CN109894133A - The preparation method of support type Ni-MoCx catalysis material and its application in chemical chain dry gas preparing synthetic gas by reforming - Google Patents
The preparation method of support type Ni-MoCx catalysis material and its application in chemical chain dry gas preparing synthetic gas by reforming Download PDFInfo
- Publication number
- CN109894133A CN109894133A CN201910199375.8A CN201910199375A CN109894133A CN 109894133 A CN109894133 A CN 109894133A CN 201910199375 A CN201910199375 A CN 201910199375A CN 109894133 A CN109894133 A CN 109894133A
- Authority
- CN
- China
- Prior art keywords
- methane
- hours
- gas
- moc
- preparation
- 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
- Y02P20/10—Process efficiency
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses support type Ni-MoCxThe preparation method of catalysis material and its application in chemical chain dry gas preparing synthetic gas by reforming.Support type Ni-MoCxCatalysis material includes MoCx, greatly than table commercial vectors and W metal, wherein MoCxMass percent be 25%-75%；The mass percent of W metal is 2.5%-7.5%；γ-Al is specifically included that than table commercial vectors material greatly2O3, SiO2, CeO2, BN, hydrotalcite etc., mass percent 22.5%-67.5%.The present invention is using support type Ni base catalysis material as matrix, auxiliary agent transition metal carbonization molybdenum material is introduced simultaneously, oxygen carrier microstructure is regulated and controled and optimized, the efficient producing synthesis gas of methane under temperate condition is realized, has both the excellent H for being suitable for fischer-tropsch synthesis process process2/ CO ratio (2-2.5 or so) and excellent cyclical stability improve energy conversion efficiency.
Description
Technical field
The present invention relates to a kind of CH4-CO2The method of chemical chain preparing synthetic gas by reforming and its application of efficient catalyst
And preparation, belong to CH4-CO2Preparing synthetic gas by reforming technical field.
Background technique
Global Oil resource is increasingly in short supply, the unclean environmental pollution for causing to get worse using the energy of the mankind, global fossil
Energy industry revolution has raised the curtain.Gas reserves is enriched, is had a very wide distribution, is cheap, is to be only second to oil and coal
The big energy in third place in the world, be translated into high level chemicals and energy-rich chemical fuel, be one be expected to solve the energy simultaneously it is short
Lack the effective way with problem of environmental pollution.In recent years, it with the breakthrough of shale gas and combustible ice production technique, is replaced with natural gas
Become worldwide research hotspot for Petroleum Production liquid fuel and basic chemical.Some experts even predict that: " 21 century will be
The century of natural gas ".The main component of natural gas is methane, and usual content is 83%-99%, therefore the activating conversion of methane has
There are important theory and strategic importance.
The trans-utilization of methane can substantially be divided into two kinds of conversion pathways of direct translation method and indirect reformer method.Directly convert
Method specifically include that the high temperature coupling of methane, the aromatisation of methane, the selective oxidation of methane and methane homogeneous catalytic oxidation
Deng；Up to the present, the depth due to the special stability and target product of methane molecule structure under harsh reaction condition
Oxidation, making the method, technically there is no big breakthroughs, still remote away from realization industrialization target.The indirect reformer technology of methane is main
Including three kinds of methods: methane vapor reforming (steam reforming of methane, SRM), methane-CO 2 reformation
(dry reforming of methane, DRM) and methane portion oxidation (partial oxidation of methane,
POM).Wherein, SRM is the main technique of traditional industrialized extensive producing synthesis gas.Severe reaction conditions (800C with
On), and take high steam/hydrocarbons ratio (2.5-3.5) to operate further increasing energy consumption to prevent Ni base catalyst carbon deposition problem, and
H in synthesis gas produced2/ CO >=3 are not suitable for F-T synthesis process, it is necessary to which further separating treatment considerably increases equipment
Scale and production cost.POM is a mild exothermic process, H in synthesis gas2/ CO ratio is suitable for methanol conjunction close to 2
At and F-T synthesis unstripped gas, but POM process needs expensive space division oxygen device, and catalysis material uses precious metal material more, from
And improve process energy consumption and cost；And reaction rate is quickly, it is difficult to accurately control reaction process, target product easily occurs
Deep oxidation；Simultaneously under hot conditions, the mixing of methane and oxygen can also generate the danger of explosion, reaction bed temperature gradient
Height, easy temperature runaway is out of control, and there are very big hidden danger for technical security.
Methane-CO 2 reformation process can utilize CH simultaneously4And CO2Two big greenhouse gases have weight to environmental protection
The synthesis gas hydrogen-carbon ratio of the meaning wanted, production is about 1, is suitble to subsequent F- T synthesis long chain hydrocarbons, application prospect is huge.But it should
Reaction is also a strong endothermic reaction, and traditional CDR process reaction condition is harsh, and energy consumption is high；Simultaneous reactions activity is lower, methane
Conversion per pass it is lower, the carbon distribution inactivation of catalyst is serious under hot conditions.For such problems, in recent years, Zhu Duoyan
The person of studying carefully proposes a kind of new technique, and the Lattice Oxygen provided using oxide is come to CH4It carries out partial oxidation and produces synthesis gas, i.e.,
Chemical chain reforming technique (chemical looping reforming, CLR).This patent mainly uses chemical chain technology to reform first
Alkane-carbon dioxide preparation synthesis gas.
