Hydrogenation catalysts, processes for their preparation and use

Abstract

The application provides a hydrogenation catalyst applied to preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol, the hydrogenation catalyst comprising nickel, aluminum, a first promoting component and a second promoting component, the hydrogenation catalyst being in a granular shape; the first promoting component comprising a first metal component, the second promoting component comprising a second metal component, the first metal component comprising at least one of platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten and germanium, and the second metal component comprising at least one of lanthanide metal elements; the content of the nickel being 40-80% by weight percentage of the hydrogenation catalyst, the content of the aluminum being 20-60% by weight percentage of the hydrogenation catalyst, the content of the first promoting component being less than or equal to 10% by weight percentage of the hydrogenation catalyst, and the content of the second promoting component being less than or equal to 10% by weight percentage of the hydrogenation catalyst. The application solves the problem of high content of methyl BDO in preparation of 1,4-butanediol by hydrogenation of 1,4-butynediol. The application also provides a preparation method of the hydrogenation catalyst and application thereof.

Description

Technical Field

[0001] This invention relates to the field of metal alloy catalyst technology, and in particular to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] 1,4-Butane-1,4-diol (BDO) is an important fine chemical product, mainly used in the production of tetrahydrofuran (THF), γ-butyrolactone (GBL), polybutylene terephthalate (PBT), polyurethane (PU), copolyester ethers (COPEs), polytetramethylene glycol ether, N-methylpyrrolidone (NMP), and polyvinylpyrrolidone (PVP), etc. Taking PBT as an example, in recent years, PBT has been mainly used in PBT modification, PBT fiber drawing, PBT film drawing, and optical fiber sheathing. After reinforcement and modification, PBT can be widely used in automobile manufacturing, electronics, instrumentation, lighting, home appliances, textiles, machinery, and communications. Furthermore, reinforced and modified PBT is also used in the synthesis of vitamin B6, pesticides, herbicides and solvents, humectants, plasticizers, pharmaceutical intermediates, chain extenders, and adhesives. In addition, the rapid development of biodegradable plastic polybutylene succinate (PBS) will greatly stimulate and promote the production and development of BDO. Statistics show that the demand for BDO has grown rapidly in recent years, making it one of the fastest-growing fine chemicals. Reports indicate that the planned annual production capacity in China will reach 25 million tons in the future.

[0003] Among the various BDO production processes, the Reppe process, using formaldehyde and acetylene as raw materials, is currently the most widely adopted, technologically mature, and economically efficient route in industry. The Reppe process for producing BDO involves two steps: the first step involves the reaction of formaldehyde and acetylene with a copper acetylene catalyst to produce 1,4-butynediol (But-2-yne-1,4-diol, abbreviated as BYD); the second step is the catalytic hydrogenation of BYD to produce BDO. Therefore, BYD is an important intermediate in the catalytic hydrogenation preparation of BDO.

[0004] Depending on the process, there are generally two types of catalytic hydrogenation for the production of BDO using BYD. One type is two-stage hydrogenation: the first stage involves low-pressure hydrogenation of BYD in a suspended bed or slurry bed reactor to obtain crude BDO solution, with a reaction temperature of 60-70℃ and a reaction pressure of 2-2.5MPa, typically using conventional powdered nickel-aluminum catalysts; the second stage involves high-pressure hydrogenation of the crude BDO solution containing a small amount of hydrogenated unsaturated carbonyl compounds in a fixed bed reactor, with a reaction temperature of 120-160℃ and a reaction pressure of 12-20MPa, industrially using supported nickel catalysts. The main purpose of this second stage is to further hydrogenate the small amount of unsaturated carbonyl compounds generated in the first stage hydrogenation (such as hydroxybutyral, hemiacetal, and acetal formed by the isomerization of butenediol), converting them entirely into BDO. This process technology mainly includes the ISP process and the domestic three-dimensional process. Another process uses fixed-bed nickel-aluminum catalysts in both stages, with catalyst particles of 3-8 mm in size, mixed and packed. The pressure in both stages is 25-30 MPa, and the reaction temperature is 110-145℃. The first-stage reactor adopts liquid-phase circulation and gas-phase circulation to facilitate the rapid removal of reaction heat. This process mainly includes the Invista (pre-DuPont) process and the Frontech process. The advantages of this process are high product quality, low impurity content, and the use of a fixed-bed continuous process, which is simple to operate and stable.

[0005] Currently, the BDO plants operating in China, as well as those planned in recent years, mainly utilize the Invista (formerly DuPont) and Frontech processes. However, with the continuous upgrading of downstream customer demands, the requirements for trace impurities in BDO products are becoming increasingly stringent. For example, higher requirements are being placed on methyl-1,4-butanediol (referred to as methyl BDO). For instance, for GBL to achieve electronic-grade purity, the BDO wt% requirement must be ≥99.9%; the purity requirement for THF used in the production of polytetrahydrofuran (terathane(R) 1400, abbreviated as PTMEG) even requires BDO wt% ≥99.95%. When using BDO, the methylbutanediol content needs to be strictly controlled. However, the dehydrogenated products of methylbutanediol are 2-methylbutyrolactone or 3-methylbutyrolactone, with a boiling point difference of only 2-3°C. The dehydration of methyl BDO produces 1-methyltetrahydrofuran and 2-methyltetrahydrofuran, with a boiling point difference also within this range, making separation particularly difficult.

