CN107321351A - A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction - Google Patents
A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction Download PDFInfo
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- CN107321351A CN107321351A CN201710584699.4A CN201710584699A CN107321351A CN 107321351 A CN107321351 A CN 107321351A CN 201710584699 A CN201710584699 A CN 201710584699A CN 107321351 A CN107321351 A CN 107321351A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/74—Iron group metals
- B01J23/755—Nickel
Abstract
A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction, is related to a kind of method for preparing catalyst, and the catalyst is using nickel nitrate and nickel chloride as nickel source, using alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox as silicon source.Using DMF, absolute ethyl alcohol as solvent, using alkyl ammonium halide as surfactant, polymer microsphere template is added, classifying porous Ni/SiO is prepared using sol-gal process, hydro-thermal and solvent-thermal method2Catalyst, using catalyst of the present invention, in 700 DEG C of temperature, reacts, time of contact is 1 ghmol under normal pressure- 1Under reaction condition, methane conversion is up to 83%, and carbon dioxide conversion is up to 89%, under the same reaction time compared with traditional catalyst, carbon deposition rate reduction by 30%, and catalyst life is greatly improved.Catalyst is easily prepared, with low cost, with good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst, more particularly to a kind of height of methane/carbon dioxide reforming reaction
Imitate method for preparing catalyst.
Background technology
Current methane reforming mainly has methane steam reformation（SMR）Reformed with methane portion oxidation（POM）And methane-
CO 2 reformation（DM）.Methane steam reformation has been industrialized at present, is a highly endothermic process, it is necessary in high temperature（>800
℃）Lower reaction, and in order to prevent carbon deposit, it is necessary to be operated using high steam/hydrocarbons ratio（H2O/CH4=2.5-3）, therefore technical process energy consumption
It is high（A large amount of vapor）, investment is big, production capacity is low, can not economically meet following extensive require；Methane portion oxidation is deposited
In great potential safety hazard, once the mixed volume of methane and oxygen is in the possibility for having blast within explosion limit.The reaction
It is a mild exothermic reaction, reaction speed is exceedingly fast, catalyst surface has focus, the loss of active component can have a strong impact on catalysis
The stability of agent, in addition, catalyst carbon deposition is also to influence a key factor of reaction stability.And CO2/CH4Reformation can be simultaneously
Eliminate CH4、CO2Two kinds of main greenhouse gases and receive much concern.CO2/CH4Reforming reaction is strong endothermic reaction, and reaction needs
Carried out under high temperature（>700℃）, the high-temperature stability and reactivity for how improving reforming catalyst are the keys of technical research.
Foreign scholar has found that Ru and Rn are due to right when laboratory uses noble metal as catalyst research reforming reaction
CO2Decompose very sensitive, CO is carried out in 600 ~ 900 DEG C of temperature ranges2/CH4Reforming reaction, carbon deposit is not produced substantially, is most
It is adapted to the active component for making reforming catalyst.Although noble metal has higher catalytic activity, preferable anti-carbon and anti-sintering
Performance, but the price of noble metal catalyst is very expensive, is not suitable for large-scale industrial production.Domestic research is concentrated mainly on
On non-precious metal catalyst, research finds that its activity order is Ni>Co>Cu>Fe, the wherein activity of Ni, Co base catalyst can be with
Noble metal compares favourably, but non-precious metal catalyst poor high temperature stability, is inactivated because of carbon deposit too fast.Most researchers think
CO2/CH4The inactivation of reforming catalyst is main by CO disproportionations carbon distribution and CH4Cracking carbon distribution is caused, the sintering of active metal
It may be also a factor of inactivation.The active metal particle size and decentralization of loaded catalyst are with its catalytic activity and surely
It is qualitative to have close relationship.Result by references is shown, when Ni crystallite dimensions are smaller, and upper carbon deposition rate and the carbon of catalyst are eliminated
Speed is suitable, so that catalyst keeps stable activity.In order to prepare high dispersive, little crystal grain catalyst, generally using large surface
Long-pending carrier.For general oxide carrier, specific surface area and the inversely proportional relation in aperture, thus the carrier hole of high surface area
