CN106902829A - 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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Abstract
The invention discloses a kind of load type double-metal reforming catalyst 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 the one kind in magnesia, aluminum oxide, silica, cerium oxide, zirconium oxide.Its preparation method is：Using 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 the carbon accumulation resisting ability that existing catalyst is present is poor, preparation method is complicated, catalyst high cost.Whole preparation process process is simple of the present invention, easy to operate, synthesis condition are easy to control, it is easy to industrialize, and prepared catalyst has catalysis activity and anti-carbon performance high.
Description
Technical field
The present invention relates to a kind of load type double-metal reforming catalyst and its preparation method and application, belong to catalyst preparation
Technical field.
Background technology
Synthesizing gas by reforming methane with co 2 is effectively using natural gas, energy transmission and the increasingly serious environment of solution
Problem aspect has broad application prospects.But the reaction condition of synthesizing gas by reforming methane with co 2 is just accumulated in thermodynamics
The catalyst of carbon area, exploitation efficient stable and anti-carbon performance high is a key issue of the process industrialization.It is a large amount of at present
Research concentrates on noble metal and nickel-base catalyst, and the former is expensive, and the latter is poor because of carbon deposit serious stability.
In recent years, researcher reaches the purpose for improving anti-carbon performance by being modified to 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 metal of addition is likely to form alloy phase or work with Ni
For dopant exists with independent phase, change the electronic structure and geometry of active metal, so as to change the work of catalyst
Property and stability.
Due to base metal（Such as Co, Cu, Sn, Fe）Price advantage, nickel-base catalyst is carried out using base metal
It is doped to study hotspot.However, even identical active component, the difference of preparation method can influence active component particle diameter,
The microstructure of decentralization, 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.
The content of the invention
The present invention is intended to provide a kind of load type double-metal reforming catalyst, with Ni, Co as active component, the oxidation such as MgO
Thing is carrier, and the catalyst prepared by deposition-precipitation method can overcome conventional preparation method（Such as infusion process, co-precipitation
Method）Defect and deficiency.Present invention also offers the preparation method and application of the load type double-metal reforming catalyst.
The invention provides a kind of load type double-metal reforming catalyst, the catalyst 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 the one kind in magnesia, aluminum oxide, silica, cerium oxide, zirconium oxide.
In above-mentioned catalyst, the mass ratio of the oxide carrier, metallic nickel and metallic cobalt is 1:0.06~0.08:0.02~
0.04。
The invention provides the preparation method of above-mentioned load type double-metal reforming catalyst, comprise the following steps：
Step one, weigh nickel and cobalt precursor salt be dissolved in deionized water in be made into mixed solution A, nickel ion in solution A
Concentration is 0.01 ~ 0.2mol/L, and cobalt ions is 1 with nickel ion mol ratio:0.01~10；
Step 2, weigh during precipitating reagent is dissolved in deionized water and obtain solution B, wherein, precipitating reagent and nickel ion, cobalt ions sum
Mol ratio be 1:0.1~1；Solution B is 1 with the volume ratio of solution A:0.1~5；
Step 3, to adding oxide carrier in solution A, stir 0.5 ~ 2h at 30 ~ 100 DEG C, obtain solution C, wherein oxide
Carrier is 1 with the mass ratio of nickel ion:0.01~0.1；
Step 4, by solution B add solution C in, regulation rate of addition to ensure the pH of mixed system between 8-12, drip
Bi Hou, keeps mixed system to continue to stir 3 ~ 30h at 60 ~ 120 DEG C；
Step 5, will step 4 gained material suction filtration, washing, dry 3 ~ 20h at 80 ~ 150 DEG C, 400 ~ 900 DEG C of calcinings 3 ~
30h, obtains load type double-metal reforming catalyst.
In above method step one, described nickel precursor salt is in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride
Kind, described cobalt precursor salt is the one kind in cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride.
