CN104841448A - Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor - Google Patents
Organic silicon waste contact body borne nickel-based methanation catalyst and preparation method therefor Download PDFInfo
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Abstract
The invention belongs to the field of methanation catalysis, and relates to an organic silicon waste contact body borne nickel-based methanation catalyst and a preparation method therefor. The catalyst comprises a carrier, an active component, a modifier and an auxiliary agent, wherein the carrier is an organic silicon waste contact body, the modifier is a porous inorganic oxide, the active component is Ni, and the auxiliary agent is a transition metal oxide. By using the porous inorganic oxide modifier in the invention, on one hand, the interacting force between the active component and the carrier is enhanced, and the dispersibility of the active component is improved; on the other hand, the inorganic oxide dispersed in the active component further serves as a physical barrier, and suppresses agglomeration and sintering of Ni particles. The catalyst obtained in the invention is high in catalytic activity, high in anti-carbon deposition and anti-sintering performance and low in cost, and particularly suitable for methanation reaction systems of high-concentration CO.
Description
Technical field
The invention belongs to methanation catalyst field, particularly, the present invention relates to Ni-based methanation catalyst of a kind of abandoned catalyst in direct synthesis methylchlorosilane load and preparation method thereof.
Background technology
China is the country of " rich coal, oil-poor, weak breath ".Coal in the primary energy consumption structure of China in occupation of main status.But about 80% of consumption coal is directly transformed by burning, and heat utilization rate is low, discharges a large amount of pollutant simultaneously.Therefore, development efficient, low-carbon (LC), clean coal resources utilize technology tool to be of great significance.
Gas coal or biomass pyrolytic, gasification obtained is mainly containing H
2and CO, the Main Ingredients and Appearance of coking industry coke-stove gas is be also H
2and CO, these mists containing CO can generate CH by methanation reaction after caning be passed through the techniques such as conversion and purification
4.This can not only promote that the high effect cleaning of coal fully utilizes and improves fuel gas calorie density, provides a practicable approach for filling up China's natural gas demand gap simultaneously.Methanation relates generally to following reaction:
CO+3H
2→CH
4+H
2O Δ
rH
m＝–206kJ/mol
This reaction is strong exothermal reaction, and the instantaneous temperature runaway in beds can make methanation catalyst sinter and lose activity.In addition, because methanation reaction itself is easy to make catalyst because of carbon distribution inactivation, the anti-carbon performance of catalyst and resistance to elevated temperatures will directly affect the life-span of catalyst.Therefore, develop a kind of catalytic activity high, and can the methanation catalyst of at high temperature long-time stable work be one of key factor of synthesis gas methanation process.
Although quite a lot of about the research of methanation catalyst both at home and abroad, have partially catalyzed agent to have the use experience of large-scale industry project or demonstrative project, not all methanation catalyst is all applicable to coal preparing natural gas project.Mostly the CO hydrogenation methanation catalyst of reporting is for removing rich H
2a small amount of CO impurity in system, conventional catalyst is Ni and the Ru transition metal be carried on oxide, and the oxide carrier of employing has Al
2o
3, SiO
2, TiO
2, ZrO
2, MgO etc.These catalyst are at synthesis NH
3and substantially can reach ideal effect in the methanation reaction application of fuel cell industries removing low concentration CO, but CO concentration is higher in the synthesis gas methanation reaction that coal or gasification of biomass obtain, methanation reaction heat release is strong, can make carbon distribution and sintering phenomenon serious.Therefore, development of new, the catalyst that is applicable to high concentration CO methanation has great importance.
At present, the minority offshore company such as rope company of Top of Denmark, British Gas company, German LURGI has had the HP-HT synthesize gas methanation catalyst (as CRG, MCR etc.) of relative maturity.Mostly China is with the porous oxide such as aluminium oxide, silica for carrier about synthesis gas methanation reaction catalyst, nickel, the molybdenum isoreactivity component of different content in load, and be aided with some auxiliary agents as transition metal, alkali metal, alkaline-earth metal and rare-earth oxide etc.As patent CN101380581A, CN1041968A, CN101745401A and CN110132A etc.The methanation catalyst of existing patent Introduction is adopt porous oxide to be carrier mostly, and material thermal conductivity is poor, and easily in formation beds, local temperature is too high, causes the sintering of catalyst, and catalytic efficiency declines even inactivation.Therefore, the methanation catalyst material that exploitation heat conductivility is good, contributes to the life-span of extending catalyst.