[0006] Chinese patent CN109851477A reports on optimizing the BDO production process to reduce methyl BDO content. This primarily involves optimizing and controlling the formaldehyde content in the BYD refining stage, controlling the 1,4-isodiol content, and adding a certain amount of methanol. It is well known that reducing the formaldehyde content in the BYD refining stage requires high energy consumption and increases the BYD concentration. Furthermore, demineralized water needs to be added during hydrogenation to lower the concentration, and water needs to be removed during the final BDO product distillation stage, increasing steam consumption and distillation load. Similarly, the addition of methanol requires distillation in subsequent processes, further increasing distillation load and steam consumption.

[0007] Chinese patent CN200710096422.3 discloses a method for producing BDO, which can produce BDO with a purity of about 99.8%. The main purpose is to reduce the yield of acetal. The method involves the content of methylbutanediol, but it does not make any control to reduce its production or provide any guidance on reducing its content. In the disclosed examples, the content of methylbutanediol is between 500 and 1000 ppm, and the content of methylbutanediol is basically between 800 and 1000 ppm for most of the operation cycle. Only in the first 24 hours of operation is the content of methylbutanediol at 500 ppm.

[0008] Chinese patent CN101284762A discloses a method for preparing very pure 1,4-butanediol. Through multi-stage distillation and optimization of the distillation column structure and process, the methyl BDO content is reduced to 0.07%. However, since the physical properties of methyl BDO are very similar to those of BDO, distillation alone cannot completely solve the problem of high methyl BDO content. Currently, solutions for high methyl BDO content are based on process or equipment improvements; there are no reports on developing hydrogenation catalysts specifically for addressing this issue.

[0009] Therefore, it is necessary to develop a novel hydrogenation catalyst, its preparation method, and its application to avoid the aforementioned problems existing in the prior art. Summary of the Invention

[0010] The purpose of this invention is to provide a novel hydrogenation catalyst, its preparation method, and its application, which solves the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0011] To achieve the above objectives, the present invention provides a hydrogenation catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol. The hydrogenation catalyst comprises nickel, aluminum, a first promoting component, and a second promoting component, and the hydrogenation catalyst is in particulate form.

[0012] The first promoting component contains a first metal component, and the second promoting component contains a second metal component. The first metal component includes at least one of platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten, and germanium. The second metal component includes at least one of the lanthanide metal elements.

[0013] The content of nickel is 40-80% and the content of aluminum is 20-60% by weight percentage of the hydrogenation catalyst, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%.

[0014] The beneficial effects of the hydrogenation catalyst of the present invention are as follows: the hydrogenation catalyst comprises nickel, aluminum, a first promoting component, and a second promoting component, and the hydrogenation catalyst is in particulate form; the first promoting component comprises a first metal component, and the second promoting component comprises a second metal component; the first metal component comprises at least one selected from platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten, and germanium, and the second metal component comprises at least one lanthanide metal element; the nickel content is 40-80% and the aluminum content is 20-60% by weight percentage of the hydrogenation catalyst, and the first promoting component... The content of the first metal component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%, thereby improving the catalytic performance of the hydrogenation catalyst in the hydrogenation of 1,4-butynediol to 1,4-butanediol. The interaction between the first and second metal components optimizes the crystal phase structure of the alloy and refines the grain size, thereby improving the plasticity of the alloy and adjusting its acidity and alkalinity. Ultimately, this improves the catalytic performance of the hydrogenation catalyst. When the hydrogenation catalyst of this invention is applied to the hydrogenation of 1,4-butynediol to 1,4-butanediol, the content of methyl BDO in 1,4-butanediol is significantly reduced after hydrogenation. Therefore, this invention solves the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0015] Optionally, in the hydrogenation catalyst, the content of nickel is 45-70% and the content of aluminum is 25-50% by weight percentage, the content of the first promoting component is 0.1-5%, and the content of the second promoting component is 0.1-5%.

[0016] Optionally, the first metal component includes at least one of platinum, titanium, zirconium, bismuth, manganese and tungsten, and the second metal component includes at least one of lanthanum, cerium, neodymium and samarium.

[0017] Another object of the present invention is to provide a method for preparing a hydrogenation catalyst, comprising the following steps:

[0018] S0: Provide a metal alloy raw material, the metal alloy raw material comprising nickel, aluminum, a first promoting component and a second promoting component, the first promoting component comprising a first metal component, the second promoting component comprising a second metal component, the first metal component comprising at least one of platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten and germanium, the second metal component comprising at least one of lanthanide metal elements, wherein the content of nickel is 30-70% and the content of aluminum is 30-70% by weight percentage of the metal alloy raw material, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%.

[0019] S1: The metal alloy raw material is melted into a block alloy, and then the block alloy is crushed into alloy particles;

[0020] S2: The alloy particles are subjected to heat treatment, cyclic activation treatment and washing treatment in sequence to obtain the hydrogenation catalyst.

