CN109395782B - Composite carrier loaded nano palladium catalyst, preparation method thereof and application thereof in CO oxidation - Google Patents

Composite carrier loaded nano palladium catalyst, preparation method thereof and application thereof in CO oxidation Download PDF

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CN109395782B
CN109395782B CN201811202025.4A CN201811202025A CN109395782B CN 109395782 B CN109395782 B CN 109395782B CN 201811202025 A CN201811202025 A CN 201811202025A CN 109395782 B CN109395782 B CN 109395782B
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palladium
composite carrier
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catalyst
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CN109395782A (en
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章青
朱加明
王巧莹
李兵
姜欢欢
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Anhui Normal University
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Abstract

The invention discloses a composite carrier loaded nano palladium catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) taking Al2O3Mixing with water, adding metal halide for ultrasonic dispersion, adding cellulose, and performing ultrasonic dispersion to obtain a mixed solution; (2) adding carbonate solution into the mixed solution obtained in the step (1), mixing, crystallizing and drying to obtain a composite carrier; (3) and (3) soaking the composite carrier in the step (2) in a palladium salt solution, adjusting the pH of the solution to 7-10, adding borohydride, mixing and drying. The preparation method improves the adsorption dispersion and stability of the palladium compound; the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.

Description

Composite carrier loaded nano palladium catalyst, preparation method thereof and application thereof in CO oxidation
Technical Field
The invention relates to a nano palladium catalyst, in particular to a nano palladium catalyst loaded by a composite carrier, a preparation method thereof and application thereof in CO oxidation.
Background
With the expansion and development of modern industry and the consumption of fossil energy, the problem of environmental pollution is becoming more and more serious. Wherein the industrial waste gas and the transportationCarbon oxides in gas transmission and exhaust and coal mine tunnels pay attention to the harm of environmental pollution, especially the elimination of CO. CO is a colorless, odorless and toxic gas, has extremely strong toxicity, and seriously harms human health. At present, the elimination of CO mainly comprises a physical elimination method and a chemical elimination method. The physical elimination method mainly refers to the adsorption of CO by using some porous substances (such as activated carbon and the like) to reduce the residual amount of CO in the air, but it is difficult to select a suitable adsorption material, and the application of the method is limited because the equipment is large due to low adsorption efficiency. The chemical elimination method mainly comprises a catalytic reduction method and a catalytic oxidation method, wherein the best mode for eliminating low-concentration CO is the catalytic oxidation method, so that CO and O in air are obtained2Reaction to produce nontoxic CO2. However, the ignition point of CO in air is 700 ℃, and thus oxidative elimination at low temperature must be achieved using a catalyst. The catalyst mainly takes noble metals (Pd, Pt, Rh and Au) as active components. And for the stable catalyst, the method is complex, such as a wrapping or template method, the preparation period is long, and the process is complicated.
Therefore, the preparation of the high-performance nano Pd catalyst by using a simple method is very important.
Disclosure of Invention
The invention aims to provide a composite carrier loaded nano palladium catalyst, a preparation method thereof and application thereof in CO oxidation2O3Prepared on a composite carrier, (1) the method implants metal halide into carrier Al by utilizing a coprecipitation method2O3In the structure; (2) compounding Al with cellulose2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound; (3) the low-temperature reduction of sodium borohydride is utilized, so that the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
To achieve the above object, the present inventionA preparation method of a composite carrier loaded nano palladium catalyst is provided, and comprises the following steps: (1) taking Al2O3Mixing with water, adding metal halide for ultrasonic dispersion, adding cellulose, and performing ultrasonic dispersion to obtain a mixed solution; (2) adding carbonate solution into the mixed solution obtained in the step (1), mixing, crystallizing and drying to obtain a composite carrier; (3) and (3) soaking the composite carrier in the step (2) in a palladium salt solution, adjusting the pH of the solution to 7-10, adding borohydride, mixing and drying.
The invention also provides the composite carrier-supported nano palladium catalyst prepared by the preparation method.
Furthermore, the invention also provides an application of the composite carrier-supported nano palladium catalyst in CO oxidation.