Footpath is small, is unfavorable for reaction and diffusion of the product in catalyst duct, and then influence reaction rate.Catalyst aperture is small simultaneously,
The too strong reduction for being also unfavorable for catalyst of intermolecular forces of metal and carrier.And macroporous catalyst is used, catalyst is easy to reduction,
Product is fast in catalyst pore diffusion with reactant, however, catalyst decentralization is low, metallic active surface accumulates small, active metal
It is not fully utilized, reactivity is low.Therefore, the mutual system between metal dispersity, reduction degree and diffuser efficiency how is solved
About relation, is to prepare one of key factor of high activity metal catalyst.It is first and diplopore catalyst is due to the presence of double-pore structure
First, the specific surface area of carrier is improved, is conducive to the high degree of dispersion of active metal；Secondly, the presence of double-pore structure is also beneficial to
The diffusion of reactant and product in catalyst duct；Finally, the exotic atom oxide of introducing also functions to catalyst to reaction and helped
The effect of agent.
Inui etc. is prepared for double hole channel Ni/SiO using the strong acid corrosivity of chloroazotic acid2Catalyst, greatly improves it to two
The methanation reaction activity of carbonoxide.Tsubaki et al. introduces nano-particle by infusion process in macroporous silica hole, system
For diplopore SiO2Catalyst, has investigated reactivity worth of the catalyst in F- T synthesis, has as a result shown diplopore catalyst activity
Metal dispersity is high, CO high conversion rates, meanwhile, double-pore structure is also beneficial to compress CH4Selectivity.Tao Kai etc. is prepared for a series of
Pt bases SiO2Diplopore carrier is used for methane reforming with carbon dioxide and carried out with single macropore and single small catalyst
Comparative studies.It was found that diplopore catalyst is better than single hole catalyst.Catalytic performance is incremented by the following order with the different of carrier：
Pt/SiO2-SiO2<Pt/ZrO2-SiO2<Pt/Al2O3-SiO2.Although Pt bases SiO2Diplopore catalyst shows superior catalytic
Can, but noble metal catalyst cost is high, is unsuitable for large-scale commercial Application.In addition, the experimental results show, carrier
Surface nature, acid-base property, the interaction of carrier and active component and the active metal decentralization, the crystal grain that thus trigger are big
Small change can have important influence to catalyst reaction activity and resistance to deactivation.The reforming catalyst of current document report is carried
Body has Al2O3、SiO2、TiO2、ZrO2And composite oxides Al2O3-MgO、ZrO2-CeO2With molecular sieve etc..Therefore prepare a kind of
With appropriate pore size, pore distribution（Double hole channel）, the big catalyst carrier of specific surface area can improve active metal（Ni）
Decentralization, accelerate the diffusion of reactant and product, introduce auxiliary agent and promote reaction to carry out, be to improve catalyst efficiency and stability
Effective means, substantially reduce catalytic reforming mass produce synthesis gas cost.The content of the invention
It is an object of the invention to provide a kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction, this method
Classifying porous Ni/SiO is prepared using sol-gal process, hydro-thermal and solvent-thermal method2Catalyst, using catalyst of the present invention, in temperature
700 DEG C of degree, reacts under normal pressure, and time of contact is 1 ghmol- 1Under reaction condition, methane conversion is up to 83%, carbon dioxide
Conversion ratio is up to 89%, and catalyst life is greatly improved.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction, methods described includes procedure below：
Catalyst active center is nanoscale base metal nickel and its oxide 10-30%, using Ni as main active ingredient catalyst,
Carrier is the silica with classifying porous road structure；The reaction that catalyst is applicable is that methane and carbon dioxide is reformed
Reaction, synthesis high-grade hydrogen energy source and synthesis gas；Using nanoscale base metal nickel as main active constituent, carrier be with micropore-
The classifying porous of mesopore-macropore structure arrives silica；Preparation method hydro-thermal-sol method of catalyst, and use normal pressure air blast
Machine, which is dried, prepares classifying porous nickel-base catalyst；With N, N-dimethylformamide, ethanol are that solvent addition alkyl ammonium halide is
Surfactant, usage ratio is 0.002-2%.Polymer microsphere template is added, addition is 1-30%；The solution of preparation exists
By forming colloidal sol after 120-180 DEG C of hydro-thermal reaction, then drying-granulating obtains catalyst.
