CN111558392B - Catalyst for dry reforming reaction of methane and carbon dioxide and preparation method and application thereof - Google Patents
Catalyst for dry reforming reaction of methane and carbon dioxide and preparation method and application thereof Download PDFInfo
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- CN111558392B CN111558392B CN202010379036.0A CN202010379036A CN111558392B CN 111558392 B CN111558392 B CN 111558392B CN 202010379036 A CN202010379036 A CN 202010379036A CN 111558392 B CN111558392 B CN 111558392B
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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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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Abstract
The invention discloses a Ni @ Silicalite-1 catalyst for efficiently catalyzing methane carbon dioxide reforming reaction and a fluorine-free preparation method thereof, belonging to the technical field of catalyst preparation. The basic structural feature of the catalyst is that a high content (7.5-20 wt.%) of Ni is highly dispersively embedded in the Silicalite-1 molecular sieve crystals. The process for the preparation of the catalyst does not involve any fluoride starting material. Although the Ni content of the catalyst is high, the sintering resistance and the carbon deposition resistance of the catalyst are strong because the framework of the Silicalite-1 molecular sieve is utilized to limit the domain of Ni metal particles. The catalyst has higher Ni content and the mass transfer effect of the micropores of the Silicalite-1 molecular sieve, so that the catalytic activity and the stability of the catalyst are the same as those of the conventional amorphous SiO2The Ni-embedded nanoparticle catalyst is also extremely outstanding.
Description
Technical Field
The invention relates to a Ni-MO @ Silicalite-1 catalyst for efficiently catalyzing carbon dioxide reforming reaction of methane and a preparation method thereof, belonging to the technical field of catalyst preparation.
Background
Natural gas is one of the three most important fossil energy sources. With the continuous development of natural gas resources on land and combustible ice resources on the seabed, the importance of effective utilization of natural gas energy becomes increasingly prominent worldwide. Methane is the main component of natural gas, and its molecules are very stable and difficult to activate at lower temperature, and at the same time, in the presence of O2The existing conditions are extremely easy to generate combustion reaction, which makes the effective conversion and utilization of methane recognized as the core subject of energy research by international public.
On the other hand, the emission of carbon dioxide to the atmosphere, which is the final combustion product of coal and carbon-containing compounds, has increased year by year, and has led to the greenhouse effect of the whole earth. This greenhouse effect is threatening the continued development of the earth's mankind more and more.
Simultaneous catalytic conversion of methane and carbon dioxide to synthesis gas, i.e. CO by methane, using a suitable catalyst2Dry reforming reaction
Preparation of syngas (CO + H)2) Not only can provide necessary raw materials for Fischer-Tropsch synthetic gasoline and diesel oil and reasonably utilize natural gas resources, but also can simultaneously reduce CO2Venting to the atmosphere, alleviating the environmental problems described above.
Since nickel is cheap, it is suitable for CH4CO of2The reforming reaction has higher activity and selectivity, so that the nickel-based catalyst has been researched more at home and abroad so far. However, the catalyst has the serious defects that the heat resistance stability of the supported nano Ni particle catalyst is poor, and Ni particles are easy to sinter and grow under the condition of high-temperature catalytic reaction; carbon is very easily deposited on the Ni particles to cover the active sites. This makes such catalysts appear to gradually lose their initial excellent high activity under reaction conditions. Due to CH4And CO2High stability of the molecule and endothermic character of the above reaction, the CH4CO of2The reforming reaction must be carried out at high temperature, which makes it possible to limit the combined growth and sintering of nano-Ni particles on the carrier and to suppress the carbon deposition of the catalyst, which makes it necessary for the supported Ni catalyst to catalyze CH4CO of2The success of the dry reforming reaction is the technical key to industrial applications.
Wang Zhoujun et al (CN 104511279A) disclose a method of preparing 1-30 wt.% Ni/SiO by loading Ni nanoparticles on silica nanofibers2The catalyst is used in the carbon dioxide reforming reaction of methane.
Penghong et al (CN 105964259A) disclose a method for encapsulating Ni nanoparticles in amorphous SiO2A catalyst. Ni/SiO with multi-core shell structure2The preparation of the catalyst is characterized by a reverse microemulsion method. The preparation method is specifically in cyclohexaneAdding nickel nitrate water solution and concentrated ammonia water into solvent and polyethylene glycol mono-4-nonylphenyl ether successively, stirring at 30 deg.C, adding ethyl orthosilicate and hydrolyzing for a long time. The obtained Ni/SiO2The catalyst particles are amorphous SiO with the shape of a separation sphere and the structure of 20-30nm2The balls encapsulate one or several Ni particles.
