CN107552054A - A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method - Google Patents
A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method Download PDFInfo
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Abstract
A kind of methane dry gas reforms core shell structure nickel-base catalyst and preparation method, is precursor salt with nickel nitrate and zirconium nitrate etc., Ni MOx@SiO are made using reverse microemulsion process2(M=Zr, La, Ce) multinuclear core-shell material.The addition of metal oxide is the 1 ~ 5% of catalyst weight in catalyst, and the addition of nickel is the 5 ~ 10% of catalyst weight.The addition of metal oxide clearly enhances the anti-sintering and carbon accumulation resisting ability of catalyst.At ambient pressure, reaction gas composition is CH4:CO2=1.05:1, air speed 1,8000ml.gcat ‑1.h‑1, reaction temperature is that the catalyst shows high activity, high stability, high anti-carbon and anti-sintering property under 800 DEG C of reaction condition.The present invention have the advantages that to prepare simply, to environment non-secondary pollution, cost is low, high catalytic efficiency.
Description
Technical field
The invention belongs to technical field of chemical industry.It is related to methane dry gas reforming catalyst and preparation method thereof.
Background technology
CO2It is a kind of most important greenhouse gases, with the rapid development of global economy, the depletion rate of fossil fuel adds
It hurry up, the CO that the mankind are discharged2Gas gradually increases, and causes energy crisis and environmental problem getting worse, recycling CO2This
The carbon source of kind of abundance, converts it into high valuable chemicals, alleviating energy crisis and can mitigate greenhouse effects simultaneously,
Progressively turn into the hot subject of whole world research.At present, CO is industrially utilized2Main path be carbon capture and storage, but this
Kind method not only expends memory space, and utilization rate of carbon dioxide is low, and the cost that large-scale application is promoted is still expensive.Therewith
Compare, using chemical method by CO2It is to realize Resources of Carbon Dioxide using significantly more efficient to change into high valuable chemicals
Means, such as CO2Preparing methanol by hydrogenation, CO2Methanation, CO2Esterification carbonic ester, CO2With methane reforming（Also referred to as methane dry gas
Reforming reaction）Prepare synthesis gas etc..Wherein, methane dry gas reforming reaction（DRM）It is considered as to be expected to realize recycling two
One of effective way of carbonoxide, the reaction is directly with CH4（The main component of natural gas and shale gas, greenhouse effects CO2
25 times）And CO2Two kinds of greenhouse gases prepare synthesis gas as catalytic material conversion, and then prepare methanol, liquid fuel and stone
The high valuable chemicals such as wax hydrocarbon, realizing CO2The money such as natural gas and shale gas can also be effectively utilized while recycling
Source.In addition, the natural gas and shale gas resource reserve in China are very abundant, it is to realize that China passes through to develop this important energy source
Help sustainable development important channel compared with methane directly is used as into fuel this conventional method, methane dry gas reforming reaction will
CO2The higher synthesis gas of calorific value is changed into, is reducing CO2The utilization ratio of methane can also be improved while discharge.Industrialization at present
Methane-steam reforming prepare synthesis gas H2 / CO ratios about 3, and synthesis gas prepared by methane dry gas reforming reaction
H2 Close to 1, both mix to facilitate regulation H/CO ratios2 / CO ratios, for F- T synthesis（Fischer–Tropsch
synthesis）Prepare the hydrocarbon of Long carbon chain.Based on above advantage and application, it is considered as current that methane dry gas, which is reformed,
Realize CO2Recycling, alleviate fossil energy crisis and mitigate one of most practical and effective technology of greenhouse effects.
The common catalyst of methane dry gas reforming reaction has the transition metal such as the noble metal catalysts such as Pt, Rh, Ru and Co, Ni
Catalyst.Although noble metal catalyst has preferable catalytic activity and stability, its resource-constrained and expensive is unfavorable
In large-scale industrial production.Ni bases catalyst turns into methane dry gas reformation hydrogen production because price is relatively cheap, initial activity is high
Ideal catalyst, but Ni particles are easily assembled during high temperature reformation, carbon distribution causes the rapid deactivation of catalyst, and this is also limitation
The main bottleneck of its commercial Application, so how to improve the coking resistivity of catalyst and anti-sintering property is that methane dry gas is reformed
React key issue urgently to be resolved hurrily.