Through the technical scheme, (1) the invention implants metal halide into carrier Al by utilizing a coprecipitation method2O3In the structure, Al is effectively changed2O3And the mode of action of the metal oxide, the electron-activating ability of the activated carrier; (2) compounding Al with cellulose2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound; (3) the low-temperature reduction of sodium borohydride is utilized, so that the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a transmission electron micrograph of a catalyst in example 7;
FIG. 2 is a graph of the performance of the catalyst in example 7 on CO oxidation elimination.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above object, the present invention provides a preparation method of a composite carrier supported nano palladium catalyst, comprising the steps of: (1) taking Al2O3Mixing with water, adding metal halide for ultrasonic dispersion, adding cellulose, and performing ultrasonic dispersion to obtain a mixed solution; (2) adding carbonate solution into the mixed solution obtained in the step (1), mixing, crystallizing and drying to obtain a composite carrier; (3) and (3) soaking the composite carrier in the step (2) in a palladium salt solution, adjusting the pH of the solution to 7-10, adding borohydride, mixing and drying.
According to the technical scheme, the metal halide is implanted into the carrier Al by utilizing a coprecipitation method2O3In the structure, Al is effectively changed2O3And the mode of action of the metal oxide, the electron-activating ability of the activated carrier; (2) compounding Al with cellulose2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound; (3) the low-temperature reduction of sodium borohydride is utilized, so that the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
The amount and ratio of addition of the raw materials can be selected within wide limits, and in a preferred embodiment of the invention, the metal halide is implanted with Al2O3On a carrier to further improve the low-temperature CO oxidation elimination performance of the catalyst, and in a preferred embodiment of the invention, Al2O3The ratio of the Al element in the metal halide to the amount of the carbonate in the metal halide is 3-20: 1: 0.9-1.1.
In a preferred embodiment of the present invention, in order to improve the performance of the catalyst for removing CO by low-temperature oxidation, the palladium salt solution contains 0.01 to 0.5g by mass of palladium element relative to 10g of the composite carrier in the step (2).
The amounts of water and borohydride salt used in step (1) for the cellulose can be chosen within wide limits, and in order to obtain a catalyst with a uniform particle size and a better low-temperature catalytic performance for CO, in a preferred embodiment of the invention, the amount of water and borohydride salt is relative to 10g of Al2O3The dosage of the cellulose is 0.1-2g, and the dosage of the water in the step (1) is 10-20 mL; the amount of borohydride salt used is 0.5-6.0mmol per 10g of the composite support in step (2) and can be selected within a wide range, and in order to obtain a catalyst having uniform particle size and good catalytic performance at low temperature for CO, the volume ratio of water to carbonate solution in step (1) is 1:0.8-1.2 in a preferred embodiment of the present invention.
The volume of the palladium salt solution can be selected within a wide range, and in order to obtain a catalyst with uniform particle size and better CO low-temperature catalytic performance, in a preferred embodiment of the invention, the volume of the palladium salt solution is 10-20mL relative to 10g of the composite carrier in the step (2).
The crystallization conditions in step (2) can be selected from a wide range, and in order to obtain a catalyst with uniform particle size and better low-temperature catalytic performance of CO, the crystallization temperature in step (2) is preferably 60-100 ℃.
The crystallization conditions in step (2) can be selected from a wide range, and in order to obtain a catalyst with uniform particle size and better low-temperature catalytic performance of CO, the crystallization time in step (2) is preferably 6-24 h.
The mixing conditions in step (3) can be selected from a wide range, and in order to obtain a catalyst with good low-temperature catalytic performance for CO, the mixing temperature after adding borohydride in step (3) is preferably 20-80 ℃.
The mixing conditions in step (3) can be selected from a wide range, and in order to obtain a catalyst with better CO low-temperature catalytic performance, the mixing time is preferably 5-24 h.
The metal halide can be selected in a wide range, and in order to obtain a catalyst with better CO low-temperature catalytic performance, the metal halide is preferably one or more of nickel halide, cobalt halide and zinc halide; further preferably, the metal halide is one or more of nickel chloride, cobalt chloride and zinc chloride.
The carbonate can be selected from a wide range, and in order to obtain a catalyst with better low-temperature catalytic performance of CO, the carbonate is preferably water-soluble carbonate, and further preferably sodium carbonate and/or potassium carbonate.
The palladium salt can be selected from a wide range, and in order to obtain a catalyst with better low-temperature catalytic performance of CO, the palladium salt is preferably a water-soluble palladium salt, and more preferably one or more of palladium chloride, palladium nitrate and palladium acetate.
