, thereby obtaining the hydrogenation catalyst.

[0087] Specifically, please refer to Table 1 for the weight percentage of each component in the metal alloy particles of Examples 1-7 and Comparative Examples 1-3 of the present invention, as well as the average particle size of the metal alloy particles. The unit of weight percentage is wt%, and the unit of average particle size is mm. "--" in Table 1 indicates that the substance is not present in the catalyst.

[0088] Table 1

[0089]

[0090]

[0091] Specifically, the specific process for preparing the hydrogenation catalyst from the metal alloy particles in Examples 1-7 and Comparative Examples 1-3 of this invention after alkaline activation treatment and water washing treatment is as follows.

[0092] Example 1

[0093] The first metal alloy particle in this embodiment is the metal alloy particle described in Example 1 of Table 1. That is, the first metal alloy particle includes nickel, aluminum, silicon and molybdenum. The content of nickel is 44 wt%, the content of aluminum is 45 wt%, the content of silicon is 10 wt%, and the content of molybdenum is 1 wt% based on the weight percentage of the first metal alloy particle. The average particle size of the first metal alloy particle is 3 mm.

[0094] In a specific implementation, 1 kg of the first metal alloy particles is accurately weighed and placed in a quartz glass tube with an inner diameter of 60 mm; 5 kg of the second deionized water is stored in the intermediate storage tank; 2 kg of 32 wt% liquid alkali, prepared from sodium hydroxide, is prepared in the liquid alkali tank; the circulating water pump draws the second deionized water from the bottom of the quartz glass tube at a rate of 40 kg / h, and after passing through the bed containing the first metal alloy particles, it flows out from the top of the quartz glass tube and returns to the intermediate storage tank; the liquid alkali is added to the intermediate storage tank by the alkali pump at a rate of 0.3 kg / h to mix with the second deionized water to obtain... During the replenishment of the diluted alkali solution, the diluted alkali solution continuously circulates and activates the first metal alloy particles. Specifically, the diluted alkali solution flows in from the bottom of the quartz glass tube, passes through the bed containing the first metal alloy particles, and then flows out from the top of the quartz glass tube back into the intermediate storage tank. After all the liquid alkali solution has been added, the alkali solution circulates back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 1 hour. The bed temperature is set to 40°C. After the activation treatment is completed, the particles are washed with the first deionized water at 50°C until the pH of the solution after washing is 7-9, thus obtaining the first hydrogenation catalyst.

[0095] The average composition of the first hydrogenation catalyst is shown in Example 1 of Table 2. That is, the first hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; based on the weight percentage of the first hydrogenation catalyst, the nickel content is 51.6 wt%, the aluminum content is 39.1 wt%, the silicon content is 8.1 wt%, and the molybdenum content is 1.2 wt%. Furthermore, the powder shedding rate of the first hydrogenation catalyst is 0.2 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained first hydrogenation catalyst is 0.2 wt%.

[0096] In the embodiments of the present invention, during the alkaline activation treatment, some fine powder inevitably falls off the surface of the metal alloy particles. In the present invention, the fine powder is collectively referred to as slag.

[0097] Example 2

[0098] The second metal alloy particles in this embodiment are the metal alloy particles described in Example 2 of Table 1. That is, the second metal alloy particles include nickel, aluminum, silicon, and molybdenum. Based on the weight percentage of the second metal alloy particles, the content of nickel is 47 wt%, the content of aluminum is 53.5 wt%, the content of silicon is 15 wt%, the content of molybdenum is 3 wt%, and the average particle size of the second metal alloy particles is 5 mm.

[0099] In a specific embodiment, the second hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 2 and Example 1 is that the intermediate storage tank contains 10 kg of the second deionized water, and the liquid alkali is added to the intermediate storage tank at a rate of 1 kg / h via the alkali pump. After all the liquid alkali has been added, the alkali solution is circulated into the quartz glass tube to continue circulating and activating the first metal alloy particles for 3 hours. The bed temperature is set to 50°C. After activation, the particles are washed with the first deionized water at 40°C.

[0100] The average composition of the second hydrogenation catalyst is shown in Example 2 of Table 2. That is, the second hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; based on the weight percentage of the second hydrogenation catalyst, the nickel content is 53.2 wt%, the aluminum content is 30 wt%, the silicon content is 12.9 wt%, and the molybdenum content is 3.9 wt%. Furthermore, the powder shedding rate of the second hydrogenation catalyst is 0.5 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained second hydrogenation catalyst is 0.5 wt%.