Methane based on chemical chain burning technology-carbon dioxide chemistry chain reforming technique is one kind developed in recent years
Methane-CO 2 reformation novel process.According to the principle that chemical looping reacts, using the Lattice Oxygen in the carrier of oxygen as oxygen
Methane portion oxidation is generated synthesis gas by source；The metal oxide of Lattice Oxygen is lost again by CO2Oxidation restores Lattice Oxygen, completionization
Learn chain circular response.In the whole process Lattice Oxygen by partial oxidation of methane at synthesis gas, can be real under lower energy consumption
The high conversion of existing methane, and react H in gas-phase product2The mass ratio of the material with CO is 2:1, is conducive to subsequent Fischer-Tropsch and closes
At etc. techniques.Meanwhile CO2Oxidation stage is conducive to the elimination of part carbon distribution while restoring Lattice Oxygen, improves catalyst
Stability.Compared with traditional CDR process, chemical chain reforming process is by CO2And H2It is effectively isolated, it is anti-to avoid Reversed Water-gas Shift
The generation answered, improves the selectivity of target product in whole process, therefore has higher efficiency of energy utilization and higher
Economy.The carrier of oxygen that design synthesis has both high activity, selectivity, oxygen storage capacity and good stability is that chemical chain method is reformed
The key point of process.
Summary of the invention
The object of the present invention is to provide a kind of high activities, highly selective and high stability methane-carbon dioxide chemistry chain
Preparing synthetic gas by reforming catalysis material, is realized by following technical proposal.
It is a kind of for the efficient oxygen carrier material of methane-carbon dioxide chemistry chain reformed syngas, including MoCx, compare table greatly
Commercial vectors and W metal, wherein MoCxMass percent be 25%-75%；The mass percent of W metal is 2.5%-
7.5%；γ-Al is specifically included that than table commercial vectors material greatly2O3, SiO2, CeO2, BN, hydrotalcite etc., mass percent is
22.5%-67.5%.
The present invention introduces auxiliary agent transition metal carbonization molybdenum material using support type Ni base catalysis material as matrix, right
Oxygen carrier microstructure is regulated and controled and is optimized, and is realized the efficient producing synthesis gas of methane under temperate condition, is had both and be suitable for Fischer-Tropsch
The excellent H of synthesis process2/ CO ratio (2-2.5 or so) and excellent cyclical stability improve energy conversion efficiency.
Another object of the present invention is to provide a kind of methane-carbon dioxide chemistry chains to reform producing synthesis gas catalysis material
Preparation method, by following each step:
1) preparation of load type metal Ni basis material: according to Ni:(Ni+ carrier) mass percent be 1-20%, match
It is set to the nickel salts solution containing aim parameter and it is small to be stirred continuously 1-2 for nickel salts solution and support powder mixed at room temperature
When, then aged at room temperature for 24 hours after, dry 12-24 hours at 100-150 DEG C, the last 400- in Muffle furnace air atmosphere
600 DEG C roast 4 hours, after to be cooled, grinding, obtain Ni/ carrier matrix material；Wherein the carrier is selected from γ-Al2O3,
SiO2, CeO2, BN, one or more of hydrotalcite；
2) preparation of molybdenum carbide auxiliary agent: by MoO3Powder is by the preparation synthesis of temperature programming carbonation reaction, specific mistake
Journey is appropriate MoO3It is carbonized in methane and hydrogen mixed gas atmosphere in 590-800 DEG C, carburizing atmosphere is 100-160ml/min's
CH4/H2Gaseous mixture, CH in gaseous mixture4Volume fraction be 20%, temperature programming carbonisation be 5 DEG C/min be warming up to 300 DEG C,
Then 1 DEG C/min is warming up to 700 DEG C, in 700 DEG C of heat preservation 2h, is slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) by molybdenum carbide promoter material obtained by Ni/ carrier matrix material obtained by step 1) and step 2) according to certain mass hundred
Divide than being mixed in room temperature mechanical, wherein the mass percent is Ni/ carrier: MoCx=1:3~3:1, it is then abundant in mortar
Grinding 1-2 hours, finally in methane and hydrogen mixed gas atmosphere in 450-600 DEG C roasting 2-3 hours to get three component Ni-
MoCx/ carried catalyst；Wherein calcination atmosphere is the CH of 100-150ml/min4/H2Gaseous mixture, CH in gaseous mixture4Volume hundred
Score is 15%.
The present invention provides catalyst obtained by the above method in methane-carbon dioxide chemistry chain reforming reaction preparing synthetic gas
Application.
