A multi-component catalyst for hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol and a preparation method thereof

Abstract

The application discloses a kind of 3-hydroxypropionic acid methyl ester hydrogenation preparation 1,3-propanediol multi-composite catalyst and preparation method thereof, the catalyst is prepared using ammonia auxiliary hydrothermal deposition method, comprising the following components: (a) main component is CuO;(b) the auxiliary is one or several of Ni, Co, Cr;(c) SiO2 is its carrier.Utilizing the method prepared on Cu-based catalyst, active metal dispersion is high, auxiliary and active metal are easy to form strong interaction between each other, and the catalyst has high activity, good long-term running stability.It can solve the problems of low activity, poor stability, low selectivity of main product 1,3-propanediol for this kind of catalyst.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalytic preparation, and particularly relates to a multi-component catalyst for hydrogenation of 3-hydroxypropionic acid methyl ester to 1,3-propanediol and a preparation method thereof. BACKGROUND

[0002] 1,3-propanediol (1,3-PDO) is a colorless, odorless, transparent liquid, which is soluble in water, alcohol and various organic solvents, and has typical properties of alcohol and diol. The main use of 1,3-PDO is to synthesize high molecular material as polymer monomer, to replace ethylene glycol and butanediol to produce polyol polyester, to be used for manufacturing new polyester fiber PTT with excellent performance, and then to be applied to clothing, carpet, electronics, automobile and other markets. With the further maturity of PTT fiber production technology and the further reduction of cost, PTT can gradually replace 5-10 % of traditional polyester fiber at reasonable price difference, and has very broad market prospect. Among them, 1,3-PDO is the core and key raw material for synthesizing PTT, and is irreplaceable.

[0003] At present, the methods for preparing 1,3-propanediol mainly include chemical synthesis and biological fermentation. The chemical synthesis method for preparing 1,3-propanediol includes EO method and propenal hydration method. The EO method, also known as oxirane carbonyl synthesis method, mainly includes two process routes, i.e. oxirane hydroformylation and oxirane hydroesterification. Among them, the oxirane hydroesterification method has low raw material cost, and the intermediate product is not easy to self-polymerize, and is easy to realize large-scale production. Moreover, the intermediate 3-hydroxypropionic acid methyl ester in the method is more stable than the intermediate 3-hydroxypropionaldehyde in the oxirane hydroformylation method, and the β-hydroxyl in the 3-hydroxypropionic acid methyl ester is easier to be removed than the ester hydrogenation, which creates more suitable ester hydrogenation active sites, and greatly improves the selectivity of the main product 1,3-propanediol.

[0004] In recent years, copper-based catalysts have become the preferred catalysts for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol due to their low production cost and the advantages of high activity, high selectivity, mild reaction conditions, and good resistance to toxicity when combined with other active additives. The addition of additives to multi-component catalysts can disperse particles and stabilize active Cu species. Patent CN101993352A reports the preparation of a multi-component metal oxide catalyst using Cu, Mn, and Zr oxides as active components via co-precipitation. This catalyst exhibits uniform distribution of active components, suppresses dehydration side reactions, thereby improving product selectivity and demonstrating excellent reaction performance and stability. Patent CN103721734A reports the use of copper oxide as the main active component, with the addition of active additives manganese oxide, molybdenum oxide, and phosphorus pentoxide, and silica as the catalyst support. This significantly improves product conversion and selectivity in the hydrogenation reaction of high-concentration methyl 3-hydroxypropionate to 1,3-propanediol. Patent CN102059125A reports a catalyst for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol. The active components of this catalyst are oxides of Cu, Mn, and Zr, prepared using an alkaline precipitant titration method with sodium carbonate or sodium hydroxide. It exhibits advantages such as high activity, high reproducibility, and mild conditions. Specifically, patent CN102059125A reports a catalyst for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol, comprising Cu, Ni, Mn, Zn, and SiO2. The catalyst is prepared using a precipitant, achieving a 1,3-propanediol yield of 80%.

