CN105561998A - Methane dry reforming catalyst, preparation method and use of methane dry reforming catalyst and method for preparing synthetic gas through methane dry reforming - Google Patents
Methane dry reforming catalyst, preparation method and use of methane dry reforming catalyst and method for preparing synthetic gas through methane dry reforming Download PDFInfo
- Publication number
- CN105561998A CN105561998A CN201410541805.7A CN201410541805A CN105561998A CN 105561998 A CN105561998 A CN 105561998A CN 201410541805 A CN201410541805 A CN 201410541805A CN 105561998 A CN105561998 A CN 105561998A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methane
- active constituent
- preparation
- metal active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a methane dry reforming catalyst and a preparation method thereof. The preparation method comprises immersion of a carrier in an immersion solution, drying and roasting. The immersion solution contains a soluble compound of a metal active ingredient and a surfactant. The catalyst active metal crystal grains have small sizes and high dispersity. The preparation method has simple processes, a low equipment investment and low energy consumption. Compared with the same type of the existing catalyst, the catalyst obtained through the preparation method has higher catalytic reaction activity and better carbon deposition resistance and lays a foundation for the industrial application of methane dry reforming preparation of synthetic gas.
Description
Technical field
The present invention relates to the method for the whole Catalysts and its preparation method of a kind of methane dry weight and application and the dry preparing synthetic gas by reforming of methane.
Background technology
Along with the increase gradually of world energy sources consumption figure, CO
2, NO
x, the environmental contaminants such as dust particles discharge capacity also increase year by year, particularly CO
2isothermal chamber gas purging causes global climate sharply to worsen, and causes great threat to the living environment of the mankind.International Energy Agency (IEA) " world energy outlook in 2007 " statistics shows, and within 2005, the whole world is by consuming the CO of oil, natural gas and coal and the discharge of emptying gas-firing
2total amount reaches 270 × l0
8ton.Wherein the U.S., China, Russia, Japan and India are 5 maximum CO
2discharge state, accounts for world CO
250% of total emission volumn.And global CO in 2011
2total emission volumn reaches 316 × l0
8ton.Estimate the further growth along with energy-consuming, to the year two thousand thirty CO
2total emission volumn will reach 420 × l0
8ton.
Worsening for alleviating the global climate caused by greenhouse gases excessive emissions, on February 16th, 2005, being intended to limit CO
2and the Kyoto Protocol of other greenhouse gas emissions is formally effective, its require developed country within the commitment period of 2008 to 2012 years greenhouse gas emission (with CO
2work as gauge) at least reduce 5% than the level of nineteen ninety.Although legally binding agreement is not reached in Copenhagen global climate summit that 7-18 day in December, 2009 holds, but finally deliver " Copenhagen agreement " with the form of conference resolution, specify that developed country and developing country are according to " common but distinguishing responsibility " reduction of greenhouse gas discharge obligation that principle should be born respectively and the action taked further, Main Countries all discloses new emission reduction targets.Chinese Government it is also proposed oneself emission reduction targets, the i.e. CO of per GDP
2reduce discharging 40%-50% (with 2005 for benchmark).As can be seen here, CO is cut down
2discharge capacity, alleviates the extensive common recognition that greenhouse effects impact has become international community.
In addition, gas reserves enriches, and is the ideal substitute of oil, along with the rise of oil price and growing with each passing day of energy demand, how to utilize natural gas to become hot issue.
Utilize methane and CO
2it is methane and a CO having great potential application foreground that synthesis gas (methane dry weight is whole) is prepared in reaction
2utilization ways, its product synthesis gas is suitable as the raw material of the industrial process such as F-T synthesis long chain hydrocarbon, ammonia synthesis, alkylated reaction, methanol-fueled CLC very much, can realize CO
2twice laid, turn waste into wealth, more the efficiency utilization of methane provides an effective way.Therefore; if the commercial applications of this technique can be realized; not only for alleviating energy crisis; the production process and the raw material route that change some chemical products are of great immediate significance; and for reducing the discharge of greenhouse gases, what alleviate that " greenhouse effects " cause has profound historical significance to the destruction of global ecological environment.
Although methane does the research progress that reforming reaction have passed through last 100 years, but this technical process fails to realize industrial applications so far, trace it to its cause, the sintering of catalyst under pyroreaction condition and carbon deposit are that this technical process of restriction realizes industrialized topmost obstacle, and particularly the carbon deposit of catalyst seems particularly outstanding under an increased pressure.Therefore, the dry reforming catalyst of methane of exploitation high activity, high stability remains the key of this area research at present.
Summary of the invention
The object of this invention is to provide the method for the whole Catalysts and its preparation method of methane dry weight that a kind of catalytic activity and coking resistivity improve greatly and application and the dry preparing synthetic gas by reforming of methane.
