CN106902829B - A kind of load type double-metal reforming catalyst and its preparation method and application - Google Patents
A kind of load type double-metal reforming catalyst and its preparation method and application Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a kind of load type double-metal reforming catalysts and its preparation method and application.The catalyst is load active component metallic nickel and metallic cobalt on oxide carrier, and the mass ratio of oxide carrier, metallic nickel and metallic cobalt is 1:0.01 ~ 0.1:0.01 ~ 0.1；The oxide carrier is one of magnesia, aluminium oxide, silica, cerium oxide, zirconium oxide.Preparation method are as follows: use deposition-precipitation method, precipitating reagent is slowly added in the solution of oxide carrier, metallic nickel and metallic cobalt, is reacted, then obtain the catalyst through suction filtration, washing, drying, calcining.The catalyst solves the problems, such as that carbon accumulation resisting ability existing for existing catalyst is poor, preparation method is complicated, catalyst high cost.Whole preparation process simple process of the present invention, easy to operate, synthesis condition is easy to control, is easy to industrialize, and prepared catalyst has high catalytic activity and anti-carbon performance.
Description
Technical field
The present invention relates to a kind of load type double-metal reforming catalysts and its preparation method and application, belong to catalyst preparation
Technical field.
Background technique
The environment that synthesizing gas by reforming methane with co 2 is got worse in effective use natural gas, energy transmission and solution
It has broad application prospects in terms of problem.But the reaction condition of synthesizing gas by reforming methane with co 2 is just in thermodynamics product
The catalyst of carbon area, exploitation efficient stable and high anti-carbon performance is a critical issue of the process industrialization.It is a large amount of at present
Research concentrates on noble metal and nickel-base catalyst, the former is expensive, and the latter is poor because of carbon deposit serious stability.
In recent years, researcher achievees the purpose that improve anti-carbon performance by being modified nickel-base catalyst.Bimetallic is urged
Agent due to its can modulation physicochemical properties, electronic effect and geometric effect between bimetallic, and show to be different from single
The peculiar property of metallic catalyst and excellent catalytic performance.Second of metal of addition is likely to form alloy phase or work with Ni
Exist for dopant with independent phase, change the electronic structure and geometry of active metal, to change the work of catalyst
Property and stability.
Due to the price advantage of base metal (such as Co, Cu, Sn, Fe), nickel-base catalyst is carried out using base metal
It is doped to research hotspot.However, even identical active component, the difference of preparation method will affect active component partial size,
The microstructure of dispersion degree, reproducibility and catalyst, and then cause the significantly different of catalyst reaction activity and selectivity, and
And also there were significant differences in terms of anti-carbon deposition ability.
Summary of the invention
The present invention is intended to provide a kind of load type double-metal reforming catalyst, using Ni, Co as active component, the oxidation such as MgO
Object is carrier, and the catalyst being prepared by deposition-precipitation method can overcome common preparation method (such as infusion process, co-precipitation
Method) defect and deficiency.The present invention also provides the preparation method and application of the load type double-metal reforming catalyst.
The present invention provides a kind of load type double-metal reforming catalyst, which is to load to live on oxide carrier
Property component metals nickel and metallic cobalt, the mass ratio of oxide carrier, metallic nickel and metallic cobalt is 1:0.01 ~ 0.1:0.01 ~ 0.1；
The oxide carrier is one of magnesia, aluminium oxide, silica, cerium oxide, zirconium oxide.
