CN105772016B - nickel-base catalyst and preparation method thereof - Google Patents
nickel-base catalyst and preparation method thereof Download PDFInfo
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- CN105772016B CN105772016B CN201610280836.0A CN201610280836A CN105772016B CN 105772016 B CN105772016 B CN 105772016B CN 201610280836 A CN201610280836 A CN 201610280836A CN 105772016 B CN105772016 B CN 105772016B
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Abstract
The invention discloses a kind of for catalytic methane and the nickel-base catalyst of CO 2 reformation preparing synthetic gas and preparation method thereof, belongs to methane and carbon dioxide catalytic reforming preparing synthetic gas field.The chemical formula of the 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%.
Description
Technical field
The present invention relates to methane and carbon dioxide catalytic reforming preparing synthetic gas fields, in particular to are used for catalytic methane and dioxy
Change the nickel-base catalyst and preparation method thereof of carbon preparing synthetic gas by reforming.
Background technique
Currently, extensive utilize of methane depends on indirect reformer, and methane carbon dioxide reformation is that methane is indirect
The relatively broad method used in Transformation Application.With the improvement of people's environmental awareness, the utilization and control of greenhouse gases
More and more attention has been paid to.In methane carbon dioxide reformation technique, catalyst is the core of the system.Carbon dioxide catalytic reforming
Methane preparing synthetic gas effectively can convert important change for carbon dioxide and methane both main greenhouse gases
Work raw material.
Moreover, CO/H can be made in reforming methane with carbon dioxide2=1: 1 synthesis gas.For many years, domestic and international researcher is put into
A large amount of man power and material studies catalysis reaction.But so far, the carbon dioxide catalytic reforming methane
Process still differs greatly with industrialized requirement.Studies have shown that being carried on by noble ruthenium (Ru), rhodium (Rh) and palladium (Pd) etc.
When on suitable carrier, reactivity and anti-carbon performance all with higher, for example, German patent DE 9400513 discloses
In Pd/ZrO2After catalyst is used continuously 500 hours, reactivity is held essentially constant.But noble metal catalyst disadvantage is
It is expensive, without advantage economically when industrialization.In base metal, nickel-base catalyst reaction with higher is lived
Property, but carbon deposition phenomenon is serious, such as carbon distribution can be covered on catalyst surface leads to catalyst inactivation, but also will cause reactor
Blocking rises catalyst bed stressor layer.
Therefore, how to solve the carbon distribution of nickel-base catalyst and sintering is 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 one kind
For catalytic methane and the nickel-base catalyst of CO 2 reformation preparing synthetic gas and preparation method thereof.The technical solution is as follows:
It is an object of the present invention to provide a kind of for the Ni-based of catalytic methane and CO 2 reformation preparing synthetic gas
Catalyst.
A further object of the invention is prepared there is provided a kind of for catalytic methane and CO 2 reformation preparing synthetic gas
The method of nickel-base catalyst.
According to an aspect of the invention, there is provided a kind of nickel for catalytic methane and CO 2 reformation preparing synthetic gas
Base catalyst, wherein the chemical formula of the nickel-base catalyst is Ni (Mo)/(CexZr1-xO2)yMgAl (O), wherein Ni is activity
Metal, Mo3And Ce .MgOxZrl-xO2For auxiliary agent, Al2O3For carrier, wherein x/1-x=0.25~4, y=1%-15%.
Specifically, the nickel-base catalyst include as mass fraction 8%~15% nickel oxide, 0.2%~0.70%
Molybdenum oxide, ceria and zirconium dioxide account for the 1%~15% of the nickel-base catalyst gross mass.
Further, the nickel-base catalyst is made using NiMgAl houghite as precursor by one step of coprecipitation
Catalyst precursor later after washed drying and roasting, uses after carrying out reduction reaction in the atmosphere of reproducibility.
Further, the atmosphere of the reproducibility is the mixed gas of hydrogen and nitrogen, the hydrogen in the mixed gas
Ratio with nitrogen is 1:1, and the reduction reaction carries out at 900-1000 DEG C.
Specifically, the nickel-base catalyst passes through Ce under 850~1050 DEG C of use condition2O3+CO2→2CeO2+ CO,
2CeO2+C(s)→Ce2O3+ CO and CO2Tri- chemical reactions of+C → 2CO carry out carbon distribution elimination.
