CN105170156B - The preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure - Google Patents
The preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure Download PDFInfo
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- CN105170156B CN105170156B CN201510569457.9A CN201510569457A CN105170156B CN 105170156 B CN105170156 B CN 105170156B CN 201510569457 A CN201510569457 A CN 201510569457A CN 105170156 B CN105170156 B CN 105170156B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
Abstract
The invention discloses a kind of preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure.Nickel metal and auxiliary agent are dispersed in the mesoporous pore size of aerogel-like structure by the methane dry reforming catalyst, the methane dry reforming catalyst of mesoporous confinement.The preparation method of the methane dry reforming catalyst is stirring reaction, then pass through low vacuum drying, high-temperature calcination, H at low temperature2TPR is reduced, the methane dry reforming catalyst of the good high activity and high stability of obtained anti-carbon and anti-sintering property.The present invention has the advantages that preparation technology is simple, cost is relatively low, environmentally safe, high catalytic efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure, belongs to nano-catalytic
Agent preparation technology and environmental protection technical field.
Background technology
In recent years, due to the consumption of non-renewable energy resources and the worsening of environment, the development and utilization of natural gas by
Increasing concern.Development and utilization for natural gas mainly has two kinds of approach, respectively direct method and indirect method.Directly
Connection is that prepared by natural gas Pintsch process or partial oxidation into the organic matters such as methanol, formaldehyde.But this method is at tail gas
Reason and pure oxygen, which use etc., has certain complexity, so limiting its application industrially.Indirect method refers to day
Right gas is first converted into synthesis gas（H2And CO）, then using synthesis gas as some chemical products of Material synthesis or liquid fuel, as methanol,
Ethanol, dimethyl ether or by methanol-to-olefins, gasoline and acetic acid etc..Due to being easily achieved for indirect method, thus it receive it is general
All over concern, it mainly includes following three kinds of approach：Methane portion oxidation, methane vapor reforming and methane dry reforming.These three
In approach, first two reaction is due to the H of reaction generation2/ CO is more than 1, and being unfavorable for follow-up F- T synthesis hydro carbons, methanol etc. has
Machine product.H obtained by methane dry reforming2/ CO is 1, can directly feed F- T synthesis and carbonylation, therefore receive much concern.
At present, the carbon distribution of catalyst and deactivation prob significantly limit the value of its commercial Application in methane dry reforming.It is how effective
Must suppress catalyst carbon deposition and active component sintering be current methane dry reforming catalyst research the most important thing.
The catalyst of methane dry reforming is broadly divided into noble metal catalyst（Ru, Pd, Pt etc.）And non-precious metal catalyst
(Fe, Co, Ni etc.), noble metal catalyst have good anti-carbon, but because of its expensive, resource scarcity, and
Noble metal active component can sinter loss under hot conditions, so increasing, research is carried out to non-precious metal catalyst is that have very much must
Want.Nickel-base catalyst has higher activity relative to other non-precious metal catalysts in base metal, therefore we are main
Nickel-base catalyst is studied to carry out methane reforming reaction.However, nickel-base catalyst there is it is fatal the shortcomings that, prolonged high temperature
Under reaction, the easy carbon distribution of nickel-base catalyst and metallic nickel sintering, so that catalyst inactivation.Theoretical research proves：Only nickel chi
It is very little it is small to a certain extent, be only possible to suppress carbon fiber nucleation and growth, so as to reach the purpose of anti-carbon.Meanwhile auxiliary agent
Addition is also beneficial to nickel-base catalyst removing carbon, so as to reach the purpose for the prolonged stability for keeping catalyst.