Hedanong et al (CN 107754844A) disclose a method for preparing nickel-based catalyst by in-situ crystallization growth of molecular sieve. The preparation method of the catalyst is characterized in that nickel salt is added into mother liquor (containing a silicon source, a structure directing agent, a mineralizer and water) for synthesizing the molecular sieve, and the catalyst is obtained by one-step crystallization synthesis for 7 days at the temperature of 150-. The structure directing agent is tetrapropylammonium bromide or tetraethylammonium hydroxide or triethylamine. The mineralizer is sodium hydroxide and sodium fluoride.
Wangshouping et al (CN 109647495A) disclosed a method of preparing Ni @ S2 catalyst by embedding nickel metal particles in Silicalite-2. The preparation method of Ni @ S2 comprises the steps of firstly using nickel acetylacetonate as a nickel precursor, and obtaining Ni-SiO by a microemulsion method2And adding the intermediate into a tetrabutylammonium hydroxide template, and crystallizing for 24-72 hours at 170-200 ℃ without solvent, thereby obtaining the Ni @ S2 catalyst with the nickel loading of 2.5-7.5 wt.%.
Wangfeng et al (CN 109225229A) disclose a Ni nanoparticle as core and amorphous silica spheres as shell Ni @ SiO2The preparation method of the core-shell structure catalyst is characterized in that the corresponding catalyst is used for the carbon dioxide reforming reaction of methane. Its Ni @ SiO2The core-shell structure catalyst has nickel loading of 3-6 wt.%, and is prepared by L-lysine through microemulsion process.
Dai et al reported a method of preparing a single-cavity S-1 molecular sieve crystal encapsulated Ni particle catalyst for use in the carbon dioxide reforming reaction of methane. The corresponding catalyst has the structural characteristic that the single-cavity Silicalite-1 molecular sieve crystal encapsulates metal Ni particles.
So far, in any previous literature, no research on preparing Silicalite-1 molecular sieve crystal multi-cavity encapsulated nano Ni particles with fluorine-free raw materials so that the content of Ni in a catalyst reaches more than 7.5 wt.% for a carbon dioxide dry reforming reaction of methane has been carried out.
Disclosure of Invention
The main technical purpose of the invention is to provide a Ni @ Silicalite-1 catalyst for carbon dioxide dry reforming reaction of methane with high activity, strong sintering resistance and strong carbon deposition resistance for preparing Silicalite-1 molecular sieve crystal multi-cavity encapsulated nano Ni particles (shown in figure 1) or Silicalite-1 molecular sieve crystal embedded nano Ni particles (shown in figure 2) by using a fluorine-free raw material and a preparation method thereof (shown in the preparation of Silicalite-1 parent molecular sieve and examples 1-7).
The invention provides a catalyst for catalyzing dry reforming reaction of methane and carbon dioxide, which has the following structure, wherein a plurality of Ni nano-particles with the average particle size of less than 5nm are dispersed and embedded in the same Silicalite-1 molecular sieve crystal grain or multi-cavity packaged Ni nano-particles with the average particle size of less than 5nm, the mass percentage of Ni metal is higher than 7.5%, and the catalyst is obtained by hydrothermal crystallization of the Silicalite-1 molecular sieve, nickel salt and an organic template agent under the condition of not using fluoride.
Further, in the above technical scheme, the preparation method of the catalyst used in the reaction is as follows:
dissolving nickel salt in deionized water, adding a Silicalite-1 molecular sieve into the deionized water, soaking and stirring the mixture till the mixture is dry, and directly grinding the mixture into powder without any calcining process;
then adding the obtained solid powder into tetrapropyl ammonium hydroxide solution and deionized water, and uniformly mixing to form slurry liquid;
then pouring the slurry liquid into a hydrothermal kettle for hydrothermal crystallization at 110-180 ℃.
And finally, drying the obtained solid, and removing the organic template agent in the air.
Further, in the above technical solution, the nickel salt is preferably nickel nitrate, but may also be nickel sulfate, nickel chloride or nickel acetate.
