CN105688916B - A kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and its application - Google Patents
A kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and its application Download PDFInfo
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Abstract
The invention belongs to chemical field, it is related to a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and its application.The present invention provides a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst, by mass percentage, including following components：Active component 20-25%；Cooperate with component 1-30%；Carrier 45-79%.The preparation method and its purposes in low temperature methane reforming reaction that the present invention still further provides a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst.A kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst of present invention offer and its application, it is applicable in the methane reforming process of the types such as the high pressure low temperature CH4 production, high pressure low temperature methane-steam reforming, high pressure low temperature methane-carbon dioxide-vapor mixing reforming of 400-800 DEG C of reaction temperature, there is higher catalytic activity and stability.
Description
Technical field
The invention belongs to chemical field, be related to a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and
It is applied.
Background technology
Natural gas is the important component that China administers haze and energy-saving and emission-reduction strategy, the year two thousand twenty as clean energy resource
Natural gas accounts for Chinese primary energy proportion and is up to 10% or more, and it is trend of the times that production application is continued to develop in China.It
The main component of right gas is methane, converts after synthesis gas again through reactions such as Ficher-Tropsch (F-T) synthesis methane to
It is the important channel for utilizing methane to prepare chemical products or liquid fuel.Meanwhile realize oven gas, periodic off-gases, flue gas etc. with
Toward be difficult to the tail gas efficiently utilized, the recycling of exhaust gas also has important practical significance.In recent years be based on environmental protection and
The purpose of industrial development, reforming of methane on Ni-Ce or hydrogen cause the great interest of industrial quarters.The many natural gases in China
Carbon dioxide content is higher in gas field, if can synthesis gas directly be produced with methane reaction for the carbon dioxide wherein contained, not only
Can save the energy consumption of separation process, improve carbon resource utilization rate, be also used as chemical energy source transmission system (CETS,
Ie..Chemical Energy Transmission System), and methane reforming technology path can from the point of view of industrial point of view
It realizes the carbon dioxide recycling of plant emissions, meet the needs of synthesis gas to substantially reduce cost of material, improve downstream
The economic benefit of product.
Methane-steam reforming, methane-CO 2 reformation and methane-carbon dioxide-vapor mixing reforming etc. are
The main path of methane reforming process at present, and loading type nickel-based catalyst is that methane reforming reaction is blanket a kind of cheap
Effective catalyst.The current methane reforming process developed still have reaction temperature it is excessively high, to the manufacturing process of reactor and
Material requires the problems such as harshness, catalyst surface carbon distribution.Therefore how selecting catalyst makes it under lower temperature conditions
Kinetically inhibit the generation of carbon distribution, while accelerating methane reforming reaction rate just to seem most important, this just needs designing
On the one hand to ensure that catalyst surface there are enough active sites to keep higher reactivity and stability when catalyst, separately
On the one hand the generation of carbon distribution can effectively be inhibited again.Wherein catalyst composition itself, auxiliary agent synergistic effect, metal and carrier
Interaction and acid-base value etc. are to influence catalyst activity position microstructure, dispersion degree, reproducibility and its reactivity, selection
Property and anti-carbon performance key factor, wherein how to be obtained under the premise of higher nickel loading uniformly, small size Nickel particle diameter
High-dispersed nickel catalyst is key problem in technology.
