CN106607033A - Supported catalyst, preparation method and application thereof and method for preparing synthetic gas through methane dry reforming - Google Patents
Supported catalyst, preparation method and application thereof and method for preparing synthetic gas through methane dry reforming Download PDFInfo
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- CN106607033A CN106607033A CN201510695625.9A CN201510695625A CN106607033A CN 106607033 A CN106607033 A CN 106607033A CN 201510695625 A CN201510695625 A CN 201510695625A CN 106607033 A CN106607033 A CN 106607033A
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Abstract
The invention provides a supported catalyst, which comprises a carrier and an active metal component and an auxiliary agent which are loaded on the carrier. The active metal component is a Ni component and/or a Co component and has the dispersion degree being 6-15%. The invention further provides a preparation method and application of the supported catalyst and a method for preparing synthetic gas through methane dry reforming. The supported catalyst can obviously improve the dispersity of the active metal component, is small in size of active metal particles, and is excellent in catalytic activity, stability and carbon deposition resistance.
Description
Technical field
The present invention relates to the research field of loaded catalyst, in particular it relates to a kind of supported catalyst
Agent, a kind of preparation method of loaded catalyst, the loaded catalyst prepared by the method,
Application and methane dry reforming preparing synthetic gas of the loaded catalyst in the reaction of methane dry reforming
Method.
Background technology
Methane dry reforming is reacted with greenhouse gases CH4And CO2For raw material, prepare with relatively low H2/CO
The synthesis gas of ratio, is highly suitable as F- T synthesis long chain hydrocarbons, ammonia synthesis, alkylated reaction, first
The raw material of the industrial process such as alcohol synthesis.The process not only can realize CO2Recycling, more
The efficient utilization of methane provides an effective way.Therefore, if can realize, the commercialization of the technique should
With not only for alleviating energy crisis, the production process and raw material route for changing some chemical products has
There is major and immediate significance, and for the discharge of greenhouse gases is reduced, mitigate " greenhouse effect " and make
Into the destruction to global ecological environment have profound historical significance.Ni bases catalyst is in methane dry weight
Show the activity that can be compared favourably with noble metal in whole reaction, but catalyst exist it is serious because
Carbon distribution and sintering and the problem of rapid deactivation, especially in high-temperature reaction process, in catalyst activity
Metal can constantly migrate aggregation and grow up, and cause catalyst activity constantly to reduce and aggravate sending out for carbon deposit
It is raw.Therefore, in how making catalyst, active metal keeps stable, prevents which in high-temperature reaction process
It is to prepare high activity, high stability Ni base to urge that middle generation migration is assembled and causes metal particle size to be grown up
The key of agent.
In order to prepare the Ni base catalyst with rock-steady structure, people are made generally using coprecipitation method
Standby catalyst (Journal of Catalysis, 249 (2007) 300)；Catalysis Today,45(1998)
35) active metal Ni, can be so caused to be evenly distributed in whole caltalyst phase space, and
Assembled with preventing active metal from migrating in high-temperature reaction process by the use of other components as space obstacle agent.
But coprecipitation method operating procedure is tediously long, and process variable is more, catalyst repeatability is difficult to ensure that.Phase
Comparatively, infusion process is a kind of relatively simple method for preparing catalyst, and industrial application is most
For extensive method for preparing catalyst.But catalyst activity metal dispersity prepared by typical impregnation method
Low, metal grain size is big, and catalyst activity is low, stability is poor.Therefore, develop it is a kind of efficiently and
Simple and easy to do catalyst is imperative.
The content of the invention
It is an object of the invention to overcome the activity stability of methane dry reforming catalyst in prior art low
The defect poor with coking resistivity, there is provided a kind of with high activity and stability and good anti-product
New loaded catalyst of charcoal performance and its preparation method and application and methane dry reforming preparing synthetic gas
Method.
Specifically, the invention provides a kind of loaded catalyst, wherein, the catalyst contains load
Body and the active metal component being supported on carrier and auxiliary agent, wherein, the active metal component is
Ni components and/or Co components, the dispersion of the active metal component is 6-15%.
Present invention also offers a kind of preparation method of loaded catalyst, the method includes, on surface
In the presence of activating agent, dipping solution is contacted with carrier, be then dried and roasting, wherein, it is described
The soluble compound of the soluble compound containing active metal component and auxiliary agent in dipping solution.
