A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application.

Abstract

This application discloses a catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method, and its application. 3DOM nickel oxide is obtained using a metal-acid coordination method, followed by a partial conversion of the 3DOM nickel oxide to nickel nitride using an ammoniation method, resulting in the 3DOM nickel nitride / nickel oxide catalyst. This application also discloses a method for using the catalyst to perform the hydrogenation reaction of 4-hydroxybutyraldehyde to prepare 1,4-butanediol.

Description

Technical Field

[0001] This application relates to a catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application, belonging to the field of chemical engineering. Background Technology

[0002] 1,4-Butanediol (BDO) is an important organic and fine chemical raw material widely used in pharmaceuticals, chemicals, textiles, papermaking, automobiles, and consumer chemicals. From 1,4-Butanediol, tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma-butyrolactone (GBL), polyurethane resins (PU resins), coatings, plasticizers, and as a solvent and brightening agent in the electroplating industry, it can be used in various applications.

[0003] Before World War II, Germany had already used the Rape process to synthesize 1,4-butanediol from acetylene and formaldehyde. This method solved the danger of operating acetylene under high pressure in many currently researched processes and remains the most important method for producing 1,4-butanediol. In the 1960s, Mitsubishi Oil & Chemical Co., Ltd. of Japan developed a process for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride, and in the 1970s, the company developed a new process for butadiene acetoxylation. In 1971, Toyo Soda Industries, Ltd. of Japan established a butadiene chlorination production plant. In addition, the United States and Japan have successively researched various synthesis methods using propylene or ethylene as raw materials.

[0004] 1,4-Butanediol is a high-value-added chemical product. In existing industrial production, the propylene process, developed by Kuraray (GB1493154A, US4465873A) and now primarily used by Lyondell (CN101084175B, WO2006068680A1, US2002111520A1) and Dalian Chemical Co., Ltd. (US5426250A, TW432037B) in Taiwan, offers advantages such as low investment, low energy consumption, and flexible capacity adjustment. However, this route typically forms 2-methyl-3-hydroxypropanal (MPA) during the carbonylation of allyl alcohol, which is subsequently hydrogenated to 2-methyl-1,3-propanediol. Therefore, the synthesis of 1,4-butanediol using the propylene process generates the byproduct 2-methyl-1,3-propanediol; compared to 1,4-butanediol, 2-methyl-1,3-propanediol has fewer applications and limited demand. Therefore, the presence of 2-methyl-1,3-propanediol as a byproduct in the production process greatly limits the scale and efficiency of the propylene route, reducing the economic viability of synthesizing 1,4-butanediol via the propylene route. Summary of the Invention

[0005] The catalyst prepared in this patent is used in the hydrogenation reaction to prepare 1,4-butanediol. The catalyst has good activity, high conversion rate of 4-hydroxybutyraldehyde and selectivity of 1,4-butanediol, and good stability.

[0006] According to one aspect of this application, a catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol is provided, said catalyst being able to improve the conversion of 4-hydroxybutyraldehyde and the selectivity of 1,4-butanediol;

[0007] The catalyst includes an active component and a support;

[0008] The active component is nickel nitride;

[0009] The carrier is three-dimensional ordered macroporous (3DOM) nickel oxide.

[0010] According to another aspect of this application, a method for preparing the above-mentioned catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol is provided, comprising the following steps:

[0011] The catalyst was prepared by a metal-acid coordination method.

[0012] 3DOM nickel oxide is obtained, and the 3DOM nickel oxide is nitrided to obtain the catalyst.

[0013] The process for obtaining 3DOM nickel oxide includes:

[0014] Raw materials containing a nickel source, citric acid, and a solvent are mixed to obtain a mixed solution. Polystyrene balls are immersed in the mixed solution, dried, and calcined to obtain the 3DOM nickel oxide.

[0015] Specifically, the process includes: mixing citric acid and a nickel source in a solvent to form solution A; placing polystyrene spheres in a vacuum container and evacuating the vacuum; using a Buchner funnel to drop solution A onto the polystyrene spheres to immerse them; and repeating this process several times after drying.

[0016] The nickel source is selected from at least one of nickel nitrate, nickel sulfate, and nickel acetate;

[0017] The solvent is selected from water and / or ethanol;

[0018] The mass ratio of citric acid to nickel source is 1:(1-3);

[0019] Optionally, the mass ratio of the citric acid to the nickel source is any value among 1:1, 1:2, and 1:3, or any range between the two.

[0020] The ratio of the total mass of the citric acid and the nickel source to the volume of the solvent is 1:(2-4)g / ml;

[0021] Optionally, the ratio of the total mass of the citric acid and the nickel source to the volume of the solvent is any value among 1:2, 1:3, and 1:4, or any range between the two.

[0022] The solid-liquid ratio of the polystyrene spheres to the mixed solution is 1:(50~70)g / ml.

[0023] Optionally, the solid-liquid ratio of the polystyrene spheres to the mixed solution is any value among 1:50 g / ml, 1:60 g / ml, and 1:70 g / ml, or any range between two of them.