[0101] Example 3

[0102] The third metal alloy particles in this embodiment are the metal alloy particles described in Example 3 of Table 1, that is, the third metal alloy particles include nickel, aluminum, silicon and molybdenum. In terms of the weight percentage of the third metal alloy particles, the content of nickel is 40 wt%, the content of aluminum is 45 wt%, the content of silicon is 11 wt%, the content of molybdenum is 4 wt%, and the average particle size of the third metal alloy particles is 3 mm.

[0103] In a specific embodiment, the third hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 3 and Example 1 is that: the intermediate storage tank contains 8 kg of the second deionized water; the liquid alkali tank contains 1.5 kg of 32 wt% liquid alkali, which is prepared by mixing sodium hydroxide and potassium hydroxide; the circulating water pump pumps the second deionized water into the bottom of the quartz glass tube at a rate of 50 kg / h; after all the liquid alkali has been added, the alkali solution is circulated back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 4 hours; the bed temperature is set to 30°C; after activation, the particles are washed with the first deionized water at 60°C.

[0104] The average composition of the third hydrogenation catalyst is shown in Example 3 of Table 2. That is, the third hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 45.3 wt%, the aluminum content is 40.3 wt%, the silicon content is 9.9 wt%, and the molybdenum content is 4.5 wt%. Furthermore, the powder shedding rate of the third hydrogenation catalyst is 0.3 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained third hydrogenation catalyst is 0.3 wt%.

[0105] Example 4

[0106] The fourth metal alloy particle in this embodiment is the metal alloy particle described in Example 4 of Table 1, that is, the fourth metal alloy particle includes nickel, aluminum, silicon and molybdenum. Based on the weight percentage of the fourth metal alloy particle, the content of nickel is 49 wt%, the content of aluminum is 37 wt%, the content of silicon is 11.6 wt%, the content of molybdenum is 2.4 wt%, and the average particle size of the fourth metal alloy particle is 6 mm.

[0107] In a specific embodiment, the fourth hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 4 and Example 1 is that: the intermediate storage tank contains 15 kg of the second deionized water; the liquid alkali tank contains 3 kg of 32 wt% liquid alkali, which is prepared by mixing potassium hydroxide and sodium carbonate; the circulating water pump draws the second deionized water into the quartz glass tube at a rate of 50 kg / h; the liquid alkali is added to the intermediate storage tank via the alkali pump at a rate of 1 kg / h; after all the liquid alkali has been added, the alkali solution is circulated back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 2 hours; and the bed temperature is set to 60°C.

[0108] The average composition of the fourth hydrogenation catalyst is shown in Example 4 of Table 2. That is, the fourth hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 56.1 wt%, the aluminum content is 31.6 wt%, the silicon content is 10.2 wt%, and the molybdenum content is 2.1 wt%. Furthermore, the powder shedding rate of the fourth hydrogenation catalyst is 0.5 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained fourth hydrogenation catalyst is 0.5 wt%.

[0109] Example 5

[0110] The fifth metal alloy particle in this embodiment is the metal alloy particle described in Example 5 of Table 1, that is, the fifth metal alloy particle includes nickel, aluminum, silicon and molybdenum. Based on the weight percentage of the fifth metal alloy particle, the content of nickel is 42wt%, the content of aluminum is 40wt%, the content of silicon is 13wt%, the content of molybdenum is 5wt%, and the average particle size of the fifth metal alloy particle is 7mm.

[0111] In a specific embodiment, the fifth hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 5 and Example 1 is that: the intermediate storage tank contains 10 kg of the second deionized water; the circulating water pump draws the second deionized water into the quartz glass tube at a rate of 20 kg / h; the liquid alkali is added to the intermediate storage tank via the alkali pump at a rate of 2 kg / h; after all the liquid alkali has been added, the alkali solution is circulated back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 4 hours; the bed temperature is set to 60°C; after activation, the particles are washed with the first deionized water at 30°C.

[0112] The average composition of the fifth hydrogenation catalyst is shown in Example 5 of Table 2. That is, the fifth hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 47.8 wt%, the aluminum content is 32.4 wt%, the silicon content is 15 wt%, and the molybdenum content is 4.8 wt%. Furthermore, the powder shedding rate of the fifth hydrogenation catalyst is 0.2 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained fifth hydrogenation catalyst is 0.2 wt%.

