CN114618477A - Catalyst, and preparation method and application thereof - Google Patents
Catalyst, and preparation method and application thereof Download PDFInfo
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- CN114618477A CN114618477A CN202011457987.1A CN202011457987A CN114618477A CN 114618477 A CN114618477 A CN 114618477A CN 202011457987 A CN202011457987 A CN 202011457987A CN 114618477 A CN114618477 A CN 114618477A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
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Abstract
The application discloses a catalyst and a preparation method and application thereof, wherein the catalyst comprises an active component, a carrier and a confinement layer; the active component is loaded on the carrier; the confinement layer is coated on the surface of the active component; the confinement layer and the support are both selected from silica; the silicon hydroxyl on the surface of the confinement layer is connected with the silicon hydroxyl on the surface of the carrier through condensation reaction; the active component includes a noble metal. The catalyst adopts a limited domain structure formed by silicon oxide to coat or semi-coat the palladium nano-particles, can effectively inhibit the curing phenomenon in roasting, reduction and regeneration, greatly improves the dispersion degree of the particles, increases a large number of reaction active sites, improves the catalytic activity and is convenient to regenerate.
Description
Technical Field
The application relates to a catalyst, a preparation method and application thereof, and belongs to the technical field of chemical catalytic materials.
Background
Hydrogen peroxide is an important inorganic chemical raw material, and is used in the synthesis of inorganic and organic intermediates and other chemicals, textile, medicine, electronics, food and metallurgical industries and other aspectsHave wide application. The anthraquinone process is the most mature and mainstream process for producing hydrogen peroxide at present. The technological process of anthraquinone process mainly includes four processes of hydrogenation, oxidation, extraction and post-treatment, in which the hydrogenation process is the core of whole process. Commercial hydrogenation catalysts used Pd/Al2O3The method has the defects of poor hydrogenation selectivity, low hydrogenation efficiency and the like of the catalyst. The development of a low-cost and high-selectivity hydrogenation catalyst for synthesizing high-concentration hydrogen peroxide is one of the key technologies and technical development trends for realizing low-cost and high-efficiency hydrogen peroxide production by an anthraquinone method at present.
Disclosure of Invention
According to one aspect of the present application, there is provided a catalyst and a method of preparing the same, the catalyst comprising an active component, a support and a confinement layer; the active component is loaded on the carrier; the confinement layer is coated on the surface of the active component; the confinement layer and the support are both selected from silica; the silicon hydroxyl on the surface of the confinement layer is connected with the silicon hydroxyl on the surface of the carrier through condensation reaction; the active component includes a noble metal. The catalyst adopts a silicon oxide precursor to limit the range of active component particles of palladium, so that the active component particles of the palladium are difficult to sinter, the dispersity is greatly improved, a large number of reaction sites are increased, and the activity of the catalyst can be improved; due to the confinement effect, the size of an atomic cluster is reduced, the electronic structure of palladium is changed, the catalytic activity and selectivity of palladium are further adjusted, the use amount of palladium can be reduced, and the catalyst cost is favorably reduced; the palladium element in the catalyst presents a highly dispersed nano-particle and monoatomic structure; because of the confinement effect of the silicon oxide, the catalyst has sintering resistance and higher recycling value in the recycling and regeneration of the catalyst.
According to one aspect of the invention, the catalyst adopts a silicon oxide precursor to limit the range of palladium active component particles, so that the palladium active component particles are not easy to sinter, the dispersity is greatly improved, a large number of reaction sites are increased, and the activity of the catalyst can be improved; due to the confinement effect, the size of the atomic cluster is reduced, the electronic structure of palladium is changed, the catalytic activity and selectivity of palladium are further adjusted, the use amount of palladium can be reduced, and the catalyst cost is favorably reduced; the palladium element in the catalyst presents a highly dispersed nano particle and single atom structure; because of the confinement effect of the silicon oxide, the catalyst has sintering resistance and higher recycling value in the recycling and regeneration of the catalyst.
In the application, the limited domain effect of the silicon oxide ensures that anthraquinone with larger molecules is not easy to directly contact the surface of palladium particles with high active hydrogen concentration, so that the excessive reaction of continuous hydrogenation is prevented, and the selectivity of the catalyst is improved; the dispersity is improved, the use of noble metal palladium is saved, and the economic benefit of the catalyst is increased. The catalyst has the advantages of simple preparation process, good stability, high reaction selectivity, less byproduct generation, easy regeneration, suitability for the process for preparing hydrogen peroxide by anthraquinone hydrogenation and good economic benefit.
According to a first aspect of the present application, there is provided a catalyst comprising an active component, a support and a confinement layer; the active component is loaded on the carrier; the confinement layer is coated on the surface of the active component;
the confinement layer and the support are both selected from silica; the silicon hydroxyl on the surface of the confinement layer is connected with the silicon hydroxyl on the surface of the carrier through condensation reaction;
the active component includes a noble metal.
