CN105772016A - Nickel-based catalyst and preparation method thereof - Google Patents
Nickel-based catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105772016A CN105772016A CN201610280836.0A CN201610280836A CN105772016A CN 105772016 A CN105772016 A CN 105772016A CN 201610280836 A CN201610280836 A CN 201610280836A CN 105772016 A CN105772016 A CN 105772016A
- Authority
- CN
- China
- Prior art keywords
- nickel
- base catalyst
- salt
- carbonate
- catalyst
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a nickel-based catalyst used for catalyzing methane and carbon dioxide to reform for preparing syngas and a preparation method thereof, and belongs to the field of syngas preparation by catalytic reforming of methane and carbon dioxide. The chemical formula of the nickel-based catalyst is Ni(Mo)/(CexZr1-xO2)yMgAl(O), wherein Ni is reactive metal, MO3.MgO and CexZr1-xO2 are assistants, Al2O3 is a carrier, x/1-x=0.25-4 and y=1-15%.
Description
Technical field
The present invention relates to methane and carbon dioxide catalytic reforming preparing synthetic gas field, particularly to for catalytic methane
Nickel-base catalyst with CO 2 reformation preparing synthetic gas and preparation method thereof.
Background technology
At present, the extensive utilization of methane depends on indirect reformer, and methane carbon dioxide reformation is first
The method of relatively broad use in the application of alkane indirect reformer.Along with the raising of people's environmental consciousness, greenhouse effect
Utilization and the control of gas increasingly receive publicity.In methane carbon dioxide reformation technique, catalyst is this
The core of system.Carbon dioxide catalytic reforming methane synthesis gas can effectively by carbon dioxide and methane this
Two kinds of main greenhouse gases are converted into important industrial chemicals.
And, reforming methane with carbon dioxide can prepare CO/H2The synthesis gas of=1: 1.For many years, grind both at home and abroad
The person of studying carefully has put into substantial amounts of man power and material and has been studied this catalytic reaction.But up to now, this dioxy
The process changing carbon catalytic reforming methane still differs greatly with industrialized requirement.Research shows, by noble metal
When ruthenium (Ru), rhodium (Rh) and palladium (Pd) even load are on suitable carrier, all there is higher reaction
Activity and anti-carbon performance, such as, German patent DE 9400513 discloses at Pd/ZrO2Catalyst is continuous
After using 500 hours, reactivity is held essentially constant.But noble metal catalyst shortcoming is expensive,
Not there is during industrialization advantage economically.In base metal, nickel-base catalyst has higher reaction and lives
Property, but carbon deposition phenomenon is serious, and such as carbon distribution can cover and cause catalysqt deactivation at catalyst surface, but also
Reactor plugs can be caused to make catalyst bed stressor layer increase.
Therefore, the carbon distribution and the sintering that how to solve nickel-base catalyst are to realize one of industrialized root problem.
Summary of the invention
In order to solve at least one aspect of the above-mentioned problems in the prior art and defect, the present invention provides
A kind of nickel-base catalyst for catalytic methane and CO 2 reformation preparing synthetic gas and preparation method thereof.Institute
State technical scheme as follows:
It is an object of the present invention to provide a kind of for catalytic methane and CO 2 reformation preparing synthetic gas
Nickel-base catalyst.
The a further object of the present invention there is provided one and prepares for catalytic methane and the synthesis of CO 2 reformation system
The method of the nickel-base catalyst of gas.
Synthesize according to an aspect of the invention, it is provided a kind of for catalytic methane and CO 2 reformation system
The nickel-base catalyst of gas, wherein, the chemical formula of described nickel-base catalyst is
Ni(Mo)/(CexZr1-xO2)yMgAl (O), wherein Ni is active metal, MO3And Ce .MgOxZr1-xO2For
Auxiliary agent, Al2O3For carrier, wherein x/1-x=0.25~4, y=1%-15%.
Specifically, described nickel-base catalyst includes nickel oxide, 0.2%~0.70% of 8%~15% in parts by weight
Molybdenum oxide, ceria and zirconium dioxide account for the 1%~15% of described nickel-base catalyst gross mass.
Further, described nickel-base catalyst is with NiMgAl houghite as precursor, by coprecipitation one
Step prepares catalyst precursor, after the most scrubbed drying and roasting, carries out reduction anti-in the atmosphere of reproducibility
Use after should.
Further, the atmosphere of described reproducibility is the mixed gas of hydrogen and nitrogen, in described mixed gas
The ratio of middle hydrogen and nitrogen is 1: 1, and described reduction reaction is carried out at 900-1000 DEG C.
Specifically, described nickel-base catalyst passes through Ce under the conditions of the use of 850~1050 DEG C2O3+CO2→
2CeO2+ CO, 2CeO2+C(s)→Ce2O3+ CO, and CO2Tri-chemical reactions of+C → 2CO carry out carbon distribution
Eliminate.
