CN106608617A - Method for preparing synthetic gas through dry reforming of methane - Google Patents
Method for preparing synthetic gas through dry reforming of methane Download PDFInfo
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- CN106608617A CN106608617A CN201510688136.0A CN201510688136A CN106608617A CN 106608617 A CN106608617 A CN 106608617A CN 201510688136 A CN201510688136 A CN 201510688136A CN 106608617 A CN106608617 A CN 106608617A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/169—Controlling the feed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the field of preparation of synthetic gas through dry reforming of methane, and discloses a method for preparing synthetic gas through dry reforming of methane. The loading amount of an active metal component Ni in a catalyst in a catalyst bed of a dry reforming reaction of methane is controlled, and a Al2O3 carrier and/or a Al2O3 carrier modified with an auxiliary agent is adopted. Even in relatively high reaction velocity, temperature dispersion of the catalyst bed is basically uniform, and an area where carbon is easily thermodynamically accumulated can be avoided, so that the catalytic stability of a catalyst is greatly improved and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention relates to the research field of methane dry reforming preparing synthetic gas, in particular it relates to a kind of methane is dry
The method of preparing synthetic gas by reforming.
Background technology
Methane dry reforming is CH4And CO2Reaction is carried out in the presence of catalyst and generates CO and H2(close
Into gas) course of reaction, reaction equation is as follows：
CH4+CO2→2CO+2H2, Δ H298K=247.3kJ/mol (1)
CO2+H2→CO+H2O,ΔH298K=40.96kJ/mol (2)
Wherein reaction equation (1) is primary response, and reaction equation (2) is that side reaction, i.e. Reversed Water-gas Shift are anti-
Should, and just because of the presence of reverse water-gas-shift reaction, cause H in product2/ CO ratios are less than 1.
Methane dry reforming is reacted two kinds in nature most cheap carbon compound CH4And CO2Transformation
Into the industrial chemicals synthesis gas with high added value, and in the synthesis gas for preparing, CO contents are higher, are suitable to
As oxo process and the raw material of F- T synthesis, thus it is with a wide range of applications.Additionally, methane is dry
Reforming reaction make use of CH simultaneously4And CO2Both greenhouse gases, are considered to have environment friendly,
Environmental problem increasingly it is serious instantly, if can realize, the industrial applications of the technical process undoubtedly have weight
Big realistic meaning.
Due to the reaction of methane dry reforming catalyst during the course of the reaction easy-sintering and carbon deposit and inactivate, so as to
Constrain the paces of the reaction industry application.The methane dry weight with preferable performance reported both at home and abroad at present
Whole catalyst mainly has three kinds：(1) the NiO-MgO solid solutions of Japan Fujimoto professors seminar exploitation
Body catalyst (Keiichi Tomishige, et al., Development of ultra-stable Ni catalysts for
CO2reforming of methane,Catal.Today,45(1998)35-39)；(2) patent
That what is reported in CN1102430C is taught the Ni/ZrO of seminar's exploitation by Tsing-Hua University Xu Baiqing2- AS is catalyzed
Agent (on the basis of the weight of catalyst, the content of Ni is 10-15 weight %)；(3) University of Petroleum opens
The Ni/meso-ZrO for sending out2Catalyst (Mehran Rezaei, et al., CO2-CH4reforming over
nickel catalysts supported on mesoporous nanocrystalline zirconia with high
surface area,Energy&Fuels,21(2007),581-589).Although these catalyst have shown
Preferable stability, but these catalyst are only applicable to relatively low reaction velocity.When reaction velocity is higher than
When 40000 mls/g of hours, catalyst is easy to (be usually no more than 20 during the course of the reaction
Hour) inactivate because of sintering and carbon deposit, so as to constrain paces of the above-mentioned catalyst in commercial Application.
The content of the invention
It is an object of the invention to it is relatively low to there is reaction velocity in overcoming the reaction of prior art methane dry reforming
Or the coking resistivity difference of catalyst causes the short defect of the service life of catalyst, there is provided one kind has
The method of the new methane dry reforming preparing synthetic gas of the long service life of higher reaction velocity and catalyst.