In the application, on one hand, the highly dispersed metal nanoparticles in the impregnation are not aggregated and grown in the roasting and reduction of the catalyst preparation through the silicon oxide confinement, so that the same dispersion degree is kept in the catalytic reaction stage, the particle size distribution is smaller than that of a common impregnation method, and more active sites can be provided for the catalytic reaction; on the other hand, the industrial catalyst needs to be regenerated after being deactivated, and the catalyst with silicon oxide limited area can effectively avoid the sintering problem caused by high-temperature roasting, and keep the original dispersion degree, thereby maintaining the original majority of activity and obviously reducing the catalyst cost occupying a large head in the noble metal hydrogenation reaction.
According to the current research on the reaction system, the main reaction of carbonyl hydrogenation is the first step, and the subsequent further hydrogenation is a deep hydrogenation side reaction. Therefore, avoiding excessive hydrogenation is an important way to effectively improve the selectivity of the reaction. The metallic palladium in the catalyst is the site of the activated hydrogen molecules, and the activated hydrogen species are distributed on the surface, inside and dispersed to the carrier or other metal elements near the particles by hydrogen flooding. Because palladium metal is an activation site and the concentration of hydrogen species is highest, if anthraquinone molecules directly react on palladium, side reaction of deep hydrogenation is easier to occur, and the selectivity is not favorably improved; the silicon oxide can separate anthraquinone macromolecules from palladium particles by limiting the range of the palladium particles, so that the anthraquinone molecules are hydrogenated in a region with relatively low hydrogen concentration, side reactions are inhibited, and the selectivity is improved. Comprehensively, the balance of catalytic activity and selectivity is achieved by improving the dispersion degree and limiting the reaction area, the improvement of catalyst regeneration is considered, and the catalyst has higher popularization value and application value.
Optionally, the noble metal is selected from at least one of palladium and platinum.
Optionally, the mass content of the active component in the catalyst is 0.05-0.3%;
the mass of the active component is based on the mass of the noble metal.
In the present application, the upper limit of the mass percentage of the active component in the catalyst is selected from 0.25 wt%, 0.4 wt%, 0.5 wt%, and the lower limit of the mass percentage of the active component in the catalyst is selected from 0.1 wt%, 0.25 wt%, 0.4 wt%.
In the application, the mass percentage of the active component in the catalyst is preferably 0.05-0.3 wt%.
Optionally, the mass content of the confinement layer in the catalyst is 0.05-0.5%;
the mass of the confinement layer is based on the mass of silicon dioxide.
Alternatively, the upper limit of the mass percent of silica in the catalyst is selected from 0.25 wt%, 0.4 wt%, 1.9 wt%, 2 wt%, and the lower limit of the mass percent of silica in the catalyst is selected from 0.1 wt%, 0.25 wt%, 0.4 wt%, 1.9 wt%.
In the present application, the content of the silicon oxide in the catalyst is preferably 0.05 to 0.5 wt%.
Optionally, the confinement layer is fully or partially coated on the surface of the active component.
Optionally, the pore diameter of the carrier is 2-50 nm; the specific surface area is 50-250 m2(ii)/g; the pore volume is 0.5-1.5 ml/g; the bulk density is 0.3 to 1.0 g/ml.
Optionally, the particle size of the active component is 0.5-4.0 nm.
According to a second aspect of the present application, there is provided a method of preparing the above catalyst, the method comprising:
(1) loading a mixture containing a noble metal ammonia complex source and silicon dioxide to obtain an intermediate product I;
(2) reacting the mixture containing the intermediate product I, the silicon dioxide source and the initiator I, and roasting to obtain an intermediate product II;
(3) and reducing the intermediate product II in a hydrogen-containing atmosphere to obtain the catalyst.
Optionally, the silica source is selected from hydrolyzable compounds of silicon;
the initiator is selected from any one of acid and alkali;
the source of noble metal ammine complexes is selected from noble metal ammine complex salts.
Optionally, in the hydrogen-containing atmosphere, an inert gas is further contained, and the inert gas is selected from at least one of nitrogen and inert gas.
Optionally, the volume percentage of the hydrogen in the hydrogen-containing atmosphere is 10-30%.
Optionally, the silicon hydrolyzable compound is selected from at least one of an orthosilicate compound and a silicate compound;
the acid is at least one of nitric acid, hydrochloric acid, sulfuric acid, hydrobromic acid and phosphoric acid;
the alkali is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water;
preferably, the orthosilicate ester compound is selected from at least one of methyl orthosilicate and ethyl orthosilicate; the silicate compound is selected from at least one of sodium silicate and potassium silicate.
Optionally, in the step (2), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-6 h;
the roasting conditions are as follows: the temperature is 400-500 ℃; the time is 4-8 h;
in the step (3), the reduction conditions are as follows: the temperature is 80-400 ℃; the time is 4-8 h.
