UA26168U - Method for application of multi-component system of oxide based on 3d-metals on carbonic nanotubes at synthesis of catalysts of co oxidation reaction - Google Patents

Abstract

A method for application of multi-component system of oxide base on 3d-metals on the carbon nanotubes at synthesis of the catalysts of the CO oxidation reaction includes step by step impregnation of nickel, cobalt and iron carbon nanotubes with the solution of the compound Cu2(OH)3NO3, which is preliminarily prepared by dissolution of corresponding quantity of metals in the nitric acid.

Description

Description of the invention

This useful model refers to the method of applying a catalytically active mass to carbon nanotubes 2 in the preparation of catalytic systems, in particular to the method of obtaining catalysts for the oxidation of CO to CO." More specifically, to the method of obtaining catalysts based on carbon nanotubes (CNTs), which are catalyst carriers.

Prediction of catalytic activity and synthesis of catalysts is a challenging problem. The catalyst must combine high selectivity with a high rate of product formation and maintain these properties for 70 of the entire period of operation. The main factor determining these qualities is the nature of the catalytically active phase, as well as the carrier material. The search for carriers for catalysts that would not reduce the activity of bulk samples is an urgent issue (|1). The synthesis of allotropic modifications of carbon - fullerenes and nanotubes - has opened up new prospects for the development of carbon chemistry and physics. The use of nanotubes as carriers is determined by their chemical resistance and developed surface. Catalysts can be obtained by filling the inner cavities of nanotubes and 12 by decorating them, in particular, directly by synthesizing the nanotubes themselves |21. Similar works related to the use of nanotubes as a basis for catalysts show the prospects of this direction, where their unique properties can be most fully realized.

This application discloses and describes Si-Co-Re oxide catalysts applied to carbon nanotubes for the ecologically important CO oxidation reaction. The mentioned reaction is also one of the most studied processes in heterogeneous catalysis, and therefore is convenient for modeling deep oxidation reactions in the gas phase involving molecular oxygen (11).

The use of CNTs as catalyst carriers is due to their high chemical resistance and sufficiently developed surface.

An industrial catalyst based on ruthenium applied to multilayered CNTs was studied in the hydrogenation reaction of cinnamic aldehyde (2, C). CNTs with a diameter of 4 nm and a length of up to 1 km were synthesized using the electric arc method. The catalyst was applied by impregnation with a solution of ruthenium 2,5-pentanedionate (acetylacetonate) followed by drying in a No/Mo stream at 423K. The amount of active mass was

Oh, 2 mass. 95. The specific surface area of the Ki/BNT catalyst was determined by Mo adsorption at 77K and was 27m/g; the distance between adjacent CNT layers is 0.353 nm. The size of the metal particles on the CNT surface, according to TEM data, varies from 3 to 7 nm. It was shown that there is a homogeneous distribution of metal clusters on the outer surface of the CNT. The use of this catalyst increases the yield of hydrocinnamic alcohol in the hydrogenation reaction of cinnamic aldehyde to 8095. At the same time, the recovery selectivity increases to 9295 compared to 20-4095 at --

Ky/AI2O»z with the same size of Ky particles. (Se)

The rhodium-based catalyst applied to CNTs (Imas.ob5) (4) is effective in the reaction of thermal decomposition of MO.

The massive catalyst has a temperature of 10095 conversion 6002. A catalyst with Tmas.o KI on VNT 100960 cm converts CO to CO" at 45020. A sample consisting of Imas.bo KI on y-AI2Oz at 70022; converts CO to only 5496.

In work |5)| presented data on the catalytic activity of KiB applied to CNTs in the hydrogenation reaction of 20 benzene. It is shown that the catalyst is in an amorphous state. w-in

The action of the MiMo catalyst applied to carbon nanofibers of flat and tubular types IE| studied in the hydrodesulfurization reaction of gas oil containing 340-350 ppm sulfur. Catalysts were prepared by the method of impregnation of the carrier with solutions of Mi and Mo acetylacetonates (ratio of 2 wt.% of MiO and 1 wt.% of MoO with) with sequential treatment with solutions of 1095 NMO»z and 1595 HO». For comparison, a traditional one was prepared in parallel

MiMo-catalyst deposited on AI2Oz containing 4 wt.bo of MiO and 1 b wt.o of MoOz. As a result of the study, it was established that the MiMo catalyst applied to the tubular type reduces the amount of sulfur to 57 ppm (flat to 180 ppm), while the traditional MiMo/AI2Oz reduces it to 141 ppm. The authors assume that (2) the reason for the increased catalytic activity of tubular-type nanofibers is their relatively high specific surface area with a large number of morphological defects.

In work (9-12), the oxidation of methanol on Ri, Ky, and PEKy binary alloy, which electrochemical

Me, method applied to different carbon carriers. Mesoporous carbon nanofibers had a specific surface area of 10 m2/g, and CNTs obtained by the method of catalytic growth and template synthesis were 220 m g/g and Zb0Om2/g, respectively.