[0021] The beneficial effects of the preparation method of the hydrogenation catalyst described in this invention are as follows: the preparation method of the hydrogenation catalyst is simple and suitable for large-scale production, and the prepared hydrogenation catalyst can solve the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0022] Optionally, in the metal alloy raw material, the content of nickel is 40-59% and the content of aluminum is 40-59% by weight, the content of the first promoting component is 0.1-5%, and the content of the second promoting component is 0.1-5%.

[0023] Optionally, the first metal component includes at least one of platinum, titanium, zirconium, bismuth, manganese and tungsten, and the second metal component includes at least one of lanthanum, cerium, neodymium and samarium.

[0024] Optionally, the first promoting component is an elemental form of the first metal component or an aluminum alloy of the first metal component, and the second promoting component is an elemental form of the second metal component or an aluminum alloy of the second metal component.

[0025] Optionally, the particle size of the metal particles is 1-8 mm.

[0026] Optionally, the heat treatment temperature is 300-800 degrees Celsius, and the heat treatment time is 1-8 hours.

[0027] Optionally, the heat treatment is carried out in an inert atmosphere or a nitrogen atmosphere, the temperature of the heat treatment is 300-600 degrees Celsius, and the time of the heat treatment is 1-4 hours.

[0028] Optionally, the cyclic activation treatment step includes: subjecting the heat-treated alloy particles to the cyclic activation treatment using an alkaline solution, wherein the alkaline solution is a sodium hydroxide solution with a concentration of 0.1-10% and a weight hourly space velocity (WHSV) of 5-100 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-100 degrees Celsius, and the time of the cyclic activation treatment is 1-8 hours.

[0029] Optionally, the concentration of the sodium hydroxide solution is 0.3-5%, and the weight hourly space velocity (WHSV) of the sodium hydroxide solution is 10-50 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-80 degrees Celsius, and the time of the cyclic activation treatment is 2-5 hours.

[0030] Optionally, the washing process includes: washing the alloy particles that have undergone the cyclic activation treatment with deionized water until the pH value of the deionized water after the washing treatment is 7-9, and stopping the washing treatment at a temperature of 25-100 degrees Celsius.

[0031] Another object of the present invention is to provide an application of a hydrogenation catalyst, wherein the hydrogenation catalyst is placed in a fixed-bed reactor, and 1,4-butynediol aqueous solution and hydrogen are introduced into the fixed-bed reactor in parallel through nitrogen purging to carry out the hydrogenation reaction, thereby obtaining 1,4-butanediol.

[0032] The beneficial effects of applying the hydrogenation catalyst described in this invention are as follows: when the hydrogenation catalyst is applied to the hydrogenation of 1,4-butynediol to prepare 1,4-butanediol, the conversion rate of 1,4-butynediol is above 99.5%, the content of methyl BDO is below 0.007%, and the content of butanol is below 0.61%. This invention solves the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to prepare 1,4-butanediol.

[0033] Optionally, the 1,4-butynediol aqueous solution comprises formaldehyde and 1,4-butynediol, wherein the content of 1,4-butynediol is 10-60% by weight, the content of formaldehyde is 0.1-1.0%, the pH value of the 1,4-butynediol aqueous solution is 4-8, and the weight hourly space velocity of the 1,4-butynediol aqueous solution is 0.01-10 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-10):1, the temperature of the hydrogenation reaction is 25-150 degrees Celsius, and the pressure of the hydrogenation reaction is 0.1013-30 MPa.

[0034] Optionally, in the 1,4-butynediol aqueous solution, the content of 1,4-butynediol is 20-50% by weight, the content of formaldehyde is 0.2-0.5%, the pH value of the 1,4-butynediol aqueous solution is 4-6, and the weight hourly space velocity of the 1,4-butynediol aqueous solution is 0.1-5 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-5):1, the temperature of the hydrogenation reaction is 80-150 degrees Celsius, and the pressure of the hydrogenation reaction is 25-30 MPa. Attached Figure Description Detailed Implementation

[0035] 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.

[0036] An embodiment of the present invention provides a hydrogenation catalyst for the hydrogenation of 1,4-butynediol to 1,4-butanediol. The hydrogenation catalyst comprises nickel, aluminum, a first promoting component, and a second promoting component, and the hydrogenation catalyst is in particulate form.

[0037] The first promoting component contains a first metal component, and the second promoting component contains a second metal component. The first metal component includes at least one of platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten, and germanium. The second metal component includes at least one of the lanthanide metal elements.

[0038] The content of nickel is 40-80% and the content of aluminum is 20-60% by weight percentage of the hydrogenation catalyst, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%.

