CN109833872B - Cobalt oxide bulk phase catalyst capable of regulating and controlling product distribution and preparation method and application thereof - Google Patents
Cobalt oxide bulk phase catalyst capable of regulating and controlling product distribution and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of bulk phase catalysts, and discloses a cobalt oxide bulk phase catalyst capable of regulating and controlling product distribution, a preparation method and application thereof, wherein the series of catalysts take cobalt oxide as a main catalyst; during preparation, a hydrothermal method is utilized to synthesize the cobalt oxide catalyst by adopting different hydrothermal times, and a series of Co is obtained by drying and roasting3O4-xh catalyst, wherein x represents hydrothermal time 0-3 h. The catalyst prepared by the invention is suitable for the reaction of preparing carbon monoxide and methane by carbon dioxide hydrogenation, adopts Co as an active component, realizes gradient regulation and control from 95% carbon monoxide selectivity to 90% methane selectivity by regulating hydrothermal time, has the characteristics of simple structure, convenient preparation and low operation pressure, and simultaneously maintains long-time stability.
Description
Technical Field
The invention relates to the technical field of bulk phase catalysts, in particular to a cobalt oxide bulk phase catalyst exposing different crystal faces, a preparation method thereof and application of the catalyst in regulating and controlling distribution of a carbon dioxide hydrogenation product.
Background
The carbon dioxide hydrogenation is beneficial to reducing the concentration of carbon dioxide in the atmosphere, and can also generate high-efficiency fuels such as carbon monoxide, methane, methanol, dimethyl ether, ethanol, hydrocarbons and the like, thereby being convenient for storage and transportation. Wherein, the carbon monoxide and the methane are easily generated in thermodynamics and kinetics, and the carbon monoxide is used for preparing gasoline and diesel oil and C by the Fischer-Tropsch reaction2-C4The raw material of higher alcohol is also an important raw material for preparing various fine chemicals such as medicines, cosmetics, polyesters and the like; in addition, methane is a clean and efficient fuel, so that carbon dioxide is catalytically converted into carbon monoxide or methane and the likeOne-carbon products are of more interest.
Due to CO2The chemical property is stable, the activation is difficult, and the conversion rate of the reaction is generally low; on the other hand, carbon monoxide and methane are two products with different hydrogenation degrees of carbon dioxide, and the hydrogenation degrees are not well controlled under a hydrogen-rich condition, and the two products are often generated concomitantly, so that the selectivity of the two products is not high; how to design efficient catalysts for kinetic control to promote CO2Activating conversion and adjusting product selectivity so as to efficiently obtain carbon monoxide or methane is an urgent problem to be solved.
At present, CO is generally accepted2The distribution of the hydrogenation products has the following regulation and control paths. Firstly, adjusting the particle size of metal particles on a supported metal catalyst; secondly, the carbon dioxide adsorption property at the interface of the active metal and the oxide carrier is adjusted by changing the carrier species, thereby achieving the purpose of changing the product distribution. In the two methods, the structure of the catalyst is complex, and the reaction site is undefined, so that the preparation method is complex, is not easy to repeat, is easy to be interfered by environmental factors, and cannot realize gradient regulation on the catalytic effect. Co-based catalysts are widely used in carbon dioxide hydrogenation reactions. How to further improve the catalyst to have stronger CO2Activation capacity and higher selectivity to carbon monoxide or methane, especially with stability to CO2The research of hydrogenation is focused.
