CN106512999A - Dry-gas reforming catalyst for methane and preparation method for dry-gas reforming catalyst for methane - Google Patents
Dry-gas reforming catalyst for methane and preparation method for dry-gas reforming catalyst for methane Download PDFInfo
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- CN106512999A CN106512999A CN201610788640.2A CN201610788640A CN106512999A CN 106512999 A CN106512999 A CN 106512999A CN 201610788640 A CN201610788640 A CN 201610788640A CN 106512999 A CN106512999 A CN 106512999A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention provides a dry-gas reforming catalyst for methane. According to the dry-gas reforming catalyst, metals M and N are introduced onto a metal Ni so as to form a metallic active ingredient, i.e., Ni-M-N, wherein the metal M is any selected from Co, Fe, Cu, Ru and Rh, and the metal N is any selected from Mg, Ca, Ba, Na and K; and the metallic active ingredient is loaded to a carrier, so as to form the dry-gas reforming catalyst for the methane, wherein the mass of the metal Ni accounts for 1% to 20% that of the carrier, the mass of the metal M accounts for 0.1% to 20% that of the carrier, the mass of the metal N accounts for 1% to 20% that of the carrier, and the life of the dry-gas reforming catalyst for the methane is not shorter than 1,000h. By a preparation method for the dry-gas reforming catalyst for the methane, the high-temperature reaction activity of the dry-gas reforming catalyst for the methane can be improved greatly, and the high-temperature resistance is high, so that the life of the dry-gas reforming catalyst for the methane is prolonged greatly.
Description
Technical field
The present invention relates to catalyst field, more particularly to a kind of methane dry gas reforming catalyst and preparation method thereof.
Background technology
It is the emphasis and difficulties of research both at home and abroad in recent decades that dry gas is reformed, and the reaction is simultaneously using methane and two
Carbonoxide both greenhouse gases prepare synthesis gas (H as raw material2And CO), advantageously reduce the discharge of greenhouse gases.This
Outward, dry gas is reformed in the synthesis gas for obtaining, H21 is slightly less than with CO contents ratio, can be directly as the unstripped gas of F- T synthesis.
In existing document, common report is that Ni base catalyst is applied to dry gas reforming reaction.Chinese invention patent is (public
The number of opening CN 1344671A) announce containing MoO3Or WO3Ni/SiO2And Ni/Al2O3Catalyst, compared with low-speed (8400mL.g-1.h-1), higher conversion ratio can be kept at normal pressure and 780 DEG C, but the life test of catalyst only has 20h.As Ni bases are catalyzed
Agent under the high temperature conditions, active metal centre easily build up grow up and course of reaction in carbon distribution it is serious so that catalyst is inactivated very
Hurry up.So, the life-span of high temperature catalyst is the problem that the research is badly in need of considering.
Researcher adds the additives such as Co, Mg in follow-up work, successively on the basis of Ni base catalyst, and effect is to make
The dispersion that Ni-Co alloys promote Ni is obtained, the introducing of Mg can strengthen the alkalescence of carrier to promote CO2Absorption, so as to accelerate first
The speed of alkane dry gas reforming reaction.Chinese invention patent (102407119 A of publication number CN) is disclosed with NixMg1-xAl2O4With
CoxMg1-xAl2O4Mixture for active component catalyst and preparation method thereof, the catalyst carried by catalyst of cordierite
Body, honeycomb-like cordierite is processed in salpeter solution, drying is washed out, cordierite substrates are obtained, according still further to active component
Content is different, takes cobalt nitrate, nickel nitrate and magnesium nitrate and aluminum nitrate is configured to solution, ammoniacal liquor is added dropwise, and stirring forms precipitation, then
Filtration drying roasting is obtained cordierite-base body catalyst, but the preparation method is cumbersome.After the successive reaction test of 20h, still
There is a small amount of carbon distribution to produce.
Chinese invention patent (publication number CN 102416328A) discloses the catalyst that a kind of dry gas reformation prepares synthesis gas
And preparation method thereof, the catalyst is by Ni, Fe, CeO2、MgAl2O4Composition, preparation method is first to prepare mesoporous MgAl2O4Spinelle
Carrier, then prepare Ni base catalyst suspensions, eventually passes filtration, washing, drying, roasting and makes.The carrier point of the catalyst
Spar adopts sol-gal process and the urea deposits precipitation method to be obtained, and preparation process is comparatively laborious.Reaction of the catalyst in 140h
In test, methane conversion slowly declining, and without reaction detection its stability of longer time.