The invention provides the dry reforming catalyst of a kind of methane, this catalyst contains carrier and load metal active constituent on this carrier, it is characterized in that, by H
2the metal active constituent decentralization of this catalyst that chemiadsorption records is 3-20%.
Present invention also offers the preparation method of the dry reforming catalyst of a kind of methane, the method comprises floods carrier maceration extract, then dry, roasting, and it is characterized in that, described maceration extract contains soluble compound and the surfactant of metal active constituent.
Present invention also offers the dry reforming catalyst of the methane obtained by above-mentioned preparation method.
Present invention also offers the dry reforming catalyst of above-mentioned methane in the whole application prepared in synthesis gas of methane dry weight.
Present invention also offers the method for the dry preparing synthetic gas by reforming of a kind of methane, the method under the dry preparing synthetic gas by reforming condition of methane, makes methane and CO under being included in the dry reforming catalyst existence of above-mentioned methane
2contact.
The dry reforming catalyst of methane that the preparation method of the dry reforming catalyst of methane provided by the invention obtains has the decentralization of the active metal significantly improved, thus catalytic activity and coking resistivity substantially increase, the commercial Application preparing synthesis gas process for methane dry weight is whole lays the foundation.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Graph of a relation between the methane conversion of Fig. 1 when to be the obtained catalyst of the obtained catalyst of the embodiment of the present invention 1 and comparative example 1 do reforming reaction for methane under the differential responses time.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the dry reforming catalyst of a kind of methane, this catalyst contains carrier and load metal active constituent on this carrier, wherein, by H
2the metal active constituent decentralization of this catalyst that chemiadsorption records is 3-20%.
In the present invention, metal active constituent decentralization is by H
2chemiadsorption adopts Micromeritics (ASAP-2010C) chemical adsorption instrument to measure.Concrete, by 0.2g sample first through 300 DEG C of degassed process 1 hour, be then warming up to 700 DEG C of reductase 12s hour, then be cooled to 40 DEG C and carry out H
2chemisorbed operates.Afterwards according to chemisorbed H
2amount by following formulae discovery metal active constituent decentralization and metal active constituent mean particle size.
Metal active constituent decentralization D:
Metal active constituent mean particle size d:
Wherein V
adrefer to H under standard state
2monolayer adsorption amount, unit is mL; W
sbe sample quality, unit is g; FW
mebe the molal weight of metal active constituent, unit is g/mol; F
mebe the load capacity of metal active constituent in catalyst, unit is % by weight; V
mbe the moles of gas volume under index state, unit is mL/mol; SA
mebe the specific area of metal active constituent, unit is m
2/ g
cat; ρ
mebe the density of metal active constituent, unit is g/cm
3.
The computational methods of above-mentioned metal active constituent decentralization and metallic particles average grain diameter are applicable to the calculating to various metal active constituent.Such as, for nickel,
The decentralization D of nickel:
The mean particle size d of nickel:
For bimetallic component or many metal components, average molar mass can be calculated as FW according to inventory
me, ρ
nithe averag density of metal active constituent, F
methe total load amount of metal active constituent in catalyst, SA
meit is total specific area of metal active constituent.
Under preferable case, the metal active constituent decentralization of this catalyst is 4-16%.And the metal active constituent decentralization of existing similar catalyst is less than 2% usually, much smaller than decentralization of the present invention.
Under further preferable case, the metal active constituent mean particle size d of this catalyst is 1-25nm, is more preferably 5-20nm.And the metal active constituent mean particle size of existing similar catalyst is greater than 30nm usually, much larger than metal active constituent mean particle size of the present invention.
The dry reforming catalyst of methane according to the present invention, under preferable case, with the total amount of catalyst for benchmark, with the content of the described metal active constituent of elemental metal for 2-20 % by weight, be more preferably 3-15 % by weight, further be preferably 4-12 % by weight, surplus is carrier or is carrier and optional auxiliary agent.
The dry reforming catalyst of methane according to the present invention, described metal active constituent can be the various active metal components that can be applicable to the dry reforming catalyst of methane, described metal active constituent include but not limited in Cu, Fe, Co, Ni, Ru, Rh, Ir and Pt one or more, be preferably Co, Ni, Pt, Cu-Ni, Co-Ni or Ni-Pt, more preferably Co, Ni or Co-Ni.
The single component oxide carrier that described carrier can be applicable to the dry reforming catalyst of methane for various and/or bi-component or three components composite oxide carrier, described single component oxide carrier can be such as SiO
2, TiO
2, MgO, Al
2o
3, ZrO
2, CeO
2, La
2o
3in one or more, described bi-component or three components composite oxide carrier can be such as SiO
2-Al
2o
3, TiO
2-SiO
2, Al
2o
3-ZrO
2and TiO
2-SiO
2-Al
2o
3in one or more.Described carrier is preferably TiO
2, MgO, Al
2o
3, ZrO
2and Al
2o
3-ZrO
2in one or more, more preferably TiO
2, MgO and Al
2o
3in one or more.