For the borohydride, a wide range of selection can be made, and in order to obtain a catalyst with better low-temperature catalytic performance of CO, preferably, the borohydride is a water-soluble borohydride, and more preferably, the borohydride is sodium borohydride and/or potassium borohydride.
In the above technical solution, for Al2O3There are many options, for example, acidic alumina, basic or neutral alumina, in order to favor the dissolution of the metal halide under acidic or neutral conditions, and therefore, further in order to reduce the step of adjusting the acidity, in a preferred embodiment of the invention, for Al2O3Selection of raw materials of (1), preferablyAcidic Al2O3. Further, to benefit from Al2O3And co-precipitation of metal halides, preferably, Al2O3Is selected to be below 200 mesh, and in a preferred embodiment of the invention commercial, 100-200 mesh acidic Al is selected2O3。
In the above technical solution, the carbonate solution can be added at a plurality of rates and modes, and can be added to the mixed solution in the step (1) by pouring at one time, or can be added to the mixed solution in the step (1) by dropping.
In the above technical solution, the frequency of ultrasonic dispersion can be selected in a wide range, for example, 20-60kHz, and the catalyst with uniform particle size can be obtained, and in the examples of the present invention, the ultrasonic frequency is 40 kHz.
In the above technical solution, the mixing manner in step (2) can be selected in various ways, such as stirring, shaking, etc., and the present invention can be implemented, which is not described herein again.
In the above technical scheme, in the step (2), the crystallized product can be directly dried, or dried after being neutralized in water washing, and used as an intermediate product, which does not affect the generation of the final product of the invention.
The choice of reactor can take many forms, such as a beaker, flask, reaction vessel, etc., and in a preferred embodiment of the invention, a reaction vessel is chosen. In the step (3), preferably, in the mixing step after adding the borohydride salt, the reaction is carried out under the condition that the reaction vessel is sealed with a lid.
And (3) directly drying the product in the step (3) to be used as a catalyst, washing the product to be neutral before drying, and then drying the product to be used, wherein the good catalytic effect is achieved.
In the above technical solutions, there are various ways to adjust the pH of the solution in step (3), for example, a small amount of acidic solution such as hydrochloric acid, nitric acid, citric acid, etc. may be added, or a small amount of alkaline solution may be added dropwise, and for the adjustment of pH, the method belongs to a conventional technical means in the art, and is not described herein again.
The invention also provides the composite carrier-supported nano palladium catalyst prepared by the preparation method.
According to the technical scheme, the metal halide is implanted into the carrier Al by utilizing a coprecipitation method2O3In the structure, Al is effectively changed2O3And the mode of action of the metal oxide, the electron-activating ability of the activated carrier; (2) compounding Al with cellulose2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound; (3) the low-temperature reduction of sodium borohydride is utilized, so that the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
Furthermore, the invention also provides an application of the composite carrier-supported nano palladium catalyst in CO oxidation.
According to the technical scheme, the metal halide is implanted into the carrier Al by utilizing a coprecipitation method2O3In the structure, Al is effectively changed2O3And the mode of action of the metal oxide, the electron-activating ability of the activated carrier; (2) compounding Al with cellulose2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound; (3) the low-temperature reduction of sodium borohydride is utilized, so that the links of high-temperature roasting and high-temperature hydrogen reduction are avoided, and the thermal stability of Pd species is improved. The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
The present invention will be described in detail below by way of examples.
Example 1
1.7g of sodium carbonate was weighed and completely dissolved in 15g of water to obtain a sodium carbonate solution for use.
16.5g of acidic Al are weighed2O3(commercial, 100-mesh) and 16.5g of water are mixed and placed in a reaction kettle, then 3.8g of nickel chloride is added, ultrasonic dispersion is carried out for 10min, then 0.4g of cellulose is added, after full ultrasonic dispersion, the sodium carbonate solution is gradually dripped, fully and uniformly stirred, crystallization is carried out for 10h at the temperature of 80 ℃, then water washing is carried out until the solution is neutral, drying is carried out for standby application, and the nickel-doped Al is obtained2O3The composite carrier of (1), the molar ratio of Al to Ni is 10:1, and is marked as A.
10g of the above Al was weighed2O3The composite carrier is soaked in 17mL of palladium chloride solution with palladium concentration of 10mg/mL (namely the load of Pd in the dried catalyst is controlled to be 1%), the pH value of the solution is adjusted to 8, 0.8g of sodium borohydride is added, the solution is sealed by a cover, the solution is stirred for 10 hours at the temperature of 40 ℃, the solution is washed to be neutral by water, the solution is placed in a dryer and dried at room temperature, and the 1% Pd/A-C catalyst is obtained and is marked as Cat 1.