[0039] Specifically, the hydrogenation catalyst comprises nickel, aluminum, a first promoting component, and a second promoting component, and the hydrogenation catalyst is in particulate form; the first promoting component comprises a first metal component, and the second promoting component comprises a second metal component. The first metal component includes at least one selected from platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten, and germanium, and the second metal component includes at least one lanthanide metal element; the nickel content is 40-80% by weight of the hydrogenation catalyst, the aluminum content is 20-60%, and the content of the first promoting component is less than or equal to... The content of the second promoting component is less than or equal to 10%, which improves the catalytic performance of the hydrogenation catalyst in the hydrogenation of 1,4-butynediol to 1,4-butanediol. The interaction between the first and second metal components optimizes the crystal structure of the alloy and refines the grain size, thereby improving the plasticity and acid-base properties of the alloy, ultimately enhancing the catalytic performance of the hydrogenation catalyst. When the hydrogenation catalyst of this invention is applied to the hydrogenation of 1,4-butynediol to 1,4-butanediol, the content of methyl BDO in 1,4-butanediol is significantly reduced after hydrogenation. Therefore, this invention solves the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0040] In some embodiments of the present invention, the hydrogenation catalyst contains, by weight percentage, 45-70% nickel, 25-50% aluminum, 0.1-5% first promoting component, and 0.1-5% second promoting component. In some specific embodiments, by weight percentage of the hydrogenation catalyst, the nickel content is 45-55%, the aluminum content is 40-50%, the first promoting component is 0.5-3%, and the second promoting component is 0.5-3%.

[0041] In some embodiments of the present invention, the first metal component includes at least one selected from platinum, titanium, zirconium, bismuth, manganese, and tungsten, and the second metal component includes at least one selected from lanthanum, cerium, neodymium, and samarium.

[0042] An embodiment of the present invention provides a method for preparing a hydrogenation catalyst, comprising the following steps:

[0043] S0: Provide a metal alloy raw material, the metal alloy raw material comprising nickel, aluminum, a first promoting component and a second promoting component, the first promoting component comprising a first metal component, the second promoting component comprising a second metal component, the first metal component comprising at least one of platinum, ruthenium, molybdenum, titanium, zirconium, copper, iron, chromium, cobalt, niobium, manganese, boron, bismuth, tungsten and germanium, the second metal component comprising at least one of lanthanide metal elements, wherein the content of nickel is 30-70% and the content of aluminum is 30-70% by weight percentage of the metal alloy raw material, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%.

[0044] S1: The metal alloy raw material is melted into a block alloy, and then the block alloy is crushed into alloy particles;

[0045] S2: The alloy particles are subjected to heat treatment, cyclic activation treatment, and washing treatment in sequence to obtain the hydrogenation catalyst. The preparation method of the hydrogenation catalyst provided by the present invention is simple, suitable for large-scale production, and the prepared hydrogenation catalyst can solve the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0046] In some embodiments of the present invention, the nickel content in the metal alloy raw material is 40-59% by weight, the aluminum content is 40-59%, the content of the first promoting component is 0.1-5%, and the content of the second promoting component is 0.1-5%. In some specific embodiments, the nickel content is 40-49% by weight, the aluminum content is 50-59%, the content of the first promoting component is 0.5-3%, and the content of the second promoting component is 0.5-3%.

[0047] In some embodiments of the present invention, the first metal component includes at least one selected from platinum, titanium, zirconium, bismuth, manganese, and tungsten, and the second metal component includes at least one selected from lanthanum, cerium, neodymium, and samarium.

[0048] In some embodiments of the present invention, the first promoting component is an elemental form of the first metal component or an aluminum alloy of the first metal component, and the second promoting component is an elemental form of the second metal component or an aluminum alloy of the second metal component. In some specific embodiments, the first promoting component is an aluminum alloy of the first metal component, and the second promoting component is an aluminum alloy of the second metal component.

[0049] In some embodiments of the present invention, the particle size of the metal particles is 0.5-15 mm. In some specific embodiments, the particle size of the metal particles is 1-8 mm.

[0050] In some embodiments of the present invention, the heat treatment temperature is 300-800 degrees Celsius, and the heat treatment time is 1-8 hours.

[0051] In some embodiments of the present invention, the heat treatment is carried out in an inert atmosphere or a nitrogen atmosphere, the temperature of the heat treatment is 300-600 degrees Celsius, and the time of the heat treatment is 1-4 hours.

[0052] In some embodiments of the present invention, the step of the cyclic activation treatment includes: the alloy particles that have undergone the heat treatment are subjected to the cyclic activation treatment using an alkaline solution, wherein the alkaline solution is a sodium hydroxide solution with a concentration of 0.1-10% and a weight hourly space velocity (WHSV) of 5-100 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-100 degrees Celsius, and the time of the cyclic activation treatment is 1-8 hours. In some specific embodiments, the concentration of the sodium hydroxide solution refers to the percentage of the weight of sodium hydroxide in the sodium hydroxide solution.

[0053] In some embodiments of the present invention, the concentration of the sodium hydroxide solution is 0.3-5%, and the weight hourly space velocity (WHSV) of the sodium hydroxide solution is 10-50 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-80 degrees Celsius, and the time of the cyclic activation treatment is 2-5 hours.

[0054] In some embodiments of the present invention, the washing process includes: washing the alloy particles that have undergone the cyclic activation treatment with deionized water until the pH value of the deionized water after the washing treatment is 7-9, and stopping the washing treatment at a temperature of 25-100 degrees Celsius.

[0055] An embodiment of the present invention provides an application of a hydrogenation catalyst. The hydrogenation catalyst is placed in a fixed-bed reactor, and 1,4-butynediol aqueous solution and hydrogen are introduced into the fixed-bed reactor in parallel through nitrogen purging to carry out the hydrogenation reaction, thereby obtaining 1,4-butanediol.

