CN110590715B - Surface-modified Pd-based catalyst and preparation method and application thereof - Google Patents
Surface-modified Pd-based catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a surface-modified Pd-based catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing palladium salt and a silane coupling agent for coordination to obtain surface-modified palladium salt colloidal particles; (2) and (2) reacting the surface-modified palladium salt colloidal particles obtained in the step (1) with a carrier in an organic solvent to obtain the surface-modified Pd-based catalyst. The catalyst has stable structure, and the catalytic hydrogenation reaction has the characteristic of high-selectivity ring hydrogenation.
Description
Technical Field
The invention relates to a surface-modified Pd-based catalyst, a preparation method and application thereof, belonging to the field of preparation of heavy metal catalysts.
Background
The rapid development of society and economy causes the excessive consumption of non-renewable fossil resources including coal, oil and natural gas, so that the reserves of the non-renewable fossil resources are reduced and the exploitation difficulty is increased. Meanwhile, the growing environmental problems also arouse the attention of people to new energy sources. Biomass is the only renewable carbon resource, and research and development and application of biomass are receiving wide attention. The conversion of biomass utilizes catalytic conversion of its platform compounds. Furfural and 5-hydroxymethylfurfural are platform compounds of five-carbon and six-carbon sources, respectively, of biomass. At present, chemicals obtained by catalytic hydrogenation of furfural and 5-hydroxymethylfurfural are concentrated on side chain aldehyde group hydrogenation products or side chain aldehyde group and ring over-hydrogenation products. However, obtaining a simple ring hydrogenation product is a great challenge, and only reports of byproducts are shown at present, and the yields of the tetrahydrofurfuryl and 5-hydroxymethyl tetrahydrofurfuryl are low. Therefore, the realization of high-selectivity ring hydrogenation to obtain the tetrahydrofurfuryl and 5-hydroxymethyl tetrahydrofurfuryl has important academic and industrial application values.
As an important transition metal, a palladium-based catalyst is widely used in hydrogenation reactions such as C ═ C double bonds, C ═ O double bonds, and C — O single bonds, because of its advantages such as high catalytic activity and selectivity, and good stability. However, since the C ═ O group in furfural or 5-hydroxymethylfurfural is more active than the C ═ C double bond in furan rings, C ═ O tends to hydrogenate first on ordinary supported catalysts.
Disclosure of Invention
The invention aims to provide a surface-modified Pd-based catalyst, and a preparation method and application thereof.
The invention provides a preparation method of a surface-modified Pd-based catalyst, which comprises the following steps: (1) mixing palladium salt and a silane coupling agent for coordination to obtain surface-modified palladium salt colloidal particles;
(2) and (2) reacting the surface-modified palladium salt colloidal particles obtained in the step (1) with a carrier in an organic solvent to obtain the surface-modified Pd-based catalyst.
In the preparation method, the mass ratio of the silane coupling agent to the palladium salt is 15-35: 1;
the coordination conditions in step (1) are as follows: stirring for 12-48 hours at room temperature, specifically stirring for 12 hours;
the palladium salt comprises palladium nitrate and/or palladium chloride;
the silane coupling agent comprises 3-aminopropyltriethoxysilane (KH550 for short) or N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (DL 602 for short).
In the preparation method, the mass ratio of the organic solvent to the silane coupling agent can be 80-240: 1;
the mass ratio of the carrier to the silane coupling agent can be 0.7-4: 1;
in the step (2), the reaction temperature can be 90-130 ℃, specifically 100 ℃, and the reaction time can be 12-48 hours, specifically 12 hours;
the organic solvent is an alcoholic solution; the alcohol solution is methanol, ethanol, a mixed solution of methanol and water in any proportion or a mixed solution of ethanol and water in any proportion;
the carrier is alumina, activated carbon (AC for short) and silicon dioxide.
In the above preparation method, in the step (2), the step of reacting the surface-modified palladium salt colloidal particles with the carrier is as follows: dissolving the surface-modified palladium salt colloidal particles in the organic solvent, and stirring and mixing; and then adding the carrier, stirring, mixing, heating and refluxing for reaction to obtain the surface-modified Pd-based catalyst.