The size of the catalyst particles (clusters) reached several nm. This explains the high catalytic activity

RIVER rafting on VNT.

In the work I7/| studied the catalytic activity of Ri deposited on carbon nanofibers in the oxidation reaction

CO. The size of the catalyst particles varies from 1.5 to 1.8 nm. Flat and tubular nanofibers were used with a specific surface area of 101m2/g and 213m7/g, respectively, which was measured by Mo adsorption at 77K. The amount of PE was mass... These catalysts were obtained by impregnation of the carrier with a solution of H»RISI 5.6NoO in isopropyl alcohol. To remove the solvent, the samples were heated to 90°C and then dried at 40°C for 60 hours. The most active catalysts of this series had a temperature of 10095 for the conversion of CO to CO. 20020. The authors attribute the decrease in catalytic activity to the small size of the Ri particles.

However, all of the above works do not describe catalytic systems for the oxidation reaction of CO to CO »5.

The closest analogue is the catalytic system described in works |8, 9).

This useful model is based on CNT. Carbon nanotubes with a diameter of 20 nm and a length of up to several microns were synthesized on nickel and cobalt catalysts at 5202C for 6 hours in an environment consisting of 9895 CO, 1956 CH; and 195 No according to the methodology |10). The obtained nanotubes were washed with a solution of nitric acid and dried. The obtained nanotubes were impregnated with Si-So-Re nitrate solution with the indicated ratio of metals. The amount of active mass was varied from 10 to 25 mass.oo.

The method of application of a multicomponent oxide system, which is an active catalyst for the oxidation of CO to CO" according to this useful model, which fundamentally differs from the state of the art in the method of its preparation. Namely, the catalyst is synthesized by stepwise impregnation of nickel, cobalt and iron carbon nanotubes with a solution of the compound Si(OH)zMO»z with an interval from 1 hour to 35 days, with a concentration from 1 to 47 wt.bu. The compound Si(OH)ZzMOz is previously obtained by dissolving the appropriate amount of metals in 7/0 nitric acid.

A more preferable method is the synthesis of an active catalyst for the oxidation of CO to CO" according to this useful model, which is synthesized by step-by-step impregnation of nickel, cobalt and iron carbon nanotubes with a solution of the compound Si(OH)ZMO", which is a multi-component oxide system based on za-metals, with an interval of 1 up to 14 days and with a concentration of 5 to 25 mass. 9 years.

The catalytic activity of the samples in the reaction of oxidation of carbon monoxide by molecular oxygen was measured on a flow-type installation at atmospheric pressure with chromatographic analysis of the reaction mixture.

The reaction mixture consisted of 2095 05, 295 CO and 7895 Ne. The measure of catalytic activity was the temperature of the 10095th transformation of CO into CO" (129),

The state of the surface of the catalysts was studied by the thermodesorption method with mass spectrometric registration of the flying particles. After the catalytic experiment, the samples were transferred to a quartz cuvette and the thermal desorption (TD) spectrum was immediately recorded.

The catalytic activity of all studied samples is shown in the table. вв нн жита со зо Ann ни я PO ЭХ

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PEK IN NNYA PON "NNYA NOYA SHOE in "

PERU PON NNYA POP I PAUL NN SHEU

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For a better understanding of the useful model, it is necessary to use the figures attached to this application.

Figure 1 shows the catalytic activity of a sample consisting of nickel carbon nanotubes and 1 mass of active catalytic mass. Figure 2 shows the thermodesorption spectrum of a sample consisting of nickel carbon nanotubes and 1 mass of active catalytic mass: 1-H»O; 2 - CO"; Z - O". - Figure 3 shows the thermodesorption spectrum of a sample consisting of nickel carbon nanotubes and

Fu 50 2Omas.bo of active catalytic mass: 1-H»O; 2 - CO"; Z - O".

Fig. 4 shows the thermodesorption spectrum of a sample consisting of cobalt carbon nanotubes with 20 wt.% of active catalytic mass: 1-NhBO; 2 - CO"; Z - O".

Fig. 5 shows the thermodesorption spectrum of a sample consisting of cobalt carbon nanotubes and 15 wt.bo of active catalytic mass: 1-NhBO; 2 - CO"; Z - O".

The characteristic dependence of the degree of conversion of CO into CO 5 on temperature is shown in Fig. 1. As can be seen from the data presented in this figure, a hysteresis is observed on this dependence, which confirms the operation of the catalyst.