Organosilicon industry is prepared in methylchlorosilane technique can produce a large amount of waste catalysts.These waste catalysts are made up of the zinc of porous silicon, copper, carbon and trace, and average grain diameter is comparatively thin, exposes and easily causes oxidation even to burn in atmosphere, and environmental pollution is serious, are also the hidden danger in safety in production simultaneously.Along with the production-scale continuous expansion of China's organic silicon monomer, the amount of waste catalyst constantly increases, and is China's silicone industry sustainable development problem demanding prompt solution to the disposal and utilization of waste catalyst always.At present, large quantifier elimination has been carried out to the process of waste catalyst both at home and abroad.Patent US4758352 to reclaiming silicon from waste catalyst, copper is studied, waste catalyst being carried out deep conversion is white carbon, SiCl
4, HSiCl
3, the product such as phenyl chlorosilane.For the ease of transport and process, by the process of waste catalyst deactivation, as patent US4892694 is processed into stable particle or bead.Although carried out large quantifier elimination to the process of waste catalyst, still there is the problems such as the serious and value-added content of product of complex disposal process, secondary pollution is lower.Therefore, a kind of simple, clean in the urgent need to finding, simultaneously can the method for higher value application waste catalyst.
Summary of the invention
For the deficiency that above-mentioned technology exists, the abandoned catalyst in direct synthesis methylchlorosilane that the present invention adopts Heat stability is good, pyroconductivity high, cheap and easy to get is carrier, in conjunction with the surface modification technology of porous inorganic oxide, obtain a kind of Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load, not only increase anti-sintering and the anti-carbon performance of catalyst, and achieve the higher value application of waste catalyst.
Based on this, an object of the present invention is the Ni-based methanation catalyst providing a kind of abandoned catalyst in direct synthesis methylchlorosilane load.
To achieve these goals, present invention employs following technical scheme:
A Ni-based methanation catalyst for abandoned catalyst in direct synthesis methylchlorosilane load, described catalyst comprises active component, carrier, modifier and auxiliary agent, and wherein, described active component is nickel; Carrier is abandoned catalyst in direct synthesis methylchlorosilane; Modifier is porous inorganic oxide, and auxiliary agent is transition metal oxide.
Preferably, with the content meter of oxide, the gross mass of catalyst is 100%, and the mass percent that each component accounts for catalyst gross mass is respectively:
Active component 10 ~ 70%
Auxiliary agent 0.5 ~ 15%
Carrier and modifier surplus, the mass ratio of modifier and carrier is 0.05 ~ 2.
Described active component nickel is with oxide basis, and the content of active component is such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%.For low temperature methanation catalyst process, the mass percent of the preferred active component of the present invention is 10 ~ 25%; For high-temperature methanation process, the mass percent of the preferred active component of the present invention is 25 ~ 60%, and is 30 ~ 50% economical rationality the most.
The content of described auxiliary agent is such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%.
The mass ratio of described modifier and carrier is as being 0.08,0.1,0.3,0.5,0.7,0.9,1.1,1.3,1.5,1.7 or 1.9.For low temperature methanation catalyst process, the mass ratio of the preferred modifier of the present invention and carrier is 0.05 ~ 0.3; For high-temperature methanation process, the mass ratio of the preferred modifier of the present invention and carrier is 0.25 ~ 2.
The Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load of the present invention, adopts the abandoned catalyst in direct synthesis methylchlorosilane with excellent heat endurance and pyroconductivity to be carrier, can improve the heat conductivility of catalyst, thus improves anti-sintering and the carbon accumulation resisting ability of catalyst.Porous inorganic oxide modifier on the one hand can interaction force between enhanced activity component and carrier, improve the decentralization of active component Ni particle, porous inorganic oxide intersperses among between active component Ni particle or is covered on Ni particle on the other hand, the effect of physical barrier can also be played, suppress reunion and the sintering of Ni particle.Auxiliary agent transition metal has the effect of electronic auxiliary and structural promoter concurrently for the methanation catalyst taking nickel as active component, there is provided electronics to contribute to CO dissociating at catalyst surface on the one hand, add the carrying out of fast response, in addition, interact with NiO, stop growing up of Ni crystal grain.In catalyst of the present invention, need to control the ratio between active component and auxiliary agent, auxiliary agent content is too low, and catalyst activity improves not obvious; Otherwise too much auxiliary agent then easily causes part Ni active sites to be capped, and makes catalyst catalytic performance reduce.
Preferably, described modifier is Al
2o
3, TiO
2, ZrO
2, MgO or SiO
2deng in the mixture of any one or at least two kinds.
Preferably, described auxiliary agent is V
2o
5, Cr
2o
3, CeO
2, La
2o
3or MnO
2deng in the mixture of any one or at least two kinds.
In the present invention, described abandoned catalyst in direct synthesis methylchlorosilane is that silicone industry utilizes that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process, main containing one or more in Si, Cu and C etc., and one or more in the component such as Zn, Fe, Al and Sn of trace.Wherein Si content is 50 ~ 95% (weight ratios), Cu content in 1 ~ 20% (weight ratio), C content 1 ~ 20% (weight ratio).
Preferably, described abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
Preferably, described pretreatment comprises the following steps:
(a) by abandoned catalyst in direct synthesis methylchlorosilane in 300 ~ 700 DEG C (such as 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 650 DEG C) calcining 0.5 ~ 5h (such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h), then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filtration, drying, ball milling, Ball-milling Time is 12 ~ 24h (such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h).