In the above preparation method, the step (2) further comprises a step of post-treating the surface-modified Pd-based catalyst;
the post-treatment comprises the steps of sequentially carrying out centrifugation, washing, drying and reduction reaction.
In the above preparation method, the reduction reaction conditions are as follows: and introducing hydrogen, wherein the flow rate of the hydrogen can be 30-120 mL/min, the pressure is normal, the temperature can be 250-600 ℃, and the time can be 2-5 h.
In the present invention, the reduction reaction is carried out with PdCl2Reducing the metal Pd into Pd, and performing catalytic action;
the atmospheric pressure is common knowledge in the art and is one atmosphere.
The invention also provides the surface-modified Pd-based catalyst prepared by the preparation method.
In the surface-modified Pd-based catalyst, the mass percentage of palladium can be 0.5-5 wt%, the particle size is less than 5nm, the mass percentage of the silane coupling agent can be 20-41 wt%, the average pore diameter is 7.3-13.4 nm, and the specific surface area can be 180-250 m2/g；
In the surface modified Pd-based catalyst, the surface of metal Pd particles is modified by organic functional groups through coordination of amino groups in a silane coupling agent, and the modified metal Pd particles are also connected to a carrier through the organic functional groups on the surface in the silane coupling agent. By increasing the coverage of the Pd-based catalyst, the surface of the metal Pd is divided into small spaces, so that the high-selectivity hydrogenation of C-C double bonds in furan rings is realized.
The invention further provides the application of the surface-modified Pd-based catalyst in selective furan ring hydrogenation reaction for retaining aldehyde groups.
In the above application, the selective furan ring hydrogenation reaction for retaining aldehyde group is any one of the following reactions 1) to 2):
1) performing cyclic hydrogenation on furfural to obtain tetrahydrofurfural;
2) and (3) performing ring hydrogenation on the 5-hydroxymethylfurfural to obtain 5-hydroxymethyltetrahydrofurfural.
In the invention, the specific reaction equation of the selective furan ring hydrogenation reaction for retaining aldehyde groups is as follows:
1) hydrogenation of furfural to obtain tetrahydrofurfural is shown as formula I:
2) the hydrogenation of 5-hydroxymethyl furfural to obtain 5-hydroxymethyl-tetrahydrofurfural is shown as formula II:
in the above application, the selective furan ring hydrogenation reaction conditions for retaining aldehyde groups are as follows: the solvent is at least one of water, methanol, ethanol and 1, 4-dioxane;
the mass ratio of the solvent to the furfural or the 5-hydroxymethylfurfural can be 2-20: 1;
the mass ratio of the furfural or the 5-hydroxymethylfurfural to the surface-modified Pd-based catalyst can be 5-100: 1, specifically 5:1 and 10: 1;
the reaction temperature can be 0-30 ℃, specifically 15 ℃, 30 ℃ or 15-30 ℃, the pressure of hydrogen can be 0.2-2 MPa, specifically 0.2MPa, 0.8MPa, 1MPa or 2MPa, and the reaction time can be 4-20 hours, specifically 4 hours, 15 hours or 20 hours.
In the invention, the reaction result of obtaining the tetrahydrofurfuryl aldehyde by catalyzing furfural hydrogenation by the surface-modified Pd-based catalyst is as follows: the conversion rate of furfural can be 40-100%, specifically 40.5%, 93.5% or 100%, and the selectivity of tetrahydrofurfural can be 70-87%, specifically 82.6%, 84.6%, 87.2%, 85.2% or 86.6%;
the reaction result of the surface-modified Pd-based catalyst for catalyzing the hydrogenation of 5-hydroxymethylfurfural to obtain 5-hydroxymethyltetrahydrofurfural is as follows: the conversion rate of 5-hydroxymethylfurfural can be 30-100%, specifically 35.5%, 88.6% or 100%, and the selectivity of 5-hydroxymethylfurfural can be 70-85%, specifically 80.6%, 83.2%, 83.6% or 84.6%.