[0005] Existing patents and literature do not mention the use of ammonia-assisted hydrothermal deposition to form a composite copper-based hydrogenation catalyst from CuO as the main catalyst and Ni, Co, Cr, and SiO2 as auxiliary agents. Ammonia-assisted hydrothermal deposition is a catalyst preparation method that involves preparing an active metal precursor into a metal ammonia complex ion, reacting it with the support precursor in an aqueous solution of surfactant and polyol, and depositing it onto the support surface under high-temperature hydrothermal conditions. The ammonia-assisted hydrothermal deposition method adsorbs the formed metal ammonia complex positive ions onto the support negative ions, enhancing the dispersion effect. Hydrothermal deposition allows for a more stable dispersion of metal ions on the support. Summary of the Invention

[0006] To address the problems of low activity, poor stability, and low selectivity of the main product 1,3-propanediol in current catalysts, this invention provides a multi-component composite catalyst for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol and its preparation method.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A multi-component composite catalyst for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol comprises the following components:

[0009] (a) the main component is CuO;

[0010] (b) the auxiliary agent is one or more of Ni, Co, and Cr;

[0011] (c) SiO2 is the carrier thereof.

[0012] Further, the content of each component is 10-55% for the main component, 0.1-10% for the auxiliary agent, and 45-90% for SiO2, with the sum of the percentages being 100%.

[0013] Further, the preparation method of the 3-hydroxypropionic acid methyl ester hydrogenation 1,3-propanediol multi-component composite catalyst is as follows:

[0014] (1) A certain amount of CuO precursor and auxiliary agent are dissolved in deionized water, and stirring is continued until a transparent solution is obtained;

[0015] (2) Ammonia water with a mass fraction of 25% is added to the solution of step (1), and stirring is performed for 2 hours to form a metal complex ion mixed solution;

[0016] (3) CTAB is added to the solution of step (2), and stirring is performed for 2 hours to form a stable transparent solution;

[0017] (4) A mixed solution of SiO2 carrier precursor and polyol is added dropwise to the solution of step (3), and stirring is performed for 1 hour, and then stirring is performed for 2 hours at room temperature. The resultant is transferred to a stainless steel hydrothermal synthesis kettle;

[0018] (5) The stainless steel hydrothermal synthesis kettle is placed in a hydrothermal oven equipped with a rotating shaft, and hydrothermal synthesis is performed at 70-110 ℃ for 24-96 h. After cooling to room temperature, the precipitate is suction-filtered and washed until the suctioned liquid is neutral;

[0019] (6) The precipitate obtained in step (5) is dried at 80-150 ℃ for 6-48 h;

[0020] (7) The solid obtained in step (6) is calcined at 500-1000 ℃ for 6-48 h;

[0021] (8) The solid obtained in step (7) is ground, tabletted, broken, and sieved to obtain the catalyst.

[0022] Further, the precursor of the main component CuO in step (1) is one or more of copper nitrate, copper sulfate, copper acetate, copper acetylacetonate, and copper chloride, and is preferably copper nitrate.

[0023] Further, the auxiliary agent in step (2) is one or more of Ni, Co, and Cr, and the precursor thereof is one or more of nitrate, acetate, and sulfate, and is preferably nitrate.

[0024] Further, the amount of ammonia used in step (2) is 5-10 times the total moles of metal Cu and the additive.

[0025] Further, the amount of CTAB used in step (3) is 0.1-2.0 times the total moles of metal Cu and the additive.

[0026] Further, the SiO2 carrier precursor in step (4) can be tetraethyl orthosilicate, silica sol, or low specific surface area fumed silica.

[0027] Further, the SiO2 carrier precursor in step (4) is preferably tetraethyl orthosilicate, and in the mixed solution of tetraethyl orthosilicate and polyol, the molar ratio of tetraethyl orthosilicate to polyol is 1:2-1:5.

[0028] Further, the polyol in step (4) is one or more of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 1,4-cyclohexane dimethanol.

[0029] Further, the drying atmosphere in step (6) is vacuum drying or atmospheric air drying.