Example 2
The procedure and conditions were as in example 1 except that the amount of nickel chloride added was adjusted to 12.5g, i.e., the molar ratio of Al to Ni was adjusted to 3:1 and noted as B, to obtain a 1% Pd/B-C catalyst noted as Cat 2.
Example 3
The procedure and conditions were as in example 2 except that the palladium chloride was adjusted to palladium acetate to give a 1% PdC/B-C catalyst noted Cat 3.
Example 4
The procedure and conditions were as in example 2 except that the palladium chloride was adjusted to palladium nitrate to give a 1% PdN/B-C catalyst, noted Cat 4.
Example 5
The procedure and conditions were as in example 2 except that the amount of palladium chloride added was adjusted to adjust the Pd loading to 0.5% to give a 0.5% Pd/B-C1 catalyst, noted Cat 5.
Example 6
The procedure and conditions were as in example 2 except that the amount of cellulose added was adjusted to 2.0g to give a 1% Pd/B-C2 catalyst, noted Cat 6.
Example 7
The procedure and conditions were as in example 1 except that the amount of nickel chloride added was adjusted to 2.0g, i.e., the molar ratio of Al to Ni was adjusted to 20:1 and noted as C, to obtain a 1% Pd/C-C catalyst noted as Cat 7. The particle size of the catalyst is shown in FIG. 1 by transmission electron microscopy.
As can be seen from FIG. 1, the palladium particles in the catalyst have a small particle size and are uniformly dispersed on the carrier. The results of the measurements of the CO conversion at different temperatures were as in application example 1 and are shown in FIG. 2.
Example 8
The procedure and conditions were as in example 2 except that the amount of palladium chloride added was adjusted to adjust the Pd loading to 0.5% and the amount of cellulose added to 0.8g, to give a 0.5% Pd/C-C0 catalyst, which was designated Cat 8.
Example 9
The procedure was as in example 2 except that nickel chloride was adjusted to cobalt chloride and the molar ratio of Al to Co was adjusted to 3:1 to give a catalyst, noted Cat 9.
Example 10
The procedure was as in example 2 except that nickel chloride was adjusted to zinc chloride and the molar ratio of Al to Zn was adjusted to 3:1 to give a catalyst, noted Cat 10.
Example 11
(1) Taking 10g of Al2O3Mixing with 10mL of water, adding nickel chloride for ultrasonic dispersion, adding 0.1g of cellulose, and performing ultrasonic dispersion to obtain a mixed solution;
(2) adding 8mL of carbonate solution into the mixed solution obtained in the step (1), mixing, stirring at 60-100 ℃ for 6-24h, crystallizing, and drying to obtain a composite carrier;
wherein, Al2O3The mass ratio of Al element in the nickel chloride, nickel element in the nickel chloride and sodium carbonate is 3: 1: 0.9,
(3) and (3) soaking 10g of the composite carrier in the step (2) in 15mL of palladium salt solution, adjusting the pH value of the solution to 10, adding 0.01mol of sodium borohydride, mixing at 20 ℃ for 24h, and drying, wherein the mass content of palladium element in the palladium salt solution is 0.01 g. The catalyst was obtained and was designated Cat 11.
Example 12
(1) Taking 10g of Al2O3Mixing with 20mL of water, adding nickel chloride for ultrasonic dispersion, adding 2g of cellulose for ultrasonic dispersion to obtain a mixed solution;
(2) adding 24mL of carbonate solution into the mixed solution obtained in the step (1), mixing, stirring at 100 ℃ for 6h, crystallizing, and drying to obtain a composite carrier;
wherein, Al2O3The mass ratio of Al element in the nickel chloride, nickel element in the nickel chloride and sodium carbonate is 20: 1: 1.1,
(3) and (3) soaking 10g of the composite carrier in the step (2) in 10mL of palladium salt solution, adjusting the pH value of the solution to 8, adding 0.05mol of sodium borohydride, mixing at 80 ℃ for 5h, and drying, wherein the mass content of palladium element in the palladium salt solution is 0.5 g. A catalyst was obtained, which was designated Cat 12.
Comparative example 1
The procedure and conditions were as in example 2 except that no sodium borohydride was added to give the catalyst which was designated Cat-D1.
