CN114100619B - 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a methane carbon dioxide reforming catalyst and a preparation method thereof, and belongs to the technical field of reforming catalysts. The methane carbon dioxide reforming catalyst has the structure of A/La x Ce 1‑x NiO 3 . Wherein A is alkali metal or alkaline earth metal, x is more than or equal to 0 and less than or equal to 1. The methane carbon dioxide reforming catalyst provided by the invention can be used for effectively avoiding carbon deposition in the methane carbon dioxide reaction process, and has higher stability and effectively avoiding inactivation; the invention also provides a simple and easy preparation method.
Description
Technical Field
The invention relates to a methane carbon dioxide reforming catalyst and a preparation method thereof, and belongs to the technical field of reforming catalysts.
Background
Carbon dioxide (CO) 2 ) And methane (CH) 4 ) As greenhouse gases, it is generally considered as the culprit of the problem of the current greenhouse effect. By reducing the dependence on fossil fuels and minimizing the emission of greenhouse gases into the environment, the trend of global warming can be slowed down. Hydrogen is one of the most promising alternative energy sources because it has the function of reducing NO x And CO x Emissions advantages, and water is a byproduct of combustion. Methane carbon dioxide reforming is an important mode of industrial hydrogen production and can realize two modes at the same timeAn effective way for reasonably utilizing two greenhouse gases, namely carbon oxide and methane. Methane carbon dioxide reforming can produce synthesis gas with a proper H/C ratio, and the synthesis gas can be effectively 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 are mainly divided into 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 relatively expensive, so that the noble metal catalysts are not suitable for industrial production. Non-noble metal catalysts include cobalt, copper, iron, nickel-based catalysts, which are relatively inexpensive, but which have severe carbon deposition during the reaction and are susceptible to sintering deactivation at high temperatures. The modification of the reforming catalyst by adopting alkali metal or alkaline earth metal as an auxiliary agent is a common mode 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 carbon deposition eliminating effect 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 deactivated.
Perovskite has excellent electrical conductivity, magnetism, thermoelectric property, piezoelectricity and other properties, and has low preparation cost, thermodynamic and mechanical stability at high temperature, and is an excellent oxygen ion and electron conductor at high temperature. In recent years, perovskite is widely used in a plurality of catalytic fields, has excellent catalytic performance, has simple preparation process and low cost, has high-temperature activity and stability, reduces carbon deposit of the catalyst, and delays the deactivation process of the catalyst. And carbon deposition is effectively avoided in the catalytic reaction process. Perovskite oxides (e.g. LaNiO 3 、La 0.9 Ce 0.1 NiO 3 ) 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, especially the carbon deposition resistance of the catalyst in a mode of doping alkali metal or alkaline earth metal in the crystal structure is more obvious, but the carbon deposition resistance of the perovskite catalyst still has higher lifting space.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects in the prior art, and provide the methane carbon dioxide reforming catalyst which can effectively avoid carbon deposition in the process of methane carbon dioxide reaction, has higher stability and effectively avoids inactivation; the invention also provides a simple and easy preparation method.
The methane carbon dioxide reforming catalyst has the structure of A/La x Ce 1-x NiO 3 . Wherein A is alkali metal or alkaline earth metal, 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 dripping the mixed aqueous solution of lanthanum nitrate, cerium nitrate and nickel nitrate into the solution in the step (1), and mixing to form sol;
(3) Heating the sol obtained 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 80-150 ℃ to obtain fluffy solid;
(5) Roasting the solid obtained in the step (4) at 600-1300 ℃ to obtain La x Ce 1-x NiO 3 ；
(6) Taking an aqueous nitrate solution of alkali metal or alkaline earth metal and La obtained in the step (5) x Ce 1-x NiO 3 Mixing to obtain suspension, and rotary evaporating to dry water slowly to disperse alkali metal or alkaline earth metal into La x Ce 1-x NiO 3 A surface;
(7) Drying the solid obtained in the step (6) at 80-120 ℃ and roasting at 350-550 ℃ to obtain A/La x Ce 1-x NiO 3 A catalyst.