The research of methane reforming catalyst at present is concentrated mainly on nickel-base catalyst anti-carbon under high temperature, condition of normal pressure and resists
The research of sintering character.The document report the (the 36th delivered on International Journal of Hydrogen Energy
Volume, page 7094,2011；Author：Jianqiang Zhu etc.), with neutral SiO2For the Ni/SiO of carrier2Catalyst carbon dioxide
Reforming reaction activity is low, easily inactivates because of carbon distribution.Chinese patent (patent publication No. CN103949265A) discloses a kind of normal pressure
Lower methane tri-reforming catalyst.Methane titanium dioxide under a kind of normal pressure of Chinese patent (patent publication No. CN104248959A) disclosure
Carbon preparing synthetic gas by reforming Ni/Nd/SBA-15 catalyst.Pertinent literature does not propose that effectively work is reacted in control under high nickel loading
The method of catalyst surface Nickel particle diameter under condition.And industrially in order to which meet demand usually realizes catalysis by improving nickel loading
The greater activity and long-range stability of agent, this just sacrifices the anti-carbon performance of catalyst and raising catalyst is needed to use temperature
Degree, especially dry reforming catalyst temperature in use is difficult to be down to 850 DEG C or less.Higher reaction temperature does not only result in catalyst burning
Knot, component are lost in seriously, while also challenging to futurity industry, thus research meets industrial requirement at a lower temperature
The Ni-based low temperature methane reforming catalyst of anti-carbon high dispersive high load has important practical significance.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of high dispersive high load high activities
Low temperature methane reforming nickel-base catalyst and its application, for overcoming methane reforming under existing methane reforming, especially high pressure to be catalyzed
Agent stability is poor, component easy-sintering, loss defect；The techniques such as steam reforming, high temperature carbon dioxide reformation are to equipment material
It is required that high, high energy consumption and operating condition excessively tail gas, the exhaust gas such as the disadvantage of harshness and oven gas, periodic off-gases, flue gas are difficult to
The problems such as recycling.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of high dispersive high load high activity
Low temperature methane reforming nickel-base catalyst, by mass percentage, including following components：
Active component 20-25%；
Cooperate with component 1-30%；
Carrier 45-79%；
Wherein, the active component is nickel (Ni)；The coordinated groups be selected from calcium (Ca), yttrium (Y), magnesium (Mg), lanthanum (La),
One or more of cerium (Ce), zirconium (Zr) combine；The carrier is aluminium oxide (Al2O3)。
The collaboration component forms " cooperateing with-activity " site with active component.
Second aspect of the present invention provides a kind of preparation of high dispersive high load high activity low temperature methane reforming nickel-base catalyst
Method includes the following steps：
1) it according to active component, the proportioning of collaboration component and carrier in nickel catalyst agent prescription, is separately added into a solvent
Active component presoma, collaboration component presoma, support precursor form dispersion liquid, heating stirring mixing；
2) by mixed dispersion liquid in step 1), to get the catalyst after dry, roasting.
The presoma refers to the blank sample of target product, i.e., before achieving that target product by certain steps
Grade product.
The proportioning of active component, collaboration component and carrier refers specifically to be urged according to Ni-based in the agent prescription according to nickel catalyst
Active component, collaboration component, the mass percent of carrier in agent, are mole by the amount conversion needed for each substance, with respectively
The amount for calculating the active component presoma needed for obtaining, cooperateing with component presoma and support precursor.The active component forerunner
The molar ratio between active component nickel element in body in nickel element and nickel-base catalyst is 1：1.The collaboration component presoma
Middle each element is 1 with the molar ratio cooperateed between component corresponding element in nickel-base catalyst：1.The support precursor aluminium member
The molar ratio between carrier aluminium element in element and nickel-base catalyst is 1：1.
Preferably, in step 1), the solvent combines for one or both of water or alcohol.
It is highly preferred that the water is deionized water.
It is highly preferred that the alcohol is selected from the combination of one or more of methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol.Described third
Alcohol, butanol, the various isomers of amylalcohol are usable.
Preferably, in step 1), the active component presoma selected from nickel, the inorganic salts of nickel, nickel organic salt in one
Kind or several combinations.
It is highly preferred that the inorganic salts of the nickel are selected from the combination of one or more of nickel nitrate, nickel sulfate, nickel chloride.
It is highly preferred that the organic salt of the nickel is selected from the combination of one or both of citric acid nickel, nickel acetate.
Preferably, in step 1), the calculation formula of the solvent adding amount is：V=n/C；Wherein, V is solvent adding amount,
ml；N is the molal quantity of nickel element in active component presoma, mol；C is the molar concentration of nickel element in active component presoma,
mol/L。
It is highly preferred that the molar concentration of nickel element is 0.01-10mol/L in the active component presoma.
Preferably, in step 1), it is described collaboration component presoma selected from cooperate with component, cooperate with component compound in one
Kind or several combinations.
It is highly preferred that the coordinated groups are selected from the combination of one or more of calcium, yttrium, magnesium, lanthanum, cerium, zirconium.
It is highly preferred that it is described collaboration component compound selected from calcium, yttrium, magnesium, lanthanum, cerium, zirconium compound in one kind or
Several combinations.
It is further preferred that the compound of the calcium, yttrium, magnesium, lanthanum, cerium is selected from calcium, yttrium, magnesium, lanthanum, the acetate of cerium, nitre
One or more of hydrochlorate, chlorate, sulfate, oxide combine.