Research background more than can be seen that it is multiple it is improved under the conditions of dry gas reform catalyst catalytic life
Strengthen, but the process of industrialization of the process has still been obstructed, main cause has still faced high temperature catalyst short life and quick
The problem of inactivation.
The content of the invention
The invention aims to solve the deficiencies in the prior art, there is provided a kind of methane dry gas reforming catalyst and its system
Preparation Method, solves the problems, such as that dry gas reforming catalyst is easily inactivated under the high temperature conditions.
The purpose of the present invention is achieved through the following technical solutions：
It is an object of the present invention to provide a kind of methane dry gas reforming catalyst, introduces metal M and N on W metal,
Metal active constituent Ni-M-N is formed, the metal M is selected from any one in Co, Fe, Cu, Ru, Rh, and the metal N is selected from
Any one in Mg, Ca, Ba, Na, K；
The metal active constituent is supported on formation methane dry gas reforming catalyst, the quality of the W metal on a carrier
The 1%-20% of carrier quality is accounted for, the quality of the metal M accounts for the 0.1%-20% of carrier quality, and the quality of the metal N is accounted for
The 1%-20% of carrier quality.
Performance test, the methane dry gas are carried out to the methane dry gas reforming catalyst by methane dry gas reforming reaction
The life-span of reforming catalyst >=1000h.
A kind of above-mentioned methane dry gas reforming catalyst, wherein, the carrier is selected from Al2O3、SiO2、ZrO2、La2Oa、
CeO2, MgO, one or more in magnesium aluminate spinel.
A kind of above-mentioned methane dry gas reforming catalyst, wherein, the methane dry gas reforming reaction is in fixed bed reactors
In carry out, concrete steps include：
Methane dry gas reforming catalyst is added in fixed bed reactors, while being passed through CO2And CH4Reform with methane dry gas
Catalyst is contacted, the CO2And CH4Flow it is identical, the CO2And CH4Flow be 60～100ml/min, reaction temperature is
400～1000 DEG C.
A kind of above-mentioned methane dry gas reforming catalyst, wherein, the life-span of the methane dry gas reforming catalyst is 1000h
～3000h, when being 1000h～3000h in the life-span of methane dry gas reforming catalyst, in methane dry gas reforming reaction, CH4Conversion
Rate is 85%-96%, CO2Conversion ratio is 85%-97%.
Second object of the present invention is to provide a kind of preparation method of methane dry gas reforming catalyst, using infusion process or
Hydro-thermal method prepares any of the above-described described methane dry gas reforming catalyst.
Methane dry gas reforming catalyst is prepared using infusion process at least to comprise the following steps：
Step 1, weighs water soluble nickel salt, the soluble-salt of metal M, the soluble-salt of metal N, matches somebody with somebody in being dissolved in deionized water
It is set to solution；
Step 2, weighs carrier in a beaker, under agitation the solution configured in step 1 is added dropwise in carrier, complete
12～72h is stirred at room temperature into after, obtains catalyst precursor；
Step 3, the catalyst precursor obtained in step 2 is dried in an oven, and baking temperature is 60～120 DEG C, is done
The dry time is 1～48h, and dried catalyst precursor is calcined in Muffle furnace, and calcining heat is 150～800 DEG C, calcining
Time is 1～48h.
Step 4, the reduction of catalyst precursor：The catalyst precursor obtained in step 3 and quartz sand are well mixed,
In adding fixed bed reactors, the mass ratio of the catalyst precursor and quartz sand is 1: 1～1: 20；It is passed through H simultaneously2Carry out
Reduction, is passed through H2Flow be 10～200ml/min, reduction temperature be 400～1000 DEG C, the recovery time be 0.5～4h；Generate
W metal and metal M, the alloy Ni-M-N of metal N, the alloy Ni-M-N are supported on carrier, are obtained the reformation of methane dry gas and are urged
Agent.
