CN103386307A - Preparation method for Ni-Mg/Al2O3 catalyst - Google Patents
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Abstract
The invention relates to a preparation method for a Ni-Mg/Al2O3 catalyst. The method comprises the following steps of 1) preparing an acidic solution I and an alkaline solution II, wherein the acidic solution I comprises active ingredient raw materials, auxiliary raw materials and a metal cation raw material corresponding to a carrier; the alkaline solution II comprises an anion raw material corresponding to the carrier; the two solutions are mixed and subjected to a precipitation reaction, so that an alkaline reaction environment with a pH value larger than 8 is formed and a precursor of the catalyst is generated; (2) transferring the precursor of the catalyst obtained by the step (1) into an autoclave to carry out a hydrothermal reaction, so that a slurry of the catalyst is obtained; and (3) washing, filtering, drying and sintering the slurry of the catalyst obtained by the step (2) to obtain the catalyst. The preparation method for the catalyst overcomes the disadvantages of nonuniformity, low strength, difficult control due to wide pH value variation range during the hydrothermal process, high requirements for the material of the autoclave and the like in a conventional coprecipitation method, and has the characteristics of simple and controllable reaction process, good repeatability, low cost, low requirements for equipment, etc.
Description
Technical field
The present invention relates to the technical field that catalyst and inorganic synthetic chemistry are intersected, particularly, the present invention relates to a kind of Ni-Mg/Al
2O
3The preparation method of catalyst.
Background technology
The coal resources of China are relatively abundant, and for a long time, in the primary energy consumption structure of China, coal is all in occupation of main status.With respect to coal methyl alcohol processed, coal derived DME, the technology such as DCL/Direct coal liquefaction, the efficiency of coal instead of natural gas processed high (more than 60%), unit calorific value water consumption is few, CO
2Discharge capacity is low, used heat utilization rate high (by-product high temperature and high pressure steam).Rely on this, if take coal as raw material by methanation reaction production instead of natural gas, not only meet the efficient developing direction of utilizing of Coal Clean, carry by pipeline simultaneously and carry out industry and civilian after the pressure regulation distribution, can effectively utilize the abundant coal resources in the outlying areas such as Xinjiang, the Inner Mongol.
The key of synthesis gas methanation is the development of new effective catalyst.Catalyzing carbon monoxide a small amount of in the hydrogen rich gas atmosphere is changed into technique and the catalyst of the existing many maturations of methane process both at home and abroad, and the Patents report is also being arranged aspect coke-stove gas, water-gas and semiwater gas methanation catalyst.Patent CN1121898, CN101185892 have studied respectively the methanation catalyst that is used for purifying ammonia synthesis process and a small amount of CO of fuel cell unstripped gas, and wherein the concentration of CO is not more than 1% usually; Patent CN101391218, CN102259003 have reported the catalyst that is used for gas employing methanation of coke oven, the content of methane high (23-27%) in coke-stove gas wherein, and the content of CO is less, usually at 5-8%.The required full methanation catalyst of above-mentioned methanation catalyst and coal preparing natural gas project has very large difference on performance requirement, can not meet the needs of synthesis gas methanation process.
Since the seventies in last century, domestic research about synthesis gas full methanation catalyst and patented technology report increase, and CN101468311, CN102114425 adopt infusion process to prepare methanation of coal gas Ni/Al
2O
3Catalyst, but this class catalyst is only applicable to operate under lower temperature and normal pressure usually, under higher temperature, sintering, deactivation phenomenom can occur; CN102029162 adopts coprecipitation to develop a kind of synthesis gas full methanation Ni/Al that is applicable to HTHP
2O
3-ZrO
2Catalyst, the method is the conventional process of industrial extensive synthetic powder material, but in coprecipitation process, can cause the local inhomogeneous of precipitating reagent by outside to adding precipitating reagent in solution, thereby precipitation can not evenly be occurred in whole solution, thereby there is certain inhomogeneity in the catalyst that the method makes.