[0113] Example 6

[0114] The sixth metal alloy particle in this embodiment is the metal alloy particle described in Example 6 of Table 1, that is, the sixth metal alloy particle includes nickel, aluminum, silicon and molybdenum. In terms of the weight percentage of the sixth metal alloy particle, the content of nickel is 50 wt%, the content of aluminum is 39.5 wt%, the content of silicon is 10 wt%, the content of molybdenum is 0.5 wt%, and the average particle size of the sixth metal alloy particle is 3 mm.

[0115] In a specific embodiment, the sixth hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 6 and Example 1 is that: the intermediate storage tank contains 9 kg of the second deionized water; the liquid alkali tank contains 2.5 kg of 32 wt% liquid alkali, which is prepared by mixing potassium hydroxide and lithium hydroxide; the circulating water pump draws the second deionized water into the quartz glass tube at a rate of 60 kg / h; the liquid alkali is added to the intermediate storage tank via the alkali pump at a rate of 1 kg / h; after all the liquid alkali has been added, the alkali solution is circulated back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 4 hours.

[0116] The average composition of the sixth hydrogenation catalyst is shown in Example 6 of Table 2. That is, the sixth hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 59.8 wt%, the aluminum content is 30.8 wt%, the silicon content is 8.8 wt%, and the molybdenum content is 0.6 wt%. Furthermore, the powder shedding rate of the sixth hydrogenation catalyst is 0.5 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained sixth hydrogenation catalyst is 0.5 wt%.

[0117] Example 7

[0118] The seventh metal alloy particle in this embodiment is the metal alloy particle described in Example 7 of Table 1, that is, the seventh metal alloy particle includes nickel, aluminum, silicon and molybdenum. Based on the weight percentage of the seventh metal alloy particle, the content of nickel is 46 wt%, the content of aluminum is 40.5 wt%, the content of silicon is 12 wt%, the content of molybdenum is 1.5 wt%, and the average particle size of the seventh metal alloy particle is 3 mm.

[0119] In a specific embodiment, the seventh hydrogenation catalyst was prepared according to the method described in Example 1. The difference between Example 7 and Example 1 is that: the intermediate storage tank contains 9 kg of the second deionized water; the liquid alkali tank contains 3 kg of 32 wt% liquid alkali, which is prepared by mixing sodium hydroxide and sodium bicarbonate; the circulating water pump draws the second deionized water into the quartz glass tube at a rate of 30 kg / h; the liquid alkali is added to the intermediate storage tank via the alkali pump at a rate of 0.8 kg / h; after all the liquid alkali has been added, the alkali solution is circulated back into the quartz glass tube to continue circulating and activating the first metal alloy particles for 3 hours; the bed temperature is set to 55°C; after activation, the particles are washed with the first deionized water at 40°C.

[0120] The average composition of the seventh hydrogenation catalyst is shown in Example 7 of Table 2. That is, the seventh hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 53.5 wt%, the aluminum content is 33.1 wt%, the silicon content is 12.1 wt%, and the molybdenum content is 1.3 wt%. Furthermore, the powder shedding rate of the seventh hydrogenation catalyst is 0.3 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained seventh hydrogenation catalyst is 0.3 wt%.

[0121] Comparative Example 1

[0122] The eighth metal alloy particle in this embodiment is the metal alloy particle described in Comparative Example 1 of Table 1, that is, the eighth metal alloy particle includes nickel, aluminum and molybdenum. The content of nickel is 46 wt%, the content of aluminum is 52 wt%, the content of molybdenum is 2 wt%, and the average particle size of the eighth metal alloy particle is 3 mm.

[0123] In a specific embodiment, the eighth hydrogenation catalyst was prepared according to the method described in Example 1.

[0124] The average composition of the eighth hydrogenation catalyst is shown in Comparative Example 1 in Table 2. That is, the eighth hydrogenation catalyst comprises nickel, aluminum, and molybdenum; based on the weight percentage of the eighth hydrogenation catalyst, the nickel content is 52.9 wt%, the aluminum content is 44.8 wt%, and the molybdenum content is 2.3 wt%. Furthermore, the powder shedding rate of the eighth hydrogenation catalyst is 1.1 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained eighth hydrogenation catalyst is 1.1 wt%.