The shape of described carrier can be powdery, cylindrical, spherical, clover, bunge bedstraw herb, dish, Raschig ring etc., is preferably bunge bedstraw herb and Raschig ring shape.
Present invention also offers the preparation method of the dry reforming catalyst of a kind of methane, the method comprises floods carrier maceration extract, then dry, roasting, and it is characterized in that, described maceration extract contains soluble compound and the surfactant of metal active constituent.
According to the present invention, although add a small amount of surfactant can realize object of the present invention, under preferable case, in described maceration extract, the mol ratio of described surfactant and metallic atom is 0.01 ~ 2, is more preferably 0.05 ~ 1, more preferably 0.1 ~ 0.5.
Described surfactant can be one or more in anionic surfactant, amphoteric surfactant and nonionic surface active agent.Under further preferable case, described surfactant is one or more in stearic acid, oleic acid, laurate, lecithin, dodecyl alanine, alkyl dimethyl betaine, fatty glyceride, polyalcohol, tween and P123.
The present inventor studies discovery, use P123 as surfactant of the present invention time, catalytic activity and the coking resistivity of catalyst improve greatly, therefore the present invention particularly preferably described surfactant be P123.
According to the present invention, in described maceration extract, with elemental metal, the concentration of the soluble compound of metal active constituent is 10-195 grams per liter, more preferably 14.6-191.6 grams per liter, the consumption of carrier to make in gained catalyst with the total amount of catalyst, for benchmark, with the content of the described metal active constituent of elemental metal for 2-20 % by weight, to be preferably 3-15 % by weight.
According to the present invention, the soluble compound of described metal active constituent can be the various soluble compounds of metal active constituent, the soluble compound of preferred described metal active constituent is water soluble salt and the hydrate thereof of metal active constituent, as nitrate and/or chloride and hydrate thereof.Under preferable case, the soluble compound of described metal active constituent is Cu (NO
3)
26H
2o, Co (NO
3)
26H
2o, Ni (NO
3)
26H
2o, Fe (NO
3)
39H
2o, (NH
4)
2ptCl
6, RhCl
33H
2o and H
2irCl
66H
2one or more in O, are more preferably Co (NO
3)
26H
2o and/or Ni (NO
3)
26H
2o.
The solvent of maceration extract is preferably water, is more preferably deionized water.
The single component oxide carrier that described carrier can be applicable to the dry reforming catalyst of methane for various and/or bi-component or three components composite oxide carrier, described single component oxide carrier can be such as SiO
2, TiO
2, MgO, Al
2o
3, ZrO
2, CeO
2, La
2o
3in one or more, described bi-component or three components composite oxide carrier can be such as SiO
2-Al
2o
3, TiO
2-SiO
2, Al
2o
3-ZrO
2and TiO
2-SiO
2-Al
2o
3in one or more.Described carrier is preferably TiO
2, MgO, Al
2o
3, ZrO
2and Al
2o
3-ZrO
2in one or more, more preferably TiO
2, MgO and Al
2o
3in one or more.
The shape of described carrier can be powdery, cylindrical, spherical, clover, bunge bedstraw herb, dish, Raschig ring etc., is preferably bunge bedstraw herb and Raschig ring shape.
According to the present invention, the method for dipping and condition can be carried out with reference to prior art, such as, can be incipient impregnation, also can be supersaturation dippings.Dipping can carry out at 10-80 DEG C.
The temperature of described drying can be 80 ~ 140 DEG C, is preferably 100-120 DEG C; Time can be 1 ~ 10 hour, is preferably 5-10 hour.
The temperature of described roasting can be 400 ~ 1000 DEG C, is preferably 500-800 DEG C; Time can be 1 ~ 10 hour, is preferably 2-6 hour.
Compared with prior art, its advantage is the preparation method of the dry reforming catalyst of methane provided by the invention:
1, the surface tension of water is reduced by adding surfactant in dipping solution, be conducive to maceration extract sprawling at carrier surface, thus be conducive to the dispersion of metal active constituent at carrier surface, finally make metal active constituent in prepared catalyst have higher decentralization and less crystallite dimension.
2, adopt infusion process preparation, preparation method is simple, and preparation condition is easy to accurate control, and the repeatability of catalyst is fine.
3, adopt infusion process preparation, therefore maintain the mechanical strength of carrier, no matter in a fluidized bed reactor, or in fixed bed reactors, all there is very high activity and stability.