Present invention also offers by obtained in said method loaded catalyst.
Present invention also offers application of the loaded catalyst in the reaction of methane dry reforming.
Present invention also offers a kind of method of methane dry reforming preparing synthetic gas, the method is included in methane
Under the conditions of dry reforming preparing synthetic gas, methane and carbon dioxide is contacted with catalyst, wherein, it is described to urge
Agent is above-mentioned loaded catalyst prepared by the present invention.
Support type obtained in the preparation method that the loaded catalyst and the present invention that the present invention is provided is provided is urged
The dispersion of the active metal component that agent can be significantly improved and less active metal crystal grain chi
It is very little, so as to substantially increase catalysis activity and stability and coking resistivity.Catalyst in the present invention
The reason for good performance is probably：By active metal and auxiliary agent with altogether in catalyst preparation process
The mode of dipping is loaded on carrier simultaneously, makes the two form metal composite oxide by high-temperature process new
Phase structure, so that active metal dispersion height, crystallite dimension are little in prepared catalyst, and
And as the space obstacle of auxiliary agent is acted on, can effectively prevent active metal component in high-temperature reaction process
Migration aggregation；So as to keep its stability, high catalytic activity and coking resistivity.From 1 He of embodiment
The reactivity worth comparison diagram of the catalyst of comparative example 1 can be seen that the catalyst of present invention offer can be super
(120000mlg under high-speed-1·h-1) high activity ground continuous and steady operation do not lost more than 1500 hours
It is living.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description,
It is used for explaining the present invention together with detailed description below, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 is the reactivity worth of the catalyst methane dry reforming reaction obtained by embodiment 1；
Fig. 2 is the reactivity worth of the catalyst methane dry reforming reaction obtained by comparative example 1；
Fig. 3 is the reactivity worth of the catalyst methane dry reforming reaction obtained by comparative example 2.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of loaded catalyst, wherein, the catalyst contains carrier and load
Active metal component and auxiliary agent on carrier, wherein, the active metal component be Ni components and/or
Co components, the dispersion of the active metal component is 6-15%.In order to obtain more preferable catalysis activity
And coking resistivity, it is preferable that the dispersion of the active metal component is 10-14%.
In the present invention, the mean particle size of the active metal component can be 2-50nm, preferably
For 2-10nm.
According to the loaded catalyst that the present invention is provided, the content of the active metal component is referred to now
There is technology to be determined.For example, on the basis of the gross weight of the catalyst, with elemental metal, institute
The content for stating active metal component can be 2-20 weight %, preferably 3-15 weight %, further excellent
Elect 4-10 weight % as.It should be noted that as active metal component is actually present in the form of an oxide,
And thus above-mentioned active metal component causes the content ratio of active metal component with the content meter of metallic element
It is actual little.Obviously, when the catalyst only contains above-mentioned active metal component, auxiliary agent and carrier,
The content of active metal component, auxiliary agent and carrier in terms of oxide is necessarily satisfying for 100%.
In the present invention, the content of active metal component is measured using ICP method.
In the present invention, with metal atoms, the mol ratio of the auxiliary agent and the active metal component can
Think 0.01-5：1, preferably 0.1-2:1.
In the present invention, conventional selection of the species of the auxiliary agent for this area.For example, the auxiliary agent
Can be metal oxide auxiliary agent, preferably alkaline earth and/or rare-earth oxide auxiliary agent；It is further excellent
Elect MgO, CaO, BaO, La as2O3、CeO2、Sm2O3、ZrO2And Y2O3In at least one
Kind.
According to the present invention, there is no particular limitation for the species of the carrier, can be the routine of this area
Select.For example, the carrier can be that single component oxide carrier or bi-component or three components are compound
Oxide carrier.Under preferable case, the carrier is selected from SiO2、TiO2、MgO、Al2O3、
ZrO2、CeO2、La2O3、SiO2-Al2O3、TiO2-SiO2、Al2O3- MgO and
TiO2-SiO2-Al2O3In one or more.
In the present invention, the conventional selection for being shaped as this area of the carrier.For example, the carrier
Shape can be at least one in cylindrical, spherical, Herba Trifolii Pratentis, Herba Galii Bungei, dish and Raschig ring,
Preferably Herba Galii Bungei and/or Raschig ring shape.