[0125] Comparative Example 2

[0126] The ninth metal alloy particle in this embodiment is the metal alloy particle described in Comparative Example 2 of Table 1, that is, the ninth metal alloy particle includes nickel, aluminum, silicon and molybdenum. Based on the weight percentage of the ninth metal alloy particle, the content of nickel is 46 wt%, the content of aluminum is 40.5 wt%, the content of silicon is 12 wt%, the content of molybdenum is 2 wt%, and the average particle size of the ninth metal alloy particle is 3 mm.

[0127] In a specific embodiment, the activation treatment was carried out according to the preparation method of Example 1 in Chinese Patent Publication No. CN106693992B to prepare the ninth hydrogenation catalyst.

[0128] The average composition of the ninth hydrogenation catalyst is shown in Comparative Example 2 in Table 2. That is, the ninth hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; based on the weight percentage of the ninth hydrogenation catalyst, the content of nickel is 52 wt%, the content of aluminum is 35.6 wt%, the content of silicon is 10.6 wt%, and the content of molybdenum is 1.8 wt%. Furthermore, the powder shedding rate of the ninth hydrogenation catalyst is 0.4 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained ninth hydrogenation catalyst is 0.4 wt%.

[0129] Comparative Example 3

[0130] The tenth metal alloy particle in this embodiment is the metal alloy particle described in Comparative Example 3 of Table 1, that is, the tenth metal alloy particle includes nickel, aluminum, silicon and molybdenum. Based on the weight percentage of the tenth metal alloy particle, the content of nickel is 46 wt%, the content of aluminum is 40.5 wt%, the content of silicon is 12 wt%, the content of molybdenum is 2 wt%, and the average particle size of the tenth metal alloy particle is 3 mm.

[0131] In a specific embodiment, the activation treatment was carried out according to the preparation method of Example 3 in Chinese Patent Publication No. CN106693992B to prepare the tenth hydrogenation catalyst.

[0132] The average composition of the tenth hydrogenation catalyst is shown in Comparative Example 3 in Table 2. That is, the tenth hydrogenation catalyst comprises nickel, aluminum, silicon, and molybdenum; by weight percentage, the nickel content is 52 wt%, the aluminum content is 35.6 wt%, the silicon content is 10.6 wt%, and the molybdenum content is 1.8 wt%. Furthermore, the powder shedding rate of the tenth hydrogenation catalyst is 0.6 wt%, meaning the ratio of the weight of the powder residue obtained from the quartz glass tube to the weight of the obtained tenth hydrogenation catalyst is 0.6 wt%.

[0133] In the specific implementation scheme, the weight percentage of each component in the hydrogenation catalyst prepared by Examples 1-7 and Comparative Examples 1-3, the total amount of second deionized water and liquid alkali used during activation, and the powder loss rate are shown in Table 2. The weight percentage is in wt%, the total amount of second deionized water and liquid alkali used during activation is in kg, and the powder loss rate is in %. "--" in Table 2 indicates that the substance is not present in the catalyst.

[0134] Table 2

[0135]

[0136]

[0137] As shown in Table 2, the alloy catalyst prepared by using nickel-aluminum-silicon eutectic has better activation strength.

[0138] Examples 1-7 and Comparative Example 1 are all hydrogenation catalysts prepared according to the preparation method of the present invention. The difference lies in that the metal alloy particles in Examples 1-7 are silicon-containing metal alloy particles, while the metal alloy particles in Comparative Example 1 are silicon-free metal alloy particles. Table 2 shows that the powder loss rate of the hydrogenation catalysts prepared in Examples 1-7 is 0.2-0.5 wt%, while the powder loss rate of the hydrogenation catalyst prepared in Comparative Example 1 is 1.1 wt%. This analysis shows that the powder loss rate of the hydrogenation catalyst prepared with silicon-containing metal alloy particles is lower than that of the hydrogenation catalyst prepared with silicon-free metal alloy particles. Therefore, the addition of silicon can make the other metals bond more firmly during smelting, resulting in a lower powder loss rate during alkaline treatment. This leads to a higher strength and lower powder loss rate in the obtained hydrogenation catalyst, thus improving the yield of the hydrogenation catalyst.

