A catalyst for preparing 1,3-butanediol by hydrogenating 3-hydroxybutyraldehyde, and a preparation method and application thereof

Abstract

The application discloses a catalyst for preparing 1,3-butanediol by hydrogenating 3-hydroxybutyraldehyde and a preparation method and application thereof. The catalyst comprises an active component, a modifier and a carrier. The active component is selected from oxides of nickel and / or cobalt; and the modifier is selected from oxides of rhenium and / or rhodium. The active component and the modifier are loaded on the surface of the carrier. The carrier is selected from a pre-processed hierarchical pore molecular sieve. The pre-processing comprises alkali treatment and hydrogen ion exchange. The hierarchical pore molecular sieve has a silica-alumina ratio ranging from 15 to 25, a microporous structure and a mesoporous structure. The micropore specific surface area of the hierarchical pore molecular sieve is 150-200 m 2 / g, the mesopore specific surface area is 170-230 m 2 / g, the micropore volume is 0.10-0.20 cm 3 / g, the mesopore volume is 0.20-0.40 cm 3 / g, and the mesopore size is 2-30 nm. The catalyst can improve the conversion rate of acetaldehyde and the selectivity of 3-hydroxybutyraldehyde, has a fast reaction speed and a high yield, and can be applied to large-scale production. The preparation method of the catalyst is stable, controllable and reproducible.

Description

Technical Field

[0001] This application relates to a catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol, its preparation method and application, belonging to the field of chemical engineering. Background Technology

[0002] 1,3-Butanediol can also be used in the production of unsaturated polyester resins, plasticizers, humectants, and softeners, and has wide applications in industrial production. 1,3-Butanediol is a colorless, viscous liquid with good water solubility. It is readily soluble in organic solvents such as ethanol, acetone, and methyl / ethyl ketone, but sparingly soluble in aliphatic hydrocarbons, aromatic hydrocarbons, and carbon tetrachloride. Due to the presence of two hydroxyl groups, it is chemically reactive and has relatively low toxicity, making it a widely used fine chemical in the chemical, pharmaceutical, and cosmetic industries.

[0003] Currently, three main processes are being researched: biosynthesis, acetaldehyde condensation hydrogenation, and formaldehyde-propylene condensation hydrolysis. Research on the biosynthesis of 1,3-butanediol focuses on two main aspects. One is providing substrates for selective oxidation by microorganisms to obtain high-purity optically active 1,3-butanediol; the other is constructing biosynthetic routes, introducing non-natural synthetic routes into engineered bacteria to directly synthesize 1,3-butanediol. Aldol condensation refers to the nucleophilic addition of aldehydes, ketones, carboxylic acids, and esters containing α-hydrogen to carbonyl compounds under alkaline conditions, extending the carbon chain by forming new C-C bonds. The Prins reaction refers to the condensation of aldehydes or ketones with alkenes or alkynes under acidic catalysis; different products can be obtained by changing the reaction conditions. Among these, acetaldehyde condensation hydrogenation is currently the most important chemical synthesis process, accounting for over 95% of the market share. This process mainly consists of two steps: acetaldehyde condensation to produce 3-hydroxybutyraldehyde and 3-hydroxybutyraldehyde hydrogenation to produce 1,3-butanediol. The preparation of the hydrogenation catalyst and the optimization of the hydrogenation process are among the key research contents. Summary of the Invention

[0004] The catalyst prepared in this patent is used in the hydrogenation reaction to prepare 1,3-butanediol. The catalyst has good activity, high conversion rate of 3-hydroxybutyraldehyde and selectivity of 1,3-butanediol, and good stability.

[0005] According to one aspect of this application, a catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol is provided, the catalyst comprising an active component, a modifier, and a support;

[0006] The active component is selected from nickel oxide and / or cobalt oxide;

[0007] The modifier is selected from oxides of rhenium and / or oxides of rhodium.

[0008] The active component and the modifier are loaded on the surface of the carrier;

[0009] The carrier is selected from pretreated multi-level porous molecular sieves;

[0010] The pretreatment includes sequential alkaline treatment and hydrogen ion exchange.