[0030] The obtained catalyst can be used for the reaction of hydrogenating 3-hydroxypropionic acid methyl ester to 1,3-propanediol, and the specific operation is as follows:

[0031] The catalyst loading amount is 10.0 ml. Before feeding, the catalyst is reduced with hydrogen, so that the active component exists in the form of an element, and the reduction conditions are as follows: temperature 200-450 DEG C, pressure 0.1-8.0 MPa, hydrogen flow rate 10-200 ml / min, and time 0.5-36 h. During the reaction, 3-hydroxypropionic acid methyl ester is diluted with methanol, the mass concentration of 3-hydroxypropionic acid methyl ester is 5-20 %, the temperature is 140-200 DEG C, the pressure is 3-8 MPa, the raw material space velocity is 0.01-3.0 h-1, and the hydrogen ester ratio is 200-600. -1

[0032] The beneficial effects of the present application are as follows:

[0033] The present application adopts an ammonia-assisted hydrothermal deposition method to form a composite copper-based hydrogenation catalyst by using a main catalyst CuO, an additive, and SiO2. The Cu-based catalyst prepared by using the method has high active metal dispersion, and strong interaction between the additive and the active metal, so that the catalyst has high activity and good long-term running stability. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 TEM images of the catalysts of Example 1 (left) and Comparative Example 1 (right).

[0035] Figure 2 ​Stability of the catalysts of Example 1 and Comparative Example 1 with reaction time.

[0036] Figure 3 H2-TPR profile of the catalysts of Example 1 and Comparative Example 3. DETAILED DESCRIPTION

[0037] In order to make the content of the present application more convenient to understand, the technical solutions described in the present application are further described below in combination with specific embodiments, but the present application is not limited thereto.

[0038] Example 1 35Cu-2.5Ni / SiO2-NHTD

[0039] Copper nitrate trihydrate 13.21 g, nickel nitrate hexahydrate 1.24 g were weighed and dissolved in 100 ml of deionized water with continuous stirring until a transparent solution was obtained; then 32.4 g of ammonia water (25%) was added to the solution, and stirred for 2 hours to form a metal complex ion mixed solution; 10.86 g of CTAB was weighed and added to the above metal complex ion mixed solution, and stirred for 2 hours to form a stable transparent solution; 21.5 g of tetraethyl orthosilicate and 7.8 g of ethylene glycol were weighed and configured into a mixed solution, and stirred for 1 hour, then added dropwise to the above transparent solution containing metal complex ions-CTAB, and then stirred at room temperature for 2 hours, and then transferred to a stainless steel hydrothermal synthesis kettle. The stainless steel hydrothermal synthesis kettle was placed in a hydrothermal oven equipped with a rotating shaft, and hydrothermal synthesis was carried out at 90 °C for 48 h. After cooling to room temperature, the precipitate was suction filtered and washed until the suction liquid was neutral. The precipitate obtained by suction filtration in the above precipitate liquid was dried at 120 °C for 24 h; the obtained solid was calcined at 750 °C for 12 h under nitrogen atmosphere. The 35Cu-2.5Ni / SiO 2- After the NHTD catalyst was compacted and formed, it was crushed and sieved into 14-20 mesh granular catalyst for testing of catalytic performance.

[0040] Comparative Example 1 35Cu-2.5Ni / SiO2-DP

[0041] Copper nitrate trihydrate 13.21 g, nickel nitrate hexahydrate 1.24 g were weighed and dissolved in 100 ml of deionized water with continuous stirring until a clear solution was obtained; 21.5 g of tetraethyl orthosilicate was weighed and dissolved in 50 ml of methanol, and the tetraethyl orthosilicate-methanol solution was added dropwise to the above metal ion mixed solution, and stirred for 1 hour; 5.5 g of sodium hydroxide was weighed and dissolved in 100 ml of deionized water, and the sodium hydroxide solution was added dropwise to the metal ion-tetraethyl orthosilicate solution, and stirred at 60°C for 4 hours; after the precipitation was completed, the formed precipitate was cooled to room temperature and then suction filtered and washed until the suction filtrate was neutral. The precipitate obtained by suction filtration in the above precipitate solution was dried at 120°C for 24 hours; the obtained solid was calcined at 750°C for 12 hours under a nitrogen atmosphere. After the 35Cu-2.5Ni / SiO2-DP catalyst was compactly molded, it was crushed and sieved into a 14-20 mesh granular catalyst, which was used for the test of catalytic performance.