Preferably, described acid is H
2sO
4, HCl, H
3pO
4, HNO
3or the mixture of any one or at least two kinds in acetic acid.
Preferably, the concentration of described acid is 0.1 ~ 4.0mol/L.
Preferably, the use amount of described acid dissolves required sour 1 ~ 3 times of measuring completely for making institute's containing metal oxide in abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, the number of times of described pickling is at least one times.
Preferably, described pickling time is 2 ~ 12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h.
Preferably, described baking temperature is 100 ~ 200 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C or 190 DEG C, and the time is 5 ~ 24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h.
Two of object of the present invention is the preparation method of the Ni-based methanation catalyst providing a kind of abandoned catalyst in direct synthesis methylchlorosilane load as above, said method comprising the steps of:
By synthesizing activity component, auxiliary agent and the raw material needed for modifier components, according to the composition of catalyst, and stream adds in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane, drip precipitating reagent (namely above-mentioned four kinds of raw materials add in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane simultaneously) simultaneously, and hierarchy of control pH is 7.5 ~ 11 (such as 7.8, 8.2, 8.5, 8.8, 9.2, 9.5, 9.8, 10, 10.3, 10.6 or 10.9), make precipitation by metallic ion complete, obtain Catalyst precursor solutions, then filter, washing, dry, calcining and reduction, obtain the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
In the present invention, described abandoned catalyst in direct synthesis methylchlorosilane is that silicone industry utilizes that silicon is raw material, copper or the solid residue of its compound for producing in Catalyst Production organosilicon methyl chlorosilane monomer process, main containing one or more in Si, Cu and C etc., and one or more in the component such as Zn, Fe, Al and Sn of trace.Wherein Si content is 50 ~ 95% (weight ratios), Cu content in 1 ~ 20% (weight ratio), C content 1 ~ 20% (weight ratio).
Preferably, described abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment.
Preferably, described pretreatment comprises the following steps:
(a) by abandoned catalyst in direct synthesis methylchlorosilane in 300 ~ 700 DEG C (such as 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 650 DEG C) calcining 0.5 ~ 5h (such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h), then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filtration, drying, ball milling, Ball-milling Time is 12 ~ 24h (such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h).
Preferably, described acid is H
2sO
4, HCl, H
3pO
4, HNO
3or the mixture of any one or at least two kinds in acetic acid.
Preferably, the concentration of described acid is 0.1 ~ 4.0mol/L.
Preferably, the use amount of described acid dissolves required sour 1 ~ 3 times of measuring completely for making institute's containing metal oxide in abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, the number of times of described pickling is at least one times.
Preferably, described pickling time is 2 ~ 12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h.
Preferably, described baking temperature is 100 ~ 200 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C or 190 DEG C, and the time is 5 ~ 24h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h.
Preferably, the preparation method of described abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid is:
Abandoned catalyst in direct synthesis methylchlorosilane is scattered in water, be heated to 40 ~ 90 DEG C (such as 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C or 85 DEG C), then the pH value adopting precipitating reagent regulation system is 7.5 ~ 11 (such as 7.8,8.2,8.5,8.8,9.2,9.5,9.8,10,10.3,10.6 or 10.9), obtains the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, described precipitating reagent is NaOH, KOH, Na
2cO
3, K
2cO
3, ammonium carbonate and ammoniacal liquor the aqueous solution in the combination of any one or at least two kinds, its concentration is 0.2 ~ 2.0mol/L.
Preferably, the raw material needed for synthesizing activity component, auxiliary agent and modifier components all as a solution and stream add in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane.
Preferably, the raw material needed for synthesis modification agent is selected from the nitrate of aluminium, magnesium, zirconium, titanium or silicon, carbonate, chloride, silicate or ester.
Preferably, the raw material needed for synthesizing activity component is the combination of any one or at least two kinds in nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate.
Preferably, the raw material needed for additive synthesis is selected from nitrate or the carbonate of chromium, manganese, cerium or lanthanum, or vanadyl acetylacetonate.
Preferably, add nitric acid dissolve when the carbonate of aluminium, magnesium, zirconium or titanium and the carbonate of chromium, manganese, cerium or lanthanum use and form solution.
Preferably, be dissolved in ethanol when the chloride of titanium, ester or vanadyl acetylacetonate use and form solution.
Preferably, under the condition stirred, drip raw material, mixing time is 3 ~ 10h, such as 4h, 5h, 6h, 7h, 8h or 9h.
Preferably, described calcining heat is 400 ~ 700 DEG C, such as 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 650 DEG C, and calcination time is 2 ~ 6h, such as 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h.During calcining, control temperature is 400 – ~ 700 DEG C, and calcining heat is too low, and the interphase interaction of carrier and active component will be made to weaken, and active component easily runs off, and temperature is too high, and active component is obviously reunited, and is difficult to reduction, makes catalyst activity reduction.