[0011] The silica-to-alumina ratio of the multi-level porous molecular sieve ranges from 15 to 25.

[0012] The multi-level porous molecular sieve has a microporous structure and a mesoporous structure;

[0013] The micropore specific surface area of ​​the multi-level porous molecular sieve is 150–200 m². 2 / g, micropore volume is 0.10~0.20cm³ 3 / g;

[0014] The mesoporous specific surface area of ​​the multi-level porous molecular sieve is 170–230 m². 2 / g, mesopore volume is 0.20~0.40cm³ 3 / g, with mesopore diameters of 2–30 nm.

[0015] In the context of this application, unless otherwise stated, the terms "silicon-to-aluminum ratio" or "Si / Al" refer to the molar ratio of silicon to aluminum in a molecular sieve.

[0016] In the catalyst, the content of the active component is 10-30 wt%;

[0017] The mass of the active component is expressed as the mass of the metal oxide;

[0018] In the catalyst, the upper limit of the content of the active component is selected from 30 wt%, 25 wt%, and 20 wt%, and the lower limit is selected from 10 wt%, 15 wt%, and 20 wt%.

[0019] In the catalyst, the content of the modifier is 0.1% to 5% of the molar amount of the active component;

[0020] The molar amount of the modifier is expressed as the molar amount of the metal element therein;

[0021] The molar amount of the active component is expressed as the molar amount of the metal element therein.

[0022] In the catalyst, the content of the modifier is selected from the upper limit of 5%, 4%, and 3% of the molar amount of the active component, and the lower limit is selected from 0.1%, 1%, and 2%.

[0023] Optionally, the hierarchical porous molecular sieve is selected from Na-type and / or K-type hierarchical porous molecular sieves.

[0024] According to another aspect of this application, a method for preparing the above-mentioned catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol is provided, comprising the following steps:

[0025] The raw materials containing pretreated hierarchical porous molecular sieves, active component precursors, modifier precursors and solvents are mixed, dried (III), and calcined (III) to obtain the catalyst for the hydrogenation of 3-hydroxybutyraldehyde to prepare 1,3-butanediol.

[0026] The pretreatment includes sequential alkaline treatment and hydrogen ion exchange.

[0027] The active component precursor is selected from at least one of nickel nitrate, nickel sulfate, nickel acetate, cobalt nitrate, cobalt sulfate, or cobalt acetate.

[0028] The modifier precursor is selected from ammonium perrhenate and / or rhodium chloride trihydrate;

[0029] The solvent is selected from deionized water and / or ethanol;

[0030] The ratio of the total mass of the active component precursor, modifier precursor, and hierarchical porous molecular sieve to the solvent is 1 g: 2-3 ml. The upper limit of the ratio of the total mass of the active component precursor, modifier precursor, and hierarchical porous molecular sieve to the solvent is selected from 1:2 g / ml and 1:2.5 g / ml, and the lower limit is selected from 1:3 g / ml and 1:2.5 g / ml.

[0031] The alkaline treatment process includes the following steps:

[0032] Molecular sieve I is immersed in an alkaline solution, washed, dried, and calcined to obtain an alkaline-treated molecular sieve.

[0033] The molecular sieve is selected from at least one of NaY molecular sieve, ZSM-5 molecular sieve or MCM22 molecular sieve;

[0034] The alkaline solution is selected from NaOH solution and / or KOH solution;

[0035] The concentration of the alkaline solution is 0.1–0.3 mol / L; the upper limit of the concentration of the alkaline solution is selected from 0.3 mol / L and 0.2 mol / L, and the lower limit is selected from 0.1 mol / L and 0.2 mol / L.

[0036] The ratio of the molecular sieve to the alkaline solution is 1g:20-30ml; the upper limit of the ratio of the molecular sieve to the alkaline solution is selected from 1g:20ml and 1g:25ml, and the lower limit is selected from 1g:30ml and 1g:25ml.

[0037] The immersion time I is 0.5 to 1.5 hours; the upper limit of the immersion time I is selected from 1.5 hours, 1.25 hours, and 1 hour, and the lower limit is selected from 0.5 hours, 0.75 hours, and 1 hour.