It is further preferred that the compound of the zirconium in basic zirconium chloride, zirconium nitrate, zirconyl nitrate, zirconium oxide one
Kind or several combinations.The zirconium oxide is nano zircite, and average grain diameter is in 1000nm or less.
Preferably, in step 1), the support precursor is selected from one or both of the hydroxide of aluminium oxide, aluminium group
It closes.
It is highly preferred that the aluminium oxide is selected from α-Al2O3、β-Al2O3、γ-Al2O3、δ-Al2O3、η-Al2O3、θ-Al2O3、
κ-Al2O3、ρ-Al2O3、χ-Al2O3One or more of combination.
It is highly preferred that the hydroxide of the aluminium is selected from α-Al (OH)3、β-Al(OH)3、β'-Al(OH)3、α-AlOOH、β-
AlOOH,α'One or more of-AlOOH is combined.
Preferably, in step 1), dispersant is additionally added in the solvent.
It is highly preferred that the dispersant is selected from lauryl sodium sulfate, neopelex, cetyl trimethyl
One or more of ammonium bromide, polyvinylpyrrolidone, polyethylene glycol combine.
It is highly preferred that the quality that the dispersant is added is the 0.01-10% (mass percent) of solvent quality.
Preferably, in step 1), the computer heating control dispersion liquid temperature is between 40-200 DEG C.
It is highly preferred that the computer heating control dispersion liquid temperature is between 80-150 DEG C.
Preferably, in step 1), described be stirred is stirred, is disposably stirred, gradually selected from gradually dropwise addition
One or more in return stirring mixing mixed are stirred mode.
Preferably, the time being stirred is 2-4h.
Preferably, described to be stirred the middle pH value for adjusting dispersion liquid between 7-12 in step 1).
It is highly preferred that the reagent of the pH value for adjusting dispersion liquid is alkaline solution.
It is further preferred that the alkaline solution is selected from ammonium carbonate, urea, ammonium hydroxide, sodium carbonate, sodium hydroxide, potassium hydroxide
One or more of mixed aqueous solutions.
Preferably, in step 2), the condition of the drying is：Atmosphere：Static or moving air atmosphere；Temperature：90-200
℃；Time：20-48h.
It is highly preferred that the condition of the drying is：Atmosphere：Static or moving air atmosphere；Temperature：100-150℃；When
Between：20-30h.
Preferably, in step 2), the condition of the roasting is：Atmosphere：Static or moving air atmosphere；Temperature：500-
1500℃；Time：2-20h.
It is highly preferred that the condition of the roasting is：Atmosphere：Static or moving air atmosphere；Temperature：500-1300℃；When
Between：2-6h.
Preferably, each preparation process carries out optional circular treatment in the step 2).
It is highly preferred that the optional circular treatment refers to being needed each preparation process in step 2) according to practical preparation
It sequentially repeats or in which separate step part repeats.
Third aspect present invention provides a kind of purposes of high dispersive high load high activity low temperature methane reforming nickel-base catalyst,
For the nickel-base catalyst is used in low temperature methane reforming reaction.
Preferably, the reaction condition of the applicable low temperature methane reforming reaction of the nickel-base catalyst is：Reaction temperature is
400-800℃；Reaction pressure is 0-4MPa；Reaction volume air speed is 1000-150000cm3/(gh)；Synthesis gas is by CO2、
H2O、CH4In at least two constituted.Wherein, in the methane-vapor low-temperature reformate reaction, the H2O/CH4Molar ratio
For 2.5-3.5：1, preferably 3：1.In the methane-carbon dioxide low-temperature reformate reaction, the CO2/CH4Molar ratio be 1-
3：1, preferably 2.4：1.In the methane-carbon dioxide-vapor low-temperature reformate reaction, the CO2/H2O/CH4Molar ratio
For 1-2：1：1, preferably 1.4：1：1.
Preferably, the nickel-base catalyst needs to carry out reduction activation before for low temperature methane reforming reaction；It is described
Reduction activation step is：Nickel-base catalyst is placed on reducing atmosphere and encloses middle reduction activation, reduction activation temperature is 600-900
DEG C, preferably 700-800 DEG C；The reduction activation time is 2-6h, preferably 3h；Wherein, reducing gas includes H2、N2, by H2And N2
Synthesis gas, inert gas and the H of composition2Mixed gas, inert gas and N2Gaseous mixture, inert gas and synthesis gas it is mixed
Close any one in gas；The volume space velocity that the reducing atmosphere encloses is 30000-120000cm3/(gh)。
It is highly preferred that after the nickel-base catalyst carries out reduction activation, Nickel particle diameter is evenly distributed between 5-8nm.