Present invention also offers a kind of preparation method of loaded catalyst, the method includes, on surface
In the presence of activating agent, dipping solution is contacted with carrier, be then dried and roasting, wherein, it is described
The soluble compound of the soluble compound containing active metal component and auxiliary agent in dipping solution.
In the present invention, there is no particular limitation for the consumption of the surfactant.But in order to be formed
The more preferable catalyst of activity more high stability, the surfactant and the activity gold with metal atoms
The mol ratio of the consumption of the soluble compound of category component can be 0.001-2:1, preferably
0.001-1:1, more preferably 0.01-0.8:1.
In the present invention, the species of the surfactant can be the conventional selection of this area.Example
Such as, the surfactant can be selected from anionic surfactant, amphoteric surfactant and non-
At least one in ionic surfactant；Preferably stearic acid, Oleic acid, lauric acid, lecithin
Fat, dodecyl alanine, alkyl dimethyl betaine, fatty glyceride, polyhydric alcohol, tell
At least one in temperature 60 and P123；In more preferably P123, Oleic acid and polysorbate60 at least
It is a kind of.
In the present invention, the consumption of the soluble compound of the active metal component is not particularly limited
It is fixed, can be the conventional selection of this area.For example, in order that in gained catalyst, with the catalysis
On the basis of the gross weight of agent, with elemental metal, the content of the active metal component is 2-20 weights
Amount %, preferably 3-15 weight %, more preferably 4-10 weight %, relative to 100 weight portions
Carrier, the consumption of the soluble compound of the active metal component can be 10-100 weight portions, excellent
Elect 15-75 weight portions, more preferably 20-50 weight portions as.
According to the present invention, the species of the soluble compound of the active metal component is art technology
Personnel know, and can be the conventional selection of this area.For example, the solubility of the active metal component
Compound can be selected from Ni (NO3)2·6H2O、Co(NO3)2·6H2O、Ni(acac)2、Co(acac)3、
Ni(CH3COO)2·6H2O and Co (CH3COO)2·6H2At least one in O, preferably
Ni(NO3)2·6H2O and/or Co (NO3)2·6H2O。
According to the present invention, the carrier can be single component oxide carrier or bi-component or three components
Composite oxide carrier.Under preferable case, the carrier is selected from SiO2、TiO2、MgO、Al2O3、
ZrO2、CeO2、La2O3、SiO2-Al2O3、TiO2-SiO2、Al2O3- MgO and
TiO2-SiO2-Al2O3In one or more.
According to the present invention, in the dipping solution, with elemental metal, active metal component it is solvable
Property compound and auxiliary agent soluble compound total concentration can be 21.8-162.8 g/l, the use of carrier
Amount cause gained catalyst on the basis of the gross weight of catalyst, with elemental metal it is described activity gold
The content of category component is 2-20 weight %, preferably 3-15 weight %, more preferably 4-10 weight %.
In the present invention, there is no particular limitation for the consumption of the auxiliary agent.For example, with metal atoms,
The mol ratio of the soluble compound of the auxiliary agent and the soluble compound of the active metal component can
Think 0.01-5：1, preferably 0.1-2：1.
In the present invention, conventional selection of the species of the soluble compound of the auxiliary agent for this area.
For example, the soluble compound of the auxiliary agent can be selected from alkaline earth and/or rare earth metal solubility chemical combination
Thing；Preferably, the soluble compound of the auxiliary agent is selected from magnesium salt, calcium salt, strontium salt, barium salt, cerium
At least one in salt, lanthanum salt, zirconates and yttrium salt；It is highly preferred that the solubility chemical combination of the auxiliary agent
At least one of the thing in magnesium salt, barium salt, lanthanum salt and yttrium salt, more preferably lanthanum salt and/or magnesium
Salt.
According to the present invention, there is no particular limitation for the condition that the dipping solution is contacted with carrier.Example
Such as, the condition that the dipping solution is contacted with carrier includes：Temperature can be 10-50 DEG C, preferably
15-30℃；Time can be 0.5-10 hours, preferably 2-5 hours.
There is no particular limitation for the way of contact of the present invention to the dipping solution and carrier.For example, may be used
So that first surfactant to be mixed with the dipping solution of the soluble compound containing active metal component,
Then contact with carrier.