[0038] The temperature of the impregnation I is 65-90°C; the upper limit of the temperature of the impregnation I is selected from 90°C, 85°C, and 80°C, and the lower limit is selected from 65°C, 70°C, and 75°C.

[0039] The washing step I is washing until neutral;

[0040] The washing process I is performed using water and / or ethanol;

[0041] The temperature of the drying process I is 80-130°C; the upper limit of the temperature of the drying process I is selected from 130°C, 120°C, and 110°C, and the lower limit is selected from 80°C, 90°C, and 100°C.

[0042] The drying time I is 8 to 24 hours; the upper limit of the drying time I is selected from 24 hours, 20 hours, and 16 hours, and the lower limit is selected from 8 hours, 12 hours, and 16 hours.

[0043] The temperature of the calcination I is 150 to 650°C; the upper limit of the temperature of the calcination I is selected from 650°C, 600°C, and 550°C, and the lower limit is selected from 450°C, 500°C, and 550°C.

[0044] The roasting time I is 1 to 6 hours. The upper limit of the roasting time I is selected from 6 hours, 5 hours, and 4 hours, and the lower limit is selected from 1 hour, 2 hours, and 3 hours.

[0045] The hydrogen ion exchange process includes the following steps:

[0046] The alkali-treated molecular sieve II is impregnated in an ammonium salt solution, II is washed, II is dried, and II is calcined to obtain the multi-level porous molecular sieve;

[0047] The ammonium salt solution is selected from NH4NO3 solution;

[0048] The concentration of the ammonium salt solution is 0.4–1.2 mol / L; the upper limit of the concentration of the ammonium salt solution is selected from 1.2 mol / L, 1.0 mol / L, and 0.8 mol / L, and the lower limit is selected from 0.4 mol / L, 0.6 mol / L, and 0.8 mol / L.

[0049] The solid-liquid ratio of the alkali-treated molecular sieve to the ammonium salt solution is 1g:20-30ml;

[0050] The upper limit of the solid-liquid ratio of the alkali-treated molecular sieve to the ammonium salt solution is selected from 1g:20ml and 1g:25ml, and the lower limit is selected from 1g:30ml and 1g:25ml.

[0051] The immersion time II is 4 to 8 hours; the upper limit of the immersion time II is selected from 8 hours, 7 hours, and 6 hours, and the lower limit is selected from 4 hours, 5 hours, and 6 hours.

[0052] The temperature of the impregnation II is 65-90°C; the upper limit of the temperature of the impregnation II is selected from 90°C, 85°C, and 80°C, and the lower limit is selected from 65°C, 70°C, and 75°C.

[0053] Wash II is washing until neutral;

[0054] Washing II is performed using water and / or ethanol;

[0055] The temperature of the drying process II is 80–130°C; the upper limit of the temperature of the drying process II is selected from 130°C, 120°C, and 110°C, and the lower limit is selected from 80°C, 90°C, and 100°C.

[0056] The drying time II is 8 to 24 hours; the upper limit of the drying time II is selected from 24 hours, 20 hours, and 16 hours, and the lower limit is selected from 8 hours, 12 hours, and 16 hours.

[0057] The temperature of the second calcination is 450-650°C; the upper limit of the temperature of the second calcination is selected from 650°C, 600°C, and 550°C, and the lower limit is selected from 450°C, 500°C, and 550°C.

[0058] The roasting time II is 1 to 6 hours. The upper limit of the roasting time II is selected from 6 hours, 5 hours, and 4 hours, and the lower limit is selected from 1 hour, 2 hours, and 3 hours.

[0059] The temperature of the drying process III is 80–130°C; the upper limit of the temperature of the drying process III is selected from 130°C, 120°C, and 110°C, and the lower limit is selected from 80°C, 90°C, and 100°C.

[0060] The drying time for the third stage is 8 to 24 hours; the upper limit of the drying time for the third stage is selected from 24 hours, 20 hours, and 16 hours, and the lower limit is selected from 8 hours, 12 hours, and 16 hours.

[0061] The temperature of the calcination III is 450-650℃; the upper limit of the temperature of the calcination III is selected from 650℃, 600℃, and 550℃, and the lower limit is selected from 450℃, 500℃, and 550℃.