Present invention also offers the dry reforming catalyst of the methane obtained by above-mentioned preparation method and in the whole application prepared in synthesis gas of methane dry weight.
According to catalyst prepared by method provided by the invention, needed in presence of hydrogen, active metal to be carried out reduction activation before doing reforming reaction for methane, reducing condition is: reduction temperature is 300 ~ 800 DEG C, be preferably 400 ~ 750 DEG C, more preferably 550 ~ 700 DEG C; Recovery time is 0.5 ~ 10 hour, be preferably 1 ~ 5 hour, more preferably 2 ~ 4 hours, described reduction can be carried out in pure hydrogen, also can carry out in the gaseous mixture of hydrogen and inert gas, as carried out in the gaseous mixture of hydrogen and nitrogen and/or argon gas, Hydrogen Vapor Pressure is 0.1 ~ 2MPa, is preferably 0.1 ~ 1MPa.
Present invention also offers the method for the dry preparing synthetic gas by reforming of a kind of methane, the method under the dry preparing synthetic gas by reforming condition of methane, makes methane and CO under being included in the dry reforming catalyst existence of above-mentioned methane
2contact.
Described contact can be carried out in fixed bed reactors or fluidized-bed reactor.Wherein, powder catalyst particle is suitable for adopting fluidized-bed reactor, and the larger preformed catalyst of other particle size is suitable for adopting fixed bed reactors.
The present inventor also finds, by by catalyst and mixing diluents, can significantly improve the conversion ratio of methane and carbon dioxide.Therefore the preferred described contact of the present invention is also carried out in the presence of a diluent, and respectively in g and ml, the w/v of described loaded catalyst and diluent is 1:10-30.
Described diluent can be the various solid particles without catalytic activity, such as, can be quartz sand.
The condition of contact comprises by volume, CH
4/ CO
2=0.7 ~ 1.1, be preferably 0.8 ~ 1.0, reaction temperature is 550-850 DEG C, and be preferably 600 ~ 800 DEG C, be more preferably 700-800 DEG C, pressure (gauge pressure) is 0 ~ 3MPa, and be preferably 0 ~ 1MPa, unstripped gas air speed is 2000 ~ 120000mlg
-1h
-1, be preferably 10000 ~ 60000mlg
-1h
-1.
The present invention is described further for the following examples.In following examples, the consumption of metal active constituent compound all refers to the consumption of wherein metal active constituent and metallic element.
Embodiment 1
(1) catalyst preparing
By the Ni (NO of 1.765g
3)
26H
2o is dissolved in 5.6ml deionized water and obtains nickel nitrate solution, until molten clear after add the P123 of 0.34g, mix and obtain maceration extract.Get the Al of 4g
2o
3support dispersion is in maceration extract, and leave standstill process after 2 hours, evaporating water, is then placed in baking oven 120 DEG C of dryings 10 hours.Dried sample is placed in Muffle furnace 600 DEG C of roastings 3 hours, and gained catalyst is designated as NiO/Al
2o
3-1, be 8 % by weight with the content of the described metal active constituent of elemental metal.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 14.4%, and the average grain diameter of metal active constituent is 7.0nm.
(2) evaluating catalyst
Take above-mentioned NiO/Al
2o
3-1 catalyst 0.1g, is diluted to 2ml with 40 ~ 60 order quartz sands, and load in the quartz tube reactor of internal diameter φ 8, under normal pressure, in pure hydrogen atmosphere, 700 DEG C of reduction activate for 3 hours.After reduction terminates, be warming up to 750 DEG C in a hydrogen atmosphere, switch unstripped gas (CH
4/ CO
2=1/1 volume) react, reaction velocity is 60000mlg
-1h
-1, reaction pressure is normal pressure.After stable reaction carries out 10 hours, analyzed tail gas formed by gas-chromatography on-line period.Calculate: X
cH4=86.6%, X
cO2=87.4%, H
2/ CO=1.03.
Comparative example 1
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference does not add any surfactant in maceration extract, and gained catalyst is designated as NiO/Al
2o
3-D1.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 1.7%, and the average grain diameter of metal active constituent is 60.0nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=72.6%,X
CO2=73.3%,H
2/CO=1.02。
The result of methane conversion embodiment 1 and comparative example 1 catalyst obtained under the differential responses time is plotted in Fig. 1.As seen in Figure 1, embodiment 1 gained catalyst has higher catalytic reaction activity and stability (anti-carbon performance).