According to a further aspect in the invention, present invention also offers one to prepare for catalytic methane and titanium dioxide
The method of the nickel-base catalyst of carbon preparing synthetic gas by reforming, the method comprises the following steps:
(1) carbonate of scheduled volume is dissolved formation carbonate solution;
(2) by the soluble nickel salt of scheduled volume, solubility magnesium salt, aluminum soluble salt, soluble zirconium, solvable
Property molybdenum salt and solubility cerium salt dissolve formed mixed solution;
(3) in described mixed solution, add carbonate solution and aqueous slkali and be stirred obtaining suspension,
Wherein controlling to add speed makes the pH value of mixed solution maintain in a preset range;
(4) described suspension is placed in crystallization still carries out Crystallizing treatment, and suspended by after crystallization
Liquid carries out washing to neutrality and through sucking filtration process formation filter cake;
(5) described filter cake is dried at 80 DEG C~100 DEG C, afterwards by the filter cake of drying at 700 DEG C~900 DEG C
Roasting is to obtain composite oxides;
(6) by described composite oxides at 900 DEG C~1000 DEG C, it is passed through reproducibility mixed gas and reduces
Obtain described nickel-base catalyst.
Specifically, described soluble nickel salt, solubility magnesium salt, aluminum soluble salt, solubility zirconates, solvable
Property molybdenum salt and solubility cerium salt be the corresponding nitrate of metal, hydrochlorate and sulfate;
Described aqueous slkali is any one in sodium hydroxide, potassium hydroxide and ammonium hydroxide or their any group
Close;
Described carbonate be any one in sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate or they appoint
Meaning combination;
Described pH value is in the range of 8.0 to 11.
Further, described soluble molybdenum salt is ammonium heptamolybdate, and the time of described Crystallizing treatment is 1-24 hour,
The time of described drying is 1-12 hour, and the time of described roasting is 6-10 hour,
Carry out in the water bath with thermostatic control of 60 DEG C when carrying out step (1) and (2);In described step (3)
Described mixed solution is added dropwise in described sodium carbonate liquor, and is simultaneously added dropwise described aqueous slkali to described
In sodium carbonate liquor, strong stirring also keeps pH value in the scope of 8.0-11, continues to stir after being added dropwise to complete
Mix 1-3 hour, carry out step (4) afterwards.
Specifically, described nickel-base catalyst all does diluent by quartz sand with before reduction before use,
The method obtaining described nickel-base catalyst in the middle reduction of step (6) comprises the following steps:
Described nickel-base catalyst and quartz sand mix homogeneously are put in atmospheric fixed bed quartz ampoule and reacts;
In quartz ampoule, it is passed through the mixed gas of hydrogen and nitrogen, and carries out syllogic hyperthermic treatment, described three
Segmentation hyperthermic treatment includes:
First paragraph: from room temperature to 450 DEG C, 5 DEG C/min of heating rate, time-consuming 150min;
Second segment: from 450 DEG C to 900 DEG C, 1 DEG C/min of heating rate, time-consuming 450min;
3rd section: at 900 DEG C, constant temperature 120min is to obtain described nickel-base catalyst.
Preferably, the gas in quartz ampoule is switched to CO2/CH4=1, with 150mL/min, air speed is
60000mL/g.h-1Measure stability and the activity of described nickel-base catalyst.
The nickel-base catalyst that embodiments of the invention are provided and the method preparing nickel-base catalyst have following excellent
At least one in point:
(1) nickel-base catalyst of the present invention passes through Ce4+/Ce3+CO in middle oxygen vacancies and reaction atmosphere2Set up
The dynamic equilibrium of autonomous elimination carbon distribution eliminates carbon distribution.
(2) present invention passes through Co deposited synthesis a kind of reactivity height, good stability and can pass through
Ce4+/Ce3+Middle oxygen vacancies and reaction atmosphere set up the catalyst of the dynamic equilibrium of the carbon that disappears.
(3) described nickel-base catalyst for methane and carbon dioxide catalytic reforming preparing synthetic gas time, this is Ni-based urges
Agent can make the conversion ratio of methane and carbon dioxide close to thermodynamic equilibrium value, and in GHSV (air speed)
=60000mL/g.h-1Time this nickel-base catalyst such as use the conversion ratio of methane after 658h still to tie up at 900 DEG C
Hold at 95-96%.And averagely carbon deposition rate only has 0.017mgc/gcath-1, when this nickel-base catalyst is at 1000 DEG C
During use, this nickel-base catalyst does not has any inactivation sign after using 610h, and average carbon deposition rate is only
0.0043mgc/gcath-1, thus solve the problem that nickel-base catalyst inactivates carbon distribution fast, easy.
Accompanying drawing explanation
These and/or other aspect of the present invention and advantage are from description of preferred embodiments below in conjunction with the accompanying drawings
Will be apparent from easy to understand, wherein:
Fig. 1 is the CH when using according to No. 1 nickel-base catalyst provided by the present invention4Conversion ratio view;
Fig. 2 is the CH when using according to No. 2 nickel-base catalysts provided by the present invention4Conversion ratio view;
Fig. 3 is the CH when using according to No. 3 nickel-base catalysts provided by the present invention4Conversion ratio view;
Fig. 4 is to use according to CH during No. 1 nickel-base catalyst provided by the present invention at 900 DEG C and 1000 DEG C4
The comparison diagram of conversion ratio.
Detailed description of the invention
Below by embodiment, and combine accompanying drawing 1-4, technical scheme is made more specifically
Bright.In the description, same or analogous drawing reference numeral indicates same or analogous parts.Following with reference to attached
The explanation of embodiment of the present invention is intended to explain the present general inventive concept of the present invention by figure, and should not
It is interpreted as a kind of restriction to the present invention.