[0062] The roasting time III is 1 to 6 hours; the upper limit of the roasting time III is selected from 6 hours, 5 hours, and 4 hours, and the lower limit is selected from 1 hour, 2 hours, and 3 hours.

[0063] Optionally, the mixture is stirred;

[0064] The stirring temperature is 60-80℃; the upper limit of the stirring temperature is selected from 80℃ and 70℃, and the lower limit is selected from 60℃ and 70℃.

[0065] The stirring time is 5 to 10 hours. The upper limit of the stirring time is selected from 10 hours, 9 hours, and 8 hours, and the lower limit is selected from 5 hours, 6 hours, and 7 hours.

[0066] According to another aspect of this application, a method for preparing 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde is provided, the method being an excess impregnation method, comprising the following steps:

[0067] The material containing hydrogen and an aqueous solution of 3-hydroxybutyraldehyde is contacted with a catalyst and reacted to obtain a product containing 1,3-butanediol.

[0068] The catalyst is selected from the above-mentioned catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol or the catalyst prepared by the above-mentioned preparation method for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol.

[0069] The mass fraction of the 3-hydroxybutyraldehyde aqueous solution is 20-50%; the upper limit of the mass fraction of the 3-hydroxybutyraldehyde aqueous solution is selected from 50% and 40%, and the lower limit is selected from 20% and 30%.

[0070] The mass hourly space velocity (MSV) of the 3-hydroxybutyraldehyde aqueous solution was 2 h⁻¹. -1 ~4h -1 The upper limit of the mass hourly space velocity (MSV) of the 3-hydroxybutyraldehyde aqueous solution is selected from 4 h. -1 3h -1 The lower limit is selected from 2h. -1 3h -1 .

[0071] The mass hourly space velocity of the hydrogen gas is 80 h⁻¹. -1 ~120h -1 The upper limit of the mass hourly space velocity of the hydrogen gas is selected from 120 h⁻¹. -1 110h -1 100h -1 The lower limit is selected from 80h -1 90h -1 100h -1 .

[0072] The reaction temperature is 70–110°C; the upper limit of the reaction temperature is selected from 110°C, 100°C, and 90°C, and the lower limit is selected from 70°C, 80°C, and 90°C.

[0073] The reaction time is 1 to 4 hours; the upper limit of the reaction time is selected from 4 hours and 3 hours, and the lower limit is selected from 1 hour and 2 hours.

[0074] The reaction pressure is 2-5 MPa; the upper limit of the reaction pressure is selected from 5 MPa and 4 MPa, and the lower limit is selected from 2 MPa and 3 MPa.

[0075] Optionally, the reaction is carried out in a fixed-bed reactor.

[0076] The beneficial effects that this application can produce include:

[0077] The catalyst provided in this application can be used in the hydrogenation of 3-hydroxybutyraldehyde to prepare 1,3-butanediol, and improves the conversion rate of acetaldehyde and the selectivity of the generated 3-hydroxybutyraldehyde. The reaction is fast, the yield is high, and it can be applied to large-scale production. The catalyst preparation method is stable, controllable, and reproducible. Attached Figure Description

[0078] Figure 1 The nitrogen physical adsorption-desorption curves are shown for the multi-level porous molecular sieve material in Example 1 of this application.

[0079] Figure 2 This is the pore size distribution curve of the multi-stage porous molecular sieve material in Example 1 of this application. Detailed Implementation

[0080] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0081] 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. Specific surface area and pore size distribution were characterized using a Quanta QuadraSorb SI4 physical adsorption analyzer.

[0082] The conversion rate and selectivity calculation formulas in the embodiments of this application are as follows (using 3-hydroxybutyraldehyde conversion rate as the evaluation index):

[0083] 3-Hydroxybutyraldehyde conversion rate = (Initial carbon number of 3-hydroxybutyraldehyde - Carbon number of 3-hydroxybutyraldehyde in the product) * 100 / Initial molar number of 3-hydroxybutyraldehyde

[0084] 1,3-Butanediol selectivity = number of carbon atoms in 1,3-butanediol * 100 / ∑(number of carbon atoms in 1,3-butanediol + number of carbon atoms in other products).