As described above, a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst of the present invention and its answering
With having the advantages that：
(1) nickel-base catalyst in the present invention is applicable in is rich in first with natural gas or oven gas, periodic off-gases, flue gas etc.
The tail gas of alkane, high pressure low temperature CH4 production, high pressure low temperature methane-steam reforming, the height that exhaust gas is raw material
Force down more air sources such as warm methane-carbon dioxide-vapor mixing reforming, multi-state type methane reforming process, can evade
The techniques such as steam reforming, high temperature carbon dioxide reformation require high, high energy consumption and operating condition excessively harshness to equipment material
Disadvantage has wide industrial utilization foreground and value.
(2) a kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst of the invention and its application, can
In conjunction with energy industry reality, efficiently uses oven gas, periodic off-gases, flue gas etc. and be difficult to the tail gas efficiently utilized, exhaust gas work in the past
It for raw material, makes full use of factory's waste heat as heat source, realizes that exhaust gas-heat sourcesization utilize, reduce operation cost of enterprises.
(3) nickel-base catalyst in the present invention has 20-25% high nickel loadings and can be protected after reduction activation
Polymolecularity (Nickel particle diameter high uniformity is distributed between 5-8nm) is held, and can be under the conditions of low temperature (400-800 DEG C) of high activity
Reaction can effectively avoid migration under nickel component high temperature from reuniting and heat loss problem, and lower reaction temperature is also more conducive to maintain
The stabilization of activated centre micro-structure, to make, methane reforming catalytic activity is high, stability is good, is not easy carbon distribution, high pressure resistant low temperature.
Description of the drawings
Fig. 1 is shown as the Ni-Ca/Al of the present invention2O3Catalyst is in H2/N2The lower 800 DEG C of reduction 3 of=60/60ml/min atmosphere
Hour and the at room temperature scale after dilute oxygen Passivation Treatment are transmission electron microscope (TEM) figure of 50nm.
Fig. 2 is shown as the Ni-Ca/Al of the present invention2O3Catalyst is in H2/N2The lower 800 DEG C of reduction 3 of=60/60ml/min atmosphere
Hour and the at room temperature scale after dilute oxygen Passivation Treatment are transmission electron microscope (TEM) figure of 5nm.
Fig. 3 is shown as the Ni-Ca/Al of the present invention2O3Catalyst is in 800 DEG C of furnace temperature, air speed 122400cm3/ (gh), reaction
Pressure 0.5MPa, unstripped gas CO2/CH4Low temperature CH4 production activity curve under conditions of molar ratio 2.4.
Fig. 4 is shown as the Ni-Ca/Al of the present invention2O3Catalyst is in 750 DEG C of furnace temperature, air speed 122400cm3/ (gh), reaction
Pressure 0.5MPa, unstripped gas CO2/CH4Low temperature CH4 production performance map under conditions of molar ratio 2.4.
Fig. 5 is shown as the Ni-Ca-La/Al of the present invention2O3Catalyst is in 710 DEG C of furnace temperature, air speed 144000cm3It is/(gh), anti-
Answer pressure 0.5MPa, unstripped gas H2O/CH4Low temperature methane-vapor low-temperature reformate reactivity worth figure under conditions of molar ratio 3.
Fig. 6 is shown as the Ni-Ca-La/Al of the present invention2O3Catalyst is in 750 DEG C of furnace temperature, air speed 144000cm3It is/(gh), anti-
Answer pressure 0.5MPa, unstripped gas H2O/CH4Low temperature methane-vapor low-temperature reformate reactivity worth figure under conditions of molar ratio 3.
Fig. 7 is shown as the Ni-Ca-La/Al of the present invention2O3Catalyst is in 750 DEG C of furnace temperature, air speed 122400cm3It is/(gh), anti-
Answer pressure 0.5MPa, unstripped gas CO2/CH4Low temperature CH4 production performance map under conditions of molar ratio 2.4.
Fig. 8 is shown as the Ni-Ce-Zr-Y/Al of the present invention2O3Catalyst is in 700 DEG C of furnace temperature, air speed 122400cm3/(gh)、
Unstripped gas CO2/H2O/CH4Low temperature methane-carbon dioxide-vapor mixing reforming reactivity worth under conditions of molar ratio 1.4/1/1
Figure.