Methane dry gas reforming catalyst is prepared using hydro-thermal method, is at least comprised the following steps：
Step 1, weighs water soluble nickel salt, the soluble-salt of metal M, the soluble-salt of metal N, matches somebody with somebody in being dissolved in deionized water
It is set to solution；
Step 2, weighs carrier in a beaker, under agitation the solution configured in step 1 is added dropwise in carrier, molten
Precipitating reagent is instilled after drop is complete in beaker, after the completion of by gained mixture ultrasonically treated 0.5～2h, then will be ultrasonically treated after
Mixture be transferred in water heating kettle so as to carry out hydro-thermal reaction in homogeneous reactor, reaction temperature is 100～300 DEG C, instead
It is 1～24h between seasonable, stir speed (S.S.) is 10～50 turns/min, carries out filtering after the completion of reaction, collects solid matter, is urged
Agent presoma；
Step 3, the catalyst precursor obtained in step 2 is dried in an oven, and baking temperature is 60～120 DEG C, is done
The dry time is 1～48h, and dried catalyst precursor is calcined in Muffle furnace, and calcining heat is 150～800 DEG C, calcining
Time is 1～48h；
Step 4, the reduction of catalyst precursor：The catalyst precursor obtained in step 3 and quartz sand are well mixed,
In adding fixed bed reactors, the mass ratio of the catalyst precursor and quartz sand is 1: 1～1: 20；It is passed through H simultaneously2Carry out
Reduction, is passed through H2Flow be 10～200ml/min, reduction temperature be 400～1000 DEG C, the recovery time be 0.5～4h, generate
W metal and metal M, the alloy Ni-M-N of metal N, the alloy Ni-M-N are supported on carrier, are obtained the reformation of methane dry gas and are urged
Agent.
Preferably, in 2 the step of methane dry gas reforming catalyst is prepared using hydro-thermal method, the precipitating reagent is selected from ammonia
One kind in water, urea, NaOH.
Prepare in the method for methane dry gas reforming catalyst, wherein in above-mentioned employing infusion process or hydro-thermal method, the step 3
In, also include：
Steam treatment：Catalyst precursor and quartz sand after calcining is well mixed, in adding fixed bed reactors,
The catalyst precursor and quartz sand mass ratio are 1: 1～1: 20, persistently overheating, and heating rate is 0.5～10 DEG C/min, is risen
Temperature is passed through vapor to after 400～1000 DEG C, and the steam treatment time is 0.5～48h.
Prepare in the method for methane dry gas reforming catalyst, wherein in above-mentioned employing infusion process or hydro-thermal method, in the step
In rapid 1, one of which of the water soluble nickel salt in nickel nitrate, nickel acetate, nickel chloride, the soluble compound of nickel sulfate.
Prepare in the method for methane dry gas reforming catalyst, wherein in above-mentioned employing infusion process or hydro-thermal method, in the step
In rapid 1, the soluble-salt of the metal M is selected from cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate, ferric nitrate, iron chloride, sulfuric acid
One of which in iron, copper nitrate, copper sulphate, copper chloride, copper acetate, ruthenium trichloride, the soluble compound of rhodium chloride.
Prepare in the method for methane dry gas reforming catalyst, wherein in above-mentioned employing infusion process or hydro-thermal method, in the step
In rapid 1, the soluble-salt of the metal N is selected from magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, barium nitrate, barium chloride, nitric acid
Solubilityization in sodium, sodium sulphate, sodium chloride, sodium carbonate, sodium acetate, potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, potassium acetate
One of which in compound.
Prepare in the method for methane dry gas reforming catalyst, wherein in above-mentioned employing infusion process or hydro-thermal method, in the step
In rapid 2, the carrier is selected from Al2O3、SiO2、ZrO2、La2O3、CeO2, MgO, one or more in magnesium aluminate spinel.
In sum, the present invention is by introducing alloying element Co, Fe, Cu, Ru, Rh and alkali metal or alkali on W metal
Earth metal element M g, Ca, Ba, Na, K are promoting and improve high temperature active, the stability of methane dry gas reforming catalyst.Add and close
Gold element Co, Fe, Cu, Ru, Rh promote the dispersion of Ni base major catalysts using alloy, add alkali metal or alkaline-earth metal unit
Plain Mg, Ca, Ba, Na, K etc. can strengthen the alkalescence of carrier, promote unstrpped gas CO2Absorption.
The present invention removes labile acid carrier components (effectively suppressing carbon distribution) also by steam treatment, using alkali
Earth metal and carrier form the undefined structure of island to promote CO2Reaction, so as to reduce methane dissociation generation carbon distribution.And
And, steam treatment allows carrier that more oxygen vacancies positions are presented, and under here induction, the carbon of methane high temperature dissociation is easily combined with oxygen
Generate CO to promote reaction.