In order to solve the above problems, the present inventor has carried out deep grinding to the reaction of methane dry reforming
Study carefully.As can be seen that the reaction of methane dry reforming is the heat absorption of a volume increase first from thermodynamics of reactions
Reaction, and its heat absorption intensity is very big, if reaction carries out too acutely causing beds temperature drop
Excessively, causing the carbon deposit of one of catalyst deactivation cause, to react (CO dismutation reactions) be a low temperature
Favourable reaction.Therefore, if reaction too acutely may result in catalyst carbon deposit and excessively inactivate.Secondly
The present inventor carries out research discovery by the technique to existing methane dry reforming preparing synthetic gas, existing
The reaction for having technology methane dry reforming preparing synthetic gas is carried out typically in fixed bed reactors, wherein forming whole
The catalyst of individual beds is same catalyst, and active metal component Ni contains in catalyst
Amount is generally 10-20 weight portions (on the basis of the catalyst of 100 weight portions).Due to active metal group
The content divided is higher, and the catalysis activity of catalyst is stronger, causes, in the case where reaction velocity is higher, to urge
At agent bed inlet reaction too acutely, so as to cause catalyst because of carbon distribution rapid deactivation, and this
Planting inactivation makes the aft section of beds also successively inactivate along the flow direction of material quickly, so as on the one hand
Cause the service life of beds short, on the other hand also due to the priority inactivation of beds, leads
The unstable of integer catalyzer reactivity in whole course of reaction is caused, or even reactor can be blocked.Thus
Present inventor completes the present invention.
Specifically, the invention provides a kind of method of methane dry reforming preparing synthetic gas, the method is included in
Under the conditions of methane dry reforming preparing synthetic gas, methane and carbon dioxide is contacted with beds, form institute
The catalyst for stating beds contains active metal component Ni and carrier, wherein, the carrier is Al2O3
Carrier and/or the Al obtained with additive modification2O3Carrier, relative to the catalyst of 100 weight portions, with gold
Category element meter, the content of the active metal component Ni can be 3.5-8.5 weight portions, preferably 4-7
Weight portion.
The present invention is by active metal component in catalyst in control methane dry reforming catalysts bed
The load capacity of Ni, and adopt Al2O3Carrier and/or the Al obtained with additive modification2O3Carrier so that i.e.
Just, under higher reaction velocity, the distribution of catalyst layer bed tempertaure is substantially uniform, avoids the easy carbon deposit of thermodynamics
Region, so as to substantially increase the catalytic stability and catalyst service life of catalyst.Such as embodiment
In 1, the temperature of the bed of the differing heights of catalyst keeps basically identical, and 1 active metal group of comparative example
The load capacity of Ni is divided to exceed the scope, reaction bed temperature difference is larger.Catalyst can simultaneously
Long-period stable operation and higher catalysis activity is maintained, the catalysis of such as catalyst of embodiment 1 is lived
Property maintain higher level, 250 hours activity of stable operation are not changed substantially, but comparative example 1
When operation was to 60 hours, activity just there occurs and be decreased obviously middle catalyst.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is catalyst 5Ni/8Mg-Al used in embodiment 12O3With catalyst used in comparative example 1
9Ni/8Mg-Al2O3By methane dry reforming react preparing synthetic gas when reaction bed temperature profiles versus
As a result；
Fig. 2 is catalyst 5Ni/8Mg-Al in embodiment 12O3Estimation of stability result；
Fig. 3 is catalyst 9Ni/8Mg-Al in comparative example 12O3Estimation of stability result.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of methane dry reforming preparing synthetic gas, the method is included in methane dry weight
Under the conditions of whole preparing synthetic gas, methane and carbon dioxide is contacted with beds, form the catalyst
The methane dry reforming catalyst of bed contains active metal component Ni and carrier, wherein, the carrier is
Al2O3Carrier and/or the Al obtained with additive modification2O3Carrier, relative to the catalyst of 100 weight portions,
With elemental metal, the content of the active metal component Ni is 3.5-8.5 weight portions, preferably 4-7
Weight portion.
The present invention is by active metal in catalyst in strict control methane dry reforming catalysts bed
The load capacity of component Ni within the above range, and coordinates Al2O3Carrier and/or obtained with additive modification
Al2O3Carrier so that even if under higher reaction velocity, reaction bed temperature distribution is substantially uniform,
The easy carbon deposit region of thermodynamics is avoided, so as to the catalytic stability and catalyst that substantially increase catalyst are used
Life-span.