Specific implementation mode
With reference to specific embodiment, the present invention is further explained, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device；All pressure values and range all refer to relative pressure.The component agent used in the following example is conventional reagent,
Commercially available acquisition.The polyvinylpyrrolidone (PVP) is the nonionic producing high-molecular of CAS 9003-39-8
Close object.The polyethylene glycol (PEG) is the polymer of CAS 25322-68-3.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relation between one or more equipment/device mentioned in the present invention is not repelled
The front and back two equipment/devices specifically mentioned there may also be other equipment/device or at these of the unit equipment/device it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1
By Ni-Ca/Al2O3In finished catalyst mass percent be 75% alumina catalyst support 5g as calculation basis, and
Be 20% with active component Ni element mass percents, to cooperate with the mass percent of component Ca elements be 5% to be calculated, according to
Molar ratio is 1 between corresponding element：1 calculates, and obtains required preparation Ni-Ca/Al2O3The reactant quality of finished catalyst, wherein
Alpha-alumina is 5.000g, nickel nitrate 6.606g, calcium nitrate 1.964g.And according to formula V=n/C with nickel member in reaction solution
A concentration of 0.13mol/L of element calculate needed for deionized water and n-butanol mixed solvent (deionized water and the volume of n-butanol it
Than being 1：1) dosage is 175ml.And according to the dosage of the 1% of solvent quality calculating neopelex.
Alpha-alumina, nickel nitrate, calcium nitrate, neopelex use are disposably stirred mode and added jointly
The in the mixed solvent for adding to deionized water and n-butanol composition is made into dispersion liquid, heating keep dispersion liquid temperature be 90 DEG C of constant temperature simultaneously
It is sufficiently stirred 4 hours, proper amount of sodium carbonate is during which added dropwise and keeps dispersion liquid pH=9, subsequent solvent flashing and in 120 DEG C of moving airs
It is fully 20 hours dry in atmosphere, then obtain 6.67g through roasting 5 hours and being cooled to room temperature in 700 DEG C of static atmosphere of air
Ni-Ca/Al2O3Finished catalyst.
By the Ni-Ca/Al of above-mentioned acquisition2O3Catalyst uses 50%H at 800 DEG C2/N2In-situ reducing 3 hours, in H2/
N2The reduction and scale after dilute oxygen Passivation Treatment is respectively that the transmission of 50nm, 5nm are electric at room temperature under=60/60ml/min atmosphere
Mirror (TEM) figure is shown in Fig. 1,2.Ni-Ca/Al after reduction2O3Catalyst can be used to methane-carbon dioxide low-temperature reformate reaction,
800 DEG C of furnace temperature, air speed 122400cm3/ (gh), reaction pressure 0.5MPa, unstripped gas CO2/CH4It is tested under conditions of molar ratio 2.4
The performance of catalyst, the results are shown in Figure 3.In 750 DEG C of furnace temperature, air speed 122400cm3/ (gh), reaction pressure 0.5MPa,
Unstripped gas CO2/CH4The performance of catalyst is tested under conditions of molar ratio 2.4, the results are shown in Figure 4.
As seen from Figure 1, the sample nickel particle under reducing atmosphere after reduction activation is evenly distributed and grain on carrier
Diameter distribution height concentrates between 5-7nm；As it is clear from fig. 2 that finding nickel particle diameter about 5nm after engineer's scale is further amplified.By
Fig. 3 can be seen that corresponding sample dry reforming performance in 800 DEG C of furnace temperature and stablize, methane, carbon dioxide in reaction 30 hours
Conversion ratio is stepped up, and does not inactivate sign；As seen from Figure 4, furnace temperature is further decreased to 750 DEG C, dry reforming performance
Still performance is stablized, and does not inactivate sign.This shows that the catalyst sample of high load high dispersive shows the anti-product of good low temperature
Carbon performance shows outstanding catalyst activity and stability.