In the final catalyst prepared by the invention, alkali metal or alkaline earth metal accounts for 0.1 to 0.5 percent 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 holes is high, and the generation of carbon deposit on the surface of the catalyst in the reaction process can be effectively slowed down. The nickel-based perovskite oxide is reduced, then 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 after the catalyst is reduced can be uniformly dispersed on the surface of the metal nickel, so that sintering agglomeration of the auxiliary agent in the heat treatment process and the reaction process can be effectively avoided when a small amount of auxiliary agent exists; when an excessive amount of the auxiliary agent is present, the auxiliary agent tends to have a problem of poor catalyst activity due to covering a large number of active sites, and thus the amount of the auxiliary agent 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 type nickel-based catalyst is adopted, and meanwhile, in the preparation process, the alkali metal or alkaline earth metal is highly dispersed on the surface of the perovskite oxide in a rotary evaporation mode, so that the defects of the traditional doping mode are avoided, the effect of the alkali metal or alkaline earth metal can be better exerted, and the catalyst can be used for effectively avoiding carbon deposition in the methane carbon dioxide reaction process, and meanwhile, the catalyst has higher stability and is effectively prevented from being deactivated;
(2) The preparation method provided by the invention is simple, the raw material cost is low, and the production cost of the catalyst in actual production is expected to be greatly reduced.
Drawings
FIG. 1 is a CH when catalysts prepared in examples and comparative examples were used 4 A plot of conversion versus time.
Detailed Description
The invention is further illustrated below in connection with 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 evenly mixed to form a solution. Mixing 0.1mol of lanthanum nitrate and 0.1mol of nickel nitrate into deionized water, dripping into aqueous solution of citric acid, and uniformly mixing to form sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel was then dried at 80 ℃. Roasting the dried solid at 900 ℃ to obtain LaNiO 3 。
Dissolving 0.073g of sodium nitrate in deionized water, mixing sodium nitrate solution with 20g of obtained LaNiO 3 Mixing to obtain suspension, and rotary evaporating the suspension on a rotary evaporator to evaporate water slowly to disperse alkali metal into LaNiO 3 A surface. Drying the solid obtained after evaporation to dryness at 120 ℃, and roasting at 450 ℃ to obtain Na/LaNiO 3 A catalyst.
The mass content of sodium oxide in the final catalyst was 0.5%.
Example 2
0.12mol of citric acid is poured into deionized water and evenly mixed to form a solution. Mixing 0.09mol of lanthanum nitrate, 0.01mol of cerium nitrate and 0.1mol of nickel nitrate into deionized water, dripping into aqueous solution of citric acid, and uniformly mixing to form sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel is then dried at 90 ℃. Roasting the dried solid at 800 ℃ to obtain La 0.9 Ce 0.1 NiO 3 。
Dissolving 0.072g of potassium nitrate in deionized water, mixing the potassium nitrate solution with 20g of obtained La 0.9 Ce 0.1 NiO 3 Mixing to obtain suspension, and rotary evaporating the suspension on a rotary evaporator to slowly evaporate water to disperse potassium ions into La 0.9 Ce 0.1 NiO 3 A surface. Drying the solid obtained after evaporating to dryness at 120deg.C, and roasting at 450deg.C to obtain K/La 0.9 Ce 0.1 NiO 3 A catalyst.
The mass content of potassium oxide in the final catalyst was 0.5%.