[0042] Comparative Example 2 35Cu-2.5Ni / SiO2-IMP

[0043] Copper nitrate trihydrate 13.21 g, nickel nitrate hexahydrate 1.24 g were weighed and dissolved in 100 ml of deionized water with continuous stirring until a clear solution was obtained; 21.5 g of tetraethyl orthosilicate was weighed and dissolved in 50 ml of methanol, and the tetraethyl orthosilicate-methanol solution was added dropwise to the above metal ion mixed solution, and stirred for 1 hour; 5.5 g of sodium hydroxide was weighed and dissolved in 100 ml of deionized water, and the sodium hydroxide solution was added dropwise to the metal ion-tetraethyl orthosilicate solution, and stirred at 60°C for 4 hours; after the precipitation was completed, the formed precipitate was cooled to room temperature and then suction filtered and washed until the suction filtrate was neutral. The precipitate obtained by suction filtration in the above precipitate solution was dried at 120°C for 24 hours; the obtained solid was calcined at 750°C for 12 hours under a nitrogen atmosphere. After the 35Cu-2.5Ni / SiO2-DP catalyst was compactly molded, it was crushed and sieved into a 14-20 mesh granular catalyst, which was used for the test of catalytic performance.

[0044] Comparative Example 3 35Cu / SiO2-NHTD

[0045] Weigh 13.21 g of copper nitrate trihydrate and dissolve in 100 ml of deionized water with continuous stirring until a clear solution is obtained. Then add 29.70 g of ammonia water (25%) to the solution and stir thoroughly for 2 hours to form a metal complex ion mixed solution. Weigh 9.93 g of CTAB and add to the metal complex ion mixed solution and stir thoroughly for 2 hours to form a stable transparent solution. Weigh 22.5 g of tetraethyl orthosilicate and 8.0 g of ethylene glycol to form a mixed solution, stir thoroughly for 1 hour, and then add dropwise to the metal complex ion-CTAB-containing transparent solution. After stirring thoroughly at room temperature for 2 hours, transfer to a stainless steel hydrothermal synthesis kettle. Place the stainless steel hydrothermal synthesis kettle in a hydrothermal oven equipped with a rotating shaft, and hydrothermally synthesize at 90°C for 48 hours. After cooling to room temperature, filter and wash the precipitate until the filtrate is neutral. Dry the precipitate obtained by filtration at 120°C for 24 hours. Calcine the obtained solid at 750°C for 12 hours under a nitrogen atmosphere. After compacting the 35Cu / SiO 2- After compacting the NHTD catalyst, crush and sieve to obtain a 14-20 mesh granular catalyst for testing of catalytic performance.

[0046] Comparative Example 4 2.5Ni / SiO2-NHTD

[0047] Weigh 1.24 g of nickel nitrate hexahydrate and dissolve in 100 ml of deionized water with continuous stirring until a clear solution is obtained. Then add 2.3 g of ammonia water (25%) to the solution and stir thoroughly for 2 hours to form a metal complex ion mixed solution. Weigh 0.93 g of CTAB and add to the metal complex ion mixed solution and stir thoroughly for 2 hours to form a stable transparent solution. Weigh 33.8 g of tetraethyl orthosilicate and 11.9 g of ethylene glycol to form a mixed solution, stir thoroughly for 1 hour, and then add dropwise to the metal complex ion-CTAB-containing transparent solution. After stirring thoroughly at room temperature for 2 hours, transfer to a stainless steel hydrothermal synthesis kettle. Place the stainless steel hydrothermal synthesis kettle in a hydrothermal oven equipped with a rotating shaft, and hydrothermally synthesize at 90°C for 48 hours. After cooling to room temperature, filter and wash the precipitate until the filtrate is neutral. Dry the precipitate obtained by filtration at 120°C for 24 hours. Calcine the obtained solid at 750°C for 12 hours under a nitrogen atmosphere. After compacting the 2.5Ni / SiO2-NHTD catalyst, crush and sieve to obtain a 14-20 mesh granular catalyst for testing of catalytic performance.