In above method step 2, described precipitating reagent is in sodium carbonate, urea, potassium carbonate, NaOH, 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, is comprised the following steps：
Step one, weigh nickel and cobalt precursor salt be dissolved in deionized water in be made into mixed solution A, nickel ion in solution A
Concentration is 0.05 ~ 0.15mol/L, and cobalt ions is 1 with nickel ion mol ratio:1~4；
Step 2, weigh during precipitating reagent is dissolved in deionized water and obtain solution B, wherein, precipitating reagent and nickel ion, cobalt ions sum
Mol ratio be 1:0.3 ~ 0.5, solution B is 1 with the volume ratio of solution A:0.2~0.6；
Step 3, to adding oxide carrier in solution A, stir 0.5 ~ 2h at 60 ~ 80 DEG C, obtain solution C, wherein oxide is carried
Body is 1 with the mass ratio of nickel ion:0.06~0.08；
Step 4, by solution B add solution C in, adjust rate of addition（5~10mL/min）To ensure the pH of mixed system in 9-
Between 10, after completion of dropping, mixed system is kept to continue to stir 6 ~ 8h at 80 ~ 100 DEG C；
Step 5, will step 4 gained material suction filtration, washing, dry 6 ~ 12h at 90 ~ 120 DEG C, 700 ~ 800 DEG C of calcinings 10 ~
15h, obtains load type double-metal reforming catalyst.
The invention provides application of the above-mentioned load type double-metal reforming catalyst in methane reforming with carbon dioxide.
In described application, catalyst need to use 50% H using preceding2/N2Gaseous mixture reduces 1h, and suitable reaction condition is
Unstrpped gas methane is 1 with the volume ratio of carbon dioxide：1, reaction temperature is 800 DEG C, and normal pressure, feed space velocity is 36000h-1.Should
Catalyst is used for methane reforming with carbon dioxide, can obtain reactivity close to equilibrium conversion, long lifespan, product
H2/ CO ratios are close to 1.
Catalyst is using preceding being reduced, it is therefore an objective to：The catalyst metals prepared are with oxide（Such as NiO, CoO）
Form is present, using preceding needing to be reduced to metallic state.
Because NiO, CoO and MgO lattice parameter are close, solid solution can be formed, made between active metal and carrier with very
Strong interaction, can obtain the active metal of high degree of dispersion after reduction, most is made yet with very strong interaction
NiO, CoO are present in MgO body phases and are difficult to be reduced, and the active metal for restoring is very few, cause catalysis activity not high.In order to improve
The reproducibility of active metal, while making active component can be uniformly dispersed on carrier, the present invention uses for reference deposition-precipitation method（It 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
The surface of carrier is deposited in, its distribution in body phase is reduced.
Beneficial effects of the present invention：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst that the present invention is provided, solves what existing catalyst was present
Anti-carbon deposition ability is poor, preparation method is complicated, catalyst high cost problem.Preparation method process is simple, behaviour that the present invention is provided
Make convenient, synthesis condition easy to control, it is easy to industrialize, and prepared catalyst has catalysis activity and coking resistivity high.
Brief description of the drawings
Fig. 1 is the bimetallic catalytic that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with comparative example 1, comparative example 2
Agent XRD after carrying out reduction.
Fig. 2 is the bimetallic catalytic that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with comparative example 1, comparative example 2
The TPR figures of agent.
Fig. 3 is the bimetallic catalytic that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with 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 examples.
