CN114100619A - Methane carbon dioxide reforming catalyst and preparation method thereof - Google Patents
Methane carbon dioxide reforming catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a methane and carbon dioxide reforming catalyst and a preparation method thereof, belonging to the technical field of reforming catalysts. The methane carbon dioxide reforming catalyst has the structure of A/LaxCe1‑xNiO3. Wherein A is alkali metal or alkaline earth metal, and x is more than or equal to 0 and less than or equal to 1. The methane carbon dioxide reforming catalyst disclosed by the invention can be used for effectively avoiding carbon deposition in the methane carbon dioxide reaction process, and is high in stability and effectively avoiding inactivation; the invention also provides a simple and feasible preparation method.
Description
Technical Field
The invention relates to a methane and carbon dioxide reforming catalyst and a preparation method thereof, belonging to the technical field of reforming catalysts.
Background
Carbon dioxide (CO)2) And methane (CH)4) As a greenhouse gas, it is generally considered to be the main culprit for the problem of the current greenhouse effect. The trend toward global warming can be slowed by reducing the dependence on fossil fuels and minimizing the emission of greenhouse gases into the environment. Hydrogen is one of the most promising alternative energy sources because it has reduced NOxAnd COxThe advantage of drainage and water is a by-product of combustion. The reforming of methane and carbon dioxide is an important mode for industrial hydrogen production, and is an effective way for realizing reasonable utilization of two greenhouse gases, namely carbon dioxide and methane. The methane and the carbon dioxide can be reformed to produce the synthesis gas with proper H/C ratio, and the synthesis gas can be efficiently used for Fischer-Tropsch synthesis to produce chemicals with high added value.
At present, catalysts for preparing synthesis gas by reforming methane and carbon dioxide mainly comprise noble metal catalysts and non-noble metal catalysts, and the noble metal catalysts have a series of advantages of strong carbon deposition resistance, long service life of the catalysts and the like, but are expensive, so that the catalysts are not suitable for industrial production. Non-noble metal catalysts comprise cobalt, copper, iron and nickel-based catalysts, and the catalysts are relatively low in price, but in the reaction process, the catalysts are seriously deposited with carbon and are easy to sinter and deactivate under the high-temperature condition. The modification of the reforming catalyst by adopting alkali metal or alkaline earth metal as an auxiliary agent is a common way for eliminating carbon deposition, but the temperature in the reforming reaction process is higher, when the content of the auxiliary agent is lower, the auxiliary agent is easy to sinter in the reaction process, the effect of eliminating the carbon deposition is obviously reduced, and when the content of the auxiliary agent is higher, the auxiliary agent is easy to cover a large amount of active components, so that the catalyst is obviously inactivated.
The perovskite has a plurality of properties such as excellent conductivity, magnetism, thermoelectricity, piezoelectricity and the like, and has low preparation cost and thermodynamics and piezoelectricity at high temperatureMechanical stability, and excellent oxygen ion and electron conductors under high temperature conditions. In recent years, perovskite is widely used in a plurality of catalysis fields, and shows excellent catalytic performance, the preparation process is simple, the cost is low, the perovskite catalyst has high-temperature activity and stability, the carbon deposit of the catalyst is reduced, and the inactivation process of the catalyst is delayed. Carbon deposition is effectively avoided in the catalytic reaction process. Perovskite oxides (e.g. LaNiO)3、La0.9Ce0.1NiO3) The catalyst is used for methane carbon dioxide reforming reaction, shows excellent catalytic performance, and the carbon deposition phenomenon of the catalyst is relatively weakened in the reaction process, particularly the carbon deposition resistance of the catalyst in the mode of doping alkali metal or alkaline earth metal in the crystal structure of the catalyst is more obvious, but the carbon deposition resistance of the perovskite catalyst still has higher promotion space.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a methane carbon dioxide reforming catalyst which can effectively avoid the generation of carbon deposition in the reaction process of methane carbon dioxide and has higher stability and effectively avoid inactivation; the invention also provides a simple and feasible preparation method.
The methane carbon dioxide reforming catalyst has the structure of A/LaxCe1-xNiO3. Wherein A is alkali metal or alkaline earth metal, and x is more than or equal to 0 and less than or equal to 1.
Preferably, the alkali metal is Na or K.
Preferably, the alkaline earth metal is Mg, Ca, Ba or Sr.