In the present invention, it is preferred to the carrier of the methane dry reforming catalyst is obtained with additive modification
Al2O3Carrier, the auxiliary agent are alkaline earth oxide and/or the one kind or many in rare-earth oxide
Kind.Further preferably the auxiliary agent is at least one in magnesium, calcium, barium, strontium, cerium, lanthanum, zirconium and yttrium,
At least one more preferably in magnesium, barium, lanthanum and yttrium, is still more preferably magnesium and/or lanthanum.
The above-mentioned Al obtained with additive modification2O3Carrier can be by using the presoma containing the auxiliary agent
Aqueous solution to Al2O3Carrier carries out impregnation process, then by the Al after dipping2O3Carrier is dried
Obtain with roasting.The presoma of the auxiliary agent can for water miscible magnesium salt, calcium salt, strontium salt, barium salt,
At least one in cerium salt, lanthanum salt, zirconates and yttrium salt, more preferably water miscible magnesium salt, barium salt, lanthanum
At least one in salt and yttrium salt, more preferably water miscible lanthanum salt and/or magnesium salt.For example, it is common
Water soluble salt can be Mg (NO3)2·6H2O、Ca(NO3)2·6H2O、Ba(NO3)2·6H2O、
Ce(NO3)3·6H2O、La(NO3)3·6H2O and Y (NO3)3·6H2At least one in O, in order to obtain
More preferable modified effect, the water soluble salt are preferably Mg (NO3)2·6H2O、Ba(NO3)2·6H2O、
Ce(NO3)3·6H2O、La(NO3)3·6H2O and Y (NO3)3·6H2At least one in O, it is further excellent
Elect Mg (NO as3)2·6H2O and/or La (NO3)3·6H2O。
There is no particular limitation for consumption of the present invention to auxiliary agent.For example, relative to 100 weight portions helping
Agent is modified the Al for obtaining2O3Carrier, in terms of oxide, the content of the auxiliary agent can be 0.1-15 weight
Part, preferably 1-15 weight portions.
A preferred embodiment of the invention, the carrier are the Al that La and/or Mg is modified2O3
Carrier, and relative to the Al obtained with additive modification of 100 weight portions2O3Carrier, in terms of oxide,
The content of auxiliary agent La and/or Mg be 3-13 weight portions, preferred 6-12 weight portions.
A preferred embodiment of the invention, relative to the catalyst of 100 weight portions, with metal
Element meter, the content of the active metal component is 4.5-6.5 weight portions.
In the present invention, described in the support modification method, the mode of impregnation process is not particularly limited
It is fixed, can for example be equi-volume impregnating commonly used in the art, or supersaturation infusion process, or
Said method is combined.The temperature and time of the impregnation process is not particularly limited, as long as can will be required
Auxiliary component is loaded on carrier.The condition that such as described carrier impregnation is processed includes：Temperature can be with
For 10-50 DEG C, preferably 15-35 DEG C；Time can be 0.5-10 hours, preferably 1-3 hours.
The condition of carrier impregnation process used in the present invention and the drying and roasting of impregnated carrier is equal
Can be selected according to its knowledge grasped by those skilled in the art, such as described baking temperature can be with
For 60-150 DEG C, preferably 90-120 DEG C；Drying time can be 1-20 hours, and preferably 5-10 is little
When.
The temperature of the roasting can be 500-1100 DEG C, preferably 700-1000 DEG C；Roasting time can be with
For 1-15 hours, preferably 2-5 hours.
In the present invention, the catalyst can be by by the soluble compound containing active metal component
Impregnation liquid be impregnated on the carrier be obtained, contain nonionic surfactant in the impregnation liquid.
The nonionic surfactant can be existing various nonionic surfactants, for example can be with
It is stearic acid, Oleic acid, lauric acid, lecithin, dodecyl alanine, fatty glyceride, many
First alcohol, Polysorbate (such as tween) and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) three block are altogether
At least one in polymers (P123).In order to obtain the more preferable catalyst of performance, the non-ionic surface
Activating agent is preferably at least one in polyhydric alcohol, tween and P123, more preferably P123.