The most active was the sample consisting of nickel carbon nanotubes and 20Omas.9o of the catalytically active phase (1100-472C). Among the cobalt carbon nanotubes, sample 60, which contains 15oMas.9o of the active phase (7100-9522), showed the highest activity. In the prototype (8, 9|) it was shown that the presence of the Si2(OH)zMO»z phase in the samples contributes to the growth of their catalytic activity. This phase, however, exists up to a temperature of 1802С, above which it is completely transformed into СцО.

TD spectra were taken from all samples. Peaks of NOO and CO were observed in the TD spectra." 65 HO desorption peaks had a symmetrical appearance. This indicates that on the surface of these samples there are fragments of water - OH groups, from which the Н 250 molecule is formed during desorption. The following forms can be distinguished according to the values of the desorption temperature: r.- up to 10092, r.-100-2002С, B4 -200-3009 (Fig. 2-5). For low-activity samples, only liquid forms of water were recorded on TD spectra (Figs. 2, 4). For highly active samples against the background of r.-forms, r.- and Du-forms of water are registered (Fig. 3, 5).

The CO" peaks on TD spectra are asymmetric, which indicates molecular desorption from the surface. The following forms of CO can be distinguished by the maximum temperatures of the dissociation peaks: o4-up to 1102С, d25-110-2002С, с5-200-3002С, o,-above 3002С. For low-activity samples (Figs. 2, 4), o, az" c4" forms of CO were recorded. For highly active catalysts (Figs. 3, 5), against the background of these forms of CO, the o2-form of CO" was registered.

It should be noted that HO and CO" are desorbed from the surface of low-activity samples at different temperatures of 70 (Figs. 2, 4). For highly active samples (Fig. 3, 5). HO and CO" are desorbed at the same temperatures. Thus, it is shown that the catalytic samples according to the present invention are more active for Si-So-be massive catalyst than for the prototype. It should also be noted that when the catalytic activity increases, a larger amount of the do-form of CO is desorbed from the surface."

The following examples illustrate techniques that ensure the production of catalytic systems according to the given 75 yield. It should be noted that it will be obvious to one skilled in the art that any transformations known in the art will produce the same technical result.

In addition, it should be noted that the following examples in no way limit the invention, but only provide some criterion of patentability - industrial suitability.

Example 1. Obtaining sample 1.

Pure metals (in grams) Cy-0.0437, Co-0.0023, Re-0.0024 were taken and dissolved in 1.28 ml of 5095-NMO with. 0.9158 g of laboratory-synthesized carbon nanotubes on the MiO catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25096.

Example 2. Obtaining sample 2.

Pure metals (in grams) Cy-0.0437, Co-0.0023, Re-0.0024 were taken and dissolved in 1.28 ml of 5095-NMO with. 0.9158 g of laboratory-synthesized carbon nanotubes on the MiO catalyst were impregnated with this solution. Then pt") the liquid phase was removed by drying in air at a temperature not exceeding 25026.

Again (in grams) Cy-0.0076, Co-0.0004, Re-0.0004 were taken and dissolved in 0.22 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9o of active mass were infiltrated with this solution. Then the liquid phase was removed by drying in air at a temperature of no more than 25020. со 3о Example 3. Preparation of sample 3. (Се)

We took pure metals (in grams) Cy-0.0284, Co-0.0015, Re-0.0016 and dissolved in 0.8 ml of 5095-NMO with. This solution was impregnated with 0.395 g of laboratory-synthesized carbon nanotubes on the MiO catalyst. Then -- the liquid phase was removed by drying in air at a temperature of no more than 25096. (Ce) from Example 4. Preparation of sample 4.

Pure metals (in grams) Cy-0.0437, Co-0.0023, Re-0.0024 were taken and dissolved in 1.28 ml of 5095-NMO with. 0.9158 g of laboratory-synthesized carbon nanotubes on the MiO catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25026.

Again took (in grams) Cy-0.0141, Co-0.0007, Re-0.0009 and dissolved in O4 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9o of active mass were infiltrated with this solution «0. Then the liquid phase was removed by drying in air at a temperature of no more than 25096.s

Example 5. Preparation of sample 5. :z» Pure metals (in grams) Cy-0.0334, Co-0.0018, Re-0.0018 were taken and dissolved in 0.9 ml of 5095-NMO z. 0.34805 g of laboratory-synthesized carbon nanotubes on the MiO catalyst were impregnated with this solution. Then

The liquid phase was removed by drying in air at a temperature of no more than 25026.ko Example 6. Preparation of sample 6.

Pure metals (in grams) Cy-0.0139, Co-0.0007, Re-0.0008 were taken and dissolved in O04ml 5095-NMO with. Hereby

0.29 g of laboratory-synthesized carbon nanotubes on the Co2O3z catalyst were impregnated with Me solution. Then - the liquid phase was removed by drying in air at a temperature of no more than 25096.

Example 7. Obtaining a sample 7.