The preparation method of the methane carbon dioxide reforming catalyst comprises the following steps:
(1) pouring citric acid into deionized water, and mixing to form a solution;
(2) respectively dropping mixed aqueous solutions of lanthanum nitrate, cerium nitrate and nickel nitrate into the solution in the step (1), and mixing to form sol;
(3) heating the sol in the step (2) to 60-80 ℃, and evaporating water to gradually change the sol into gel;
(4) drying the gel obtained in the step (3) at the temperature of 80-150 ℃ to obtain fluffy solid;
(5) roasting the solid obtained by drying in the step (4) at the temperature of 600 ℃ and 1300 ℃ to obtain LaxCe1-xNiO3；
(6) Taking an aqueous solution of nitrate of alkali metal or alkaline earth metal and La obtained in the step (5)xCe1-xNiO3Mixing to obtain suspension, performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness, so that alkali metal or alkaline earth metal can be uniformly dispersed to LaxCe1-xNiO3A surface;
(7) drying the solid obtained in the step (6) at the temperature of between 80 and 120 ℃, and roasting the dried solid at the temperature of between 350 and 550 ℃ to obtain A/LaxCe1-xNiO3A catalyst.
In the finally prepared catalyst, the alkali metal or alkaline earth metal accounts for 0.1-0.5% of the mass of the catalyst.
In the reaction process of the perovskite type methane carbon dioxide catalyst, the migration speed of electrons and oxygen cavities is high, and the generation of carbon deposition on the surface of the catalyst in the reaction process can be effectively slowed down. After the nickel-based perovskite oxide is reduced, the metal nickel is exposed on the surface of the perovskite oxide, a small amount of alkali metal or alkaline earth metal is uniformly dispersed on the surface of the perovskite oxide, and the alkali metal or alkaline earth metal auxiliary agent can be uniformly dispersed on the surface of the metal nickel after the catalyst is reduced, so that the sintering agglomeration of the auxiliary agent in the heat treatment process and the reaction process can be effectively avoided when a small amount of the auxiliary agent exists; when an excessive amount of the promoter is present, the promoter may cause a problem of poor catalyst activity for covering a large number of active sites, and thus the amount of the promoter needs to be controlled. The catalyst prepared by the invention has higher stability, and the service life of the catalyst is greatly prolonged.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, while the advantages of the perovskite oxide are fully utilized, the alkali metal or alkaline earth metal modified perovskite nickel-based catalyst is adopted, and meanwhile, the rotary evaporation mode is adopted in the preparation process, so that the alkali metal or alkaline earth metal is highly dispersed on the surface of the perovskite oxide, the defects of the traditional doping mode are avoided, and the effect of the alkali metal or alkaline earth metal can be better exerted, so that the catalyst can be effectively prevented from generating carbon deposition when used in the reaction process of methane and carbon dioxide, and meanwhile, the catalyst has higher stability and can be effectively prevented from being inactivated;
(2) the preparation method is simple, the cost of the raw materials is low, and the production cost of the catalyst in actual production is expected to be greatly reduced.
Drawings
FIG. 1 is CH when catalysts prepared in examples and comparative examples are used4The conversion rate is shown as a trend with time.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. 0.1mol of lanthanum nitrate and 0.1mol of nickel nitrate are taken to be dissolved in deionized water, and then the solution is dropped into the aqueous solution of citric acid to be mixed evenly to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at the temperature of 80 ℃. Baking the dried solid at 900 ℃ to obtain LaNiO3。
0.073g of sodium nitrate is dissolved in deionized water, and the sodium nitrate solution and 20g of the obtained LaNiO are mixed3Mixing to obtain suspension, and performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness so that alkali metal can be uniformly dispersed to LaNiO3A surface. Drying the solid obtained after evaporation to dryness at 120 ℃, and roasting at 450 ℃ to obtain Na/LaNiO3A catalyst.
The mass content of sodium oxide in the final catalyst was 0.5%.
Example 2
Taking 0.12molThe citric acid is poured into deionized water and mixed evenly to form a solution. 0.09mol of lanthanum nitrate, 0.01mol of cerium nitrate and 0.1mol of nickel nitrate are taken to be dissolved in deionized water, and then the mixture is dripped into a citric acid water solution and mixed evenly to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at the temperature of 90 ℃. Baking the dried solid at 800 ℃ to obtain La0.9Ce0.1NiO3。
Dissolving potassium nitrate 0.072g in deionized water, and mixing with the obtained potassium nitrate solution 20g0.9Ce0.1NiO3Mixing to obtain a suspension, and performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness so that potassium ions can be uniformly dispersed to La0.9Ce0.1NiO3A surface. Drying the solid obtained after evaporation to dryness at 120 ℃, and roasting at 450 ℃ to obtain K/La0.9Ce0.1NiO3A catalyst.
