CN117019159A - Composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate - Google Patents

Composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate Download PDF

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CN117019159A
CN117019159A CN202311031153.8A CN202311031153A CN117019159A CN 117019159 A CN117019159 A CN 117019159A CN 202311031153 A CN202311031153 A CN 202311031153A CN 117019159 A CN117019159 A CN 117019159A
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stirring
gel
alcohol
preparing
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翟庆阁
蔡俊鑫
黄明志
黄闽岳
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Petrochemical Co Ltd
Sinochem Quanzhou Energy Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a compound catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and a preparation method thereof, wherein the compound catalyst comprises the following components: (a) a main component CuO; (b) an electronic auxiliary barium strontium titanate; (c) Hydrogenation active auxiliary NiO, mnO 2 、MoO 3 One or more of the following; (d) Carrier and pore-enlarging agent SiO 2 . Wherein, the hydrogenation active auxiliary agent is helpful for the catalyst to activate hydrogen, and the electronic auxiliary agent barium strontium titanate and the main component CuO act to easily form active sites for improving the conversion of 1, 3-propanediol, so the composite catalyst is used for 3-hydroxy propionic acidThe activity of the methyl ester hydrogenation for preparing the 1, 3-propanediol is high, the selectivity of the product is high, and the problems of low activity and low selectivity of the 1, 3-propanediol of the existing methyl 3-hydroxypropionate hydrogenation catalyst can be solved.

Description

Composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and a preparation method thereof.
Background
1, 3-propanediol (1, 3-PDO) is a colorless, odorless, salty, hygroscopic viscous liquid. 1,3-PDO is not only a raw material for producing unsaturated polyester, plasticizer, surfactant, emulsifier and demulsifier, but also is mainly used as a polymer monomer for synthesizing PTT (polytrimethylene terephthalate) fiber with terephthalic acid (PTA). Compared with PET, PBT, PA and other fibers, the PTT has the advantages of excellent rebound resilience, dyeability and the like, and can develop personalized fashion fabric with comfortable wearing, good elasticity, rich colors and various tissue changes. With further maturation of PTT fiber production technology and further reduction of cost, PTT can gradually replace 5-10% of traditional polyester fibers under reasonable price, and has very broad market prospect, wherein 1,3-PDO is a key raw material for synthesizing PTT and is not replaceable.
The intermediate methyl 3-hydroxypropionate is prepared by utilizing the methyl oxirane hydro-esterification reaction, and then the 1,3-PDO is prepared by catalytic hydrogenation, so that the method is a necessary way for realizing the mass production of cheap 1, 3-PDO. The method has low cost of raw materials, is easy to realize large-scale production by process amplification, and provides cheap raw materials for the mass production of PTT fibers. However, compared with an acrolein hydration hydrogenation method and a glycerase catalytic method, the technology for producing 1, 3-propanediol through ethylene oxide methyl esterification and hydrogenation reaction has high technical difficulty, and particularly has high requirements on the hydrogenation activity of a 3-hydroxy methyl propionate catalyst and the selection of main products, which is the technical core of the technology.
The copper-based 3-hydroxy methyl propionate hydrogenation catalyst has the advantages of low production cost, high activity, high selectivity, mild reaction condition, good toxicity resistance and the like due to combination with other active auxiliary agents. Under the condition of alcohol solvent, the patent CN 1911507A adds organic amine in advance to complex, adds fatty alcohol orthosilicate and fatty alcohol aluminum as carrier precursors, and then adds a colloid forming agent to heat to form sol-gel to prepare a copper-based single-component catalyst with low load, thus effectively improving the sintering resistance and the service life of the catalyst, and the catalytic activity of the catalyst is still to be improved because only single-component copper is adopted in the preparation process; in addition, the organic amine reagent is used, has pungent smell and is not friendly to people and environment. In the patent CN101385980A, organic silane is used as a precursor of a carrier, manganese is used as a co-agent, copper salt, manganese salt and the organic silane are mixed firstly and then dissolved in an alcohol-water solvent, and then the mixture is heated and stirred to form a sol-gel method to prepare the copper-based binary catalyst, wherein the catalyst has low-temperature hydrogenation catalytic activity. In the patent CN 106111155A, the alkaline precipitant and the metal ion mixture are used for coprecipitation to prepare the catalyst of one or more of the silicon oxide loaded active main component Cu and the active auxiliary agent Zn, zr, mn, la, P, mo, ni, so that the requirements of high activity and selectivity can be met.