[0139] Examples 1-7 and Comparative Example 1 were hydrogenation catalysts prepared according to the preparation method of the present invention, while Comparative Examples 2 and 3 were hydrogenation catalysts prepared according to the preparation methods disclosed in existing patents. From the data in Table 2 regarding the total amount of second deionized water and liquid alkali used during activation, it can be seen that in Examples 1-7 and Comparative Example 1, the total amount of second deionized water and liquid alkali used during activation was less than or equal to 12 kg, while in Comparative Example 2, the total amount of second deionized water and liquid alkali used during activation was 38 kg, and in Comparative Example 3, the total amount of second deionized water and liquid alkali used during activation was 90 kg. This analysis shows that the preparation method of the hydrogenation catalyst provided by the present invention consumes far less alkali during the activation process than the preparation methods disclosed in existing patents. Therefore, the preparation method of the hydrogenation catalyst provided by the present invention can significantly reduce catalyst production costs, and also produces less waste liquid, making it more environmentally friendly.

[0140] Figure 3 This is a schematic diagram illustrating the application of the hydrogenation catalyst in the preparation of 1,3-butanediol according to an embodiment of the present invention.

[0141] In some embodiments of the present invention, the application of the hydrogenation catalyst in the preparation of 1,3-butanediol is described in reference to... Figure 3 This includes the following steps:

[0142] S100: Acetaldehyde is condensed under the action of an alkaline catalyst to obtain a condensation solution, wherein the condensation solution includes acetaldehyde, butenal and 3-hydroxybutanal.

[0143] S200: The condensate is heat-treated under stirring to obtain a 3-hydroxybutyraldehyde mixed solution;

[0144] S300: The gas-liquid mixture consisting of the 3-hydroxybutyraldehyde mixed solution and hydrogen is passed through the hydrogenation catalyst to carry out a hydrogenation reaction to obtain 1,3-butanediol.

[0145] Specifically, by heat-treating the condensate under stirring in step S200, the utilization rate of the raw material acetaldehyde can be significantly improved, making the reaction of the raw material acetaldehyde more complete, reducing its recovery energy consumption, and further increasing the yield of 3-hydroxybutyraldehyde. This solves the problem of low acetaldehyde utilization in the prior art and achieves the goal of higher yield of the target product 1,3-butanediol. In step S300, a gas-liquid mixture consisting of a 3-hydroxybutyraldehyde mixed solution and hydrogen is passed through the hydrogenation catalyst to carry out the hydrogenation reaction. The hydrogenation catalyst has high hydrogenation activity, which can reduce hydrogenation costs and energy consumption while maintaining the quality of 1,3-butanediol, making it suitable for industrial production.

[0146] In some embodiments of the present invention, the alkaline catalyst is a supported solid alkaline catalyst.

[0147] In some embodiments of the present invention, the reaction temperature of the heat treatment in step S200 is 30-100℃, and the reaction time is 1-5h. This is beneficial to improving the utilization rate of the raw material acetaldehyde, making the reaction of the raw material acetaldehyde more complete, reducing its recovery energy consumption, further improving the yield of 3-hydroxybutyraldehyde, achieving the goal of increasing the yield of the target compound 1,3-butanediol, and solving the problem of low acetaldehyde utilization rate in the prior art.

[0148] In some specific embodiments of the present invention, the heat treatment in step S200 is the stirring heat treatment of the condensation liquid in air, and the reaction temperature of the heat treatment in step S200 is 50-80℃, and the reaction time is 1-3h.

[0149] In some embodiments of the present invention, the hydrogenation reaction in step S300 is carried out in a fixed-bed reactor, the reaction temperature is 50-140°C, the reaction pressure is 2-10 MPa, and the volume hourly space velocity of the 3-hydroxybutyraldehyde mixed solution is 0.1-6 h⁻¹. -1 This allows the hydrogenation catalyst to maintain high hydrogenation activity, while preserving the quality of the 1,3-butanediol, thereby reducing hydrogenation costs and energy consumption, making it suitable for industrial production.

[0150] In the embodiments of the present invention, the volume hourly space velocity of the 3-hydroxybutyraldehyde mixed solution refers to the amount of 3-hydroxybutyraldehyde mixed solution treated per unit volume of hydrogenation catalyst per unit time.