As described in the background section, in order to overcome nickel-base catalyst of the prior art to be deposited at least in part
Deficiency, at least one embodiment of the present invention provides a kind of for catalytic methane and CO 2 reformation
The nickel-base catalyst of preparing synthetic gas.The chemical formula of this nickel-base catalyst is Ni (Mo)/(CexZr1-xO2)yMgAl (O),
Wherein Ni is active metal, MO3And Ce .MgOxZr1-xO2For auxiliary agent, Al2O3For carrier, wherein
X/1-x=0.25~4, y=1%-15%.Specifically, the presoma of described nickel-base catalyst is NiMgAl class water
Talcum.In one embodiment, described nickel-base catalyst include in parts by weight 8%~15% nickel oxide,
The molybdenum oxide of 0.2%~0.70%, ceria and zirconium dioxide account for described nickel-base catalyst gross mass
1%~15%.Described nickel-base catalyst is with NiMgAl houghite as precursor, by coprecipitation one step system
Obtain catalyst precursor, after the most scrubbed drying and roasting, after carrying out reduction reaction in the atmosphere of reproducibility
Use.In an example of the present invention, the atmosphere of described reproducibility is the mixed gas of hydrogen and nitrogen,
In described mixed gas, the ratio of hydrogen and nitrogen is 1: 1, and described reduction reaction is carried out at 900-1000 DEG C.
Certainly, the invention is not restricted to the combination of hydrogen and nitrogen, any of reducibility gas all can be used herein
In the present invention.
Specifically, the use condition of described nickel-base catalyst is 850~1050 DEG C.
Described nickel-base catalyst passes through Ce in above-mentioned use condition (such as 900 DEG C)2O3+CO2→
2CeO2+ CO, 2CeO2+C(s)→Ce2O3+ CO, CO2Tri-chemical reactions of+C → 2CO carry out carbon distribution and disappear
Remove.
Above-mentioned close for catalytic methane and CO 2 reformation system it addition, present invention also offers a kind of preparation
The method becoming the nickel-base catalyst of gas, said method comprising the steps of:
(1) carbonate of scheduled volume is dissolved formation carbonate solution;
(2) by the soluble nickel salt of scheduled volume, solubility magnesium salt, aluminum soluble salt, solubility zirconates, can
Molybdenum salts and solubility cerium salt dissolve and form mixed solution;
(3) in described mixed solution, add carbonate solution and aqueous slkali and be stirred obtaining suspension,
Wherein controlling to add speed makes the pH value of mixed solution maintain in a preset range;
(4) described suspension is placed in crystallization still carries out Crystallizing treatment, and suspended by after crystallization
Liquid carries out washing to neutrality and through sucking filtration process formation filter cake;
(5) described filter cake is dried at 80 DEG C~100 DEG C, afterwards by the filter cake of drying at 700 DEG C~900 DEG C
Roasting is to obtain composite oxides;
(6) by described composite oxides at 900 DEG C~1000 DEG C, it is passed through reproducibility mixed gas and reduces
Obtain described nickel-base catalyst.
In step (2), described soluble nickel salt, solubility magnesium salt, aluminum soluble salt, solubility zirconates,
Soluble molybdenum salt and solubility cerium salt are the corresponding nitrate of metal, hydrochlorate and sulfate.Described alkali is molten
Liquid is any one in sodium hydroxide, potassium hydroxide and ammonium hydroxide or their combination in any.Described carbonic acid
Salt is any one in sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate or their combination in any.Here,
It should be noted that soluble nickel salt described herein, solubility magnesium salt, aluminum soluble salt, solubility zirconates,
As long as soluble molybdenum salt and solubility cerium salt can dissolve formation solution, it is not necessarily limited to above-mentioned enumerating
Example.In like manner, described aqueous slkali and carbonate solution also need not be formed by the above-mentioned example enumerated.
Specifically, described pH value is in the range of 8.0 to 11.
In one example, ZrO2Presoma can be ZrO (NO3)2xH2The solubility zirconates such as O, MoO3
Presoma be (NH3)Mo7O24.4H2O (ammonium heptamolybdate).It addition, the time of described Crystallizing treatment is
1-24 hour, the time of described drying was 1-12 hour, and the time of described roasting is 6-10 hour.
Carry out in the water bath with thermostatic control of such as 60 DEG C when carrying out step (1) and (2);In described step (3)
Middle described mixed solution is added dropwise in described sodium carbonate liquor, and is simultaneously added dropwise described aqueous slkali to institute
Stating in sodium carbonate liquor, strong stirring also keeps pH value in the scope of 8.0-11, continues after being added dropwise to complete
Stir 1-3 hour, carry out step (4) afterwards.
In another example, described nickel-base catalyst all does diluent by quartz sand with before reduction before use.
The method obtaining described nickel-base catalyst in the middle reduction of step (6) comprises the following steps:
Described nickel-base catalyst and quartz sand mix homogeneously are put in atmospheric fixed bed quartz ampoule and reacts;
In quartz ampoule, it is passed through the mixed gas of hydrogen and nitrogen, and carries out syllogic hyperthermic treatment, described three
Segmentation hyperthermic treatment includes:
First paragraph: from room temperature to 450 DEG C, 5 DEG C/min of heating rate, time-consuming 150min;
Second segment: from 450 DEG C to 900 DEG C, 1 DEG C/min of heating rate, time-consuming 450min;
3rd section: at 900 DEG C, constant temperature 120min is to obtain described nickel-base catalyst.