In the present invention, the nonionic surfactant with the active metal component of metal atoms
Mol ratio can be 0.001-2：1, in order to obtain the more preferable catalyst of performance, the mol ratio is preferably
0.001-1:1, more preferably 0.002-0.01:1.Wherein when nonionic surfactant is polymer,
The molal quantity of the nonionic surfactant is according to the number-average molecular weight of nonionic surfactant come really
It is fixed.
Active metal component Ni can be loaded to Al by infusion process to the catalyst by the present invention2O3
Carrier and/or the Al obtained with additive modification2O3Prepare on carrier.The infusion process can for example be this
The conventional equi-volume impregnating in field, or supersaturation infusion process, or said method combination.
The soluble compound of the active metal component used by the infusion process can be the routine of this area
Select, for example, can be Ni (NO3)2·6H2O、NiCO3·2Ni(OH)2·4H2O and
Ni(CH3COO)2·4H2One or more in O, preferably Ni (NO3)2·6H2O.The dipping
The concentration of the soluble compound of the active metal component in liquid can be the conventional selection of this area.Example
Such as, the concentration of the soluble compound of the active metal component in the impregnation liquid can be 14-34 weights
Amount %, preferably 15-27 weight %.
The condition of the catalyst impregnation process includes：Temperature can be 10-50 DEG C, preferably 15-35 DEG C；
Time can be 0.5-10 hours, preferably 1-3 hours.
The impregnation liquid of the soluble compound containing active metal component impregnated in modified Al2O3Carrier
Need methane dry reforming catalyst could be obtained through dry and roasting after upper.Wherein, the dried strip
Part includes：Baking temperature can be 60-150 DEG C, preferably 90-120 DEG C；Drying time can be with 1-20
Hour, preferably 5-10 hours.The roasting condition includes：Sintering temperature can be 400-1000 DEG C,
Preferably 500-800 DEG C；Roasting time can be 1-15 hours, preferably 2-5 hours.
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 component to be carried out reduction activation.Wherein, the condition of reduction activation
Including：Reduction temperature can be 300-800 DEG C, preferably 500-700 DEG C；Recovery time can be 0.5-10
Hour, preferably 2-5 hours.The reduction activation can be carried out in pure hydrogen, also can be in hydrogen and lazy
Property gas gaseous mixture in carry out, if carried out in gaseous mixture of the hydrogen with nitrogen and/or argon, reduction
Pressure can be 0-2MPa, preferably 0-0.5MPa.In the present invention, the pressure is gauge pressure.
Using the present invention provide method carry out methane dry reforming catalytic reaction when, methane and carbon dioxide with
There is no particular limitation for the method for the catalyst contact, can be the conventional selection of this area, for example,
Methane and carbon dioxide can be each sent in reactor while contacting with catalyst, it is also possible to by methane
Mixture is formed with carbon dioxide to contact with the catalyst again, it is preferable that by methane and carbon dioxide shape
Resulting mixture is contacted with the catalyst again.
Methane and CO are used according to the methane dry reforming reaction that the present invention is provided2Prepare for raw material reaction and close
During into gas, the catalytic condition includes that reaction temperature can be 550-900 DEG C, preferably
700-850℃；Reaction pressure can be 0-3MPa, preferably 0-1MPa；Methane and carbon dioxide rubs
Your ratio can be 0.7-1.1：1, preferably 0.8-1：1, the cumulative volume of feed gas methane and carbon dioxide
Air speed can be 2000-200000mlg-1·h-1, preferably 10000-120000mlg-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) constituted using gas chromatography on-line period analytical calculation tail gas, so as to calculate methane and two
Oxidation charcoal percent conversion；
2) temperature of catalyst layer bed differing heights is measured using thermocouple.
Embodiment 1
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Weigh the Mg (NO of 5.53g3)2·6H2O is dissolved in 14g deionized waters, is configured to carrier impregnation liquid；
It is to be dissolved to finish the Al for being impregnated in 10g2O3On carrier, dipping temperature is 25 DEG C, stands 2 hours.