A kind of method for preparing high-efficient catalyst of described methane/carbon dioxide reforming reaction, the active component nickel with
It is nickel source to make Nickelous nitrate hexahydrate and six water nickel chlorides, and load capacity is 10-30%（Weight）.
A kind of method for preparing high-efficient catalyst of described methane/carbon dioxide reforming reaction, the carrier is with alkoxy
Silane, high-purity silicon powder, high-purity gas-phase silica, Ludox are silicon source.
A kind of method for preparing high-efficient catalyst of described methane/carbon dioxide reforming reaction, the reaction temperature is
600-800℃。
Advantages of the present invention is with effect：
Not enough the present invention be directed to existing methane/carbon dioxide catalytic reforming reaction catalyst performance is urged there is provided a kind of new
Agent, so as to improve the effect of reaction；Classifying porous Ni/SiO is prepared using sol-gal process, hydro-thermal and solvent-thermal method2Catalysis
Agent, using catalyst of the present invention, in 700 DEG C of temperature, reacts, time of contact is 1 ghmol under normal pressure- 1Under reaction condition, first
Alkane conversion ratio is up to 83%, and carbon dioxide conversion is up to 89%, under the same reaction time compared with traditional catalyst, carbon deposition rate drop
Low by 30%, catalyst life is greatly improved.
Brief description of the drawings
Fig. 1 is that DMF is solvent catalyst scanning electron microscopic picture；
Fig. 2 is that ethanol is solvent catalyst scanning electron microscopic picture.
Embodiment
With reference to embodiment, the present invention is described in detail.
The preparation method of the classifying porous catalyst of catalytic methane of the present invention/carbon dioxide catalytic reforming reaction is implemented
Step is：
Catalyst active center is nanoscale base metal nickel and its oxide 10-30%, using Ni as main active ingredient catalyst,
Carrier is the silica with classifying porous road structure.Catalyst methane and carbon dioxide carry out reforming reaction, synthesize Gao Pin
Position hydrogen energy source and synthesis gas.Catalyst is using nanoscale base metal nickel as main active constituent.Catalyst carrier is with micropore-Jie
The classifying porous of hole-macroporous structure arrives silica.Preparation method hydro-thermal-sol method of catalyst, and use normal pressure air blower
It is dried and prepares classifying porous nickel-base catalyst.Wherein active component nickel is so that Nickelous nitrate hexahydrate and six water nickel chlorides are nickel
Source, load capacity is 10-30%（Weight）.Carrier is using alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox as silicon
Source.It is that solvent adds alkyl ammonium halide as surfactant using DMF, ethanol, usage ratio is 0.002-2%,
Polymer microsphere template is added, addition is 1-30%.The solution of preparation forms molten after by 120-180 DEG C of hydro-thermal reaction
Glue, then drying-granulating obtain catalyst；Methane and carbon dioxide reforming reaction, its reaction temperature is 600-800 DEG C.
Embodiment 1
Step one：The water nickel nitrates of 0.918g six, 60mlDMF, 2.8ml tetraethyl orthosilicate are weighed in beaker, is continued at room temperature
Stirring 5-10 minutes is until obtain limpid without particle green solution.