Disclosure of Invention
The invention aims to solve the technical problem that the selectivity of single products such as carbon monoxide or methane is poor (< 60%) in the carbon dioxide hydrogenation reaction, and provides a cobalt oxide bulk phase catalyst capable of regulating and controlling the product distribution, a preparation method thereof and application thereof in the carbon dioxide hydrogenation, so that the defects of complex products and low selectivity of the single products in the carbon dioxide hydrogenation reaction are overcome, and the selectivity of carbon monoxide is more than 90% to the selectivity of methane is more than 90% by regulating the hydrothermal time in the preparation process, thereby realizing the controllable regulation of the product distribution.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a cobalt oxide bulk catalyst capable of regulating and controlling product distribution is prepared by the following preparation method:
(1) dissolving cobalt acetate in ethylene glycol to form a mixed solution with the concentration of 0.5-1.5M/L, and heating the mixed solution to 150-200 ℃;
(2) preparing 0.5-1M/L potassium carbonate aqueous solution, dropwise adding the potassium carbonate aqueous solution into the mixed solution of cobalt acetate and ethylene glycol at the speed of 20-50 drops/min, wherein the mass ratio of the used potassium carbonate solution to the mixed solution of cobalt acetate and ethylene glycol is 1:5-1: 3;
(3) after hydrothermal reaction at the temperature of 150-3O4-xh cobalt oxide bulk catalyst, wherein x represents hydrothermal time.
Preferably, the concentration of the mixed solution of cobalt acetate and ethylene glycol in the step (1) is 1M/L.
Preferably, the heating temperature in step (1) is 180 ℃.
Preferably, the concentration of the potassium carbonate aqueous solution in the step (2) is 0.5M/L.
Preferably, the temperature for vacuum drying in step (3) is 80 ℃.
Preferably, the vacuum drying in step (3) is performed in a vacuum oven.
Preferably, the roasting temperature in the step (3) is 450 ℃ and the roasting time is 4 h.
A method for preparing the cobalt oxide bulk catalyst, which comprises the following steps:
(1) dissolving cobalt acetate in ethylene glycol to form a mixed solution with the concentration of 0.5-1.5M/L, and heating the mixed solution to 150-200 ℃;
(2) preparing 0.5-1M/L potassium carbonate aqueous solution, dropwise adding the potassium carbonate aqueous solution into the mixed solution of cobalt acetate and ethylene glycol at the speed of 20-50 drops/min, wherein the mass ratio of the used potassium carbonate solution to the mixed solution of cobalt acetate and ethylene glycol is 1:5-1: 3;
(3) after hydrothermal reaction at the temperature of 150-3O4-xh cobalt oxide bulk catalyst, wherein x represents hydrothermal time.
An application of the cobalt oxide bulk phase catalyst is used for preparing a carbon product by carbon dioxide hydrogenation.
Further, the method comprises the following steps:
(1) tabletting the cobalt oxide bulk phase catalyst to obtain a 20-40 mesh granular catalyst;
(1) the prepared granular catalyst is loaded into a fixed bed reactor, the temperature of the fixed bed reactor is raised to the reaction temperature of 250-350 ℃, reaction gas is introduced for reaction, wherein the molar ratio of hydrogen to carbon dioxide is 2-3, balance gas is nitrogen, and the reaction airspeed based on the carbon dioxide is 1-10h-1。
The invention has the beneficial effects that:
the invention takes bulk cobalt oxide as a main component, and can prepare a series of Co with different morphologies and exposed different crystal faces by changing the hydrothermal time3O4A catalyst.
On the one hand, Co which does not undergo hydrothermal reaction3O4The catalyst presents a particle structure within 0h, mainly exposes (111) crystal faces and is easier to be reduced in a reducing atmosphere; the catalyst is suitable for low pressure condition, has good effect on carbon dioxide hydrogenation reaction, and particularly Co3O4The catalytic activity can be well improved within-0 h, C-O bond breaking can be promoted, the generation of methane is facilitated, and finally the selectivity of methane reaches 90%.
On the other hand, Co having a hydrothermal time of 2 hours3O4The catalyst presents a rod-like structure for 2h, and the (110) crystal face is mainly exposed; for the carbon dioxide hydrogenation reaction, the conversion rate of the carbon dioxide is higher than 10 percent, and Co3O4The selectivity of carbon monoxide reaches 95% in-2 h, and the stability is good.
Thus, the present invention provides for differential exposureCo of crystal face3O4Has different reducibility, and the reduction degree of the catalyst in a reducing atmosphere is gradually reduced along with the increase of hydrothermal time, wherein Co is3O4The reducibility is obviously stronger than that of Co after-0 h3O42h, Co with different crystal faces in the carbon dioxide hydrogenation reaction process3O4Presents a gradient of carbon monoxide selectivity or methane selectivity, promoting the activation of carbon dioxide during the reaction. At the same time, due to Co3O4The method has the advantages of low price, low toxicity and capability of realizing the regulation of the carbon dioxide hydrogenation-carbon product by a simple method under relatively low pressure, thereby having certain industrial significance.