Then the extrusion on banded extruder.The wet bar of gained is placed in Muffle furnace after 120 DEG C of dryings 8 hours
800 DEG C of roastings 3 hours.Resulting vehicle is designated as 8Mg-Al2O3。
(2) preparation of catalyst
Weigh the Ni (NO of 1.06g3)2·6H2The P123 of O and 0.211g is stirred in being dissolved in 5.2g deionized waters
Dissolving is mixed, this impregnation liquid be impregnated in into the above-mentioned carrier 8Mg-Al of 4g2O3In, it is placed in after standing 2 hours
It is vacuum dried on Rotary Evaporators, is subsequently placed in baking oven 120 DEG C of dryings 8 hours.Dried sample
650 DEG C of roastings 3 hours are placed in Muffle furnace, gained catalyst is designated as 5Ni/8Mg-Al2O3。
(3) activity rating
Weigh 5Ni/8Mg-Al2O3Catalyst 0.05g, is diluted to 2ml with 40-60 mesh quartz sands, loads
Internal diameterQuartz tube reactor in, under normal pressure, in pure hydrogen atmosphere, 700 DEG C of reductase 12 hours are lived
Change.After reduction terminates, 750 DEG C are warming up in a hydrogen atmosphere, switch unstripped gas (methane and titanium dioxide
The mol ratio of carbon is 1:1) reacted, reaction velocity is 120000mlg-1·h-1, reaction pressure is normal
Pressure.Reaction bed temperature such as Fig. 1 institutes under the different catalysts bed height that reaction is measured for 20 hours
Show.The methane and carbon dioxide conversion ratio of 0-250 hours is as shown in Fig. 2 wherein react 2 hours and 50
The reaction result of hour is listed in Table 1 below.
Embodiment 2
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Weigh the La (NO of 1.7g3)3·6H2O is dissolved in 14g deionized waters, is configured to carrier impregnation liquid；
It is to be dissolved to finish the Al for being impregnated in 10g2O3On carrier, dipping temperature is 35 DEG C, stands 1 hour.
Then the extrusion on banded extruder.The wet bar of gained is placed in Muffle furnace after 90 DEG C of dryings 10 hours
1000 DEG C of roastings 2 hours.Resulting vehicle is designated as 6La-Al2O3。
(2) preparation of catalyst
Weigh the Ni (NO of 0.84g3)2·6H2The P123 of O and 0.166g is stirred in being put into 5.2g deionized waters
Mix dissolving；This catalyst impregnating solution be impregnated in into the above-mentioned carrier 6La-Al of 4g2O3In, after standing 3 hours
It is placed on Rotary Evaporators and is vacuum dried, is subsequently placed in baking oven 110 DEG C of dryings 5 hours.It is dried
Sample places in Muffle furnace 800 DEG C of roastings 5 hours, and gained catalyst is designated as 4Ni/6La-Al2O3。
(3) activity rating
Weigh 4Ni/6La-Al2O3Catalyst 0.05g, is diluted to 2ml with 40-60 mesh quartz sands, loads
Internal diameterQuartz tube reactor in, under normal pressure, in pure hydrogen atmosphere, 600 DEG C of reduction are lived for 4 hours
Change.After reduction terminates, 850 DEG C are warming up in a hydrogen atmosphere, switch unstripped gas (methane and titanium dioxide
The mol ratio of carbon is 0.8:1) reacted, reaction velocity is 10000mlg-1·h-1, reaction pressure is normal
Pressure.Gained reaction result is listed in Table 1 below.
Embodiment 3
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Weigh the Mg (NO of 8.68g3)2·6H2O is dissolved in 14g deionized waters, is configured to carrier impregnation liquid；
It is to be dissolved to finish the Al for being impregnated in 10g2O3On carrier, dipping temperature is 15 DEG C, stands 3 hours.
Then the extrusion on banded extruder.The wet bar of gained is placed in Muffle furnace after 110 DEG C of dryings 5 hours
700 DEG C of roastings 5 hours.Resulting vehicle is designated as 12Mg-Al2O3。
(2) preparation of catalyst
Weigh the Ni (NO of 1.39g3)2·6H2The P123 of O and 0.05g is stirred in being put into 5.2g deionized waters
Dissolving；This catalyst impregnating solution be impregnated in into the above-mentioned carrier 12 Mg-Al of 4g2O3In, after standing 1 hour
It is placed on Rotary Evaporators and is vacuum dried, is subsequently placed in baking oven 90 DEG C of dryings 10 hours.It is dried
Sample places in Muffle furnace 1000 DEG C of roastings 2 hours, and gained catalyst is designated as 7Ni/12Mg-Al2O3。
(3) activity rating
Weigh 7Ni/12Mg-Al2O3Catalyst 0.05g, is diluted to ml with 40-60 mesh quartz sands, loads
Internal diameterQuartz tube reactor in, under normal pressure, in pure hydrogen atmosphere, 500 DEG C of reduction are lived for 5 hours
Change.After reduction terminates, 700 DEG C are warming up in a hydrogen atmosphere, switch unstripped gas (methane and titanium dioxide
The mol ratio of carbon is 0.9:1) reacted, reaction velocity is 80000mlg-1·h-1, reaction pressure is
0.5MPa.Gained reaction result is listed in Table 1 below.