Embodiment 2
(1) catalyst preparing
By the Co (NO of 1.75g
3)
26H
2o is dissolved in 4ml deionized water and obtains cobalt nitrate aqueous solution, until molten clear after add the P123 of 0.33g, mix and obtain maceration extract.All the other steps are with the preparation method of corresponding catalyst in embodiment 1, and gained catalyst is designated as Co
3o
4/ Al
2o
3, be 8 % by weight with the content of the described metal active constituent of elemental metal.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 13.9%, and the average grain diameter of metal active constituent is 7.2nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=84.4%,X
CO2=86.2%,H
2/CO=1.03。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=83.9%,X
CO2=86.0%,H
2/CO=1.01。
Embodiment 3
(1) catalyst preparing
By the Ni (NO of 0.873g
3)
26H
2co (the NO of O and 0.872g
3)
26H
2o is dissolved in the mixed aqueous solution obtaining nickel nitrate and cobalt nitrate in 4ml deionized water, until molten clear after add the P123 of 0.34g, mix and obtain maceration extract.All the other steps are with the preparation method of corresponding catalyst in embodiment 1, and gained catalyst is designated as Ni-Co/Al
2o
3, be 8 % by weight with the content of the described metal active constituent of elemental metal.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 15.6%, and the average grain diameter of metal active constituent is 6.4nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=91.6%,X
CO2=92.1%,H
2/CO=1.05。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=91.4%,X
CO2=91.7%,H
2/CO=1.03。
Embodiment 4
(1) catalyst preparing
By the Ni (NO of 2.81g
3)
26H
2o is dissolved in 4ml deionized water and obtains nickel nitrate aqueous solution, until molten clear after add the P123 of 0.55g, mix and obtain maceration extract.All the other steps are with the preparation method of corresponding catalyst in embodiment 1, and gained catalyst is designated as NiO/Al
2o
3-2, be 12 % by weight with the content of the described metal active constituent of elemental metal.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 12.1%, and the average grain diameter of metal active constituent is 8.3nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=88.5%,X
CO2=90.3%,H
2/CO=1.02。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=87.6%,X
CO2=88.5%,H
2/CO=1.01。
Embodiment 5
(1) catalyst preparing
According to method Kaolinite Preparation of Catalyst in the same manner as in Example 1, difference is that carrier selects MgO, and gained catalyst is designated as NiO/MgO.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 4.4%, and the average grain diameter of metal active constituent is 22.9nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=81.3%,X
CO2=81.7%,H
2/CO=1.03。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=78.6%,X
CO2=79.4%,H
2/CO=1.01。
Embodiment 6
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is that oleic acid selected by surfactant, and gained catalyst is designated as NiO/Al
2o
3-3.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 10.3%, and the average grain diameter of metal active constituent is 9.9nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=82.3%,X
CO2=83.7%,H
2/CO=1.01。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=81.8%,X
CO2=82.4%,H
2/CO=1.03。
Embodiment 7
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is that polysorbate60 selected by surfactant, and gained catalyst is designated as NiO/Al
2o
3-4.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 11.7%, and the average grain diameter of metal active constituent is 8.5nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=82.4%,X
CO2=83.9%,H
2/CO=1.01。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=82.0%,X
CO2=82.9%,H
2/CO=1.0。
Embodiment 8
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is the mol ratio of surfactant and metallic atom is 0.4, and gained catalyst is designated as NiO/Al
2o
3-5.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 9.7%, and the average grain diameter of metal active constituent is 10.3nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=85.1%,X
CO2=86.6%,H
2/CO=1.03。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=83.4%,X
CO2=84.1%,H
2/CO=1.02。
Embodiment 9
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is the sintering temperature of catalyst is 700 DEG C, and gained catalyst is designated as NiO/Al
2o
3-6.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 7.6%, and the average grain diameter of metal active constituent is 13.3nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=78.4%,X
CO2=80.1%,H
2/CO=1.0。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=78.0%,X
CO2=80.0%,H
2/CO=1.03。
Embodiment 10
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is the roasting time of catalyst is 5 hours, and gained catalyst is designated as NiO/Al
2o
3-7.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 12.2%, and the average grain diameter of metal active constituent is 8.2nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=82.4%,X
CO2=83.7%,H
2/CO=1.02。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=82.2%,X
CO2=83.4%,H
2/CO=1.03。
Embodiment 11
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is that lecithin selected by surfactant, and gained catalyst is designated as NiO/Al
2o
3-8.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 10.2%, and the average grain diameter of metal active constituent is 9.8nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=82.7%,X
CO2=83.4%,H
2/CO=1.02。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=81.5%,X
CO2=82.1%,H
2/CO=1.03。
Embodiment 12
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1, difference is that softex kw selected by surfactant, and gained catalyst is designated as NiO/Al
2o
3-9.In this catalyst recorded by hydrogen chemisorption method, metal active constituent decentralization is 6.4%, and the average grain diameter of metal active constituent is 15.6nm.