[0048] Comparative Example 5 35Cu-2.5Ni / SiO2-HTD

[0049] Copper nitrate trihydrate 13.21 g, cobalt nitrate hexahydrate 1.24 g were weighed and dissolved in 100 ml of deionized water with continuous stirring until a clear solution was obtained. Then 32.5 g of ammonia water (25%) was added to the solution with continuous stirring for 2 hours to form a metal complex ion mixed solution. 10.86 g of CTAB was weighed and added to the above metal complex ion mixed solution with continuous stirring for 2 hours to form a stable transparent solution. 21.5 g of tetraethyl orthosilicate and 7.8 g of ethylene glycol were weighed and mixed to form a mixed solution, which was added dropwise to the above transparent solution containing metal complex ions-CTAB with continuous stirring at room temperature for 2 hours. The stainless steel hydrothermal synthesis kettle was then placed in a hydrothermal oven equipped with a rotating shaft and hydrothermally synthesized at 90 °C for 48 h. After cooling to room temperature, the precipitate was filtered and washed until the filtrate was neutral. The precipitate obtained by filtration was dried at 120 °C for 24 h. The obtained solid was calcined at 750 °C for 12 h under a nitrogen atmosphere. The 35CuO-3Co / SiO2 catalyst was compacted and molded, then crushed and sieved into 14-20 mesh granular catalyst for catalytic performance testing.

[0050] Example 2 35CuO-3Co / SiO2

[0051] Copper nitrate trihydrate 13.21 g, cobalt nitrate hexahydrate 1.24 g were weighed and dissolved in 100 ml of deionized water with continuous stirring until a clear solution was obtained. Then 32.5 g of ammonia water (25%) was added to the solution with continuous stirring for 2 hours to form a metal complex ion mixed solution. 10.86 g of CTAB was weighed and added to the above metal complex ion mixed solution with continuous stirring for 2 hours to form a stable transparent solution. 21.5 g of tetraethyl orthosilicate and 7.8 g of ethylene glycol were weighed and mixed to form a mixed solution, which was added dropwise to the above transparent solution containing metal complex ions-CTAB with continuous stirring at room temperature for 2 hours. The stainless steel hydrothermal synthesis kettle was then placed in a hydrothermal oven equipped with a rotating shaft and hydrothermally synthesized at 90 °C for 48 h. After cooling to room temperature, the precipitate was filtered and washed until the filtrate was neutral. The precipitate obtained by filtration was dried at 120 °C for 24 h. The obtained solid was calcined at 750 °C for 12 h under a nitrogen atmosphere. The 35CuO-3Co / SiO2 catalyst was compacted and molded, then crushed and sieved into 14-20 mesh granular catalyst for catalytic performance testing.

[0052] Example 3 35CuO-2Cr / SiO2

[0053] Weigh 13.21 g of copper nitrate trihydrate, 1.54 g of chromium nitrate nonahydrate and dissolve in 100 ml of deionized water, continuously stir until a transparent solution; then add 31.8 g of ammonia water (25%) to the solution, stir thoroughly for 2 hours to form a metal complex ion mixed solution; weigh 11.1 g of CTAB and add to the above metal complex ion mixed solution, stir thoroughly for 2 hours to form a stable transparent solution; weigh 21.8 g of tetraethyl orthosilicate and 7.9 g of ethylene glycol to form a mixed solution, stir thoroughly for 1 hour, and then add dropwise to the above transparent solution containing metal complex ions-CTAB, then stir thoroughly at room temperature for 2 hours, and then move to a stainless steel hydrothermal synthesis kettle. Put the stainless steel hydrothermal synthesis kettle in a hydrothermal oven equipped with a rotating shaft, and hydrothermally synthesize at 90 °C for 48 h. After cooling to room temperature, the formed precipitate is suction filtered and washed until the filtrate is neutral. The precipitate obtained by suction filtration in the above precipitate solution is dried at 120 °C for 24 h; the obtained solid is calcined at 750 °C for 12 h under a nitrogen atmosphere. After the 35CuO-2Cr / SiO2 catalyst is compacted and formed, it is broken and sieved into 14-20 mesh granular catalyst for testing of catalytic performance.