[0151] In some specific embodiments of the present invention, the hydrogenation reaction in step S300 is carried out in a fixed-bed reactor, the reaction temperature is 50-100°C, the reaction pressure is 3-8 MPa, and the volume hourly space velocity of the 3-hydroxybutyraldehyde mixed solution is 0.5-5 h⁻¹. -1 .

[0152] In some embodiments of the present invention, the acetaldehyde content in the condensation liquid is 5-10 wt%, the butenal content is 0.5-3 wt%, and the 3-hydroxybutyraldehyde content is 60-80 wt%, based on the weight percentage of the condensation liquid.

[0153] In some specific embodiments of the present invention, the condensation liquid further includes a small amount of impurities and water. In the condensation liquid, the content of acetaldehyde is 5-10 wt%, the content of butenal is 0.5-3 wt%, the content of 3-hydroxybutyraldehyde is 60-80 wt%, the content of impurities is 1-2 wt%, and the remainder is water, based on the weight percentage of the condensation liquid.

[0154] In some specific embodiments of the present invention, the impurities include trace amounts of butyraldehyde, acetic acid, ethanol, and other substances.

[0155] Examples 8-11 involve condensing acetaldehyde under the action of an alkaline catalyst to obtain a condensation solution; the condensation solution is then subjected to stirring and heat treatment to obtain a 3-hydroxybutyraldehyde mixed solution.

[0156] Example 8

[0157] In a specific implementation embodiment, the condensation solution contains, by weight percentage, 5 wt% acetaldehyde, 0.5 wt% butenal, 60 wt% 3-hydroxybutyraldehyde, and 1 wt% impurities. The condensation solution is stirred at 60°C for 2 hours in air. The resulting 3-hydroxybutyraldehyde mixed solution contains, by weight percentage, 1 wt% acetaldehyde, 1.5 wt% butenal, 63 wt% 3-hydroxybutyraldehyde, and 1.2 wt% impurities.

[0158] Example 9

[0159] In a specific implementation embodiment, the condensation solution contains, by weight percentage, 8 wt% acetaldehyde, 2 wt% butenal, 70 wt% 3-hydroxybutyraldehyde, and 1.5 wt% impurities. The condensation solution is stirred at 50°C for 3 hours in air. The resulting 3-hydroxybutyraldehyde mixed solution contains, by weight percentage, 1.8 wt% acetaldehyde, 3.8 wt% butenal, 74.4 wt% 3-hydroxybutyraldehyde, and 1.6 wt% impurities.

[0160] Example 10

[0161] In a specific implementation embodiment, the condensation solution contains, by weight percentage, 10 wt% acetaldehyde, 3 wt% butenal, 70 wt% 3-hydroxybutyraldehyde, and 2 wt% impurities. The condensation solution is stirred at 70°C for 2 hours in air. The resulting 3-hydroxybutyraldehyde mixed solution contains, by weight percentage, 2.3 wt% acetaldehyde, 4 wt% butenal, 76.7 wt% 3-hydroxybutyraldehyde, and 2.3 wt% impurities.

[0162] Example 11

[0163] In a specific implementation, the condensation solution contains, by weight percentage, 8 wt% acetaldehyde, 1.8 wt% butenal, 80 wt% 3-hydroxybutyraldehyde, and 1.5 wt% impurities. The condensation solution is stirred at 80°C for 1 hour in air. The resulting 3-hydroxybutyraldehyde mixed solution contains, by weight percentage, 2 wt% acetaldehyde, 3.2 wt% butenal, 84.6 wt% 3-hydroxybutyraldehyde, and 1.8 wt% impurities.

[0164] Analysis of Examples 8-11 shows that after heating and stirring, the acetaldehyde content in the raw materials decreases, while the content of the generated 3-hydroxybutyraldehyde increases, with the highest content of 3-hydroxybutyraldehyde observed in Example 11. The high content of 3-hydroxybutyraldehyde results in good conversion and selectivity in subsequent hydrogenation examples; therefore, the 3-hydroxybutyraldehyde mixed solution obtained in Example 11 was selected for hydrogenation preparation experiments with hydrogen gas.

[0165] Specifically, in a fixed-bed reactor, a gas-liquid mixture consisting of a 3-hydroxybutyraldehyde mixed solution prepared in Example 11 and hydrogen gas was passed through the hydrogenation catalysts prepared in Examples 1-7 to carry out hydrogenation reactions, respectively, to produce 1,3-butanediol. The catalyst performance was evaluated by analyzing the conversion rates of acetaldehyde, butenal, and 3-hydroxybutyraldehyde, as well as the selectivity of the produced 1,3-butanediol, using gas chromatography.