According to another aspect of the present invention, it prepares the present invention also provides a kind of for catalytic methane and CO 2 reformation
The method of the nickel-base catalyst of preparing synthetic gas, method includes the following steps:
(1) it dissolves the carbonate of predetermined amount to form carbonate solution；
(2) by the soluble nickel salt of predetermined amount, soluble magnesium salt, aluminum soluble salt, soluble zirconium, soluble molybdenum salt and
Soluble cerium salt dissolves to form mixed solution；
(3) carbonate solution and aqueous slkali are added into the mixed solution and are stirred to obtain suspension, wherein
Control adding speed maintains the pH value of mixed solution in one preset range；
(4) suspension is placed into crystallization kettle and carries out Crystallizing treatment, and the suspension after crystallization is carried out
Washing forms filter cake to neutrality and through filtering processing；
(5) filter cake is dried at 80 DEG C~100 DEG C, the filter cake of drying is roasted at 700 DEG C~900 DEG C later with
Obtain composite oxides；
(6) it by the composite oxides at 900 DEG C~1000 DEG C, is passed through reproducibility mixed gas and is restored to obtain institute
State nickel-base catalyst.
Specifically, the soluble nickel salt, soluble magnesium salt, aluminum soluble salt, soluble zirconates, soluble molybdenum salt and
Soluble cerium salt is nitrate, hydrochloride and the sulfate of corresponding metal；
The aqueous slkali is any one of sodium hydroxide, potassium hydroxide and ammonium hydroxide or their any combination；
The carbonate is any one of sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate or their any combination；
The pH value is in the range of 8.0 to 11.
Further, the soluble molybdenum salt is ammonium heptamolybdate, and the time of the Crystallizing treatment is 1-24 hours, the baking
The dry time is 1-12 hours, and the time of the roasting is 6-10 hours,
It is carried out in 60 DEG C of water bath with thermostatic control when carrying out step (1) and (2)；By the mixing in the step (3)
Solution is added dropwise in the sodium carbonate liquor, and the aqueous slkali is added dropwise simultaneously into the sodium carbonate liquor, is strongly stirred
It mixes and keeps pH value in the range of 8.0-11, continue stirring 1-3 hours after being added dropwise to complete, carry out step (4) later.
Specifically, the nickel-base catalyst makees diluent by quartz sand before using preceding and reduction,
In the step (6) reduction obtain the nickel-base catalyst method the following steps are included:
The nickel-base catalyst and quartz sand are uniformly mixed to be put into atmospheric fixed bed quartz ampoule and reacted；
It is passed through the mixed gas of hydrogen and nitrogen in quartz ampoule, and carries out three-stage heating treatment, the three-stage liter
Temperature is handled
First segment: from room temperature to 450 DEG C, heating rate 5 DEG C/min, time-consuming 150min；
Second segment: from 450 DEG C to 900 DEG C, heating rate 1 DEG C/min, time-consuming 450min；
Third section: at 900 DEG C, constant temperature 120min is to obtain the nickel-base catalyst.
Preferably, the gas in quartz ampoule is switched into CO2/CH4=1, with 150mL/min, air speed 60000mL/g.h-1To measure the stability and activity of the nickel-base catalyst.
During nickel-base catalyst provided by the embodiment of the present invention and the method for preparing nickel-base catalyst have the following advantages that
At least one:
(1) nickel-base catalyst of the invention passes through Ce4+/Ce3+CO in middle oxygen vacancies and reaction atmosphere2It establishes and independently disappears
Carbon distribution is eliminated in the dynamic equilibrium of carbon remover.
(2) present invention is high by a kind of reactivity of Co deposited synthesis, stability is good and can pass through Ce4+/Ce3+
Middle oxygen vacancies and reaction atmosphere establish the catalyst of the dynamic equilibrium for the carbon that disappears.
(3) when the nickel-base catalyst being used for methane and carbon dioxide catalytic reforming preparing synthetic gas, the nickel-base catalyst energy
Enough make the conversion ratio of methane and carbon dioxide close to thermodynamic equilibrium value, and in GHSV (air speed)=60000mL/g.h-1When should
Nickel-base catalyst for example at 900 DEG C using 658h after the conversion ratio of methane remain within 95-96%.And average carbon deposition rate
Only 0.017mgc/gcath-1, when the nickel-base catalyst is in 1000 DEG C of uses, the nickel-base catalyst is after using 610h without appointing
What inactivation sign, average carbon deposition rate only have 0.0043mgc/gcath-1, so that solving nickel-base catalyst inactivates fast, easy carbon distribution
The problem of.