[0054] Example 4 35CuO-2.5Ni-1.0Cr / SiO2

[0055] Weigh 13.21 g of copper nitrate trihydrate, 1.54 g of chromium nitrate nonahydrate and dissolve in 100 ml of deionized water, continuously stir until a transparent solution; then add 31.8 g of ammonia water (25%) to the solution, stir thoroughly for 2 hours to form a metal complex ion mixed solution; weigh 11.1 g of CTAB and add to the above metal complex ion mixed solution, stir thoroughly for 2 hours to form a stable transparent solution; weigh 21.8 g of tetraethyl orthosilicate and 7.9 g of ethylene glycol to form a mixed solution, stir thoroughly for 1 hour, and then add dropwise to the above transparent solution containing metal complex ions-CTAB, then stir thoroughly at room temperature for 2 hours, and then move to a stainless steel hydrothermal synthesis kettle. Put the stainless steel hydrothermal synthesis kettle in a hydrothermal oven equipped with a rotating shaft, and hydrothermally synthesize at 90 °C for 48 h. After cooling to room temperature, the formed precipitate is suction filtered and washed until the filtrate is neutral. The precipitate obtained by suction filtration in the above precipitate solution is dried at 120 °C for 24 h; the obtained solid is calcined at 750 °C for 12 h under a nitrogen atmosphere. After the 35CuO-2Cr / SiO2 catalyst is compacted and formed, it is broken and sieved into 14-20 mesh granular catalyst for testing of catalytic performance.

[0056] Example 5 35CuO-2.0Ni-1.3Co / SiO2

[0057] Copper nitrate trihydrate 13.21 g, nickel nitrate hexahydrate 1.24 g, and cobalt nitrate hexahydrate 0.49 g were weighed and dissolved in 100 ml of deionized water, and stirred until a transparent solution was obtained; then 33.0 g of ammonia water (25%) was added to the solution, and stirred for 2 hours to form a metal complex ion mixed solution; 11.5 g of CTAB was weighed and added to the metal complex ion mixed solution, and stirred for 2 hours to form a stable transparent solution; 21.3 g of tetraethyl orthosilicate and 7.8 g of ethylene glycol were configured into a mixed solution, and stirred for 1 hour, then added dropwise to the above-mentioned transparent solution containing metal complex ions-CTAB, and then stirred at room temperature for 2 hours, and then transferred to a stainless steel hydrothermal synthesis kettle. The stainless steel hydrothermal synthesis kettle was placed in a hydrothermal oven equipped with a rotating shaft, and hydrothermal synthesis was carried out at 90°C for 48 hours. After cooling to room temperature, the precipitate was suction filtered and washed until the suction liquid was neutral. The precipitate obtained by suction filtration was dried at 120°C for 24 hours; the obtained solid was calcined at 750°C for 12 hours under a nitrogen atmosphere. After the 35CuO-2.0Ni-1.3Co / SiO2 catalyst was compacted and formed, it was broken and sieved into a 14-20 mesh granular catalyst for catalytic performance testing.

[0058] Catalyst evaluation

[0059] The performance of the catalyst was evaluated in a high-pressure fixed-bed reactor using a methanol solution of 3-hydroxypropionic acid methyl ester as the reactant. The catalyst loading was 10.0 ml. The catalyst was reduced with hydrogen before feeding, and the reduction conditions were: temperature 320°C, pressure 6 MPa, hydrogen flow rate 100 ml / min, and time 5 h. The reaction conditions were: 3-hydroxypropionic acid methyl ester diluted with methanol to a mass concentration of 5%, temperature 150°C, pressure 6 MPa, raw material space velocity 0.1 h -1 , and hydrogen to ester ratio 500.