Example 3
0.12mol of citric acid is poured into deionized water and evenly mixed to form a solution. Mixing 0.07mol of lanthanum nitrate, 0.03mol of cerium nitrate and 0.1mol of nickel nitrate into deionized water, dripping into aqueous solution of citric acid, and uniformly mixing to form sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel is then dried at 100 ℃. Roasting the dried solid at 600 ℃ to obtain La 0.7 Ce 0.3 NiO 3 。
0.37g of magnesium nitrate was dissolved in deionized water, and the magnesium nitrate solution was mixed with 20g of the obtained La 0.7 Ce 0.3 NiO 3 Mixing to obtain suspension, and rotary evaporating the suspension on a rotary evaporator to slowly evaporate water to disperse magnesium ions into La 0.7 Ce 0.3 NiO 3 A surface. Drying the solid obtained after evaporating to dryness at 120 ℃, and roasting at 450 ℃ to obtain Mg/La 0.7 Ce 0.1 NiO 3 A catalyst.
The mass content of magnesium oxide in the final catalyst was 0.5%.
Example 4
0.12mol of citric acid is poured into deionized water and evenly mixed to form a solution. Mixing lanthanum nitrate 0.05mol, cerium nitrate 0.05mol and nickel nitrate 0.1mol into deionized water, dripping into aqueous solution of citric acid, and mixing to obtain sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel was then dried at 110 ℃. Roasting the dried solid at 700 ℃ to obtain La 0.5 Ce 0.5 NiO 3 。
0.17g of barium nitrate was dissolved in deionized waterIn the sub water, barium nitrate solution and 20g of obtained La 0.7 Ce 0.3 NiO 3 Mixing to obtain suspension, and rotary evaporating the suspension on a rotary evaporator to slowly evaporate water to disperse magnesium ions into La 0.7 Ce 0.3 NiO 3 A surface. Drying the solid obtained after evaporation to dryness at 100 ℃, and roasting at 450 ℃ to obtain Ba/La 0.5 Ce 0.5 NiO 3 A 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 evenly mixed to form a solution. Mixing lanthanum nitrate 0.02mol, cerium nitrate 0.08mol and nickel nitrate 0.1mol into deionized water, dripping into aqueous solution of citric acid, and mixing to obtain sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel was then dried at 120 ℃. Roasting the dried solid at 1000 ℃ to obtain La 0.2 Ce 0.8 NiO 3 。
Dissolving 0.204g of strontium nitrate in deionized water, mixing the strontium nitrate solution with 20g of obtained La 0.2 Ce 0.8 NiO 3 Mixing to obtain suspension, and rotary evaporating the suspension on a rotary evaporator to slowly evaporate water to disperse strontium ions into La 0.2 Ce 0.8 NiO 3 A surface. Drying the solid obtained after evaporating to dryness at 110deg.C, and roasting at 450deg.C to obtain Sr/La 0.2 Ce 0.8 NiO 3 A 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 evenly mixed to form a solution. Mixing 0.02mol of lanthanum nitrate, 0.08mol of cerium nitrate, 0.1mol of nickel nitrate and 0.21g of barium nitrate into deionized water, dripping into aqueous solution of citric acid, and uniformly mixing to form sol. Will thenThe sol was warmed to 80 ℃ to evaporate water, which gradually turned into a gel. The gel was then dried at 120 ℃. Roasting the dried solid at 1000 ℃ to obtain Ba-La 0.2 Ce 0.8 NiO 3 A 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 evenly mixed to form a solution. 0.09mol of lanthanum nitrate and 0.01mol of cerium nitrate, 0.1mol of nickel nitrate and 0 were taken. 132g And (3) dissolving potassium nitrate into deionized water, then dripping the potassium nitrate into a citric acid aqueous solution, and uniformly mixing to form sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel is then dried at 90 ℃. Roasting the dried solid at 800 ℃ to obtain K-La 0.9 Ce 0.1 NiO 3 。
The mass content of potassium oxide in the final catalyst was 0.5%.