[0085] Examples 1-28

[0086] Preparation of catalysts

[0087] Taking item 1 in Table 1 as an example, the NaY molecular sieve (silicon-to-aluminum ratio of 3:1) was treated with a 0.2 mol / L NaOH solution (solid-liquid ratio of molecular sieve to alkali solution of 1:30 g / ml) for 0.5 hours while maintaining the solution temperature at 65℃. After washing until neutral, it was dried at 100℃ for 12 hours and calcined at 550℃ for 3 hours to obtain Na-type hierarchical porous molecular sieve material. The Na-type hierarchical porous molecular sieve material was then treated with a 0.8 mol / L NH4NO3 solution (solid-liquid ratio of hierarchical porous molecular sieve to NH4NO3 solution of 1:30 g / ml) for 6 hours while maintaining the solution temperature at 80℃. After washing, it was dried at 100℃ for 12 hours and calcined at 550℃ for 3 hours to obtain hierarchical porous molecular sieve material. Nickel nitrate, ammonium perrhenate, and a synthesized hierarchical porous molecular sieve (the content of the active component (based on its oxide) accounts for 25 wt% of the mass of the synthesized catalyst, and the amount of modifier added is 2% of the molar amount of the active component) were mixed in deionized water at a solid-liquid ratio of 1:3 g / ml. The mixture was then stirred in a water bath at 80°C for 8 hours and dried in an oven at 100°C for 12 hours to obtain a mixture. The mixture was then calcined in a high-temperature furnace at 500°C for 4 hours to obtain the catalyst, designated as catalyst #1.

[0088] Figure 1 The figure shows the nitrogen physical adsorption-desorption curves of the hierarchical porous molecular sieve material in Example 1 of this application. From the figure, it can be concluded that the specific surface area of ​​the micropores in the hierarchical porous molecular sieve is 150–200 m². 2 / g, mesoporous specific surface area is 170-230m² 2 / g.

[0089] Figure 2 This is the pore size distribution curve of the multi-stage porous molecular sieve material in Example 1 of this application.

[0090] The figure shows that the micropore volume of the hierarchical porous molecular sieve is 0.10–0.20 cm³. 3 / g, mesopore volume is 0.20~0.40cm³ 3 / g, with mesopore diameters of 2–30 nm.

[0091] Following the steps below, adjust the type, amount, and reaction parameters of each raw material to obtain a series of hierarchical porous molecular sieve materials numbered 1 to 28, denoted as hierarchical porous molecular sieve 1 to hierarchical porous molecular sieve 28, as shown in Tables 1 and 2 below:

[0092] Table 1

[0093]

[0094]

[0095]

[0096] Table 2

[0097]

[0098]

[0099] The columns in Tables 1 and 2 are explained as follows:

[0100] The ZSM-5 molecular sieve has a silica-to-alumina ratio of 25.

[0101] The silica-to-alumina ratio of MCM22 molecular sieve is 30.

[0102] Alkali solution types: NaOH (alkali 1), KOH (alkali 2).

[0103] Solid-liquid ratio: Solid-liquid ratio of molecular sieve to alkaline solution (solid-liquid ratio 1), solid-liquid ratio of multi-level porous molecular sieve to NH4NO3 solution (solid-liquid ratio 2).

[0104] Following the steps below, using the synthesized hierarchical porous molecular sieves 1 to 28 as carriers, the types and amounts of each raw material and reaction parameters were adjusted to obtain the sequence number 1. # ~28 # A series of catalysts, denoted as Catalyst 1 # ~Catalyst 28 # As shown in Table 3 below:

[0105] Table 3

[0106]

[0107]

[0108] The columns in Table 3 are explained as follows:

[0109] Active components:

[0110] Nickel sources: nickel nitrate (Ni1), nickel sulfate (Ni2), nickel acetate (Ni3).

[0111] Cobalt sources: cobalt nitrate (Co1), cobalt sulfate (Co2), cobalt acetate (Co3).

[0112] Modifier:

[0113] Ammonium perrhenate (Re), rhodium chloride trihydrate (Rh).