[0166] In the specific implementation scheme, 100 mL of the hydrogenation catalyst prepared in Examples 1-7 is loaded into a fixed-bed reaction tube with an inner diameter of 50 mm. The 3-hydroxybutyraldehyde mixed solution prepared in Example 11, along with hydrogen gas, is introduced from the bottom of the reactor after passing through a preheater. The reaction pressure is 8 MPa, the reaction temperature is 90 °C, and the feed volume hourly space velocity of the 3-hydroxybutyraldehyde mixed solution is 5 h⁻¹. -1 The obtained products were analyzed by gas chromatography. The specific results of acetaldehyde conversion, butenaldehyde conversion, 3-hydroxybutyraldehyde conversion, and the selectivity of the prepared 1,3-butanediol are shown in Table 3.

[0167] Table 3

[0168]

[0169]

[0170] As shown in Table 3, after the 3-hydroxybutyraldehyde mixed solution prepared in Example 11 and the gas-liquid mixture composed of hydrogen were passed through the hydrogenation catalysts prepared in Examples 1-7 for hydrogenation reaction, the conversion rates of acetaldehyde in the 3-hydroxybutyraldehyde mixed solution prepared in Example 11 were all above 99%, the conversion rates of butenal were all above 98%, and the highest conversion rate of 3-hydroxybutyraldehyde reached 100%, while the selectivity of 1,3-butanediol reached a maximum of 99.5%. This indicates that the hydrogenation catalyst prepared by the present invention has good hydrogenation activity and high hydrogenation selectivity in the reaction of 3-hydroxybutyraldehyde to 1,3-butanediol.

[0171] While embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations fall within the scope and spirit of the invention as set forth in the claims. Furthermore, the invention described herein may have other embodiments and can be implemented or carried out in various ways.

Claims

1. A hydrogenation catalyst, characterized in that, It is used in the hydrogenation reaction of 3-hydroxybutyraldehyde to prepare 1,3-butanediol, wherein the hydrogenation catalyst includes nickel, aluminum, silicon, and molybdenum; The content of nickel is 40-60 wt%, the content of aluminum is 20-40 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt%, based on the weight percentage of the hydrogenation catalyst. The hydrogenation catalyst has a particulate structure with a porous surface. The particulate structure includes a semi-through-pore portion and a solid portion. The semi-through-pore portion includes a plurality of pore structures and is disposed on the surface of the solid portion. The preparation method of the hydrogenation catalyst includes the following steps: S0: Provide a metal raw material, said metal raw material including nickel, aluminum, silicon, and molybdenum, wherein, by weight percentage of said metal raw material, the content of nickel is 35-60 wt%, the content of aluminum is 30-50 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt%; S1: The metal raw material is melted at high temperature into an alloy block, and then the alloy block is crushed into metal alloy particles, the average particle size of the metal alloy particles being 2-8 mm. S2: The metal alloy particles are subjected to cyclic activation treatment with alkaline solution to obtain alkaline-activated alloy particles; S3: The alloy particles activated by alkali are washed with deionized water until the pH of the collected waste liquid is 7-9, in order to obtain the hydrogenation catalyst. The step S2, which involves cyclically activating the metal alloy particles with an alkaline solution, includes: S21: Provide an intermediate storage tank containing second deionized water, and inject the second deionized water into a reactor containing the metal alloy particles through a circulation pump. After the second deionized water flows through the metal alloy particles, it returns to the intermediate storage tank to form a circulation loop. S22: Liquid alkali is added to the intermediate storage tank by an alkali pump, and the liquid alkali is mixed with the second deionized water to obtain the diluted alkali solution; S23: The alkaline solution is injected into the reactor through the circulating pump, and the alkaline solution flows through the metal alloy particles to activate the metal alloy particles, and then returns to the intermediate storage tank. S24: Repeat steps S22 and S23 until all the liquid alkali of the preset amount is added to the intermediate storage tank, then continue with step S23 so that the alkali solution activates the metal alloy particles for 1-6 hours.