Drawings
FIG. 1 shows Co prepared in examples 1, 12, 13, 14 and 153O4The distribution of the product obtained by the catalyst catalytic carbon dioxide hydrogenation is changed along with the time (350 ℃, 30bar, space velocity is 3 h)-1，CO2/N2/H2＝1/1/3)；
FIG. 2 shows Co prepared in examples 1, 12 and 143O4H-TPR diagram of catalyst;
FIG. 3 shows Co prepared in examples 1 and 143O4TEM image of the catalyst; wherein a is Co3O4Conventional TEM image of-0 h, b is Co3O4Conventional TEM image of-2 h, c is Co3O4High power TEM image of-0 h, d is Co3O4High power TEM image of-2 h, e is Co3O4Model diagram of-0 h, f is Co3O4-2h of a model map;
FIG. 4 shows Co prepared in examples 1, 12 and 143O4The carbon monoxide selectivity and the carbon dioxide conversion rate obtained by the catalyst catalyzing carbon dioxide hydrogenation at different temperatures are along with the change of the reaction temperature (300 ℃ 350 ℃, 30bar, space velocity of 3 h)-1，CO2/N2/H2＝1/1/3)。
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
(1) 4.8g of cobalt acetate ((CH)3COO)2Co) was added to 60ml ethylene glycol ((CH)2OH)2) Heating the solution to 180 ℃ with the concentration of the formed solution being 1M/L, standing and stirring;
(2) adding potassium carbonate (K)2CO3) Dissolving in deionized water to obtain solution with concentration of 0.5M/L;
(3) dropwise adding a potassium carbonate solution (20 drops/min) into the mixed solution of the cobalt acetate and the ethylene glycol in the step (1), wherein the amount of the potassium carbonate solution is 20ml, performing hydrothermal reaction for 0h at 180 ℃, and finally centrifuging and washing the suspension for four times;
(4) drying the solid obtained in the step (3) at 80 ℃ for 12 h;
(5) and (4) roasting the solid obtained in the step (4) at 450 ℃ for 4h to obtain the cobalt oxide catalyst.
(6) Tabletting the powder catalyst into 20-40 mesh granular catalyst;
(7) loading the pressed cobalt oxide catalyst into a fixed bed reactor, and introducing N2When the reaction temperature reaches 350 ℃, the reaction gas is switched to reaction gas, wherein the molar ratio of carbon dioxide to hydrogen is 3:1, and the balance gas is nitrogen (CO)2＝10ml/min,H2＝30mL/min，N210mL/min), the space velocity of the reaction based on carbon dioxide is 3h-1。
The catalyst activity is expressed in terms of carbon monoxide and methane (mL/min) produced and selectivity, the product selectivity being calculated as follows:
conversion rate:
and (3) selectivity:
wherein, FCO2,inRepresents the volumetric flow rate of carbon dioxide at the inlet of the reactor, FCO2,outRepresents the inverse ofThe gas volume flow rate of carbon dioxide at the outlet of the reactor, i represents the reaction product, including CH4And CO, n represents the number of carbons contained in these substances.
The reaction product was analyzed on-line by gas chromatography, and the relationship between the product rate and selectivity with time is shown in Table 1.
TABLE 1 product Selectivity at different reaction times
As can be seen from Table 1, the catalyst has high activity and good stability, and the reaction data is basically unchanged after 5 hours of reaction.
Example 2:
the reaction was carried out by the method of example 1 except that the mass of cobalt acetate added in step (1) was 2.4g, and the concentration of the resulting solution was 0.5M/L.
Example 3:
the reaction was carried out by the method of example 1 except that the mass of cobalt acetate added in step (1) was 7.2g, and the concentration of the resulting solution was 1.5M/L.
Example 4:
the reaction was carried out by the method of example 1, except that the hydrothermal temperature of step (1) and step (3) were 150 ℃.