Preferably, described reduction temperature is 400 ~ 800 DEG C, such as 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C or 750 DEG C, and the recovery time is 1 ~ 3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8h.
The preparation method of the Ni-based methanation catalyst of exemplary abandoned catalyst in direct synthesis methylchlorosilane load comprises the following steps:
1) pretreatment of abandoned catalyst in direct synthesis methylchlorosilane carrier:
1-1) by abandoned catalyst in direct synthesis methylchlorosilane 300 – 700 DEG C, calcining 0.5 ~ 5h, then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
1-2) abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling, then filtration, dry and ball milling, Ball-milling Time is 12 ~ 24h;
2) preparation of catalyst:
2-1) by step 1) in the pretreated abandoned catalyst in direct synthesis methylchlorosilane that obtains be scattered in water, be heated to 40 ~ 90 DEG C, the pH value adopting precipitating reagent regulation system is 7.5 ~ 11, obtains the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane;
2-2) by the raw material needed for synthesizing activity component, auxiliary agent and modifier, according to the composition of catalyst, be configured to solution separately, and stream joins 2-1) in the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid that obtains, drip precipitating reagent simultaneously, and hierarchy of control pH value is 7.5 – 11, stirs 3 ~ 10h, obtain catalyst precursor mixed liquor;
2-3) filtered by catalyst precursor, wash and drying, products therefrom calcines 2 ~ 6h at 400 ~ 700 DEG C, and afterwards at 400 ~ 800 DEG C, reduction 1 ~ 3h, forms the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
Compared with the prior art, the present invention has following beneficial effect:
1, the present invention adopts cheap abandoned catalyst in direct synthesis methylchlorosilane to be used as methanation catalyst carrier, the catalyst activity prepared is high, good stability, anti-sintering and anti-carbon performance by force, are particularly useful for the methanation catalyst reaction of high concentration CO, show good activity and stability.
2, the methanation catalyst prepared of the present invention, low raw-material cost, reduces the cost of catalyst, and method of operating is simple, is easy to large-scale production.
3, by the CO methanation of this catalyst application high concentration, not only light-off temperature is low, has high activity at low temperatures, and under high temperature, the activity of catalyst still can keep stable.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of abandoned catalyst in direct synthesis methylchlorosilane after the process that obtains of embodiment 1 and pure silicon;
Fig. 2 to be the catalyst multiplication factor of the abandoned catalyst in direct synthesis methylchlorosilane load that comparative example 1 obtains be 100000 TEM figure;
Fig. 3 to be the catalyst multiplication factor of the abandoned catalyst in direct synthesis methylchlorosilane load that embodiment 2 obtains be 100000 TEM figure;
Fig. 4 is embodiment 6 and 8 and certain commercial catalysts CH in methanation reaction life test
4yield over time.
Detailed description of the invention
Technical scheme of the present invention is further illustrated by detailed description of the invention below in conjunction with accompanying drawing.
Embodiment 1
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane:
1) body that given up by organosilicon touches and is placed in Muffle furnace, at 300 DEG C, calcine 5h, then broken, to sieve out particle diameter be that the sample of 0.5 – 100 μm is for subsequent use;
2) abandoned catalyst in direct synthesis methylchlorosilane after above-mentioned for 10g screening is positioned in beaker, add the nitric acid of 30mL 2mol/L, be put on magnetic stirring apparatus, 12h is stirred at 20 DEG C, supernatant liquor is poured in waste liquid bottle, repeatedly cleans afterwards with water, until cleaning solution is neutral, then filter, by gained sample in 100 DEG C of oven drying 24h; Dried sample is placed in ball milling 12h on ball mill, gained silicon waste catalyst called after WCM, stores good for subsequent use.
The preparation of catalyst: round-bottomed flask 3.20g WCM being placed in 50mL deionized water, 60 DEG C of water-bath rapid stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, 0.21g La (NO
3)
36H
2o is dissolved in 50mL water respectively, by 0.95g TiCl
4be dissolved in 50mL absolute ethyl alcohol, and configure the sal volatile of 0.5mol/L, then by above-mentioned 4 kinds of solution and drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, its pH is controlled about 8, after 60 DEG C of stirring in water bath 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 6h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst obtained is labeled as CAT-1.
X ' the Pert PRO MPD type Multi-functional X ray diffractometer produced Dutch Panalytical company (PANalytical) by the abandoned catalyst in direct synthesis methylchlorosilane carrier of above-mentioned process carries out XRD test.
Fig. 1 gives the XRD spectra of abandoned catalyst in direct synthesis methylchlorosilane carrier handled by embodiment 1 and pure silicon.Silicon waste catalyst carrier after process and pure silicon show identical characteristic diffraction peak, illustrate that the abandoned catalyst in direct synthesis methylchlorosilane purity after process is very high.