Further, in the technical scheme, the optimal mass ratio of the Silicalite-1 molecular sieve to the tetrapropylammonium hydroxide and the water is 10/(8-30)/(70-400).
Further, in the technical scheme, the optimal mass ratio of the nickel salt to the Silicalite-1 molecular sieve calculated according to the metal is 8/100-25/100.
Further, in the above technical solution, the crystallization time is directly related to the crystallization temperature used, and the lower the crystallization temperature is, the longer the crystallization time is required. The optimal crystallization temperature is 150-170 ℃, and the optimal crystallization time is 18-72 hours.
The invention provides a catalyst for dry reforming reaction of methane and carbon dioxide. The highest reaction space velocity can reach 180,000 mL/g.h at the reaction temperature of 800 ℃.
The catalyst obtained by the method is characterized in that a plurality of Ni nano-particles or multi-cavity packaged Ni nano-particles are dispersed and embedded in the same Silicalite-1 molecular sieve crystal grain, and the mass percentage of Ni metal is higher than 7.5%. The average diameter of Ni metal particles in the Silicalite-1 molecular sieve crystals after the catalyst is reduced is between 0.2 and 5 nm.
Due to the difference of the optimal mass ratio of the Silicalite-1 molecular sieve to the tetrapropylammonium hydroxide and the optimal crystallization temperature and the optimal crystallization time, the catalyst Ni @ Silicalite-1 obtained by the preparation steps has the structural expression that a plurality of Ni nano-particles with the average particle size of less than 5nm are dispersedly embedded in each Silicalite-1 molecular sieve crystal grain or the Ni nano-particles with the average particle size of less than 5nm are encapsulated in a plurality of cavities in each Silicalite-1 molecular sieve crystal grain.
Advantageous effects
The catalyst of the present invention has the following four advantageous effects compared with conventional catalysts. (1) No fluoride raw material is used, so that no fluorine pollution is caused to the environment; (2) high Ni content (Ni metal content between 7.5-20 wt.%), and thus higher activity per amount of catalyst; (3) the nano Ni particles are dispersed and encapsulated in the multi-cavity crystal of the molecular sieve, so that the sintering resistance is better; (4) the molecular sieve multi-cavity crystal can transfer mass more effectively, so that the dry reforming reaction of methane can be catalyzed at high space velocity.
Drawings
FIG. 1 is the structure of a multi-cavity Silicalite-1 encapsulated nano Ni particle catalyst of the Ni @ Silicalite-1 catalyst obtained in example 1;
FIG. 2 is a structure of a Silicalite-1 molecular sieve crystal-embedded nano Ni particles of the Ni @ Silicalite-1 catalyst obtained in example 2;
FIG. 3 shows the crystal-encapsulated Ni particles of the single-cavity Silicalite-1 molecular sieve of the Ni @ Silicalite-1 catalyst obtained in comparative example 1.
Detailed Description
See examples 1-6 for specific embodiments. The catalyst structure for dry reforming of methane by carbon dioxide proposed by the present invention can be obtained from the following examples 1 to 6, but the patent requirements for catalysts of corresponding structures for dry reforming of methane by carbon dioxide proposed by the present invention are not limited to examples 1 to 6. The parent Silicalite-1 molecular sieve used in the catalyst of the invention is obtained from the following preparation method or purchased Silicalite-1 molecular sieve raw powder.
Preparation of Silicalite-1 molecular sieve:
45.83g of tetraethoxysilane was mixed uniformly with 48.32g of tetrapropylammonium hydroxide (25 wt.%), 40.54g of absolute ethanol and 145.92g of deionized water, and then stirred at 25 ℃ for 5 hours. The obtained mixed liquid is poured into a hydrothermal kettle to be hydrothermally crystallized for 72 hours at the temperature of 170 ℃. And (4) drying the obtained solid by centrifugation, and roasting the dried solid in air at 540 ℃ for 4 hours to obtain the Silicalite-1 parent molecular sieve.
Example 1
7.69g of Ni (NO)3)2·6H2O was dissolved in 12 ml of deionized water. Then 6g of the Silicalite-1 parent molecular sieve obtained by the above Silicalite-1 molecular sieve preparation method was added thereto, stirred to dryness at 50 ℃ and ground into a powder. Then, 58.6g of tetrapropylammonium hydroxide having a concentration of 25 wt.% and 181.4g of deionized water were added to the resulting powder, mixed uniformly, and poured into a hydrothermal kettle to be hydrothermally crystallized at 170 ℃ for 72 hours. The resulting solid was dried by centrifugation and calcined in air at 540 ℃ for 4 hours.