[0024] The drying temperature is 50–80°C;

[0025] Optionally, the drying temperature is any value among 50°C, 60°C, 70°C, and 80°C, or a range between any two.

[0026] The drying time is 1 to 3 hours;

[0027] Optionally, the drying time is any value among 1h, 2h, and 3h, or a range between any two.

[0028] The calcination temperature is 450–650°C;

[0029] Optionally, the calcination temperature is any value among 450°C, 500°C, 550°C, 600°C, and 650°C, or a range between any two.

[0030] The calcination time is 1 to 6 hours.

[0031] Optionally, the calcination time is any value among 1h, 2h, 3h, 4h, 5h, and 6h, or a range between any two.

[0032] The nitriding atmosphere is an ammonia atmosphere;

[0033] The nitriding temperature is 300–350°C;

[0034] Optionally, the nitriding temperature is any value among 300°C, 310°C, 320°C, 330°C, 340°C, and 350°C, or a range between any two.

[0035] The nitriding time is 1 to 3 hours.

[0036] Optionally, the nitriding time is any value among 1h, 2h, and 3h, or a range between any two.

[0037] According to another aspect of this application, a method for preparing 1,4-butanediol by hydrogenation of 4-hydroxybutanal is provided, comprising the following steps:

[0038] In a reactor, a raw material containing hydrogen gas and a solution of 4-hydroxybutyraldehyde is introduced and reacted with a catalyst to obtain a product containing 1,4-butanediol.

[0039] The catalyst is selected from the catalysts described above or the catalysts prepared by the methods described above.

[0040] The reactor is a fixed-bed reactor.

[0041] The mass fraction of the 4-hydroxybutyraldehyde solution is 20-50 wt%.

[0042] Optionally, the mass fraction of the 4-hydroxybutyraldehyde solution is any value among 20wt%, 30wt%, 40wt%, and 50wt%, or a range between any two.

[0043] The mass hourly space velocity (MSV) of the 4-hydroxybutyraldehyde solution is 2–4 h⁻¹. -1 ;

[0044] Optionally, the mass hourly space velocity (MSV) of the 4-hydroxybutyraldehyde solution is 2 h⁻¹. -1 3h -1 4h -1 Any value in the range or any value between the two.

[0045] The mass hourly space velocity of the hydrogen gas is 80–120 h⁻¹. -1 .

[0046] Optionally, the mass hourly space velocity of the hydrogen gas is 80 h⁻¹. -1 90h -1 100h -1 110h -1 120h -1 Any value in the range or any value between the two.

[0047] The reaction temperature is 70–180°C;

[0048] Optionally, the reaction temperature is any value or a range between 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, and 180°C.

[0049] The reaction time is 1–4 hours;

[0050] Optionally, the reaction time is any value among 1h, 2h, 3h, and 4h, or a range between any two.

[0051] The reaction pressure is 1–11 MPa.

[0052] Optionally, the pressure of the reaction is any value or a range between 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, and 11 MPa.

[0053] The beneficial effects that this application can produce include:

[0054] 1) The catalyst provided in this application can be applied to the hydrogenation of 4-hydroxybutyraldehyde to prepare 1,4-butanediol, and improves the conversion rate of 4-hydroxybutyraldehyde and the selectivity of the generated 1,4-butanediol.

[0055] 2) The preparation method of the catalyst provided in this application is stable, controllable, and reproducible.

[0056] 3) The method for preparing 1,4-butanediol by hydrogenation of 4-hydroxybutanal provided in this application uses the catalyst provided in this application, which has a fast reaction rate and high yield and can be applied to large-scale production. Attached Figure Description

[0057] Figure 1 Scanning electron microscopy (SEM) (JSM-7800F) on catalyst 1 # Morphology testing was performed on the 3DOM nickel nitride / nickel oxide catalyst. Detailed Implementation

[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0059] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially. The gas chromatograph used was an Agilent 7890B gas chromatograph.

[0060] Example 1

[0061] Preparation of catalysts

[0062] Taking item 1 in Table 1 as an example, citric acid and nickel nitrate hexahydrate were mixed in deionized water at a mass ratio of 1:2 to form solution A (the ratio of the total mass of citric acid and nickel source to the volume of the solvent was 1:2 g / ml). The solid-liquid ratio of polystyrene spheres to the mixed solution was 1:50 g / ml. The solution was placed in a vacuum container and evacuated. Solution A was added dropwise to the polystyrene spheres using a Buchner funnel to immerse them. After drying at 70°C for 2 hours, the above steps were repeated several times. The solution was then calcined at 550°C for 3 hours in a calcining furnace to obtain 3DOM nickel oxide. The 3DOM nickel oxide was then nitrided in an ammonia atmosphere at 325°C for 2 hours to obtain a 3DOM nickel nitride / nickel oxide catalyst, denoted as catalyst 1#.

[0063] Following the steps below, the types and amounts of each raw material and the reaction parameters were adjusted to obtain a series of 3DOM nickel nitride / nickel oxide catalysts numbered 1 to 28, denoted as hierarchical porous molecular sieves 1 to 28, as shown in Table 1 below:

[0064] Table 1

[0065]

[0066]

[0067]

[0068] The explanations for each column in Table 1 above are as follows:

[0069] Nickel sources: nickel nitrate hexahydrate (Ni1), nickel sulfate hexahydrate (Ni2), nickel acetate tetrahydrate (Ni3).