When measuring stability and the activity of described nickel-base catalyst, the gas in quartz ampoule is switched to
CO2/CH4=1, with 150mL/min, air speed is 60000mL/g.h-1Measure.
It is exemplified below out using coprecipitation to prepare the Ni-based of the present invention with NiMgAl houghite presoma to urge
The stability of one of concrete example of the preparation method of agent and this nickel-base catalyst and the assay method of activity.
Specifically, by a certain amount of Na2CO3It is dissolved in 120mL deionized water, and is placed on 60 DEG C of perseverances
In warm water bath, afterwards by 150mL dissolved with ammonium heptamolybdate and the nitrate of Ni, Mg and Al, Ce and
The nitrate of Zr mixes to form mixing salt solution.Simultaneously by above-mentioned mixing salt solution and NaOH solution
(2mol/L) being added dropwise in above-mentioned sodium carbonate liquor, strong stirring also keeps pH value to maintain 8.0-11.
Continue stirring 1-3h after dripping, then suspension is proceeded in the crystallizing kettle of 100mL, in 80 DEG C of baking ovens
Crystallization such as 24h, after crystallization completes, washs suspension, sucking filtration, by filter cake 80-100 DEG C in an oven
Dry certain time (such as 12h).Then roasting, specifically 700-900 DEG C of roasting 6-10h in Muffle furnace
After obtain composite oxides.
Needing explanation, during forming mixing salt solution, the mol ratio keeping (Ni+Mg)/Al is 3,
And to keep the mol ratio of Ce/Zr be 1-4.After firing, it is ensured that CeO in calcined catalyst2And ZrO2
Total mass fraction is 1-15%.During above-mentioned dropping, keep (n (CO3 2-)/n(Mn+) metal ion
Amount=2/3 of material, M represents various metal herein.
The catalyst activity of the present invention and estimation of stability are at the reaction unit of atmospheric fixed bed (internal diameter is 8mm)
On carry out, weigh catalyst 0.3g and mix homogeneously with quartz sand 1.5g and put into quartz ampoule reaction gas.?
CH4-CO2N it is passed through before reforming reaction2/H2=1 (20mL/min) uses temperature programming controller to control temperature, with
Syllogic temperature programming, first paragraph: room temperature~450 DEG C, 5 DEG C/min of heating rate, time-consuming 150min;The
Two-stage nitration: 450 DEG C~900 DEG C, heating rate 1 DEG C/min to 900 DEG C, time-consuming 450min;3rd section:
It is passed through constant temperature 120min at 900 DEG C, both obtains Ni (Mo)/(CexZr1-xO2)yMgAl (O) catalyst.Then
Gas is switched to CO2/CH4=1 (150mL/min) air speed is 60000mL/g.h-1Measure the steady of catalyst
Qualitative and active.
In order to measure and compare stability and the activity of nickel-base catalyst provided by the present invention, in three below
No. 1 nickel-base catalyst, No. 2 nickel-base catalysts and No. 3 nickel-base catalysts are obtained under different operating conditions.
For preparing the example 1 of No. 1 nickel-base catalyst:
By the anhydrous Na of 9.8g2CO3It is dissolved in 120mL deionized water to be placed in there-necked flask, weighs 0.036g
Ammonium heptamolybdate, 10.5g aluminum nitrate, 20.2g magnesium nitrate, the cerous nitrate of 0.13g, 2.4g nickel nitrate, 0.02g
These salt also are dissolved in 150mL deionized water forming mixing salt solution by zirconium nitrate.Afterwards, at 60 DEG C
Above-mentioned mixing salt solution and NaOH solution (2mol/L) are added dropwise over above-mentioned Na simultaneously2CO3In solution,
Strong stirring also keeps pH value to maintain 9.3.It is sufficiently stirred for 3h after dripping, is then added to crystallization
80-100 DEG C of crystallization 24h in still, is washed out to neutrality, and sucking filtration, by filter cake 80-100 DEG C of drying in an oven
24 hours.Then 800 DEG C of roasting 10h in Muffle furnace, it is thus achieved that No. 1 described nickel-base catalyst.
Needing explanation, during forming mixing salt solution, the mol ratio keeping (Ni+Mg)/Al is 3,
And to keep the mol ratio of Ce/Zr be 3.After firing, it is ensured that CeO in calcined catalyst2And ZrO2Always
Mass fraction be 1%, the mass fraction of NiO is 12%, MoO3Mass fraction be 0.5%.Above-mentioned
Dropping during, keep (n (CO3 2-)/n(Mn+) amount=2/3 of material of metal ion, M represents each herein
Plant metal.
For preparing the example 2 of No. 2 nickel-base catalysts:
By the anhydrous Na of 9.7g2CO3It is dissolved in 120mL deionized water to be placed in there-necked flask, weighs 0.036g,
Ammonium heptamolybdate, 10.31g aluminum nitrate, 20.0g magnesium nitrate, the cerous nitrate of 0.4g, 2.4g nickel nitrate, 0.2g nitre
These salt are also dissolved in 150mL deionized water, to form mixing salt solution by acid zirconium.Afterwards, at 60 DEG C
Above-mentioned mixing salt solution and NaOH solution (2mol/L) are added dropwise over above-mentioned Na simultaneously2CO3In solution,
Strong stirring also keeps pH value to maintain 9.5.It is sufficiently stirred for 1h after dripping, is then added to crystallization
80-100 DEG C of crystallization 24h in still, is washed out to neutrality, and sucking filtration, by filter cake 80-100 DEG C of drying in an oven
24 hours.Then roasting 800 DEG C of roasting 10h in Muffle furnace, thus prepare No. 2 nickel-base catalysts.