(2) evaluating catalyst
Activating catalyst carry out methane and do reforming reaction under the same conditions as example 1, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=76.5%,X
CO2=78.1%,H
2/CO=1.02。
The reaction result that stable reaction was carried out after 120 hours is as follows:
X
CH4=73.2%,X
CO2=75.4%,H
2/CO=1.01。
Embodiment 13
(1) catalyst preparing
According to the method Kaolinite Preparation of Catalyst in embodiment 1.
(2) evaluating catalyst
According to the method for embodiment 1 catalyst activated and carry out methane and do reforming reaction, unlike, do not load 40 ~ 60 order quartz sands in quartz tube reactor as diluent, the reaction result that stable reaction was carried out after 10 hours is as follows:
X
CH4=82.1%,X
CO2=80.6%,H
2/CO=1.03。
The reaction result that stable reaction was carried out after 100 hours is as follows:
X
CH4=78.6%,X
CO2=76.5%,H
2/CO=1.02。
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. the dry reforming catalyst of methane, this catalyst contains carrier and load metal active constituent on this carrier, it is characterized in that, by H
2the metal active constituent decentralization of this catalyst that chemiadsorption records is 3-20%.
2. the dry reforming catalyst of methane according to claim 1, wherein, by H
2the metal active constituent mean particle size of this catalyst that chemiadsorption records is 1-30nm.
3. the dry reforming catalyst of methane according to claim 1 and 2, wherein, with the total amount of catalyst for benchmark, with the content of the described metal active constituent of elemental metal for 2-20 % by weight.
4. the dry reforming catalyst of methane according to claim 1 or 2 or 3, wherein, described metal active constituent is one or more in Fe, Co, Ni, Ru, Rh, Ir and Pt, described carrier is single component oxide carrier and/or bi-component or three components composite oxide carrier, and described single component oxide carrier is SiO
2, TiO
2, MgO, Al
2o
3, ZrO
2, CeO
2, La
2o
3in one or more, described bi-component or three components composite oxide carrier are SiO
2-Al
2o
3, TiO
2-SiO
2, Al
2o
3-ZrO
2and TiO
2-SiO
2-Al
2o
3in one or more.
5. a preparation method for the dry reforming catalyst of methane, the method comprises floods carrier maceration extract, then dry, roasting, and it is characterized in that, described maceration extract contains soluble compound and the surfactant of metal active constituent.
6. preparation method according to claim 5, wherein, in described maceration extract, the mol ratio of described surfactant and metallic atom is 0.01 ~ 2.
7. the preparation method according to claim 5 or 6, wherein, described surfactant is one or more in anionic surfactant, amphoteric surfactant and nonionic surface active agent.
8. according to the preparation method in claim 5-7 described in any one, wherein, described surfactant is one or more in stearic acid, oleic acid, laurate, lecithin, dodecyl alanine, alkyl dimethyl betaine, fatty glyceride, polyalcohol, tween and P123.
9. preparation method according to claim 5, wherein, in described maceration extract, with elemental metal, the concentration of the soluble compound of metal active constituent is 14-195 grams per liter, the consumption of carrier to make in gained catalyst with the total amount of catalyst for benchmark, with the content of the described metal active constituent of elemental metal for 2-20 % by weight.
10. preparation method according to claim 5, wherein, the soluble compound of described metal active constituent is the water soluble salt of metal active constituent, described metal active constituent is one or more in Cu, Fe, Co, Ni, Ru, Rh, Ir and Pt, described carrier is single component oxide carrier and/or bi-component or three components composite oxide carrier, and described single component oxide carrier is SiO
2, TiO
2, MgO, Al
2o
3, ZrO
2, CeO
2, La
2o
3in one or more, described bi-component or three components composite oxide carrier are SiO
2-Al
2o
3, TiO
2-SiO
2, Al
2o
3-ZrO
2and TiO
2-SiO
2-Al
2o
3in one or more.
11. preparation methods according to claim 5, wherein, the temperature of described drying is 80 ~ 140 DEG C, and the time is 1 ~ 10 hour; The temperature of described roasting is 400 ~ 1000 DEG C, and the time is 1 ~ 10 hour.
The dry reforming catalyst of the methane that preparation method in 12. claim 5-11 described in any one obtains.
The dry reforming catalyst of methane in 13. claim 1-4 and 12 described in any one is in the whole application prepared in synthesis gas of methane dry weight.
The method of 14. 1 kinds of dry preparing synthetic gas by reforming of methane, under the method dry reforming catalyst of methane be included in claim 1-4 and 12 described in any one exists, under the dry preparing synthetic gas by reforming condition of methane, makes methane and CO
2contact.