Hydro-thermal method refers in special closed reactor, use water as medium, by reactor is heated, form the environment of a HTHP in reaction system, with this understanding, the reunion between the presoma particulate is destroyed, particulate is from dissolving in the hydro-thermal medium simultaneously,, by the hydrolysis ion aggregation different with polycondensation reaction generation, when the relative concentration of ion aggregation, during in the less crystallization relative saturation of solubility, start to separate out nucleus.Along with the carrying out of crystallization process, the concentration of hydro-thermal medium intermediate ion aggregation becomes again lower than the solubility of presoma, makes presoma dissolve and proceeds.So repeatedly, as long as hydro-thermal reaction time long enough, presoma will dissolve fully, generate simultaneously corresponding crystal grain.The synthetic catalyst particle purity of the method is high, and particle diameter is little and be evenly distributed, and crystal grain is grown complete, and crystalline form is easily controlled, and by factors such as regulator solution pH value, reaction temperature, pressure and times, can effectively control reaction and crystal growth.
patent CN102029161, CN101716513, it is catalyst based that CN101716513 all adopts sluggish precipitation to utilize the hydrothermal chemistry building-up process to prepare full methanation Ni, at first the method makes treats that precipitation of metal salts solution mixes with excessive water-soluble slow-releasing type alkali (urea etc.), cause in advance a kind of very uniform system, then react in the high pressure water heating kettle, by controlling temperature of reaction kettle, precipitating reagent is slowly decomposed, improve gradually the pH value of solution, precipitation is slowly carried out, the methanation catalyst that the method makes is even, purity and crystallization degree are high, have good high temperature and hydrothermal stability, but because precipitating reagent is slowly to decompose, cause the pH value of solution in course of reaction to become alkalescence by acidity gradually, the reactor material is had relatively high expectations, the addition of precipitating reagent is subjected to hydrothermal temperature simultaneously, reaction time, the impact of the many factors such as stirring, actual industrial production difficulty.Therefore develop new full methanation Ni-Mg/Al
2O
3The preparation method of catalyst is very significant.
Summary of the invention
, for addressing the above problem, the invention provides a kind of Ni-Mg/Al
2O
3The preparation method of catalyst.
Ni-Mg/Al of the present invention
2O
3The preparation method of catalyst comprises the following steps:
1) prepare acid solution I, alkaline solution II, wherein acid solution I comprises the corresponding metal cation raw material of active component raw material, auxiliary agent raw material and carrier, the alkaline solution II comprises the corresponding anion raw material of carrier, two kinds of solution mix the generation precipitation reaction, form the alkaline reaction environment of pH value more than 8, generate catalyst precursor;
2) catalyst precursor that step 1) is obtained moves in autoclave and carries out hydrothermal treatment consists and aging, obtains catalyst pulp;
3) with step 2) catalyst pulp that obtains forms catalyst through washing, filtration, dry roasting.
According to Ni-Mg/Al of the present invention
2O
3Method for preparing catalyst, it is 40-90 ℃ that step 1) is kept reaction temperature in precipitation reactor, simultaneously by heat and mass transport method between forced fluid liquid, clash into strong microcosmic mixing occurs as two solution subtends, create high and uniform degree of supersaturation environment in precipitation reactor, two kinds of solution are reacted rapidly, realize the preparation of nanocatalyst precursor.
Two to fluid impact, mutual motion and shear action violent between the stream group from different directions promote the microcosmic of reactant on molecular scale to mix, formed high moment degree of supersaturation in reaction zone, and the degree of supersaturation height is even, the speed that this moment, the nucleus generating rate increased much larger than nucleus, a large amount of nucleus are separated out, the concentration of reactant molecule descends rapidly, there is no more molecular aggregates in solution to nucleus, limit the degree that nucleus increases, be conducive to simultaneously the surface-stable of nucleus.
According to Ni-Mg/Al of the present invention
2O
3The preparation method of catalyst, described acid solution I are the nitrate solution of nickel, magnesium, aluminium, and described nitrate solution can be also the solution that oxalates, carbonate or the subcarbonate of nickel, magnesium, aluminium forms through nitric acid dissolve.Described alkaline solution II is NaAlO
2Solution.