By the preparation method of the present invention, the pyroreaction activity of methane dry gas reforming catalyst, resistance to height is greatly improved
Warm ability is strong, makes the life-span of methane dry gas reforming catalyst have increased significantly, the methane dry gas Reforming catalyst of the present invention
Agent can under conditions of high-speed (air speed：5000-60000mL/g/h) realize remaining in that in catalyst reaction 1000h and be more than
The conversion ratio of 90% methane and the CO more than 90%2Conversion ratio, makes CO and H2Selectivity all reach 95%.
Specific embodiment
Embodiment 1
Methane dry gas reforming catalyst Ni-Co-Mg/SiO2Preparation and performance test
(1) preparation of methane dry gas reforming catalyst
A. the preparation of catalyst precursor
The catalyst is prepared using co-impregnation, weighs 0.2973g Nickelous nitrate hexahydrates (Ni (NO3)2.6H2O)、
0.2963g cabaltous nitrate hexahydrates (Co (NO3)2.6H2) and 0.6330g magnesium nitrate hexahydrates (Mg (NO O3)2.6H2O), it is dissolved in 10ml
Mixed solution is configured in deionized water；2.0g SiO are weighed again2In a beaker, above-mentioned mixed solution is instilled under stirring
To SiO2In, 72h is stirred at room temperature after dripping off, the catalyst precursor for obtaining.
Then the catalyst precursor for obtaining is dried into 24h in 80 DEG C of baking oven, finally by before dried catalyst
Drive in body addition Muffle furnace, 5h is calcined at 500 DEG C.
B. the reduction of catalyst precursor
Reduction reaction is carried out in fixed bed reactors, weighs catalyst precursor and 0.3g quartz sands after 0.3g calcinings
It is well mixed, is then charged in fixed bed reactors, catalyst precursor is at 850 DEG C with the H that flow is 100ml/min2Also
Former 2h, generates alloy Ni-Co-Mg, and alloy Ni-Co-Mg is supported on carrier S iO2On, obtain methane dry gas reforming catalyst Ni-
Co-Mg/SiO2。
(2) methane dry gas reforming catalyst Ni-Co-Mg/SiO2Performance test
Using methane dry gas reforming reaction to methane dry gas reforming catalyst Ni-Co-Mg/SiO2Performance tested,
In fixed bed reactors, methane dry gas reforming catalyst Ni-Co-Mg/SiO is added2, flow is then passed to for 100ml/min
CH4With the CO that flow is 100ml/min2, react at normal pressure, 850 DEG C.
Methane dry gas reforming catalyst Ni-Co-Mg/SiO2Life-span, CH4Conversion ratio, CO2The evaluation result of conversion ratio is such as
Following table：
| Reaction time/h | 1 | 20 | 40 | 60 | 80 | 100 |
| CH4Conversion ratio/% | 93.1 | 92.2 | 91.3 | 90.4 | 89.5 | 88.4 |
| CO2Conversion ratio/% | 95.2 | 93.1 | 89.4 | 88.5 | 87.3 | 86.5 |
Comparative example 1
Methane dry gas reforming catalyst Ni/SiO2Preparation and performance test
(1) preparation of methane dry gas reforming catalyst
The catalyst is prepared using infusion process, weighs 0.5945g Nickelous nitrate hexahydrates (Ni (NO3)2.6H2O), it is dissolved in 10ml
Solution is configured in deionized water；2.0g SiO are weighed again2In a beaker, the solution of configuration is added dropwise to into SiO under stirring2
In, 72h is stirred at room temperature after dripping off, and obtains catalyst precursor.Then by the catalyst precursor for obtaining in 80 DEG C of baking
24h is dried in case, is finally added dried catalyst precursor in Muffle furnace, is calcined 4h at 700 DEG C.
Weigh the catalyst precursor after 0.3g calcinings to be well mixed with 0.3g quartz sands, be then charged into fixed bed reactors
In, catalyst precursor is at 850 DEG C with the H that flow is 100ml/min2Reductase 12 h, obtains methane dry gas reforming catalyst Ni/
SiO2。
(2) catalyst performance test
By methane dry gas reforming catalyst Ni/SiO2It is added in fixed bed reactors, while being passed through flow for 100ml/
The CH of min4With the CO that flow is 100ml/min2, react at normal pressure, 850 DEG C.