The invention has the following advantages:
the catalyst of the invention has stable structure. The invention reserves side chain aldehyde group for biomass-based platform compound furfural and 5-hydroxymethyl furfural, realizes low-temperature high-selectivity ring hydrogenation, and respectively generates the tetrahydrofuran and the 5-hydroxymethyl tetrahydrofuran. The invention firstly provides a reaction for modulating the hydrogenation selectivity of C ═ C double bonds and C ═ O double bonds by using a surface-modified Pd-based catalyst to realize high-selectivity ring hydrogenation.
Drawings
FIG. 1 is a schematic diagram of the preparation process and structure of the catalyst of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Examples 1,
Preparation of metal salt colloidal particles: 0.1g of palladium chloride was dissolved in 1.5g of 3-aminopropyltriethoxysilane (KH 550). Stirring at room temperature (25 ℃) for 12 hours to obtain stable nano-palladium colloid particles.
Anchoring metal salt colloidal particles on a support: firstly, the obtained palladium salt colloidal particles are dissolved in 120mL of ethanol, and are stirred and mixed uniformly. Then, 6g of alumina carrier was added and stirred to mix well. Heating in oil bath at 100 deg.C, stirring, refluxing for 12 hr, filtering, washing filter cake, and vacuum drying at 40 deg.C for 24 hr. The catalyst is recorded as 0.1Pd1.5KH550/Al2O3。
Reducing off-line in a tubular reduction furnace, charging 0.1g of the above catalyst, H2Controlling the flow rate to be 30mL/min, and reducing for 5 hours by programming the temperature to 250 ℃ to obtain the surface modified palladium-based catalyst. Putting 0.1g of the reduced catalyst into a high-pressure reaction kettle for furfural hydrogenation reaction, taking 10g of water and 0.5g of furfural, purging the air in the replacement kettle by using hydrogen, and filling 0.2Mpa H2And reacted at 30 ℃ for 4 hours. The conversion rate of furfural was 40.5%, and the selectivity of tetrahydrofurfural was 87.2%.
Examples 2,
The catalyst synthesis method and reduction conditions used were the same as in example 1 of the present invention.
0.1g of the reduced catalyst is put into a high-pressure reaction kettle for carrying out hydrogenation reaction on 5-hydroxymethylfurfural, 10g of water and 0.5g of 5-hydroxymethylfurfural are taken, hydrogen is used for purging and replacing the air in the kettle, and 0.2Mpa H is filled2And reacted at 30 ℃ for 4 hours. The conversion rate of 5-hydroxymethylfurfural was 35.5%, and the selectivity of 5-hydroxymethyltetrahydrofurfural was 83.2%.
Examples 3,
The catalyst synthesis method and reduction conditions were the same as those in inventive example 1 except that the ratio of 3-aminopropyltriethoxysilane to ethanol solution was changed to 2.5g and 200mL, respectively. The catalyst is recorded as 0.1Pd2.5KH550/Al2O3。
Putting 0.1g of the reduced catalyst into a high-pressure reaction kettle for furfural hydrogenation reaction, taking 10g of water and 0.5g of furfural, purging the air in the replacement kettle by using hydrogen, and filling 0.8Mpa H2And reacted at 30 ℃ for 4 hours. The conversion rate of furfural was 93.5%, and the selectivity of tetrahydrofurfural was 85.2%.
Examples 4,
The catalyst synthesis method and reduction conditions used were the same as in example 3 of the present invention.
0.1g of the reduced catalyst is put into a high-pressure reaction kettle for carrying out hydrogenation reaction on 5-hydroxymethylfurfural, 10g of water and 0.5g of 5-hydroxymethylfurfural are taken, hydrogen is used for purging and replacing the air in the kettle, and H of 0.8Mpa is filled2And reacted at 30 ℃ for 4 hours. Conversion of 5-hydroxymethylfurfural to 88.6%, 5-hydroxymethyltetrahydrofurfuralThe selectivity was 84.6%.