[0114] Solvents: Deionized water (solution 1), ethanol (solution 2), and a mixed solution of ethanol and deionized water (solution 3).

[0115] Application Examples 1-28

[0116] The catalyst is used in the hydrogenation reaction to prepare 1,3-butanediol.

[0117] Catalysts 1 to 28 prepared in Example 1 # ~Catalyst 28 # The catalyst is used for the hydrogenation preparation of 1,3-butanediol, and is packed in a fixed-bed reactor. H2 and the feedstock, wherein the feedstock is a 40% aqueous solution of 3-hydroxybutyraldehyde, are introduced at a reaction temperature of 100°C for 2 hours, and the mass hourly space velocity (MHSV) of the feedstock is 3 h⁻¹. -1 The mass space velocity of H2 is 100 h⁻¹ -1 The reaction pressure is 3 MPa, and the hydrogenation reaction produces 1,3-butanediol.

[0118] After the reaction stabilized (i.e., when the reaction chromatogram data were normal), both the reactants and products were analyzed using online gas chromatography. The reaction results are shown in Table 4.

[0119] Table 4

[0120]

[0121]

[0122] Application Examples 29–45

[0123] Catalyst 1 prepared in Table 3 # The hydrogenation reaction to prepare 1,3-butanediol was carried out. After the reaction parameters were varied and 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 5.

[0124] Table 5

[0125]

[0126] Comparative Example 1

[0127] Nickel nitrate, ammonium perrhenate, and synthesized NaY molecular sieve (silicon-to-aluminum ratio 3:1) (the content of the active component (based on its oxides) accounts for 25 wt% of the mass of the synthesized catalyst, and the amount of modifier added is 2% of the molar amount of the active component) were mixed in deionized water at a solid-liquid ratio of 1:3 g / ml. The mixture was then stirred in a water bath at 80°C for 8 hours and dried in an oven at 100°C for 12 hours to obtain a mixture. The mixture was then calcined in a high-temperature furnace at 500°C for 4 hours to obtain the catalyst. This is designated as control catalyst 1#.

[0128] The catalyst is used in the hydrogenation reaction to prepare 1,3-butanediol.

[0129] Comparative catalyst 1#, prepared in Comparative Example 1, was used for the hydrogenation preparation of 1,3-butanediol. The catalyst was packed in a fixed-bed reactor. H2 and a feedstock (3-hydroxybutyraldehyde aqueous solution with a mass fraction of 40%) were introduced. The reaction was carried out at a temperature of 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 was 3 MPa, and the hydrogenation reaction produced 1,3-butanediol. The conversion rate of 3-hydroxybutyraldehyde was 72.3%, and the selectivity of 1,3-butanediol was 81.2%.

[0130] 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 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde, characterized in that, Includes the following steps: The material containing hydrogen and an aqueous solution of 3-hydroxybutyraldehyde is contacted with a catalyst and reacted to obtain a product containing 1,3-butanediol. The catalyst includes an active component, a modifier, and a support; The active component is selected from nickel oxide and / or cobalt oxide; The modifier is selected from oxides of rhenium and / or oxides of rhodium; The active component and the modifier are loaded on the surface of the carrier; The carrier is selected from pretreated multi-level porous molecular sieves; The pretreatment includes sequential alkaline treatment and hydrogen ion exchange. The silica-to-alumina ratio of the multi-level porous molecular sieve is in the range of 15 to 25. The multi-level porous molecular sieve has a microporous structure and a mesoporous structure; The micropore specific surface area of ​​the multi-level porous molecular sieve is 150~200 m². 2 / g, micropore volume is 0.10~0.20cm³ 3 / g; The mesoporous specific surface area of ​​the multi-level porous molecular sieve is 170~230m². 2 / g, mesopore volume is 0.20~0.40cm³ 3 / g, with mesopore diameter of 2~30nm.

2. The method for preparing 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde according to claim 1, characterized in that, In the catalyst, the content of the active component is 10~30 wt%; The content of the active component is expressed as the mass of the metal oxide; In the catalyst, the content of the modifier is 0.1-5% of the molar amount of the active component; The molar amount of the modifier is expressed as the molar amount of the metal element therein; The molar amount of the active component is expressed as the molar amount of the metal element therein. The multi-level porous molecular sieve is selected from Na-type and / or K-type multi-level porous molecular sieves.