Example 5:
the reaction was carried out by the method of example 1, except that the hydrothermal temperature of step (1) and step (3) were both 200 ℃.
Example 6:
the reaction was carried out by the method of example 1 except that the concentration of the potassium carbonate solution in step (2) was 0.75M/L.
Example 7:
the reaction was carried out by the method of example 1 except that the concentration of the potassium carbonate solution in step (2) was 1M/L.
Example 8:
the reaction was carried out by the method of example 1 except that the dropping rate of the potassium carbonate solution of step (3) was 35 drops/min.
Example 9:
the reaction was carried out by the method of example 1 except that the dropping rate of the potassium carbonate solution of step (3) was 50 drops/min.
Example 10:
the reaction was carried out by the method of example 1 except that the amount of the potassium carbonate solution to be added dropwise in step (3) was 12 ml.
Example 11:
the reaction was carried out by the method of example 1 except that the amount of the potassium carbonate solution to be added dropwise in step (3) was 15 ml.
Example 12:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 0.5 h.
Example 13:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 1 h.
Example 14:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 2 hours.
Example 15:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 3 hours.
Example 16:
the reaction was carried out by the method of example 1, except that the drying temperature in step (4) was 90 ℃.
Example 17:
the reaction was carried out by the method of example 1, except that the drying temperature in step (4) was 100 ℃.
Example 18:
the reaction was carried out by the method of example 1 except that the calcination temperature in step (5) was 400 ℃.
Example 19:
the reaction was carried out by the method of example 1 except that the calcination temperature in step (5) was 500 ℃.
Example 20:
the reaction was carried out by the method of example 1, except that the calcination time in step (5) was 2 hours.
Example 21:
the reaction was carried out by the method of example 1, except that the calcination time in step (5) was 6 hours.
Example 22:
the reaction was carried out by the method of example 1, except that the reaction temperature of step (7) was 250 ℃.
Example 23:
the reaction was carried out by the method of example 1, except that the reaction temperature in step (7) was 300 ℃.
Example 24:
the reaction was carried out by the method of example 1, except that the reaction temperature of step (7) was 330 ℃.
Example 25:
the reaction was carried out by the method of example 1, except that the reaction temperature in step (7) was 340 ℃.
Example 26:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 0.5h and the reaction temperature of step (7) was 250 ℃.
Example 27:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 0.5h and the reaction temperature of step (7) was 300 ℃.
Example 28:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 0.5h and the reaction temperature of step (7) was 330 ℃.
Example 29:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 0.5h and the reaction temperature of step (7) was 340 ℃.
Example 30:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 2 hours and the reaction temperature of step (7) was 250 ℃.
Example 31:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 2 hours and the reaction temperature of step (7) was 300 ℃.
Example 32:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 2 hours and the reaction temperature of step (7) was 330 ℃.
Example 33:
the reaction was carried out by the method of example 1 except that the hydrothermal time of step (3) was 2 hours and the reaction temperature of step (7) was 340 ℃.
Example 34:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide in step (7) was 1 hour-1。
Example 35:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide in step (7) was 5 hours-1。
Example 36:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide in step (7) was 10 hours-1。
Example 37:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 2 hours and the volume space velocity of carbon dioxide of step (7) was 1 hour-1。
Example 38:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 2 hours and the volume space velocity of carbon dioxide of step (7) was 5 hours-1。
Example 39:
the reaction was carried out by the method of example 1, except that the hydrothermal time of step (3) was 2 hours and the space velocity of carbon dioxide volume of step (7) was 10 hours-1。
Example 40:
the reaction was carried out using the procedure of example 1, except that the molar ratio of hydrogen to carbon dioxide in step (7) was 2: 1.
For the results and data of the above examples, the activity data at 4h of reaction were compared to examine the effect of different parameters on the catalyst reactivity. With the exception of the conditions specified below, changes in the above conditions allowed the preparation of our catalyst and exhibited similar performance in the carbon dioxide hydrogenation reaction.
The effect of (I) hydrothermal reaction time on catalyst reactivity, see Table 2 and FIG. 1. The reaction conditions were the same as in examples 1, 12, 13, 14 and 15.