Embodiment 4
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Carrier is prepared using condition same as Example 1 and method.
(2) preparation of catalyst
Catalyst is prepared using the method for embodiment 1, except for the difference that, impregnation liquid does not contain surfactant
P123, gained catalyst are designated as 5Ni-1/8Mg-Al2O3。
(3) activity rating
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1, gained is anti-
Should the results are shown in Table 1.
Embodiment 5
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Carrier is prepared using condition same as Example 1 and method.
(2) preparation of catalyst
Catalyst is prepared using the method for embodiment 1, except for the difference that, the surfactant in impregnation liquid
P123 is replaced by the Polyethylene Glycol of identical molar ratio, and gained catalyst is designated as 5Ni-2/8Mg-Al2O3。
(3) activity rating
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1, gained is anti-
Should the results are shown in Table 1.
Embodiment 6
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
In the present embodiment, carrier uses non-modified Al2O3Carrier, is designated as Al2O3Carrier.
(2) preparation of catalyst
Catalyst is prepared using the method for embodiment 1, except for the difference that, the carrier for being used is non-modified
Al2O3Carrier, gained catalyst are designated as 5Ni/Al2O3。
(3) activity rating
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1, gained is anti-
Should the results are shown in Table 1.
Comparative example 1
The method that the embodiment is used for the methane dry reforming preparing synthetic gas for illustrating present invention offer.
(1) preparation of catalyst carrier
Carrier is prepared using condition same as Example 1 and method.
(2) preparation of catalyst
Catalyst is prepared using the method for embodiment 1, except for the difference that, the Ni (NO for being used3)2·6H2O
Weight be 2.01g, gained catalyst is designated as 9Ni/8Mg-Al2O3。
(3) activity rating
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1, gained is anti-
Should the results are shown in Table 1.Catalyst bed under the different catalysts bed height that reaction is measured for 20 hours
Layer temperature is as shown in Figure 1.The methane and carbon dioxide conversion ratio of 0-60 hours is as shown in Figure 3.
Comparative example 2
The method that the comparative example is used for the methane dry reforming preparing synthetic gas for illustrating reference.
(1) preparation of catalyst carrier
Carrier is prepared using condition same as Example 1 and method.
(2) preparation of catalyst
Catalyst is prepared using the method for embodiment 1, except for the difference that, the Ni (NO for being used3)2·6H2O
Weight be 0.2g, gained catalyst is designated as 1Ni/8Mg-Al2O3。
(3) activity rating
Activated catalyst carry out methane dry reforming reaction under the same conditions as example 1, gained is anti-
Should the results are shown in Table 1.
Table 1
| Embodiment is numbered | The reaction methane conversion (%) of 2 hours | The reaction methane conversion (%) of 50 hours |
| Embodiment 1 | 43.7 | 63.1 |
| Embodiment 2 | 67.8 | 76.5 |
| Embodiment 3 | 38.5 | 53.2 |
| Embodiment 4 | 36.9 | 54.3 |
| Embodiment 5 | 42.6 | 61.7 |
| Embodiment 6 | 39.4 | 52.5 |
| Comparative example 1 | 76.7 | 48.2 |
| Comparative example 2 | 12.5 | 26.7 |
The methane dry weight of the active metal component Ni containing different content is can be seen that by the result of table 1
Whole catalyst has different catalysis activities and stability, relative to the catalyst of 100 weight portions, with gold
Category element meter, the content of the active metal component Ni is 3.5-8.5 weight portions, preferably 4-7 weight
Part when, with more preferable reaction stability, and can be seen that from the result of comparative example 1 and work as active metal
When component Ni content exceedes in the scope, the reaction of methane dry reforming carries out fierceness, causes catalyst fast
Speed inactivation.