Application example 1
30mg of the catalysts of examples 1 to 12 and comparative examples 1 to 4 were weighed and loaded into a mini-fixed bed reactor, the catalyst was pre-reduced at 200 ℃ for 0.5h in a hydrogen atmosphere, then cooled to room temperature, purged with inert gas Ar for 20min, and then switched to CO/O2The reaction was carried out with/Ar reaction gas (volume ratio, 1/1/98). Space velocity of raw material gas 50000h-1The results of the CO oxidation elimination performance are shown in Table 1.
TABLE 1
Catalyst and process for preparing same CO conversion (%) Ignition temperature (. degree.C.)
Cat 1 100 150
Cat 2 100 180
Cat 3 100 180
Cat 4 100 180
Cat 5 100 150
Cat 6 100 180
Cat 7 100 130
Cat 8 100 160
Cat 9 100 170
Cat 10 100 170
Cat 11 100 160
Cat 12 100 150
Cat D1 100 290
According to the detection results, it can be seen that:
(1) because the CO-precipitation method is used to significantly lower the CO ignition temperature of the metal halide (nickel, cobalt or zinc), we speculate that the metal halide (nickel, cobalt or zinc) is implanted into the carrier Al2O3In the structure, Al is effectively changed2O3And the mode of action of the metal oxide, the electron-activating ability of the carrier is activated.
(2) The CO ignition temperature can be obviously reduced after the cellulose is added, and the reason is considered that the cellulose is used for compounding Al2O3Modification of the support to improve Al2O3The surface group characteristic of the carrier improves the adsorption dispersion and stability of the palladium compound;
(3) under the condition of reduction without adding sodium borohydride, the prepared catalyst precursor needs to be subjected to high-temperature roasting and hydrogen reduction, catalyst particles are easy to agglomerate and sinter, and the links of high-temperature roasting and high-temperature hydrogen reduction are avoided by utilizing the low-temperature reduction of the sodium borohydride, so that the thermal stability of Pd species is improved.
The preparation method is simple and easy to control, has high popularization and application values, and the catalyst shows excellent CO low-temperature oxidation elimination performance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of a composite carrier loaded nano palladium catalyst is characterized by comprising the following steps:
(1) taking Al2O3Mixing with water, adding metal halide for ultrasonic dispersion, adding cellulose, and performing ultrasonic dispersion to obtain a mixed solution;
(2) adding carbonate solution into the mixed solution obtained in the step (1), mixing, crystallizing and drying to obtain a composite carrier;
(3) soaking the composite carrier in the step (2) in a palladium salt solution, adjusting the pH of the solution to 7-10, adding borohydride, mixing and drying;
the metal halide is one or more of nickel chloride, cobalt chloride and zinc chloride.
2. The method according to claim 1, wherein Al2O3The ratio of the Al element in the metal halide to the amount of the carbonate in the metal halide is 3-20: 1: 0.9-1.1.
3. The production method according to claim 2, wherein the palladium element content in the palladium salt solution is 0.01 to 0.5g by mass relative to 10g of the composite carrier in the step (2).
4. The production method according to any one of claims 1 to 3, wherein the amount of Al is 10g2O3The dosage of the cellulose is 0.1-2g, and the dosage of the water in the step (1) is 10-20 mL; the amount of the borohydride salt to be used is 0.5 to 5.0mmol relative to 10g of the composite carrier in the step (2).
5. The production method according to claim 4, wherein the volume ratio of water to the carbonate solution in step (1) is 1: 0.8-1.2;
and/or, the volume of the palladium salt solution is 10-20mL relative to 10g of the composite carrier in the step (2).
6. The preparation method according to claim 1, wherein the conditions for crystallization in step (2) include: the temperature is 60-100 ℃; and/or the time is 6-24 h.
7. The preparation method according to claim 1, wherein the mixing conditions after the addition of the borohydride salt in the step (3) are: the temperature is 20-80 ℃; and/or the time is 5-24 h.
8. The production method according to claim 1, wherein the carbonate is sodium carbonate and/or potassium carbonate;
and/or the palladium salt is one or more of palladium chloride, palladium nitrate and palladium acetate;
and/or the borohydride salt is sodium borohydride and/or potassium borohydride.
9. The composite carrier supported nano-palladium catalyst prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the composite carrier-supported nano-palladium catalyst of claim 9 in CO oxidation.
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