Example 2
With 5.43g Ni (NO)3)2·6H2O instead of 7.69g of Ni (NO) in example 13)2·6H2O was dissolved in 12 ml of deionized water and the other treatments were the same as in example 1.
Comparative example 1
Example 1 was repeated, but in contrast to example 1, Ni (NO) was added3)2·6H2The O solution is dipped in a Silicalite-1 molecular sieve and stirred until the obtained solid is dried, the solid is calcined in air at 400 ℃ for two hours and cooled, the calcined solid is ground into powder, and then the powder is mixed with tetrapropylammonium hydroxide and deionized water to be uniform for hydrothermal crystallization.
The structure of the Ni @ Silicalite-1 catalyst obtained in example 1 of the present invention is a multi-cavity Silicalite-1 encapsulated nano Ni particle catalyst (FIG. 1), the structure of the Ni @ Silicalite-1 catalyst obtained in example 2 of the present invention is Silicalite-1 molecular sieve crystal-embedded nano Ni particles (FIG. 2), and the structure of the Ni @ Silicalite-1 catalyst obtained in comparative example 1 is single-cavity Silicalite-1 molecular sieve crystal-encapsulated Ni particles (FIG. 3).
The structure of the obtained catalyst is that single-cavity Silicalite-1 encapsulates nanometer Ni particles (figure 3) or multi-cavity Silicalite-1 molecular sieve crystals encapsulates Ni particles (figure 1), and only the result that nickel salt is loaded on the Silicalite-1 molecular sieve crystals is that whether the nickel salt (comparative example 1) or not (example 1) is subjected to a calcination process before being mixed with an organic template. The structure of these two catalysts makes the respective catalysts significantly different in catalytic performance.
The obtained catalyst structurally comprises multi-cavity Silicalite-1 molecular sieve crystal encapsulated Ni particles (figure 1) or Silicalite-1 molecular sieve crystals embedded with a plurality of nano Ni particles (figure 2), and is related to the adding amount of nickel salt, the proportion of nickel salt/Silicalite-1 solid powder to organic template and deionized water, and the hydrothermal crystallization temperature and time. However, when the nickel content in the obtained catalyst is the same, the difference in the fine structure of the catalyst has little influence on the performance of the catalyst (see attached table 1).
Example 3
With 2.49g Ni (NO)3)2·6H2O instead of 7.69g of Ni (NO) in example 13)2·6H2O was dissolved in 12 ml of deionized water and the other treatments were the same as in example 1.
Example 4
The 58.6g tetrapropylammonium hydroxide (25 wt.%) and 181.4g deionized water of example 1 were replaced with 29.3g tetrapropylammonium hydroxide (25 wt.%) and 90.7g deionized water, respectively, while the Silicalite-1 precursor molecular sieve used in example 1 was changed to the purchased raw Silicalite-1 molecular sieve powder without any treatment, and the hydrothermal crystallization time was changed from 72 hours to 24 hours. The other treatment conditions were the same as in example 1.
Example 5
58.6g of tetrapropylammonium hydroxide (25 wt.%) and 181.4g of deionized water in example 1 were replaced with 19.9g of tetrapropylammonium hydroxide (25 wt.%) and 100.1g of deionized water, respectively, while the hydrothermal crystallization time in example 1 was changed from 72 hours to 24 hours.
Example 6
54.7g of tetrapropylammonium hydroxide (25 wt.%) and 65.3g of deionized water were used instead of 58.6g of tetrapropylammonium hydroxide (25 wt.%) and 181.4g of deionized water, respectively, in example 1, while the hydrothermal crystallization time in example 1 was changed from 72 hours to 24 hours.
To confirm the beneficial effects of the structured catalyst of the present invention, Ni @ Silicalite-1 with Ni metal content of 19.5 wt.% was prepared by the conventional method to have the same chemical composition, but to have a single-cavity S-1 molecular sieve crystal-encapsulated Ni particle structure (obtained from comparative example 1), and amorphous SiO particles2The encapsulated Ni particle structure (obtained from comparative example 2 described below), and the supported Ni/Silicalite-1 structure (obtained from comparative example 3 described below) were compared with the catalysts of the present invention (see examples 1-6) under the same reaction conditions (see example 7) (see attached Table 1).