Comparative example 1
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane:
1) body that given up by organosilicon touches and is placed in Muffle furnace, at 300 DEG C, calcine 5h, then broken, to sieve out particle diameter be that the sample of 0.5 ~ 100 μm is for subsequent use;
2) abandoned catalyst in direct synthesis methylchlorosilane after above-mentioned for 10g screening is positioned in beaker, add the nitric acid of 30mL 2mol/L, be put on magnetic stirring apparatus, 12h is stirred at 20 DEG C, supernatant liquor is poured in waste liquid bottle, repeatedly cleans afterwards with water, until cleaning solution is neutral, then filter, by gained sample in 100 DEG C of oven drying 24h; Dried sample is placed in ball milling 12h on ball mill, gained silicon waste catalyst called after WCM, stores good for subsequent use.
The preparation of catalyst: round-bottomed flask 3.20g WCM being placed in 50mL deionized water, 60 DEG C of water-bath rapid stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, be dissolved in 50mL water, and configure the sal volatile of 0.5mol/L, then by above-mentioned 4 kinds of solution and drip is added in round-bottomed flask, detect pH value with pH meter in dropping process, its pH is controlled about 8, after 60 DEG C of stirring in water bath 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 6h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst obtained is labeled as CAT-0.
By the distribution situation of JEM-2010F model transmission electron microscope observation Ni on abandoned catalyst in direct synthesis methylchlorosilane that above-mentioned CAT-0 catalyst is produced in company of NEC, result illustrates that Ni crystallite dimension prepared by this method is little and even.
Embodiment 2
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment silicon waste catalyst into 400 DEG C, acid used replaces with HCl.
The preparation of catalyst: round-bottomed flask 2.72g WCM being placed in 50mL deionized water, 40 DEG C of water-bath rapid stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, 2.94g Al (NO
3)
39H
2o, 0.33g 50wt%Mn (NO
3)
2be dissolved in 50g water respectively, and configure the NaOH solution of 0.2mol/L, then by above-mentioned 4 kinds of solution and drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, its pH is controlled about 9, after 40 DEG C of stirring in water bath 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 500 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst obtained is labeled as CAT-2.
The dispersion of the JEM-2010F model transmission electron microscope observation Ni that above-mentioned CAT-2 catalyst is produced in company of NEC on silicon waste catalyst and distribution, and aluminium oxide improver distribution situation in the catalyst.Result to illustrate in CAT-2 that Ni crystallite dimension is little and be evenly distributed, an improver aluminium oxide part is evenly distributed on silicon waste catalyst, a part intersperses among between active component Ni particle or is covered on Ni particle, therefore can play the effect of physical barrier, suppresses the reunion of Ni particle, sintering.
Embodiment 3
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 700 DEG C, acid used replaces with sulfuric acid.
The preparation of catalyst: round-bottomed flask 2.72g WCM being placed in 50mL deionized water, 90 DEG C of water-bath rapid stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, 2.55g Mg (NO
3)
26H
2o, 0.2gCe (NO
3)
36H
2o is dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, its pH is controlled about 8,90 DEG C of stirring in water bath are after 8 hours, and filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dryings 12 hours.Gained sample is calcined 2 hours at 700 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-3.
Embodiment 4
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with phosphoric acid.
The preparation of catalyst: round-bottomed flask 2.72g WCM being placed in 50mL deionized water, 60 DEG C of water-bath rapid stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, 1.40g Zr (NO
3)
45H
2o, 0.35g vanadyl acetylacetonate is dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, detect pH value with pH meter in dropping process, its pH is controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-4.
Embodiment 5
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with acetic acid.
The preparation of catalyst: round-bottomed flask 2.40g WCM being placed in 50mL deionized water, 60 DEG C of water-bath rapid stirring 0.5h, by 1.56g Ni (NO
3)
26H
2o, 5.88g Al (NO
3)
39H
2o, 0.53gLa (NO
3)
36H
2o is dissolved in 50g water respectively, and configure the ammoniacal liquor of 2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-5.
Embodiment 6
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with HCl.
The preparation of catalyst: round-bottomed flask 2.60g WCM being placed in 50mL deionized water, 60 DEG C of water-bath uniform stirring 0.5h, by 6.24g Ni (NO
3)
26H
2o, 2.80g Zr (NO
3)
45H
2o, 0.5g vanadyl acetylacetonate is dissolved in 50g water respectively, and configures the K of 1mol/L
2cO3 solution, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, detect pH value with pH meter in dropping process, controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-6.
Embodiment 7
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with HCl.
The preparation of catalyst: round-bottomed flask 2.20g WCM being placed in 50mL deionized water, 60 DEG C of water-bath uniform stirring 0.5h, by 6.10g Ni (NO
3)
26H
2o, 5.09g Mg (NO
3)
26H
2o, 0.82g 50wt%Mn (NO
3)
2be dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, its pH is controlled about 10, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, heating rate 2 DEG C/min; Then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-7.