[0056] Specifically, the hydrogenation catalyst was applied to the hydrogenation of 1,4-butynediol to prepare 1,4-butanediol, achieving a conversion rate of over 99.5%, with methyl BDO content below 0.007% and butanol content below 0.61%. This invention solves the problem of high methyl BDO content in the hydrogenation of 1,4-butynediol to 1,4-butanediol.

[0057] In some embodiments of the present invention, the 1,4-butynediol aqueous solution comprises formaldehyde and 1,4-butynediol, wherein the content of 1,4-butynediol is 10-60% by weight percentage, the content of formaldehyde is 0.1-1.0%, the pH value of the 1,4-butynediol aqueous solution is 4-8, and the weight hourly space velocity of the 1,4-butynediol aqueous solution is 0.01-10 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-10):1, the temperature of the hydrogenation reaction is 25-150 degrees Celsius, and the pressure of the hydrogenation reaction is 0.1013-30 MPa.

[0058] In some embodiments of the present invention, the 1,4-butynediol aqueous solution contains 20-50% 1,4-butynediol by weight, the formaldehyde content is 0.2-0.5%, the pH value of the 1,4-butynediol aqueous solution is 4-6, and the weight hourly space velocity (WHSV) of the 1,4-butynediol aqueous solution is 0.1-5 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-5):1, the temperature of the hydrogenation reaction is 80-150 degrees Celsius, and the pressure of the hydrogenation reaction is 25-30 MPa.

[0059] The beneficial effects of this invention are as follows: by adding the first and second metal components, the crystal structure of the alloy is optimized, resulting in finer grains, improved plasticity, and balanced acidity and alkalinity. Heat treatment further enhances the uniformity and stability of the alloy's crystal structure. Consequently, in the application of the activated hydrogenation catalyst in the preparation of BDO via the BYD hydrogenation reaction, the content of methyl BDO in the BDO solution after hydrogenation is significantly reduced, meeting the market demand for high-quality BDO products. Simultaneously, it reduces butanol content, increases BDO yield, reduces waste generation, and saves energy.

[0060] Example 1

[0061] The following metal alloy raw materials are provided: 430 grams of nickel plate, 270 grams of aluminum ingot, 100 grams of aluminum-manganese alloy with 10% manganese content, and 200 grams of aluminum-cerium alloy with 10% cerium content. After being mixed evenly, the mixture is added to a graphite crucible, heated to 1500 degrees Celsius to melt, and then poured into a mold. After cooling, an alloy block is obtained. The aluminum-manganese alloy with 10% manganese content means that the manganese content is 10% by weight of the aluminum-manganese alloy, and the aluminum-cerium alloy with 10% cerium content means that the cerium content is 10% by weight of the aluminum-cerium alloy.

[0062] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 2-5 mm. The composition of the alloy particles was as follows (by weight percentage): nickel 43%, aluminum 54%, manganese 1%, and cerium 2%. This composition and content of the alloy particles is denoted as Ni. 43 Al 54 Mn1Ce2 has the same composition and content as the metal alloy raw material and alloy particles.

[0063] The alloy particles were heat-treated at 400 degrees Celsius for 3 hours in a nitrogen atmosphere and then cooled to room temperature for later use.

[0064] Accurately weigh 250 grams of heat-treated alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 5 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 20 h⁻¹. -1 The bed temperature was 50°C for 2 hours of cyclic activation treatment, and then the bed temperature was raised to 60°C for another 1.5 hours of cyclic activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 50°C until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The resulting hydrogenation catalyst was designated as Sample 1. ICP analysis showed that Sample 1 contained the following composition by weight percentage: 50.02% nickel, 46.49% aluminum, 1.16% manganese, and 2.33% cerium. Therefore, the composition and content of Sample 1 are denoted as Ni. 50.02 Al 46.49 Mn 1.16 Ce 2.33 .

[0065] Example 2

[0066] The following metal alloy raw materials are provided: 420 grams of nickel plate, 280 grams of aluminum ingot, 150 grams of aluminum-titanium alloy with 10% titanium content, and 150 grams of aluminum-cerium alloy with 10% cerium content. After being mixed evenly, the mixture is added to a graphite crucible, heated to 1500 degrees Celsius to melt, and then poured into a mold. After cooling, an alloy block is obtained. The aluminum-titanium alloy with 10% titanium content means that the titanium content is 10% by weight of the aluminum-titanium alloy, and the aluminum-cerium alloy with 10% cerium content means that the cerium content is 10% by weight of the aluminum-cerium alloy.

[0067] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 2-5 mm. The composition of the alloy particles was as follows (by weight percentage): nickel 42%, aluminum 55%, titanium 1.5%, and cerium 1.5%. This composition and content of the alloy particles is denoted as Ni.42 Al 55 Ti 1.5 Ce 1.5 The composition and content of the metal alloy raw materials and alloy particles are the same;

[0068] The alloy particles were heat-treated at 500 degrees Celsius for 2 hours in a nitrogen atmosphere and then cooled to room temperature for later use.

[0069] Accurately weigh 250 grams of heat-treated alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 10 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 40 h⁻¹. -1 The bed temperature was 45°C for 2 hours of cyclic activation treatment, and then the bed temperature was raised to 50°C for another 2 hours of cyclic activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 40°C until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The resulting hydrogenation catalyst was designated as Sample 2. ICP analysis showed that Sample 2 contained the following composition by weight percentage: 48.70% nickel, 47.83% aluminum, 1.74% titanium, and 1.74% cerium. Therefore, the composition and content of Sample 2 are denoted as Ni. 48.70 Al 47.83 Ti 1.74 Ce 1.74 .