In above-mentioned catalyst, the mass ratio of the oxide carrier, metallic nickel and metallic cobalt be 1:0.06 ~ 0.08:0.02 ~
0.04。
The present invention provides the preparation methods of above-mentioned load type double-metal reforming catalyst, comprising the following steps:
Step 1: the precursor salt for weighing nickel and cobalt is dissolved in deionized water and is made into mixed solution A, in solution A nickel from
The concentration of son is 0.01 ~ 0.2mol/L, and cobalt ions and nickel ion molar ratio are 1:0.01 ~ 10；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, wherein precipitating reagent and nickel ion, cobalt ions
The sum of molar ratio be 1:0.1 ~ 1；The volume ratio of solution B and solution A is 1:0.1 ~ 5；
Step 3: oxide carrier is added into solution A, in 30 ~ 100 DEG C of 0.5 ~ 2h of stirring, solution C is obtained, wherein oxygen
The mass ratio of compound carrier and nickel ion is 1:0.01 ~ 0.1；
Step 4: solution B is added in solution C, the pH for adjusting rate of addition to guarantee mixed system drips between 8-12
After adding, mixed system is kept to continue 3 ~ 30h of stirring at 60 ~ 120 DEG C；
Step 5: step 4 obtained material is filtered, is washed, dry 3 ~ 20h at 80 ~ 150 DEG C, 3 are calcined at 400 ~ 900 DEG C
~ 30h obtains load type double-metal reforming catalyst.
In above method step 1, the nickel precursor salt is nickel nitrate, nickel acetate, nickel sulfate, one in nickel chloride
Kind, the cobalt precursor salt is one of cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride.
In above method step 2, the precipitating reagent is sodium carbonate, in urea, potassium carbonate, sodium hydroxide, potassium hydroxide
One kind.
In above method step 4, rate of addition is 1 ~ 20 mL/min.
A kind of preferred preparation method is provided, comprising the following steps:
Step 1: the precursor salt for weighing nickel and cobalt is dissolved in deionized water and is made into mixed solution A, in solution A nickel from
The concentration of son is 0.05 ~ 0.15mol/L, and cobalt ions and nickel ion molar ratio are 1:1 ~ 4；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, wherein precipitating reagent and nickel ion, cobalt ions
The sum of molar ratio be 1:0.3 ~ 0.5, the volume ratio of solution B and solution A is 1:0.2 ~ 0.6；
Step 3: oxide carrier is added into solution A, in 60 ~ 80 DEG C of 0.5 ~ 2h of stirring, solution C is obtained, wherein aoxidizing
The mass ratio of object carrier and nickel ion is 1:0.06 ~ 0.08；
Step 4: solution B is added in solution C, rate of addition (5 ~ 10mL/min) is adjusted to guarantee the pH of mixed system
Between 9-10, after being added dropwise, mixed system is kept to continue 6 ~ 8h of stirring at 80 ~ 100 DEG C；
Step 5: step 4 obtained material is filtered, is washed, dry 6 ~ 12h at 90 ~ 120 DEG C, calcined at 700 ~ 800 DEG C
10 ~ 15h obtains load type double-metal reforming catalyst.
The present invention provides application of the above-mentioned load type double-metal reforming catalyst in methane reforming with carbon dioxide.
In the application, catalyst is before use, 50% H need to be used2/N2Gaseous mixture restores 1h, and suitable reaction condition is
The volume ratio of unstrpped gas methane and carbon dioxide is 1:1, and reaction temperature is 800 DEG C, normal pressure, feed space velocity 36000h-1.It should
Catalyst is used for methane reforming with carbon dioxide, and for available reactivity close to equilibrium conversion, the service life is long, product
H2/ CO ratio is close to 1.
Catalyst is restored before use, it is therefore an objective to: the catalyst metals prepared are with oxide (such as NiO, CoO)
Form exists, and needs to be reduced to metallic state before use.
Since NiO, CoO and MgO lattice parameter are close, solid solution can be formed, makes to have very between active metal and carrier
The active metal of high degree of dispersion can be obtained in strong interaction after reduction, however since very strong interaction makes most
NiO, CoO are present in MgO body and are mutually difficult to be reduced, and the active metal restored is very few, cause catalytic activity not high.In order to improve
The reproducibility of active metal, while can be uniformly dispersed in active component on carrier, the present invention uses for reference deposition-precipitation method and (is usually used in
Prepare the preparation method of polymolecularity noble metal catalyst), it is by regulating and controlling preparation process, the metal ion in solution is uniform
It is deposited in the surface of carrier, reduces it in the distribution of body phase.