Alternatively, the upper limit of the reduction temperature is selected from 300 ℃, 350 ℃, 400 ℃, 500 ℃, and the lower limit of the reduction temperature is selected from 250 ℃, 300 ℃, 350 ℃, 400 ℃. The upper limit of the reduction time is 4h, 8h and 12h, and the lower limit of the reduction time is 1h, 2h and 3 h.
Optionally, the mass ratio of the noble metal ammonia complex source to the silica source is 0.42-5.08: 5: 1.27 to 8.67;
wherein the mass of the noble metal ammine complex source is based on the mass of the noble metal ammine complex source, the mass of the silica is based on the mass of the silica itself, and the mass of the silica source is based on the mass of the silica source.
Optionally, the method comprises at least the steps of:
a) obtaining a solution containing a palladium precursor, and soaking a carrier in the solution to obtain a catalyst precursor;
b) obtaining a solution containing a silicon oxide precursor, and soaking the obtained catalyst precursor in the solution to obtain a catalyst precursor containing the silicon oxide precursor;
c) and (3) obtaining a solution containing a silicon oxide precursor hydrolysis polycondensation initiator, and soaking the obtained catalyst precursor containing the silicon oxide precursor into the solution to obtain the catalyst precursor containing the limited-area silicon oxide precursor.
Optionally, the palladium precursor comprises palladium-ammonia complex, and the silicon oxide precursor comprises methyl orthosilicate, ethyl orthosilicate, sodium silicate and the like.
Specifically, in the present application, the silica confinement precursor is obtained by an impregnation method, in which a solution containing a silica precursor is further impregnated on the basis of a catalyst precursor in which a palladium precursor has been impregnated, and then the silica precursor is hydrolyzed to form a chain-like or network-like gel, which is dehydrated by a drying and baking method to form a silica confinement layer covering the palladium nanoparticles.
Optionally, a) comprises the following steps:
a-1) mixing a solution containing an active component source with ammonia water to obtain a solution containing a metal ammonia complex;
a-2) dipping a carrier in the mixed solution to obtain a catalyst precursor.
Specifically, a-1) a solution containing a source of an active component is mixed with aqueous ammonia under heating to obtain a solution containing a metal ammonia complex.
In the step a-1), ammonia water is concentrated ammonia water, and the mass concentration of the concentrated ammonia water is 25-28 wt%.
In the step a-2), the pH value of the ammonia water used for the metal ammonia complex solution is 10-12. For example, pH 10, pH 11, pH 12.
Optionally, the mass percentage concentration of the active component in the mixed solution is 0.01-0.3 wt%.
Optionally, the mass percentage concentration of the silicon oxide in the mixed solution is 0.1-0.5 wt%.
The content of the active component in the mixed solution is calculated by the content of the metal element; the content of silica in the mixed solution is calculated as the content of silica molecules.
The palladium source is optionally a soluble palladium salt selected from at least one of the salts of palladium, e.g., palladium nitrate, palladium chloride, palladium bromide, palladium iodide.
Alternatively, the silica source is a soluble silicon compound selected from at least one of the hydrolyzable compounds of silicon, for example, methyl orthosilicate, ethyl orthosilicate, sodium silicate or potassium silicate, and the like.
In the present application, the palladium-ammonia complex formed is an inorganic ammonia complex, and the kind of the anion of the complex is not limited, and may be, for example, a halogen ion or a nitrate ion. The palladium-ammonia complex may be tetraammine palladium nitrate, tetraammine palladium chloride, tetraammine palladium bromide, tetraammine palladium iodide, etc.
In the application, the formed limited-domain silica precursor is a chain or net-shaped gel of silica, can be dehydrated and condensed through high-temperature roasting, is combined with a carrier which is also the silica, and plays a role in coating and semi-coating the loaded palladium nanoparticles to achieve the limited-domain effect.
According to a third aspect of the present application, there is provided a method for preparing hydrogen peroxide, the method comprising: reacting II raw materials containing anthraquinone in the presence of a catalyst to obtain the catalyst;
the catalyst is at least one selected from the group consisting of the above-mentioned catalysts and the catalysts prepared according to the above-mentioned methods.
Alternatively, the conditions of reaction II are: the temperature is 30-60 ℃; the time is 2-4 h.
Optionally, the anthraquinone is selected from at least one of 2-ethyl anthraquinone, 2-pentyl anthraquinone.