Needing explanation, during forming mixing salt solution, the mol ratio keeping (Ni+Mg)/Al is 3,
And to keep the mol ratio of Ce/Zr be 1.After firing, it is ensured that CeO in calcined catalyst2And ZrO2Always
Mass fraction be 5%, the mass fraction of NiO is 12%, MoO3Mass fraction be 0.5%.Above-mentioned
Dropping during, keep (n (CO3 2-)/n(Mn+) amount=2/3 of material of metal ion, M represents each herein
Plant metal.
For preparing the example 3 of No. 3 nickel-base catalysts:
By the anhydrous Na of 9.48g2CO3It is dissolved in 120mL deionized water to be placed in there-necked flask, weighs
0.036g ammonium heptamolybdate, 10.11g aluminum nitrate, 18.8g magnesium nitrate, the cerous nitrate of 0.7g, 2.4g nickel nitrate,
These salt are also dissolved in 150mL deionized water, to form mixing salt solution by 1.5g zirconium nitrate.Afterwards, exist
Above-mentioned mixing salt solution and NaOH solution (2mol/L) are added dropwise over above-mentioned Na at 60 DEG C simultaneously2CO3Molten
In liquid, strong stirring also keeps pH value to maintain 10.0.It is sufficiently stirred for 1h after dripping, is then added to
80-90 DEG C of crystallization 24h in crystallization still, is washed out to neutrality, and sucking filtration, by filter cake 80-100 DEG C in an oven
Dry 24 hours.Then roasting 800 DEG C of roasting 10h in Muffle furnace, thus prepare No. 3 nickel-base catalysts.
Needing explanation, during forming mixing salt solution, the mol ratio keeping (Ni+Mg)/Al is 3,
And to keep the mol ratio of Ce/Zr be 0.25.After firing, it is ensured that CeO in calcined catalyst2And ZrO2
Total mass fraction is 9%, and the mass fraction of NiO is 12%, MoO3Mass fraction be 0.5%.Upper
During the dropping stated, keep (n (CO3 2-)/n(Mn+) amount=2/3 of material of metal ion, M represents herein
Various metals.
Weigh above-mentioned No. 1, No. 2 and No. 3 each 300mg of nickel-base catalyst, add 1500mg quartz sand and make dilute
Release agent, grind tabletting and be placed in the quartz tube reactor that internal diameter is 8mm, be passed through H2/N2(1: 1),
Reductase 12 hour at 900 DEG C.Under normal pressure, with the flow velocity of 300ml/min by CO2/CH4(1: 1) is passed through reaction
Device, gas chromatographic detection tail gas forms.Result as Figure 1-3, shows to use 1,2, No. 3 catalyst equal
CH can be made4Conversion ratio all reach more than 90%.Specifically, 1-3 nickel-base catalyst is little in use 600
Time after, the conversion ratio of methane is held at more than 90% and without obvious carbon distribution.
It addition, be also weighed out No. 1 nickel-base catalyst 300mg, add 1500mg quartz sand and make diluent, make
Grain is placed in the quartz tube reactor that internal diameter is 8mm, is passed through H2/N2(1: 1), reductase 12 at 1000 DEG C
Hour.Under normal pressure, with the flow velocity of 300ml/min by CO2/CH4(1: 1) is passed through reactor, and gas chromatogram is examined
Survey tail gas forms.In conjunction with the determination experiment result at above-mentioned 900 DEG C, thus obtain at 900 DEG C and 1000 DEG C
CH under the conditions of two kinds4Conversion ratio comparison diagram.As seen from Figure 4, when this No. 1 nickel-base catalyst is at 1000 DEG C
During use, this catalyst does not has any inactivation sign after using 610h, and average carbon deposition rate only has 0.0043
mgc/gcath-1。
The nickel catalyst performance of the present invention is much better than tradition Ni/Al2O3Deng catalyst,
Ni(Mo)/(CexZr1-xO2)yMgAl (O) is when methane reforming reaction by using carbon dioxide, at 900 DEG C, and CO2∶
CH4=1: 1, GHSV=60000ml/g.h-1Reaction condition under, the conversion ratio of methane can be made to reach more than 95%,
This nickel-base catalyst activity can be steady in a long-term, maintains more than 658 hours and without deactivation phenomenom, and at 1000 DEG C
The conversion ratio of methane maintains 98-99%, 610h and does not inactivate sign.
The dynamic equilibrium eliminating carbon distribution the following detailed description of the present invention once.
The catalyst of the present invention can be with the CO in reaction gas component2Build the dynamic equilibrium eliminating carbon distribution.