Embodiment 2
By Ni-Ca-La/Al2O3The alumina catalyst support 5g that mass percent is 75% in finished catalyst as calculate according to
According to, and with active component Ni element mass percents be 20%, to cooperate with the mass percent of component Ca elements be 3%, coordinated groups
Divide the mass percent of La elements to be calculated for 2%, is 1 according to molar ratio between corresponding element：1 calculates, and obtains required system
Standby Ni-Ca-La/Al2O3The reactant quality of finished catalyst, wherein β-Al (OH)3For 7.650g, nickel acetate 5.653g, second
Sour calcium is 0.879g, lanthanum nitrate 0.312g.And according to formula V=n/C by nickel element concentration in reaction solution for 0.2mol/L in terms of
The dosage for calculating the required absolute ethyl alcohol as solvent is 113.6ml.And according to the use of the 1% of solvent quality calculating polyethylene glycol
Amount.
Use respectively the absolute ethyl alcohol of 113.6ml as solvent prepare nickel acetate-calcium acetate mixed solution, lanthanum nitrate hexahydrate,
β-Al(OH)3Solution for standby, first at β-Al (OH)3Polyethylene glycol is added in solution and is heated to 120 DEG C of constant temperature.Again by lanthanum nitrate
Solution is added dropwise to the β-Al (OH) of 120 DEG C of constant temperature in 20min3Solution is sufficiently stirred nickel acetate-calcium acetate after 1 hour again
Mixed solution pours into rapidly above-mentioned mixed dispersion liquid, continues constant temperature and stirs 1 hour, appropriate urea is during which added dropwise and keeps dispersion liquid pH=
9, subsequent solvent flashing is simultaneously fully dry in 120 DEG C of static atmosphere of air, then small through roasting 5 in 900 DEG C of moving air atmosphere
When and be cooled to room temperature the Ni-Ca-La/Al for obtaining 6.67g2O3Finished catalyst.
By the Ni-Ca-La/Al of above-mentioned acquisition2O3Catalyst uses 50%H at 800 DEG C2/N2After in-situ reducing 3 hours, i.e.,
It can be used for methane-vapor low-temperature reformate reaction, in 710 DEG C of furnace temperature, air speed 144000cm3/ (gh), reaction pressure 0.5MPa,
Unstripped gas H2O/CH4The performance of catalyst is tested under conditions of molar ratio 3, the results are shown in Figure 5.In 750 DEG C of furnace temperature, sky
Fast 144000cm3/ (gh), reaction pressure 0.5MPa, unstripped gas H2O/CH4The property of catalyst is tested under conditions of molar ratio 3
Can, the results are shown in Figure 6.Methane-carbon dioxide low-temperature reformate reaction is can also be used for, in 750 DEG C of furnace temperature, air speed
122400cm3/ (gh), reaction pressure 0.5MPa, unstripped gas CO2/CH4The property of catalyst is tested under conditions of molar ratio 2.4
Can, the results are shown in Figure 7.
As seen from Figure 5, sample water in 710 DEG C of furnace temperature outstanding, methane conversion in reaction 30 hours of reforming performance
Rate is stablized 65% or more；When 750 DEG C of furnace temperature, methane conversion can be stablized 80% or more and without inactivation sign.Together
Sample, in 750 DEG C of furnace temperature, dry reforming performance is outstanding it can be seen from Fig. 6,7, and 30 hours methane conversions of reaction can be stablized
75% or more, carbon dioxide conversion can be stablized 50% or more, and sample does not inactivate sign.This shows high load high score
Scattered catalyst sample shows good low temperature anti-carbon performance, shows outstanding catalyst activity and stability.
Embodiment 3
By Ni-Ce-Zr-Y/Al2O3The alumina catalyst support 5g that mass percent is 74.8% in finished catalyst is as calculating
Foundation, and with active component Ni element mass percents be 20%, cooperate with the mass percent of component Ce elements to be 3%, collaboration
It is 0.2% to be calculated that the mass percent of component Zr elements, which is 2%, cooperates with the mass percent of component Y element, according to correspondence
Molar ratio is 1 between element：1 calculates, and obtains required preparation Ni-Ce-Zr-Y/Al2O3The reactant quality of finished catalyst,
Middle γ-Al2O3It is for 5.000g, nickel nitrate 6.624g, cerous nitrate 0.621g, zirconium nitrate 0.629g, yttrium nitrate
0.058g.And nickel element concentration is the deionization as solvent needed for 0.2mol/L is calculated using in reaction solution according to formula V=n/C
The dosage of water is 113.9ml.And according to the dosage of the 1% of solvent quality calculating polyethylene glycol.