Numerous researchers pass through strong metal-support interaction on Ni to carrier, making it preferably scattered
To prevent the reunion of nickel.In view of methane dry reforming, this reaction needs to carry out at a higher temperature, therefore selected carrier
Must have good heat endurance, such as Al2O3、SiO2、MgO、MgO-Al2O3、La2O3-ZrO2、CeO2-ZrO2And molecule
Sieve, foamed ceramics etc..But activity can not effectively be ensured by relying solely on the strong interaction between nickel and metallic carrier
Component still has good dispersiveness under the conditions of pyroreaction.Researcher also grinds to influence of the auxiliary agent for catalyst
Study carefully, typically can all be added during catalyst is made has oxygen storage capacity or can provide the metallic element of alkali position, such as
Ce, Ca, Mg, Sc etc..The addition of auxiliary agent can strengthen the bond strength of metallic nickel nano granule and carrier, and strengthen carbon distribution
Elimination, but reunion and the sintering of metallic nickel nano granule can not be avoided.The studies above not can effectively solve the problem that Ni-based urge
The problem of easy sintering present in agent and easy carbon deposit.This method just passes through nickel metal, auxiliary agent and carrier in synthesis solidifying
The method of glue is combined together, compared to more traditional carrying method cause the particle of nickel metal it is smaller, it is nickel metal dispersiveness more
The interaction force of good, nickel metal and carrier is stronger, the auxiliary agent elimination for strengthening carbon deposit, and can form class airsetting
Plastic structure, aerogel-like structure have high specific surface area and meso-hole structure, and this special structure can not only expose more
Active component, which improves catalyst activity, can also preferably limit the scope of activities of nickel metal, it is therefore prevented that the sintering of nickel metal.
The content of the invention
The present invention relates to a kind of Ni-based methane dry reforming method for preparing catalyst of aerogel-like method, belongs to nanocatalyst system
Standby technique and environmental protection technical field.The small nano nickel particles of size are dispersed in nickel-base catalyst obtained by the preparation method
In the mesopore orbit for the aerogel-like structure that refractory oxide is formed, cell walls can play a part of confinement, while auxiliary agent
Addition cause interaction between nickel metal and metallic carrier, strengthen the elimination of carbon deposit, therefore fine must can inhibit
Growing up for metallic nickel nano granule, substantially reduces soot level, is that a kind of catalytic performance is good in methane reforming, and prepared
The simple nanocatalyst of journey.
The method for preparing catalyst of the present invention, it is characterised in that comprise the steps of：
Appropriate nickel precursor salt is weighed, aluminium precursor salt and auxiliary agent precursor salt are dissolved in deionized water and ethanol mixing
In solution,（The ratio of hydrate alcohol is 1:1~3:1, nickel precursor salt, aluminium precursor salt and the quality of auxiliary agent presoma and solvent
Than for 3:20~5:20）Magnetic agitation adds expoxy propane to clarifying（Expoxy propane and the mass ratio of precursor salt are 2:1~3:
1）, continue the min of stirring 3 ~ 10, then stand 12 ~ 24 h, form hydrogel, add the mixing of the tert-butyl alcohol and ethanol that have configured
Solution（Volume ratio 2:5~3:5）, it is closed, it is put into 40 ~ 60 DEG C of baking oven 12 ~ 24 hours, then takes out, pours out solution, then add
Enter the mixed solution of the tert-butyl alcohol configured and ethanol（Volume ratio 7:10~9:10）, it is closed be put into 12 in 40 ~ 60 DEG C of baking oven ~
24 hours, take out, pour out solution, add the mixed solution of the tert-butyl alcohol configured and ethanol（Volume ratio 1:1~1.1:1）, fall
Go out solution, dried for 40 ~ 60 DEG C under conditions of low vacuum, heating rate is 1 ~ 2 DEG C/min under air atmosphere, and 700 ~ 800 DEG C are forged
Burn 4 ~ 6h.Then it is reduced again, utilizes H2- TPR, first lead to N2Pre-process 30min at 300 DEG C, be cooled to after room temperature with
H2/N2（Volume ratio 1:9）Gaseous mixture（30mL/min）1h is reduced at 850 DEG C ~ 950 DEG C and obtains the Ni-based methane of aerogel-like structure
Dry reforming catalyst.
Present invention be characterized in that entered after hydrogel is formed using the water in volatile solvent and hydrogel and ethanol
Row exchange, this solvent can be the tert-butyl alcohol or adiponitrile so that the hydrogel of formation without complexity freeze-drying and
The carbon dioxide limit is dried with regard to that can obtain aeroge.
Present invention be characterized in that the carrier metal of the Ni-based methane dry reforming catalyst of prepared aerogel-like structure
Can be Al2O3Can also be SiO2, this quasi-metal oxides has higher heat endurance, and is more prone to form class gas
Gel structure, form higher specific surface area.