Embodiment 8
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with HCl.
The preparation of catalyst: round-bottomed flask 2.08g WCM being placed in 50mL deionized water, 60 DEG C of water-bath uniform stirring 0.5h, by 5.40g Ni (NO
3)
26H
2o, 5.88g Al (NO
3)
39H
2o, 0.8gCe (NO
3)
36H
2o is dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, its pH is controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2600 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-8.
Embodiment 9
The preparation of catalyst carrier (process of silicon waste catalyst): the same with embodiment 1 treatment step, just replaces with toluene and HCl by organic solvent used for process abandoned catalyst in direct synthesis methylchlorosilane and acid.
The preparation of catalyst: round-bottomed flask 2.08g WCM being placed in 50mL deionized water, 60 DEG C of water-bath uniform stirring 0.5h, by 2.15g NiCl
26H
2o, 2.80g Zr (NO
3)
45H
2o, 0.84gLa (NO
3)
36H
2o is dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2500 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-9.
Embodiment 10
The pretreatment of abandoned catalyst in direct synthesis methylchlorosilane: the same with embodiment 1 treatment step, just change the sintering temperature of pretreatment abandoned catalyst in direct synthesis methylchlorosilane into 400 DEG C, acid used replaces with HCl.
The preparation of catalyst: round-bottomed flask 2.08g WCM being placed in 50mL deionized water, 60 DEG C of water-bath uniform stirring 0.5h, by 3.10g Ni (NO
3)
26H
2o, 5.09g Mg (NO
3)
26H
2o, 1.32g 50wt%Mn (NO
3)
2be dissolved in 50g water respectively, and configure the KOH solution of 0.2mol/L, then above-mentioned 4 kinds of solution drip is added in round-bottomed flask, pH value is detected with pH meter in dropping process, controlled about 9, after 60 DEG C of water-bath uniform stirring 8h, filtering and washing is about 7 to pH, by the sample that obtains in 100 DEG C of dry 12h.Gained sample calcines 4h at 400 DEG C in air atmosphere, and heating rate 2 DEG C/min, then in H
2700 DEG C of reductase 12 h in atmosphere, the catalyst of preparation is labeled as CAT-10.
Catalyst performance evaluation
The test of normal pressure methanation catalyst reactivity worth is carried out to embodiment 1,2,3,4,5,6,7,8,9,10 and certain commercial catalysts.500mg 20 ~ 40 object catalyst is loaded in crystal reaction tube, passes into H
2(flow velocity: 100mL/min) temperature programmed reduction, heating rate 2 DEG C/min, reductase 12 h at 400 DEG C, is cooled to 260 DEG C afterwards.Reactor feed gas consists of H
2: CO:N
2volume flow rate is than being 3:1:1, and reaction pressure is normal pressure, and mass space velocity is 30000mLh
-1g
-1reaction temperature: 260 – 550 DEG C, low-temperature space (260 – 360 DEG C) is with one, 20 DEG C of intervals point, high-temperature region (400 – 550 DEG C) is with one, 50 DEG C of intervals point, each temperature spot constant temperature about 60min samples, and carries out analysis raw material and gaseous product composition by Micro3000 gas-chromatography.
The active testing result of the catalyst that above-described embodiment and comparative example are prepared in implementing is as shown in the table:
Note:
Wherein: n is the molal quantity of corresponding component
Table is visible thus, the Ni-based methanation catalyst activity of the pure abandoned catalyst in direct synthesis methylchlorosilane load prepared by comparative example 1 is poor, the activity of abandoned catalyst in direct synthesis methylchlorosilane via catalyst obtained after inorganic oxide modification is significantly improved, to the conversion ratio of CO and CH under 550 DEG C of high temperature
4the selective limiting value all having reached calculation of thermodynamics under this temperature and pressure.The nickel content (20 ~ 40wt%) prepared with existing method is higher, the catalyst simultaneously adding auxiliary agent is compared (Chinese patent CN1041968A and CN101468311A), and in embodiment 1,2,3,4, the nickel oxide content of preparation is that the activity of the catalyst of 20wt% is also apparently higher than the activity of prior art Kaolinite Preparation of Catalyst.In addition, add manganese oxide, low temperature active that vanadic anhydride auxiliary agent can significantly improve catalyst, as 260 DEG C, under normal pressure, the conversion ratio of CO on CAT-6 catalyst just can reach 80%, illustrate that catalyst of the present invention is compared with commercial catalysts, not only has higher high temperature active, there is excellent low temperature active simultaneously.
