CN115920948A - Preparation method and application of Ni-based catalyst prepared by strengthening radio frequency plasma - Google Patents
Preparation method and application of Ni-based catalyst prepared by strengthening radio frequency plasma Download PDFInfo
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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method and application of a Ni-based catalyst prepared by strengthening radio frequency plasma, belonging to CO 2 And CH 4 Greenhouse gases and environmental protection catalysis. First, metering Ni (NO) 3 ) 2 ·6H 2 O、La(NO 3 ) 2 ·6H 2 O (based on the total mass of the carrier and the active component Ni as 100%, the mass percent of the active component Ni in the catalyst is 10%, and the mass percent of La is 3%) and citric acid (C) 6 H 8 O 7 ·H 2 O)，n(C 6 H 8 O 7 ·H 2 N (metal ion) = 1.5, and an appropriate amount of deionized water is added to dissolve the metal ion, so that the transparent membrane is obtainedA clear solution; heating the solution in a magnetic stirrer at a constant temperature of 60 ℃ to form sol, adding a measured MCM-41 molecular sieve carrier, continuously stirring for 1h, aging at room temperature for 6h, and then placing the aged solution in a drying oven at 110 ℃ to obtain a catalyst precursor; treated with RF plasma (power 200W, atmosphere N) 2 And the time is 2 h) to obtain the La modified Ni/La/MCM-41/Sol/PN catalyst. The catalyst prepared by the method has the advantages of obviously improved catalytic activity, simple process, easy operation and low cost.
Description
Technical Field
The invention belongs to CO 2 The field of reforming methane reaction, in particular to a method for preparing CO 2 A preparation method and application of the reforming catalyst.
Background
Statistics show that nearly 10 million tons of carbon dioxide are now released into the atmosphere per month. The increasing carbon dioxide content of the ambient air leads to dangerous temperature increases at the earth's surface. In such cases, it may be helpful to convert greenhouse gases into valuable chemicals. At present, CO is mixed with 2 The method is used for the production of fossil fuels and chemical energy products, and has good application prospect. The methane reformed by the carbon dioxide can effectively utilize greenhouse gas to generate H 2 And CO synthesis gas, and further other industrial raw materials, and the production of other industrial raw materials is promoted while improving the recycling of greenhouse gases, so that this reaction has been receiving increasing attention in recent years.
CH 4 And CO 2 The reaction of (2) is carried out at a high temperature of 800 ℃, so that the activation energy of the reaction is high, the activation energy of the reaction needs to be reduced by a catalyst, and the side reaction is more. The noble metal catalysts (Pd, pt, rh, ru and Ir) have been studied to have good catalytic activity, stability and anti-carbon property, but the use of noble metals as catalysts is very costly and difficult to be applied to industrialization. The Ni-based catalyst and the Co-based catalyst have good catalytic activity and low application cost, but the cracking of methane can be promoted while the conversion of methane and carbon dioxide in the reaction is promoted under the high-temperature reaction, so that the catalyst deactivation caused by easy sintering and carbon deposition of the Ni-based catalyst is the greatest obstacle of the wide application of the Ni-based catalyst, and therefore, how to improve the carbon deposition resistance and the stability of the Ni-based catalyst is particularly important while the catalytic activity of the Ni-based catalyst is ensured.
Qian et al prepared SBA-15 carrier by hydrothermal synthesis with P123 as template, and added La of different contents to Ni (NO) 3 ) 2 The aqueous solution is co-impregnated with SBA-15, and the catalyst precursor is placed in a muffle furnace for roasting after water bath drying to obtain the Ni/La/SBA-15 catalyst which has higher reforming activity and stability. Yet surface activeThe price of the agent P123 is relatively expensive and the preparation of the SBA-15 of the carrier is relatively cumbersome. Mo et Al prepared Ni/La/Al by hydrolytic deposition 2 O 3 Catalyst with NH 2 (CH 2 ) 2 OH is used as a precipitator, and quantitative nickel nitrate and NO La (NO) are added 3 ) 3 Dissolving in hydrothermal synthesis reactor, and adding Al 2 O 3 And NH was added at a rate of 1mL/min 2 (CH 2 ) 2 OH is dropped into the mixture. After aging for 2 hours, the reactor was placed in an oven to dry and then cooled to room temperature. Washing the mixture to neutrality by using distilled water in a Buchner funnel to obtain a filter cake, putting the filter cake into an oven to be dried for 3 hours, and then roasting in a muffle furnace to obtain Ni/La/Al with different contents 2 O 3 A catalyst. The prepared catalyst has high activity and stability, but the preparation process is complex and takes a long time.