Detailed description of the invention
These and or other aspects and advantage of the invention will become from description of preferred embodiments with reference to the accompanying drawing
It obtains obviously and is readily appreciated that, in which:
Fig. 1 is CH when using provided No. 1 nickel-base catalyst according to the present invention4Conversion ratio view；
Fig. 2 is CH when using provided No. 2 nickel-base catalysts according to the present invention4Conversion ratio view；
Fig. 3 is CH when using provided No. 3 nickel-base catalysts according to the present invention4Conversion ratio view；
Fig. 4 is at 900 DEG C and 1000 DEG C using CH when provided No. 1 nickel-base catalyst according to the present invention4Conversion
The comparison diagram of rate.
Specific embodiment
1-4 below by way of examples and with reference to the accompanying drawings, the technical solutions of the present invention will be further described.?
In specification, the same or similar drawing reference numeral indicates the same or similar component.Following reference attached drawings are to embodiment party of the present invention
The explanation of formula is intended to explain present general inventive concept of the invention, and is not construed as to a kind of limitation of the invention.
As described in the background section, in order at least partly overcome present in nickel-base catalyst in the prior art not
Foot, at least one embodiment of the present invention provides a kind of urges for catalytic methane and the Ni-based of CO 2 reformation preparing synthetic gas
Agent.The chemical formula of the nickel-base catalyst is Ni (Mo)/(CexZr1-xO2)yMgAl (O), wherein Ni is active metal, Mo3.MgO
And CexZrl-xO2For auxiliary agent, Al2O3For carrier, wherein x/1-x=0.25~4, y=1%-15%.Specifically, described Ni-based to urge
The presoma of agent is NiMgAl houghite.In one embodiment, the nickel-base catalyst includes 8% as mass fraction
~15% nickel oxide, 0.2%~0.70% molybdenum oxide, ceria and zirconium dioxide account for the nickel-base catalyst gross mass
1%~15%.Catalyst is made using NiMgAl houghite as precursor, by one step of coprecipitation in the nickel-base catalyst
Precursor later after washed drying and roasting, uses after carrying out reduction reaction in the atmosphere of reproducibility.At of the invention one
In example, the atmosphere of the reproducibility is the mixed gas of hydrogen and nitrogen, the ratio of hydrogen and nitrogen in the mixed gas
Example is 1:1, and the reduction reaction carries out at 900-1000 DEG C.Certainly, herein the present invention is not limited to the combination of hydrogen and nitrogen,
Any of reducibility gas may be incorporated for the present invention.
Specifically, the use condition of the nickel-base catalyst is 850~1050 DEG C.
The 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 elimination.
In addition, the present invention also provides it is a kind of prepare it is above-mentioned for catalytic methane and CO 2 reformation preparing synthetic gas
The method of nickel-base catalyst, the described method comprises the following steps:
(1) it dissolves the carbonate of predetermined amount to form carbonate solution；
(2) by the soluble nickel salt of predetermined amount, soluble magnesium salt, aluminum soluble salt, soluble zirconates, soluble molybdenum salt with
And soluble cerium salt dissolves to form mixed solution；
(3) carbonate solution and aqueous slkali are added into the mixed solution and are stirred to obtain suspension, wherein
Control adding speed maintains the pH value of mixed solution in one preset range；
(4) suspension is placed into crystallization kettle and carries out Crystallizing treatment, and the suspension after crystallization is carried out
Washing forms filter cake to neutrality and through filtering processing；
(5) filter cake is dried at 80 DEG C~100 DEG C, the filter cake of drying is roasted at 700 DEG C~900 DEG C later with
Obtain composite oxides；
(6) it by the composite oxides at 900 DEG C~1000 DEG C, is passed through reproducibility mixed gas and is restored to obtain institute
State nickel-base catalyst.
In step (2), the soluble nickel salt, soluble magnesium salt, aluminum soluble salt, soluble zirconates, soluble molybdenum
Salt and soluble cerium salt are nitrate, hydrochloride and the sulfate of corresponding metal.The aqueous slkali is sodium hydroxide, hydroxide
Any one of potassium and ammonium hydroxide or their any combination.The carbonate is sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and carbon
Any one of sour ammonium or their any combination.Here, it should be noted that soluble nickel salt described herein, soluble magnesium
As long as salt, aluminum soluble salt, soluble zirconates, soluble molybdenum salt and soluble cerium salt can dissolve to form solution, without
It is necessarily limited to enumerated example.Similarly, the aqueous slkali and carbonate solution also need not must be by enumerated example shapes
At.