[0070] Solvents: Deionized water (solution 1), ethanol (solution 2), and a mixed solution of ethanol and deionized water (solution 3).

[0071] The conversion rate and selectivity calculation formulas in the embodiments of this application are as follows (using 4-hydroxybutyraldehyde conversion rate as the evaluation index):

[0072] 4-Hydroxybutyraldehyde conversion rate = (initial carbon number of 4-hydroxybutyraldehyde - carbon number of 4-hydroxybutyraldehyde in the product) * 100 / initial molar number of 4-hydroxybutyraldehyde

[0073] 1,4-Butanediol selectivity = (number of carbon atoms in 1,4-butanediol) * 100 / ∑(number of carbon atoms in 1,4-butanediol + number of carbon atoms in other products)

[0074] Example 2

[0075] The catalyst is used in the hydrogenation reaction to prepare 1,4-butanediol.

[0076] Catalysts 1 to 28 prepared in Example 1 # ~Catalyst 28 # The catalyst is used for the hydrogenation preparation of 1,4-butanediol, and is packed in a fixed-bed reactor. H2 and a feedstock, 40 wt% aqueous solution of 4-hydroxybutyraldehyde, are introduced. The reaction is carried out at 100°C for 2 hours, with a mass hourly space velocity (MHSV) of 3 h⁻¹. -1 The mass space velocity of H2 is 100 h⁻¹ -1 The reaction pressure is 8 MPa, and the hydrogenation reaction produces 1,4-butanediol.

[0077] After the reaction stabilized (i.e., when the reaction chromatogram data showed no abnormalities), both the reactants and products were analyzed using online gas chromatography. The reaction results are shown in Table 3.

[0078] Table 2

[0079]

[0080]

[0081] As can be seen from the table, the prepared catalysts used in hydrogenation reactions do not show significant differences in reaction conversion and selectivity.

[0082] Example 3

[0083] Catalyst 1 prepared in Table 2 # The hydrogenation reaction to prepare 1,4-butanediol was carried out. After the reaction parameters were varied and the reaction stabilized (i.e., when the chromatographic data showed no abnormalities), both the reactants and products were analyzed using online gas chromatography. The reaction results are shown in Table 4.

[0084] Table 3

[0085]

[0086]

[0087] The table shows that reaction temperature and reaction pressure have a significant impact on the reaction conversion rate.

[0088] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing 1,4-butanediol by hydrogenation of 4-hydroxybutyraldehyde, characterized in that, Includes the following steps: In a reactor, a raw material containing hydrogen gas and a solution of 4-hydroxybutyraldehyde is introduced and reacted with a catalyst to obtain a product containing 1,4-butanediol. The reaction temperature is 70~150℃; The reaction pressure is 1~10MPa; The mass fraction of the 4-hydroxybutyraldehyde solution is 20~50 wt%; The catalyst includes an active component and a support; The active component is nickel nitride; The carrier is a three-dimensional ordered macroporous nickel oxide; The method for preparing the catalyst includes the following steps: A three-dimensional ordered macroporous nickel oxide was obtained, and the three-dimensional ordered macroporous nickel oxide was nitrided to obtain the catalyst.

2. The method for preparing 1,4-butanediol by hydrogenation of 4-hydroxybutyraldehyde according to claim 1, characterized in that, The process for obtaining three-dimensional ordered macroporous nickel oxide includes: Raw materials containing nickel source, citric acid and solvent are mixed to obtain a mixed solution. Polystyrene balls are immersed in the mixed solution, dried and calcined to obtain the three-dimensional ordered macroporous nickel oxide.

3. The method according to claim 2, characterized in that, The nickel source is selected from at least one of nickel nitrate, nickel sulfate, and nickel acetate; The solvent is selected from water and / or ethanol; The mass ratio of citric acid to nickel source is 1:(1~3). The ratio of the total mass of the citric acid and the nickel source to the volume of the solvent is 1:(2~4) g / ml; The solid-liquid ratio of the polystyrene spheres to the mixed solution is 1:(50~70)g / ml.

4. The method according to claim 2, characterized in that, The drying temperature is 50~80℃; The drying time is 1-3 hours; The calcination temperature is 450~650℃; The calcination time is 1 to 6 hours.

5. The method according to claim 1, characterized in that, The nitriding atmosphere is an ammonia atmosphere; The nitriding temperature is 300~350℃; The nitriding time is 1 to 3 hours.

6. The method according to claim 1, characterized in that, The reactor is a fixed-bed reactor.

7. The method according to claim 1, characterized in that, The mass hourly space velocity (MSV) of the 4-hydroxybutyraldehyde solution is 2-4 h⁻¹ -1 ; The mass hourly space velocity of the hydrogen gas is 80-120 h⁻¹. -1 .

8. The method according to claim 1, characterized in that, The reaction time is 1 to 4 hours.

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