Ni granular sizes have very to active and anti-carbon performance of the Ni bases catalyst in methane dry gas reforming reaction
Significant impact.Compared with big Ni particles, in the small more difficult nucleation of Ni particle surface carbon distributions and growth, while cruelly
The avtive spot of dew is also more.If Ni particles can be controlled in 10 below nm during methane dry gas reforming reaction, just
It can be very good to suppress Ni base catalyst carbon depositions, so as to significantly improve the activity of catalyst, stability and anti-carbon performance.So far
Untill the present, people are suppressing Ni particle aggregations, are improving Ni base catalyst methane dry gas reforming reaction performances and reaction mechanism
Etc. study extensively, and achieve certain achievement.Such as：Add alkali metal or alkali-earth metal modified nickel
Based catalyst carrier performance；Perovskite is prepared, spinelle or solid solution etc. have the nickel-base catalyst of specific structure；Select CeO2
Deng the carrier with stronger oxygen storage capacity and oxygen mobility or the nickel-base catalyst prepared using it as auxiliary agent, these methods can carry
The decentralization of high nickel particle and the activity and anti-carbon performance for improving catalyst.In recent years, active component is wrapped in one
Before the catalyst with core-casing structure for determining to prepare in the inorganic matter in duct shows to use well in terms of the inhibitory activity component sintering
Scape.It is with SiO to study at present more2Outer cladding thing is done, because it has preferable high high-temp stability, is reformed in methane dry gas
It etc. good structural stability can also be kept in pyroreaction, and then inhibitory activity component nickel particle can effectively assemble, carry
Its high activity and anti-sintering property.The physics confinement effect of core shell structure can also suppress the generation of carbon distribution simultaneously, so as to improve
The anti-carbon performance of catalyst.But the Ni@SiO of synthesis2Catalyst still suffers from the clustering phenomena of nickel particle during the course of the reaction,
According to the literature, the Ni and metal oxide such as ZrO with redox or soda acid property2、La2O3、CeO2Deng with stronger
Interaction, the aggregation not easy to migrate in pyroreaction.Because above-mentioned oxide has a good ionic conductivity, surface have compared with
More active oxygen, and have low lewis acidity site.Therefore, the present invention is prepared for more using reverse micro emulsion method
The Ni-MOx@SiO of core core shell structure2Catalyst, find above-mentioned oxide doping clearly enhance the anti-sintering of catalyst with
Carbon accumulation resisting ability, and Ni-MOx@SiO2Catalyst has superior stability.
The content of the invention
The purpose of the present invention is to propose to a kind of high anti-sintering methane dry gas of anti-carbon to reform core shell structure nickel-base catalyst
（Ni-MOx@SiO2）And preparation method.
A kind of metal oxide provided by the invention（MOx）Modified methane dry gas reforms core shell structure nickel-base catalyst,
It is simple with preparation method, the features such as reactivity is high, anti-carbon and anti-agglutinatting property ability are strong, stability is good, applied to
During methane dry gas reformation hydrogen production, it is industrialized that its catalytic activity and stability are well positioned to meet methane dry gas reformation hydrogen production
Need.
The present invention is achieved by the following technical solutions.
A kind of methane dry gas of the present invention reforms core shell structure nickel-base catalyst, and metal oxide adds in catalyst
Dosage is the 1 ~ 5% of catalyst weight, and the addition of nickel is the 5 ~ 10% of catalyst weight；With SiO2Outer cladding thing is done, itself and work
Property component nickel there is stronger interaction and preferable high high-temp stability, reform etc. in methane dry gas and also may be used in pyroreaction
To keep good structural stability.
Described metal oxide（MOx）For zirconium nitrate（La2O3）, lanthanum nitrate CeO2）Or cerous nitrate（ZrO2）.
A kind of methane dry gas of the present invention reforms the preparation method of core shell structure nickel-base catalyst, including following step
Suddenly.