Beneficial effects of the present invention:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst provided by the invention, solves existing catalyst and deposits
Anti-carbon deposition ability is poor, preparation method is complicated, catalyst high cost problem.Preparation method technique letter provided by the invention
It is single, easy to operate, synthesis condition is easy to control, be easy to industrialize, and prepared catalyst have high catalytic activity and anti-carbon deposit
Performance.
Detailed description of the invention
Fig. 1 is bimetallic catalyst prepared by the embodiment of the present invention 1 and bimetallic catalytic prepared by comparative example 1, comparative example 2
The XRD diagram of agent after carrying out reduction.
Fig. 2 is bimetallic catalyst prepared by the embodiment of the present invention 1 and bimetallic catalytic prepared by comparative example 1, comparative example 2
The TPR of agent schemes.
Fig. 3 is bimetallic catalyst prepared by the embodiment of the present invention 1 and bimetallic catalytic prepared by comparative example 1, comparative example 2
The graph of pore diameter distribution of agent.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.7946g nickel nitrate and 0.1976g cobalt nitrate is dissolved in 20mL deionized water and is made into mixed solution A；
(2) it weighs 0.8194g urea and is dissolved in 60mL deionized water and obtain solution B；
(3) 2g magnesium oxide carrier is added into solution A and obtains solution C in 80 DEG C of stirring 2h；
(4) solution B is added in solution C, adjusts rate of addition (8mL/min) to guarantee the pH of mixed system on 10 left sides
The right side after being added dropwise, keeps mixed system to continue to stir 8h at 80 DEG C；
(5) 6h dry at step 4 obtained material suction filtration, washing, 100 DEG C is obtained into support type in 800 DEG C of calcining 10h
Bimetallic methane carbon dioxide reformation catalyst.
Embodiment 2:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.2435g nickel chloride and 0.1615g cobalt chloride is dissolved in 10mL deionized water and is made into mixed solution A；
(2) it weighs 0.1023g urea and is dissolved in 10mL deionized water and obtain solution B；
(3) 1g alumina support is added into solution A and obtains solution C in 30 DEG C of stirring 2h；
(4) solution B is added in solution C, adjust rate of addition (5mL/min) with guarantee the pH of mixed system 8 or so,
After being added dropwise, mixed system is kept to continue to stir 15h at 60 DEG C；
(5) 12h dry at step 4 obtained material suction filtration, washing, 80 DEG C is obtained into support type in 600 DEG C of calcining 16h
Bimetallic methane carbon dioxide reformation catalyst.
Embodiment 3:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.4966g nickel nitrate and 0.0.4770g cobaltous sulfate is dissolved in 30mL deionized water and is made into mixed solution
A；
(2) it weighs 0.4086g sodium hydroxide and is dissolved in 60mL deionized water and obtain solution B；
(3) 2g magnesium oxide carrier is added into solution A and obtains solution C in 50 DEG C of stirring 2h；
(4) solution B is added in solution C, adjusts rate of addition (12mL/min) to guarantee the pH of mixed system on 12 left sides
The right side after being added dropwise, keeps mixed system to continue to stir 8h at 100 DEG C；
(5) 5h dry at step 4 obtained material suction filtration, washing, 150 DEG C is obtained into support type in 600 DEG C of calcining 10h
Bimetallic methane carbon dioxide reformation catalyst.
Embodiment 4:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.850g nickel acetate and 3.381g cobalt acetate is dissolved in 100mL deionized water and is made into mixed solution A；
(2) it weighs 3.602g sodium carbonate and is dissolved in 50mL deionized water and obtain solution B；
(3) 10g silica supports are added into solution A and obtain solution C in 70 DEG C of stirring 1.5h；
(4) solution B is added in solution C, adjusts rate of addition (10mL/min) to guarantee the pH of mixed system on 9 left sides
The right side after being added dropwise, keeps mixed system to continue to stir 5h at 120 DEG C；
(5) 10h dry at step 4 obtained material suction filtration, washing, 90 DEG C is obtained into support type in 500 DEG C of calcining 20h
Bimetallic methane carbon dioxide reformation catalyst.