Further, in the above-mentioned technical solutions, the methane-carbon dioxide chemistry chain reforming reaction recycle in two steps into
Row, first by CH4It is passed through reactor, is reacted with Lattice Oxygen species partial oxidation in catalysis material and synthesis gas is made；Then will
CO2It is passed through reactor, redox reaction occurs, CO is made, while catalyst is regenerated.
Further, in the above-mentioned technical solutions, reaction temperature is 500-800 DEG C.
Further, in the above-mentioned technical solutions, reaction pressure is normal pressure.
Above-mentioned gained catalysis material after tabletting, sieving, be made granularity be 40-60 mesh powder, by following processes into
Row performance evaluation: activity rating carries out on the miniature fixed-bed reactor of homemade normal pressure, and evaluating apparatus is mainly by reaction gas
Simulation system, reaction system and detection system three parts are constituted.The long 40mm of quartz tube reactor, internal diameter are in reaction system
4mm.Active testing amount of samples is 100mg, and catalyst bed upper and lower ends filled high-temperature cotton and quartz sand reduce reactor
Dead volume.Reactor is heated using temperature programmed control electric tube furnace, and temperature-controlled precision is ± 0.1 DEG C.Reaction gas simulation system is adopted
Control climate is carried out with micro mass flow controller, precision is ± 0.1ml/min.Experiment is initial, is passed through high-purity argon gas to arrange
Then net air switches to 15%CH4/H2Gaseous mixture pre-processes 1-2 hours at 500 DEG C, stablizes under high-purity argon gas protection
To goal response temperature, the reaction temperature is 500 DEG C -800 DEG C；5%CH is switched to by automatic gas switching valve again4/Ar
Gaseous mixture switches to after 2min is swept in pure Ar air-blowing after reacting 1min and is passed through 5%CO2/ Ar gaseous mixture 1min is to realize active oxygen carrier
Body regeneration, carries out multiple circular response.Wherein purge zone Ar flow velocity is 150ml/min, CH4/ Ar gaseous mixture and CO2/Ar mixing
Gas velocity is 100ml/min, and gaseous product is monitored on-line by mass spectrometer.
The advantages of present invention has and effect:
1. the present invention is by with support type Ni-MoCxIt, will for methane-carbon dioxide chemistry chain reforming technique of catalysis material
CH4Partial oxidation reaction and CO2Activation dissociation reaction be divided into two steps progress, be conducive to CH4The realization of high conversion improves
The conversion ratio of reaction mass, the utilization efficiency of catalyst and the separative efficiency of product；It effectively reduces in reaction process simultaneously
Side reaction (such as reverse water-gas-shift reaction) generation, improve the selectivity of catalyst, extend the service life of catalyst；
Carbon dioxide oxidation panel can also to a certain extent eliminate the carbon distribution of catalyst surface, not only obtain CO after the reaction,
It is also able to achieve the regeneration of catalyst, improves the service life；The use for reducing separation equipment can be adjusted effectively by adding molybdenum carbide auxiliary agent
Control synthesis gas H2The ratio of/CO is conducive to the progress of methanol-fueled CLC and F-T process flow, has good prospects for commercial application,
For CH4-CO2The industrialization of reforming reaction opens new road.
2. Ni-MoC prepared by the present inventionx/Al2O3Type catalytic material is applied to methane-carbon dioxide chemistry chain and reforms instead
Answer has higher CH under lower reaction temperature4Conversion ratio and faster conversion rate and superior circulation are steady
It is qualitative, and catalyst preparation process is simple, it is easy to accomplish industrialization.Gained oxygen carrier of the invention is added to auxiliary agent MoCxMaterial
Support type Ni-MoCxMaterial has higher reactivity worth than the conventional load type Ni base load oxysome of no addition auxiliary agent, specifically
Show as higher methane conversion and more excellent cyclical stability.Wherein active most preferably MoCxDoping is 50%
Oxygen carrier material (MoCxMass percent 50%, Ni/Al2O3Mass percent 50%, Ni/Al2O3The quality hundred of middle W metal
Divide than for 10%), when reaction temperature is 500 DEG C methane initial conversion is 56% or so, carbon dioxide initial conversion is
60% or so, H2/ CO ratio is 2.35 or so；Methane initial conversion 92% or so at 600 DEG C, carbon dioxide initial conversion are
83% or so, H2/ CO ratio is 2.45 or so；Methane initial conversion reaches 100% at 700 DEG C, carbon dioxide initial conversion
For 93% or so, H2/ CO ratio is 2.5 or so.