Disclosure of Invention
Aiming at the problems of small specific surface area, low activity, easiness in removing hydroxyl groups in the methyl 3-hydroxypropionate and low selectivity of 3-propanediol of the existing catalyst, the invention provides a composite catalyst for preparing 1, 3-propanediol by hydrogenating the methyl 3-hydroxypropionate and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate comprises the following components:
(a) A main component CuO;
(b) Electronic auxiliary strontium barium titanate;
(c) A hydrogenation co-agent;
(d) Carrier and pore-enlarging agent SiO 2 ；
The hydrogenation active auxiliary agent is NiO, mnO 2 、MoO 3 One or more of them.
Further, the total weight percentage is 100%, and the contents of the components are as follows: main unit30-70% of components, 0.5-10% of electronic auxiliary agent, 1.0-15% of hydrogenation active auxiliary agent and SiO 2 10-35%。
The preparation method of the composite catalyst for preparing 1, 3-propanediol by hydrogenating the methyl 3-hydroxypropionate comprises the following steps:
(1) Tetrabutyl titanate, strontium nitrate and barium nitrate are taken as raw materials, are dissolved in absolute ethyl alcohol together, are stirred at a high speed to form barium strontium titanate sol, then ethylene glycol is added, and after continuous stirring at a high speed, the mixed sol is kept still for 12 hours at room temperature to gel, so that barium strontium titanate gel is obtained;
(2) Dissolving a CuO precursor and a hydrogenation active auxiliary precursor in an alcohol-water solution with a certain proportion according to the component proportion, stirring and heating to 40-90 ℃, slowly dropwise adding tetraethoxysilane, stirring and uniformly mixing to obtain gel, stirring and aging for 2-8 hours at 40-90 ℃;
(3) Adding the barium strontium titanate gel prepared in the step (1) into the aged gel prepared in the step (2) according to a proportion, stirring and mixing strongly for 6 hours, and standing and aging for 12 hours;
(4) Drying the mixed gel obtained in the step (3) at 80-150 ℃ for 4-40 hours, and roasting at 300-750 ℃ for 4-24 hours to obtain the composite catalyst.
Further, the dosages of tetrabutyl titanate, strontium nitrate and barium nitrate in the step (1) are converted according to the mole ratio of the three elements of titanium, strontium and barium being 1:0.7:0.3.
Further, the dosage of the glycol in the step (1) is 2-6 times of the total molar weight of three elements of titanium, strontium and barium.
Further, the rotating speed of the high-speed stirring in the step (1) is 300-600r/min, the time of the first high-speed stirring is 4-8 hours, and the time of the high-speed stirring after adding the ethylene glycol is 12-48 hours.
Further, the CuO precursor in the step (2) is one or more of copper nitrate, copper sulfate, copper acetate and copper chloride, preferably copper nitrate.
Further, in the step (2), the hydrogenation co-agent precursor is one or more soluble salts such as nitrate, hydrochloride, acetate, ammonium salt of Ni, mn, mo, and the like, preferably nickel nitrate, manganese nitrate, and ammonium molybdate.
Further, in the step (2), the alcohol-water solution is a mixture of one or more of monohydric alcohol and polyhydric alcohol and water, preferably an ethylene glycol water solution; the alcohol concentration of the alcohol-water solution is 30-70 vol%.
Further, the alcohol orthosilicate in step (2) is specifically ethyl orthosilicate or methyl orthosilicate, preferably ethyl orthosilicate.
Further, the rotation speed of the strong stirring in the step (3) is 400r/min.
Further, the drying in the step (4) is vacuum drying or normal pressure drying.
Further, the roasting atmosphere in the step (4) is air.
The obtained composite catalyst can be used for preparing 1, 3-propanediol by hydrogenating 3-hydroxy methyl propionate.