Present invention be characterized in that support precursor salt, auxiliary agent precursor salt and nickel precursor salt are added to solution simultaneously
In so that auxiliary element and nickel metal have good dispersiveness in the catalyst, improve the catalytic activity of catalyst.
The content amount of nickel is 8wt% ~ 12wt% in the present invention, content catalyst activity is not high very little and content is easily led too much
The formation of larger nickel particle is caused to be unfavorable for methane dry reforming.
Present invention be characterized in that described auxiliary element can be one kind in Sc, Ce, Ca, Mg, Zr, these elements
Alkali position is provided in methane dry reforming catalyst or has good oxygen storage capacity, the stability of catalyst is effectively improved and resists
Carbon distribution ability.
Calcination process of the present invention, programming rate are 1 ~ 2 DEG C/min, and calcining heat is 700 ~ 800 DEG C, air atmosphere
Calcination time is 4 ~ 6h, and programming rate is too fast and calcination time is long can all cause catalyst structure to collapse, and calcination time is too short
Possible precursor salt is decomposed not exclusively, and calcining heat is too high, can destroy the structure of catalyst.
Compared with prior art, the catalyst that prepared by the present invention has the following advantages that：
（1）Preparation process of the present invention is simple, easily operated, requires low to experimental facilities, cost is low, and environment will not also be made
Into secondary pollution.
（2）Catalyst of the inventive method obtained by compared to traditional infusion process, aerogel-like structure can be formed, it is this
Special meso-hole structure, it is not only only had the ability that stronger anti-metal is reunited while there has also been good carbon accumulation resisting ability,
Improve the activity of catalyst.
（3）The inventive method is that nickel presoma, auxiliary agent presoma and support precursor are formed into aerogel-like structure together,
So that gained catalyst has higher specific surface area, stronger interaction, higher nickel metal dispersity.
（4）The metal nickel nano crystalline substance size for the catalyst that the present invention obtains is smaller, can be very along with mesoporous confinement effect
The good formation for suppressing carbon distribution in methane dry reforming.
（5）The present invention adds auxiliary element in the catalyst, and these auxiliary elements carry in methane dry reforming catalyst
For alkali position or there is good oxygen storage capacity, the effective stability and carbon accumulation resisting ability for improving catalyst.
Brief description of the drawings
Fig. 1 is the gained methane dry reforming catalyst aerogelNiScAl of the embodiment of the present invention 1 transmission electron microscope（TEM）
Image.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Weigh AlCl3·6H2O(2.96g),Sc(NO3)2·6H2O(0.098g),Ni(NO3)2·6H2O (0.36g) dissolves
In deionized water and ethanol（Water and each 10ml of alcohol）Mixed solution in, magnetic agitation is transparent to solution, adds 7.86g epoxy
Propane, magnetic agitation 10min, 24 h are then stood, form hydrogel, configure the mixed solution 10ml of ethanol and the tert-butyl alcohol（Second
The volume ratio 2 of alcohol and the tert-butyl alcohol:1）It is added in gel, it is closed, 24h in 50 DEG C of baking oven is put into, taking-up is poured out supernatant, matched somebody with somebody
Put the mixed solution 10ml of ethanol and the tert-butyl alcohol（The volume ratio 4 of ethanol and the tert-butyl alcohol:5）It is added in gel, it is closed, it is put into 50
DEG C baking oven in 24h, taking-up pours out supernatant, configures the mixed solution 10ml of ethanol and the tert-butyl alcohol（The body of ethanol and the tert-butyl alcohol
Product ratio 1:1）It is added in gel, is then dried in the environment of 50 DEG C of low vacuum, it is 1 to take out heating rate under air atmosphere
DEG C/min, 800 DEG C of calcining 4h.Then it is reduced again, utilizes H2- TPR, first lead to N230min is pre-processed at 300 DEG C, it is cold
But to after room temperature with H2/N2（Volume ratio 1:9）Gaseous mixture（30mL/min）1h is reduced at 950 DEG C and obtains the nickel of aerogel-like structure
Methylmethane dry reforming catalyst, as shown in Figure 1.
Test the catalytic activity of above-mentioned catalyst：Weigh 0.15g（40-60 mesh）The catalyst prepared is put into fixed bed
Catalyst performance test is carried out in quartz tube reactor, CH4 and CO2 sample sizes are 1:1（Flow is 15mL/min), it is living
Property test from 450 DEG C to 800 DEG C, catalyst just has certain activity at 450 DEG C, active highest at 800 DEG C, CH4 and CO2's
Conversion ratio is reducible respectively to reach 96% and 100%.Catalyst stability test is carried out at 750 DEG C, the CH4 after 30h reaction
94% and 99% or so are kept at CO2 conversion ratios, catalyst still keeps good activity, the phenomenon not inactivated.
Embodiment 2
Weigh AlCl3·6H2O(2.96g),Ce(NO3)2·6H2O(0.054g),Ni(NO3)2·6H2O (0.36g) dissolves
In deionized water and ethanol（Water and each 10ml of alcohol）Mixed solution in, magnetic agitation is transparent to solution, adds 7.86g epoxy
Propane, magnetic agitation 10min, 24 h are then stood, form hydrogel, configure the mixed solution 10ml of ethanol and the tert-butyl alcohol（Second
The volume ratio 2 of alcohol and the tert-butyl alcohol:1）It is added in gel, it is closed, 24h in 50 DEG C of baking oven is put into, taking-up is poured out supernatant, matched somebody with somebody
Put the mixed solution 10ml of ethanol and the tert-butyl alcohol（The volume ratio 4 of ethanol and the tert-butyl alcohol:5）It is added in gel, it is closed, it is put into 50
DEG C baking oven in 24h, taking-up pours out supernatant, configures the mixed solution 10ml of ethanol and the tert-butyl alcohol（The body of ethanol and the tert-butyl alcohol
Product ratio 1:1）It is added in gel, is then dried in the environment of 50 DEG C of low vacuum, it is 1 to take out heating rate under air atmosphere
DEG C/min, 800 DEG C of calcining 4h.Then it is reduced again, utilizes H2- TPR, first lead to N230min is pre-processed at 300 DEG C, it is cold
But to after room temperature with H2/N2（Volume ratio 1:9）Gaseous mixture（30mL/min）1h is reduced at 950 DEG C and obtains the nickel of aerogel-like structure
Methylmethane dry reforming catalyst.
Test the catalytic activity of above-mentioned catalyst：Weigh 0.15g（40-60 mesh）The catalyst prepared is put into fixed bed
Catalyst performance test is carried out in quartz tube reactor, CH4 and CO2 sample sizes are 1:1（Flow is 15mL/min), it is living
Property test from 450 DEG C to 800 DEG C, catalyst just has certain activity at 450 DEG C, active highest at 800 DEG C, CH4 and CO2's
Conversion ratio is reducible respectively to reach 95% and 99%.Catalyst stability test is carried out at 750 DEG C, the CH4 after 30h reaction
86% and 94% or so are kept at CO2 conversion ratios, catalyst still keeps good activity, the phenomenon not inactivated.
Embodiment 3
Weigh tetraethyl orthosilicate (2.39 g), Sc (NO3)2·6H2O(0.098g),Ni(NO3)2·6H2O (0.36g) is molten
Solution is in deionized water and ethanol（Water and each 10ml of alcohol）Mixed solution in, magnetic agitation is transparent to solution, adds 7.86g ring
Ethylene Oxide, magnetic agitation 10min, 24 h are then stood, form hydrogel, configure the mixed solution 10ml of ethanol and the tert-butyl alcohol
（The volume ratio 2 of ethanol and the tert-butyl alcohol:1）It is added in gel, it is closed, 24h in 50 DEG C of baking oven is put into, supernatant is poured out in taking-up
Liquid, configure the mixed solution 10ml of ethanol and the tert-butyl alcohol（The volume ratio 4 of ethanol and the tert-butyl alcohol:5）It is added in gel, it is closed,
24h in 50 DEG C of baking oven is put into, supernatant is poured out in taking-up, configures the mixed solution 10ml of ethanol and the tert-butyl alcohol（Ethanol and tertiary fourth
The volume ratio 1 of alcohol:1）It is added in gel, is then dried in the environment of 50 DEG C of low vacuum, takes out the speed that heated up under air atmosphere
Rate is 1 DEG C/min, 800 DEG C of calcining 4h.Then it is reduced again, utilizes H2- TPR, first lead to N2Pre-processed at 300 DEG C
30min, it is cooled to after room temperature with H2/N2（Volume ratio 1:9）Gaseous mixture（30mL/min）1h is reduced at 950 DEG C and obtains aerogel-like
The Ni-based methane dry reforming catalyst of structure.