Although the catalyst prepared by the method of the literature can obtain better reaction performance for preparing synthesis gas by reforming carbon dioxide, the catalyst still has the problems of higher cost, complex preparation process, difficult industrialization and the like. Therefore, research on a Ni-based reforming catalyst with simple preparation process, low cost and excellent performance is an urgent need for industrial application. The La auxiliary agent is introduced into the simple and easy-to-operate plasma enhanced sol-gel method to prepare the supported Ni/MCM-41 catalyst, and the influence of the plasma treatment time and different plasma enhanced preparation methods on the structure and the reforming catalytic activity of the MCM-41 carrier supported Ni-based catalyst is researched, so that the method is rarely reported at present.
The design idea of the method is to prepare the supported Ni-based catalyst with highly dispersed active components. Firstly, taking a mesoporous molecular sieve MCM-41 with high specific surface area as a carrier, and loading an active component Ni to improve the dispersion degree of catalytic activity and reduce the particle size; the plasma enhanced treatment catalyst is introduced in the preparation process, so that the interaction between the catalytic active component and the carrier is further increased, the adsorption capacity of the catalyst on carbon dioxide is enhanced, and the catalytic activity and stability of the catalyst are further improved. Based on the earlier exploration, the contents of active components and auxiliaries are optimized by an impregnation method, wherein the mass fraction of Ni is 10%, and the mass fraction of the auxiliaries is 3%. On the basis, the catalyst is modified by a metal auxiliary agent with stronger promotion performance reported in the literature. Then, metal additives such as Co, ce, la, zr and the like are explored and examined, and the stability difference of the catalyst modified by different additives is found to be remarkable, and La is the most preferable, but the activity and the stability are not high on the whole. Then we analyze: the stability of the catalyst mainly lies in the interaction force between the active component and the carrier and the size of Ni particles, so that the introduction of plasma to modify the catalyst is further explored, the difference of the stability of precursors prepared by different methods after plasma modification is obvious, the coupling of precursor preparation and catalyst plasma enhanced preparation is optimized, and the optimal Ni-based reforming catalyst is finally obtained through optimization.
Disclosure of Invention
The invention aims to provide CO 2 A preparation method and application of a reforming catalyst. The method has the advantages of simple process, easy operation and low cost. The catalytic activity and stability of the catalyst after cold plasma treatment are obviously improved, and compared with the basic Ni/MCM-41 catalyst, the initial conversion rate of methane at 700 ℃ is 81.7% (improved by 44.8%), and the conversion rate of carbon dioxide is 81.00% (improved by 31.2%). After 10h of reaction, CH 4 And CO 2 The conversion of (A) was reduced by only 0.8% and 0.8%, respectively. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
CO (carbon monoxide) 2 The preparation method and the application of the reforming catalyst comprise the following steps:
(1) Weighing the stoichiometric ratio of Ni (NO) 3 ) 2 ·6H 2 O、La(NO 3 ) 2 ·6H 2 O (the total mass of the carrier and the active component Ni is 100%, the mass percent of the active component Ni in the catalyst is 10%, the mass percent of the auxiliary agent is 3%), and a gelling agent citric acid (C) 6 H 8 O 7 ·H 2 O, n (metal ion) n (C) 6 H 8 O 7 ·H 2 O) = 1.5, adding 30ml of deionized water, and stirring until the deionized water is completely dissolved to obtain a transparent solution;
(2) Adding a magnetic stirrer into the mixed slurry obtained in the step (1), and rotationally stirring in a constant-temperature heating magnetic stirrer until sol is formed;
(3) Adding the measured MCM-41 molecular sieve carrier into the gel obtained in the step (2) to obtain mixed slurry, and continuously stirring;
(4) Aging the sol obtained in the step (3) at room temperature;
(5) Drying the sol obtained in the step (4) in an oven to obtain a catalyst precursor;
(6) Grinding the precursor obtained in step (5) to fine powder, and treating with plasma (200W 2 2 h) after 10% Ni/3% La/Sol/PN catalyst.
According to the scheme, the gelling agent is citric acid (C) 6 H 8 O 7 ·H 2 O)。
Preferably, the gelling agent is added in an amount of n (metal ion): n (C) 6 H 8 O 7 ·H 2 O)＝1:1.5。
According to the scheme, the carrier is an MCM-41 molecular sieve.
According to the scheme, the mass percent of the active component Ni is 10% by taking the mass of the carrier as 100%.
According to the scheme, the mass percent of the auxiliary agent La is 3% by taking the mass of the carrier as 100%.