Specifically, the 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, MoO3Presoma be
(NH3)Mo7O24.4H2O (ammonium heptamolybdate).In addition, the time of the Crystallizing treatment is 1-24 hours, the time of the drying is 1-
12 hours, the time of the roasting was 6-10 hours.
It is carried out in such as 60 DEG C of water bath with thermostatic control when carrying out step (1) and (2)；It will be described in the step (3)
Mixed solution is added dropwise in the sodium carbonate liquor, and the aqueous slkali is added dropwise simultaneously into the sodium carbonate liquor, by force
Power stirs and maintains pH value in the range of 8.0-11, continues stirring 1-3 hours after being added dropwise to complete, and carries out step (4) later.
In another example, the nickel-base catalyst makees diluent by quartz sand before using preceding and reduction.
In the step (6) reduction obtain the nickel-base catalyst method the following steps are included:
The nickel-base catalyst and quartz sand are uniformly mixed to be put into atmospheric fixed bed quartz ampoule and reacted；
It is passed through the mixed gas of hydrogen and nitrogen in quartz ampoule, and carries out three-stage heating treatment, the three-stage liter
Temperature is handled
First segment: from room temperature to 450 DEG C, heating rate 5 DEG C/min, time-consuming 150min；
Second segment: from 450 DEG C to 900 DEG C, heating rate 1 DEG C/min, time-consuming 450min；
Third section: at 900 DEG C, constant temperature 120min is to obtain the nickel-base catalyst.
In the stability and activity for measuring the nickel-base catalyst, the gas in quartz ampoule is switched into CO2/CH4=1,
With 150mL/min, air speed 60000mL/g.h-1To measure.
It is exemplified below out and nickel-base catalyst of the invention is prepared using coprecipitation with NiMgAl houghite presoma
The stability and active measuring method of one of specific example of preparation method and the nickel-base catalyst.
Specifically, by a certain amount of Na2CO3It is dissolved in 120mL deionized water, and places it in 60 DEG C of thermostat water baths,
It is molten that 150mL is mixed to form salt-mixture dissolved with the nitrate of the nitrate of ammonium heptamolybdate and Ni, Mg and Al, Ce and Zr later
Liquid.Above-mentioned mixing salt solution and NaOH solution (2mol/L) are added dropwise in above-mentioned sodium carbonate liquor simultaneously, strong stirring
And pH value is kept to maintain 8.0-11.Continue to stir 1-3h after dripping, then suspension be transferred in the crystallizing kettle of 100mL,
Crystallization for example for 24 hours, after the completion of crystallization, washs suspension in 80 DEG C of baking ovens, filters, by filter cake 80-100 in an oven
DEG C drying certain time (such as 12h).Then it roasts, is specifically obtained after 700-900 DEG C of roasting 6-10h in Muffle furnace compound
Oxide.
It should be noted that keeping the molar ratio of (Ni+Mg)/Al is 3, and is kept during forming mixing salt solution
The molar ratio of Ce/Zr is 1-4.After firing, guarantee CeO in calcined catalyst2And ZrO2Total mass fraction is 1-
15%.During above-mentioned dropwise addition, (n (CO is kept3 2-)/n(Mn+) metal ion substance amount=2/3, M is indicated each herein
Kind metal.
The reaction unit of catalyst activity and estimation of stability of the invention at atmospheric fixed bed (internal diameter 8mm) is enterprising
Row, weighing catalyst 0.3g is uniformly mixed with quartz sand 1.5g to be put into quartz ampoule reaction gas.In CH4-CO2Lead to before reforming reaction
Enter N2/H2=1 (20mL/min) controls temperature, with three-stage temperature programming, first segment using temperature programming controller: room temperature~
450 DEG C, heating rate 5 DEG C/min, time-consuming 150min；Second segment: 450 DEG C~900 DEG C, 1 DEG C/min to 900 DEG C of heating rate,
Time-consuming 450min；Third section: being passed through constant temperature 120min at 900 DEG C, has both obtained Ni (Mo)/(CexZr1-xO2)yMgAl (O) catalysis
Agent.Then gas is switched into CO2/CH4=1 (150mL/min) air speed is 60000mL/g.h-1To measure the stabilization of catalyst
Property and activity.
It is different at following three in order to measure and the stability and activity of nickel-base catalyst more provided by the present invention
No. 1 nickel-base catalyst, No. 2 nickel-base catalysts and No. 3 nickel-base catalysts are obtained under operating condition.