The catalyst CTA-6 obtained to embodiment 6,8 and the stability of certain commercial catalysts in pressurization methanation reaction are tested.500mg 20 ~ 40 object catalyst is loaded in crystal reaction tube, passes into H
2(flow velocity: 30mL/min) temperature programmed reduction, heating rate 2 DEG C/min, reductase 12 hour at 600 DEG C.Reactor feed gas consists of H
2: CO:N
2volume flow rate is than being 3:1:1, and reaction pressure is 3.0MPa, and mass space velocity is 30000mLg
-1h
-1, reaction temperature is 550 DEG C.We select certain commercial catalysts (NiO mass fraction is 45%, with titanium aluminum oxide for carrier) to compare.Note: CH
4yield=(CO Zhuanization Shuai ╳ CH
4selective)/100
Adopt the carbon deposition quantity on carbon and sulfur analytical instrument detection stability test rear catalyst.
Fig. 4 is methanation catalyst and certain commercial catalysts catalytic life evaluation result: CH in methanation reaction of silicon waste catalyst load prepared by embodiment 6,8
4yield with the change in reaction time.As seen from Figure 4, commercial catalysts in course of reaction, CH
4yield there is obvious downward trend.3.0MPa, after 550 DEG C of reaction 70h, CH
4yield drop to 78% by 89%.Thermal gravimetric analysis results shows that the carbon deposition quantity in commercial catalysts reaches 15wt%.After reacting 70h under similarity condition, the silicon waste catalyst catalyst of the load nickel oxide that the present invention proposes, CH on CAT-6 and CAT-8
4conversion ratio basicly stable, the carbon deposition quantity after reaction on CAT-6 only has 2wt%, and CAT-8 carbon deposition quantity only has 3wt%.Illustrate that the catalytic activity of the catalyst that the present invention proposes, heat endurance and anti-carbon performance are all better than selected commercialized catalyst.
As mentioned above, compare with the commercial catalysts selected by testing with methanation catalyst obtained in prior art, the catalyst based aspect such as catalyst activity, anti-sintering, anti-carbon performance of abandoned catalyst in direct synthesis methylchlorosilane that the present invention proposes all has obvious advantage, and what this catalyst produced at coal or biomass pyrolytic or gasification is rich in CO and H
2the methanation such as gaseous mixture and industrial oven gas in have a good application prospect.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a Ni-based methanation catalyst for abandoned catalyst in direct synthesis methylchlorosilane load, described catalyst comprises active component, carrier, modifier and auxiliary agent, and wherein, described active component is nickel; Carrier is abandoned catalyst in direct synthesis methylchlorosilane; Modifier is porous inorganic oxide, and auxiliary agent is transition metal oxide.
2. catalyst as claimed in claim 1, it is characterized in that, with the content meter of oxide, the gross mass of catalyst is 100%, and the mass percent that each component accounts for catalyst gross mass is respectively:
Active component 10 ~ 70%
Auxiliary agent 0.5 ~ 15%
Carrier and modifier surplus, the mass ratio of modifier and carrier is 0.05 ~ 2.
3. catalyst as claimed in claim 2 is characterized in that, the mass percent of active component is 10 ~ 25%;
Preferably, the mass percent of active component is 25 ~ 60%, preferably 30 ~ 50%;
Preferably, the mass ratio of modifier and carrier is 0.05 ~ 0.3;
Preferably, the mass ratio of modifier and carrier is 0.25 ~ 2.
4. the catalyst as described in one of claim 1-3, is characterized in that, described modifier is Al
2o
3, TiO
2, ZrO
2, MgO or SiO
2in the mixture of any one or at least two kinds;
Preferably, described auxiliary agent is V
2o
5, Cr
2o
3, CeO
2, La
2o
3or MnO
2in the mixture of any one or at least two kinds;
Preferably, described abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment;
Preferably, described pretreatment comprises the following steps:
(a) by abandoned catalyst in direct synthesis methylchlorosilane at 300 ~ 700 DEG C of calcining 0.5 ~ 5h, then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filtration, drying, ball milling, and Ball-milling Time is 12 ~ 24h;
Preferably, described acid is H
2sO
4, HCl, H
3pO
4, HNO
3or the mixture of any one or at least two kinds in acetic acid;
Preferably, the concentration of described acid is 0.1 ~ 4.0mol/L;
Preferably, the use amount of described acid dissolves required sour 1 ~ 3 times of measuring completely for making institute's containing metal oxide in abandoned catalyst in direct synthesis methylchlorosilane;
Preferably, the number of times of described pickling is at least one times;
Preferably, described pickling time is 2 ~ 12h;
Preferably, described baking temperature is 100 ~ 200 DEG C, and the time is 5 ~ 24h.