According to the scheme, the plasma treatment power is 200W, the atmosphere is nitrogen, and the treatment time is 2h.
According to the scheme, the stirring temperature is 60 ℃;
preferably, the rotating stirring time is 4-5h;
the continuous stirring time is 1h;
the aging time is 6h;
the drying time is 11-13h;
the drying temperature is 100-120 ℃.
The invention has the following advantages:
1. the cold plasma enhanced sol-gel method of the inventionLa-doped Ni-based catalyst for CH 4 /CO 2 The catalytic activity of the catalyst is obviously improved compared with that of Ni-based catalyst prepared by impregnation in the reforming reaction, the initial conversion rates of methane and carbon dioxide reach 81.7 percent and 81.0 percent respectively at 700 ℃, and the initial conversion rates are obviously improved compared with the conventional 10 percent Ni/MCM-41 catalyst. Evaluation of the stability for 10h showed that after 10h of reaction, CH 4 The conversion of (a) is reduced by only 0.8%.
2. The Ni/La/Sol/PN molecular sieve catalyst is prepared by adopting a plasma enhanced Sol-gel method, and the preparation method has the advantages of simple process, low cost and easy control.
FIG. 1 is a graph showing stability tests of catalysts prepared in examples 1, 2, 3, 4 and 5.
FIG. 2 is a graph showing stability tests of catalysts prepared in examples 1, 2, 6, 7, 8 and 9.
FIG. 3 is a graph showing stability tests of catalysts prepared in examples 2, 6, 10, 11, 12 and 13.
Fig. 4 is an XRD spectrum of the catalysts prepared in examples 1, 2 and 13.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
EXAMPLE 1 preparation of Ni/MCM-41 catalyst
0.991g of Ni (NO) 3 ) 2· 6H 2 And dissolving O in 30ml of deionized water by stirring, adding 1.80g of MCM-41 molecular sieve carrier, soaking for 45min at room temperature, evaporating the mixed slurry to dryness in a water bath at 60 ℃, drying for 12h at 110 ℃, and roasting for 4h at 550 ℃ in an air atmosphere to obtain the Ni/MCM-41 catalyst. Example 1 the catalyst composition is shown in table 1.
Evaluation of catalyst stability
The stability evaluation of the catalyst was carried out in a self-made continuous flow fixed bed reactor. The reaction tube is a quartz tube with an inner diameter of 6mm and a length of 33cm, the reaction temperature is measured by a thermocouple arranged in the middle of the reaction tube, and a temperature programming controller is used for controlling the reaction temperature. The gas flow is controlled by a mass flow meterThe space velocity is 36000 ml/(g) cat Min), the reaction temperature was 700 ℃ and the reaction time was 10h, sampling every 30 min. And (4) detecting on line by using a gas chromatographic analyzer. The catalytic performance of the catalyst at various time points is plotted in figure 1. CH (CH) 4 And CO 2 The conversion after 10h of reaction and the start of (2) are shown in Table 2.
Examples 2 to 5
Compared with the example 1, the catalyst is prepared by only using the different auxiliary agents with the mass percent of 3 percent, and the other processes are the same as the example 1. The catalyst compositions of examples 2 to 5 are shown in table 1.
Evaluation of catalyst stability
The stability evaluation of the catalyst was carried out in a homemade continuous flow fixed bed reactor according to the evaluation method of example 1. The reaction tube is a quartz tube with an inner diameter of 6mm and a length of 33cm, the reaction temperature is measured by a thermocouple arranged in the middle of the reaction tube, and a temperature programming controller is used for controlling the reaction temperature. The gas flow is controlled by a mass flowmeter, and the airspeed is 36000 ml/(g) cat Min), the reaction temperature is 700 ℃, the reaction time is 10h, and samples are taken every 30 min. The gas chromatography analyzer is used for online detection. CH (CH) 4 And CO 2 The conversion after 10h of reaction and the start of (2) are shown in Table 2.
Examples 6 to 9
Compared with the embodiment 1, the difference is the precursor processing mode, and the other processes are the same as the embodiment 1, and the details are as follows: 0.991g of Ni (NO) 3 ) 2· 6H 2 O and 0.187gLa (NO) 3 ) 2· 6H 2 Adding O into deionized water, stirring to dissolve, adding 1.74g MCM-41 molecular sieve carrier, soaking at room temperature for 45min, evaporating the mixed slurry in 80 deg.C water bath, oven drying at 110 deg.C overnight to obtain catalyst precursor, treating with plasma (200W 2 Different treatment time), namely the Ni/La/MCM-41/PNxh catalyst is prepared. The catalyst compositions of examples 6 to 9 are shown in table 1.