Examples 5,
The synthesis method and reduction conditions of the catalyst used were the same as those in example 1 of the present invention except that the proportions of 3-aminopropyltriethoxysilane and ethanol solution were changed to 5g and 400mL, respectively, and the carrier was changed to activated carbon. The catalyst was recorded as 0.1Pd5KH 550/AC.
Reducing off-line in a tubular reduction furnace, charging 0.1g of the above catalyst, H2Controlling the flow rate to be 50mL/min, and reducing for 3 hours by programming the temperature to 350 ℃ to obtain the surface modified palladium-based catalyst. Putting the reduced catalyst 0.1g into a high-pressure reaction kettle for furfural hydrogenation reaction, taking 10g of water and 0.5g of furfural, purging the air in the replacement kettle by using hydrogen, and filling 1Mpa H2The reaction was carried out at 15 ℃ for 15 hours. The conversion rate of furfural was 100%, and the selectivity of tetrahydrofurfural was 86.6%.
Examples 6,
The catalyst synthesis method and reduction conditions used were the same as in example 5 of the present invention.
Putting 0.1g of the reduced catalyst into a high-pressure reaction kettle for carrying out hydrogenation reaction on 5-hydroxymethylfurfural, taking 10g of water and 0.5g of 5-hydroxymethylfurfural, purging and replacing the air in the kettle by hydrogen, and filling 1Mpa of H2The reaction was carried out at 15 ℃ for 15 hours. The conversion rate of 5-hydroxymethylfurfural was 100%, and the selectivity of 5-hydroxymethyltetrahydrofurfural was 83.6%.
Example 7,
The catalyst synthesis and reduction conditions were the same as in inventive example 6, except that KH550 was replaced by DL602, and the ratio of the ethanol solution was 7g and 600 mL. The catalyst is recorded as 0.1Pd7DL602/Al2O3。
Reducing off-line in a tubular reduction furnace, charging 0.1g of the above catalyst, H2The flow rate is controlled to be 70mL/min, the temperature is programmed to 350 ℃, and reduction is carried out for 3 hours to obtain the surface modified palladium-based catalyst. Putting the reduced catalyst into a high-pressure reaction kettle for furfural hydrogenation reaction, taking 10g of water and 1g of furfural, purging and replacing the air in the kettle by hydrogen, and filling 2Mpa H2The reaction was carried out at 15 ℃ for 15 hours. The conversion rate of furfural is 100%, and the selectivity of the tetrahydrofurfural is 82.6%.
Example 8,
The catalyst synthesis method and reduction conditions used were the same as in example 7 of the present invention.
0.1g of the reduced catalyst is put into a high-pressure reaction kettle for carrying out hydrogenation reaction on 5-hydroxymethylfurfural, 10g of water and 1g of 5-hydroxymethylfurfural are taken, hydrogen is used for purging and replacing the air in the kettle, and 2Mpa H is filled2The reaction was carried out at 15 ℃ for 15 hours. The conversion rate of 5-hydroxymethylfurfural is 100%, and the selectivity of 5-hydroxymethyltetrahydrofurfural is 80.6%.
Examples 9,
The catalyst synthesis method and reduction conditions were the same as those in inventive example 8 except that the compounding ratio of 3-aminopropyltriethoxysilane was changed to 8.5g and the carrier was changed to silica. The catalyst is recorded as 0.1Pd8.5KH550/SiO2。
Reducing off-line in a tubular reduction furnace, charging 0.1g of the above catalyst, H2Controlling the flow rate to be 70mL/min, and reducing for 3 hours by programming the temperature to 500 ℃ to obtain the surface modified palladium-based catalyst. Putting 0.1g of the reduced catalyst into a high-pressure reaction kettle for furfural hydrogenation reaction, taking 10g of water and 1g of furfural, purging and replacing the air in the kettle by hydrogen, and filling 2Mpa H2And reacted at 15 ℃ for 20 hours. The conversion rate of furfural was 100%, and the selectivity of tetrahydrofurfural was 84.6%.
Examples 10,
The catalyst synthesis method and reduction conditions used were the same as in example 9 of the present invention.