15. methods according to claim 14, wherein, described contact is carried out in fixed bed reactors or fluidized-bed reactor, by volume, CH
4/ CO
2=0.7 ~ 1.1, reaction temperature 600 ~ 800 DEG C, pressure 0 ~ 3MPa, unstripped gas air speed is 2000 ~ 120000mlg
-1h
-1.
16. methods according to claims 14 or 15, wherein, described contact is also carried out in the presence of a diluent, and respectively in g and ml, the w/v of described loaded catalyst and diluent is 1:10-30.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410541805.7A CN105561998B (en) | 2014-10-14 | 2014-10-14 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410541805.7A CN105561998B (en) | 2014-10-14 | 2014-10-14 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105561998A true CN105561998A (en) | 2016-05-11 |
CN105561998B CN105561998B (en) | 2018-07-31 |
Family
ID=55872952
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410541805.7A Active CN105561998B (en) | 2014-10-14 | 2014-10-14 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105561998B (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106607034A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Supported catalyst and its preparation method and application, and method for preparing synthetic gas through methane dry-reforming |
CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
CN108927171A (en) * | 2017-05-26 | 2018-12-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of the transesterification prenol processed of prenyl acetate and its application |
CN109046364A (en) * | 2018-07-24 | 2018-12-21 | 南昌大学 | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts |
CN109718788A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN109718799A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN109718807A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
ES2700900R1 (en) * | 2016-08-05 | 2019-05-27 | Korea Advanced Inst Sci & Tech | DRY RENOVATED CATALYST USING A METAL OXIDE SUPPORT AND PROCEDURE FOR PREPARING SYNTHESIS GAS USING THE SAME |
CN110652984A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
CN111250091A (en) * | 2020-03-03 | 2020-06-09 | 广东工业大学 | Supported catalyst and preparation method thereof |
CN111545215A (en) * | 2020-06-22 | 2020-08-18 | 中国科学技术大学 | Perovskite loaded monatomic catalyst and preparation method and application thereof |
US11322766B2 (en) | 2020-05-28 | 2022-05-03 | Saudi Arabian Oil Company | Direct hydrocarbon metal supported solid oxide fuel cell |
CN114904524A (en) * | 2022-05-13 | 2022-08-16 | 西北大学 | Amorphous catalyst, preparation method and application |
US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1751789A (en) * | 2005-09-02 | 2006-03-29 | 浙江大学 | Prepn. method and application of high-dispersion loading type nickel-based catalyst |
CN101306368A (en) * | 2008-07-09 | 2008-11-19 | 山西大学 | Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation |
CN102658145A (en) * | 2012-03-21 | 2012-09-12 | 中南民族大学 | Preparation method and application of MgO (111) load nickel-base catalyst |
CN103007945A (en) * | 2012-12-24 | 2013-04-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
-
2014
- 2014-10-14 CN CN201410541805.7A patent/CN105561998B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1751789A (en) * | 2005-09-02 | 2006-03-29 | 浙江大学 | Prepn. method and application of high-dispersion loading type nickel-based catalyst |
CN101306368A (en) * | 2008-07-09 | 2008-11-19 | 山西大学 | Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation |
CN102658145A (en) * | 2012-03-21 | 2012-09-12 | 中南民族大学 | Preparation method and application of MgO (111) load nickel-base catalyst |
CN103007945A (en) * | 2012-12-24 | 2013-04-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106607034B (en) * | 2015-10-23 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN106607034A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Supported catalyst and its preparation method and application, and method for preparing synthetic gas through methane dry-reforming |
US11618015B2 (en) | 2016-08-05 | 2023-04-04 | Korea Advanced Institute Of Science And Technology | Dry reforming catalyst using metal oxide support, and method for preparing synthetic gas by using same |
CN110325275B (en) * | 2016-08-05 | 2022-08-09 | 韩国科学技术院 | Dry reforming catalyst using metal oxide support and method for preparing syngas by using the same |
JP2019533576A (en) * | 2016-08-05 | 2019-11-21 | コリア アドバンスト インスティチュート オブ サイエンス アンド テクノロジー | Dry reforming catalyst using metal oxide support and method for producing synthesis gas using the same |
CN110325275A (en) * | 2016-08-05 | 2019-10-11 | 韩国科学技术院 | Dry reforming catalyst using metal oxide carrier and method that synthesis gas is prepared by using it |
ES2700900R1 (en) * | 2016-08-05 | 2019-05-27 | Korea Advanced Inst Sci & Tech | DRY RENOVATED CATALYST USING A METAL OXIDE SUPPORT AND PROCEDURE FOR PREPARING SYNTHESIS GAS USING THE SAME |
CN108927171B (en) * | 2017-05-26 | 2021-04-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing isopentenol by transesterification of isopentenyl acetate and application thereof |