Evaluation of catalyst stability
According to the evaluation method of example 1, the stability of the catalyst was evaluatedThe preparation is carried out in a continuous flow fixed bed reactor. The reaction tube is a quartz tube with an inner diameter of 6mm and a length of 33cm, the reaction temperature is measured by a thermocouple arranged in the middle of the reaction tube, and a temperature programming controller is used for controlling the reaction temperature. The gas flow is controlled by a mass flowmeter, and the airspeed is 36000 ml/(g) cat Min), the reaction temperature was 700 ℃ and the reaction time was 10h, sampling every 30 min. The gas chromatography analyzer is used for online detection. CH (CH) 4 And CO 2 The initial and the conversion after 10h of reaction are shown in Table 2.
Examples 10 to 11
Different from the embodiment 1, the preparation method of the catalyst and the treatment mode of the precursor are as follows: 0.991g of Ni (NO) was weighed 3 ) 2· 6H 2 O and 0.187g La (NO) 3 ) 2· 6H 2 O, dissolving in 30ml deionized water, adding 1.74g MCM-41 carrier, putting the mixed slurry into a magnetic stirring pot, and adding NH at room temperature 3 ·H 2 Adjusting pH to 11 by O, aging in a 70 ℃ magnetic stirring kettle under stirring for 2 hours, filtering, washing, drying in an oven at 110 ℃ overnight to obtain a catalyst precursor, calcining at 550 ℃ for 4 hours in a muffle furnace to obtain 10% of Ni/3% La/CP/C catalyst, or treating with plasma (200W, N) 2 And 2 h), namely preparing the Ni/La/MCM-41/CP/PN catalyst. The catalyst compositions of examples 10 to 11 are shown in table 1.
Examples 12 to 13
Different from the embodiment 1, the preparation method of the catalyst and the treatment mode of the precursor are as follows: 0.991g of Ni (NO) was weighed 3 ) 2· 6H 2 O and 0.187g La (NO) 3 ) 2· 6H 2 O and citric acid (C) 6 H 8 O 7 ·H 2 O), n (metal ion): n (C) 6 H 8 O 7 ·H 2 O) = 1.5 after gel is formed in a magnetic stirrer heated at the constant temperature of 60 ℃, 1.74g of MCM-41 molecular sieve is added and continuously stirred for 1 hour, the mixture is taken out and aged for 6 hours at the room temperature, then the mixture is taken out and placed in a 110 ℃ oven to obtain a catalyst precursor, the catalyst precursor is roasted for 4 hours at the temperature of 550 ℃ by a muffle furnace to obtain the Ni/La/MCM-41/Sol/C catalyst, or the mixture is subjected to plasma treatment to obtain the Ni/La/MCM-41/Sol/C catalystPrinciple (200W, N) 2 And 2 h), thus obtaining the Ni/La/MCM-41/Sol/PN catalyst. The catalyst compositions of examples 12 to 13 are shown in table 1.
Evaluation of catalyst stability
According to the evaluation method of example 1, the stability evaluation of the catalyst was carried out in a self-made continuous flow fixed bed reactor. The reaction tube was a quartz tube having an inner diameter of 6mm and a length of 33cm, the reaction temperature was measured by a thermocouple placed in the middle of the reaction tube, and the reaction temperature was controlled using a temperature programmed controller. The gas flow is controlled by a mass flowmeter, and the airspeed is 36000 ml/(g) cat Min), the reaction temperature was 700 ℃ and the reaction time was 10h, sampling every 30 min. The gas chromatography analyzer is used for online detection. CH (CH) 4 And CO 2 The conversion after 10h of reaction and the start of (2) are shown in Table 2.
Examples molecular sieve catalysts composition table:
specific examples the molecular sieve catalyst composition is shown in table 1:
the graphs of the catalytic performance of the catalyst at 700 ℃ according to the evaluation method of example 1 are shown in FIGS. 1 to 3. Its CH 4 And CO 2 See table 2 for initial and final conversion.