Methane dry gas reforming catalyst Ni/SiO2Life-span, CH4Conversion ratio, CO2The evaluation result of conversion ratio such as following table：
| Reaction time/h | 1 | 20 | 40 | 60 | 80 | 100 | ＞ 100 |
| CH4Conversion ratio/% | 88.2 | 82.5 | 77.6 | 73.4 | 70.6 | 68.5 | Inactivation |
| CO2Conversion ratio/% | 90.1 | 85.2 | 81.4 | 77.6 | 74.3 | 71.5 | Inactivation |
From the evaluation result of the methane dry gas reforming catalyst of comparative example 1 and embodiment 1, using present invention side
Dry gas reforming catalyst Ni-Co-Mg/SiO prepared by method2With the dry gas reforming catalyst Ni/SiO of comparative example 12In reaction
In the case of time identical, using Ni-Co-Mg/SiO2CH4And CO2Conversion ratio both greater than using catalyst n i/SiO2's
CH4And CO2Conversion ratio.
It follows that the methane dry gas reforming catalyst prepared using the inventive method is greatly improved CH4And CO2Turn
Rate.
Embodiment 2
Methane dry gas reforming catalyst Ni-Co-Ca/Al2O3Preparation and performance test
(1) preparation of methane dry gas reforming catalyst
A. the preparation of catalyst precursor
The catalyst is prepared using co-impregnation, weighs 0.2973g Nickelous nitrate hexahydrates (Ni (NO3)2.6H2O)、
0.2963g cabaltous nitrate hexahydrates (Co (NO3)2.6H2) and 0.65720g calcium nitrate tetrahydrates (Ca (NO O3)2.4H2O), it is dissolved in
Mixed solution is configured in 10ml deionized waters；2.0g Al are weighed again2O3In a beaker, by above-mentioned mixed solution under stirring
It is added dropwise to Al2O3In, 72h is stirred at room temperature after dripping off, and obtains catalyst precursor.
Then the catalyst precursor for obtaining is dried into 24h in 80 DEG C of baking oven, finally by before dried catalyst
Drive in body addition Muffle furnace, 5h is calcined at 500 DEG C.
B. steam treatment：Steam treatment is carried out in fixed bed reactors, before weighing the catalyst after 0.3g calcinings
Drive body to be well mixed with 0.3g quartz sands, be then charged in fixed bed reactors, with the ramp of 10 DEG C/min to 850 DEG C,
Vapor is then passed to, 2h is processed.
C. the reduction of catalyst precursor：Reduction reaction is carried out in fixed bed reactors, weighs urging after 0.3g calcinings
Agent presoma is well mixed with 0.3g quartz sands, is then charged in fixed bed reactors, and catalyst precursor is used at 850 DEG C
H of the flow for 100ml/min2Reductase 12 h.
(2) methane dry gas reforming catalyst Ni-Co-Ca/Al2O3Performance test
By methane dry gas reforming catalyst Ni-Co-Ca/Al2O3In adding fixed bed reactors, while being passed through 100ml/min
CH4With the CO of 100ml/min2, react at normal pressure, 850 DEG C.
Methane dry gas reforming catalyst Ni-Co-Ca/Al2O3Life-span, CH4Conversion ratio, CO2The evaluation result of conversion ratio is such as
Following table：
From embodiment 2 and comparative example 1, the evaluation result of the methane dry gas reforming catalyst of embodiment 1, adopt
Dry gas reforming catalyst Ni-Co-Ca/Al prepared by the inventive method2O3With the dry gas reforming catalyst Ni/ of comparative example 1
SiO2Compare, methane dry gas reforming catalyst Ni-Co-Ca/Al2O3Life-span to be far longer than methane dry gas reforming catalyst Ni/
SiO2, methane dry gas reforming catalyst Ni-Co-Ca/Al2O3The also very strong activity when being 1000h in the reaction time, and methane
Dry gas reforming catalyst Ni/SiO2After the reaction time is more than 100h, activity is decreased obviously or even loses activity.
And it is suitable for the methane dry gas reforming catalyst Ni-Co-Ca/Al after steam treatment2O3When CH4And CO2's
Conversion ratio is apparently higher than the methane dry gas reforming catalyst Ni-Co-Mg/SiO using embodiment 12When CH4And CO2Conversion ratio,
From the evaluation result of embodiment 2, using methane dry gas reforming catalyst Ni-Co-Ca/Al2O3When CH4And CO2Turn
Rate is both greater than 90%.