Embodiment 1：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.7946g nickel nitrates and be made into mixed solution A during 0.1976g cobalt nitrates are dissolved in 20mL deionized waters；
（2）Weigh during 0.8194g urea is dissolved in 60mL deionized waters and obtain solution B；
（3）To 2g magnesium oxide carriers are added in solution A, 2h is stirred at 80 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（8mL/min）To ensure the pH of mixed system in 10 or so, drop
Add after finishing, keep mixed system to continue to stir 8h at 80 DEG C；
（5）6h will be dried at step 4 gained material suction filtration, washing, 100 DEG C, 10h is calcined at 800 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Embodiment 2：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.2435g nickel chlorides and be made into mixed solution A during 0.1615g cobalt chlorides are dissolved in 10mL deionized waters；
（2）Weigh during 0.1023g urea is dissolved in 10mL deionized waters and obtain solution B；
（3）To 1g alumina supports are added in solution A, 2h is stirred at 30 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（5mL/min）To ensure that the pH of mixed system, 8 or so, is added dropwise
After finishing, mixed system is kept to continue to stir 15h at 60 DEG C；
（5）12h will be dried at step 4 gained material suction filtration, washing, 80 DEG C, 16h is calcined at 600 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Embodiment 3：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.4966g nickel nitrates and be made into mixed solution A during 0.0.4770g cobaltous sulfates are dissolved in 30mL deionized waters；
（2）Weigh during 0.4086g NaOH is dissolved in 60mL deionized waters and obtain solution B；
（3）To 2g magnesium oxide carriers are added in solution A, 2h is stirred at 50 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（12mL/min）To ensure the pH of mixed system in 12 or so, drop
Add after finishing, keep mixed system to continue to stir 8h at 100 DEG C；
（5）5h will be dried at step 4 gained material suction filtration, washing, 150 DEG C, 10h is calcined at 600 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Embodiment 4：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.850g nickel acetates and be made into mixed solution A during 3.381g cobalt acetates are dissolved in 100mL deionized waters；
（2）Weigh during 3.602g sodium carbonate is dissolved in 50mL deionized waters and obtain solution B；
（3）To 10g silica supports are added in solution A, 1.5h is stirred at 70 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（10mL/min）To ensure the pH of mixed system in 9 or so, drop
Add after finishing, keep mixed system to continue to stir 5h at 120 DEG C；
（5）10h will be dried at step 4 gained material suction filtration, washing, 90 DEG C, 20h is calcined at 500 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Embodiment 5：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.5385g nickel sulfates and be made into mixed solution A during 0.8589g cobaltous sulfates are dissolved in 80mL deionized waters；
（2）Weigh during 1.1433g potassium hydroxide is dissolved in 20mL deionized waters and obtain solution B；
（3）To 3g cerium oxide carriers are added in solution A, 0.5h is stirred at 100 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（13mL/min）To ensure the pH of mixed system in 11 or so, drop
Add after finishing, keep mixed system to continue to stir 10h at 90 DEG C；
（5）8h will be dried at step 4 gained material suction filtration, washing, 120 DEG C, 12h is calcined at 700 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Embodiment 6：
A kind of high activity bimetallic methane carbon dioxide reformation catalyst is prepared using the inventive method, is comprised the following steps：
（1）Weigh 0.2975g nickel acetates and be made into mixed solution A during 0.1482g cobalt nitrates are dissolved in 50mL deionized waters；
（2）Weigh during 0.5118g urea is dissolved in 75mL deionized waters and obtain solution B；
（3）To 1g Zirconia carriers are added in solution A, 2h is stirred at 60 DEG C, obtain solution C；
（4）By in solution B addition solution C, rate of addition is adjusted（15mL/min）To ensure the pH of mixed system in 10 or so, drop
Add after finishing, keep mixed system to continue to stir 20h at 70 DEG C；
（5）8h will be dried at step 4 gained material suction filtration, washing, 130 DEG C, 25h is calcined at 400 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Comparative example 1
Bimetallic methane carbon dioxide reformation catalyst is prepared using coprecipitation, is comprised the following steps：
（1）0.7946g nickel nitrates, 0.1976g cobalt nitrates and 12.82g magnesium nitrates are dissolved in 200mL deionized waters be made into it is mixed
Close solution A；
（2）10g NaOH is dissolved in 150mL deionized waters and obtains solution B；
（3）5.512g sodium carbonate is dissolved in 200mL deionized waters and obtains solution C；
（4）Solution A and solution B are poured into two constant pressure funnels respectively, solution C is poured into there-necked flask, in 60 DEG C of bars
To solution A is added dropwise in there-necked flask under part, during adjust pH value of solution using solution B, pH is maintained 10 or so；
（5）By step 4 obtain be deposited in 60 DEG C at aging 18h, then filtering and washing to filtrate in neutrality；
（6）Step 5 gained material is dried overnight for 120 DEG C in drying box, 10h is calcined at 800 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Comparative example 2
Bimetallic methane carbon dioxide reformation catalyst is prepared using infusion process, is comprised the following steps：
（1）0.7946g nickel nitrates and 0.1976g cobalt nitrates are dissolved in 6mL deionized waters and are made into mixed solution A；
（2）To 2g magnesium oxide carriers are added in solution A, stir at room temperature to dry；
（3）Step 2 gained material is dried overnight for 120 DEG C in drying box, 10h is calcined at 800 DEG C, obtain the double gold of support type
Category methane carbon dioxide reformation catalyst.