It is used to prepare 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 three-necked flask, weighs seven molybdic acid of 0.036g
These salt are simultaneously dissolved in by ammonium, 10.5g aluminum nitrate, 20.2g magnesium nitrate, the cerous nitrate of 0.13g, 2.4g nickel nitrate, 0.02g zirconium nitrate
To form mixing salt solution in 150mL deionized water.Later, simultaneously by above-mentioned mixing salt solution and NaOH solution at 60 DEG C
Above-mentioned Na is added dropwise in (2mol/L)2CO3In solution, strong stirring simultaneously keeps pH value to maintain 9.3.It is sufficiently stirred after dripping
3h is then added to 80-100 DEG C of crystallization in crystallization kettle and for 24 hours, is washed out to neutrality, filters, in an oven by filter cake
80-100 DEG C dries 24 hours.Then 800 DEG C of roasting 10h in Muffle furnace obtain No. 1 nickel-base catalyst.
It should be noted that keeping the molar ratio of (Ni+Mg)/Al is 3, and is kept during forming mixing salt solution
The molar ratio of Ce/Zr is 3.After firing, guarantee CeO in calcined catalyst2And ZrO2Total mass fraction is 1%, NiO
Mass fraction be 12%, MoO3Mass fraction be 0.5%.During above-mentioned dropwise addition, (n (CO is kept3 2-)/n(Mn+)
Amount=2/3 of the substance of metal ion, M indicates various metals herein.
It is used to prepare 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 three-necked flask, weighs 0.036g, seven molybdic acids
These salt are simultaneously dissolved in by ammonium, 10.31g aluminum nitrate, 20.0g magnesium nitrate, the cerous nitrate of 0.4g, 2.4g nickel nitrate, 0.2g zirconium nitrate
In 150mL deionized water, to form mixing salt solution.Later, simultaneously by above-mentioned mixing salt solution and NaOH solution at 60 DEG C
Above-mentioned Na is added dropwise in (2mol/L)2CO3In solution, strong stirring simultaneously keeps pH value to maintain 9.5.It is sufficiently stirred after dripping
1h is then added to 80-100 DEG C of crystallization in crystallization kettle and for 24 hours, is washed out to neutrality, filters, in an oven by filter cake
80-100 DEG C dries 24 hours.Then 800 DEG C of roasting 10h in Muffle furnace are roasted, so that No. 2 nickel-base catalysts be made.
It should be noted that keeping the molar ratio of (Ni+Mg)/Al is 3, and is kept during forming mixing salt solution
The molar ratio of Ce/Zr is 1.After firing, guarantee CeO in calcined catalyst2And ZrO2Total mass fraction is 5%, NiO
Mass fraction be 12%, MoO3Mass fraction be 0.5%.During above-mentioned dropwise addition, (n (CO is kept3 2-)/n(Mn+)
Amount=2/3 of the substance of metal ion, M indicates various metals herein.
It is used to prepare 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 three-necked flask, weighs seven molybdic acid of 0.036g
These salt are simultaneously dissolved in by ammonium, 10.11g aluminum nitrate, 18.8g magnesium nitrate, the cerous nitrate of 0.7g, 2.4g nickel nitrate, 1.5g zirconium nitrate
In 150mL deionized water, to form mixing salt solution.Later, simultaneously by above-mentioned mixing salt solution and NaOH solution at 60 DEG C
Above-mentioned Na is added dropwise in (2mol/L)2CO3In solution, strong stirring simultaneously keeps pH value to maintain 10.0.It is sufficiently stirred after dripping
1h is then added in crystallization kettle 80-90 DEG C of crystallization for 24 hours, is washed out to neutrality, filters, by filter cake 80- in an oven
100 DEG C dry 24 hours.Then 800 DEG C of roasting 10h in Muffle furnace are roasted, so that No. 3 nickel-base catalysts be made.
It should be noted that keeping the molar ratio of (Ni+Mg)/Al is 3, and is kept during forming mixing salt solution
The molar ratio of Ce/Zr is 0.25.After firing, guarantee CeO in calcined catalyst2And ZrO2Total mass fraction is 9%,
The mass fraction of NiO is 12%, MoO3Mass fraction be 0.5%.During above-mentioned dropwise addition, (n (CO is kept3 2-)/n(Mn +) metal ion substance amount=2/3, M indicates various metals herein.