Embodiment 3
Methane dry gas reforming catalyst Ni-Co-Mg/SiO2Preparation and performance test
(1) methane dry gas reforming catalyst is prepared using hydro-thermal method
A. the preparation of catalyst precursor
Weigh 0.2973g Nickelous nitrate hexahydrates (Ni (NO3)2.6H2O), 0.2963g cabaltous nitrate hexahydrates (Co (NO3)2.6H2) and 0.6330g magnesium nitrate hexahydrates (Mg (NO O3)2.6H2O), mixed solution is configured in being dissolved in 140ml deionized waters；
2.0g SiO are weighed again2In a beaker, above-mentioned mixed solution is added dropwise to into SiO under stirring2In, drip in backward beaker
Instill 2.548g ammoniacal liquor, after the completion of by gained mixture ultrasonically treated 1h, then will be ultrasonically treated after mixture be transferred to water
In hot kettle so as to carry out hydro-thermal reaction in homogeneous reactor, reaction temperature is 180 DEG C, and the reaction time is 6h, and stir speed (S.S.) is
10 turns/min, carry out filtering after the completion of reaction, collect solid matter, obtain catalyst precursor.
Then the catalyst precursor for obtaining is dried into 24h in 80 DEG C of baking oven, finally by before dried catalyst
Drive in body addition Muffle furnace, 5h is calcined at 500 DEG C.
B. steam treatment：Steam treatment is carried out in fixed bed reactors, before weighing the catalyst after 0.3g calcinings
Drive body to be well mixed with 0.3g quartz sands, be then charged in fixed bed reactors, with the ramp of 10 DEG C/min to 850 DEG C,
Vapor is then passed to, 2h is processed.
C. the reduction of catalyst precursor：Reduction reaction is carried out in fixed bed reactors, weighs urging after 0.3g calcinings
Agent presoma is well mixed with 0.3g quartz sands, is then charged in fixed bed reactors, and catalyst precursor is used at 850 DEG C
H of the flow for 100ml/min2Reductase 12 h.
(2) methane dry gas reforming catalyst Ni-Co-Mg/SiO2Performance test
By methane dry gas reforming catalyst Ni-Co-Mg/SiO2In adding fixed bed reactors, while being passed through 100ml/min
CH4With the CO of 100ml/min2, react at normal pressure, 850 DEG C.
Methane dry gas reforming catalyst Ni-Co-Mg/SiO2Life-span, CH4Conversion ratio, CO2The evaluation result of conversion ratio is such as
Following table：
| Reaction time/h | 1 | 200 | 400 | 600 | 800 | 1000 |
| CH4Conversion ratio/% | 94.3 | 94.2 | 94.4 | 94.1 | 94.4 | 94.5 |
| CO2Conversion ratio/% | 96.6 | 96.3 | 96.5 | 96.4 | 96.6 | 96.3 |
From the evaluation result of the methane dry gas reforming catalyst of embodiment 3 and embodiment 1, prepared using hydro-thermal method,
And the methane dry gas reforming catalyst Ni-Co-Mg/SiO after steam treatment2CH4And CO2Conversion ratio, hence it is evident that be higher than
The methane dry gas reforming catalyst Ni-Co-Mg/SiO that used in embodiment 1 prepared by infusion process2When CH4And CO2Conversion ratio, and
And catalyst life is greatly improved, from the evaluation result of embodiment 3, after reaction 1000h, prepared by hydro-thermal method, and pass through
Methane dry gas reforming catalyst Ni-Co-Mg/SiO after steam treatment2CH4And CO2Conversion ratio be both greater than 94%.
In sum, the present invention is by introducing alloying element Co, Fe, Cu, Ru, Rh and alkali metal or alkali on W metal
Earth metal element M g, Ca, Ba, Na, K are promoting and improve high temperature active, the stability of methane dry gas reforming catalyst.Add and close
Gold element Co, Fe, Cu, Ru, Rh promote the dispersion of Ni base major catalysts using alloy, add alkali metal or alkaline-earth metal unit
Plain Mg, Ca, Ba, Na, K etc. can strengthen the alkalescence of carrier, promote unstrpped gas CO2Absorption.