Step 2：Weigh 0.02g cetyl trimethylammonium bromides and add above-mentioned solution, stir.
Step 3：Solution is poured into water heating kettle, heated 720 minutes at 180 DEG C.Product is obtained after cooling.Gained is molten
Glue is dried 900 minutes at 70 DEG C, obtains brownish solid-state caking.
Step 4：Grinding, calcining, 400 DEG C of calcination stage design temperature（Temperature rise period sets 5 DEG C/min）, setting time
For 240 minutes.Calcined product is black powder.Tabletting, granulation, filters out the sample of 20-40 mesh.
Step 5：Weigh catalyst 0.1g and activity rating is carried out on continuous fixed bed reactor.Methane conversion
For 76%, carbon dioxide conversion is 82%, and carbon monoxide selective is 92%, and catalyst runs 300 hours without substantially inactivation.Urge
Agent pattern such as Fig. 1 DMF are solvent catalyst scanning electron microscopic picture.
Embodiment 2
Step one：0.918g Nickelous nitrate hexahydrates are weighed, 65ml absolute ethyl alcohols, 2.8ml tetraethyl orthosilicates are stirred 5-10 minutes
Obtain limpid without particle green solution.Other step be the same as Examples 1.
Step 2: three, four be the same as Examples 1.
Step 5：Weigh catalyst 0.1g and activity rating is carried out on continuous fixed bed reactor.Methane conversion
For 83%, carbon dioxide conversion is 91%, and carbon monoxide selective is 93%, and catalyst runs 300 hours without substantially inactivation.Urge
The ethanol of agent pattern below figure 2 is solvent catalyst scanning electron microscopic picture.
Embodiment 3
Step 1: two be the same as Examples 1.
Step 3：Solution is poured into water heating kettle, heated 240 minutes at 180 DEG C.Product is obtained after cooling.Gained is molten
Glue is dried 900 minutes at 70 DEG C.
Step 4: five be the same as Examples 1
Weigh catalyst 0.1g and activity rating is carried out on continuous fixed bed reactor.Methane conversion is 65%, titanium dioxide
Efficiency of carbon con version is 78%, and carbon monoxide selective is 90%., catalyst runs 120 hours catalyst and deactivation phenomenom occurs, thermogravimetric point
Analyse carbon distribution substantially, catalyst pattern is in random state.
Embodiment 4
Take the 2ml polystyrene microsphere aqueous solution, 60mlDMF, 2.8ml tetraethyl orthosilicates, 0.918g Nickelous nitrate hexahydrates.Will be upper
State material and pour into beaker, mix 20 minutes；Pour into water heating kettle and carry out hydro-thermal reaction, temperature is set as 180 DEG C, and the time is set as
720 minutes.After take out, sample property is green colloidal sol, is dried 12 hours under conditions of 80 DEG C.Drying sample is taken out, is ground,
Load potcal pot calcination, 400 DEG C of calcining heat（5 DEG C/min of temperature rise period）, 240 minutes time.Terminate sample to take out, tabletting, make
Grain.
Weigh catalyst 0.1g and activity rating is carried out on continuous fixed bed reactor.Methane conversion is 79%, two
Carbon oxide conversion rate is 87%, and carbon monoxide selective is 92%., catalyst run 300 hours catalyst show slightly inactivation.
Embodiment 6
Take the 2ml poly (methyl methacrylate) micro-sphere aqueous solution, 60mlDMF, 2.8ml tetraethyl orthosilicates, the hydration nitre of 0.918g six
Sour nickel.Above-mentioned substance is poured into beaker, mixed 15 minutes；Pour into water heating kettle and carry out hydro-thermal reaction, temperature is set as 180 DEG C, when
Between be set as 720 minutes.After take out, sample property is green colloidal sol, is dried 12 hours under conditions of 80 DEG C.Take out and dry sample
Product, grinding loads potcal pot calcination, 400 DEG C of calcining heat（5 DEG C/min of temperature rise period）, 240 minutes time.Terminate sample to take out,
Tabletting, granulation.