The results of the evaluation of the stability of the specific catalyst are shown in table 2:
characterization of XRD
In fig. 4, no characteristic diffraction peak of the La-related compound was found, indicating that the La oxide was well dispersed on the catalyst surface. The characteristic diffraction peak of 2 theta =22 ° is amorphous SiO 2 Whether of LaDoping is also a plasma treated catalyst, still maintaining amorphous SiO 2 Indicating that the structure of the support is not destroyed. Compared with the conventional Ni/MCM-41 catalyst, the NiO characteristic peak intensity of the Ni/La/MCM-41 catalyst is weakened, the peak width is widened, and the La doping can improve the dispersion of the NiO on the surface of the catalyst. Compared with the Ni/La/MCM-41 catalyst, the NiO characteristic peak intensity of the Ni/La/MCM-41/Sol/PN catalyst is obviously weakened, and the peak width is widened, so that the particle size of the NiO can be obviously reduced and the dispersibility of the NiO on the surface of the catalyst can be improved by the plasma-assisted enhanced Sol-gel method. This is probably because the sol-gel method can promote the formation of NiO to be uniform at a molecular level on the surface of the catalyst, and further improve the dispersibility of NiO and reduce the particle size of NiO after plasma treatment, thereby improving the catalytic activity and stability of the catalyst.
Claims (9)
1. A preparation method and application of a Ni-based catalyst prepared by radio frequency plasma reinforcement are characterized by comprising the following steps:
(1) Weighing the stoichiometric ratio of Ni (NO) 3 ) 2 ·6H 2 O、La(NO 3 ) 2 ·6H 2 O (the total mass of the carrier and the active component Ni is 100%, the mass percent of the active component Ni in the catalyst is 10%, the mass percent of the auxiliary agent is 3%), and a gelling agent citric acid (C) 6 H 8 O 7 ·H 2 O, n (metal ion) n (C) 6 H 8 O 7 ·H 2 O) = 1.5, adding 30ml of deionized water, and stirring until the deionized water is completely dissolved to obtain a transparent solution;
(2) Adding a magnetic stirrer into the mixed slurry obtained in the step (1), and rotationally stirring in a constant-temperature heating magnetic stirrer until sol is formed;
(3) Adding the measured MCM-41 molecular sieve carrier into the gel obtained in the step (2) to obtain mixed slurry, and continuously stirring;
(4) Aging the sol obtained in the step (3) at room temperature;
(5) Drying the sol obtained in the step (4) in an oven to obtain a catalyst precursor;
(6) Grinding the precursor obtained in step (5) to fine powder, and treating with plasma (200W 2 2 h) after 10% Ni/3% La/Sol/PN catalyst.
2. The method for CO of claim 1 2 A method for producing a reforming catalyst, characterized in that the gelling agent is citric acid (C) 6 H 8 O 7 ·H 2 O)。
3. Use for CO according to claims 1-2 2 A process for producing a reforming catalyst, characterized in that the gelling agent is added in an amount of n (metal ion): n (C) 6 H 8 O 7 ·H 2 O)＝1:1.5。
4. Use according to any of claims 1-3 for CO 2 The preparation method of the reforming catalyst is characterized in that the carrier is an MCM-41 molecular sieve.
5. The method for CO according to any one of claims 1-4 2 The preparation method of the reforming catalyst is characterized in that the total mass of a carrier and an active component Ni is 100%, and the mass percent of the active component Ni in the catalyst is 10%.
6. The method for CO according to any one of claims 1-5 2 The preparation method of the reforming catalyst is characterized in that the mass percent of the auxiliary agent La is 3% and the mass percent of the carrier is 100%.
7. The method for CO according to any one of claims 1-6 2 The preparation method of the reforming catalyst is characterized in that the cold plasma treatment time is 2h, the power is 200W, and the atmosphere is N 2 。
8. The method for CO according to any one of claims 1-7 2 Method for preparing reforming catalystThe method is characterized in that the stirring temperature is 60 ℃;
the rotating stirring time is 4-5h;
the continuous stirring time is 1h;
the aging time is 6h;
the drying time is 11-13h;
the drying temperature is 100-120 ℃.
9. Use according to any of claims 1-8 for CO 2 Use of a reforming catalyst in the carbon dioxide reforming of methane.
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| CN101462058A (en) * | 2007-12-20 | 2009-06-24 | 上海焦化有限公司 | Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry |
| WO2012167351A1 (en) * | 2011-06-08 | 2012-12-13 | University Of Regina | Sulfur tolerant catalysts for hydrogen production by carbon dioxide reforming of methane-rich gas |
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| CN101462058A (en) * | 2007-12-20 | 2009-06-24 | 上海焦化有限公司 | Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry |
| WO2012167351A1 (en) * | 2011-06-08 | 2012-12-13 | University Of Regina | Sulfur tolerant catalysts for hydrogen production by carbon dioxide reforming of methane-rich gas |
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| XUMEI TAO等: "Highly active Ni-Ce/TiO2-Al2O3 catalysts:Influence of preparation methods", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, 24 March 2016 (2016-03-24), pages 6271 - 6276, XP029499756, DOI: 10.1016/j.ijhydene.2016.03.031 * |
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