Comparative example 2 0.07 mol of polyoxyethylene (n ═ 20) hexadecyl ether and 200 ml of cyclohexane were uniformly mixed at room temperature with continuous stirring, 7 ml of 1M nickel nitrate aqueous solution and 9 ml of hydrazine hydrate having a concentration of 80 wt.% were added dropwise, then the temperature was raised to 50 ℃ to react for 30 minutes, then 5.5 g of tetraethyl orthosilicate and ammonia water were added to hydrolyze for two hours, and then the mixture was dried and finally calcined in air at 540 ℃ for 4 hours.
Comparative example 3 7.69g of Ni (NO)3)2·6H2O was dissolved in 12 ml of deionized water, and then 6g of Silicalite-1 molecular sieve was added thereto, immersed at 50 ℃ for 12 hours, stirred to dryness, and ground into powder. Mixing the obtained solidDrying and calcining at 540 deg.C for 4 hr.
Example 7 CO of methane2Determination of Dry reforming reactivity
The reaction was carried out in a quartz tube fixed bed reactor having an inner diameter of 6 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Weighing 10mg of catalyst (40-60 meshes) and 0.19g of quartz sand (40-60 meshes), uniformly mixing, placing in a quartz tube, and adding H2The catalyst was pretreated at 750 ℃ for 1h and then evaluated for activity under the following conditions: reactive gas distribution CO2：CH4The space velocity of the reaction gas is 180,000 mL/g.h, and the reaction temperature is 800 ℃.
Composition, physical Structure and CO to methane of the catalyst of attached Table 12Comparison of catalytic Activity of Dry reforming reactions
Claims (5)
1. A preparation method of a catalyst for dry reforming reaction of methane and carbon dioxide is provided, the catalyst has the following structure, a plurality of Ni nano-particles with the average particle size of less than 5nm are dispersed and embedded in the same Silicalite-1 molecular sieve crystal grain or multi-cavity packaged Ni nano-particles with the average particle size of less than 5nm, the mass percentage of Ni metal is higher than 7.5%, the catalyst is obtained by hydrothermal crystallization of the Silicalite-1 molecular sieve, nickel salt and an organic template agent under the condition of not using fluoride, and the catalyst is characterized by comprising the following steps:
(1) dissolving nickel salt in deionized water, adding a Silicalite-1 molecular sieve into the deionized water, soaking and stirring the mixture till the mixture is dry, and directly grinding the mixture into powder without calcining;
(2) then adding the obtained solid powder into tetrapropyl ammonium hydroxide solution and deionized water, and uniformly mixing to form slurry liquid;
(3) then pouring the slurry liquid into a hydrothermal kettle for hydrothermal crystallization at 110-180 ℃;
(4) and finally, drying the obtained solid, and removing the organic template agent in the air.
2. The method of claim 1, wherein: in the step (1), the nickel salt is selected from nickel nitrate, nickel sulfate, nickel chloride or nickel acetate.
3. The method of claim 1, wherein: in the step (1), the mass ratio of the nickel salt to the Silicalite-1 molecular sieve is 8/100-25/100 according to the metal calculation.
4. The method of claim 1, wherein: in the step (2), the mass ratio of the Silicalite-1 molecular sieve to the tetrapropylammonium hydroxide to the water is 10/(8-30)/(70-400).
5. The method of claim 1, wherein: in the step (3), the crystallization temperature is 150-170 ℃, and the crystallization time is 18-72 hours.
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| CN102745648A (en) * | 2011-04-22 | 2012-10-24 | 太原理工大学 | Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation |
| CN104084231A (en) * | 2014-07-15 | 2014-10-08 | 上海穗杉实业有限公司 | Nickel-base methanation catalyst for removing trace of CO in H2 and preparation method thereof |
| CN106000443A (en) * | 2016-05-24 | 2016-10-12 | 昆明理工大学 | Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis |
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| CN102745648A (en) * | 2011-04-22 | 2012-10-24 | 太原理工大学 | Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation |
| CN104084231A (en) * | 2014-07-15 | 2014-10-08 | 上海穗杉实业有限公司 | Nickel-base methanation catalyst for removing trace of CO in H2 and preparation method thereof |
| CN106000443A (en) * | 2016-05-24 | 2016-10-12 | 昆明理工大学 | Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis |
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