The invention has the remarkable advantages that:
the invention uses the main catalyst CuO, the electronic auxiliary agent, the hydrogenation auxiliary agent and SiO 2 The catalyst is prepared into a large specific surface area composite catalyst by a sol-gel method, and hydrogenation auxiliary agent NiO and MnO are used 2 、MoO 3 Reducing the reduction temperature of CuO, improving the reduction degree, thereby improving the hydrogen activating capacity of the catalyst, and promoting the formation of proper Cu on the catalyst by using high dielectric constant material barium strontium titanate as an electron auxiliary agent 0 /Cu + Active site to promote the adsorption of ester group in methyl 3-hydroxy propionate and raise the selectivity of 1, 3-propylene glycol.
Detailed Description
The composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate comprises the following components in percentage by weight, wherein the sum of the weight percentages is 100 percent: 30-70% of CuO as main component, 0.5-10% of barium strontium titanate as electronic auxiliary agent, niO as hydrogenation active auxiliary agent and MnO as auxiliary agent 2 、MoO 3 One or more of 1.0-15%, carrier and pore-enlarging agent SiO 2 10-35%。
The preparation method of the composite catalyst for preparing 1, 3-propanediol by hydrogenating the methyl 3-hydroxypropionate comprises the following steps:
(1) Respectively weighing tetrabutyl titanate, strontium nitrate and barium nitrate according to the mole ratio of the three elements of titanium, strontium and barium of 1:0.7:0.3, dissolving the tetrabutyl titanate, the strontium nitrate and the barium nitrate in absolute ethyl alcohol together, stirring at a high speed of 300-600r/min for 4-8 hours to form barium strontium titanate sol, adding glycol with the total mole amount of 2-6 times of the three elements of titanium, strontium and barium, continuing stirring at a high speed of 300-600r/min for 12-48 hours, standing the mixed sol for 12 hours at room temperature, and gelatinizing the mixed sol to obtain barium strontium titanate gel;
(2) Dissolving a CuO precursor and a hydrogenation active agent precursor in an alcohol-water solution with the concentration of 30-70 vol% according to the component proportion, stirring and heating to 40-90 ℃, slowly dropwise adding alcohol orthosilicate, stirring and uniformly mixing to obtain gel, and stirring and aging for 2-8 hours at 40-90 ℃;
(3) Adding the barium strontium titanate gel prepared in the step (1) into the aged gel in the step (2) according to a proportion, stirring and mixing strongly at 400r/min for 6 hours, and standing and aging for 12 hours;
(4) Drying the mixed gel obtained in the step (3) at 80-150 ℃ for 4-40 hours, and roasting at 300-750 ℃ for 4-24 hours to obtain the composite catalyst.
Wherein, the CuO precursor in the step (2) is one or more of copper nitrate, copper sulfate, copper acetate and copper chloride. The hydrogenation active auxiliary agent precursor is one or more of nitrate, hydrochloride, acetate, ammonium salt and other soluble salts of Ni, mn and Mo. The alcohol-water solution is a mixture of water and one or more of monohydric alcohol and polyhydric alcohol.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 140CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-53SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g of tetrabutyl titanate, 0.15g of strontium nitrate and 0.078g of barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-Ni-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 1.94 g nickel nitrate hexahydrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging at 70 ℃ for 6 hours to obtain Cu-Ni-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-Ni-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 140CuO-5NiO-55SiO 2
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 1.94 g nickel nitrate hexahydrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding tetraethyl orthosilicate (TEOS) 19.07 g, continuously stirring and aging for 6 hours at the temperature of 70 ℃, and standing and aging for 24 hours to form gel; drying at constant temperature of 120 ℃ and normal pressure in an oven for 16 hours, and roasting at 550 ℃ for 6 hours in air atmosphere to prepare the catalyst which is 40CuO-5NiO-55SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 240CuO-2Ba 0.3 Sr 0.7 TiO 3 -58SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g tetrabutyl titanate, 0.15g strontium nitrate and 0.078g barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2. 12.2 g copper nitrate trihydrate, adding the copper nitrate trihydrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 20.1 g of Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging at 70 ℃ for 6 hours to obtain Cu-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO3-58SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 340CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-53SiO 2 -DP
（1）Ba 0.3 Sr 0.7 TiO 3 Is prepared from
The barium strontium titanate gel prepared in example 1 was dried in an oven at 120℃for 5 hours and then calcined at 550℃for 6 hours to obtain Ba 0.3 Sr 0.7 TiO 3 And (3) powder.