Deionized water is used to prepare nitrate mixed solution (nickel nitrate, cerous nitrate, zirconium nitrate, yttrium nitrate as solvent respectively
Volume ratio be 3.5：1.5：1.5：And γ-Al 0.5)2O3Solution for standby, first in γ-Al2O3In solution add polyethylene glycol and
It is heated to 120 DEG C of constant temperature.Nitrate mixed solution is added dropwise to the γ-Al of 120 DEG C of constant temperature in 20min again2O3Solution, fully
During which stirring 2 hours is added dropwise appropriate potassium hydroxide aqueous solution and keeps dispersion liquid pH=8, subsequent solvent flashing and in 120 DEG C of static state
It is fully dry in air atmosphere, then obtain 6.68g's through roasting 5 hours and being cooled to room temperature in 700 DEG C of moving air atmosphere
Ni-Ce-Zr-Y/Al2O3Finished catalyst.
By the Ni-Ce-Zr-Y/Al of above-mentioned acquisition2O3Catalyst uses 50%H at 800 DEG C2/N2After in-situ reducing 3 hours,
Methane-carbon dioxide-vapor low-temperature reformate reaction is can be used to, in 700 DEG C of furnace temperature, air speed 122400cm3/ (gh), reaction
Pressure 0.5MPa, unstripped gas CO2/H2O/CH4The performance of catalyst is tested under conditions of molar ratio 1.4/1/1, result is as schemed
Shown in 8.
As seen from Figure 8, sample water in 700 DEG C of furnace temperature is reformed performance and is stablized, methane conversion in reaction 30 hours
Rate is stablized 55% or more, and carbon dioxide conversion is stablized 20% or more, this shows the catalyst sample of high load high dispersive
Good low temperature anti-carbon performance is shown, outstanding catalyst activity and stability are shown.
Embodiment 4
By Ni-Mg-La/Al2O3The alumina catalyst support 5g that mass percent is 45% in finished catalyst as calculate according to
According to, and with active component Ni element mass percents be 25%, to cooperate with the mass percent of component Mg elements be 25%, coordinated groups
Divide the mass percent of La elements to be calculated for 5%, is 1 according to molar ratio between corresponding element：1 calculates, and obtains required system
Standby Ni-Mg-La/Al2O3The reactant quality of finished catalyst, wherein beta-alumina are 5.000g, citric acid nickel be 26.331g,
Magnesium sulfate is 13.754g, lanthanum chloride 0.981g.And according to formula V=n/C it is 0.2mol/L with nickel element concentration in reaction solution
The dosage for calculating the required absolute methanol as solvent is 236.7ml.And calculate cetyl front three according to the 5% of solvent quality
The dosage of base ammonium bromide.
The absolute methanol of 236.7ml is used to prepare citric acid nickel-magnesium sulfate mixed solution, lanthanum chloride respectively as solvent molten
Liquid, beta-alumina solution for standby first add cetyl trimethylammonium bromide in beta-alumina solution and are heated to 150 DEG C of perseverances
Temperature.Lanthanum chloride solution is added dropwise to the beta-alumina solution of 150 DEG C of constant temperature in 20min again, is sufficiently stirred lemon after 1 hour again
Lemon acid nickel-magnesium sulfate mixed solution pours into rapidly above-mentioned mixed dispersion liquid, continues constant temperature and stirs 1 hour, appropriate carbon is during which added dropwise
Sour ammonium keeps dispersion liquid pH=12, and subsequent solvent flashing is simultaneously fully dry in 150 DEG C of static atmosphere of air, then is flowed through 1200 DEG C
It is roasted 15 hours in dynamic air atmosphere and is cooled to room temperature the Ni-Mg-La/Al for obtaining 11.11g2O3Finished catalyst.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (4)
1. a kind of preparation method of nickel-base catalyst, which is characterized in that include the following steps：
1) according to active component, the proportioning of collaboration component and carrier in nickel catalyst agent prescription, it is separately added into activity in a solvent
Component presoma, collaboration component presoma, support precursor form dispersion liquid, heating stirring mixing；
2) by mixed dispersion liquid in step 1), to get the catalyst after dry, roasting；
The nickel catalyst agent prescription, by mass percentage, including following components：
Active component 20-25%；
Cooperate with component 1-30%；
Carrier 45-79%；
Wherein, the active component is nickel；The coordinated groups are selected from one or more of calcium, yttrium, magnesium, lanthanum, cerium, zirconium group
It closes；The carrier is aluminium oxide；