Comparative example 3
0.12mol of citric acid is poured into deionized water and evenly mixed to form a solution. Mixing lanthanum nitrate 0.02mol, cerium nitrate 0.08mol and nickel nitrate 0.1mol into deionized water, dripping into aqueous solution of citric acid, and mixing to obtain sol. The sol was then warmed to 80 ℃ to evaporate the water, gradually turning it into a gel. The gel was then dried at 120 ℃. Roasting the dried solid at 1000 ℃ to obtain La 0.2 Ce 0.8 NiO 3 。
Catalyst reaction performance evaluation:
the reaction properties were examined with 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 H was used before the catalyst was used 2 Reducing at 700 deg.c and 3000 hr volume space velocity -1 The reaction pressure is 0.05MPa; after the reduction is finished, methane and carbon dioxide are introduced, and the reaction conditions are as followsIs CH 4 /CO 2 =1, reaction temperature 800 ℃, reaction pressure 0.1MPa, volume space velocity 7000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The product was analyzed by gas chromatography on line and the reaction results are shown in Table 1.
TABLE 1
| Catalyst | CH 4 Conversion (%) | 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 were used 4 The conversion rate trend with time is shown in fig. 1. As can be seen from fig. 1, the catalyst prepared according to the present invention showed higher catalytic activity and stability than the comparative example 1.
Claims (9)
1. A methane carbon dioxide reforming catalyst characterized by: the structure of the catalyst is A/La x Ce 1-x NiO 3 ；
Wherein A is alkali metal or alkaline earth metal, x is more than or equal to 0 and less than or equal to 1, and the alkali metal or alkaline earth metal is dispersed in perovskite oxide La x Ce 1-x NiO 3 A surface;
the alkali metal or alkaline earth metal accounts for 0.1-0.5% of the mass of the catalyst.
2. A methane carbon dioxide reforming catalyst according to claim 1, characterised in that: the alkali metal is Na or K.
3. A methane carbon dioxide reforming catalyst according to claim 1, characterised in that: the alkaline earth metal is Mg, ca, ba or Sr.
4. A method for preparing the methane carbon dioxide reforming catalyst according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) Pouring citric acid into deionized water, and mixing to form a solution;
(2) Respectively dripping the mixed aqueous solution of lanthanum nitrate, cerium nitrate and nickel nitrate into the solution in the step (1), and mixing to form sol;
(3) Heating the sol obtained 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 in the step (4) to obtain La x Ce 1-x NiO 3 ；
(6) Taking an aqueous nitrate solution of alkali metal or alkaline earth metal and La obtained in the step (5) x Ce 1-x NiO 3 Mixing to obtain suspension, and rotary evaporating to disperse alkali metal or alkaline earth metal into La x Ce 1-x NiO 3 A surface;
(7) Drying and roasting the solid obtained in the step (6) to obtain A/La x Ce 1-x NiO 3 A catalyst.
5. The method for preparing a methane carbon dioxide reforming catalyst according to claim 4, wherein: in the step (3), the temperature is raised to 60-80 ℃.
6. The method for preparing a methane carbon dioxide reforming catalyst according to claim 4, wherein: in the step (4), drying is carried out at 80-150 ℃.
7. The method for preparing a methane carbon dioxide reforming catalyst according to claim 4, wherein: in the step (5), roasting is carried out at 600-1300 ℃.
8. The method for preparing a methane carbon dioxide reforming catalyst according to claim 4, wherein: in step (6), the suspension is subjected to rotary evaporation on a rotary evaporator.
9. The method for preparing a methane carbon dioxide reforming catalyst according to claim 4, wherein: in the step (7), the mixture is dried at 80-120 ℃ and baked at 350-550 ℃.
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| CN104923251A (en) * | 2006-06-01 | 2015-09-23 | 株式会社科特拉 | Catalysts |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN108654592A (en) * | 2018-04-29 | 2018-10-16 | 华中科技大学 | A kind of perovskite catalyst and preparation method thereof and home position testing method |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923251A (en) * | 2006-06-01 | 2015-09-23 | 株式会社科特拉 | Catalysts |
| CN107042111A (en) * | 2017-01-11 | 2017-08-15 | 成都理工大学 | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing |
| CN108654592A (en) * | 2018-04-29 | 2018-10-16 | 华中科技大学 | A kind of perovskite catalyst and preparation method thereof and home position testing method |
| 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 |
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