Above-mentioned No. 1, No. 2 and No. 3 each 300mg of nickel-base catalyst is weighed, 1500mg quartz sand is added and makees diluent, grinding pressure
Piece is placed in the quartz tube reactor that internal diameter is 8mm, is passed through H2/N2(1: 1), the reductase 12 hour at 900 DEG C.Under normal pressure, with
The flow velocity of 300ml/min is by CO2/CH4(1: 1) is passed through reactor, gas chromatographic detection tail gas composition.As a result as shown in Figure 1-3,
Show make CH using 1,2, No. 3 catalyst4Conversion ratio all reach 90% or more.Specifically, 1-3 nickel-base catalyst exists
90% or more is held at using the conversion ratio of methane after 600 hours and without obvious carbon distribution.
In addition, having also weighed No. 1 nickel-base catalyst 300mg, 1500mg quartz sand is added and makees diluent, granulation is placed on interior
Diameter is to be passed through H in the quartz tube reactor of 8mm2/N2(1:1), the reductase 12 hour at 1000 DEG C.Under normal pressure, with 300ml/min
Flow velocity by CO2/CH4(1: 1) is passed through reactor, gas chromatographic detection tail gas composition.It is real in conjunction with the measurement at above-mentioned 900 DEG C
It tests as a result, to obtain CH under the conditions of 900 DEG C and 1000 DEG C two kinds4Conversion ratio compare figure.As seen from Figure 4, when this No. 1
Nickel-base catalyst does not have any inactivation sign after the catalyst is using 610h in 1000 DEG C of uses, and average carbon deposition rate only has
0.0043mgc/gcath-1。
Nickel catalyst performance of the invention is much better than traditional Ni/Al2O3Equal catalyst, Ni (Mo)/(CexZr1-xO2)yMgAl
(O) when being used for methane reforming reaction by using carbon dioxide, at 900 DEG C, CO2∶CH4=1: 1, GHSV=60000ml/g.h-1Reaction item
Under part, the conversion ratio of methane can be made to reach 95% or more, which can be steady in a long-term, maintain 658 hours or more
And without deactivation phenomenom, and 98-99% is maintained in the conversion ratio of 1000 DEG C of methane, 610h does not inactivate sign.
The following detailed description of the dynamic equilibrium of elimination carbon distribution of the invention once.
Catalyst of the invention can be with the CO in reaction gas component2Construct the dynamic equilibrium of an elimination carbon distribution.Occur
Possibility reaction under the 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 disproportionation of the cracking reaction (1) and CO that are mainly derived from methane of carbon distribution is anti-in methane reforming with carbon dioxide
It answers.When temperature is higher than 700 DEG C, disproportionation will not occur, and the main source of carbon distribution mostlys come from the cracking of methane.Due to
CeO2With Ce4+/Ce3+Middle oxygen vacancies, and CeO2+C→Ce2O3The minimum thermodynamic temperature of+CO is 900 DEG C, CeO2+Ni→Ce2O3+
The NiO reaction cannot occur at secondary temperature, therefore while guarantee elimination carbon distribution, active component is not oxidized.However it reacts
(4) it will descend to occur at normal temperature, therefore in order to construct the balance of an elimination carbon distribution, reaction temperature selected to be higher than 900 DEG C.
Carbon deposit a part of catalyst surface passes through CO2+ C → 2CO (back reaction of disproportionation) is removed.Another part passes through reaction
(4) it removes, is reduced into Ce2O3Revert to CeO further through reaction (3)2Pass through the carbon deposit constantly quilt on the equilibrium catalyst surface
It eliminates, and state is returned to by autoreactivity catalyst to maintain the higher activity of catalyst and stability.
Therefore the catalyst passes through the CO in reaction atmosphere2With the CeO in catalyst2Establish the dynamic equilibrium of an elimination carbon distribution.
During nickel-base catalyst provided by the embodiment of the present invention and the method for preparing nickel-base catalyst have the following advantages that
At least one:
(1) nickel-base catalyst of the invention passes through Ce4+/Ce3+Middle oxygen vacancies and reaction atmosphere establish autonomous elimination carbon distribution
Dynamic equilibrium eliminate carbon distribution.
(2) present invention is high by a kind of reactivity of Co deposited synthesis, stability is good and can pass through Ce4+/Ce3+
Middle oxygen vacancies and reaction atmosphere establish the catalyst of the dynamic equilibrium for the carbon that disappears.