The present invention removes labile acid carrier components (effectively suppressing carbon distribution) also by steam treatment, using alkali
Metal and carrier form the undefined structure of island to promote CO2Reaction, so as to reduce its dissociation generate carbon distribution.And,
Steam treatment allows carrier that more oxygen vacancies positions are presented, under here sky acupoint induction, CO2Dissociation be easier, so as to CH4It is high
Temperature dissociates the carbon for producing easily and CO2The oxygen that dissociation is generated combines and generates CO to promote reaction.
By the preparation method of the present invention, the pyroreaction activity of methane dry gas reforming catalyst, resistance to height is greatly improved
Warm ability is strong, makes the life-span of methane dry gas reforming catalyst have increased significantly, the methane dry gas Reforming catalyst of the present invention
Agent can under conditions of high-speed (air speed：5000-60000mL/g/h) realize remaining in that in catalyst reaction 1000h and be more than
The conversion ratio of 90% methane and the CO more than 90%2Conversion ratio, makes CO and H2Selectivity reach 95%.
Embodiment described above is merely to illustrate the technological thought of the present invention and feature, its object is to make in the art
Technical staff will appreciate that present disclosure and implement according to this, it is impossible to limit only with the present embodiment the present invention patent model
Enclose, i.e., all equal changes made according to disclosed spirit or modification, still fall in the scope of the claims of the present invention.
Claims (12)
1. a kind of methane dry gas reforming catalyst, it is characterised in that introduce metal M and N on W metal, form metal active group
Ni-M-N, the metal M is divided to be selected from any one in Co, Fe, Cu, Ru, Rh, the metal N is in Mg, Ca, Ba, Na, K
Any one；
The metal active constituent is supported on formation methane dry gas reforming catalyst on a carrier, and the quality of the W metal accounts for load
The quality of the 1%-20% of weight, the metal M accounts for the 0.1%-20% of carrier quality, and the quality of the metal N accounts for carrier
The 1%-20% of quality.
Performance test is carried out by methane dry gas reforming reaction to the methane dry gas reforming catalyst, the methane dry gas is reformed
The life-span of catalyst >=1000h.
2. a kind of methane dry gas reforming catalyst according to claim 1, it is characterised in that the carrier is selected from Al2O3、
SiO2、ZrO2、La2O3、CeO2, MgO, one or more in magnesium aluminate spinel.
3. a kind of methane dry gas reforming catalyst according to claim 1, it is characterised in that the methane dry gas is reformed anti-
Should carry out in fixed bed reactors, concrete steps include：
Methane dry gas reforming catalyst is added in fixed bed reactors, while being passed through CO2And CH4With methane dry gas Reforming catalyst
Agent is contacted, the CO2And CH4Flow it is identical, the CO2And CH4Flow be 60～100ml/min, reaction temperature is 400
～1000 DEG C.
4. a kind of methane dry gas reforming catalyst according to claim 3, it is characterised in that the methane dry gas is reformed and urged
The life-span of agent is 1000h～3000h, when being 1000h～3000h in the life-span of methane dry gas reforming catalyst, methane dry gas
In reforming reaction, CH4Conversion ratio is 85%-96%, CO2Conversion ratio is 85%-97%.
5. a kind of preparation method of methane dry gas reforming catalyst, it is characterised in that Claims 1 to 4 is prepared using infusion process
Arbitrary described methane dry gas reforming catalyst, at least comprises the following steps：
Step 1, weighs water soluble nickel salt, the soluble-salt of metal M, the soluble-salt of metal N, is configured in being dissolved in deionized water
Solution；
Step 2, weighs carrier in a beaker, under agitation the solution configured in step 1 is added dropwise in carrier, after the completion of
12～72h is stirred at room temperature, catalyst precursor is obtained；
Step 3, the catalyst precursor obtained in step 2 is dried in an oven, and baking temperature is 60～120 DEG C, when being dried
Between be 1～48h, dried catalyst precursor calcine in Muffle furnace, calcining heat be 150～800 DEG C, calcination time
For 1～48h.
Step 4, the reduction of catalyst precursor：The catalyst precursor obtained in step 3 and quartz sand are well mixed, are added
In fixed bed reactors, the mass ratio of the catalyst precursor and quartz sand is 1: 1～1: 20；It is passed through H simultaneously2Carry out also
Original, is passed through H2Flow be 10～200ml/min, reduction temperature be 400～1000 DEG C, the recovery time be 0.5～4h；Generate gold
Category Ni and metal M, the alloy Ni-M-N of metal N, the alloy Ni-M-N are supported on carrier, obtain methane dry gas Reforming catalyst
Agent.