In the present invention, the product after the contact to dipping solution with carrier is dried and roasting, wherein,
It is dried and the condition of roasting is known for those skilled in the art.For example, dry condition includes：Temperature can
Think 80-140 DEG C, preferably 100-120 DEG C；Time can be 1-10 hours, and preferably 5-10 is little
When.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.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers the loaded catalyst prepares the application in synthesis gas in methane dry reforming.
When the catalyst prepared according to the method that the present invention is provided is used for the reaction of methane dry reforming, before reaction
Need in presence of hydrogen, active metal to be carried out reduction activation.Wherein, the condition of reduction activation includes：
Reduction temperature can be 300-800 DEG C, and preferably 400-750 DEG C, the recovery time can be 0.5-10 hours,
Preferably 1-5 hours；The reduction activation can be carried out in pure hydrogen, also can be in hydrogen and noble gases
Gaseous mixture in carry out, if carried out in gaseous mixture of the hydrogen with nitrogen and/or argon, reduction pressure can
Think 0-2MPa, preferably 0-1MPa.In the present invention, the pressure is gauge pressure.
Present invention also offers a kind of method of methane dry reforming preparing synthetic gas, it is dry that the method is included in methane
Under the conditions of preparing synthetic gas by reforming, methane and carbon dioxide is contacted with catalyst, wherein, the catalyst
For above-mentioned loaded catalyst of the invention.
Wherein, there is no particular limitation for the method that methane and carbon dioxide is contacted with the catalyst, can be with
Routine for this area is selected, for example, methane and carbon dioxide can each be sent in reactor while
Contact with catalyst, it is also possible to which methane and carbon dioxide formation mixture is contacted with the catalyst again,
Preferably, methane and carbon dioxide formation mixture is contacted with the catalyst again.
The catalyst prepared according to the carrier that the present invention is provided is used for catalytic methane and CO2Prepared by reaction closes
During into gas, using fixed bed reactors or fluidized-bed reactor.The bar of the methane dry reforming preparing synthetic gas
Part includes：The mol ratio of methane and carbon dioxide can be 0.7-1.1:1, preferably 0.8-1：1；Reaction
Temperature can be 550-850 DEG C, preferably 600-800 DEG C；Pressure can be 0-3MPa, preferably
0-1MPa；Total air speed of unstripped gas can be 2000-120000mlg-1·h-1, preferably
60000-120000ml·g-1·h-1。
Hereinafter will be described the present invention by embodiment.
In following examples, the performance test of product is carried out using following methods：
1) metal dispersity is changed using Micromeritics (ASAP-2010C) by hydrogen chemisorption method
Learn adsorption instrument to measure.Specifically, by 0.2g samples elder generation 300 DEG C of Jing degassing process 1 hour, then
Being warming up to 700 DEG C of reductase 12 hours, then be cooled to 40 DEG C carries out hydrogen chemisorption operation.Basis afterwards
The amount of chemisorbed hydrogen calculates the dispersion and metallic particles of active metal component by following formula
Mean diameter；
Active metal dispersion D：
Mean diameter d of active metal particles：
Wherein VadThe monolayer adsorption amount of hydrogen under standard state is referred to, unit is mL；WsIt is sample matter
Amount, unit is g；FWMeIt is metal MeMolal weight, unit is g/mol；FMeIn being catalyst
The load capacity of metal, unit are %；VmThe moles of gas volume under standard state is referred to, unit is
mL/mol；SAMeIt is the specific surface area of metal, unit is m2/g；ρMeIt is the density of metal, unit
For kg/m3；
2) constituted using gas chromatography on-line period analytical calculation tail gas；
3) content of active metal component is measured using ICP method.
Embodiment 1
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
By the Ni (NO of 1.765g3)2·6H2Mg (the NO of O and 1.167g3)2·6H2O is dissolved in 8.4ml and goes
Stirring and dissolving in ionized water, is subsequently adding the P123 of 0.61g, and mix homogeneously obtains dipping solution.Take
The SiO of 4g2Support dispersion in dipping solution, temperature be 25 DEG C at stand 2 hours after, evaporating water,
It is subsequently placed in baking oven 120 DEG C of dryings 10 hours.Dried sample is placed in 600 DEG C of roastings in Muffle furnace
3 hours, gained catalyst was designated as 6Mg-Ni/SiO2.With metal atoms, the auxiliary agent and the work
Property metal component mol ratio be 0.75:1, the content with the active metal component Ni of elemental metal is as 8
Weight %.The dispersion of active metal component described in the catalyst is 12.7%, active metal component
Mean particle size is 5.4nm.