2. The hydrogenation catalyst according to claim 1, characterized in that, In the hydrogenation catalyst, the content of nickel is 45-60 wt%, the content of aluminum is 30-40 wt%, the content of silicon is 8-13 wt%, and the content of molybdenum is 0.5-5 wt%, based on the weight percentage of the hydrogenation catalyst.

3. The application of a hydrogenation catalyst as described in any one of claims 1-2 in the preparation of 1,3-butanediol, characterized in that, Includes the following steps: S100: Acetaldehyde is condensed under the action of an alkaline catalyst to obtain a condensation solution, wherein the condensation solution includes acetaldehyde, butenal and 3-hydroxybutanal. S200: The condensate is heat-treated under stirring to obtain a 3-hydroxybutyraldehyde mixed solution; S300: The gas-liquid mixture consisting of the 3-hydroxybutyraldehyde mixed solution and hydrogen is passed through the hydrogenation catalyst to carry out a hydrogenation reaction to obtain 1,3-butanediol.

4. The application according to claim 3, characterized in that, The heat treatment in step S200 is performed at a temperature of 30-100°C for 1-5 hours.

5. The application according to claim 3, characterized in that, The hydrogenation reaction in step S300 is carried out in a fixed-bed reactor at a reaction temperature of 50-140°C and a reaction pressure of 2-10 MPa. The volume hourly space velocity (VHSV) of the 3-hydroxybutyraldehyde mixed solution is 0.1-6 h⁻¹. -1 .

6. The application according to claim 3, characterized in that, In the condensation solution, the content of acetaldehyde is 5-10 wt%, the content of butenal is 0.5-3 wt%, and the content of 3-hydroxybutyraldehyde is 60-80 wt%, based on the weight percentage of the condensation solution.

7. A method for preparing a hydrogenation catalyst as described in any one of claims 1-2, characterized in that, Includes the following steps: S0: Provide a metal raw material, said metal raw material including nickel, aluminum, silicon, and molybdenum, wherein, by weight percentage of said metal raw material, the content of nickel is 35-60 wt%, the content of aluminum is 30-50 wt%, the content of silicon is 5-15 wt%, and the content of molybdenum is 0.1-6 wt%; S1: The metal raw material is melted at high temperature into an alloy block, and then the alloy block is crushed into metal alloy particles, the average particle size of the metal alloy particles being 2-8 mm. S2: The metal alloy particles are subjected to cyclic activation treatment with alkaline solution to obtain alkaline-activated alloy particles; S3: The alloy particles activated by alkali are washed with deionized water until the pH of the collected waste liquid is 7-9, in order to obtain the hydrogenation catalyst. The step S2, which involves cyclically activating the metal alloy particles with an alkaline solution, includes: S21: Provide an intermediate storage tank containing second deionized water, and inject the second deionized water into a reactor containing the metal alloy particles through a circulation pump. After the second deionized water flows through the metal alloy particles, it returns to the intermediate storage tank to form a circulation loop. S22: Liquid alkali is added to the intermediate storage tank by an alkali pump, and the liquid alkali is mixed with the second deionized water to obtain the diluted alkali solution; S23: The alkaline solution is injected into the reactor through the circulating pump, and the alkaline solution flows through the metal alloy particles to activate the metal alloy particles, and then returns to the intermediate storage tank. S24: Repeat steps S22 and S23 until all the liquid alkali of the preset amount is added to the intermediate storage tank, then continue with step S23 so that the alkali solution activates the metal alloy particles for 1-6 hours.

8. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, In step S2, the activation treatment time is 1-6 hours, the activation treatment temperature is greater than or equal to room temperature and less than or equal to 60°C, and the alkaline solution is a solution of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate and sodium bicarbonate.

9. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, In step S3, the temperature of the washing process is greater than or equal to room temperature and less than or equal to 80°C.

10. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, The weight of the second deionized water in the intermediate storage tank is 5-20 times the weight of the metal alloy particles, and the total weight of the liquid alkali added to the intermediate storage tank is 1-4 times the weight of the metal alloy particles.

11. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, In step S23, the feed mass hourly space velocity of the circulating pump is 10-80 h⁻¹. -1 .

12. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, The liquid alkali is a liquid alkali with a mass concentration of 32wt%.

13. The method for preparing the hydrogenation catalyst according to claim 7, characterized in that, The liquid alkali is a 32wt% liquid alkali prepared by one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and sodium bicarbonate.

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