In the hydrogenation process of producing hydrogen peroxide by the anthraquinone method, anthraquinone molecules are large and are limited in diffusion in the catalyst, so that excessive hydrogenation of the anthraquinone can be caused to generate irreversible side reactions after the anthraquinone molecules are left on the catalyst for a long time, and the selectivity is reduced. Therefore, one method for preventing the excessive hydrogenation caused by the long-term retention of the anthraquinones is to reduce the concentration of the active hydrogen species at the positions of the anthraquinones, and to effectively improve the reaction selectivity because the side reactions cannot proceed due to the lack of reactants. The activity reduction caused by the reduction of the concentration of the active hydrogen species can be solved and improved by improving the dispersion degree of the active components and providing a larger number of reaction sites. Due to the great improvement of the dispersity, the use amount of the noble metal can be reduced partially, and the economic benefit for reducing the cost of the catalyst is greatly improved. In practical application, the active components in the catalyst often depend on forming chemical bonds with a carrier or by virtue of pore channel confinement, carbon deposition is often required to be removed by virtue of a combustion method after the catalyst is deactivated in a reaction in which organic matters participate, the dispersity is often reduced due to Ostwald ripening, and the activity after regeneration is far lower than that before deactivation.
The metal ammonia complex is strongly adsorbed with the surface of the carrier in an environment above the isoelectric point of the carrier in a static manner, the complex is dispersed on the surface of the carrier in a molecular level manner, and the loaded metal ammonia complex is coated or semi-coated by the silicon oxide confinement effect in the process and is fixed on an adsorption site. When the strong electrostatic adsorption between the metal ammonia complex and the carrier is lost after high-temperature roasting and reduction, the silicon oxide confinement effect can keep palladium atoms at the initial position without aging growth, thereby ensuring higher dispersion degree.
The beneficial effects that this application can produce include:
(1) the adoption of the silicon oxide confinement can effectively prevent the curing phenomenon in the process of roasting and reducing the catalyst, effectively improve the dispersion degree, obtain reaction active sites of multiple times and improve the reaction rate and the production capacity;
(2) the limited domain effect of the silicon oxide enables the anthraquinone to react in the area with lower concentration of active hydrogen species, thereby inhibiting the occurrence of side reaction, improving the selectivity and prolonging the service life of the catalyst;
(3) the palladium in the silicon oxide confinement is not easy to sinter, the regeneration and recovery activity of the catalyst is obviously improved, the recycling frequency of the catalyst is improved, the cost of the catalyst is further reduced, and the economic benefit is improved.
Drawings
FIG. 1 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 1;
FIG. 2 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 2;
FIG. 3 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 3;
FIG. 4 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 4;
FIG. 5 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 5;
FIG. 6 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 6;
FIG. 7 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 7;
FIG. 8 is a graph showing the results of evaluation of the hydrogenation performance of sample No. 8;
FIG. 9 is a HRTEM test of sample # 1;
FIG. 10 is an HRTEM test of sample # 1;
fig. 11 is a statistical graph of the particle size distribution of the palladium nanoparticles of sample # 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In accordance with one embodiment of the present application,
1. a silicon oxide limited-area palladium-based catalyst for preparing hydrogen peroxide by anthraquinone hydrogenation uses mesoporous silicon oxide as a carrier, and the catalyst is composed of Pd @ SiO2/SiO2The catalyst is prepared by an impregnation method, washing, drying, roasting and reducing, and is subjected to anthraquinone hydrogenation activity test at a reaction temperature of 30-60 ℃, wherein the content of palladium in the catalyst is 0.05-0.3 wt%, and the content of silicon oxide in the confinement layer is 0.1-0.5 wt%.
2. The carrier is formed mesoporous silica, the carrier is spherical, and the aperture of catalyst particles is 2-50 nm.
3. The specific surface area of the carrier is 200-450 m2(iii) a pore volume of 0.5 to 1.5ml/g and a bulk density of 0.6 to 1.0 g/ml.
4. A hydrogen reduction method is adopted.
5. Firstly, preparing an acidic palladium solution into an ammonia complex precursor, soaking the precursor solution on a silicon oxide carrier, and then washing, drying, reducing and the like to obtain the palladium catalyst, wherein the atmosphere is nitrogen or hydrogen balanced by inert gases such as argon and the like.
6. One of sodium silicate, potassium silicate and the like is prepared into an aqueous solution, or one of methyl orthosilicate, ethyl orthosilicate and the like is prepared into an ethanol solution, and the ethanol solution is soaked on the dried palladium precursor.
7. The palladium source used for preparing the palladium-based catalyst is palladium nitrate, palladium chloride, palladium bromide or palladium iodide, and the concentration of the palladium source is generally 400-2500 ppm.
8. The silicon source used for preparing the limited-area silicon oxide is soluble silicate or orthosilicate, such as sodium silicate, potassium silicate, methyl orthosilicate or ethyl orthosilicate, and the like, and the concentration of the silicon source is generally 700-
9. The prepared palladium-based catalyst is highly dispersed on a silicon oxide carrier in a nano shape, and the particle size of the palladium nano is 0.7-2.1 nm.