(2) evaluating catalyst
Weigh above-mentioned 6Mg-Ni/SiO2Catalyst 0.1g, is diluted to 2ml with 40-60 mesh quartz sands, dress
Enter in the quartz tube reactor of internal diameter 8mm, under normal pressure, in pure hydrogen atmosphere, 700 DEG C of reduction are entered for 3 hours
Row activation.After reduction terminates, 750 DEG C are warming up in a hydrogen atmosphere, switch unstripped gas
(CH4/CO2=1/1) reacted, reaction velocity is 120000mlg-1·h-1, reaction pressure is normal
Pressure.After stable reaction carries out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.Calculate
Obtain：XCH4=62.9%, XCO2=61.5%, H2/ CO=0.96.
In embodiment 1, the estimation of stability result of the catalyst of gained is listed in Fig. 1, when specially reacting
Between methane in the methane dry reforming reaction that is catalyzed by the catalyst of 0-1700 hour and dioxy
Change efficiency of carbon con version.
Embodiment 2
The embodiment is used for the preparation method of the catalyst and catalyst for illustrating present invention offer and its answers
With.
(1) catalyst preparation
By the Ni (NO of 0.873g3)2·6H2Co (the NO of O, 0.872g3)2·6H2O's and 1.955g
La(NO3)3·6H2O is dissolved in stirring and dissolving in 8.4ml deionized waters, is subsequently adding the polysorbate60 of 1.57g,
Mix homogeneously obtains dipping solution.Take the SiO of 4g2To in dipping solution, temperature is 30 DEG C to support dispersion
It is lower stand 2 hours after, evaporating water is subsequently placed in baking oven 100 DEG C of dryings 7 hours.It is dried
Sample is placed in Muffle furnace 800 DEG C of roastings 2 hours, and gained catalyst is designated as 4La-Ni-Co/SiO2.With
Metal atoms, the auxiliary agent are 0.75 with the mol ratio of the active metal component：1, with metal unit
The total content of the active metal Ni and Co of element meter is 8 weight %.Activity gold described in the catalyst
The dispersion of category Ni components is 10.9%, and the mean particle size of active metal component is 9.1nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=65.4%, XCO2=66.7%, H2/ CO=1.02.
Embodiment 3
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
By the Ni (NO of 2.81g3)2·6H2Mg (the NO of O and 0.31g3)2·6H2O be dissolved in 8.4ml go from
Stirring and dissolving in sub- water, is subsequently adding the Oleic acid of 1.36g, and mix homogeneously obtains dipping solution.Take 4g
SiO2Support dispersion in dipping solution, temperature be 15 DEG C at stand 5 hours after, evaporating water,
It is subsequently placed in baking oven 110 DEG C of dryings 5 hours.Dried sample is placed in 500 DEG C of roastings 6 in Muffle furnace
Hour, gained catalyst is designated as 1Mg-Ni/SiO2.With metal atoms, the auxiliary agent and the activity
The mol ratio of metal component is 0.125:1, the content with the active metal Ni of elemental metal is as 12
Weight %.The dispersion of active metal component described in the catalyst is 12.4%, active metal component
Mean particle size is 6.1nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=58.6%, XCO2=59.7%, H2/ CO=1.01.
Embodiment 4
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, the consumption of P123 is 0.348g,
Gained catalyst is designated as 6Mg-Ni/SiO2-2.Described in the catalyst, the dispersion of active metal component is
11.6%, the mean particle size of active metal component is 5.8nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=59.3%, XCO2=60.4%, H2/ CO=1.02.
Embodiment 5
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, Mg (NO3)2·6H2The use of O
Measure as 3.08g, gained catalyst is designated as 10Mg-Ni/SiO2-3.With metal atoms, the auxiliary agent with
The mol ratio of the active metal component is 2:1, with the content of the active metal component Ni of elemental metal
For 7.4 weight %.The dispersion of active metal component described in the catalyst is 13.5%, active metal
The mean particle size of component is 4.7nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=64.6%, XCO2=62.9%, H2/ CO=1.01.