(3) when the nickel-base catalyst being used for methane and carbon dioxide catalytic reforming preparing synthetic gas, the nickel-base catalyst energy
Enough make the conversion ratio of methane and carbon dioxide close to thermodynamic equilibrium value, and in GHSV (air speed)=60000mL/g.h-1When should
Nickel-base catalyst 900 DEG C using 658h after the conversion ratio of methane remain within 95-96%.And average carbon deposition rate only has
0.017mgc/gcath-1, when the nickel-base catalyst is in 1000 DEG C of uses, the nickel-base catalyst does not have any mistake after using 610h
Sign living, average carbon deposition rate only have 0.0043mgc/gcath-1, so that solving nickel-base catalyst inactivates asking for fast, easy carbon distribution
Topic.
It should be noted that catalyst provided by the present invention has preferable compared with catalyst known in the art
Catalytic activity, be because the catalyst in do not form cerium zirconium sosoloid, but in the form of ceria exist, this due to
The mode of adding raw materials is first to be made into mixed solution to be precipitated again in the preparation process of catalyst of the present invention, this charging side
Formula is unfavorable for Zr4+It is inserted into Ce4+Lattice in forming CeZrO2Solid solution.The more difficult reduction of solid solution rear catalyst is formed,
Catalyst is caused to have poor activity.In addition, the catalyst is roasted at 800 DEG C, higher maturing temperature makes active gold
Belonging to has strong active force between carrier.This can increase the stability of catalyst, and reduce the generation of carbon distribution, last of the invention
Catalyst is evaluated at 900 DEG C or more, can establish the dynamic equilibrium an of carbon distribution and the carbon that disappears at such a temperature.
Although some embodiments of this present general inventive concept have been shown and have illustrated, those of ordinary skill in the art will be managed
Solution can make a change these embodiments in the case where the principle and spirit without departing substantially from this present general inventive concept, of the invention
Range is limited with claim and their equivalent.
Claims (8)
1. a kind of nickel-base catalyst for catalytic methane and CO 2 reformation preparing synthetic gas, which is characterized in that
The chemical formula of the nickel-base catalyst is Ni (Mo)/(CexZr1-xO2)yMgAl (O), wherein Ni is active metal, Mo3.MgO
And CexZrl-xO2For auxiliary agent, Al2O3For carrier, wherein x/1-x=0.25~4, y=1%-15% as mass fraction,
Wherein the nickel-base catalyst passes through body before the obtained catalyst of one step of coprecipitation using NiMgAl houghite as precursor
The suspension of body later after washed drying and roasting, uses, and cerium is with two after carrying out reduction reaction in the atmosphere of reproducibility
The form of cerium oxide is present in the nickel-base catalyst, carries out crystallization wherein the suspension is placed into crystallization kettle
Processing, and the suspension after crystallization is washed to neutrality and forms filter cake through filtering processing；The filter cake is 80 DEG C~100
It dries at DEG C, later roasts the filter cake of drying to obtain composite oxides, by the combined oxidation at 700 DEG C~900 DEG C
Object is passed through reproducibility mixed gas and is restored to obtain the nickel-base catalyst at 900 DEG C~1000 DEG C.
2. the nickel-base catalyst according to claim 1 for catalytic methane and CO 2 reformation preparing synthetic gas, special
Sign is,
The nickel-base catalyst includes 8%~15% nickel oxide, 0.2%~0.70% molybdenum oxide as mass fraction, and two
Cerium oxide and zirconium dioxide account for the 1%~15% of the nickel-base catalyst gross mass.
3. the nickel-base catalyst according to claim 1 for catalytic methane and CO 2 reformation preparing synthetic gas, special
Sign is,
The atmosphere of the reproducibility is the mixed gas of hydrogen and nitrogen, and the ratio of hydrogen and nitrogen is in the mixed gas
1:1, the reduction reaction carry out at 900-1000 DEG C.
4. the nickel-base catalyst according to claim 3 for catalytic methane and CO 2 reformation preparing synthetic gas, special
Sign is,
The nickel-base catalyst passes through Ce under 850~1050 DEG C of use condition2O3+CO2→2CeO2+ CO, 2CeO2+C(s)→
Ce2O3+ CO and CO2Tri- chemical reactions of+C → 2CO carry out carbon distribution elimination.