In step 1), the solvent combines for one or both of water or alcohol；The active component presoma is selected from nickel, nickel
One or more of the organic salt combination of inorganic salts, nickel；The collaboration component presoma is selected from collaboration component, cooperates with component
One or more of compound combines；The support precursor is selected from one or both of the hydroxide of aluminium oxide, aluminium
Combination；
The coordinated groups are selected from the combination of one or more of calcium, yttrium, magnesium, lanthanum, cerium, zirconium；The compound of the collaboration component
One or more of compound selected from calcium, yttrium, magnesium, lanthanum, cerium, zirconium combines；
In step 1), dispersant is additionally added in the solvent；The quality that the dispersant is added is the 0.01- of solvent quality
10%；
The dispersant is selected from lauryl sodium sulfate, neopelex, cetyl trimethylammonium bromide, polyethylene
One or more of pyrrolidones combines；
In step 1), the computer heating control dispersion liquid temperature is between 80-150 DEG C；
It is described to be stirred the middle pH value for adjusting dispersion liquid between 7-12 in step 1)；In step 2), the condition of the drying
For：Atmosphere：Static or moving air atmosphere；Temperature：90-200℃；Time：20-48h；
In step 2), the condition of the roasting is：Atmosphere：Static or moving air atmosphere；Temperature：500-1500℃；Time：2-
20h。
2. the purposes for the nickel-base catalyst that preparation method according to claim 1 prepares, which is characterized in that the use
Way is by the nickel-base catalyst in low temperature methane reforming reaction；The nickel-base catalyst is anti-for low temperature methane reforming
Before answering, need to carry out reduction activation.
3. the purposes for the nickel-base catalyst that preparation method according to claim 2 prepares, which is characterized in that the nickel
The reaction condition of the applicable low temperature methane reforming reaction of base catalyst is：Reaction temperature is 400-800 DEG C；Reaction pressure is 0-
4MPa；Reaction volume air speed is 1000-150000cm3/gh；Synthesis gas is by CO2、H2O、CH4In at least two constituted.
4. the purposes for the nickel-base catalyst that preparation method according to claim 2 prepares, which is characterized in that described to go back
Former activation step is：Nickel-base catalyst is placed on reducing atmosphere and encloses middle reduction activation, reduction activation temperature is 600-900 DEG C；
The reduction activation time is 2-6h；Wherein, reducing gas includes H2、N2, by H2And N2Synthesis gas, inert gas and the H of composition2It is mixed
Close gas, inert gas and N2Gaseous mixture, inert gas and synthesis gas gaseous mixture in any one；The reducing atmosphere
The volume space velocity enclosed is 30000-120000cm3/gh。
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| CN107199047B (en) * | 2016-03-17 | 2020-02-21 | 华东理工大学 | Nickel-based methanation catalyst dispersed in SBA-15 pore channel and preparation and application thereof |
| AU2017306504B2 (en) * | 2016-08-05 | 2020-05-21 | Korea Advanced Institute Of Science And Technology | Dry reforming catalyst using metal oxide support, and method for preparing synthetic gas by using same |
| CN106391021A (en) * | 2016-08-19 | 2017-02-15 | 内蒙古大学 | Preparation method and use of high dispersion supported catalyst for methane reforming with carbon dioxide |
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| CN111001408B (en) * | 2019-12-04 | 2023-02-10 | 中国科学院上海高等研究院 | Catalyst with double-alloy composite micro-mesoporous structure, preparation method and application |
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| CN114768811B (en) * | 2022-03-09 | 2024-03-26 | 太原理工大学 | High-loading nickel-aluminum catalyst and preparation method and application thereof |
| CN114558624B (en) * | 2022-03-24 | 2023-12-05 | 南京工业大学 | Mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof |
| CN115282970B (en) * | 2022-08-03 | 2023-12-08 | 高潞空气化工产品(上海)能源科技有限公司 | Nickel-based catalyst for oxide film limited-area low-carbon alkane dry reforming and preparation method and application thereof |
| CN115228475A (en) * | 2022-08-05 | 2022-10-25 | 天津大学 | Mixed valence state nickel-based methane steam reforming catalyst and preparation method thereof |
| KR20240056410A (en) * | 2022-10-21 | 2024-04-30 | 주식회사 엘지화학 | Catalyst for reforming of methane, method for manufacturing thereof and method for reforming of methane |
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