Simultaneously, when the present invention adopts hydro-thermal method to process soda acid pairing generation catalyst precursor, fill the wear-resistant ball of different-grain diameter grating in high-pressure bottle, realize the ball milling refinement in precipitation precursor ageing process, thus the particle of formation single-size and pattern.
Ni-Mg/Al of the present invention
2O
3Method for preparing catalyst, precipitation ageing process wherein can continued operations, also can intermittently operated.During intermittently operated, at first two kinds of solution react and form catalyst precursor in precipitation reactor, be transferred to after question response is completed in high-pressure reactor and carry out hydrothermal treatment consists and aging; During continued operation, by being set, feed rate controls the time of staying of catalyst precursor in precipitation reactor, the presoma overflow that precipitation is completed is to the high pressure reactor, by changing size and the inner member of high-pressure reactor, the hydrothermal aging time of regulating catalyst precursor in reactor.
According to Ni-Mg/Al of the present invention
2O
3The preparation method of catalyst, described step 2) in autoclave, reaction temperature is 100-220 ℃, and the reaction time is 4-24 hour, and reaction pressure equals the saturated vapor pressure of catalyst precursor under reaction temperature.
Reaction temperature raises and is conducive to the desolventizing of growth unit at plane of crystal, and diffusion into the surface etc. promote crystal growth and transformation of crystal; Reaction time is the kinetic factor of hydro-thermal reaction, has reflected the speed of hydro-thermal reaction.Along with the rising of hydrothermal temperature and the prolongation in reaction time, intergranule interacts, and some crystallite sizes reduce even to disappear, and some crystallite sizes increase, the macroscopic view result is when reaction time one timing, hydrothermal temperature is higher, and crystallite size is larger, and particle size distribution is wider, reaction temperature one regularly, along with the hydro-thermal reaction time lengthening, crystallite size increases, and particle size distribution strengthens.By optimizing, the preferred hydrothermal temperature of the present invention is 100-220 ℃, and the reaction time is 4-24 hour.
According to Ni-Mg/Al of the present invention
2O
3The preparation method of catalyst, is characterized in that, the dried product of step 3) formed catalyst at 500-800 ℃ of roasting 4-10 hour.One of characteristics of the present invention be exactly by soda acid match-spinelle that the hydro-thermal composite algorithm obtains to have high-temperature stability is as catalyst carrier, roasting process is the important step that guarantees this type of high-temperature stable compound generation.Sintering temperature is too high, will cause in catalyst this kind compound content too high, causes the catalyst activity bit quantity to reduce, later stage reduction difficulty, and sintering temperature is lower, is unfavorable for that this type of high-temperature stable compound generates.So preferred sintering temperature of the present invention is 500-800 ℃.
Use Ni-Mg/Al of the present invention
2O
3The catalyst that the preparation method of catalyst prepares, be applicable to the HTHP methanation of coal gasification gained synthesis gas; This catalyst has good catalytic activity and stability in the scope of application of 350-650 ℃.
The present invention provides a kind of simple and convenient process for preparing of good catalyst for the methanation of carbon monoxide, especially for the synthesis gas methanation provide a kind of cheapness, efficiently, the preparation method of the catalyst of high hydrothermal stability.
Ni-Mg/Al provided by the invention
2O
3The preparation method of catalyst, its advantage are that catalyst preparation process is simple and easy to control, good reproducibility, and cost is cheap, and is low for equipment requirements.
Description of drawings
Fig. 1 is Ni-Mg/Al of the present invention
2O
3The preparation method's of catalyst simple process figure.
Fig. 2 is the methanation activity comparison diagram of the embodiment of the present invention 1 gained catalyst A and comparative example 1 gained catalyst C.
Fig. 3 is the methanation activity comparison diagram of the embodiment of the present invention 2 gained catalyst B and comparative example 2 gained catalyst D.
Fig. 4 is the TEM(transmission electron microscope of the embodiment of the present invention 2 gained catalyst B) figure.
Fig. 5 is the methanation activity comparison diagram of the embodiment of the present invention 4 gained catalyst E, F, G, H.