Generation may react under this system:
CH4+CO2→2CO+2H2 (1)
CH4→C+H2 (2)
2CO→CO2+C (3)
Ce2O3+CO2→2CeO2+CO (4)
2CeO2+C(s)→2Ce2O3+CO (5)
The cracking reaction (1) being mainly derived from methane of carbon distribution and the qi of CO in methane reforming with carbon dioxide
Change reaction.When temperature is higher than 700 DEG C, disproportionation will not occur, and the main source of carbon distribution mostlys come from first
The cracking of alkane.Due to CeO2There is Ce4+/Ce3+Middle oxygen vacancies, and CeO2+C→Ce2O3+ CO low grade fever
Mechanics temperature is 900 DEG C, CeO2+Ni→Ce2O3This reaction of+NiO can not occur at secondary temperature, therefore protects
While card eliminates carbon distribution, active component is not oxidized.But reaction (4) will be descended to occur at normal temperatures, because of
This, in order to build a balance eliminating carbon distribution, have selected reaction temperature higher than 900 DEG C.Amassing of catalyst surface
A charcoal part passes through CO2+ C → 2CO (back reaction of disproportionation) is removed.Another part is by reaction (4)
Remove, be reduced into Ce2O3Further through reaction (3) revert to CeO2By this equilibrium catalyst surface
Carbon deposit be constantly eliminated, and return to state by id reaction catalyst thus maintain catalysis
Activity that agent is higher and stability.Therefore this catalyst is by the CO in reaction atmosphere2With in catalyst
CeO2Establish the dynamic equilibrium eliminating carbon distribution.
The nickel-base catalyst that embodiments of the invention are provided and the method preparing nickel-base catalyst have following excellent
At least one in point:
(1) nickel-base catalyst of the present invention passes through Ce4+/Ce3+Middle oxygen vacancies and reaction atmosphere establish and independently disappear
The dynamic equilibrium of carbon remover eliminates carbon distribution.
(2) present invention passes through Co deposited synthesis a kind of reactivity height, good stability and can pass through
Ce4+/Ce3+Middle oxygen vacancies and reaction atmosphere set up the catalyst of the dynamic equilibrium of the carbon that disappears.
(3) described nickel-base catalyst for methane and carbon dioxide catalytic reforming preparing synthetic gas time, this is Ni-based urges
Agent can make the conversion ratio of methane and carbon dioxide close to thermodynamic equilibrium value, and in GHSV (air speed)
=60000mL/g.h-1Time this nickel-base catalyst use the conversion ratio of methane after 658h to remain within 900 DEG C
95-96%.And averagely carbon deposition rate only has 0.017mgc/gcath-1, when this nickel-base catalyst makes at 1000 DEG C
This nickel-base catalyst of used time does not has any inactivation sign after using 610h, and average carbon deposition rate only has 0.0043
mgc/gcath-1, thus solve the problem that nickel-base catalyst inactivates carbon distribution fast, easy.
It should be noted that compared with catalyst known in the art, catalyst provided by the present invention has
Have and be preferably catalyzed activity, be because in this catalyst being formed without cerium zirconium sosoloid, but with ceria
Presented in, this due to add in the preparation process of catalyst of the present invention the mode of raw material be first be made into mixed
Closing solution to precipitate, this feed way is unfavorable for Zr again4+It is inserted into Ce4+Lattice in thus formed
CeZrO2Solid solution.Form the more difficult reduction of solid solution rear catalyst, cause catalyst to have poor activity.Separately
Outward, the roasting at 800 DEG C of this catalyst, higher sintering temperature makes to have between active metal and carrier strong
Active force.This can increase the stability of catalyst, and the generation of minimizing carbon distribution, the catalysis of the last present invention
Agent, 900 DEG C of evaluations carried out above, can set up a carbon distribution and the dynamic equilibrium of the carbon that disappears at such a temperature.
Although some embodiments of this present general inventive concept are shown and explanation, those of ordinary skill in the art
It will be appreciated that in the case of without departing substantially from the principle of this present general inventive concept and spirit, these embodiments can be done
Going out to change, the scope of the present invention limits with claim and their equivalent.
Claims (10)
1. one kind is used for catalytic methane and the nickel-base catalyst of CO 2 reformation preparing synthetic gas, it is characterised in that
The chemical formula of described nickel-base catalyst is Ni (Mo)/(CexZr1-xO2)yMgAl (O), wherein Ni is activity
Metal, MO3And Ce .MgOxZr1-xO2For auxiliary agent, Al2O3For carrier, wherein x/1-x=0.25~4,
Y=1%-15%.
The most according to claim 1 urge for catalytic methane and the Ni-based of CO 2 reformation preparing synthetic gas
Agent, it is characterised in that
Described nickel-base catalyst includes the oxidation of nickel oxide, 0.2%~0.70% of 8%~15% in parts by weight
Molybdenum, ceria and zirconium dioxide account for the 1%~15% of described nickel-base catalyst gross mass.
The most according to claim 1 and 2 for catalytic methane with the nickel of CO 2 reformation preparing synthetic gas
Base catalyst, it is characterised in that
Described nickel-base catalyst, with NiMgAl houghite as precursor, prepares catalysis by coprecipitation one step
Agent precursor, after the most scrubbed drying and roasting, uses after carrying out reduction reaction in the atmosphere of reproducibility.
The most according to claim 3 urge for catalytic methane and the Ni-based of CO 2 reformation preparing synthetic gas
Agent, it is characterised in that
The atmosphere of described reproducibility is the mixed gas of hydrogen and nitrogen, hydrogen and nitrogen in described mixed gas
The ratio of gas is 1: 1, and described reduction reaction is carried out at 900-1000 DEG C.