CN108927171A (en) * | 2017-05-26 | 2018-12-04 | 中国科学院大连化学物理研究所 | A kind of catalyst of the transesterification prenol processed of prenyl acetate and its application |
CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
CN109718799A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN109718788A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN109718807B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
CN109718807A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
CN109718788B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
CN110652984B (en) * | 2018-06-28 | 2023-04-11 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
CN110652984A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
CN109046364A (en) * | 2018-07-24 | 2018-12-21 | 南昌大学 | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts |
CN111250091A (en) * | 2020-03-03 | 2020-06-09 | 广东工业大学 | Supported catalyst and preparation method thereof |
US11322766B2 (en) | 2020-05-28 | 2022-05-03 | Saudi Arabian Oil Company | Direct hydrocarbon metal supported solid oxide fuel cell |
US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
CN111545215A (en) * | 2020-06-22 | 2020-08-18 | 中国科学技术大学 | Perovskite loaded monatomic catalyst and preparation method and application thereof |
CN111545215B (en) * | 2020-06-22 | 2022-09-30 | 中国科学技术大学 | Perovskite-loaded monatomic catalyst and preparation method and application thereof |
US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
CN114904524A (en) * | 2022-05-13 | 2022-08-16 | 西北大学 | Amorphous catalyst, preparation method and application |
CN114904524B (en) * | 2022-05-13 | 2023-08-22 | 西北大学 | Amorphous catalyst, preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN105561998B (en) | 2018-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105561998A (en) | Methane dry reforming catalyst, preparation method and use of methane dry reforming catalyst and method for preparing synthetic gas through methane dry reforming | |
Wang et al. | Template-free preparation of bimetallic mesoporous Ni-Co-CaO-ZrO2 catalysts and their synergetic effect in dry reforming of methane | |
Khoja et al. | Evaluating the performance of a Ni catalyst supported on La2O3-MgAl2O4 for dry reforming of methane in a packed bed dielectric barrier discharge plasma reactor | |
Ay et al. | Dry reforming of methane over CeO2 supported Ni, Co and Ni–Co catalysts | |
Luisetto et al. | Co and Ni supported on CeO2 as selective bimetallic catalyst for dry reforming of methane | |
US8431506B2 (en) | Biotemplated inorganic materials | |
De Diego et al. | Operation of a 10 kWth chemical-looping combustor during 200 h with a CuO–Al2O3 oxygen carrier | |
Hwang et al. | Methanation of carbon dioxide over mesoporous Ni–Fe–Ru–Al2O3 xerogel catalysts: Effect of ruthenium content | |
Nair et al. | Kinetics of methanol oxidation over mesoporous perovskite catalysts | |
Monteiro et al. | Dry reforming of methane using modified sodium and protonated titanate nanotube catalysts | |
CN106000405B (en) | A kind of multi-stage porous loading type nickel-based catalyst, preparation method and application | |
ZHENG et al. | Direct synthesis of ethanol via CO2 hydrogenation over the Co/La-Ga-O composite oxide catalyst | |
CN106607034B (en) | A kind of method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas | |
CN105562113A (en) | Catalyst carrier and supported catalyst and their preparation methods and use and method for producing synthetic gas through dry reforming of methane | |
Dai et al. | Kinetics of catalytic decomposition of hydrous hydrazine over CeO2-supported bimetallic Ni–Pt nanocatalysts | |
Kim et al. | Inverse opal-like, Ca3Al2O6-stabilized, CaO-based CO2 sorbent: stabilization of a highly porous structure to improve its cyclic CO2 uptake | |
Li et al. | Highly active urchin-like MCo2O4 (M= Co, Cu, Ni or Zn) spinel for toluene catalytic combustion | |
US20120024757A1 (en) | Method for forming a catalyst comprising catalytic nanoparticles and a catalyst support | |
Liu et al. | Density functional theory study on the reaction mechanism of spinel CoFe2O4 with CO during chemical-looping combustion | |
Lu et al. | Synergistic catalysis of methane combustion using Cu–Ce–O hybrid nanoparticles with high activity and operation stability | |
Yan et al. | The role of Zr in NiZrAl oxides catalyst and the evaluation on steam reforming of glycerol for hydrogen product | |
Prasad et al. | Production of hydrogen and carbon nanofibers through the decomposition of methane over activated carbon supported Pd catalysts | |
Kim et al. | Enhanced morphological preservation and redox activity in Al-incorporated NiFe2O4 for chemical looping hydrogen production | |
Alli et al. | Effect of thermal treatment conditions on the stability of MOF-derived Ni/CeO2 catalyst for dry reforming of methane | |
Zou et al. | Preparation adjacent Ni-Co bimetallic nano catalyst for dry reforming of methane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |