CN105561998B - The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas - Google Patents
The method of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas Download PDFInfo
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- CN105561998B CN105561998B CN201410541805.7A CN201410541805A CN105561998B CN 105561998 B CN105561998 B CN 105561998B CN 201410541805 A CN201410541805 A CN 201410541805A CN 105561998 B CN105561998 B CN 105561998B
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Abstract
The present invention relates to a kind of methane dry reforming catalyst and preparation method thereof, this method includes impregnating carrier with maceration extract, then dry, roasting, which is characterized in that the maceration extract contains the soluble compound and surfactant of metal active constituent.The catalyst activity metal grain size of the preparation of catalyst provided by the present invention is small, dispersion degree is high, and the preparation method of the present invention is simple for process, equipment investment and low energy consumption, and prepared catalyst is compared with previous similar catalyst in the process of the present invention, catalytic reaction activity greatly improves, coking resistivity is remarkably reinforced, and the commercial Application to prepare synthesis gas process for methane dry reforming is laid a good foundation.
Description
Technical field
The present invention relates to a kind of methane dry reforming catalyst and its preparation method and application and methane dry reforming preparing synthetic gas
Method.
Background technology
Along with the gradual increase of world energy sources consumption figure, CO2、NOx, the environmental contaminants such as dust particles discharge capacity
Also increase year by year, especially CO2The discharge of isothermal chamber gas causes global climate drastically to deteriorate, and is caused to the living environment of the mankind
Great threat.International Energy Agency (IEA)《World energy outlook in 2007》Statistical data shows that the whole world passed through consumption in 2005
The CO of oil, natural gas and coal and emptying burning natural gas discharge2Total amount reaches 270 × l08Ton.Wherein the U.S., China,
Russia, Japan and India are 5 maximum CO2State is discharged, world CO is accounted for2The 50% of total emission volumn.And whole world CO in 20112
Total emission volumn has had reached 316 × l08Ton.It is expected that with the further growth of energy-consuming, to the year two thousand thirty CO2Total emission volumn will
Reach 420 × l08Ton.
Deteriorate to alleviate the global climate caused by greenhouse gases excessive emissions, on 2 16th, 2005, it is intended to limit CO2
And other greenhouse gas emissions《The Kyoto Protocol》It is formally effective, it is required that commitment period of the developed country in 2008 to 2012 years
Interior greenhouse gas emission is (with CO2Work as gauge) at least reduce 5% than the horizontal of nineteen ninety.7-18 days in December, 2009 holds taxi driver brother
Although legally binding agreement is not reached in the summit of Ben Hagen global climates, finally delivered in the form of conference is resolved
《Copenhagen agreement》, further specify developed country and developing country according to " common but distinguishing responsibility " principle
The reduction of greenhouse gas discharge obligation that should be undertaken respectively and the action taken, Main Countries all disclose new emission reduction targets.
Chinese Government also proposed the emission reduction targets of oneself, the i.e. CO of per GDP2Emission reduction 40%-50% (on the basis of 2005).By
This is as it can be seen that abatement CO2Discharge capacity, alleviating greenhouse effects influences to have become the extensive common recognition of international community.
In addition, gas reserves is abundant, it is the ideal substitute of oil, along with the rise and energy demand of oil price
It is growing day by day, how using natural gas to have become hot issue.
Utilize methane and CO2It is the methane for having great potential application foreground that reaction, which prepares synthesis gas (methane dry reforming),
And CO2Utilization ways, reaction product synthesis gas be highly suitable as F- T synthesis long chain hydrocarbons, ammonia synthesis, alkylated reaction,
The raw material of the industrial process such as methanol-fueled CLC, may be implemented CO2Waste utilization, turn waste into wealth, more methane is efficient using carrying
An effective way is supplied.Therefore, if the commercial applications of the technique can be realized, not only for alleviating energy crisis, change certain
The production process and raw material route of a little chemical products are of great immediate significance, and the discharge for reducing greenhouse gases,
It has profound historical significance to the destruction of global ecological environment caused by mitigating " greenhouse effects ".
Although methane dry reforming reacts the research progress for having had been subjected to last 100 years, which fails to realize work so far
Industry application, to find out its cause, sintering and carbon deposit of the catalyst under the conditions of pyroreaction are to restrict the technical process to realize industry
The most important obstacle changed, especially the carbon deposit of catalyst seems especially prominent under an increased pressure.Therefore, develop high activity,
The methane dry reforming catalyst of high stability is still the key of the current area research.
Invention content
The object of the present invention is to provide the methane dry reforming catalyst that a kind of catalytic activity and coking resistivity greatly improve
And its preparation method and application and methane dry reforming preparing synthetic gas method.
The present invention provides a kind of methane dry reforming catalyst, which contains the gold of carrier and load on this carrier
Belong to active component, which is characterized in that by H2The metal active constituent dispersion degree for the catalyst that chemiadsorption measures is 3-
20%.
The present invention also provides a kind of preparation method of methane dry reforming catalyst, this method includes by carrier maceration extract
Impregnated, it is then dry, roast, which is characterized in that the maceration extract contain metal active constituent soluble compound and
Surfactant.
The present invention also provides the methane dry reforming catalyst made from above-mentioned preparation method.
The present invention also provides application of the above-mentioned methane dry reforming catalyst in methane dry reforming prepares synthesis gas.
The present invention also provides a kind of method of methane dry reforming preparing synthetic gas, this method is included in above-mentioned methane dry reforming
In the presence of catalyst, under the conditions of methane dry reforming preparing synthetic gas, make methane and CO2Contact.
Methane dry reforming catalyst made from the preparation method of methane dry reforming catalyst provided by the invention has notable
The dispersion degree of the active metal of raising is prepared for methane dry reforming and is closed to which catalytic activity and coking resistivity substantially increase
It lays the foundation at the commercial Application of gas technique.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that catalyst made from catalyst made from the embodiment of the present invention 1 and comparative example 1 is reacted for methane dry reforming
When methane conversion under the differential responses time between relational graph.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methane dry reforming catalyst, which contains the gold of carrier and load on this carrier
Belong to active component, wherein by H2The metal active constituent dispersion degree for the catalyst that chemiadsorption measures is 3-20%.
In the present invention, metal active constituent dispersion degree is by H2Chemiadsorption uses Micromeritics (ASAP-
2010C) chemical adsorption instrument measures.Specifically, 0.2g samples are then heated to first through 300 DEG C of degassing process 1 hour
700 DEG C of reductase 12 hours, then it is cooled to 40 DEG C of progress H2Chemisorption operates.Later according to chemisorption H2Amount pass through following public affairs
Formula calculates metal active constituent dispersion degree and metal active constituent mean particle size.
Metal active constituent dispersion degree D：
Metal active constituent mean particle size d：
Wherein VadRefer to H under standard state2Monolayer adsorption amount, unit mL；WsIt is sample quality, unit g；FWMe
It is the molal weight of metal active constituent, unit g/mol；FMeIt is the load capacity of metal active constituent in catalyst, unit is
Weight %；VmRefer to the moles of gas volume under standard state, unit mL/mol；SAMeIt is the specific surface area of metal active constituent, it is single
Position is m2/gcat；ρMeIt is the density of metal active constituent, unit g/cm3。
The computational methods of above-mentioned metal active constituent dispersion degree and metallic particles average grain diameter are suitable for living to various metals
The calculating of property component.For example, by taking nickel as an example,
The dispersion degree D of nickel：
The mean particle size d of nickel：
For bimetallic component or more metal components, average molar mass can be calculated according to inventory as FWMe, ρNi
It is the averag density of metal active constituent, FMeIt is the total load amount of metal active constituent in catalyst, SAMeIt is metal active group
The total specific surface area divided.
Under preferable case, the metal active constituent dispersion degree of the catalyst is 4-16%.And the gold of existing similar catalyst
Belong to active component dispersion degree and be usually less than 2%, much smaller than the dispersion degree of the present invention.
In the case of further preferably, the metal active constituent mean particle size d of the catalyst is 1-25nm, more preferably
5-20nm.And the metal active constituent mean particle size of existing similar catalyst is typically larger than 30nm, much larger than the present invention's
Metal active constituent mean particle size.
Methane dry reforming catalyst according to the present invention, under preferable case, on the basis of the total amount of catalyst, with metal member
The content of the metal active constituent of element meter is 2-20 weight %, and more preferably 3-15 weight % is still more preferably 4-
12 weight %, surplus are carrier or are carrier and optional auxiliary agent.
Methane dry reforming catalyst according to the present invention, the metal active constituent can be suitable for methane dry weight
The various active metal components of whole catalyst, the metal active constituent include but not limited to Cu, Fe, Co, Ni, Ru, Rh, Ir and
It is one or more in Pt, preferably Co, Ni, Pt, Cu-Ni, Co-Ni or Ni-Pt, further preferably Co, Ni or Co-Ni.
The carrier can be various single component oxide carrier and/or bi-component suitable for methane dry reforming catalyst
Or three component composite oxide carriers, the single component oxide carrier for example can be SiO2、TiO2、MgO、Al2O3、ZrO2、
CeO2、La2O3In it is one or more, the bi-component or three component composite oxide carriers for example can be SiO2-Al2O3、
TiO2-SiO2、Al2O3-ZrO2And TiO2-SiO2-Al2O3In it is one or more.The carrier is preferably TiO2、MgO、Al2O3、
ZrO2And Al2O3-ZrO2In one or more, further preferably TiO2, MgO and Al2O3In it is one or more.
The shape of the carrier can be powdery, cylinder, spherical shape, clover, bunge bedstraw herb, dish, Raschig ring etc., preferably
For bunge bedstraw herb and Raschig ring shape.
The present invention also provides a kind of preparation method of methane dry reforming catalyst, this method includes by carrier maceration extract
Impregnated, it is then dry, roast, which is characterized in that the maceration extract contain metal active constituent soluble compound and
Surfactant.
According to the present invention, although a small amount of surfactant, which is added, can be realized the purpose of the present invention, under preferable case,
In the maceration extract, the molar ratio of the surfactant and metallic atom is 0.01~2, more preferably 0.05~1, further
Preferably 0.1~0.5.
The surfactant can be that anionic surfactant, amphoteric surfactant and non-ionic surface are lived
It is one or more in property agent.In the case of further preferably, the surfactant is stearic acid, oleic acid, lauric acid, lecithin
One kind in fat, dodecyl alanine, alkyl dimethyl betaine, fatty glyceride, polyalcohol, tween and P123 or
It is a variety of.
The present inventor the study found that when using P123 as surfactant of the present invention, catalyst
Catalytic activity and coking resistivity greatly improve, therefore the surfactant specifically preferred according to the invention is P123.
According to the present invention, in the maceration extract, with elemental metal, the concentration of the soluble compound of metal active constituent
Dosage for 10-195 grams per liters, more preferable 14.6-191.6 grams per liters, carrier makes in gained catalyst with the total amount of catalyst
On the basis of, with the content of the metal active constituent of elemental metal for 2-20 weight %, preferably 3-15 weight %.
According to the present invention, the soluble compound of the metal active constituent can be the various solvable of metal active constituent
Property compound, the soluble compound of the preferably described metal active constituent is water soluble salt and its hydration of metal active constituent
Object, such as nitrate and/or chloride and its hydrate.Under preferable case, the soluble compound of the metal active constituent is
Cu(NO3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)3·9H2O、(NH4)2PtCl6、RhCl3·3H2O
And H2IrCl6·6H2It is one or more in O, more preferably Co (NO3)2·6H2O and/or Ni (NO3)2·6H2O。
The solvent of maceration extract is preferably water, more preferably deionized water.
The carrier can be various single component oxide carrier and/or bi-component suitable for methane dry reforming catalyst
Or three component composite oxide carriers, the single component oxide carrier for example can be SiO2、TiO2、MgO、Al2O3、ZrO2、
CeO2、La2O3In it is one or more, the bi-component or three component composite oxide carriers for example can be SiO2-Al2O3、
TiO2-SiO2、Al2O3-ZrO2And TiO2-SiO2-Al2O3In it is one or more.The carrier is preferably TiO2、MgO、Al2O3、
ZrO2And Al2O3-ZrO2In one or more, further preferably TiO2, MgO and Al2O3In it is one or more.
The shape of the carrier can be powdery, cylinder, spherical shape, clover, bunge bedstraw herb, dish, Raschig ring etc., preferably
For bunge bedstraw herb and Raschig ring shape.
According to the present invention, the method and condition of dipping is referred to prior art progress, such as can be incipient impregnation,
It can also be supersaturated dipping.Dipping can carry out at 10-80 DEG C.
The temperature of the drying can be 80~140 DEG C, preferably 100-120 DEG C；Time can be 1~10 hour, excellent
It is selected as 5-10 hours.
The temperature of the roasting can be 400~1000 DEG C, preferably 500-800 DEG C；Time can be 1~10 hour,
Preferably 2-6 hours.
The preparation method of methane dry reforming catalyst provided by the invention compared with prior art, the advantage is that：
1, the surface tension of water is reduced by adding surfactant into dipping solution, is conducive to maceration extract in carrier table
Face is sprawled, final to make metal in prepared catalyst to be conducive to dispersion of the metal active constituent in carrier surface
Active component has higher dispersion degree and smaller crystallite dimension.
2, it is prepared using infusion process, preparation method is simple, and preparation condition is easy to accurately control, and the repeatability of catalyst is very
It is good.
3, it is prepared using infusion process, therefore maintains the mechanical strength of carrier, no matter in a fluidized bed reactor, or
All there is very high activity and stability in fixed bed reactors.
The present invention also provides the methane dry reforming catalyst made from above-mentioned preparation method and its in methane dry reforming system
Application in standby synthesis gas.
The catalyst prepared according to the method provided by the invention needs to deposit in hydrogen before reacting for methane dry reforming
Under, active metal is subjected to reduction activation, reducing condition is：Reduction temperature be 300~800 DEG C, preferably 400~750 DEG C,
Further preferably 550~700 DEG C；Recovery time is 0.5~10 hour, preferably 1~5 hour, further preferably 2~4
Hour, the reduction can be carried out in pure hydrogen, can also be carried out in the gaseous mixture of hydrogen and inert gas, such as in hydrogen and nitrogen
It is carried out in the gaseous mixture of gas and/or argon gas, Hydrogen Vapor Pressure is 0.1~2MPa, preferably 0.1~1MPa.
The present invention also provides a kind of method of methane dry reforming preparing synthetic gas, this method is included in above-mentioned methane dry reforming
In the presence of catalyst, under the conditions of methane dry reforming preparing synthetic gas, make methane and CO2Contact.
The contact can carry out in fixed bed reactors or fluidized-bed reactor.Wherein, powder little particle is urged
Agent is suitable for using fluidized-bed reactor, and the larger preformed catalyst of other particle sizes is suitable for using fixed bed reactors.
Present inventor has further discovered that by mixing catalyst with diluent, methane and dioxy can be significantly improved
Change charcoal percent conversion.Therefore the preferably described contact of the present invention also carries out in the presence of a diluent, described negative respectively in terms of g and ml
The w/v of supported catalyst and diluent is 1：10-30.
The diluent can be the various solid particles without catalytic activity, such as can be quartz sand.
The condition of contact includes CH by volume4/CO2=0.7~1.1, preferably 0.8~1.0, reaction temperature 550-
850 DEG C, preferably 600~800 DEG C, more preferably 700-800 DEG C, pressure (gauge pressure) are 0~3MPa, preferably 0~1MPa, original
Material gas air speed is 2000~120000mlg-1·h-1, preferably 10000~60000mlg-1·h-1。
The present invention is described further for the following examples.In following embodiment, metal active constituent compound
Dosage refer both to the wherein metal active constituent i.e. dosage of metallic element.
Embodiment 1
(1) catalyst preparation
By the Ni (NO of 1.765g3)2·6H2O, which is dissolved in 5.6ml deionized waters, obtains nickel nitrate solution, is added after dissolved clarification
The P123 of 0.34g is uniformly mixed and obtains maceration extract.Take the Al of 4g2O3In support dispersion to maceration extract, stewing process is after 2 hours,
Evaporating water is subsequently placed in baking oven 120 DEG C of dryings 10 hours.It is small that sample after drying is placed in 600 DEG C of roastings 3 in Muffle furnace
When, gained catalyst is denoted as NiO/Al2O3- 1, with the content of the metal active constituent of elemental metal for 8 weight %.By
Metal active constituent dispersion degree is 14.4% in the catalyst that hydrogen chemisorption method measures, the average grain of metal active constituent
Diameter is 7.0nm.
(2) evaluating catalyst
Weigh above-mentioned NiO/Al2O3- 1 catalyst 0.1g is diluted to 2ml with 40~60 mesh quartz sands, is packed into internal diameter φ's 8
In quartz tube reactor, 700 DEG C of reduction are activated for 3 hours in pure hydrogen atmosphere under normal pressure.After reduction, in hydrogen atmosphere
Under be warming up to 750 DEG C, switching unstripped gas (CH4/CO2=1/1 volume) it is reacted, reaction velocity 60000mlg-1·h-1,
Reaction pressure is normal pressure.After stable reaction carries out 10 hours, by gas-chromatography on-line period and analyzes tail gas and form.It calculates
It arrives：XCH4=86.6%, XCO2=87.4%, H2/ CO=1.03.
Comparative example 1
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that not adding any surface-active in maceration extract
Agent, gained catalyst are denoted as NiO/Al2O3-D1.Metal active constituent disperses in the catalyst measured by hydrogen chemisorption method
Degree is 1.7%, and the average grain diameter of metal active constituent is 60.0nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=72.6%, XCO2=73.3%, H2/ CO=1.02.
The result for the methane conversion that embodiment 1 and 1 catalyst of comparative example obtain under the differential responses time is plotted in Fig. 1
In.As seen in Figure 1,1 gained catalyst of embodiment has higher catalytic reaction activity and stability (anti-carbon
Can).
Embodiment 2
(1) catalyst preparation
By the Co (NO of 1.75g3)2·6H2O, which is dissolved in 4ml deionized waters, obtains cobalt nitrate aqueous solution, is added after dissolved clarification
The P123 of 0.33g is uniformly mixed and obtains maceration extract.Remaining step with the preparation method of corresponding catalyst in embodiment 1, urge by gained
Agent is denoted as Co3O4/Al2O3, with the content of the metal active constituent of elemental metal for 8 weight %.It is inhaled by hydrogen chemistry
Metal active constituent dispersion degree is 13.9% in the catalyst that attached method measures, and the average grain diameter of metal active constituent is 7.2nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=84.4%, XCO2=86.2%, H2/ CO=1.03.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=83.9%, XCO2=86.0%, H2/ CO=1.01.
Embodiment 3
(1) catalyst preparation
By the Ni (NO of 0.873g3)2·6H2Co (the NO of O and 0.872g3)2·6H2O, which is dissolved in 4ml deionized waters, obtains nitre
The P123 of 0.34g is added in the mixed aqueous solution of sour nickel and cobalt nitrate after dissolved clarification, is uniformly mixed and obtains maceration extract.Remaining step
With the preparation method of corresponding catalyst in embodiment 1, gained catalyst is denoted as Ni-Co/Al2O3, with the gold of elemental metal
The content for belonging to active component is 8 weight %.Metal active constituent dispersion degree in the catalyst measured by hydrogen chemisorption method
It is 15.6%, the average grain diameter of metal active constituent is 6.4nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=91.6%, XCO2=92.1%, H2/ CO=1.05.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=91.4%, XCO2=91.7%, H2/ CO=1.03.
Embodiment 4
(1) catalyst preparation
By the Ni (NO of 2.81g3)2·6H2O, which is dissolved in 4ml deionized waters, obtains nickel nitrate aqueous solution, is added after dissolved clarification
The P123 of 0.55g is uniformly mixed and obtains maceration extract.Remaining step with the preparation method of corresponding catalyst in embodiment 1, urge by gained
Agent is denoted as NiO/Al2O3- 2, with the content of the metal active constituent of elemental metal for 12 weight %.By hydrogen chemistry
Metal active constituent dispersion degree is 12.1% in the catalyst that absorption method measures, and the average grain diameter of metal active constituent is
8.3nm。
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=88.5%, XCO2=90.3%, H2/ CO=1.02.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=87.6%, XCO2=88.5%, H2/ CO=1.01.
Embodiment 5
(1) catalyst preparation
Catalyst is prepared according to method in the same manner as in Example 1, except that carrier selects MgO, gained catalyst
It is denoted as NiO/MgO.Metal active constituent dispersion degree is 4.4% in the catalyst measured by hydrogen chemisorption method, and metal is lived
Property component average grain diameter be 22.9nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=81.3%, XCO2=81.7%, H2/ CO=1.03.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=78.6%, XCO2=79.4%, H2/ CO=1.01.
Embodiment 6
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that surfactant selects oleic acid, gained catalyst
It is denoted as NiO/Al2O3-3.Metal active constituent dispersion degree is 10.3% in the catalyst measured by hydrogen chemisorption method, gold
The average grain diameter for belonging to active component is 9.9nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=82.3%, XCO2=83.7%, H2/ CO=1.01.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=81.8%, XCO2=82.4%, H2/ CO=1.03.
Embodiment 7
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that surfactant selects polysorbate60, gained catalysis
Agent is denoted as NiO/Al2O3-4.Metal active constituent dispersion degree is 11.7% in the catalyst measured by hydrogen chemisorption method,
The average grain diameter of metal active constituent is 8.5nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=82.4%, XCO2=83.9%, H2/ CO=1.01.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=82.0%, XCO2=82.9%, H2/ CO=1.0.
Embodiment 8
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that the molar ratio of surfactant and metallic atom
It is 0.4, gained catalyst is denoted as NiO/Al2O3-5.Metal active constituent point in the catalyst measured by hydrogen chemisorption method
Divergence is 9.7%, and the average grain diameter of metal active constituent is 10.3nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=85.1%, XCO2=86.6%, H2/ CO=1.03.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=83.4%, XCO2=84.1%, H2/ CO=1.02.
Embodiment 9
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that the calcination temperature of catalyst is 700 DEG C, gained
Catalyst is denoted as NiO/Al2O3-6.Metal active constituent dispersion degree is in the catalyst measured by hydrogen chemisorption method
7.6%, the average grain diameter of metal active constituent is 13.3nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=78.4%, XCO2=80.1%, H2/ CO=1.0.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=78.0%, XCO2=80.0%, H2/ CO=1.03.
Embodiment 10
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that the roasting time of catalyst is 5 hours, gained
Catalyst is denoted as NiO/Al2O3-7.Metal active constituent dispersion degree is in the catalyst measured by hydrogen chemisorption method
12.2%, the average grain diameter of metal active constituent is 8.2nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=82.4%, XCO2=83.7%, H2/ CO=1.02.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=82.2%, XCO2=83.4%, H2/ CO=1.03.
Embodiment 11
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that surfactant selects lecithin, gained catalysis
Agent is denoted as NiO/Al2O3-8.Metal active constituent dispersion degree is 10.2% in the catalyst measured by hydrogen chemisorption method,
The average grain diameter of metal active constituent is 9.8nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=82.7%, XCO2=83.4%, H2/ CO=1.02.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=81.5%, XCO2=82.1%, H2/ CO=1.03.
Embodiment 12
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that surfactant selects cetyl trimethyl
Ammonium bromide, gained catalyst are denoted as NiO/Al2O3-9.Metal active constituent in the catalyst measured by hydrogen chemisorption method
Dispersion degree is 6.4%, and the average grain diameter of metal active constituent is 15.6nm.
(2) evaluating catalyst
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction carries out 10
Reaction result after hour is as follows：
XCH4=76.5%, XCO2=78.1%, H2/ CO=1.02.
Reaction result after stable reaction carries out 120 hours is as follows：
XCH4=73.2%, XCO2=75.4%, H2/ CO=1.01.
Embodiment 13
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1.
(2) evaluating catalyst
Methane dry reforming reaction is activated and carried out to catalyst according to the method for embodiment 1, unlike, quartz ampoule
40~60 mesh quartz sands are not packed into reactor as diluent, the reaction result after stable reaction carries out 10 hours is as follows：
XCH4=82.1%, XCO2=80.6%, H2/ CO=1.03.
Reaction result after stable reaction carries out 100 hours is as follows：
XCH4=78.6%, XCO2=76.5%, H2/ CO=1.02.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of methane dry reforming catalyst, this method include impregnating carrier with maceration extract, then do
Dry, roasting, which is characterized in that the maceration extract contains the soluble compound and surfactant of metal active constituent, described
Surfactant is P123.
2. preparation method according to claim 1, wherein in the maceration extract, the surfactant and metallic atom
Molar ratio be 0.01~2.
3. preparation method according to claim 1, wherein in the maceration extract, with elemental metal, metal active constituent
Soluble compound a concentration of 14-195 grams per liters, the dosage of carrier make be with the total amount of catalyst in gained catalyst
Benchmark, with the content of the metal active constituent of elemental metal for 2-20 weight %.
4. preparation method according to claim 1, wherein the soluble compound of the metal active constituent is lived for metal
Property component water soluble salt, the metal active constituent be Cu, Fe, Co, Ni, Ru, Rh, Ir and Pt in one or more, institute
It is single component oxide carrier and/or bi-component or three component composite oxide carriers to state carrier, and the single component oxide carries
Body is SiO2、TiO2、MgO、Al2O3、ZrO2、CeO2、La2O3In one or more, the bi-component or three component combined oxidations
Object carrier is SiO2-Al2O3、TiO2-SiO2、Al2O3-ZrO2And TiO2-SiO2-Al2O3In it is one or more.
5. preparation method according to claim 1, wherein the temperature of the drying is 80~140 DEG C, and the time is 1~10
Hour；The temperature of the roasting is 400~1000 DEG C, and the time is 1~10 hour.
6. methane dry reforming catalyst made from the preparation method described in any one of claim 1-5.
7. application of the methane dry reforming catalyst in methane dry reforming prepares synthesis gas described in claim 6.
8. a kind of method of methane dry reforming preparing synthetic gas, this method includes being urged using the methane dry reforming described in claim 6
Agent under the conditions of methane dry reforming preparing synthetic gas, makes methane and CO then in the presence of the methane dry reforming catalyst2It connects
It touches.
9. according to the method described in claim 8, wherein, the contact in fixed bed reactors or fluidized-bed reactor into
Row, by volume, CH4/CO2=0.7~1.1,600~800 DEG C, 0~3MPa of pressure of reaction temperature, unstripped gas air speed is 2000
~120000mlg-1·h-1。
10. method according to claim 8 or claim 9, wherein the contact also carries out in the presence of a diluent, respectively with g and
Ml is counted, and the w/v of the methane dry reforming catalyst and diluent is 1：10-30.
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| CN106607034B (en) * | 2015-10-23 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
| KR102056384B1 (en) * | 2016-08-05 | 2020-01-22 | 한국과학기술원 | Metal Oxide Supported Catalyst for Dry Reforming and Method of Preparing Syngas Using the Same |
| CN108927171B (en) * | 2017-05-26 | 2021-04-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing isopentenol by transesterification of isopentenyl acetate and application thereof |
| CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
| CN109718799A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
| CN109718807B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
| CN109718788B (en) * | 2017-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming |
| CN110652984B (en) * | 2018-06-28 | 2023-04-11 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
| CN109046364A (en) * | 2018-07-24 | 2018-12-21 | 南昌大学 | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts |
| CN111250091A (en) * | 2020-03-03 | 2020-06-09 | 广东工业大学 | Supported catalyst and preparation method thereof |
| US11322766B2 (en) | 2020-05-28 | 2022-05-03 | Saudi Arabian Oil Company | Direct hydrocarbon metal supported solid oxide fuel cell |
| US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
| CN111545215B (en) * | 2020-06-22 | 2022-09-30 | 中国科学技术大学 | Perovskite-loaded monatomic catalyst and preparation method and application thereof |
| US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
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| US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
| US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
| CN114904524B (en) * | 2022-05-13 | 2023-08-22 | 西北大学 | Amorphous catalyst, preparation method and application |
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| CN101306368B (en) * | 2008-07-09 | 2010-06-02 | 山西大学 | Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation |
| CN102658145B (en) * | 2012-03-21 | 2013-12-25 | 中南民族大学 | Preparation method and application of MgO (111) load nickel-base catalyst |
| CN103007945B (en) * | 2012-12-24 | 2015-06-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
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