Detailed description of the invention
4 width of attached drawing of the present invention:
Fig. 1 is 1 gained MoC of embodimentx+ 10%Ni/Al2O3(1/1) catalyst, 1 gained 5%Ni/CeO of comparative example2Catalysis
2 gained 10%Ni/Al of agent and comparative example2O3The XRD comparison diagram of catalyst；
Fig. 2 is 1 gained MoC of embodimentx+ 10%Ni/Al2O3(1/1) 1 gained 5%Ni/CeO of catalyst and comparative example2It urges
Catalytic performance figure under the conditions of agent is 500 DEG C in methane-carbon dioxide chemistry chain reforming reaction；
Fig. 3 is 1 gained MoC of embodimentx+ 10%Ni/Al2O3(1/1) 2 gained 10%Ni/Al of catalyst and comparative example2O3It urges
Catalytic performance figure of the agent in methane-carbon dioxide chemistry chain reforming reaction under 600 DEG C of reaction conditions；
Fig. 4 is 1 gained MoC of embodimentx+ 10%Ni/Al2O3(1/1) catalyst is reformed in methane-carbon dioxide chemistry chain
Catalytic performance figure in reaction under 700 DEG C of reaction conditions.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
γ-Al in following embodiments2O3From Kang Diya, sasol, but it is not limited to the source.
Embodiment 1
Catalyst preparation:
1) γ-Al is measured first2O3The water absorption rate of powder is 1.4ml H2O/gAl2O3.According to Ni:(Ni+Al2O3) matter
Measuring percentage is 10%, weighs 2g γ-Al2O3Powder sample and 0.35g nickel nitrate, then according to commercial γ-Al2O3Powder
Water absorption rate above-mentioned nickel nitrate is dissolved in by 2.8ml deionized water wiring solution-forming using equi-volume impregnating, by above-mentioned Ni salting liquid
With commercial γ-Al2O3Powder mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, then aged at room temperature for 24 hours after in 100-
12-24 hours dry at 150 DEG C, finally 500 DEG C roasting 4 hours obtain after to be cooled, grinding in Muffle furnace air atmosphere
Ni/Al2O3Basis material.
2) 1.8g MoO is weighed3In 20%CH4/H2It is carbonized in mixed atmosphere in 700 DEG C, gaseous mixture gas flow is
160ml/min, temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, 700 DEG C then are warming up to 1 DEG C/min,
700 DEG C of heat preservation 2h, are slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) 10%Ni/Al obtained by 2g step 1 is weighed2O3Molybdenum carbide promoter material obtained by basis material and 2g step 2 according to
Mass percent 1:1 is mixed in room temperature mechanical, and Yu Yanbo is fully ground 1-2 hours, finally in 15%CH4/H2In mixed atmosphere
500 DEG C roast 2 hours, and wherein gaseous mixture gas flow is 100ml/min, obtains MoCx+ 10%Ni/Al2O3(SSI 1/1)
Catalyst.
Catalyst activity evaluation:
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%CH of 100ml/min4/H2Then gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 500 DEG C, 600 DEG C, 700 DEG C.Wherein, it is 56% or so, two that reaction temperature, which is 500 DEG C of methane initial conversions,
Carbonoxide initial conversion is 60% or so, H2/ CO ratio is 2.35 or so；Methane initial conversion 92% or so at 600 DEG C, two
Carbonoxide initial conversion is 83% or so, H2/ CO ratio is 2.45 or so；Methane initial conversion reaches 100% at 700 DEG C,
Carbon dioxide initial conversion is 93% or so, H2/ CO ratio is 2.5 or so.
Comparative example 1
Catalyst preparation
Commercialization γ-Al is measured first2O3The water absorption rate of powder is 1.4mlH2O/gAl2O3.According to Ni:(Ni+Al2O3) quality
Percentage is 10%, weighs 2g γ-Al2O3Powder sample and 0.35g nickel nitrate, then according to commercial γ-Al2O3Powder
Above-mentioned nickel nitrate is dissolved in 2.8ml deionized water wiring solution-forming using equi-volume impregnating by water absorption rate, by above-mentioned Ni salting liquid with
Commercial γ-Al2O3Powder mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, then aged at room temperature for 24 hours after in 100-
12-24 hours dry at 150 DEG C, finally 500 DEG C roasting 4 hours obtain after to be cooled, grinding in Muffle furnace air atmosphere
10%Ni/Al2O3Catalyst.
Catalyst activity evaluation
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%H of 100ml/min2Then/Ar gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 600 DEG C, 800 DEG C.Wherein, 600 DEG C when methane initial conversion 60% or so, carbon dioxide initial conversion
For 52% or so, H2/ CO ratio is 9.5 or so；Methane initial conversion 62% or so at 700 DEG C, carbon dioxide initial conversion
For 55% or so, H2/ CO ratio is 9.2 or so；Methane initial conversion 70% or so at 800 DEG C, carbon dioxide initial conversion
For 60% or so, H2/ CO ratio is 9.0 or so.
Embodiment 1
Catalyst preparation:
1) commercialization CeO is measured first2The water absorption rate of powder is 3.1ml H2O/gAl2O3.According to Ni:(Ni+CeO2) quality
Percentage is 10%, weighs 2g CeO2Powder sample and 0.35g nickel nitrate, then according to commercial CeO2The water absorption rate of powder is adopted
Above-mentioned nickel nitrate is dissolved in 2.8ml deionized water wiring solution-forming with equi-volume impregnating, by above-mentioned Ni salting liquid and commercialization CeO2
Powder mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, then aged at room temperature for 24 hours after at 100-150 DEG C it is dry
12-24 hours, finally 500 DEG C roasting 4 hours obtained Ni/Al after to be cooled, grinding in Muffle furnace air atmosphere2O3Matrix
Material.