The most according to claim 4 urge for catalytic methane and the Ni-based of CO 2 reformation preparing synthetic gas
Agent, it is characterised in that
Described nickel-base catalyst passes through Ce under the conditions of the use of 850~1050 DEG C2O3+CO2→2CeO2+ CO,
2CeO2+C(s)→Ce2O3+ CO, and CO2Tri-chemical reactions of+C → 2CO carry out carbon distribution elimination.
6. one kind prepare according to according to any one of right 1-5 for catalytic methane and CO 2 reformation system
The method of the nickel-base catalyst of synthesis gas, said method comprising the steps of:
(1) carbonate of scheduled volume is dissolved formation carbonate solution;
(2) by the soluble nickel salt of scheduled volume, solubility magnesium salt, aluminum soluble salt, soluble zirconium, solvable
Property molybdenum salt and solubility cerium salt dissolve formed mixed solution;
(3) in described mixed solution, add carbonate solution and aqueous slkali and be stirred obtaining suspension,
Wherein controlling to add speed makes the pH value of mixed solution maintain in a preset range;
(4) described suspension is placed in crystallization still carries out Crystallizing treatment, and suspended by after crystallization
Liquid carries out washing to neutrality and through sucking filtration process formation filter cake;
(5) described filter cake is dried at 80 DEG C~100 DEG C, afterwards by the filter cake of drying at 700 DEG C~900 DEG C
Roasting is to obtain composite oxides;
(6) by described composite oxides at 900 DEG C~1000 DEG C, it is passed through reproducibility mixed gas and reduces
Obtain described nickel-base catalyst.
Method the most according to claim 6, it is characterised in that
Described soluble nickel salt, solubility magnesium salt, aluminum soluble salt, solubility zirconates, soluble molybdenum salt with
And solubility cerium salt is the corresponding nitrate of metal, hydrochlorate and sulfate;
Described aqueous slkali is any one in sodium hydroxide, potassium hydroxide and ammonium hydroxide or their any group
Close;
Described carbonate be any one in sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate or they appoint
Meaning combination;
Described pH value is in the range of 8.0 to 11.
Method the most according to claim 7, it is characterised in that
Described soluble molybdenum salt is ammonium heptamolybdate, and the time of described Crystallizing treatment is 1-24 hour, described drying
Time be 1-12 hour, the time of described roasting is 6-10 hour,
Carry out in the water bath with thermostatic control of 60 DEG C when carrying out step (1) and (2);In described step (3)
Described mixed solution is added dropwise in described sodium carbonate liquor, and is simultaneously added dropwise described aqueous slkali to described
In sodium carbonate liquor, strong stirring also keeps pH value in the scope of 8.0-11, continues to stir after being added dropwise to complete
Mix 1-3 hour, carry out step (4) afterwards.
Method the most according to claim 6, it is characterised in that
Described nickel-base catalyst all does diluent by quartz sand with before reduction before use,
The method obtaining described nickel-base catalyst in the middle reduction of step (6) comprises the following steps:
Described nickel-base catalyst and quartz sand mix homogeneously are put in atmospheric fixed bed quartz ampoule and reacts;
In quartz ampoule, it is passed through the mixed gas of hydrogen and nitrogen, and carries out syllogic hyperthermic treatment, described three
Segmentation hyperthermic treatment includes:
First paragraph: from room temperature to 450 DEG C, 5 DEG C/min of heating rate, time-consuming 150min;
Second segment: from 450 DEG C to 900 DEG C, 1 DEG C/min of heating rate, time-consuming 450min;
3rd section: at 900 DEG C, constant temperature 120min is to obtain described nickel-base catalyst.
Method the most according to claim 9, it is characterised in that
Gas in quartz ampoule is switched to CO2/CH4=1, with 150mL/min, air speed is 60000mL/g.h-1
Measure stability and the activity of described nickel-base catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610280836.0A CN105772016B (en) | 2016-04-29 | 2016-04-29 | nickel-base catalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610280836.0A CN105772016B (en) | 2016-04-29 | 2016-04-29 | nickel-base catalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105772016A true CN105772016A (en) | 2016-07-20 |
CN105772016B CN105772016B (en) | 2018-12-14 |
Family
ID=56400222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610280836.0A Active CN105772016B (en) | 2016-04-29 | 2016-04-29 | nickel-base catalyst and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105772016B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106513000A (en) * | 2016-11-30 | 2017-03-22 | 中国科学院上海高等研究院 | Supported nickel-based catalyst, and preparation method and application thereof |
CN109718782A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method of methane hydrogen sulfide reformation hydrogen production |
CN110035821A (en) * | 2016-12-15 | 2019-07-19 | 俄罗斯石油公司 | Natural gas or associated gas is converted to during self-heating recapitalization the catalyst and preparation method thereof of synthesis gas |
CN112237917A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Low-carbon alkane dry reforming catalyst carrier and catalyst thereof |
CN112717914A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Methane and carbon dioxide reforming catalyst, preparation method and application |