[0070] Example 3

[0071] The following metal alloy raw materials are provided: 420 grams of nickel plate, 280 grams of aluminum ingot, 100 grams of aluminum-bismuth alloy with 5% bismuth content, and 200 grams of aluminum-samarium alloy with 5% samarium content. After being mixed evenly, the mixture is added to a graphite crucible and heated to 1400 degrees Celsius to melt it. Then, it is poured into a mold and cooled to obtain an alloy block. The 5% bismuth aluminum-bismuth alloy means that the bismuth content is 5% by weight of the aluminum-bismuth alloy, and the 5% samarium aluminum-samarium alloy means that the samarium content is 5% by weight of the aluminum-samarium alloy.

[0072] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 2-4 mm. The composition of the alloy particles was as follows (by weight percentage): nickel 42%, aluminum 56.5%, bismuth 0.5%, and samarium 1%. This composition and content of the alloy particles is denoted as Ni. 42 Al 56.5 Bi 0.5 Sm1, the composition and content of the metal alloy raw materials and alloy particles are the same;

[0073] The alloy particles were heat-treated at 450 degrees Celsius for 2 hours in a nitrogen atmosphere and then cooled to room temperature for later use.

[0074] Accurately weigh 250 grams of heat-treated alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 10 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 40 h⁻¹. -1 The bed temperature was 45°C for 3 hours of cyclic activation treatment, and then the bed temperature was raised to 60°C for another hour of cyclic activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 40°C until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The hydrogenation catalyst was obtained and designated as Sample 3. ICP analysis showed that the composition of Sample 3 was as follows (by weight percentage): nickel 49.56%, aluminum 48.67%, bismuth 0.59%, and samarium 1.18%, which is the same composition and content as Sample 1, designated as Ni. 49.56 Al 48.67 Bi 0.59 Sm 1.18 .

[0075] Example 4

[0076] The following metal alloy raw materials are provided: 440 grams of nickel plate, 60 grams of aluminum ingot, 300 grams of aluminum-zirconium alloy with 5% zirconium content, and 200 grams of aluminum-cerium alloy with 10% cerium content. After being mixed evenly, the mixture is added to a graphite crucible, heated to 1500 degrees Celsius to melt, and then poured into a mold. After cooling, an alloy block is obtained. The aluminum-zirconium alloy with 5% zirconium content means that the zirconium content is 5% by weight of the aluminum-zirconium alloy, and the aluminum-cerium alloy with 10% cerium content means that the cerium content is 10% by weight of the aluminum-cerium alloy.

[0077] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 2-4 mm. The composition of the alloy particles was as follows (by weight percentage): nickel 44%, aluminum 52.5%, zirconium 1.5%, and cerium 2%. This composition and content of the alloy particles is denoted as Ni. 44 Al 52.5 Zr 1.5 Ce2 has the same composition and content as the metal alloy raw material and alloy particles.

[0078] The alloy particles were heat-treated at 450 degrees Celsius for 4 hours in an argon atmosphere and then cooled to room temperature for later use.

[0079] Accurately weigh 250 grams of heat-treated alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 10 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 40 h⁻¹. -1 The bed temperature was 45°C for 2 hours of cyclic activation treatment, and then the bed temperature was raised to 60°C for another 2 hours of cyclic activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 40°C until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The resulting hydrogenation catalyst was designated as Sample 4. ICP analysis showed that Sample 4 contained the following composition by weight percentage: 50.96% nickel, 44.99% aluminum, 1.74% zirconium, and 2.32% cerium. Therefore, the composition and content of Sample 4 are denoted as Ni. 50.96 Al 44.99 Zr 1.74 Ce 2.32 .

[0080] Example 5

[0081] The following metal alloy raw materials are provided: 450 grams of nickel plate, 100 grams of aluminum ingot, 150 grams of aluminum-titanium alloy with 10% titanium content, and 300 grams of aluminum-lanthanum-cerium alloy with 5% lanthanum and 5% cerium content. After being mixed evenly, the mixture is added to a graphite crucible, heated to 1500 degrees Celsius to melt, and then poured into a mold. After cooling, an alloy block is obtained. The aluminum-titanium alloy with 10% titanium content means that the titanium content is 10% by weight of the aluminum-titanium alloy. The aluminum-lanthanum-cerium alloy with 5% lanthanum and 5% cerium content means that the lanthanum content is 5% and the cerium content is 5% by weight of the aluminum-lanthanum-cerium alloy.

[0082] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 3-6 mm. The composition of the alloy particles was as follows (by weight percentage): nickel 45%, aluminum 50.5%, titanium 1.5%, lanthanum 1.5%, and cerium 1.5%. This composition and content of the alloy particles is denoted as Ni. 45 Al 50.5 Ti 1.5 La 1.5 Ce 1.5 The composition and content of the metal alloy raw materials and alloy particles are the same;

[0083] The alloy particles were heat-treated at 450 degrees Celsius for 4 hours in a nitrogen atmosphere and then cooled to room temperature for later use.