2) 1.8g MoO is weighed3In 20%CH4/H2It is carbonized in mixed atmosphere in 700 DEG C, gaseous mixture gas flow is
160ml/min, temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, 700 DEG C then are warming up to 1 DEG C/min,
700 DEG C of heat preservation 2h, are slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) 10%Ni/CeO obtained by 2g step 1 is weighed2Molybdenum carbide promoter material obtained by basis material and 2g step 2 according to
Mass percent 1:1 is mixed in room temperature mechanical, and Yu Yanbo is fully ground 1-2 hours, finally in 15%CH4/H2In mixed atmosphere
500 DEG C roast 2 hours, and wherein gaseous mixture gas flow is 100ml/min, obtains MoCx+ 10%Ni/CeO2(SSI 1/1) is urged
Agent.
Catalyst activity evaluation:
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%CH of 100ml/min4/H2Then gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 500 DEG C, 600 DEG C, 700 DEG C.Wherein, it is 53% or so, two that reaction temperature, which is 500 DEG C of methane initial conversions,
Carbonoxide initial conversion is 57% or so, H2/ CO ratio is 2.32 or so；Methane initial conversion 90% or so at 600 DEG C, two
Carbonoxide initial conversion is 87% or so, H2/ CO ratio is 2.25 or so；Methane initial conversion reaches 100% at 700 DEG C,
Carbon dioxide initial conversion is 91% or so, H2/ CO ratio is 2.34 or so.
Comparative example 2
Catalyst preparation
Commercialization CeO is measured first2The water absorption rate of powder is 3.1mlH2O/gCeO2.According to Ni:(Ni+CeO2) quality percentage
Than being 5%, 2gCeO is weighed2Powder sample and 0.175g nickel nitrate, then according to commercial CeO2Water absorption rate use of powder etc.
Above-mentioned nickel nitrate is dissolved in 6.2ml deionized water wiring solution-forming by volume impregnation method, by above-mentioned Ni salting liquid and commercialization CeO2Powder
Mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, 12-24 is then dried at 100-150 DEG C after for 24 hours in aged at room temperature
Hour, finally 500 DEG C roasting 4 hours obtain 5%Ni/CeO after to be cooled, grinding in Muffle furnace air atmosphere2Catalyst.
Catalyst activity evaluation
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%H of 100ml/min2Then/Ar gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Methane initial conversion is 40% or so when to answer temperature be 500 DEG C, and carbon dioxide initial conversion is 28% or so, H2/ CO ratio
It is 7.8 or so；Methane initial conversion is 60% or so at 600 DEG C, and carbon dioxide initial conversion is 50% or so, H2/CO
Than being 4.8 or so.
Embodiment 3
The step of the present embodiment and process conditions etc. and embodiment 1 are all the same, and difference is only that following two o'clocks, 1. weigh
1g10%Ni/Al2O3Basis material is mixed according to mass percent 1:3 in room temperature mechanical with 3g carbonization molybdenum material, abundant in mortar
Grinding 1-2 hours, finally in 15%CH4/H2It is roasted 2 hours for 500 DEG C in mixed atmosphere, MoC is madex+ 10%Ni/Al2O3(SSI
1/3) catalyst；2. carrying out activity rating to it, methane initial conversion 82% or so, titanium dioxide when reaction temperature is 600 DEG C
Carbon initial conversion is 75% or so, H2/ CO ratio is 3.0 or so.
Embodiment 4
The step of the present embodiment and process conditions etc. and embodiment 1 are all the same, and difference is only that following two o'clocks, 1. weigh
3g10%Ni/Al2O3Basis material is mixed according to mass percent 1:1 in room temperature mechanical with 1g carbonization molybdenum material, abundant in mortar
Grinding 1-2 hours, finally in 15%CH4/H2It is roasted 2 hours for 500 DEG C in mixed atmosphere, MoC is madex+ 10%Ni/Al2O3(SSI
3/1) catalyst；2. carrying out activity rating to it, methane initial conversion 75% or so, titanium dioxide when reaction temperature is 600 DEG C
Carbon initial conversion is 68% or so, H2/ CO ratio is 2.35 or so.
Embodiment 5
Catalyst preparation:
1) commercialization SiO is measured first2The water absorption rate of powder is 0.8ml H2O/gAl2O3.According to Ni:(Ni+SiO2) quality
Percentage is 10%, weighs 2g SiO2Powder sample and 0.35g nickel nitrate, then according to commercial SiO2The water absorption rate of powder is adopted
Above-mentioned nickel nitrate is dissolved in 2.8ml deionized water wiring solution-forming with equi-volume impregnating, by above-mentioned Ni salting liquid and commercialization SiO2
Powder mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, then aged at room temperature for 24 hours after at 100-150 DEG C it is dry
12-24 hours, finally 500 DEG C roasting 4 hours obtained Ni/SiO after to be cooled, grinding in Muffle furnace air atmosphere2Matrix
Material.