Data Detection：
There is provided the bimetallic catalyst that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with comparative example 1, comparative example 2
XRD after carrying out reduction, as shown in Figure 1.Compareed with standard spectral peak, 2 θ=36.8o, 42.8o, 62.3o, 74.6o, 78.5oPlace
Diffraction maximum, belong 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, 78.5oThe single diffraction maximum in place represent NiO and CoO with
MgO forms solid solution.From the figure, it can be seen that bimetallic prepared by the bimetallic catalyst and comparative example 1 of present invention preparation
Catalyst occurs in that metal simple-substance is not presented bimetallic catalyst prepared by Ni, the peak of Co metal simple-substances, but comparative example 2
Peak, it may be possible to which also commercial weight is less than the Monitoring lower-cut of XRD very little.
The bimetallic prepared with comparative example 1, comparative example 2 there is provided bimetallic catalyst prepared by the embodiment of the present invention 1 is urged
The TPR figures of agent, as shown in Figure 2.As seen from the figure, the bimetallic catalytic that prepared by the embodiment of the present invention 1, comparative example 1 and comparative example 2
Agent reduction gender gap is obvious.Bimetallic catalyst prepared by the embodiment of the present invention 1 and comparative example 1 is present 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 little.
The bimetallic prepared with comparative example 1, comparative example 2 there is provided bimetallic catalyst prepared by 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 the prepared bimetallic catalyst of the present invention
Footpath 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, the prepared bimetallic catalyst specific surface area of 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 the bimetallic catalytic that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with comparative example 1, comparative example 2
The metal surface area of agent, particle diameter and dispersiveness compare.
The metallic character of the prepared bimetallic methane carbon dioxide reformation catalyst of the present invention of table 1
It can be seen that, the decentralization of the prepared bimetallic catalyst active metal of the present invention is substantially better than comparative example 1 and comparative example
2.Because bimetallic catalyst reproducibility prepared by comparative example 2 is very poor（Fig. 2）, therefore the active metal amount for restoring is seldom, causes
Metal dispersity is poor.Although bimetallic catalyst reproducibility prepared by comparative example 1 is more than the prepared bimetallic catalyst of the present invention,
The active metal amount that it is restored is big, but the active metals surface area exposed after the catalyst reduction is more prepared than the present invention double
Metallic catalyst is small, and metal dispersity is poor, and metal particle size is big.Because preparation method of the invention does not exist comparative example
Local supersaturation in 1 preparation process, by making precipitating reagent, uniformly hydrolysis discharges OH in the solution-, active gold can be made
Belong to the precipitation of uniform ion, produce less metallic particles, more active surfaces can be exposed after carrying out reduction.
Embodiment 7：Active appraisal experiment
The bimetallic catalyst that embodiment 1 is prepared be used for methane reforming with carbon dioxide, and by catalytic effect with it is right
Catalyst activity prepared by ratio 1 and comparative example 2 is compared.
Specific experiment is：By 0.2g Catalyst packings in fixed bed reactors, reaction temperature is 800 DEG C, 0.1MPa,
CH4And CO2Flow is 60mL/min, and air speed is 36000h-1.Reaction procatalyst 120mL/min（50% H2/N2）Gaseous mixture
Reduction 1h.Gathered by gas sampling bag, offline in gas chromatographic analysis.Chromatographic condition is：Argon gas makees carrier gas, carburettor temperature
120 DEG C, 70 DEG C of post furnace temperature, thermal conductivity temperature 70 C, electric current is 50mA.Determine simultaneously 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 conversion ratio of reactant, the selectivity of product.
Embodiment 8：Life assessment is tested
The step of according to embodiment 7, extend the time of methane reforming with carbon dioxide, life assessment experiment is carried out to it.
Table 2 is the bimetallic catalytic that bimetallic catalyst prepared by the embodiment of the present invention 1 is prepared with comparative example 1, comparative example 2
The activity and life assessment results contrast of agent.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 reaction 8h, carbon deposition quantity of catalyst is 0；Double gold prepared by comparative example 1 and comparative example 2
The initial CH of metal catalyst4、CO2Conversion ratio is significantly lower than the bimetallic catalyst prepared by the present invention, after reaction 8h, the He of comparative example 1
Bimetallic catalyst coke content prepared by comparative example 2 is respectively 1.7 wt% and 2.8 wt%.
In order to investigate the life-span of bimetallic catalyst prepared by the present invention, the CH after its reaction 8h, 50h and 200h is contrasted4、
CO2Conversion ratio, as can be seen from Table 2, by after prolonged reaction, the prepared bimetallic catalyst of the present invention still keeps higher
CH4、CO2Conversion ratio, its carbon deposition quantity is only 1.2wt% after reaction 200h, much smaller than double gold prepared by comparative example 1 and comparative example 2
The carbon deposition quantity of metal catalyst 8h（Table 2）.It can be seen that, not only there is bimetallic catalyst prepared by the inventive method catalysis high to live
Property, and coking resistivity is good, and catalyst life is long.
The reactivity worth of the prepared bimetallic methane carbon dioxide reformation catalyst of the present invention of table 2
Claims (9)
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 mass ratio of oxide carrier, metallic nickel and metallic cobalt is 1:0.01~0.1:0.01~0.1；
The oxide carrier is the one kind in magnesia, aluminum oxide, silica, cerium oxide, zirconium oxide.
2. load type double-metal reforming catalyst according to claim 1, it is characterised in that：The oxide carrier, gold
The mass ratio of category nickel and metallic cobalt is 1:0.06~0.08:0.02~0.04.
3. the preparation method of the load type double-metal reforming catalyst described in a kind of claim 1 or 2, it is characterised in that including with
Lower step：
Step one, weigh nickel and cobalt precursor salt be dissolved in deionized water in be made into mixed solution A, nickel ion in solution A
Concentration is 0.01 ~ 0.2mol/L, and cobalt ions is 1 with nickel ion mol ratio:0.01~10；
Step 2, weigh during precipitating reagent is dissolved in deionized water and obtain solution B, wherein, precipitating reagent and nickel ion, cobalt ions sum
Mol ratio be 1:0.1~1；Solution B is 1 with the volume ratio of solution A:0.1~5；
Step 3, to adding oxide carrier in solution A, stir 0.5 ~ 2h at 30 ~ 100 DEG C, obtain solution C, wherein oxide
Carrier is 1 with the mass ratio of nickel ion:0.01~0.1；
Step 4, by solution B add solution C in, regulation rate of addition to ensure the pH of mixed system between 8-12, drip
Bi Hou, keeps mixed system to continue to stir 3 ~ 30h at 60 ~ 120 DEG C；
Step 5, will step 4 gained material suction filtration, washing, dry 3 ~ 20h at 80 ~ 150 DEG C, 400 ~ 900 DEG C of calcinings 3 ~
30h, obtains load type double-metal reforming catalyst.
4. the preparation method of load type double-metal reforming catalyst according to claim 3, it is characterised in that：Step one
In, described nickel precursor salt is the one kind in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, and described cobalt precursor salt is nitre
One kind in sour cobalt, cobalt acetate, cobaltous sulfate, cobalt chloride.
5. the preparation method of load type double-metal reforming catalyst according to claim 3, it is characterised in that：Step 2
In, described precipitating reagent is the one kind in sodium carbonate, urea, potassium carbonate, NaOH, potassium hydroxide.
6. the preparation method of load type double-metal reforming catalyst according to claim 3, it is characterised in that：Step 4
In, rate of addition is 1 ~ 20 mL/min.
7. the preparation method of load type double-metal reforming catalyst according to claim 3, it is characterised in that：Including following
Step：
Step one, weigh nickel and cobalt precursor salt be dissolved in deionized water in be made into mixed solution A, nickel ion in solution A
Concentration is 0.05 ~ 0.15mol/L, and cobalt ions is 1 with nickel ion mol ratio:1~4；
Step 2, weigh during precipitating reagent is dissolved in deionized water and obtain solution B, wherein, precipitating reagent and nickel ion, cobalt ions sum
Mol ratio be 1:0.3~0.5；Solution B is 1 with the volume ratio of solution A:0.2~0.6；
Step 3, to adding oxide carrier in solution A, stir 0.5 ~ 2h at 60 ~ 80 DEG C, obtain solution C, wherein oxide is carried
Body is 1 with the mass ratio of nickel ion:0.06~0.08；
Step 4, will be during solution B adds solution C, regulation rate of addition is added dropwise speed to ensure the pH of mixed system between 9-10
Degree control keeps mixed system to continue to stir 6 ~ 8h at 80 ~ 100 DEG C after 5 ~ 10mL/min, completion of dropping；
Step 5, will step 4 gained material suction filtration, washing, dry 6 ~ 12h at 90 ~ 120 DEG C, 700 ~ 800 DEG C of calcinings 10 ~
15h, obtains load type double-metal reforming catalyst.