[0084] Accurately weigh 250 grams of heat-treated alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 10 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 40 h⁻¹. -1 The bed temperature was 40°C for 3 hours of cyclic activation treatment, and then the bed temperature was raised to 60°C for another 2 hours of activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 40°C until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The resulting hydrogenation catalyst was designated as Sample 5. ICP analysis showed that Sample 5 contained the following composition by weight percentage: 51.21% nickel, 43.67% aluminum, 1.71% titanium, 1.71% lanthanum, and 1.70% cerium. Therefore, the composition and content of Sample 5 are denoted as Ni. 51.21 Al 43.67 Ti 1.71 La 1.71 Ce 1.70 .

[0085] Comparative Example 1

[0086] Provide metal alloy raw materials, namely 430 grams of nickel plate and 570 grams of aluminum ingot, mix them evenly and add them to a graphite crucible, heat to 1500 degrees Celsius to melt, then pour into a mold, and obtain an alloy block after cooling;

[0087] The alloy block was crushed and sieved to obtain alloy particles with a particle size of 2-5 mm. The composition of the alloy particles was as follows: nickel content was 43% and aluminum content was 57% by weight. The composition and content of the alloy particles are denoted as Ni. 43 Al 57 The composition and content of the metal alloy raw materials and alloy particles are the same;

[0088] Accurately weigh 250 grams of alloy particles and place them in a quartz glass tube with an inner diameter of 50 mm. A 1% sodium hydroxide solution flows from the bottom of the quartz glass tube through the bed containing the alloy particles at a rate of 10 L / h and then flows out from the top of the quartz glass tube. The weight hourly space velocity (WHSV) of the sodium hydroxide solution is 40 h⁻¹. -1The bed temperature was 40 degrees Celsius for 3 hours of cyclic activation treatment, and then the bed temperature was raised to 50 degrees Celsius for another 2 hours of cyclic activation treatment. After cyclic activation treatment, the bed was washed with deionized water at 40 degrees Celsius until the pH of the washed deionized water was 7-9, at which point the washing treatment was stopped. The resulting hydrogenation catalyst was designated as control sample 1. ICP analysis showed that control sample 1 contained 50.48% nickel and 49.52% aluminum by weight. Therefore, the composition and content of control sample 1 are denoted as Ni. 50.48 Al 49.52 .

[0089] Comparative Example 2

[0090] FAMC-1900, an industrial product manufactured by Shanghai Shengbang Chemical Co., Ltd., was sieved to obtain alloy particles with a particle size of 3-6 mm. These particles were then subjected to cyclic activation treatment, similar to Comparative Example 1, to obtain a hydrogenation catalyst, designated as Comparative Sample 2. ICP analysis revealed that Comparative Sample 2 contained 50.20% nickel and 49.80% aluminum by weight, denoted as Ni. 50.20 Al 49.80 .

[0091] Based on the hydrogenation catalysts prepared from samples 1-5 and comparative samples 1-2, a fixed-bed reactor was used to carry out the reaction of BYD hydrogenation to BDO.

[0092] The conditions for the hydrogenation reaction are as follows: the aqueous solution of 1,4-butynediol includes formaldehyde and 1,4-butynediol, with 1,4-butynediol comprising 40% by weight and formaldehyde comprising 0.2-1.0% by weight; the pH of the aqueous solution of 1,4-butynediol is 5-6; and the weight hourly space velocity (WHSV) of the aqueous solution of 1,4-butynediol is 1.0 h⁻¹. -1 The molar ratio of hydrogen to 1,4-butynediol in the aqueous solution is (2-5):1. The temperature of the hydrogenation reaction is 80-150℃, and the pressure of the hydrogenation reaction is 26-29MPa.

[0093] The hydrogenated solution was analyzed by chromatography to calculate the BYD conversion rate and the contents of methyl BDO and butanol in the hydrogenated solution. The contents of methyl BDO and butanol were expressed as a percentage of the weight of the hydrogenated solution.

[0094] The reaction conditions and analytical results of the catalysts used in the hydrogenation of BYD to prepare BDO for samples 1-5 and control samples 1-2 are shown in Table 1. The formaldehyde content is the formaldehyde content before hydrogenation, the methyl BDO content is the methyl BDO content after hydrogenation, and the butanol content is the butanol content after hydrogenation.

[0095] Table 1

[0096]

[0097] Note: Methyl BDO includes 1-methyl-1,4-butanediol and 2-methyl-1,4-butanediol. The data in Table 1 are analytical data of mixed samples under the same conditions, with the hydrogenation catalyst operating stably for 400-500 hours.

[0098] As shown in Table 1, compared with the control samples 1-2, the content of methyl BDO in the BDO solution of samples 1-5 was significantly reduced after hydrogenation reaction under the condition that the formaldehyde content in the BYD solution was greater than 0.3%, down to one-tenth of that in the control samples. At the same time, the content of butanol was reduced by at least 40% compared with the control samples, achieving unexpected results and showing good application prospects and huge economic benefits.