Embodiment 5:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.5385g nickel sulfate and 0.8589g cobaltous sulfate is dissolved in 80mL deionized water and is made into mixed solution A；
(2) it weighs 1.1433g potassium hydroxide and is dissolved in 20mL deionized water and obtain solution B；
(3) 3g cerium oxide carrier is added into solution A and obtains solution C in 100 DEG C of stirring 0.5h；
(4) solution B is added in solution C, adjusts rate of addition (13mL/min) to guarantee the pH of mixed system on 11 left sides
The right side after being added dropwise, keeps mixed system to continue to stir 10h at 90 DEG C；
(5) 8h dry at step 4 obtained material suction filtration, washing, 120 DEG C is obtained into support type in 700 DEG C of calcining 12h
Bimetallic methane carbon dioxide reformation catalyst.
Embodiment 6:
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the method for the present invention, including is walked as follows
It is rapid:
(1) it weighs 0.2975g nickel acetate and 0.1482g cobalt nitrate is dissolved in 50mL deionized water and is made into mixed solution A；
(2) it weighs 0.5118g urea and is dissolved in 75mL deionized water and obtain solution B；
(3) 1g Zirconia carrier is added into solution A and obtains solution C in 60 DEG C of stirring 2h；
(4) solution B is added in solution C, adjusts rate of addition (15mL/min) to guarantee the pH of mixed system on 10 left sides
The right side after being added dropwise, keeps mixed system to continue to stir 20h at 70 DEG C；
(5) 8h dry at step 4 obtained material suction filtration, washing, 130 DEG C is obtained into support type in 400 DEG C of calcining 25h
Bimetallic methane carbon dioxide reformation catalyst.
Comparative example 1
Bimetallic methane carbon dioxide reformation catalyst is prepared using coprecipitation, is included the following steps:
(1) 0.7946g nickel nitrate, 0.1976g cobalt nitrate and 12.82g magnesium nitrate are dissolved in 200mL deionized water and are matched
At mixed solution A；
(2) 10g sodium hydroxide is dissolved in 150mL deionized water and obtains solution B；
(3) 5.512g sodium carbonate is dissolved in 200mL deionized water and obtains solution C；
(4) solution A and solution B are poured into two constant pressure funnels respectively, solution C is poured into three-necked flask, in 60
Solution A is added dropwise under the conditions of DEG C into three-necked flask, adjusts pH value of solution using solution B in the process, pH is made to maintain 10 or so；
(5) it is deposited in aging 18h at 60 DEG C by what step 4 obtained, then filtering and washing to filtrate is in neutrality；
(6) by step 5 obtained material in drying box 120 DEG C be dried overnight, in 800 DEG C of calcining 10h, obtain support type
Bimetallic methane carbon dioxide reformation catalyst.
Comparative example 2
Bimetallic methane carbon dioxide reformation catalyst is prepared using infusion process, is included the following steps:
(1) 0.7946g nickel nitrate and 0.1976g cobalt nitrate are dissolved in 6mL deionized water and are made into mixed solution A；
(2) 2g magnesium oxide carrier is added into solution A, is stirred at room temperature to dry；
(3) by step 2 obtained material in drying box 120 DEG C be dried overnight, in 800 DEG C of calcining 10h, obtain support type
Bimetallic methane carbon dioxide reformation catalyst.
Data Detection:
The bimetallic of the bimetallic catalyst and comparative example 1, the preparation of comparative example 2 that provide the preparation of the embodiment of the present invention 1 is urged
The XRD diagram of agent after carrying out reduction, as shown in Figure 1.It is compareed with standard spectral peak, 2 θ=36.8o, 42.8o, 62.3o, 74.6o,
78.5oThe diffraction maximum at place belongs to MgO(JCPDS No. 78-0643)；2θ=44.2o~44.5oThe diffraction maximum at place, belongs to Ni
(JCPDS No. 04-0850) and Co(JCPDS No. 15-0806)；2θ=74.6o, 78.5oLocating single diffraction maximum indicates NiO
Solid solution is formd with CoO and MgO.From the figure, it can be seen that prepared by bimetallic catalyst prepared by the present invention and comparative example 1
There is bimetallic catalyst prepared by Ni, the peak of Co metal simple-substance, but comparative example 2 and metal is not presented in bimetallic catalyst
The peak of simple substance, it may be possible to go back the Monitoring lower-cut that commercial weight is lower than XRD very little.