（1）Nickelous nitrate hexahydrate and metal oxide precursor salt are weighed, is dissolved in distilled water wiring solution-forming, the solution
The concentration of middle metal ion is 0.04~0.20 mol/L；Ni2+Solubility is 0.28mol/L~0.59mol/L.
（2）Polyethyleneglycol -4- nonylbenzenes ether (n ≈ 5) is dissolved in hexamethylene, 4.32ml steps are added into the solution
（1）The nickel nitrate of configuration and the mixed aqueous solution of metal oxide precursor salt, 15h is stirred at 30 DEG C.Then add
The concentrated ammonia liquor of 4.32ml mass fractions 28%, continue to stir 2h at 30 DEG C, then be charged with 5ml tetraethyl orthosilicates, at 30 DEG C
Continue to stir 48 h.
（3）In step（2）Solution in add 40ml ethanol, then under 10000rp/min rotating speeds centrifuge 15min receive
Collection, it is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing.12h is dried in vacuo at 40 DEG C, in air gas after grinding
With 1~2 DEG C/min heating rates under atmosphere, 4h is calcined at 600 DEG C~800 DEG C, obtains NiO-MOx@SiO2Core-shell material.
（4）Recycling flow velocity is 30 ml/min, percentage by volume 10%H2In-Ar gaseous mixture atmosphere, 750 DEG C of conditions
Under, in fixed bed reactors situ reductase 12 h, obtain Ni-MOx@SiO2Catalyst with core-casing structure.
Metal oxide precursor salt of the present invention is zirconium nitrate, lanthanum nitrate or cerous nitrate.
Catalyst of the present invention, at ambient pressure, reaction gas composition be CH4:CO2=1.05:1, air speed 1,
8000ml.gcat -1.h-1, reaction temperature is under 800 DEG C of reaction condition, for methane dry gas reforming reaction.
The anti-sintering methane dry gas reformation multinuclear core shell structure nickel-base catalyst of high anti-carbon provided by the invention has following
Feature.
（1）Utilize metal oxide（MOx, specially La2O3、CeO2、ZrO2）The modified Ni-based methane of multinuclear core shell structure
Dry gas reforming catalyst, the doping of metal oxide enhances the interaction between nickel and carrier, therefore effectively inhibits nickel
The aggregation of particle, the anti-sintering and carbon accumulation resisting ability for enhancing catalyst.
（2）Carrier SiO2Outer cladding thing is done, because it has preferable high high-temp stability, is reformed in methane dry gas contour
Good structural stability can also be kept in temperature reaction.
（3）The catalyst of the present invention uses reverse microemulsion process, and preparation method is simple, and condition is easily controlled, catalyst
It is reproducible.
（4）Catalytic activity and stability are further improved, and are investigated by 240h continuous activity, catalyst
Activity does not decline, and is generated without carbon distribution, and active component nickel does not substantially sinter.
Brief description of the drawings
Fig. 1 is 7%Ni-3%ZrO prepared by the inventive method2@SiO2The transmission electron microscope of catalyst (after in-situ reducing processing)
Photo.
Fig. 2 is 7%Ni-3%ZrO prepared by the inventive method2@SiO2Catalyst, at ambient pressure, reaction gas composition be CH4:
CO2=1.05:1, air speed 1,8000ml.gcat -1.h-1, reaction temperature is 240h stability tests under 800 DEG C of reaction condition
Activity Results.
Fig. 3 is 7%Ni-3%ZrO prepared by the present invention2@SiO2Catalyst, at ambient pressure, reaction gas composition be CH4:CO2=
1.05:1, air speed 1,8000ml.gcat -1.h-1, reaction temperature is 240h stability tests H under 800 DEG C of reaction condition2/CO
As a result.
Fig. 4 is the 10%Ni-3%CeO prepared2@SiO2The transmission electron microscope piece of catalyst (after in-situ reducing processing).
Fig. 5 is the 10%Ni-3%La prepared2O3@SiO2The transmission electron microscope photo of catalyst (after in-situ reducing processing).
Embodiment
The present invention will be described further by following examples.
Embodiment 1.