6. a kind of preparation method of methane dry gas reforming catalyst, it is characterised in that Claims 1 to 4 is prepared using hydro-thermal method
Arbitrary described methane dry gas reforming catalyst, at least comprises the following steps：
Step 1, weighs water soluble nickel salt, the soluble-salt of metal M, the soluble-salt of metal N, is configured in being dissolved in deionized water
Solution；
Step 2, weighs carrier in a beaker, under agitation the solution configured in step 1 is added dropwise in carrier, solution drop
Precipitating reagent is instilled after complete in beaker, after the completion of by gained mixture ultrasonically treated 0.5～2h, then will be ultrasonically treated after it is mixed
Compound is transferred in water heating kettle so as to carry out hydro-thermal reaction in homogeneous reactor, reaction temperature is 100～300 DEG C, during reaction
Between be 1～24h, stir speed (S.S.) be 10～50 turns/min, carry out filtering after the completion of reaction, collect solid matter, obtain catalyst
Presoma；
Step 3, the catalyst precursor obtained in step 2 is dried in an oven, and baking temperature is 60～120 DEG C, when being dried
Between be 1～48h, dried catalyst precursor calcine in Muffle furnace, calcining heat be 150～800 DEG C, calcination time
For 1～48h；
Step 4, the reduction of catalyst precursor：The catalyst precursor obtained in step 3 and quartz sand are well mixed, are added
In fixed bed reactors, the mass ratio of the catalyst precursor and quartz sand is 1: 1～1: 20；It is passed through H simultaneously2Carry out also
Original, is passed through H2Flow be 10～200ml/min, reduction temperature be 400～1000 DEG C, the recovery time be 0.5～4h, generate gold
Category Ni and metal M, the alloy Ni-M-N of metal N, the alloy Ni-M-N are supported on carrier, obtain methane dry gas Reforming catalyst
Agent.
7. the preparation method of a kind of methane dry gas reforming catalyst according to claim 6, it is characterised in that in the step
In rapid 2, the one kind of the precipitating reagent in ammoniacal liquor, urea, NaOH.
8. the preparation method of a kind of methane dry gas reforming catalyst according to claim 5 or 6, it is characterised in that described
In step 3, also include：
Steam treatment：Catalyst precursor and quartz sand after calcining is well mixed, it is in adding fixed bed reactors, described
Catalyst precursor and quartz sand mass ratio are 1: 1～1: 20, persistently overheating, and heating rate is 0.5～10 DEG C/min, is warming up to
Vapor is passed through after 400～1000 DEG C, and the steam treatment time is 0.5～48h.
9. the preparation method of a kind of methane dry gas reforming catalyst according to claim 5 or 6, it is characterised in that in institute
State in step 1, the water soluble nickel salt in nickel nitrate, nickel acetate, nickel chloride, the soluble compound of nickel sulfate wherein
Kind.
10. the preparation method of a kind of methane dry gas reforming catalyst according to claim 5 or 6, it is characterised in that in institute
State in step 1, the soluble-salt of the metal M is selected from cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate, ferric nitrate, iron chloride, sulphur
One of which in sour iron, copper nitrate, copper sulphate, copper chloride, copper acetate, ruthenium trichloride, the soluble compound of rhodium chloride.
The preparation method of the 11. a kind of methane dry gas reforming catalysts according to claim 5 or 6, it is characterised in that in institute
State in step 1, the soluble-salt of the metal N is selected from magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, barium nitrate, barium chloride, nitre
Solubility in sour sodium, sodium sulphate, sodium chloride, sodium carbonate, sodium acetate, potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, potassium acetate
One of which in compound.
The preparation method of the 12. a kind of methane dry gas reforming catalysts according to claim 5 or 6, it is characterised in that in institute
State in step 2, the carrier is selected from Al2O3、SiO2、ZrO2、La2O3、CeO2, MgO, one or more in magnesium aluminate spinel.
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| CN114768746A (en) * | 2022-02-08 | 2022-07-22 | 中国科学院大连化学物理研究所 | Metal catalytic reactor, preparation thereof and application thereof in natural gas and CO2Application of dry gas reforming to synthesis gas |
| CN114768746B (en) * | 2022-02-08 | 2023-12-19 | 中国科学院大连化学物理研究所 | Metal catalytic reactor and preparation and use thereof in natural gas and CO 2 Application of dry gas reforming to synthesis gas |
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