The bimetallic of the bimetallic catalyst and comparative example 1, the preparation of comparative example 2 that provide the preparation of the embodiment of the present invention 1 is urged
The TPR of agent schemes, as shown in Figure 2.As seen from the figure, bimetallic catalytic prepared by the embodiment of the present invention 1, comparative example 1 and comparative example 2
It is obvious that agent restores gender gap.Bimetallic catalyst prepared by the embodiment of the present invention 1 and comparative example 1 exists with MgO without interaction
NiO, CoO reduction peak, also have the reduction peak being present in solid solution；Bimetallic catalyst prepared by comparative example 1 is before 600 DEG C
Also commercial weight be significantly greater than bimetallic catalyst prepared by embodiment 1 and comparative example 2, and bimetallic catalytic prepared by comparative example 2
Also commercial weight of the agent before 900 DEG C is seldom.
The bimetallic of the bimetallic catalyst and comparative example 1, the preparation of comparative example 2 that provide the preparation of the embodiment of the present invention 1 is urged
The graph of pore diameter distribution of agent, as shown in Figure 3.From the figure, it can be seen that the most probable hole of bimetallic catalyst prepared by the present invention
Diameter is minimum, is 9.3nm, the most probable pore size of bimetallic catalyst prepared by comparative example 1 and comparative example 2 be respectively 10.0nm and
14.5nm.It is calculated by BET formula, bimetallic catalyst specific surface area prepared by the present invention is maximum, is 68.9m2/ g is right
Bimetallic catalyst specific surface area prepared by ratio 1 and comparative example 2 is respectively 61.2 m2/ g and 42.9 m2/g。
Table 1 is bimetallic catalyst prepared by the embodiment of the present invention 1 and bimetallic catalytic prepared by comparative example 1, comparative example 2
Metal surface area, partial size and the dispersibility of agent are relatively.
The metallic character of bimetallic methane carbon dioxide reformation catalyst prepared by 1 present invention of table
It can be seen that the dispersion degree of bimetallic catalyst active metal prepared by the present invention is substantially better than comparative example 1 and right
Ratio 2.Because bimetallic catalyst reproducibility prepared by comparative example 2 is very poor (Fig. 2), therefore the active metal amount restored is seldom,
Cause metal dispersity poor.It is urged although bimetallic catalyst reproducibility prepared by comparative example 1 is greater than bimetallic prepared by the present invention
Agent, the active metal amount restored is big, but the active metals surface area exposed after the catalyst reduction is than institute of the present invention
It is small to prepare bimetallic catalyst, metal dispersity is poor, and metal particle size is big.This is because preparation method of the invention is not present
Local supersaturation in 1 preparation process of comparative example, by making precipitating reagent, uniformly hydrolysis discharges OH in the solution-, can make
Active metallic ion uniformly precipitates, and generates lesser metallic particles, can expose more active surfaces after carrying out reduction.
Embodiment 7: active appraisal experiment
The bimetallic catalyst that embodiment 1 is prepared is used for methane reforming with carbon dioxide, and by catalytic effect
The catalyst activity prepared with comparative example 1 and comparative example 2 is compared.
Specific experiment are as follows: by 0.2g Catalyst packing in fixed bed reactors, reaction temperature is 800 DEG C, 0.1MPa,
CH4And CO2Flow is 60mL/min, air speed 36000h-1.React procatalyst 120mL/min(50% H2/N2) gaseous mixture
Restore 1h.It is acquired by gas sampling bag, offline in gas chromatographic analysis.Chromatographic condition are as follows: argon gas makees carrier gas, carburettor temperature
120 DEG C, 70 DEG C of column furnace temperature, thermal conductivity temperature 70 C, electric current 50mA.Simultaneously measure ratio of the reactant in inlet gas with
Ratio and Reactor inlet gas flow rate and reactor outlet gas flow velocity of the different products in exit gas, finally calculate
The selectivity of the conversion ratio of reactant, product.