Nickelous nitrate hexahydrate and five nitric hydrate zirconium precursor body salt are weighed, distilled water is dissolved in, is made into nickel nitrate and zirconium nitrate
Concentration is respectively 0.40mol/L and 0.11 mol/L mixed aqueous solution.Weigh 40.32g polyethyleneglycol -4- nonylbenzene ethers (n
≈ 5) it is dissolved in hexamethylene, the nickel nitrate and zirconium nitrate mixed aqueous solution of the above-mentioned configurations of 4.32ml are added into the solution, 30
15h is stirred at DEG C.Then the concentrated ammonia liquor of 4.32ml mass fractions 28% is added, continues to stir 2h at 30 DEG C, then be charged with
5ml tetraethyl orthosilicates, continue stirring 2 days at 30 DEG C.40ml ethanol is added into resulting solution, then in 10000rp/min
15min is centrifuged under rotating speed to collect, and is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing is three times.The vacuum at 40 DEG C
12h is dried, 4h is calcined with 2 DEG C/min heating rates in air atmosphere after appropriate grinding at 800 DEG C, obtains NiO-ZrO2@SiO2
Core-shell material.Recycling flow velocity is 30ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, under the conditions of 750 DEG C
Fixed bed reactors situ reductase 12 h, obtains Ni-ZrO2@SiO2Core shell structure methane dry gas reforming catalyst, wherein nickel and oxygen
The mass fraction for changing zirconium is respectively 7% and 3%.Transmission electron microscope photo is shown in accompanying drawing 1.
Catalyst activity is tested：Take the NiO-ZrO of 0.05g (40-60 mesh) above-mentioned preparation2@SiO2Catalyst is with flow velocity
30ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, device situ is answered to reduce in fixed bed under the conditions of 750 DEG C
2h, it is then turned off 10%H2- Ar gaseous mixtures, it is changed to the CH that through-flow speed is 7.5ml/min4And CO2Gas.Catalyst activity is tested
From 550 DEG C to 800 DEG C, stability test is carried out at 800 DEG C；Still keep good by 240h stability tests rear catalyst
Activity, CH4And CO2Conversion ratio is very close, and respectively 90.0% and 93.0%, deactivation phenomenom does not occur.Catalytic performance result
See accompanying drawing 2 and 3.
Embodiment 2.
Nickelous nitrate hexahydrate and five nitric hydrate zirconium precursor body salt are weighed, distilled water is dissolved in, is made into nickel nitrate and zirconium nitrate
Concentration is respectively 0.59mol/L and 0.20 mol/L mixed aqueous solution.Weigh 40.32g polyethyleneglycol -4- nonylbenzene ethers (n
≈ 5) it is dissolved in hexamethylene, the nickel nitrate aqueous solution of the above-mentioned configurations of 4.32ml is added into the solution, 15h is stirred at 30 DEG C.
Then the concentrated ammonia liquor that 4.32ml mass fractions are 28% is added, continues to stir 2h at 30 DEG C, then be charged with the positive silicic acid four of 5ml
Ethyl ester, continue stirring 2 days at 30 DEG C.40ml ethanol is added into resulting solution, is then centrifuged under 10000rp/min rotating speeds
15min is collected, and is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing is three times.12h is dried in vacuo at 40 DEG C, is fitted
4h is calcined at 800 DEG C, obtains NiO-ZrO with 2 DEG C/min heating rates in air atmosphere after grinding2@SiO2Core-shell material.Again
It is 30ml/min, percentage by volume 10%H using flow velocity2- Ar gaseous mixture atmosphere, in fixed bed reactors under the conditions of 750 DEG C
Situ reductase 12 h, obtains Ni-ZrO2@SiO2Core shell structure methane dry gas reforming catalyst, the wherein quality of nickel and zirconium oxide point
Number is respectively 10% and 5%.
Embodiment 3.