Example 1
(1-1) weighing 0.4166g of PdCl2(the mass content of palladium is 59.5 percent) is dissolved in 5mL of 1mol/L diluted hydrochloric acid to prepare a solution, and PdCl is added under the condition of heating to slight boiling2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then is completely dissolved to obtain a light green transparent palladium tetraammine dichloride solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 9 to obtain a solution containing the palladium-ammonia complex;
(1-2) weighing 2.3650g of Na2SiO3·9H2Dissolving O (the content of silicon oxide is 21.1%) in 6.8mL 1mol/L strong ammonia water to prepare a solution, and stirring until the solution is completely dissolved to obtain a solution containing a silicon oxide precursor;
(1-3) weighing 5.00g of fully dried spherical mesoporous silica carrier with the carrier ratio of 450m2(iv)/g, the pore diameter is 2nm, the pore volume is 0.5mL/g, and the bulk density is 1.1g/mL, adding the solution containing the palladium-ammonia complex in the step (1-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate; (1-4) uniformly dripping the silicon oxide precursor-containing solution in the step (1-2) into the intermediate obtained in the step (1-3), fully stirring, standing for one night, and drying at 120 ℃ for 2 hours to obtain a limited-area silicon oxide precursor;
(1-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 400 ℃ for 4h to obtain a catalyst precursor;
(1-6) placing the catalyst precursor in a tube furnace in H2Reducing for 4h at 80 ℃ in the atmosphere to obtain the silica limited-area palladium-based catalyst which is marked as sample No. 1;
in sample # 1, the mass percent of palladium in this sample was 0.05 wt% and the mass percent of the confined silica in this sample was 0.1 wt%.
Example 2
(2-1) weighing 1.2516g Pd (NO)3)2·2H2Dissolving O (palladium content 39.9%) in 5mL of 1mol/L dilute nitric acid to obtain a solution, heating to slightly boiling, and adding Pd (NO)3)2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then is completely dissolved to obtain a light green transparent tetraamminepalladium dinitrate solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 10 to obtain a solution containing the palladium-ammonia complex;
(2-2) weighing 6.4193g K2SiO3(the content of silicon oxide is 38.9%) is dissolved in 6.8mL of 1mol/L strong ammonia water to prepare a solution, and the solution is stirred until the solution is completely dissolved, so that a solution containing a silicon oxide precursor is obtained;
(2-3) weighing 5.00g of fully dried spherical mesoporous silica carrier with the carrier ratio table of 280m2(iv)/g, the pore diameter is 20nm, the pore volume is 1.0mL/g, and the bulk density is 0.71g/mL, adding the solution containing the palladium-ammonia complex in the step (2-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(2-4) uniformly dripping the silicon oxide precursor-containing solution in the step (2-2) into the intermediate obtained in the step (2-3), fully stirring, standing for one night, and drying at 120 ℃ for 2 hours to obtain a limited-area silicon oxide precursor;
(2-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 400 ℃ for 8h to obtain a catalyst precursor;
(2-6) placing the catalyst precursor in a tube furnace in H2And N2Mixed gas(H2The volume percentage of the catalyst in the mixed gas is 10 percent), reducing the catalyst for 8 hours at 150 ℃ to obtain a silicon oxide limited-area palladium-based catalyst which is marked as sample No. 2; in sample # 2, the mass percent of palladium in this sample was 0.1 wt% and the mass percent of the confined silica in this sample was 0.5 wt%.
Example 3
(3-1) weighing 2.5017g of PdBr2(palladium content: 39.9%) was dissolved in 5mL of 1mol/L diluted hydrochloric acid to prepare a solution, and PdBr was added thereto under heating to slightly boiling conditions2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then completely dissolved to obtain a light green transparent dibromo-tetraammine palladium solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 11 to obtain a solution containing the palladium-ammonia complex;
(3-2) weighing 2.3650g of Na2SiO3·9H2Dissolving O (silicon oxide content 21.1%) in 6.8mL of 1mol/L concentrated ammonia water to prepare a solution, and stirring until the solution is completely dissolved to obtain a solution containing a silicon oxide precursor;
(3-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 200m2/g, the pore diameter is 50nm, the pore volume is 1.5mL/g, and the bulk density is 0.53g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (3-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(3-4) uniformly dripping the silicon oxide precursor-containing solution in the step (3-2) into the intermediate obtained in the step (3-3), fully stirring, standing for one night, and drying at 120 ℃ for 2 hours to obtain a limited-area silicon oxide precursor;
(3-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 400 ℃ for 4h to obtain a catalyst precursor;
(3-6) placing the catalyst precursor in a tube furnace, and reducing for 4H at 250 ℃ in the atmosphere of H2 to obtain the silicon oxide limited-area palladium-based catalyst which is marked as sample No. 3;
in sample # 3, the mass percent of palladium in this sample was 0.2 wt% and the mass percent of the confined silica in this sample was 0.1 wt%.