Embodiment 8: life assessment experiment
The step of according to embodiment 7, extend the time of methane reforming with carbon dioxide, life assessment reality is carried out to it
It tests.
Table 2 is bimetallic catalyst prepared by the embodiment of the present invention 1 and bimetallic catalytic prepared by comparative example 1, comparative example 2
The activity and life assessment result of agent compare.It can be seen that the initial CH of bimetallic catalyst prepared by the present invention4、CO2Conversion
Rate highest, respectively 90.5% and 95.9%, after reacting 8h, carbon deposition quantity of catalyst 0；Double gold prepared by comparative example 1 and comparative example 2
The initial CH of metal catalyst4、CO2Conversion ratio is significantly lower than bimetallic catalyst prepared by the present invention, after reacting 8h, 1 He of comparative example
Bimetallic catalyst coke content prepared by comparative example 2 is respectively 1.7 wt% and 2.8 wt%.
In order to investigate the service life of bimetallic catalyst prepared by the present invention, compares it and react the CH after 8h, 50h and 200h4、
CO2Conversion ratio, as can be seen from Table 2, after reacting for a long time, bimetallic catalyst prepared by the present invention still keeps higher
CH4、CO2Conversion ratio, its carbon deposition quantity is only 1.2wt% after reacting 200h, the double gold prepared much smaller than comparative example 1 and comparative example 2
The carbon deposition quantity (table 2) of metal catalyst 8h.As it can be seen that the bimetallic catalyst of the method for the present invention preparation not only has high catalysis living
Property, and coking resistivity is good, and catalyst life is long.
The reactivity worth of bimetallic methane carbon dioxide reformation catalyst prepared by 2 present invention of table
Claims (3)
1. a kind of load type double-metal reforming catalyst, it is characterised in that: the catalyst is the supported active on oxide carrier
Component metals nickel and metallic cobalt,
The preparation method of the load type double-metal reforming catalyst, comprising the following steps:
Step 1: weighing 0.7946g nickel nitrate and 0.1976g cobalt nitrate is dissolved in 20mL deionized water and is made into mixed solution A；
Solution B is obtained Step 2: weighing precipitating reagent urea 0.8194g and being dissolved in deionized water；
Solution C is obtained in 80 DEG C of stirring 2h Step 3: 2g magnesium oxide carrier is added into solution A；
Step 4: solution B is added in solution C, the pH with the rate of addition of 8mL/min to guarantee mixed system is added dropwise 10
After, keep mixed system to continue to stir 8h at 80 DEG C；
Step 5: 10h dry at step 4 obtained material suction filtration, washing, 100 DEG C is obtained support type in 800 DEG C of calcining 10h
Dual metal reforming catalyst.
2. a kind of load type double-metal reforming catalyst answering in methane reforming with carbon dioxide described in claim 1
With.
3. application according to claim 2, it is characterised in that: the catalyst is before use, 50% H need to be used2/N2Mixing
Gas restores 1h, and the condition of reforming reaction is that the volume ratio of unstrpped gas methane and carbon dioxide is 1:1, and reaction temperature is 800 DEG C,
Normal pressure, feed space velocity 36000h-1。
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| CN107376919B (en) * | 2017-07-19 | 2020-03-10 | 太原理工大学 | Promoting CO2Catalyst for activation and dissociation and preparation method and application thereof |
| CN107413373B (en) * | 2017-08-08 | 2019-10-22 | 太原理工大学 | A kind of fast preparation method of high-specific surface area bimetallic silicide methanation catalyst |
| CN108380218A (en) * | 2018-03-16 | 2018-08-10 | 福州大学 | A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof |
| CN112403473B (en) * | 2020-11-06 | 2022-12-30 | 上海簇睿低碳能源技术有限公司 | Synthesis method for preparing reforming catalyst through MOFs |
| CN112916018B (en) * | 2021-01-27 | 2022-06-28 | 成都理工大学 | Praseodymium-zirconium composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN114260013B (en) * | 2021-12-27 | 2024-02-20 | 太原理工大学 | Composite catalyst with hollow core-shell structure and preparation method thereof |
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