Weigh catalyst 0.1g and activity rating is carried out on continuous fixed bed reactor.Methane conversion is 81%, two
Carbon oxide conversion rate is 90%, and carbon monoxide selective is 93%., catalyst run 300 hours catalyst show slightly inactivation.
Embodiment 7
Take 0.918g Nickelous nitrate hexahydrates, 2.06ml Ludox, 20ml deionized waters.Above-mentioned solution is poured into beaker and mixed,
Stirred using 50 DEG C of constant temperature of thermostat water bath design temperature, mixing time 120 minutes.Aging is dried afterwards, finally obtains
Sticky greenish precipitate thing.End product becomes block, and fine particle is caused with mortar grinder, is fitted into crucible and calcines, calcining
400 DEG C of temperature（5 DEG C/min of temperature rise period）, 240 minutes time.Terminate sample to take out, tabletting, granulation.Weigh catalyst 0.1g
Carry out activity rating.Methane conversion is 54%, and carbon dioxide conversion is 68%, and carbon monoxide selective is 89%., catalyst
There is substantially inactivation in operation after 120 hours, catalyst thermogravimetric analysis carbon distribution is serious.
Claims (4)
1. a kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction, it is characterised in that methods described include with
Lower process：
Catalyst active center is nanoscale base metal nickel and its oxide 10-30%, using Ni as main active ingredient catalyst,
Carrier is the silica with classifying porous road structure；The reaction that catalyst is applicable is that methane and carbon dioxide is reformed
Reaction, synthesis high-grade hydrogen energy source and synthesis gas；Using nanoscale base metal nickel as main active constituent, carrier be with micropore-
The classifying porous of mesopore-macropore structure arrives silica；Preparation method hydro-thermal-sol method of catalyst, and use normal pressure air blast
Machine, which is dried, prepares classifying porous nickel-base catalyst；With N, N-dimethylformamide, ethanol are that solvent addition alkyl ammonium halide is
Surfactant, usage ratio 0.002-2% adds polymer microsphere template, addition is 1-30%；The solution of preparation is logical
Cross and colloidal sol is formed after 120-180 DEG C of hydro-thermal reaction, then drying-granulating obtains catalyst.
2. a kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction according to claim 1, its feature
It is, the active component nickel is so that Nickelous nitrate hexahydrate and six water nickel chlorides are nickel source, and load capacity is 10-30%（Weight）.
3. a kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction according to claim 1, its feature
It is, the carrier is using alkoxy silane, high-purity silicon powder, high-purity gas-phase silica, Ludox as silicon source.
4. a kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction according to claim 1, its feature
It is, the reaction temperature is 600-800 DEG C.
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| CN108371952A (en) * | 2018-02-28 | 2018-08-07 | 西京学院 | A kind of method that coordination-infusion process prepares methane-CO 2 reformation nickel-base catalyst |
| CN109499578A (en) * | 2019-01-23 | 2019-03-22 | 华东师范大学 | A kind of Ni base catalyst and preparation method thereof and the application in methyl methanol syngas is being prepared using coke-stove gas as raw material |
| CN110252385A (en) * | 2019-06-17 | 2019-09-20 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking catalyst |
| CN111370663B (en) * | 2020-03-18 | 2021-05-25 | 浙江锂宸新材料科技有限公司 | Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof |
| CN114804023A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method and application of metal-molten salt for hydrogen production from natural gas and carbon black |
| CN115069260A (en) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
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| CN111370663B (en) * | 2020-03-18 | 2021-05-25 | 浙江锂宸新材料科技有限公司 | Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof |
| CN114804023A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method and application of metal-molten salt for hydrogen production from natural gas and carbon black |
| CN115069260A (en) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
| CN115069260B (en) * | 2022-07-29 | 2023-05-05 | 南京工业大学 | Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof |
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