(2) Preparation of catalyst by precipitation method
Weighing 12.2 g copper nitrate trihydrate and 1.94 g nickel nitrate hexahydrate dissolved in 50ml deionized water, stirring for 30 min to obtain transparent solution, adding the above barium strontium titanate powder, stirring for 4 hr, and slowly18.4g of silica sol was slowly added dropwise, and after stirring thoroughly for 1 hour, the mixture was transferred to a water bath at 70℃and stirred for 2 hours. 100ml of 0.5 mol/l sodium hydroxide solution was prepared, slowly added dropwise to the above metal salt suspension, and the precipitate was aged in a water bath at 70℃for 4 hours. Filtering and washing the precipitate until the raffinate is neutral, drying the precipitate in a baking oven at 120 ℃ for 5 hours and roasting the precipitate at 550 ℃ for 6 hours to obtain a catalyst prepared by a precipitation method, which is marked as 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-53SiO 2 DP, grinding, compacting, crushing and sieving to obtain 20-40 mesh granular catalyst.
Comparative example 440CuO-2Ba 0.3 Sr 0.7 TiO 3 -5BaO-53SiO 2
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 0.293 g barium nitrate, adding the copper nitrate trihydrate and the barium nitrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring to a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring, uniformly mixing, and stirring and ageing the obtained gel at 70 ℃ for 6 hours to obtain Cu-Ba-TEOS gel;
adding the barium strontium titanate gel prepared in the example 1 into the prepared Cu-Ba-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, and standing and aging for 12 hours to prepare uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5BaO-53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 540CuO-2Ba 0.3 Sr 0.7 TiO-5MgO-53SiO 2
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 0.136 g magnesium nitrate, adding the copper nitrate trihydrate and the 0.136 g magnesium nitrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring to a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring, uniformly mixing, and ageing the obtained gel at 70 ℃ for 6 hours to obtain Cu-Mg-TEOS gel;
adding the barium strontium titanate gel prepared in the example 1 into the Cu-Mg-TEOS gel prepared in the example 1, stirring and mixing strongly at 400r/min for 6 hours, and standing and aging for 12 hours to prepare a uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO-5MgO-53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 640CuO-2SrO-5NiO-53SiO 2
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate, 1.94 g nickel nitrate hexahydrate and 0.41g strontium nitrate, adding into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging for 6 hours at 70 ℃, and standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2SrO-5NiO-53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Comparative example 740CuO-2BaO-5NiO-53SiO 2
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate, 1.94 g nickel nitrate hexahydrate and 0.34g barium nitrate, adding into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging for 6 hours at 70 ℃, and standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2BaO-5NiO-53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Example 240CuO-2Ba 0.3 Sr 0.7 TiO 3 -5MnO 2 -53SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g of tetrabutyl titanate, 0.15g of strontium nitrate and 0.078g of barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-Mn-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 2.06 g manganese nitrate (50%) into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring, uniformly mixing, stirring the obtained gel at 70 ℃ and ageing for 6 hours to obtain Cu-Mn-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-Ni-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5MnO 2 -53SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
EXAMPLE 340CuO-2Ba 0.3 Sr 0.7 TiO 3 -5MoO 3 -53SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g of tetrabutyl titanate, 0.15g of strontium nitrate and 0.078g of barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-Mo-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 12.2 g copper nitrate trihydrate and 0.68 g ammonium molybdate, adding the copper nitrate trihydrate and the 0.68 g ammonium molybdate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring the mixture into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 18.4g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging the gel at 70 ℃ for 6 hours to obtain Cu-Mo-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-Ni-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5MoO 3 -50SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Example 450CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-43SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g of tetrabutyl titanate, 0.15g of strontium nitrate and 0.078g of barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-Ni-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 15.2 g copper nitrate trihydrate and 1.94 g nickel nitrate hexahydrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 14.9 g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging at 70 ℃ for 6 hours to obtain Cu-Ni-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-Ni-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 50CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-43SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Example 535CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-58SiO 2
（1）Ba 0.3 Sr 0.7 TiO 3 Preparation of the gel:
0.34g of tetrabutyl titanate, 0.15g of strontium nitrate and 0.078g of barium nitrate are weighed as raw materials, dissolved in 10 ml absolute ethyl alcohol, stirred at a high speed of 400r/min for 6 hours to form barium strontium titanate sol, then 0.25 g glycol is added, stirring at a high speed of 400r/min is continued for 24 hours, and the mixed sol is kept at room temperature for 12 hours to gel, so that the barium strontium titanate gel is obtained for standby.