[0099] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A hydrogenation catalyst used in the hydrogenation of 1,4-butynediol to prepare 1,4-butanediol to reduce the content of methyl BDO in 1,4-butanediol, characterized in that, The hydrogenation catalyst comprises nickel, aluminum, a first promoting component, and a second promoting component, and the hydrogenation catalyst is in the form of granules. The first promoting component contains a first metal component, and the second promoting component contains a second metal component. The first metal component includes at least one of titanium, zirconium, manganese, and bismuth, and the second metal component includes at least one of cerium, lanthanum, and samarium. The content of nickel is 40-80% and the content of aluminum is 20-60% by weight percentage of the hydrogenation catalyst, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%.

2. The hydrogenation catalyst according to claim 1, characterized in that, In the hydrogenation catalyst, the content of nickel is 45-70% and the content of aluminum is 25-50% by weight percentage, the content of the first promoting component is 0.1-5%, and the content of the second promoting component is 0.1-5%.

3. A method for preparing a hydrogenation catalyst as described in any one of claims 1 to 2, characterized in that, Includes the following steps: S0: Provide a metal alloy raw material, the metal alloy raw material comprising nickel, aluminum, a first promoting component and a second promoting component, the first promoting component comprising a first metal component, the second promoting component comprising a second metal component, the first metal component comprising at least one of titanium, zirconium, manganese, and bismuth, the second metal component comprising at least one of cerium, lanthanum, and samarium, wherein, based on the weight percentage of the metal alloy raw material, the nickel content is 30-70%, the aluminum content is 30-70%, the content of the first promoting component is less than or equal to 10%, and the content of the second promoting component is less than or equal to 10%; S1: The metal alloy raw material is melted into a block alloy, and then the block alloy is crushed into alloy particles; S2: The alloy particles are subjected to heat treatment, cyclic activation treatment and washing treatment in sequence to obtain the hydrogenation catalyst.

4. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, In the metal alloy raw material, the content of nickel is 40-59% and the content of aluminum is 40-59% by weight percentage, the content of the first promoting component is 0.1-5%, and the content of the second promoting component is 0.1-5%.

5. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The first promoting component is an elemental form of the first metal component or an aluminum alloy of the first metal component, and the second promoting component is an elemental form of the second metal component or an aluminum alloy of the second metal component.

6. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The particle size of the metal particles is 1-8 mm.

7. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The heat treatment temperature is 300-800 degrees Celsius, and the heat treatment time is 1-8 hours.

8. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The heat treatment is carried out in an inert atmosphere or a nitrogen atmosphere, the temperature of the heat treatment is 300-600 degrees Celsius, and the time of the heat treatment is 1-4 hours.

9. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The cyclic activation treatment step includes: the heat-treated alloy particles undergoing cyclic activation treatment with an alkaline solution, wherein the alkaline solution is a sodium hydroxide solution with a concentration of 0.1-10% and a weight hourly space velocity (WHSV) of 5-100 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-100 degrees Celsius, and the time of the cyclic activation treatment is 1-8 hours.

10. The method for preparing the hydrogenation catalyst according to claim 9, characterized in that, The concentration of the sodium hydroxide solution is 0.3-5%, and the weight hourly space velocity (WHSV) of the sodium hydroxide solution is 10-50 h⁻¹. -1 The temperature of the cyclic activation treatment is 25-80 degrees Celsius, and the time of the cyclic activation treatment is 2-5 hours.

11. The method for preparing the hydrogenation catalyst according to claim 3, characterized in that, The washing process includes: washing the alloy particles that have undergone the cyclic activation treatment with deionized water until the pH value of the deionized water after the washing process is 7-9, and stopping the washing process at a temperature of 25-100 degrees Celsius.

12. The application of a hydrogenation catalyst as described in any one of claims 1 to 2, characterized in that, The hydrogenation catalyst was placed in a fixed-bed reactor. After purging with nitrogen, an aqueous solution of 1,4-butynediol and hydrogen were introduced into the fixed-bed reactor in a co-current flow to carry out the hydrogenation reaction, thus obtaining 1,4-butanediol.

13. The application of the hydrogenation catalyst according to claim 12, characterized in that, The 1,4-butynediol aqueous solution comprises formaldehyde and 1,4-butynediol, wherein, based on the weight percentage of the 1,4-butynediol aqueous solution, the content of 1,4-butynediol is 10-60%, the content of formaldehyde is 0.1-1.0%, the pH value of the 1,4-butynediol aqueous solution is 4-8, and the weight hourly space velocity of the 1,4-butynediol aqueous solution is 0.01-10 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-10):1, the temperature of the hydrogenation reaction is 25-150 degrees Celsius, and the pressure of the hydrogenation reaction is 0.1013-30 MPa.

14. The application of the hydrogenation catalyst according to claim 13, characterized in that, In the 1,4-butynediol aqueous solution, the content of 1,4-butynediol is 20-50% by weight, the content of formaldehyde is 0.2-0.5%, the pH value of the 1,4-butynediol aqueous solution is 4-6, and the weight hourly space velocity of the 1,4-butynediol aqueous solution is 0.1-5 h⁻¹. -1 The molar ratio of hydrogen gas to 1,4-butynediol in the aqueous solution of 1,4-butynediol is (2-5):1, the temperature of the hydrogenation reaction is 80-150 degrees Celsius, and the pressure of the hydrogenation reaction is 25-30 MPa.

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