8. the load type double-metal reforming catalyst described in a kind of claim 1 or 2 is in methane reforming with carbon dioxide
Using.
9. application according to claim 8, it is characterised in that：The catalyst need to use 50% H using preceding2/N2Mixing
Gas reduces 1h, and the condition of reforming reaction is unstrpped gas methane and the volume ratio of carbon dioxide is 1：1, reaction temperature is 800 DEG C,
Normal pressure, feed space velocity is 36000h-1。
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321352A (en) * | 2017-07-19 | 2017-11-07 | 武汉凯迪工程技术研究总院有限公司 | Ni-based reforming catalyst of recirculating fluidized bed and its preparation method and application |
| CN107376919A (en) * | 2017-07-19 | 2017-11-24 | 太原理工大学 | One kind promotes CO2Activate catalyst of dissociation and its preparation method and application |
| CN107413373A (en) * | 2017-08-08 | 2017-12-01 | 太原理工大学 | A kind of high fast preparation method than table 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 |
| CN112403473A (en) * | 2020-11-06 | 2021-02-26 | 上海簇睿低碳能源技术有限公司 | Synthetic method for preparing reforming catalyst through MOFs |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574662A (en) * | 2009-06-16 | 2009-11-11 | 定州市荣鼎水环境生化技术有限公司 | Cu-Mn complex oxide catalyst prepared by using deposition precipitation method and preparation method and application thereof |
| CN102744072A (en) * | 2012-08-03 | 2012-10-24 | 太原理工大学 | Catalyst used for reforming synthesis gas of methane carbon dioxide and preparation method and application thereof |
| CN104383927A (en) * | 2014-11-17 | 2015-03-04 | 太原理工大学 | Catalyst for methane and carbon dioxide reforming synthesis gas and preparation method of catalyst |
| US20150375211A1 (en) * | 2014-06-27 | 2015-12-31 | Neemo Inc. | Potassium-doped Ni-MgO-ZrO2 catalysts for dry reforming of methane to synthesis gas |
-
2017
- 2017-04-01 CN CN201710212571.5A patent/CN106902829B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574662A (en) * | 2009-06-16 | 2009-11-11 | 定州市荣鼎水环境生化技术有限公司 | Cu-Mn complex oxide catalyst prepared by using deposition precipitation method and preparation method and application thereof |
| CN102744072A (en) * | 2012-08-03 | 2012-10-24 | 太原理工大学 | Catalyst used for reforming synthesis gas of methane carbon dioxide and preparation method and application thereof |
| US20150375211A1 (en) * | 2014-06-27 | 2015-12-31 | Neemo Inc. | Potassium-doped Ni-MgO-ZrO2 catalysts for dry reforming of methane to synthesis gas |
| CN104383927A (en) * | 2014-11-17 | 2015-03-04 | 太原理工大学 | Catalyst for methane and carbon dioxide reforming synthesis gas and preparation method of catalyst |
Non-Patent Citations (4)
| Title |
|---|
| PETAR DJINOVIC ET AL: ""Influence of active metal loading and oxygen mobility on coke-free dry reforming of Ni–Co bimetallic catalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 刘天齐等: "《三废处理工程技术手册》", 31 December 1999 * |
| 王尚弟等: "《催化剂工程导论》", 31 December 2001 * |
| 霍俊梅: ""Ni-Co双金属催化剂在甲烷二氧化碳重整反应中的应用"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
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Application publication date: 20170630 Assignee: Shanxi wanwei Junan Technology Co., Ltd Assignor: Taiyuan University of Technology Contract record no.: X2020990000311 Denomination of invention: Supported bimetallic reforming catalyst and preparation method and application thereof Granted publication date: 20190823 License type: Common License Record date: 20200623 |