5. a preparation method for the Ni-based methanation catalyst of the abandoned catalyst in direct synthesis methylchlorosilane load as described in one of claim 1-4, is characterized in that, said method comprising the steps of:
By the raw material needed for synthesizing activity component, auxiliary agent and modifier components, according to the composition of catalyst, and stream adds in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane, drips precipitating reagent simultaneously, and hierarchy of control pH is 7.5 ~ 11, make precipitation complete, obtain Catalyst precursor solutions, then filter, washing, drying, calcining and reduction, obtain the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
6. method as claimed in claim 5, it is characterized in that, described abandoned catalyst in direct synthesis methylchlorosilane is through pretreatment;
Preferably, described pretreatment comprises the following steps:
(a) by abandoned catalyst in direct synthesis methylchlorosilane at 300 ~ 700 DEG C of calcining 0.5 ~ 5h, then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
B abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling by (), then filtration, drying, ball milling, and Ball-milling Time is 12 ~ 24h;
Preferably, described acid is H
2sO
4, HCl, H
3pO
4, HNO
3or the mixture of any one or at least two kinds in acetic acid;
Preferably, the concentration of described acid is 0.1 ~ 4.0mol/L;
Preferably, the use amount of described acid dissolves required sour 1 ~ 3 times of measuring completely for making institute's containing metal oxide in abandoned catalyst in direct synthesis methylchlorosilane;
Preferably, the number of times of described pickling is at least one times;
Preferably, described pickling time is 2 ~ 12h;
Preferably, described baking temperature is 100 ~ 200 DEG C, and the time is 5 ~ 24h.
7. the method as described in claim 5 or 6, is characterized in that, the preparation method of described abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid is:
Be scattered in by abandoned catalyst in direct synthesis methylchlorosilane in water, be heated to 40 ~ 90 DEG C, the pH value then adopting precipitating reagent regulation system is 7.5 ~ 11, obtains the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane;
Preferably, described precipitating reagent is NaOH, KOH, Na
2cO
3, K
2cO
3, ammonium carbonate and ammoniacal liquor the aqueous solution in the combination of any one or at least two kinds, its concentration is 0.2 ~ 2.0mol/L.
8. the method as described in one of claim 5-7, is characterized in that, the raw material needed for synthesizing activity component, auxiliary agent and modifier components all as a solution and stream add in the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane;
Preferably, the raw material needed for synthesis modification agent is selected from the nitrate of aluminium, magnesium, zirconium, titanium or silicon, carbonate, chloride, silicate or ester;
Preferably, the raw material needed for synthesizing activity component is the combination of any one or at least two kinds in nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate;
Preferably, the raw material needed for additive synthesis is selected from nitrate or the carbonate of chromium, manganese, cerium or lanthanum, or vanadyl acetylacetonate;
Preferably, add nitric acid dissolve when the carbonate of aluminium, magnesium, zirconium or titanium and the carbonate of chromium, manganese, cerium or lanthanum use and form solution;
Preferably, be dissolved in ethanol when the chloride of titanium, ester or vanadyl acetylacetonate use and form solution.
9. the method as described in one of claim 5-8, is characterized in that, under the condition stirred, drip raw material, mixing time is 3 ~ 10h;
Preferably, described calcining heat is 400 ~ 700 DEG C, and calcination time is 2 ~ 6h;
Preferably, described reduction temperature is 400 ~ 800 DEG C, and the recovery time is 1 ~ 3h.
10. the method as described in one of claim 5-9, is characterized in that, said method comprising the steps of:
1) pretreatment of abandoned catalyst in direct synthesis methylchlorosilane carrier:
1-1) by abandoned catalyst in direct synthesis methylchlorosilane at 300 ~ 700 DEG C, calcining 0.5 ~ 5h, then broken and sieve out the abandoned catalyst in direct synthesis methylchlorosilane that particle diameter is 0.5 ~ 100 μm;
1-2) abandoned catalyst in direct synthesis methylchlorosilane after broken and screening is carried out pickling, then filtration, dry and ball milling, Ball-milling Time is 12 ~ 24h;
2) preparation of catalyst:
2-1) by step 1) in the pretreated abandoned catalyst in direct synthesis methylchlorosilane that obtains be scattered in water, be heated to 40 ~ 90 DEG C, the pH value adopting precipitating reagent regulation system is 7.5 ~ 11, obtains the dispersion liquid of abandoned catalyst in direct synthesis methylchlorosilane;
2-2) by the raw material needed for synthesizing activity component, auxiliary agent and modifier, according to the composition of catalyst, be configured to solution separately, and stream joins 2-1) in the abandoned catalyst in direct synthesis methylchlorosilane dispersion liquid that obtains, drip precipitating reagent simultaneously, and hierarchy of control pH value is 7.5 – 11, stirs 3 ~ 10h, obtain catalyst precursor mixed liquor;
2-3) filtered by catalyst precursor, wash and drying, products therefrom calcines 2 ~ 6h at 400 ~ 700 DEG C, and afterwards at 400 ~ 800 DEG C, reduction 1 ~ 3h, forms the Ni-based methanation catalyst of abandoned catalyst in direct synthesis methylchlorosilane load.
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| CN110252362A (en) * | 2019-06-03 | 2019-09-20 | 山东科技大学 | A kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification |
| CN113019383A (en) * | 2021-03-10 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Nickel/lanthanum oxide catalyst and preparation method and application thereof |
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