From the result of Fig. 1-3 can be seen that comparative example 1 active metal component Ni contents (relative to
The catalyst of 100 weight portions, with elemental metal, the content of the active metal component Ni is 9 weight
Part) more than the scope when, methane dry reforming catalyst layer bed tempertaure skewness, catalyst inactivation
Speed, the conversion ratio of raw material methane and carbon dioxide are also gradually reduced.And active metal component Ni
Content (relative to the catalyst of 100 weight portions, with elemental metal, the active metal component Ni
Content be 5 weight portions) in the scope when, catalyst layer bed tempertaure distribution it is substantially uniform, reaction
Good stability, the conversion ratio of methane and carbon dioxide keep higher level and catalyst continuous and steady operation
More than 250 hours non-inactivations.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case 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 need not
The repetition wanted, 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
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method 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 beds, form the first of the beds
Alkane dry reforming catalyst contains active metal component Ni and carrier, it is characterised in that the carrier is Al2O3
Carrier and/or the Al obtained with additive modification2O3Carrier, relative to the catalyst of 100 weight portions, with gold
Category element meter, the content of the active metal component Ni is 3.5-8.5 weight portions, preferably 4-7 weight
Part.
2. method according to claim 1, wherein, the methane dry reforming preparing synthetic gas condition
It is 0.7-1.1 including the mol ratio of methane and carbon dioxide:1, preferably 0.8-1：1；Reaction temperature is
550-900 DEG C, preferably 700-850 DEG C；Pressure is 0-3MPa, preferably 0-1MPa；Methane and two
The cumulative volume air speed of carbonoxide is 2000-200000mlg-1·h-1, preferably
10000-120000ml·g-1·h-1。
3. method according to claim 1 and 2, wherein, the carrier is to be obtained with additive modification
The Al for arriving2O3Carrier；Relative to the Al obtained with additive modification of 100 weight portions2O3Carrier, with oxygen
Compound meter, the content of the auxiliary agent is 0.1-15 weight portions, it is preferable that the content of the auxiliary agent is 1-15
Weight portion.
4. method according to claim 3, wherein, the method for modifying of the carrier includes using
The aqueous solution of the presoma containing the auxiliary agent is to Al2O3Carrier carries out impregnation process, after then impregnating
Al2O3Carrier is dried and roasting.
5. the method according to claim 3 or 4, wherein, the presoma of the auxiliary agent is alkaline earth
Metallic compound and/or rare earth compound；Preferably, the presoma of the auxiliary agent is water miscible magnesium
At least one in salt, calcium salt, strontium salt, barium salt, cerium salt, lanthanum salt, zirconates and yttrium salt, more preferably
At least one in water miscible magnesium salt, barium salt, lanthanum salt and yttrium salt, more preferably water miscible lanthanum
Salt and/or magnesium salt.
6. the method according to any one in claim 3-5, wherein, at the carrier impregnation
The time of reason is 0.5-10 hours, preferably 1-3 hours；Al after the dipping2O3Being dried for carrier is warm
Spend for 60-150 DEG C, preferably 90-120 DEG C；Drying time is 1-20 hours, preferably 5-10 hours；
The dried Al2O3The sintering temperature of carrier is 500-1100 DEG C, preferably 700-1000 DEG C；Roasting
The burning time is 1-15 hours, preferably 2-5 hours.
7. the method according to any one in claim 1-6, wherein, the catalyst passes through
The impregnation liquid of the soluble compound containing active metal component is impregnated on the carrier and is obtained, it is described
Contain nonionic surfactant in impregnation liquid.
8. method according to claim 7, wherein, the nonionic surfactant with gold
The mol ratio of the active metal component of category atom meter is 0.001-2:1, preferably 0.001-1:1, it is further excellent
Elect 0.002-0.01 as:1.
9. the method according to claim 7 or 8, wherein, the nonionic surfactant is
P123。
10. the method according to any one in claim 1-9, wherein, the carrier is La
And/or the Al that Mg is modified2O3Carrier；Relative to the Al obtained with additive modification of 100 weight portions2O3
Carrier, in terms of oxide, the content of auxiliary agent La and/or Mg is 3-13 weight portions, preferred 6-12 weights
Amount part；Relative to the catalyst of 100 weight portions, with elemental metal, the active metal component contains
Measure as 4-6.5 weight portions.
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