CN113198447A (en) * | 2021-04-19 | 2021-08-03 | 昆明理工大学 | Novel method for synthesizing oxygen storage catalyst in space limited domain |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102307835A (en) * | 2008-12-08 | 2012-01-04 | 现代重工业株式会社 | Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide |
CN103252240A (en) * | 2013-04-07 | 2013-08-21 | 华东理工大学 | A solvothermal method for solid solution catalyst NixM1-x-yMgyO (M is Ce, co, sn, mn) used for dry gas reforming of CH4-CO2 |
-
2016
- 2016-04-29 CN CN201610280836.0A patent/CN105772016B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102307835A (en) * | 2008-12-08 | 2012-01-04 | 现代重工业株式会社 | Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide |
CN103252240A (en) * | 2013-04-07 | 2013-08-21 | 华东理工大学 | A solvothermal method for solid solution catalyst NixM1-x-yMgyO (M is Ce, co, sn, mn) used for dry gas reforming of CH4-CO2 |
Non-Patent Citations (4)
Title |
---|
DAE-WOON JEONG ET.AL: "The effect of preparation method on the catalytic", 《SCIVERSE SCIENCE DIRECT》 * |
FRANCISCO POMPEO ET.AL: "Stability improvements of Ni/a-Al2O3 catalysts to obtain", 《SCIENCE DIRECT》 * |
NAWADEE SRISIRIWAT ET.AL: "Oxidative steam reforming of ethanol over Ni/Al2O3 catalysts", 《SCIENCE DIRECT》 * |
谭鹏甲: ""Ni(Mo)/(Ce0.8Zr0.2O2)MgAl(O)金属氧化物催化剂催化CH4-CO2重整制合成气研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106513000A (en) * | 2016-11-30 | 2017-03-22 | 中国科学院上海高等研究院 | Supported nickel-based catalyst, and preparation method and application thereof |
CN110035821A (en) * | 2016-12-15 | 2019-07-19 | 俄罗斯石油公司 | Natural gas or associated gas is converted to during self-heating recapitalization the catalyst and preparation method thereof of synthesis gas |
CN110035821B (en) * | 2016-12-15 | 2020-07-07 | 俄罗斯石油公司 | Catalyst for converting natural gas or associated gas into synthesis gas in autothermal reforming process and method for preparing same |
CN109718782A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method of methane hydrogen sulfide reformation hydrogen production |
CN109718782B (en) * | 2017-10-27 | 2021-08-31 | 中国石油化工股份有限公司 | Method for preparing hydrogen by reforming methane and hydrogen sulfide |
CN112237917A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Low-carbon alkane dry reforming catalyst carrier and catalyst thereof |
CN112237917B (en) * | 2019-07-18 | 2023-04-07 | 中国石油化工股份有限公司 | Low-carbon alkane dry reforming catalyst carrier and catalyst thereof |
CN112717914A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Methane and carbon dioxide reforming catalyst, preparation method and application |
CN112717914B (en) * | 2019-10-14 | 2023-06-16 | 中国石油化工股份有限公司 | Methane carbon dioxide reforming catalyst and preparation method and application thereof |
CN113198447A (en) * | 2021-04-19 | 2021-08-03 | 昆明理工大学 | Novel method for synthesizing oxygen storage catalyst in space limited domain |
Also Published As
Publication number | Publication date |
---|---|
CN105772016B (en) | 2018-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105772016A (en) | Nickel-based catalyst and preparation method thereof | |
CN105879876B (en) | The preparation method of nickel-base catalyst for methane and carbon dioxide preparing synthetic gas by reforming | |
CN101637721B (en) | Porous yttrium-cerium-zirconium solid solution and preparation method thereof | |
US8658559B2 (en) | Implantation of Ni nano domains in refractory metal oxide support by means of sol-gel encapsulation—an effective solution to coke formation in the partial oxidation of natural gas | |
CN103442806A (en) | Fischer-tropsch catalysts and method of preparation thereof | |
KR101359990B1 (en) | Catalyst for Reforming of Methane with the Enhanced Stability for Sulfur components, Preparing Method Thereof and Methane Reforming Method Using The Catalyst | |
JP5610408B2 (en) | CeAlO3 perovskite containing transition metal | |
US10888846B2 (en) | Manganese-doped nickel-methanation catalysts | |
CN106518045A (en) | Magnesia alumina spinel and high temperature methanation catalyst and preparation methods thereof | |
CN107970907A (en) | A kind of nano composite oxide catalyst and its preparation method and application | |
WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
CN109499577A (en) | The preparation of Cu-Ni base catalyst for inverse water gas reaction and application method | |
CN103464163A (en) | Method for preparing methanation catalyst by inorganic ammonium salt combustion method | |
CN108525676A (en) | A kind of Ru-Ni/Ce-Zr composite oxide catalysts and preparation method thereof | |
CN104190427A (en) | Multiphase nickel-based catalyst as well as preparation methods and application thereof | |
JP6272609B2 (en) | Method for producing composite oxide and composite oxide catalyst | |
CN104549197B (en) | A kind of MgA12O4The preparation method of spinelle Reforming catalyst agent carrier | |
CN100497177C (en) | Method of preparing hexaaluminate inorganic material by burning urea | |
Zhang et al. | Partial oxidation of methane on Ni/CeO2-ZrO2/γ-Al2O3 prepared using different processes | |
JP5831946B2 (en) | Catalyst production method | |
JP2559715B2 (en) | Heat resistant catalyst for catalytic combustion reaction and method for producing the same | |
CN113952956B (en) | Preparation method of methane dry reforming catalyst, methane dry reforming catalyst and application thereof | |
JP5494910B2 (en) | Hydrogen production catalyst and production method thereof | |
CN103480362B (en) | Preparation method of supported sulfur-tolerant methanation catalyst | |
CN104107715B (en) | Mix metal and/or the silica composite of its oxide and application thereof in original position |
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 |