Example 4
(4-1) weighing 5.0772g of PdI2(Palladium content: 29.5%) was dissolved in 5mL of 1mol/L diluted hydrochloric acid to prepare a solution, and the solution was heated to slightly boiling condition, followed by addition of Pd (NO)3)2Dropwise adding 20mL of concentrated ammonia water into the solution until precipitation is generated and then completely dissolving to obtain a light green transparent tetraamminepalladium dinitrate solution, and fixing the volume to 100.00mL by using diluted ammonia water with the pH value of 12 to obtain a solution containing palladium-ammonia complex;
(4-2) weighing 6.4193g K2SiO3(the content of silicon oxide is 38.9%) is dissolved in 6.8mL of 1mol/L strong ammonia water to prepare a solution, and the solution is stirred until the solution is completely dissolved, so that a solution containing a silicon oxide precursor is obtained;
(4-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 450m2/g, the pore diameter is 2nm, the pore volume is 1.5mL/g, and the bulk density is 0.53g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (4-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(4-4) uniformly dripping the silicon oxide precursor-containing solution in the step (4-2) into the intermediate obtained in the step (4-3), fully stirring, standing for one night, and drying at 120 ℃ for 2 hours to obtain a limited-area silicon oxide precursor;
(4-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 400 ℃ for 8h to obtain a catalyst precursor;
(4-6) placing the catalyst precursor in a tube furnace, and reducing for 8H at 400 ℃ in the atmosphere of a mixed gas of H2 and N2 (the volume percentage of H2 in the mixed gas is 10%), so as to obtain the silicon oxide limited-area palladium-based catalyst, which is marked as sample No. 4;
in sample # 4, the mass percent of palladium in this sample was 0.3 wt% and the mass percent of the confined silica in this sample was 0.5 wt%.
Example 5
(5-1) weighing 0.4166g of PdCl2(palladium content: 59.5%) dissolvedPreparing a solution in 5mL of 1mol/L diluted hydrochloric acid, heating to slightly boiling, and adding PdCl2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then is completely dissolved to obtain a light green transparent palladium tetraammine dichloride solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 9 to obtain a solution containing the palladium-ammonia complex;
(5-2) weighing 1.2667g of methyl orthosilicate (with the silicon oxide content of 21.1%) and dissolving the methyl orthosilicate in 6.8mL of ethanol to prepare a solution, and stirring the solution until the methyl orthosilicate is completely dissolved to obtain a solution containing a silicon oxide precursor;
(5-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 200m2/g, the pore diameter is 50nm, the pore volume is 1.0mL/g, and the bulk density is 0.71g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (5-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(5-4) uniformly dripping the silicon oxide precursor-containing solution in the step (5-2) into the intermediate obtained in the step (5-3), fully stirring, standing for one night, and drying at 60 ℃ for 4 hours to obtain a limited-area silicon oxide precursor;
(5-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 500 ℃ for 4h to obtain a catalyst precursor;
(5-6) placing the catalyst precursor in a tube furnace in H2Reducing for 8h at 80 ℃ in the atmosphere to obtain the silica limited-area palladium-based catalyst which is marked as sample No. 5;
in sample # 5, the mass percent of palladium in this sample was 0.05 wt% and the mass percent of the confined silica in this sample was 0.1 wt%.
Example 6
(6-1) weighing 1.2516g Pd (NO)3)2·2H2Dissolving O (palladium content 39.9%) in 5mL of 1mol/L dilute nitric acid to obtain a solution, heating to slightly boiling, and adding Pd (NO)3)2Dripping 20mL of concentrated ammonia water into the solution until the precipitate is generated and then is completely dissolved to obtain a light green transparent tetraamminepalladium dinitrate solution, and diluting with a dilute solution with the pH value of 10Ammonia water is added to a constant volume of 100.00mL, and a solution containing palladium-ammonia complex is obtained;
(6-2) weighing 8.6683g of tetraethoxysilane (the content of silicon oxide is 28.8%) and dissolving in 6.8mL of ethanol to prepare a solution, and stirring until the solution is completely dissolved to obtain a solution containing a silicon oxide precursor;
(6-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 200m2/g, the pore diameter is 50nm, the pore volume is 0.5mL/g, and the bulk density is 1.1g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (6-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(6-4) uniformly dripping the silicon oxide precursor-containing solution in the step (2-2) into the intermediate obtained in the step (6-3), fully stirring, standing for one night, and drying at 60 ℃ for 4 hours to obtain a limited-area silicon oxide precursor;
(6-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 500 ℃ for 8h to obtain a catalyst precursor;
(6-6) placing the catalyst precursor in a tube furnace, and reducing the catalyst precursor for 8 hours at 150 ℃ in the atmosphere of H2 and N2 mixed gas (the volume percentage of H2 in the mixed gas is 10%), thus obtaining the silicon oxide limited-area palladium-based catalyst, which is marked as sample No. 6;
in sample # 6, the mass percent of palladium in this sample was 0.1 wt% and the mass percent of the confined silica in this sample was 0.5 wt%.