Embodiment 6
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, carrier selects magnesium oxide, institute
Obtain catalyst and be designated as 6Mg-Ni/MgO.Described in the catalyst, the dispersion of active metal component is
13.1%, the mean particle size of active metal component is 4.9nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=63.7%, XCO2=61.9%, H2/ CO=1.0.
Embodiment 7
The embodiment is used for the preparation method and applications of the catalyst and catalyst for illustrating present invention offer.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, carrier selects Al2O3-MgO
Complex carrier, gained catalyst are designated as 6Mg-Ni/Al2O3-MgO.Active metal described in the catalyst
The dispersion of component is 13.9%, and the mean particle size of active metal component is 4.2nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=66.7%, XCO2=65.1%, H2/ CO=1.01.
Comparative example 1
The comparative example is used for the preparation method and applications of the catalyst and catalyst for illustrating reference.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, do not use surfactant
P123, gained catalyst are designated as 6Mg-Ni/SiO2-D1.Active metal component described in the catalyst point
Divergence is 2.3%, and the mean particle size of active metal component is 44.1nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 28 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=16.3%, XCO2=21.1%, H2/ CO=0.98.
In comparative example 1, the reactivity worth of the catalyst of gained is listed in Fig. 2, and the specially response time is 0-30
Methane and carbon dioxide conversion ratio in the methane dry reforming reaction is catalyzed by the catalyst of hour.
Comparative example 2
The comparative example is used for the preparation method and applications of the catalyst and catalyst for illustrating reference.
(1) catalyst preparation
Catalyst is prepared according to the method in embodiment 1, except that, do not use auxiliary agent, gained to urge
Agent is designated as Ni/SiO2.The dispersion of active metal component described in the catalyst is 5.4%, activity gold
The mean particle size of category component is 18.7nm.
(2) evaluating catalyst
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1.Reaction is steady
Surely, after carrying out 80 hours, by gas chromatogram on-line period and analyze tail gas and constitute.It is calculated：
XCH4=32.2%, XCO2=21.0%, H2/ CO=1.02.
In comparative example 2, the reactivity worth of the catalyst of gained is listed in Fig. 3, and the specially response time is 0-100
Methane and carbon dioxide conversion ratio in the methane dry reforming reaction is catalyzed by the catalyst of hour.
It can be seen from the results above that using the present invention provide catalyst preparation method and be prepared into
The catalyst energy continuous high-efficient stable operation arrived more than 1500 hours, and in 120000mlg-1·h-1
High-speed under can also obtain higher methane and carbon dioxide conversion ratio.Thus illustrate the catalysis of the present invention
Agent has more preferable reactivity and stability and coking resistivity.
The relatively low silica supports of even reactivity be can be seen that from the result of embodiment 1-5,
Made after catalyst using the method for the present invention, it is also possible to which the dispersion for obtaining active metal component is
6-15%, catalyst have more preferable reactivity and stability and coking resistivity, can continuous high-efficient
Stable operation is more than 1500 hours.
Can be seen that what is provided using the present invention from the result of embodiment 1 and comparative example 1 and comparative example 2
The preparation method of catalyst and the catalyst for preparing there is more preferable reactivity and stability with
And coking resistivity, energy continuous high-efficient stable operation is more than 1500 hours.And it is provided without present invention side
The catalyst reaction activity of the comparative example 1 and comparative example 2 of method is low, and stability is poor, runs 30 hours
Activity just declines to a great extent.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as
Its thought without prejudice to the present invention, which should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of loaded catalyst, it is characterised in that the catalyst contains carrier and is supported on
Active metal component and auxiliary agent on carrier, wherein, the active metal component is Ni components and/or Co
Component, the dispersion of the active metal component is 6-15%.
2. catalyst according to claim 1, wherein, the granule of the active metal component is put down
Particle diameter is 2-50nm, preferably 2-10nm.
3. catalyst according to claim 1 and 2, wherein, with the gross weight of the catalyst
On the basis of, with elemental metal, the content of the active metal component is 2-20 weight %, preferably
3-15 weight %, more preferably 4-10 weight %.
4. the catalyst according to any one in claim 1-3, wherein, with metal atoms,
The auxiliary agent is 0.01-5 with the mol ratio of the active metal component：1, preferably 0.1-2:1.
5. the catalyst according to any one in claim 1-4, wherein, the auxiliary agent is gold
Category oxides additive, preferably alkaline earth and/or rare-earth oxide auxiliary agent；More preferably
MgO、CaO、BaO、La2O3、CeO2、Sm2O3、ZrO2And Y2O3In at least one.