The final catalyst had a potassium oxide mass content of 0.5%.
Example 3
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. 0.07mol of lanthanum nitrate, 0.03mol of cerium nitrate and 0.1mol of nickel nitrate are taken to be dissolved in deionized water, and then the mixture is dripped into a citric acid water solution and mixed evenly to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at the temperature of 100 ℃. Baking the dried solid at 600 ℃ to obtain La0.7Ce0.3NiO3。
0.37g of magnesium nitrate was dissolved in deionized water, and the magnesium nitrate solution was mixed with 20g of the obtained La0.7Ce0.3NiO3Mixing to obtain a suspension, and performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness so that magnesium ions can be uniformly dispersed to La0.7Ce0.3NiO3A surface. Evaporating to dry to obtain solid at 120 deg.CDrying, and roasting at 450 deg.C to obtain Mg/La0.7Ce0.1NiO3A catalyst.
The magnesium oxide mass content in the final catalyst was 0.5%.
Example 4
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. 0.05mol of lanthanum nitrate, 0.05mol of cerium nitrate and 0.1mol of nickel nitrate are taken to be dissolved in deionized water, and then the mixture is dripped into the aqueous solution of citric acid and is uniformly mixed to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at the temperature of 110 ℃. Baking the dried solid at 700 ℃ to obtain La0.5Ce0.5NiO3。
Dissolving 0.17g of barium nitrate in deionized water, and mixing the barium nitrate solution with 20g of obtained La0.7Ce0.3NiO3Mixing to obtain a suspension, and performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness so that magnesium ions can be uniformly dispersed to La0.7Ce0.3NiO3A surface. Drying the solid obtained after evaporation to dryness at 100 ℃, and roasting at 450 ℃ to obtain Ba/La0.5Ce0.5NiO3A catalyst.
The mass content of barium oxide in the final catalyst was 0.5%.
Example 5
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. 0.02mol of lanthanum nitrate, 0.08mol of cerium nitrate and 0.1mol of nickel nitrate are taken to be dissolved in deionized water, and then the mixture is dripped into a citric acid water solution and mixed evenly to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at 120 ℃. Baking the dried solid at 1000 ℃ to obtain La0.2Ce0.8NiO3。
Dissolving 0.204g of strontium nitrate in deionized water, and mixing the strontium nitrate solution with 20g of obtained La0.2Ce0.8NiO3Mixing to obtain suspension, and performing rotary evaporation on the suspension on a rotary evaporator to slowly evaporate water to dryness so that strontium ions can be uniformly dispersed to La0.2Ce0.8NiO3A surface. Drying the solid obtained after evaporation to dryness at 110 ℃, and roasting at 450 ℃ to obtain Sr/La0.2Ce0.8NiO3A catalyst.
The mass content of strontium oxide in the final catalyst was 0.5%.
Comparative example 1
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. 0.02mol of lanthanum nitrate, 0.08mol of cerium nitrate, 0.1mol of nickel nitrate and 0.21g of barium nitrate are taken to be dissolved in deionized water, and then the deionized water is dripped into a citric acid aqueous solution to be uniformly mixed to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at 120 ℃. Baking the obtained solid at 1000 deg.C to obtain Ba-La0.2Ce0.8NiO3A catalyst.
The mass content of barium oxide in the final catalyst was 0.5%.
Comparative example 2
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. Taking 0.09mol of lanthanum nitrate, 0.01mol of cerium nitrate, 0.1mol of nickel nitrate and 0 mol of lanthanum nitrate.132gThe potassium nitrate is dissolved in the deionized water, and then the potassium nitrate is dropped into the aqueous solution of the citric acid and is uniformly mixed to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at the temperature of 90 ℃. Baking the dried solid at 800 ℃ to obtain K-La0.9Ce0.1NiO3。
The final catalyst had a potassium oxide mass content of 0.5%.