2) 1.8g MoO is weighed3In 20%CH4/H2It is carbonized in mixed atmosphere in 700 DEG C, gaseous mixture gas flow is
160ml/min, temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, 700 DEG C then are warming up to 1 DEG C/min,
700 DEG C of heat preservation 2h, are slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) 10%Ni/SiO obtained by 2g step 1 is weighed2Molybdenum carbide promoter material obtained by basis material and 2g step 2 according to
Mass percent 1:1 is mixed in room temperature mechanical, and Yu Yanbo is fully ground 1-2 hours, finally in 15%CH4/H2In mixed atmosphere
500 DEG C roast 2 hours, and wherein gaseous mixture gas flow is 100ml/min, obtains MoCx+ 10%Ni/SiO2(SSI 1/1) is urged
Agent.
Catalyst activity evaluation:
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%CH of 100ml/min4/H2Then gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 500 DEG C, 600 DEG C.Wherein, it is 52% or so that reaction temperature, which is 500 DEG C of methane initial conversions, carbon dioxide
Initial conversion is 45% or so, H2/ CO ratio is 2.15 or so；Methane initial conversion 93% or so, carbon dioxide at 600 DEG C
Initial conversion is 80% or so, H2/ CO ratio is 2.45 or so.
Comparative example 3
Catalyst preparation
Commercialization SiO is measured first2The water absorption rate of powder is 0.8mlH2O/gSiO2.According to Ni:(Ni+SiO2) quality percentage
Than being 10%, 2g SiO is weighed2Powder sample and 0.35g nickel nitrate, then according to commercial SiO2Water absorption rate use of powder etc.
Above-mentioned nickel nitrate is dissolved in 2.8ml deionized water wiring solution-forming by volume impregnation method, by above-mentioned Ni salting liquid and commercialization SiO2Powder
Mixed at room temperature, and be stirred continuously 1-2 hours with glass bar, 12-24 is then dried at 100-150 DEG C after for 24 hours in aged at room temperature
Hour, finally 500 DEG C roasting 4 hours obtain 10%Ni/SiO after to be cooled, grinding in Muffle furnace air atmosphere2Catalysis
Agent.
Catalyst activity evaluation
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%H of 100ml/min2Then/Ar gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 500 DEG C, 600 DEG C.Wherein, 500 DEG C when methane initial conversion 37% or so, carbon dioxide initial conversion
For 30% or so, H2/ CO ratio is 10.5 or so；Methane initial conversion 40% or so at 600 DEG C, carbon dioxide initial conversion
For 33% or so, H2/ CO ratio is 9.8 or so.
Embodiment 6
Catalyst preparation:
1) water absorption rate for measuring commercialization BN powder first is 1.7ml H2O/gBN.According to Ni:(Ni+BN) mass percent
It is 10%, weighs 2g BN powder sample and 0.35g nickel nitrate, then according to the water absorption rate of commercial BN powder using isometric
Above-mentioned nickel nitrate is dissolved in 2.8ml deionized water wiring solution-forming by infusion process, and above-mentioned Ni salting liquid and commercialization BN powder room temperature are mixed
It closes, and is stirred continuously 1-2 hour with glass bar, then dry 12-24 hours after for 24 hours at 100-150 DEG C in aged at room temperature, most
500 DEG C roasting 4 hours obtain Ni/BN basis material after to be cooled, grinding in Muffle furnace air atmosphere afterwards.
2) 1.8g MoO is weighed3In 20%CH4/H2It is carbonized in mixed atmosphere in 700 DEG C, gaseous mixture gas flow is
160ml/min, temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, 700 DEG C then are warming up to 1 DEG C/min,
700 DEG C of heat preservation 2h, are slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) molybdenum carbide promoter material obtained by 10%Ni/BN basis material obtained by 2g step 1 and 2g step 2 is weighed according to matter
It measures percentage 1:1 to mix in room temperature mechanical, Yu Yanbo is fully ground 1-2 hours, finally in 15%CH4/H2500 in mixed atmosphere
DEG C roasting 2 hours, wherein gaseous mixture gas flow be 100ml/min, obtain MoCx+ 10%Ni/BN (SSI 1/1) catalysis
Agent.
Catalyst activity evaluation:
Methane-carbon dioxide chemistry chain reforming reaction carries out in the micro fixed-bed reactor of homemade internal diameter 4mm, real
Each road gas flow needed for testing is by mass flowmenter regulation and control, CH4Reduction section and CO2Oxidation panel gas is flowed by pneumatic
Gas switching valve automatically controls, and recycles sample introduction.The above-mentioned catalyst of 100mg is weighed to be placed in quartz tube reactor, first with
The 15%CH of 100ml/min4/H2Then gaseous mixture was reacted at a temperature of differential responses by following in 500 DEG C of pretreatment 2h
Cheng Jinhang circulation sample introduction reaction: 5%CH is switched to by automatic gas switching valve4/ Ar gaseous mixture, react 1min after switch to it is pure
Ar air-blowing is passed through 5%CO after sweeping 2min2/ Ar gaseous mixture 1min carries out multiple circular response to realize active oxygen carrier regeneration.Instead
Answering temperature is respectively 500 DEG C, 600 DEG C.Wherein, it is 45% or so that reaction temperature, which is 500 DEG C of methane initial conversions, carbon dioxide
Initial conversion is 38% or so, H2/ CO ratio is 2.35 or so；Methane initial conversion 83% or so, carbon dioxide at 600 DEG C
Initial conversion is 76% or so, H2/ CO ratio is 2.45 or so.