Fig. 6 is under high pressure stable operation performance map of the embodiment of the present invention 2 gained catalyst B.
Fig. 7 is under high pressure thermally-stabilised performance charts of the embodiment of the present invention 2 gained catalyst B.
The specific embodiment
The present invention is described in further detail to prepare the specific embodiment below in conjunction with catalyst, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.In following each embodiment, the gas percentage composition that relates to is molar percentage.
(1) preparation of solution I: take 3.965g Ni (NO
3)
26H
2O, 19.295g Mg (NO
3)
26H
2O, 29.846g Al (NO
3)
39H
2O, add the 200mL deionized water dissolving;
(2) preparation of solution II: take 29.298g NaAlO
2, add the 200mL deionized water dissolving;
(3) solution I and solution II subtend in precipitation reactor is clashed into and is reacted, and precipitation temperature is 40 ℃, and the pH value is 8;
(4) the catalyst precursor hydrothermal treatment consists and aging in high-pressure reactor after the precipitation, 220 ℃ of hydrothermal temperatures, keep reaction 4 hours;
(5) filtering precipitate, deionized water wash to neutrality and use the 500mL washed twice again; After dry, sample is at N
2Under atmosphere, 500 ℃ of roastings formed catalyst in 4 hours.The gained catalyst consists of 5%NiO-15%MgO-80%Al
2O
3, the catalyst after roasting is ground fragmentation, get 20-40 purpose powder and carry out activity rating.
Activity rating adopts the quartz ampoule fixed bed reactors of Φ 16mm, and loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 12000NmLg
-1H
-1, operating pressure is normal pressure, and reaction temperature is 350-650 ℃, and it the results are shown in Figure 2.
(1) preparation of solution I: take 15.8476g Ni (NO
3)
26H
2O, 19.2774gMg (NO
3)
26H
2O, 16.1042g Al (NO
3)
39H
2O, add the 300mL deionized water dissolving;
(2) preparation of solution II: take 26.4228g NaAlO
2, add the 200mL deionized water dissolving;
(3) solution I and solution II subtend in precipitation reactor is clashed into and is reacted, and precipitation temperature is 90 ℃, and the pH value is 12;
(4) the catalyst precursor hydrothermal treatment consists and aging in high-pressure reactor after the precipitation, 220 ℃ of hydrothermal temperatures, keep reaction 4 hours;
(5) filtering precipitate, deionized water wash to neutrality and use the 500mL washed twice again; After dry, sample is placed in Muffle furnace, and 500 ℃ of lower roastings formed catalyst in 10 hours.The gained catalyst consists of 20%NiO-15%MgO-65%Al
2O
3, the catalyst after roasting is ground fragmentation, get 20-40 purpose powder and carry out activity rating.
Activity rating adopts the quartz ampoule fixed bed reactors of Φ 16mm, and loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 12000NmLg
-1H
-1, operating pressure is normal pressure, and reaction temperature is 350-650 ℃, and it the results are shown in Figure 3.
With particle diameter be powder below 100 orders with ultrasonic dispersion after, with JEM-2100 type transmission electron microscope, catalyst B is carried out surface analysis, the results are shown in Figure 4, wherein the average grain diameter of NiO is 15nm.
The estimation of stability of catalyst B: under (1) high pressure, adopt the stainless steel fixed bed reactors of Φ 12mm, loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 780mLg
-1H
-1, reaction temperature is 500 ℃, and reaction pressure is 2.5MPa, and the reaction time is 20 hours, and it the results are shown in Figure 6.The catalyst B Evaluation of Thermal Stability: adopt the stainless steel fixed bed reactors of Φ 12mm, loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 780mLg
-1H
-1, catalyst is reacted 6h under 650 ℃, the activity of catalyst in the time of 350-650 ℃ before and after relatively reacting, it the results are shown in Figure 7.