[0060] After the reaction temperature was stabilized for 5 h, the product in the reactor rear condenser tank was collected, and GC-MC was used to quantitatively and qualitatively analyze the raw material and the product after hydrogenation, and calculate the conversion rate of 3-hydroxypropionic acid methyl ester and the selectivity of 1,3-propanediol, the calculation formula is as follows, and the reaction results are shown in Table 1:

[0061]

[0062]

[0063] Table 1

[0064]

[0065] As can be seen from Table 1, by comparing Example 1 with Comparative Example 1, it can be seen that the catalyst prepared by using the ammonia-assisted hydrothermal deposition method has smaller particle size of the main active species Cu, higher dispersion of the active metal Figure 1 , and easy formation of strong interaction between the promoter and the active metal, and the catalyst has high performance, and the catalyst activity remains high after running for 200 h, and the stability is better Figure 2 .

[0066] By comparing Example 1 with Comparative Example 3, it can be seen that the doping of the promoter affects the reduction properties of the Cu catalyst, and the H2-TPR experiment Figure 3 indicates that the doping of the promoter Ni inhibits the reduction of Cu, so that the reduction peak moves to high temperature, thereby further regulating the ratio of Cu 0 and Cu I in the active species, so as to improve the selectivity of the main product 1,3-propanediol in the catalyst.

[0067] By comparing Example 1 with Comparative Example 5, it can be seen that the addition of ammonia water in the catalyst preparation process converts the active metal precursor into a metal ammonia complex ion, improves the mixing effect of multiple ions, and easily adsorbs on the surface of SiO2 to form a silicic acid compound, which helps to disperse and stabilize the active metal, thereby improving the conversion rate.

[0068] By comparing Example 1, 2, 3, 4 and 5, it can be seen that compared with Cr and Co, the doping of the promoter Ni is more helpful to control the particle size of Cu, and the Ni-doped catalyst has better 3-hydroxypropionic acid methyl ester conversion rate.

[0069] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. A method for preparing a multi-component catalyst for hydrogenation of 3-hydroxypropionic acid methyl ester to 1,3-propanediol, characterized in that: Specifically comprising the following steps: (1) A certain amount of CuO precursor and auxiliary precursor are weighed and dissolved in deionized water, and stirring is continued until a transparent solution is obtained; (2) Ammonia water with a mass fraction of 25% is added to the solution obtained in step (1), and stirring is continued for 2 hours to form a metal complex ion mixed solution; (3) CTAB is added to the solution obtained in step (2), and stirring is continued for 2 hours to form a stable transparent solution; (4) A mixed solution of SiO2 carrier precursor and polyol is added dropwise to the solution obtained in step (3), stirring is continued for 1 hour, and then stirring is continued at room temperature for 2 hours, and the solution is transferred into a stainless steel hydrothermal synthesis kettle; (5) The stainless steel hydrothermal synthesis kettle is placed in a hydrothermal oven equipped with a rotating shaft, and hydrothermal synthesis is carried out at 70-110 ℃ for 24-96 h, and then the kettle is cooled to room temperature, and the precipitate is suction filtered and washed until the suction residue is neutral; (6) The precipitate obtained in step (5) is dried at 80-150 ℃ for 6-48 h; (7) The solid obtained in step (6) is calcined at 500-1000 ℃ for 6-48 h; (8) The solid obtained in step (7) is ground, tabletted, broken, and sieved to obtain the catalyst.

2. The method of claim 1, wherein: The CuO precursor in step (1) is one or more of copper nitrate, copper sulfate, copper acetate, copper acetylacetonate, and copper chloride.

3. The method of claim 1, wherein: The auxiliary precursor in step (1) is one or more of a nitrate, an acetate, and a sulfate.

4. The method of claim 1, wherein: The amount of ammonia water used in step (2) is 5-10 times the total molar amount of metal Cu and auxiliary.

5. The method of claim 1, wherein: The amount of CTAB used in step (3) is 0.1-2.0 times the total molar amount of metal Cu and auxiliary.

6. The method of claim 1, wherein: The SiO2 carrier precursor in step (4) is tetraethyl orthosilicate, silica sol, or low specific surface area fumed silica.

7. The method of claim 1, wherein: The polyol in step (4) is one or more of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 1,4-cyclohexane dimethanol.

8. Use of a multi-element composite catalyst prepared by the preparation method of any one of claims 1-7 in the hydrogenation of 3-hydroxypropionic acid methyl ester to 1,3-propanediol.

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