(2) Preparation of Cu-Ni-TEOS gel
50ml of ethylene glycol and 50ml of deionized water are measured respectively to prepare alcohol-water solution; weighing 10.6 g copper nitrate trihydrate and 1.94 g nickel nitrate hexahydrate into the alcohol-water solution, fully stirring for 2 hours at room temperature, transferring into a 70 ℃ water bath, continuously stirring for 6 hours, slowly dropwise adding 20.1 g Tetraethoxysilane (TEOS), stirring and uniformly mixing to obtain gel, stirring and aging at 70 ℃ for 6 hours to obtain Cu-Ni-TEOS gel;
(3) Preparation of Cu-based catalyst
Adding the prepared barium strontium titanate gel into Cu-Ni-TEOS gel, stirring and mixing strongly at 400r/min for 6 hours, standing and aging for 12 hours to obtain uniform gel; drying at 120 deg.C under normal pressure in oven for 16 hr, and calcining at 550 deg.C in air atmosphere for 6 hr to obtain catalyst, which is 35CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-58SiO 2 Grinding and granulating to obtain 20-40 mesh granular catalyst.
Catalyst evaluation
The prepared catalyst was subjected to performance evaluation on a high-pressure fixed bed reactor with a methanol solution of methyl 3-hydroxypropionate as a reactant. The catalyst loading was 20.0. 20.0 ml. The catalyst is reduced by hydrogen before feeding, so that the active components exist in the form of simple substances, and the reduction conditions are as follows: the temperature is 320 ℃, the pressure is 6.0 MPa, the hydrogen flow rate is 100 ml/min, and the time is 5 h. In the reaction, 3-hydroxy methyl propionate is diluted by methanol to 10 percent of mass concentration, the reaction temperature is 160 ℃, the reaction pressure is 6 MPa, and the space velocity of the raw material is 0.3 h -1 Hydrogen ester molar ratio 27.
After the reaction temperature is stabilized for 5 hours, collecting a product of a condensing tank behind the reactor, carrying out qualitative and quantitative analysis on the raw material and the hydrogenated product by adopting a GC-MC (gas chromatography-methyl carbonate) combined instrument, and calculating the hydrogenation reaction conversion rate of the methyl 3-hydroxypropionate and the selectivity of the 1, 3-propanediol, wherein the calculation formula is as follows, and the result is shown in table 1:
。
TABLE 1
As can be seen from the comparison of example 1 and comparative example 1 in Table 1, the hydrogenation conversion rate of methyl 3-hydroxypropionate and the selectivity of 1, 3-propanediol are both higher by adding barium strontium titanate as the catalyst of the electron auxiliary agent, because the barium strontium titanate has a perovskite structure, the separation of holes and electrons can be effectively realized, the electron conduction is facilitated, and the dispersion of active sites and the adsorption of reaction molecules are facilitated.
As is clear from the comparison between example 1 and comparative example 3, the catalyst prepared by the sol-gel method has a larger specific surface area and is more favorable for the dispersion of active sites and the adsorption of reaction molecules than the deposition precipitation method, so that the hydrogenation conversion rate of methyl 3-hydroxypropionate and the selectivity of 1, 3-propanediol are higher.
As is evident from a comparison of example 1 with comparative examples 4 and 5, if NiO is replaced with MgO or BaO, the resulting catalyst does not have good catalytic performance, which proves that the resulting CuO-Ba 0.3 Sr 0.7 TiO 3 -NiO-SiO 2 Specific interactions exist between the components in the catalyst.
As is clear from a comparison of example 1 with comparative examples 6 and 7, the electron mediator barium strontium titanate was replaced with the oxides BaO and SrO, and the selectivity of 1, 3-propanediol was low because electron conduction could not be achieved.