Comparative example 1 Kaolinite Preparation of Catalyst C
(1) preparation of solution I: take 3.965g Ni (NO
3)
26H
2O, 19.295g Mg (NO
3)
26H
2O, 29.846g Al (NO
3)
39H
2O, add the 200mL deionized water dissolving;
(2) preparation of solution II: take 29.298g NaAlO
2, add the 200mL deionized water dissolving;
(3) solution I and solution II adopt coprecipitation to react in precipitation reactor, and precipitation temperature is 40 ℃, and the pH value is 8, keep 4 hours after precipitation finishes;
(4) filtering precipitate, deionized water wash to neutrality and use the 500mL washed twice again; After dry, sample is at N
2Under atmosphere, 500 ℃ of roastings formed catalyst in 4 hours.
The gained catalyst consists of 5%NiO-15%MgO-80%Al
2O
3, the catalyst after roasting is ground fragmentation, get 20-40 purpose powder and carry out activity rating.
Activity rating adopts the quartz ampoule fixed bed reactors of Φ 16mm, and loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 12000NmLg
-1H
-1, operating pressure is normal pressure, and reaction temperature is 350-650 ℃, and it the results are shown in Figure 2.
Comparative example 2 Kaolinite Preparation of Catalyst D
(1) preparation of solution I: take 15.8476g Ni (NO
3)
26H
2O, 19.2774gMg (NO
3)
26H
2O, 16.1042g Al (NO
3)
39H
2O, add the 300mL deionized water dissolving;
(2) preparation of solution II: take 26.4228g NaAlO
2, add the 200mL deionized water dissolving;
(3) solution I and solution II adopt coprecipitation to react in precipitation reactor, and precipitation temperature is 90 ℃, and the pH value is 12, keep 6 hours after precipitation finishes;
(4) filtering precipitate, deionized water wash to neutrality and use the 500mL washed twice again; After dry, sample is placed in Muffle furnace, and 500 ℃ of lower roastings formed catalyst in 10 hours.
The gained catalyst consists of 20%NiO-15%MgO-65%Al
2O
3, the catalyst after roasting is ground fragmentation, get 20-40 purpose powder and carry out activity rating.
Activity rating adopts the quartz ampoule fixed bed reactors of Φ 16mm, and loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 12000NmLg
-1H
-1, operating pressure is normal pressure, and reaction temperature is 350-650 ℃, and it the results are shown in Figure 3.
(1) preparation of solution I: take 23.771g Ni (NO
3)
26H
2O, 12.852g Mg (NO
3)
26H
2O, 11.149g Al (NO
3)
39H
2O, add the 200mL deionized water dissolving;
(2) preparation of solution II: take 25.610g NaAlO
2, add the 200mL deionized water dissolving;
(3) solution I and solution II subtend in precipitation reactor is clashed into and is reacted, and precipitation temperature is 40 ℃, and the pH value is 10;
(4) the catalyst precursor hydrothermal treatment consists and aging in high-pressure reactor after the precipitation, 100 ℃ of hydrothermal temperatures, keep reaction 24 hours;
(5) filtering precipitate, deionized water wash to neutrality and use the 500mL washed twice again; After dry, sample is divided into four parts, is placed in respectively Muffle furnace, and 500,600,700,800 ℃ of lower roastings formed catalyst in 4 hours.The gained catalyst consists of 30%NiO-10%MgO-60%Al
2O
3, the catalyst after roasting is ground fragmentation, get 20-40 purpose powder and carry out activity rating.
Activity rating adopts the quartz ampoule fixed bed reactors of Φ 16mm, and loaded catalyst 1.5g, use H
2Reduction is 4 hours under 500 ℃; The unstripped gas proportioning is H
2: CO: N
2=3: 1: 1, reaction velocity was 12000NmLg
-1H
-1, operating pressure is normal pressure, and reaction temperature is 450-650 ℃, and it the results are shown in Figure 5.
The explanation of embodiment experimental result:
Can be found out the Ni-Mg/Al that the present invention adopts soda acid pairing-hydro-thermal composite algorithm to make by Fig. 2 and Fig. 3
2O
3No matter catalyst (embodiment 1,2), be high-activity component content or low activity constituent content, and catalyst all demonstrates than the high methanation activity of coprecipitation (comparative example 1,2).