6. the catalyst according to any one in claim 1-5, wherein, the carrier is single
Component oxide carrier or bi-component or three component composite oxide carriers；Preferably, the carrier
Selected from SiO2、TiO2、MgO、Al2O3、ZrO2、CeO2、La2O3、SiO2-Al2O3、
TiO2-SiO2、Al2O3- MgO and TiO2-SiO2-Al2O3In one or more.
7. a kind of preparation method of loaded catalyst, the method include existing in surfactant
Under, dipping solution is contacted with carrier, is then dried and roasting, wherein, in the dipping solution
The soluble compound of the soluble compound containing active metal component and auxiliary agent.
8. method according to claim 7, wherein, the surfactant and with metallic atom
The mol ratio of the consumption of the soluble compound of the active metal component of meter is 0.001-2:1, preferably
0.001-1:1, more preferably 0.01-0.8：1.
9. the method according to claim 7 or 8, wherein, the surfactant selected from it is cloudy from
At least one in subtype surfactant, amphoteric surfactant and nonionic surfactant；
Preferably stearic acid, Oleic acid, lauric acid, lecithin, dodecyl alanine, alkyl dimethyl
At least one in glycine betaine, fatty glyceride, polyhydric alcohol, polysorbate60 and P123；It is further excellent
Elect at least one in P123, Oleic acid and polysorbate60 as.
10. the method according to any one in claim 7-9, wherein, with metal atoms,
The soluble compound of the auxiliary agent with the mol ratio of the soluble compound of the active metal component is
0.01-5:1, preferably 0.1-2:1.
11. methods according to any one of claims of claim 7-10, wherein, the auxiliary agent can
Soluble compound is selected from alkaline earth and/or rare earth metal soluble compound；Preferably, the auxiliary agent can
Soluble compound is in magnesium salt, calcium salt, strontium salt, barium salt, cerium salt, lanthanum salt, zirconates and yttrium salt
It is at least one；It is highly preferred that the soluble compound of the auxiliary agent selected from magnesium salt, barium salt, lanthanum salt and
At least one in yttrium salt, more preferably lanthanum salt and/or magnesium salt.
12. methods according to any one in claim 7-11, wherein, the concentration of impregnation liquid
With consumption so that on the basis of the gross weight of the catalyst, with elemental metal, the active metal
The content of component is 2-20 weight %, preferably 3-15 weight %, more preferably 4-10 weight %；
Preferably, the soluble compound of the active metal component is selected from Ni (NO3)2·6H2O、
Co(NO3)2·6H2O、Ni(acac)2、Co(acac)3、Ni(CH3COO)2·6H2O and
Co(CH3COO)2·6H2At least one in O, more preferably Ni (NO3)2·6H2O and/or
Co(NO3)2·6H2O；The carrier is single component oxide carrier or bi-component or three component composite oxygens
Compound carrier, preferably SiO2、TiO2、MgO、Al2O3、ZrO2、CeO2、La2O3、
SiO2-Al2O3、TiO2-SiO2、Al2O3- MgO and TiO2-SiO2-Al2O3In one or more.
The supported catalyst that 13. preparation methoies by described in claim 7-12 any one are prepared
Agent.
Loaded catalyst in 14. claim 1-6 and 13 described in any one is in methane dry reforming
Prepare the application in synthesis gas.
A kind of 15. methods of methane dry reforming preparing synthetic gas, the method are included in the synthesis of methane dry reforming system
Under the conditions of gas, methane and carbon dioxide is contacted with catalyst, it is characterised in that the catalyst is power
Profit requires the catalyst in 1-6 and 13 described in any one.
16. methods according to claim 15, wherein, the methane dry reforming preparing synthetic gas are adopted
With fixed bed reactors or fluidized-bed reactor, the condition of the methane dry reforming preparing synthetic gas includes：First
The mol ratio of alkane and carbon dioxide is 0.7-1.1:1, preferably 0.8-1：1；Reaction temperature is 550-850 DEG C,
Preferably 600-800 DEG C；Pressure is 0-3MPa, preferably 0-1MPa；Total air speed of unstripped gas is
2000-120000ml·g-1·h-1, preferably 60000-120000mlg-1·h-1。
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