TABLE 2 influence of different hydrothermal times on the hydrogenation activity of carbon dioxide
As can be seen from the table, the series of cobalt oxide catalysts all show better carbon dioxide hydrogenation activity, specifically, the carbon dioxide conversion rate and the methane selectivity gradually decrease and the carbon monoxide selectivity gradually increases with the increase of the hydrothermal time, and the methane selectivity is Co3O488% reduction to Co of-0 h3O45% of-2 h, and carbon monoxide selectivity from Co3O412% of-0 h increase to Co3O495% of-2 h. As shown in FIG. 1, the reactivity of all five samples was maintained for at least 4 hours, indicating good stability of the catalyst.
As shown in the attached FIGS. 2 and 3, the morphology of the cobalt oxide shows the transition from the particle to the short rod shape with the increase of the hydrothermal time, the exposed crystal face is changed from (111) to (110) as can be seen from a Transmission Electron Microscope (TEM), and the reduction temperature is gradually increased and the reduction is gradually reduced as can be seen from the reduction of the H-TPR by hydrogen programmed temperature.
(II) reaction temperature vs. Co3O4The effect of-0 h catalytic activity, see table 3. The reaction conditions were the same as in examples 1, 22, 23, 24 and 25.
TABLE 3 influence of reaction temperature on the hydrogenation activity of carbon dioxide
As can be seen from the table, with the increase of the reaction temperature, the conversion rate of the carbon dioxide hydrogenation is obviously increased, namely the reaction activity is gradually increased; for Co3O4And (2) 0h of catalyst, wherein the product selectivity is very sensitive to the change of reaction temperature, the selectivity of carbon monoxide is gradually reduced along with the increase of the reaction temperature, the selectivity of methane is gradually increased, and the selectivity of methane reaches the maximum value when the reaction temperature is 350 ℃.
(III) reaction temperature vs. Co3O4The effect of catalytic activity at-0.5 h, see table 4 and figure 4. The reaction conditions were the same as in examples 1, 26, 27, 28 and 29.
TABLE 4 influence of reaction temperature on carbon dioxide hydrogenation Activity
As can be seen from the table, with the increase of the reaction temperature, the conversion rate of the carbon dioxide hydrogenation is obviously increased, namely the reaction activity is gradually increased; for Co3O4The product selectivity is sensitive to temperature changes, the carbon monoxide selectivity is gradually reduced along with the increase of the reaction temperature, the methane selectivity is gradually increased, and when the reaction temperature is 350 ℃, the methane selectivity reaches the maximum value, but a certain amount of carbon monoxide is still generated; the methane selectivity of Co3O4-0.5h is lower than that of Co at any reaction temperature3O4-0h。
(IV) reaction temperature vs. Co3O4The effect of catalytic activity over-2 h, see Table 5. Reaction stripThe same as in examples 1, 30, 31, 32 and 33.
TABLE 5 influence of reaction temperature on carbon dioxide hydrogenation Activity
As can be seen from the table, with the increase of the reaction temperature, the conversion rate of the carbon dioxide hydrogenation is obviously increased, namely the reaction activity is gradually increased; for Co3O4The product selectivity of the catalyst is insensitive to temperature change, the carbon monoxide selectivity is not basically changed along with the increase of the reaction temperature, the methane selectivity is also basically unchanged, and in the range of the reaction temperature of 300-350 ℃, methane is hardly produced, namely, the methane selectivity is very low, but the carbon monoxide selectivity is always kept above 95 percent at the moment, namely, the product is mainly carbon monoxide.
As shown in fig. 4, the conversion rate of the three samples is consistent with the trend of the product distribution along with the reaction temperature, but the difference of the product selectivity among them is very obvious, and the difference along with the temperature change is ubiquitous and does not change.
(V) influence of the space velocity of carbon dioxide volume on the catalytic activity of the catalyst, see Table 6. The reaction conditions were the same as in examples 1, 34, 35, 36, 37, 38 and 39.