Nickelous nitrate hexahydrate and five nitric hydrate zirconium precursor body salt are weighed, distilled water is dissolved in, is made into nickel nitrate and zirconium nitrate
Concentration is respectively 0.28mol/L and 0.04mol/L mixed aqueous solution.Weigh 40.32g polyethyleneglycol -4- nonylbenzene ethers (n
≈ 5) it is dissolved in hexamethylene, the nickel nitrate and zirconium nitrate mixed aqueous solution of the above-mentioned configurations of 4.32ml are added into the solution, 30
15h is stirred at DEG C.Then the concentrated ammonia liquor of 4.32ml mass fractions 28% is added, continues to stir 2h at 30 DEG C, then be charged with
5ml tetraethyl orthosilicates, continue stirring 2 days at 30 DEG C.40ml ethanol is added into resulting solution, then in 10000rp/min
15min is centrifuged under rotating speed to collect, and is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing is three times.The vacuum at 40 DEG C
12h is dried, 4h is calcined with 2 DEG C/min heating rates in air atmosphere after appropriate grinding at 800 DEG C, obtains NiO-ZrO2@SiO2
Core-shell material.Recycling flow velocity is 30ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, under the conditions of 750 DEG C
Fixed bed reactors situ reductase 12 h, obtains Ni-ZrO2@SiO2Core shell structure methane dry gas reforming catalyst, wherein nickel and oxygen
The mass fraction for changing zirconium is respectively 5% and 1%.
Catalyst activity is tested：Take the NiO-ZrO of 0.05g (40-60 mesh) above-mentioned preparation2@SiO2Catalyst is with flow velocity
60ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, device situ is answered to reduce in fixed bed under the conditions of 750 DEG C
2h, it is then turned off 10%H2- Ar gaseous mixtures, it is changed to the CH that through-flow speed is 7.5ml/min4And CO2Gas.Catalyst activity is tested
From 550 DEG C to 800 DEG C, stability test is carried out at 800 DEG C；Still keep good by 20h stability tests rear catalyst
Activity, CH4And CO2Conversion ratio is very close, and respectively 85.0% and 87.0%, deactivation phenomenom does not occur.
Embodiment 4.
Nickelous nitrate hexahydrate and six nitric hydrate cerium precursor salt are weighed, distilled water is dissolved in, is made into nickel nitrate and cerous nitrate
Concentration is respectively 0.59mol/L and 0.08 mol/L mixed aqueous solution.Weigh 40.32g polyethyleneglycol -4- nonylbenzene ethers (n
≈ 5) it is dissolved in hexamethylene, the nickel nitrate and cerous nitrate mixed aqueous solution of the above-mentioned configurations of 4.32ml are added into the solution, 30
15h is stirred at DEG C.Then the concentrated ammonia liquor of 4.32ml mass fractions 28% is added, continues to stir 2h at 30 DEG C, then be charged with
5ml tetraethyl orthosilicates, continue stirring 2 days at 30 DEG C.40ml ethanol is added into resulting solution, then in 10000rp/min
15min is centrifuged under rotating speed to collect, and is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing is three times.The vacuum at 40 DEG C
12h is dried, 4h is calcined with 2 DEG C/min heating rates in air atmosphere after appropriate grinding at 800 DEG C, obtains NiO-CeO2@SiO2
Core-shell material.Recycling flow velocity is 30ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, under the conditions of 750 DEG C
Fixed bed reactors situ reductase 12 h, obtains Ni-CeO2@SiO2Core shell structure methane dry gas reforming catalyst, wherein nickel and oxygen
The mass fraction for changing cerium is respectively 10% and 3%.Transmission electron microscope photo is shown in accompanying drawing 4.
Embodiment 5.