Example 7
(7-1) weighing 2.5017g of PdBr2(palladium content: 39.9%) was dissolved in 5mL of 1mol/L diluted hydrochloric acid to prepare a solution, and PdBr was added thereto under heating to slightly boiling conditions2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then completely dissolved to obtain a light green transparent dibromo-tetraammine palladium solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 11 to obtain a solution containing the palladium-ammonia complex;
(7-2) weighing 1.2667g of methyl orthosilicate (with the silicon oxide content of 21.1%) and dissolving the methyl orthosilicate in 6.8mL of ethanol to prepare a solution, and stirring the solution until the methyl orthosilicate is completely dissolved to obtain a solution containing a silicon oxide precursor;
(7-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 360m2/g, the pore diameter is 20nm, the pore volume is 1.0mL/g, and the bulk density is 0.71g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (7-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(7-4) uniformly dripping the silicon oxide precursor-containing solution in the step (7-2) into the intermediate obtained in the step (7-3), fully stirring, standing for one night, and drying at 60 ℃ for 4 hours to obtain a limited-area silicon oxide precursor;
(7-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 500 ℃ for 4h to obtain a catalyst precursor;
(7-6) placing the catalyst precursor in a tube furnace, and reducing for 8 hours at 250 ℃ in the atmosphere of H2 to obtain the silicon oxide limited-area palladium-based catalyst, which is marked as sample No. 7;
in sample 7#, the mass percent of palladium in the sample was 0.2 wt% and the mass percent of the confined silica in the sample was 0.1 wt%.
Example 8
(8-1) weighing 5.0772g of PdI2(Palladium content: 29.5%) was dissolved in 5mL of 1mol/L diluted hydrochloric acid to prepare a solution, and the solution was heated to slightly boiling condition, followed by addition of Pd (NO)3)2Dropwise adding 20mL of concentrated ammonia water into the solution until the precipitate is generated and then is completely dissolved to obtain a light green transparent tetraamminepalladium dinitrate solution, and fixing the volume to 100.00mL by using dilute ammonia water with the pH value of 12 to obtain a solution containing the palladium-ammonia complex;
(8-2) weighing 8.6683g of tetraethoxysilane (the content of silicon oxide is 28.8 percent) and dissolving the tetraethoxysilane in 6.8mL of ethanol to prepare a solution, and stirring the solution until the solution is completely dissolved to obtain a solution containing a silicon oxide precursor;
(8-3) weighing 5.00g of fully dried spherical mesoporous silica carrier, wherein the carrier ratio table is 450m2/g, the pore diameter is 2nm, the pore volume is 1.5mL/g, and the bulk density is 0.53g/mL, adding the carrier into the solution containing the palladium-ammonia complex in (8-1), violently shaking for 4h at 25 ℃, filtering, washing with deionized water, and drying for 2h at 120 ℃ to obtain an intermediate;
(8-4) uniformly dripping the silicon oxide precursor-containing solution in the step (8-2) into the intermediate obtained in the step (8-3), fully stirring, standing for one night, and drying at 60 ℃ for 4 hours to obtain a limited-area silicon oxide precursor;
(8-5) fully washing the limited-area silicon oxide precursor by using dilute nitric acid with the pH value of 5, then drying at 120 ℃ for 12h, and then roasting in a muffle furnace at 500 ℃ for 8h to obtain a catalyst precursor;
(8-6) placing the catalyst precursor in a tube furnace, and reducing for 8H at 400 ℃ in the atmosphere of H2 and N2 mixed gas (the volume percentage of H2 in the mixed gas is 10%), so as to obtain the silicon oxide limited-domain palladium-based catalyst, which is marked as sample No. 8;
in sample # 8, the mass percent of palladium in this sample was 0.3 wt% and the mass percent of the confined silica in this sample was 0.5 wt%.
Example 9
The TEM test is carried out on samples 1# to 8# respectively, and the test instrument is a Japanese JEOL JEM-ARM200F type spherical aberration correction projection electron microscope.
Taking sample # 1 as a typical representative, fig. 9 and 10 are HRTEM test images of sample # 1, fig. 9 shows that the palladium particles in the silica-confined palladium particles are coated by the silica-confined layer, fig. 10 shows that the palladium particles are dispersed in a nano-shape on the silica support, and the palladium particles have a particle size range of 0.06-2.58 nm and an average particle size of 1.17 nm. Fig. 11 is a statistical graph of the particle size distribution of palladium of sample # 1, and it can be seen from fig. 11 that most of the particle sizes are concentrated around the median 1.11nm and show a relatively uniform distribution.
Example 10
The evaluation of the catalyst is carried out in a high-pressure reaction kettle, and the method specifically comprises the following steps of preparing a working solution (the mass content of 2-amylanthraquinone in the working solution is 240g/L) from heavy aromatic hydrocarbon, diisobutylcarbinol (volume ratio is 3:2) and 2-amylanthraquinone, and respectively adding 1mL of a sample No. 1-8 catalyst and 150mL of the working solution into a 200mL high-pressure kettle (temperature is 40 ℃ and pressure is 2bar), wherein the feeding speed of the working solution is 1.0mL/min, and the hydrogen flow is 70 mL/min.