Putting 0.1g of the reduced catalyst into a high-pressure reaction kettle for carrying out hydrogenation reaction on 5-hydroxymethylfurfural, taking 10g of water and 1g of 5-hydroxymethylfurfural, purging and replacing the air in the kettle by hydrogen, and filling 2Mpa of H2And reacted at 15 ℃ for 20 hours. The conversion rate of 5-hydroxymethylfurfural is 100%, and the selectivity of 5-hydroxymethyltetrahydrofurfural is 84.5%.
Examples 11,
The catalyst, reduction conditions and reaction conditions used were the same as in example 1 of the present invention.
The catalyst is repeatedly used for 6 times, and is recycled by centrifugation and washing after each use. The conversion rate of furfural was 95.2%, and the selectivity of tetrahydrofurfural was 84.5%.
TABLE 1
Claims (7)
1. The application of a surface-modified Pd-based catalyst in selective furan ring hydrogenation reaction for retaining aldehyde group;
the selective furan ring hydrogenation reaction for retaining aldehyde groups is any one of the following reactions 1) to 2):
1) performing cyclic hydrogenation on furfural to obtain tetrahydrofurfural;
2) performing ring hydrogenation on the 5-hydroxymethylfurfural to obtain 5-hydroxymethyltetrahydrofurfural;
the preparation method of the surface-modified Pd-based catalyst comprises the following steps: (1) mixing palladium salt and a silane coupling agent for coordination to obtain surface-modified palladium salt colloidal particles;
the silane coupling agent is 3-aminopropyltriethoxysilane or N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane;
(2) and (2) reacting the surface-modified palladium salt colloidal particles obtained in the step (1) with a carrier in an organic solvent to obtain the surface-modified Pd-based catalyst.
2. Use according to claim 1, characterized in that: the mass ratio of the silane coupling agent to the palladium salt is 15-35: 1;
the coordination conditions in step (1) are as follows: stirring for 12-48 hours at room temperature;
the palladium salt includes palladium nitrate and/or palladium chloride.
3. Use according to claim 1 or 2, characterized in that: the mass ratio of the organic solvent to the silane coupling agent is 80-240: 1;
the mass ratio of the carrier to the silane coupling agent is 0.7-4: 1;
in the step (2), the reaction temperature is 90-130 ℃, and the reaction time is 12-48 h;
the organic solvent is an alcoholic solution; the alcohol solution is methanol, ethanol, a mixed solution of methanol and water in any proportion or a mixed solution of ethanol and water in any proportion;
the carrier is alumina, active carbon and silicon dioxide.
4. Use according to claim 1 or 2, characterized in that: in the step (2), the step of reacting the surface-modified palladium salt colloidal particles with the carrier is as follows: dissolving the surface-modified palladium salt colloidal particles in the organic solvent, and stirring and mixing; and then adding the carrier, stirring, mixing, heating and refluxing for reaction to obtain the surface-modified Pd-based catalyst.
5. Use according to claim 1 or 2, characterized in that: the step (2) also comprises a step of post-treating the surface modified Pd-based catalyst;
the post-treatment comprises the steps of sequentially carrying out centrifugation, washing, drying and reduction reaction.
6. Use according to claim 5, characterized in that: the conditions of the reduction reaction are as follows: and introducing hydrogen, wherein the flow rate of the hydrogen is 30-120 mL/min, the pressure is normal, the temperature is 250-600 ℃, and the time is 2-5 h.
7. Use according to claim 1 or 2, characterized in that: the selective furan ring hydrogenation reaction conditions for retaining aldehyde groups are as follows: the solvent is at least one of water, methanol, ethanol and 1, 4-dioxane;
the mass ratio of the solvent to the furfural or the 5-hydroxymethylfurfural is 2-20: 1;
the mass ratio of the furfural or the 5-hydroxymethylfurfural to the surface-modified Pd-based catalyst is 5-100: 1;
the reaction temperature is 0-30 ℃, the hydrogen pressure is 0.2-2 MPa, and the reaction time is 4-20 hours.
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