3. A method for preparing 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde according to any one of claims 1 to 2, characterized in that, The method for preparing the catalyst includes the following steps: The raw materials containing pretreated hierarchical porous molecular sieves, active component precursors, modifier precursors and solvents are mixed, dried (III), and calcined (III) to obtain a catalyst for the hydrogenation of 3-hydroxybutyraldehyde to 1,3-butanediol. The pretreatment includes sequential alkaline treatment and hydrogen ion exchange.

4. The method according to claim 3, characterized in that, The alkaline treatment process includes the following steps: Molecular sieve I is immersed in an alkaline solution, washed, dried, and calcined to obtain an alkaline-treated molecular sieve. The molecular sieve is selected from at least one of NaY molecular sieve, ZSM-5 molecular sieve or MCM22 molecular sieve; The alkaline solution is selected from NaOH solution and / or KOH solution; The concentration of the alkaline solution is 0.1~0.3 mol / L; The solid-liquid ratio of the molecular sieve to the alkaline solution is 1g:20~30ml; The immersion time for I is 0.5~1.5h; The temperature of the impregnation I is 65~90℃; The temperature of the drying process I is 80~130℃; The drying time for step I is 8~24 hours; The temperature of the calcination I is 150~650℃; The roasting time for the first stage is 1 to 6 hours.

5. The method according to claim 3, characterized in that, The hydrogen ion exchange process includes the following steps: The alkali-treated molecular sieve II is impregnated in an ammonium salt solution, II is washed, II is dried, and II is calcined to obtain the multi-level porous molecular sieve; The ammonium salt solution is selected from NH4NO3 solution; The concentration of the ammonium salt solution is 0.4~1.2 mol / L; The solid-liquid ratio of the alkali-treated molecular sieve to the ammonium salt solution is 1g:20~30ml; The immersion time for the second stage is 4-8 hours; The temperature for impregnation II is 65~90℃; The temperature of the drying II process is 80~130℃; The drying time for step II is 8-24 hours; The temperature of calcination II is 450~650℃; The roasting time for the second stage is 1 to 6 hours.

6. The method according to claim 3, characterized in that, The active component precursor is selected from at least one of nickel nitrate, nickel sulfate, nickel acetate, cobalt nitrate, cobalt sulfate, or cobalt acetate. The modifier precursor is selected from ammonium perrhenate and / or rhodium chloride; The solvent is selected from water and / or ethanol; The ratio of the total mass of the active component precursor, the modifier precursor, the hierarchical porous molecular sieve, and the solvent is 1g:2~3ml.

7. The method according to claim 3, characterized in that, The temperature of the drying III process is 80~130℃; The drying time for step III is 8-24 hours; The temperature of calcination III is 450~650℃; The roasting time for III is 1-6 hours; The mixture is stirred; The stirring temperature is 60~80℃; The stirring time is 5-10 hours.

8. The method according to claim 1, characterized in that, The method for preparing 1,3-butanediol by hydrogenation of 3-hydroxybutyraldehyde, wherein... The mass fraction of the 3-hydroxybutyraldehyde aqueous solution is 20-50%; The mass hourly space velocity (MSV) of the 3-hydroxybutyraldehyde aqueous solution was 2 h⁻¹. -1 ~ 4h -1 ; The mass hourly space velocity of the hydrogen gas is 80 h⁻¹. -1 ~ 120h -1 .

9. The method according to claim 1, characterized in that, The temperature for hydrogenating 3-hydroxybutyraldehyde to prepare 1,3-butanediol is 70~110℃; The hydrogenation time for 1,3-butanediol from 3-hydroxybutyraldehyde is 1-4 h. The pressure required for the hydrogenation of 3-hydroxybutyraldehyde to prepare 1,3-butanediol is 2-5 MPa. The hydrogenation of 3-hydroxybutyraldehyde to prepare 1,3-butanediol was carried out in a fixed-bed reactor.

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