As can be seen from a comparison of examples 1-3 with comparative example 2, the incorporation of Ni, mn, mo can enhance the catalyst activity by promoting the reduction of copper oxide, thereby enhancing the hydrogen activating ability of the catalyst.
As is further demonstrated by comparison of example 1 with examples 4 and 5, the CuO, barium strontium titanate and hydrogenation promoter in the catalyst have higher interaction, and different proportions of the three components directly affect the conversion rate of methyl 3-hydroxypropionate and the selectivity of 1, 3-propanediol, wherein the ratio of the three components is 40CuO-2Ba 0.3 Sr 0.7 TiO 3 -5NiO-53SiO 2 The catalytic effect of (a) is optimal.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. The composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate is characterized by comprising the following components:
(a) A main component CuO;
(b) Electronic auxiliary strontium barium titanate;
(c) A hydrogenation co-agent;
(d) Carrier and pore-enlarging agent SiO 2 ；
The hydrogenation active auxiliary agent is NiO, mnO 2 、MoO 3 One or more of them.
2. Complex according to claim 1The catalyst is characterized in that the total weight percentage is 100 percent, and the components are as follows: 30-70% of main component, 0.5-10% of electronic auxiliary agent, 1.0-15% of hydrogenation active auxiliary agent and SiO 2 10-35%。
3. A method of preparing the composite catalyst according to claim 1, comprising the steps of:
(1) Tetrabutyl titanate, strontium nitrate and barium nitrate are taken as raw materials, are dissolved in absolute ethyl alcohol together, are stirred at a high speed to form barium strontium titanate sol, then ethylene glycol is added, and after continuous stirring at a high speed, the mixed sol is kept still for 12 hours at room temperature to gel, so that barium strontium titanate gel is obtained;
(2) Dissolving a CuO precursor and a hydrogenation active auxiliary precursor in an alcohol-water solution according to the component proportion, stirring and heating to 40-90 ℃, slowly dropwise adding alcohol orthosilicate, stirring and uniformly mixing to obtain gel, and stirring and aging for 2-8 hours at 40-90 ℃;
(3) Adding the barium strontium titanate gel prepared in the step (1) into the aged gel prepared in the step (2) according to a proportion, stirring and mixing strongly for 6 hours, and standing and aging for 12 hours;
(4) Drying the mixed gel obtained in the step (3) at 80-150 ℃ for 4-40 hours, and roasting at 300-750 ℃ for 4-24 hours to obtain the composite catalyst.
4. The method for preparing a composite catalyst according to claim 3, wherein the amounts of tetrabutyl titanate, strontium nitrate and barium nitrate in the step (1) are converted according to the molar ratio of three elements of titanium, strontium and barium being 1:0.7:0.3; the dosage of the glycol is 2-6 times of the total molar weight of three elements of titanium, strontium and barium.
5. The method for preparing a composite catalyst according to claim 3, wherein the high-speed stirring in the step (1) is performed at a rotational speed of 300-600r/min, the time for the first high-speed stirring is 4-8 hours, and the time for the high-speed stirring after adding ethylene glycol is 12-48 hours.
6. The method for preparing a composite catalyst according to claim 3, wherein the CuO precursor in the step (2) is one or more of copper nitrate, copper sulfate, copper acetate and copper chloride;
the hydrogenation active auxiliary agent precursor is one or more of nitrate, hydrochloride, acetate and ammonium salt of Ni, mn and Mo.
7. The method for preparing a composite catalyst according to claim 3, wherein the alcohol-water solution in the step (2) is a mixture of water and one or more of monohydric alcohol and polyhydric alcohol, and the alcohol concentration is 30-70 vol%.
8. A method of preparing a composite catalyst according to claim 3, wherein the alcohol orthosilicate of step (2) is specifically ethyl orthosilicate or methyl orthosilicate.
9. The method for preparing a composite catalyst according to claim 3, wherein the rotation speed of the strong agitation in the step (3) is 400r/min.
10. Use of the composite catalyst according to claim 1 in the preparation of 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate.
CN202311031153.8A 2023-08-16 2023-08-16 Composite catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate Pending CN117019159A (en)

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