Oxidizing the hydrogenated liquid with oxygen, extracting with distilled water, and adding KMnO4The hydrogen peroxide produced was measured by titration and the hydrogenation efficiency (hydrogen efficiency) was calculated. The hydrogenated liquid refers to the working liquid taken out from the reaction kettle after the hydrogenation reaction is finished.
Wherein:
b-hydrogenation efficiency (g/L);
C—KMnO4concentration of the solution (mol/L);
V0—KMnO4volume of solution (mL);
M—H2O2molar mass (g/mol);
v is the volume (mol/L) of the hydrogenation solution.
The space-time yield STY of hydrogen peroxide is the yield of hydrogen peroxide per unit mass of palladium per unit time and is calculated according to the following formula:
wherein:
STY-Mass of Hydrogen peroxide produced per gram of Palladium per day (kg)H2O2g-1 Pdd-1)；
B-hydrogenation efficiency of the catalyst (kg. L) calculated according to the above formula-1)；
QLFlow Rate (L.d) of the anthraquinone working fluid-1)；
m-the loading mass (g) of the catalyst;
θPd-catalyst palladium content (wt%);
the results of the evaluation of the hydrogenation performance of the catalysts from the sample No. 1 to the sample No. 8 are shown in the figures 1 to 8, and the catalysts are high in activity and good in stability and are suitable for the industrial production of anthraquinone hydrogenation.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A catalyst, characterized in that the catalyst comprises an active component, a support and a confinement layer; the active component is loaded on the carrier; the confinement layer is coated on the surface of the active component;
the confinement layer and the support are both selected from silica; the silicon hydroxyl on the surface of the confinement layer is connected with the silicon hydroxyl on the surface of the carrier through condensation reaction;
the active component includes a noble metal.
2. The catalyst according to claim 1, wherein the noble metal is at least one selected from the group consisting of palladium and platinum.
3. The catalyst according to claim 1, wherein the mass content of the active component in the catalyst is 0.05-0.3%;
the mass of the active component is based on the mass of the noble metal.
4. The catalyst of claim 1, wherein the confinement layer is present in the catalyst in an amount of 0.05 to 0.5% by mass;
the mass of the confinement layer is based on the mass of silicon dioxide.
5. The catalyst of claim 1, wherein the confinement layer is fully or partially coated on the surface of the active component.
6. The catalyst according to claim 1, wherein the pore size of the carrier is 2 to 50 nm; the specific surface area is 50-250 m2(ii)/g; the pore volume is 0.5-1.5 ml/g; the bulk density is 0.3-1.0 g/ml;
preferably, the particle size of the active component is 0.5-4.0 nm.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, characterized in that it comprises:
(1) loading a mixture containing a noble metal ammonia complex source and silicon dioxide to obtain an intermediate product I;
(2) reacting the mixture containing the intermediate product I, the silicon dioxide source and the initiator I, and roasting to obtain an intermediate product II;
(3) and reducing the intermediate product II in a hydrogen-containing atmosphere to obtain the catalyst.
8. The process according to claim 7, characterized in that the silica source is selected from hydrolysable compounds of silicon;
the initiator is selected from any one of acid and alkali;
the source of noble metal ammine complexes is selected from noble metal ammine complex salts;
preferably, the silicon hydrolyzable compound is selected from at least one of an orthosilicate compound and a silicate compound;
the acid is at least one of nitric acid, hydrochloric acid, sulfuric acid, hydrobromic acid and phosphoric acid;
the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water;
preferably, the orthosilicate ester compound is selected from at least one of methyl orthosilicate and ethyl orthosilicate; the silicate compound is selected from at least one of sodium silicate and potassium silicate;
preferably, in the step (2), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-6 h;
the roasting conditions are as follows: the temperature is 400-500 ℃; the time is 4-8 h;
in the step (3), the reduction conditions are as follows: the temperature is 80-400 ℃; the time is 4-8 h;
preferably, the mass ratio of the noble metal ammonia complex source to the silica source is 0.42-5.08: 5: 1.27 to 8.67;
wherein the mass of the noble metal ammine complex source is based on the mass of the noble metal ammine complex source, the mass of the silica is based on the mass of the silica itself, and the mass of the silica source is based on the mass of the silica source.
9. A preparation method of hydrogen peroxide is characterized by comprising the following steps: reacting II raw materials containing anthraquinone in the presence of a catalyst to obtain hydrogen peroxide;
the catalyst is selected from at least one of the catalyst of any one of claims 1 to 6, the catalyst prepared according to the method of claim 7 or 8.
10. The method of claim 9, wherein the conditions of reaction II are: the temperature is 30-60 ℃; the time is 2-4 h;
preferably, the anthraquinone is selected from at least one of 2-ethyl anthraquinone and 2-amyl anthraquinone.
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