Fo We took pure metals (in grams) Cy-0.0139, Co-0.0007, Re-0.0008 and dissolved in O04ml 5095-NMO with. 0.29 g of laboratory-synthesized carbon nanotubes on the Co2O3z catalyst were impregnated with this (Che) solution. Then the liquid phase was removed by drying in air at a temperature of no more than 250 20.

We again took (in grams) Cy-0.0010, Co-0.0005, Re-0.0006 and dissolved in 0.3 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9Uo of active mass were infiltrated with this solution. Then the liquid phase was removed by drying in air at a temperature of no more than 25020.s Example 8. Preparation of sample 8.

Pure metals (in grams) Cy-0.1869, Co-0.0098, Re-0.0104 were taken and dissolved in 5.bml of 5090-NMOZ. 2.6 bg of laboratory-synthesized carbon nanotubes on the Co2O3 catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature of no more than 25026.

Example 9. Obtaining a sample 9. Pure metals (in grams) Cy-0.0139, Co-0.0007, Re-0.0008 were taken and dissolved in 04 ml of 50906-NMOz. 0.29 g of laboratory-synthesized carbon nanotubes on the Co2O3 catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25026.

We again took (in grams) Cy-0.0031, Co-0.0016, Re-0.0017 and dissolved in 0.7 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9o of active mass were infiltrated with this solution. Then the liquid phase was removed by drying in air at a temperature of no more than 25020.

Example 10. Obtaining sample 10.

Pure metals (in grams) Cy-0.0403, Co-0.0021, Re-0.0022 were taken and dissolved in 1.2 ml of 5095-NMO with. 0.42 g of laboratory-synthesized carbon nanotubes on the Co2O3z catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25096.

Example 11. Obtaining sample 11.

Pure metals (in grams) Cy-0.0462, Co-0.0024, Re-0.0026 were taken and dissolved in 1.35 ml of 5095-NMO with. 0.9365 g of laboratory-synthesized carbon nanotubes on the Re2O3z catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25026.

Example 12. Obtaining sample 12.

Pure metals (in grams) Cy-0.0462, Co-0.0024, Re-0.0026 were taken and dissolved in 1.35 ml of 5095-NMO with. 0.9365 g of laboratory-synthesized carbon nanotubes on the Re2O3z catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25096.

We again took (in grams) Cy-0.0079, Co-0.0004, Re-0.0005 and dissolved in 0.2 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9o of active mass were infiltrated with this solution 75. Then the liquid phase was removed by drying in air at a temperature of no more than 25020.

Example 13. Obtaining sample 13.

Pure metals were taken (in grams) Cy-0.0401, Co-0.0021, Re-0.0022Ta and dissolved in 1.2 ml of 5096-NMO with. 0.5596 g of laboratory-synthesized carbon nanotubes on the Re2O3z catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25026.

Example 14. Obtaining sample 14

Pure metals (in grams) Cy-0.0462, Co-0.0024, Re-0.0026 were taken and dissolved in 1.35 ml of 5095-NMO with. 0.9365 g of laboratory-synthesized carbon nanotubes on the Re2O3z catalyst were impregnated with this solution. Then the liquid phase was removed by drying in air at a temperature not exceeding 25026.

We again took (in grams) Cy-0.0191, Co-0.0010, Re-0.0011 and dissolved in 0.56 ml of 5095-NMO with. Already obtained nanotubes with 1Omas.9o of active mass were infiltrated with this solution. Then the liquid phase was removed by drying in air at a temperature of no more than 25020.

Example 15. Obtaining a sample 15.

Pure metals (in grams) Cy-0.0578, Co-0.0030, Re-0.0032 were taken and dissolved in 1.7 ml of 5095-NMO with. 0.6051 g of laboratory-synthesized carbon nanotubes on the GeoOz catalyst were impregnated with this solution. Then "I removed the liquid phase by drying in air at a temperature not exceeding 25096.

It will be obvious to a skilled specialist in this field of technology that to ensure the technical result, it is possible to use nitric acid of any concentration, which will make it possible to dissolve the mentioned metals. Gee)

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Claims (2)

The formula of the invention b5 1. The method of applying a multi-component oxide system based on non-metals to carbon nanotubes during the synthesis of CO oxidation reaction catalysts, which is characterized by stepwise impregnation of nickel, cobalt and iron carbon nanotubes with a solution of the compound SiO(OH)zMOz, which is previously obtained by oxidation of the appropriate amount metals in nitric acid with an interval from 1 hour to 35 days with a concentration from 1 to 47 wt. 9 o'clock 2. The method according to claim 1, which is distinguished by the fact that nickel, cobalt and iron carbon nanotubes are gradually impregnated with a solution of the compound Si2(OH)zMO" with an interval of 1 to 14 days and with a concentration of 5 to 25 wt. 90. - (ee) (Se) «- (Se) s - with . and? ime) (o) - Fo IR e) c 60 b5