5. a kind of prepare the nickel for being used for catalytic methane and CO 2 reformation preparing synthetic gas according to any one of right 1-4
The method of base catalyst, the described method comprises the following steps:
(1) it dissolves the carbonate of predetermined amount to form carbonate solution；
(2) by the soluble nickel salt of predetermined amount, soluble magnesium salt, aluminum soluble salt, soluble zirconium, soluble molybdenum salt and solvable
Property cerium salt dissolves to form mixed solution；
(3) carbonate solution and aqueous slkali are added into the mixed solution and is stirred to obtain suspension, wherein controlling
Adding speed maintains the pH value of mixed solution in one preset range；
(4) suspension is placed into crystallization kettle and carries out Crystallizing treatment, and the suspension after crystallization is washed
Filter cake is formed to neutrality and through filtering processing；
(5) filter cake is dried at 80 DEG C~100 DEG C, later roasts the filter cake of drying to obtain at 700 DEG C~900 DEG C
Composite oxides；
(6) it by the composite oxides at 900 DEG C~1000 DEG C, is passed through reproducibility mixed gas and is restored to obtain the nickel
Base catalyst；
The wherein soluble nickel salt, soluble magnesium salt, aluminum soluble salt, soluble zirconates, soluble molybdenum salt and solubility
Cerium salt is nitrate, hydrochloride and the sulfate of corresponding metal；The aqueous slkali is sodium hydroxide, potassium hydroxide and ammonium hydroxide
Any one of or their any combination；The carbonate is any in sodium carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate
Kind or their any combination；The pH value is in the range of 8.0 to 11.
6. according to the method described in claim 5, it is characterized in that,
The soluble molybdenum salt is ammonium heptamolybdate, and the time of the Crystallizing treatment is 1-24 hours, and the time of the drying is 1-
12 hours, the time of the roasting was 6-10 hours,
It is carried out in 60 DEG C of water bath with thermostatic control when carrying out step (1) and (2)；By the mixed solution in the step (3)
It is added dropwise in the sodium carbonate liquor, and the aqueous slkali is added dropwise simultaneously into the sodium carbonate liquor, strong stirring is simultaneously
It keeps pH value in the range of 8.0-11, continues stirring 1-3 hours after being added dropwise to complete, carry out step (4) later.
7. according to the method described in claim 5, it is characterized in that,
The nickel-base catalyst makees diluent by quartz sand before using preceding and reduction,
In the step (6) reduction obtain the nickel-base catalyst method the following steps are included:
The nickel-base catalyst and quartz sand are uniformly mixed to be put into atmospheric fixed bed quartz ampoule and reacted；
It is passed through the mixed gas of hydrogen and nitrogen in quartz ampoule, and carries out three-stage heating treatment, at the three-stage heating
Reason includes:
First segment: from room temperature to 450 DEG C, heating rate 5 DEG C/min, time-consuming 150min；
Second segment: from 450 DEG C to 900 DEG C, heating rate 1 DEG C/min, time-consuming 450min；
Third section: at 900 DEG C, constant temperature 120min is to obtain the nickel-base catalyst.
8. the method according to the description of claim 7 is characterized in that
Gas in quartz ampoule is switched into CO2/CH4=1, with 150mL/min, air speed 60000mL/g.h-1It is described to measure
The stability and activity of nickel-base catalyst.
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| RU2638534C1 (en) * | 2016-12-15 | 2017-12-14 | Публичное акционерное общество "Нефтяная компания "Роснефть" | Catalyst of converting natural or associated gas into synthesis gas in autothermal riforming process and method of its 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 |
| 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 |
| 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 |
| CN116510741A (en) * | 2023-05-11 | 2023-08-01 | 浙江工业大学 | Anti-carbon-deposition methane dry reforming catalyst and preparation method and application thereof |
| CN117019162B (en) * | 2023-06-26 | 2024-08-23 | 华南农业大学 | Ni-CeAlO for full-component conversion of methane into alcohol-suitable mixed gas3Hydrotalcite catalyst, and preparation method and application thereof |
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 |
|---|
| "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;谭鹏甲;《中国优秀硕士学位论文全文数据库工程科技I辑》;20160315(第3期);正文第27页，摘要，第93页 * |
| Oxidative steam reforming of ethanol over Ni/Al2O3 catalysts;Nawadee Srisiriwat et.al;《Science Direct》;20090204;第34卷;全文 * |
| Stability improvements of Ni/a-Al2O3 catalysts to obtain;Francisco Pompeo et.al;《Science Direct》;20090130;第34卷;全文 * |
| The effect of preparation method on the catalytic;Dae-Woon Jeong et.al;《Sciverse Science Direct》;20130902;第38卷;全文 * |
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