Test the catalytic activity of above-mentioned catalyst：Weigh 0.15g（40-60 mesh）The catalyst prepared is put into fixed bed
Catalyst performance test, CH are carried out in quartz tube reactor4And CO2Sample size is 1:1（Flow is 15mL/min), activity
Test is from 450 DEG C to 800 DEG C, and catalyst just has certain activity at 450 DEG C, active highest at 800 DEG C, CH4And CO2Turn
Rate is reducible respectively to reach 95% and 99%.Catalyst stability test is carried out at 750 DEG C, the CH after 30h reaction4With
CO2 conversion ratios are kept at 93% and 98% or so, and catalyst still keeps good activity, the phenomenon not inactivated.
Claims (4)
1. the preparation method of the Ni-based methane dry reforming catalyst of a kind of aerogel-like structure, it is characterised in that there is following work
Skill step：
A. the preparation of catalyst：Appropriate nickel precursor salt is weighed, aluminium precursor salt and auxiliary agent precursor salt are dissolved in deionization
In water and alcohol mixed solution, deionized water：The ratio of ethanol is 1:1~3:1, nickel precursor salt, before aluminium precursor salt and auxiliary agent
The mass ratio for driving body and solvent is 3:20~5:20, magnetic agitation adds expoxy propane, expoxy propane and precursor salt to clarifying
Mass ratio be 2:1~3:1, continue the min of stirring 3 ~ 10, then stand 12 ~ 24 h, form hydrogel, then carry out solution friendship
Change, add the volume ratio 2 of the mixed solution of the tert-butyl alcohol configured and ethanol, the tert-butyl alcohol and ethanol:5~3:5, it is closed, it is put into 40
12 ~ 24 hours in ~ 60 DEG C of baking oven, then take out, pour out solution, the mixing for adding the tert-butyl alcohol configured and ethanol is molten
The volume ratio 7 of liquid, the tert-butyl alcohol and ethanol:10~9:10, it is closed to be put into 40 ~ 60 DEG C of baking oven 12 ~ 24 hours, take out, pour out molten
Liquid, add the volume ratio 1 of the mixed solution of the tert-butyl alcohol configured and ethanol, the tert-butyl alcohol and ethanol:1~1.1:1, pour out molten
Liquid, 40 ~ 60 DEG C of drying under conditions of low vacuum, heating rate be 1 ~ 2 DEG C/min under air atmosphere, 700 ~ 800 DEG C calcine 4 ~
6h；
B. the reduction of catalyst：Utilize H2- TPR, first lead to N230min is pre-processed at 300 DEG C, is cooled to after room temperature with H2/N2Body
Product ratio 1:9 gaseous mixture flow velocitys are 30mL/min, and 1h is reduced at 750 ~ 800 DEG C and obtains the Ni-based methane dry weight of aerogel-like structure
Whole catalyst.
2. according to the preparation method of the Ni-based methane dry reforming catalyst of the aerogel-like structure described in claim 1, it is special
Levy one kind in being nickel nitrate, nickel chloride, nickel acetylacetonate in described nickel precursor salt.
3. according to the preparation method of the Ni-based methane dry reforming catalyst of the aerogel-like structure described in claim 1, it is special
Sign is that nickel presoma, auxiliary agent presoma and support precursor form gel together.
4. according to the preparation method of the Ni-based methane dry reforming catalyst of the aerogel-like structure described in claim 1, it is special
Levy one kind in being Sc, Mg, Ce, Ca, Zr in the auxiliary agent.
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| CN109225230A (en) * | 2018-10-19 | 2019-01-18 | 常州大学 | It is a kind of to prepare high-performance Ni/Al2O3The method of aerogel catalyst |
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