Comparative example 3
0.12mol of citric acid is poured into deionized water and mixed evenly to form a solution. Taking 0.02mol of lanthanum nitrate, 0.08mol of cerium nitrate and 0.1mol of cerium nitratel, melting nickel nitrate into deionized water, then dripping into the aqueous solution of citric acid, and uniformly mixing to form sol. Then the sol is heated to 80 ℃ to evaporate water, so that the sol gradually becomes gel. Then the obtained gel is dried at 120 ℃. Baking the dried solid at 1000 ℃ to obtain La0.2Ce0.8NiO3。
Evaluation of catalyst reaction Performance:
the reaction performance was examined by using the catalyst samples prepared in examples 1 to 5 and comparative examples 1 to 3, respectively, and the reaction was carried out in a continuous flow fixed bed reactor with a catalyst loading of 5g and using H before the catalyst was used2Reduction is carried out at the reduction temperature of 700 ℃ and the volume space velocity of 3000h-1The reaction pressure is 0.05 MPa; after the reduction is finished, introducing methane and carbon dioxide, wherein the reaction condition is CH4/CO2The reaction temperature is 800 ℃, the reaction pressure is 0.1MPa, and the volume space velocity is 7000h-1(ii) a The product was analyzed on-line by gas chromatography and the results are shown in Table 1.
TABLE 1
| Catalyst and process for preparing same | CH4Conversion (%) | Degree of reduction of catalyst Ni (%) |
| Example 1 | 85 | 75 |
| Example 2 | 84 | 71 |
| Example 3 | 88 | 78 |
| Example 4 | 90 | 81 |
| Example 5 | 89 | 80 |
| Comparative example 1 | 60 | 55 |
| Comparative example 2 | 65 | 58 |
| Comparative example 3 | 62 | 52 |
CH when catalysts prepared in examples 1 to 5 and comparative examples 1 to 3 are used4The conversion rate was shown in FIG. 1 as a trend with time. As can be seen from fig. 1, the catalyst prepared according to the present invention showed higher catalytic activity and stability relative to the comparative example 1.
Claims (10)
1. A methane carbon dioxide reforming catalyst characterized by: the catalyst has the structure of A/LaxCe1-xNiO3. Wherein A is alkali metal or alkaline earth metal, and x is more than or equal to 0 and less than or equal to 1.
2. The methane carbon dioxide reforming catalyst according to claim 1, characterized in that: the alkali metal is Na or K.
3. The methane carbon dioxide reforming catalyst according to claim 1, characterized in that: the alkaline earth metal is Mg, Ca, Ba or Sr.
4. A method for preparing a methane carbon dioxide reforming catalyst according to any one of claims 1 to 3, characterized by: the method comprises the following steps:
(1) pouring citric acid into deionized water, and mixing to form a solution;
(2) respectively dropping mixed aqueous solutions of lanthanum nitrate, cerium nitrate and nickel nitrate into the solution in the step (1), and mixing to form sol;
(3) heating the sol in the step (2), and evaporating water to gradually change the sol into gel;
(4) drying the gel obtained in the step (3) to obtain fluffy solid;
(5) roasting the solid obtained by drying in the step (4) to obtain LaxCe1-xNiO3；
(6) Taking an aqueous solution of nitrate of alkali metal or alkaline earth metal and La obtained in the step (5)xCe1-xNiO3Mixing to obtain suspension, and performing rotary evaporation to disperse alkali metal or alkaline earth metal into LaxCe1-xNiO3A surface;
(7) drying and roasting the solid obtained in the step (6) to obtain A/LaxCe1-xNiO3A catalyst.
5. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: in the step (3), the temperature is raised to 60-80 ℃.
6. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: in the step (4), drying is carried out at the temperature of 80-150 ℃.
7. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: in the step (5), the calcination is carried out at the temperature of 600-1300 ℃.
8. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: and (6) carrying out rotary evaporation on the suspension on a rotary evaporator.
9. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: in the step (7), drying is carried out at 80-120 ℃, and roasting is carried out at 350-550 ℃.
10. The method for producing a methane carbon dioxide reforming catalyst according to claim 4, characterized in that: in the catalyst prepared in the step (7), the alkali metal or the alkaline earth metal accounts for 0.1-0.5% of the mass of the catalyst.
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| CN110152677A (en) * | 2019-05-20 | 2019-08-23 | 宁波大学 | A kind of difunctional compound VPO catalysts of perovskite/cerium oxide with biomimetic features |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114588912A (en) * | 2022-03-28 | 2022-06-07 | 华中科技大学 | Preparation method and application of alkali metal-doped perovskite catalyst suitable for dry reforming of methane |
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