Nickelous nitrate hexahydrate and lanthanum nitrate hexahydrate precursor salt are weighed, is dissolved in distilled water, is made into nickel nitrate and lanthanum nitrate
Concentration is respectively 0.59mol/L and 0.08 mol/L mixed aqueous solution.Weigh 40.32g polyethyleneglycol -4- nonylbenzene ethers (n
≈ 5) it is dissolved in hexamethylene, the nickel nitrate and lanthanum nitrate mixed aqueous solution of the above-mentioned configurations of 4.32ml are added into the solution, 30
15h is stirred at DEG C.Then the concentrated ammonia liquor of 4.32ml mass fractions 28% is added, continues to stir 2h at 30 DEG C, then be charged with
5ml tetraethyl orthosilicates, continue stirring 2 days at 30 DEG C.40ml ethanol is added into resulting solution, then in 10000rp/min
15min is centrifuged under rotating speed to collect, and is 1 with acetone and hexamethylene volume ratio:1 mixed solvent washing is three times.The vacuum at 40 DEG C
12h is dried, 4h is calcined with 2 DEG C/min heating rates in air atmosphere after appropriate grinding at 800 DEG C, obtains NiO-La2O3@SiO2
Core-shell material.Recycling flow velocity is 30ml/min, percentage by volume 10%H2- Ar gaseous mixture atmosphere, under the conditions of 750 DEG C
Fixed bed reactors situ reductase 12 h, obtains Ni-La2O3@SiO2Core shell structure methane dry gas reforming catalyst, wherein nickel with
The mass fraction of cerium oxide is respectively 10% and 3%.Transmission electron microscope photo is shown in accompanying drawing 5.
Claims (4)
1. a kind of methane dry gas reforms core shell structure nickel-base catalyst, it is characterized in that the addition of metal oxide is in catalyst
The 1 ~ 5% of catalyst weight, the addition of nickel is the 5 ~ 10% of catalyst weight, with SiO2Do outer cladding thing.
2. a kind of methane dry gas according to claim 1 reforms core shell structure nickel-base catalyst, it is characterized in that described gold
Category oxide is zirconium nitrate, lanthanum nitrate or cerous nitrate.
3. a kind of methane dry gas described in claim 1 reforms the preparation method of core shell structure nickel-base catalyst, it is characterized in that bag
Include following steps：
（1）Nickelous nitrate hexahydrate and metal oxide precursor salt are weighed, is dissolved in distilled water wiring solution-forming, the GOLD FROM PLATING SOLUTION
The concentration for belonging to ion is 0.04~0.20 mol/L；Ni2+Solubility is 0.28mol/L~0.59mol/L；
（2）Polyethyleneglycol -4- nonylbenzene ethers are dissolved in hexamethylene, 4.32ml steps are added into the solution（1）The nitre of configuration
The mixed aqueous solution of sour nickel and metal oxide precursor salt, 15h is stirred at 30 DEG C；Then 4.32ml mass fractions are added
28% concentrated ammonia liquor, continue to stir 2h at 30 DEG C, then be charged with 5ml tetraethyl orthosilicates, continue to stir 48 h at 30 DEG C；
（3）In step（2）Solution in add 40ml ethanol, then under 10000rp/min rotating speeds centrifuge 15min collect, use
Acetone and hexamethylene volume ratio are 1:1 mixed solvent washing；12h is dried in vacuo at 40 DEG C, after grinding in air atmosphere
With 1~2 DEG C/min heating rates, 4h is calcined at 600 DEG C~800 DEG C, obtains NiO-MOx@SiO2Core-shell material；
（4）Recycling flow velocity is 30 ml/min, percentage by volume 10%H2In-Ar gaseous mixture atmosphere, under the conditions of 750 DEG C, solid
Fixed bed reactor situ reductase 12 h, obtains Ni-MOx@SiO2Catalyst with core-casing structure.
4. a kind of methane dry gas according to claim 3 reforms the preparation method of core shell structure nickel-base catalyst, its feature
It is that described metal oxide precursor salt is zirconium nitrate, lanthanum nitrate or cerous nitrate.
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| CN109529851A (en) * | 2018-12-26 | 2019-03-29 | 大连海事大学 | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method |
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| CN109967081A (en) * | 2019-04-01 | 2019-07-05 | 大连理工大学 | A kind of high activity, anti-carbon methane dry gas reforming catalyst and preparation method thereof |
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| CN115155599A (en) * | 2022-04-11 | 2022-10-11 | 浙江氢邦科技有限公司 | Cladding Ni-in @ SiO 2 -Al 2 O 3 Hollow mesoporous nano catalyst and preparation method and application thereof |
| CN115193460A (en) * | 2021-04-09 | 2022-10-18 | 中国科学院大连化学物理研究所 | CeO 2 Application of coated silicon carbide supported metal element catalyst in methane-carbon dioxide reforming process |
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