As seen from Figure 5, the present invention adopts the Ni-Mg/Al that soda acid pairing-hydro-thermal composite algorithm makes
2O
3Catalyst all can keep higher methanation activity when sintering temperature is 500,600,700,800 ℃, in the experimental temperature scope, 500 ℃ of lower calcined catalysts demonstrate high CH simultaneously
4Selectively, near the thermodynamical equilibrium under experiment condition.
As seen from Figure 6, the present invention adopts the Ni-Mg/Al that soda acid pairing-hydro-thermal composite algorithm makes
2O
3Catalyst can be kept certain activity under reaction condition, stability is better, and near the thermodynamic equilibria of experiment condition.
As seen from Figure 7, the present invention adopts the Ni-Mg/Al that soda acid pairing-hydro-thermal composite algorithm makes
2O
3The thermal stability of catalyst is good.
The result of above related experiment shows, the catalyst that employing soda acid pairing-hydro-thermal composite algorithm provided by the present invention makes has advantages of that catalytic activity is good and stability is high, is a kind of with low cost, synthesis gas methanation catalyst that performance has actual application prospect.
Claims (6)
1. Ni-Mg/Al
2O
3The preparation method of catalyst said method comprising the steps of:
1) prepare acid solution I, alkaline solution II, wherein acid solution I comprises the corresponding metal cation raw material of active component raw material, auxiliary agent raw material and carrier, the alkaline solution II comprises the corresponding anion raw material of carrier, two kinds of solution mix the generation precipitation reaction, form the alkaline reaction environment of pH value more than 8, generate catalyst precursor;
2) catalyst precursor that step 1) is obtained moves in autoclave and carries out hydrothermal treatment consists and aging, obtains catalyst pulp;
3) with step 2) catalyst pulp that obtains forms catalyst through washing, filtration, dry roasting.
2. Ni-Mg/Al according to claim 1
2O
3The preparation method of catalyst, is characterized in that, the reaction temperature of step 1) is 40-90 ℃, and two kinds of solution clash into precipitation reaction occurs by subtend.
3. Ni-Mg/Al according to claim 1
2O
3The preparation method of catalyst, is characterized in that step 2) the autoclave reaction temperature be 100-220 ℃, the reaction time is 4-24 hour, reaction pressure is the saturated vapor pressure of catalyst precursor under reaction temperature.
4. Ni-Mg/Al according to claim 1
2O
3The preparation method of catalyst, is characterized in that, step 3) sintering temperature 500-800 ℃, roasting time 4-10 hour.
5. Ni-Mg/Al according to claim 1
2O
3The preparation method of catalyst, is characterized in that, the nitrate solution that the nitrate that described acid solution I is nickel, magnesium, aluminium or oxalates, carbonate and carbonate form through nitric acid dissolve.
6. Ni-Mg/Al according to claim 1
2O
3The preparation method of catalyst, is characterized in that, described alkaline solution II is NaAlO
2Solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879854A (en) * | 2014-12-31 | 2016-08-24 | 神华集团有限责任公司 | Sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN114345357A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of isothermal methanation catalyst |
| CN114377679A (en) * | 2022-01-26 | 2022-04-22 | 中国科学院上海高等研究院 | Carbon dioxide capturing and converting integrated bifunctional catalyst, preparation method and application |
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2012
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879854A (en) * | 2014-12-31 | 2016-08-24 | 神华集团有限责任公司 | Sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN105879854B (en) * | 2014-12-31 | 2019-03-22 | 神华集团有限责任公司 | A kind of catalyst for methanation in presence of sulfur and its preparation method and application |
| CN114345357A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of isothermal methanation catalyst |
| CN114345357B (en) * | 2020-10-13 | 2024-05-17 | 中石化南京化工研究院有限公司 | Preparation method of isothermal methanation catalyst |
| CN114377679A (en) * | 2022-01-26 | 2022-04-22 | 中国科学院上海高等研究院 | Carbon dioxide capturing and converting integrated bifunctional catalyst, preparation method and application |
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| Publication number | Publication date |
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| CN103386307B (en) | 2015-05-20 |
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