TABLE 6 influence of the space velocity of carbon dioxide on the catalytic Activity
As can be seen from the table, the carbon dioxide conversion rate is continuously reduced with the increase of the volume space velocity of the carbon dioxide, but the selectivity of the methane and the carbon monoxide is basically unchanged, and the space velocity is 1h-1And 3h-1The difference is not great, so the optimal space velocity of the volume of the carbon dioxide is 3h-1。
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (10)
1. A cobalt oxide bulk catalyst capable of regulating and controlling product distribution is characterized by being prepared by the following preparation method:
(1) dissolving cobalt acetate in ethylene glycol to form a mixed solution with the concentration of 0.5-1.5M/L, and heating the mixed solution to 150-200 ℃;
(2) preparing 0.5-1M/L potassium carbonate aqueous solution, dropwise adding the potassium carbonate aqueous solution into the mixed solution of cobalt acetate and ethylene glycol at the speed of 20-50 drops/min, wherein the mass ratio of the used potassium carbonate solution to the mixed solution of cobalt acetate and ethylene glycol is 1:5-1: 3;
(3) after hydrothermal reaction at the temperature of 150-3O4-xh cobalt oxide bulk catalyst, wherein x represents hydrothermal time;
from Co3O40h to Co3O4And 3h, the morphology of the cobalt oxide bulk catalyst shows a transition from a particle structure to a rod-like structure, and a transition from a mainly exposed (111) crystal plane to a mainly exposed (110) crystal plane.
2. The cobalt oxide bulk catalyst with a controllable product distribution as claimed in claim 1, wherein the concentration of the mixed solution of cobalt acetate and ethylene glycol in step (1) is 1M/L.
3. A product distribution-controllable cobalt oxide bulk catalyst according to claim 1, wherein the heating temperature in step (1) is 180 ℃.
4. The cobalt oxide bulk catalyst with a controlled product distribution according to claim 1, wherein the concentration of the aqueous solution of potassium carbonate in step (2) is 0.5M/L.
5. The cobalt oxide bulk catalyst with a controlled product distribution as claimed in claim 1, wherein the temperature of vacuum drying in step (3) is 80 ℃.
6. A product distribution-controllable cobalt oxide bulk catalyst according to claim 1, wherein the vacuum drying in step (3) is performed in a vacuum oven.
7. The cobalt oxide bulk catalyst with a controllable product distribution as claimed in claim 1, wherein the calcination temperature in step (3) is 450 ℃ and the calcination time is 4 h.
8. A process for the preparation of a cobalt oxide bulk catalyst as claimed in any one of claims 1 to 7, which process is carried out according to the following steps:
(1) dissolving cobalt acetate in ethylene glycol to form a mixed solution with the concentration of 0.5-1.5M/L, and heating the mixed solution to 150-200 ℃;
(2) preparing 0.5-1M/L potassium carbonate aqueous solution, dropwise adding the potassium carbonate aqueous solution into the mixed solution of cobalt acetate and ethylene glycol at the speed of 20-50 drops/min, wherein the mass ratio of the used potassium carbonate solution to the mixed solution of cobalt acetate and ethylene glycol is 1:5-1: 3;
(3) after hydrothermal reaction at the temperature of 150-3O4-xh cobalt oxide bulk catalyst, wherein x represents hydrothermal time.
9. Use of a cobalt oxide bulk catalyst as claimed in any one of claims 1 to 7 in the hydrogenation of carbon dioxide to produce carbon monoxide and/or methane.
10. Use of a cobalt oxide bulk catalyst according to any one of claims 1 to 7, wherein the following steps are carried out:
(1) tabletting the cobalt oxide bulk phase catalyst to obtain a 20-40 mesh granular catalyst;
(1) the prepared granular catalyst is loaded into a fixed bed reactor, the temperature of the fixed bed reactor is raised to the reaction temperature of 250-350 ℃, reaction gas is introduced for reaction, wherein the molar ratio of hydrogen to carbon dioxide is 2-3, balance gas is nitrogen, and the reaction airspeed based on the carbon dioxide is 1-10h-1。
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| 不同沉淀剂对Co3O4催化剂结构及催化分解N2O活性的影响;刘启宪等;《分子催化》;20160831;第30卷(第4期);第363-371页 * |
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