Claims (5)
1. three component support type Ni-MoC of one kindxThe preparation method of catalysis material, it is characterised in that the preparation method includes as follows
Step:
1) preparation of load type metal Ni basis material: according to Ni:(Ni+ carrier) mass percent be 1-20%, be configured to
Nickel salts solution and support powder mixed at room temperature are stirred continuously 1-2 hours by the nickel salts solution containing aim parameter, so
Afterwards aged at room temperature for 24 hours after, dry 12-24 hours at 100-150 DEG C, finally 400-600 DEG C in Muffle furnace air atmosphere
Roasting 4 hours obtains Ni/ carrier matrix material after to be cooled, grinding；Wherein the carrier is selected from γ-Al2O3, SiO2,
CeO2, BN, one or more of hydrotalcite；
2) preparation of molybdenum carbide auxiliary agent: by MoO3For powder by the preparation synthesis of temperature programming carbonation reaction, detailed process is suitable
Measure MoO3It is carbonized in methane and hydrogen mixed gas atmosphere in 590-800 DEG C, carburizing atmosphere is the CH of 100-160ml/min4/H2It is mixed
Close gas, CH in gaseous mixture4Volume fraction be 20%, temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, then 1
DEG C/min is warming up to 700 DEG C, in 700 DEG C of heat preservation 2h, it is slowly dropped to after room temperature in 1%O212h is passivated in/Ar atmosphere.
3) by molybdenum carbide promoter material obtained by Ni/ carrier matrix material obtained by step 1) and step 2) according to certain mass percent
It is mixed in room temperature mechanical, wherein the mass percent is Ni/ carrier: MoCx=1:3~3:1, is then fully ground in mortar
1-2 hours, finally in methane and hydrogen mixed gas atmosphere in 450-600 DEG C roasting 2-3 hours to get three component Ni-MoCx/ carry
Body catalyst；Wherein calcination atmosphere is the CH of 100-150ml/min4/H2Gaseous mixture, CH in gaseous mixture4Percentage by volume be
15%.
2. the catalyst that preparation method as described in claim 1 obtains is in methane-carbon dioxide chemistry chain reforming reaction system synthesis
Application in gas.
3. application according to claim 2, which is characterized in that the methane-carbon dioxide chemistry chain reforming reaction is divided to two
Step circulation carries out, first by CH4It is passed through reactor, is reacted with Lattice Oxygen species partial oxidation in catalysis material and synthesis is made
Gas；Then by CO2It is passed through reactor, redox reaction occurs, CO is made, while catalyst is regenerated.
4. application according to claim 3, which is characterized in that reaction temperature is 500-800 DEG C.
5. application according to claim 3, which is characterized in that reaction pressure is normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910199375.8A CN109894133B (en) | 2019-03-15 | 2019-03-15 | Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910199375.8A CN109894133B (en) | 2019-03-15 | 2019-03-15 | Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109894133A true CN109894133A (en) | 2019-06-18 |
| CN109894133B CN109894133B (en) | 2020-06-02 |
Family
ID=66953266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910199375.8A Active CN109894133B (en) | 2019-03-15 | 2019-03-15 | Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109894133B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203259A (en) * | 2020-02-24 | 2020-05-29 | 湘潭大学 | Preparation method of core-shell microwave catalyst and application of core-shell microwave catalyst in hydrogen sulfide decomposition |
| CN111359644A (en) * | 2020-03-18 | 2020-07-03 | 中国科学院广州能源研究所 | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof |
| CN113019408A (en) * | 2021-03-12 | 2021-06-25 | 河南理工大学 | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst |
| CN113842935A (en) * | 2021-09-25 | 2021-12-28 | 大连理工大学 | Preparation method and application of carbide modified Ni-based ordered mesoporous silicon catalytic material |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837304A (en) * | 2010-04-29 | 2010-09-22 | 清华大学 | Carrier for preparing syngas Ni-based catalyst through methane partial oxidation |
| CN105107515A (en) * | 2015-09-24 | 2015-12-02 | 成都理工大学 | Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane |
| CN105540588A (en) * | 2015-12-08 | 2016-05-04 | 大连理工大学 | Application of alpha-molybdenum carbide and metal-modified alpha-molybdenum carbide catalyst to reaction for preparing carbon monoxide through hydrogenation of carbon dioxide |
-
2019
- 2019-03-15 CN CN201910199375.8A patent/CN109894133B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837304A (en) * | 2010-04-29 | 2010-09-22 | 清华大学 | Carrier for preparing syngas Ni-based catalyst through methane partial oxidation |
| CN105107515A (en) * | 2015-09-24 | 2015-12-02 | 成都理工大学 | Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane |
| CN105540588A (en) * | 2015-12-08 | 2016-05-04 | 大连理工大学 | Application of alpha-molybdenum carbide and metal-modified alpha-molybdenum carbide catalyst to reaction for preparing carbon monoxide through hydrogenation of carbon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| 何杰，薛茹君主编: "《工业催化》", 31 August 2014, 中国矿业大学出版社 * |
| 李来平，张文钲著: "《钼化学品》", 30 November 2016, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203259A (en) * | 2020-02-24 | 2020-05-29 | 湘潭大学 | Preparation method of core-shell microwave catalyst and application of core-shell microwave catalyst in hydrogen sulfide decomposition |
| CN111359644A (en) * | 2020-03-18 | 2020-07-03 | 中国科学院广州能源研究所 | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof |
| CN113019408A (en) * | 2021-03-12 | 2021-06-25 | 河南理工大学 | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst |
| CN113842935A (en) * | 2021-09-25 | 2021-12-28 | 大连理工大学 | Preparation method and application of carbide modified Ni-based ordered mesoporous silicon catalytic material |
| CN113842935B (en) * | 2021-09-25 | 2023-07-25 | 大连理工大学 | Preparation method and application of carbide modified Ni-based ordered mesoporous silicon catalytic material |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109894133B (en) | 2020-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109894133A (en) | The preparation method of support type Ni-MoCx catalysis material and its application in chemical chain dry gas preparing synthetic gas by reforming | |
| Wang et al. | Direct conversion of CO2 to aromatics with high yield via a modified Fischer-Tropsch synthesis pathway | |
| Kang et al. | Improving syngas selectivity of Fe2O3/Al2O3 with yttrium modification in chemical looping methane conversion | |
| Muroyama et al. | Carbon dioxide methanation over Ni catalysts supported on various metal oxides | |
| Zhu et al. | Carbon formation on iron-based oxygen carriers during CH4 reduction period in Chemical Looping Hydrogen Generation process | |
| Akbari-Emadabadi et al. | Production of hydrogen-rich syngas using Zr modified Ca-Co bifunctional catalyst-sorbent in chemical looping steam methane reforming | |
| Galvita et al. | Hydrogen production from methane by steam reforming in a periodically operated two-layer catalytic reactor | |
| Long et al. | Hydrogen generation from water splitting over polyfunctional perovskite oxygen carriers by using coke oven gas as reducing agent | |
| Wang et al. | Chemical looping reforming of toluene as a biomass tar model compound over two types of oxygen carriers: 2CuO-2NiO/Al2O3 and CaFe2O4 | |
| CN101773835A (en) | Catalyst for reforming methane with carbon dioxide for preparing synthetic gas and preparation method thereof | |
| Amin et al. | Study of coking and catalyst stability over CaO promoted Ni-based MCF synthesized by different methods for CH4/CO2 reforming reaction | |
| Cheng et al. | Effect of calcination temperature on the performance of hexaaluminate supported CeO2 for chemical looping dry reforming | |
| Li et al. | Effect of Pd doping in (Fe/Ni)/CeO2 catalyst for the reaction path in CO2 oxidative ethane dehydrogenation/reforming | |
| Luo et al. | Hydrogen and syngas co-production by coupling of chemical looping water splitting and glycerol oxidation reforming using Ce–Ni modified Fe-based oxygen carriers | |
| Alenazey | Utilizing carbon dioxide as a regenerative agent in methane dry reforming to improve hydrogen production and catalyst activity and longevity | |
| AU2011357640B2 (en) | Nickel-M-alumina xerogel catalyst, method for preparing same, and method for preparing methane using the catalyst | |
| EP2076332A1 (en) | Hydrogen production method by direct decomposition of natural gas and lpg | |
| KR20140133077A (en) | Combined steam and CO2 reforming method of methane in GTL process | |
| Ding et al. | Development and performance of CeO2 supported BaCoO3− δ perovskite for chemical looping steam methane reforming | |
| Cao et al. | Dry reforming of methane by La2NiO4 perovskite oxide, part I: Preparation and characterization of the samples | |
| Tian et al. | Preparation of an industrial Ni-based catalyst and investigation on CH4/CO2 reforming to syngas | |
| Lachén et al. | High purity hydrogen from coupled dry reforming and steam iron process with cobalt ferrites as oxygen carrier: Process improvement with the addition of NiAl2O4 catalyst | |
| Ergazieva et al. | Catalytic decomposition of Methane to hydrogen over Al2O3 supported mono-and bimetallic catalysts | |
| CN111097497A (en) | Method for producing hydrogen by catalyzing direct conversion of methane, catalyst and preparation method thereof | |
| Shamsi | Partial oxidation and dry reforming of methane over Ca/Ni/K (Na) catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |