CN104511279B - A kind of high-efficiency methane CO 2 reformation Ni/SiO2The preparation method of catalyst and its electrostatic spinning - Google Patents
A kind of high-efficiency methane CO 2 reformation Ni/SiO2The preparation method of catalyst and its electrostatic spinning Download PDFInfo
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Abstract
A kind of high-efficiency methane CO 2 reformation Ni/SiO2The preparation method of catalyst and its electrostatic spinning, belongs to catalyst preparation technical field.By electrostatic spinning technique, the silica nano fibrous effective catalyst for loading nickel nano particle is prepared.Its preparation process：Spinning precursor liquid, then electrostatic spinning are first configured, finally by drying and roasting finished product.Preparation method raw material of the present invention is easy to get, simple to operate, and controllability is good, amplifies beneficial to industrialization.The made catalyst of the present invention is used in the reaction of methane and carbon dioxide catalytic reforming preparing synthetic gas, has catalytic activity high, and anti-carbon performance is good, the advantages that good stability.
Description
Technical field
The present invention relates to a kind of methane carbon dioxide reformation Ni/SiO2The method of catalyst preparation, using electrostatic spinning skill
Art prepares SiO2Nano-fibre supported Ni effective catalyst, belongs to catalyst preparation technical field.
Background technology
In recent years, energy crisis and the problems such as environmental pollution gradually by the extensive concern of society.With petroleum resources
Increasingly depleted, the development and utilization of natural gas resource seem ever more important.Methane is the key component of natural gas, its trans-utilization
It is broadly divided into directly conversion and indirect reformer.Directly methane is then directly converted into chemical products by conversion, and process is simple, but is realized
Get up more difficult.Methane is first converted into synthesis gas by indirect reformer, then converts synthesis gas to other chemical products, and process is relative
Complexity, but technology relative maturity, with more prospects for commercial application.Indirect reformer mainly includes steam reformation, carbon dioxide
Reformation and partial oxidation reaction.Wherein, methane reforming with carbon dioxide can be by CH4、CO2Two kinds of main greenhouse gas conversions
To be adapted to the synthesis gas of Fiscber-Tropscb synthesis and carbonylation synthesis, alternative energy source is obtained while greenhouse effects are alleviated, to promoting to clean
Production of energy and environmental protection are significant.
The most study and catalyst system and catalyzing closest to industrial applications is nickel (Ni) base catalyst at present.Economically viable work
Industryization is that the reaction is highly endothermic process using unredeemed reason, it is necessary to carries out at relatively high temperatures, and corresponding
Under reaction condition there is serious carbon distribution in catalyst.Therefore, the key of research is to develop living under the conditions of relative low temperature
Property it is high, stability is good, the strong new and effective Ni bases catalyst system and catalyzing of carbon accumulation resisting ability.Research report, nano-catalytic agent carrier make
With the anti-carbon performance of Ni base catalyst can be improved (see Size limit of support particles in an
oxide-supported metal catalyst:Nanocomposite Ni/ZrO2 for utilization of
natural gas.Journal of Physical Chemistry C,2003,Vol.107,pp.5203-5207).Separately there is report
Road shows the nanometer confinement effect by phyllosilicate nanotube, and can build has strong resist in alcohol steam reformed reaction
Sintering and the Ni bases catalyst system and catalyzing of strong anti-carbon performance are (see Sintering-resistant Ni-based reforming
catalysts obtained via the nanoconfinement effect.Chemical Communications,
2013,Vol.49,9383-9385.).Thus, nano-carrier and confinement Ni base catalyst system and catalyzings are prepared by special preparation method
It is expected to obtain new and effective methane carbon dioxide reformation catalyst.
Electrostatic spinning technique be fluid under high voltage electric field, flow and deform, and then obtain a kind of spinning of fibrous material
Silk technology.The abundant nanofiber of species can be made by the technology, and manufacture device is simple, cost of spinning is cheap, thus
Materials science field has extensive use.But electrostatic spinning technique is applied in the preparation of catalyst but there is not yet
Wide coverage.Thus, the present invention attempts to compare electrostatic spinning technique with traditional incipient impregnation method, prepares Nanowire
Tie up the efficient catalytic system of confinement.As a result show, the SiO that the present invention is prepared by spining technology2Nanofiber specific surface area
Greatly, high temperature resistant, high mechanical strength, it makes active component Ni have preferably dispersiveness as carrier.Ni/SiO2Nanofiber is urged
Agent catalytic activity in methane carbon dioxide reformation is high, and anti-carbon performance is good, good stability.
The content of the invention
It is an object of the present invention to provide a kind of high-efficiency methane CO 2 reformation Ni/SiO2The system of catalyst and its electrostatic spinning
Preparation Method.Make its high temperature resistant, high mechanical strength, component Ni has preferably dispersiveness.Ni/SiO2Nano-fiber catalyst is in first
Catalytic activity is high in alkane CO 2 reformation, and anti-carbon performance is good, good stability.
To achieve the above object, technical scheme is as follows.
A kind of high-efficiency methane CO 2 reformation Ni/SiO2Catalyst, it is characterised in that silica nano fibrous negative
Carry scattered Ni nano particles.
A kind of electrostatic spinning technique of the present invention prepares high-efficiency methane CO 2 reformation Ni/SiO2The method of catalyst, its
It is characterised by, the efficient catalytic of the scattered Ni nano particles of silica nano fibrous load is prepared using electrostatic spinning technique
Agent.
The catalyst preparation step includes as follows：
(1) spinning precursor liquid is configured：Mass ratio is weighed as 1:(0.15-0.48):The tetraethyl orthosilicate of (0.02-0.48)
(TEOS), polyvinylpyrrolidone (PVP) and nickel salt, TEOS is then dissolved in mass ratio as 1:The diluted acid of (0.13-2.5) and
In alcohol mixeding liquid, PVP is dissolved in DMF (DMF) or is dissolved in mass ratio as 1:The DMF of (0.21-1)
In dimethyl sulfoxide (DMSO) (DMSO) mixed liquor, nickel salt is then dissolved in ethanol or/and water；After being completely dissolved, by these three solution point
Do not stir 8-14h at the uniform velocity, 0.5-2.5h is stirred after finally three solution are sufficiently mixed, obtain spinning precursor liquid；Aforesaid operations one
As carried out at a temperature of 5-60 DEG C.
(2) electrostatic spinning：The spinning precursor liquid of step (1) is fitted into syringe, then syringe is loaded into pusher
On, layer of metal paper tinsel is sticked on the receiver, and rotating speed is 50-550r/min, voltage is adjusted to 12-28kV, spinning solution push speed
Rate is 0.1-5ml/h, starts spinning；
(3) 80-150 DEG C of the spinning dry 6-24h, 350-900 DEG C of roasting 2-8h for being collected into step (2) in metal foil；
After the completion of roasting, sample is collected.
A kind of above-mentioned electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO2The method of catalyst, it is excellent
It is nickel nitrate, nickel chloride or nickel acetate etc. to select the nickel salt described in step (1).
A kind of above-mentioned electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO2The method of catalyst, it is excellent
It is watery hydrochloric acid, dust technology or dilute sulfuric acid to select the diluted acid described in step (1)；Its concentration is generally 0.055-0.184mol/L.
When TEOS is dissolved in diluted acid and ethanol, preferably TESO mass percent concentrations 56.46-77.55%；PVP dissolves
When in DMF (DMF) or in DMF (DMF) and dimethyl sulfoxide (DMSO) (DMSO), preferably
PVP mass percent concentrations 8.56-45.25%；When nickel salt is then dissolved in ethanol or/and water, preferred nickel salt mass percent
Concentration 5.16-73.32%.
High-efficiency methane CO 2 reformation Ni/SiO is prepared using a kind of above-mentioned electrostatic spinning technique2The side of catalyst
Method, the carrier of the catalyst of preparation are silica nano fibrous, even thickness, average diameter 100-500nm, and length is
0.1-500 μm, specific surface area 50-500m2/ g, there is high temperature resistant, high mechanical strength.According to the method described above, adjust
The usage ratio of tetraethyl orthosilicate (TEOS), polyvinylpyrrolidone (PVP) and nickel salt, the high-efficiency methane carbon dioxide weight of preparation
Whole Ni/SiO2Catalyst, the preferably weight/mass percentage compositions of active component Ni in the catalyst are 1%-30%, further preferably
3%-15%.
A kind of above-mentioned electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO2The method of catalyst is made
Catalyst be used for methane reforming with carbon dioxide.
Take above-mentioned high-efficiency methane CO 2 reformation Ni/SiO2Catalyst sample is placed in quartz ampoule, in hydrogen atmosphere
After 300-1000 DEG C of reduction, at a temperature of 600-1000 DEG C, flow-rate ratio is passed through as 1:1:2 methane, carbon dioxide and argon gas, enters
Row methane carbon dioxide reformation.
A kind of electrostatic spinning technique of the present invention prepares high-efficiency methane CO 2 reformation Ni/SiO2The method advantage of catalyst
It is：Method for preparing catalyst raw material is easy to get, simple to operate, and controllability is good, amplifies beneficial to industrialization.It is silica nano fibrous
Carrier makes active component Ni have preferably dispersiveness.Catalyst is used in synthesizing gas by reforming methane with co 2 reaction, tool
There is catalytic activity high, anti-carbon performance is good, the advantages that good stability.
Brief description of the drawings
Fig. 1 is Ni/SiO prepared by the present invention2The HR-TEM figures (embodiment 1) of nano-fiber catalyst.
Embodiment
With reference to embodiment, to further illustrate the present invention, but the present invention is not limited to following examples.
Embodiment 1
1st, 4.7g tetraethyl orthosilicates (TEOS) and 1.1g polyvinylpyrrolidones (PVP) and 1.13g nitric acid are weighed respectively
Nickel, then TEOS is dissolved in 0.95g watery hydrochloric acid (material concentration 0.080mol/L) and 1.25g ethanol, PVP is then in 4.12g
Dissolved in DMF (DMF) and 2.50g dimethyl sulfoxide (DMSO)s (DMSO), nickel nitrate is then dissolved in 1.82g ethanol；
After being completely dissolved, these three solution are individually placed at the uniform velocity to stir 9h on magnetic stirring apparatus, finally three solution are sufficiently mixed and put
In magnetic stirrer 0.5h, spinning precursor liquid is obtained.Operation is carried out at 25 DEG C.
2nd, the mixed liquor obtained in 1 is fitted into syringe, then syringe is loaded on pusher, pasted on the receiver
Last layer metal foil, and rotating speed is 80r/min.Voltage is adjusted to 12kV, and spinning solution push speed is 1ml/h, starts spinning.
3rd, 120 DEG C of the sample dry 16h, 700 DEG C of roasting 6h that will be obtained in 2.
4th, the sample obtained in 0.1g steps 3 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 65.34%, 79.01%；H2, CO highest selectivity be 90.36%, 98.21% respectively.
Embodiment 2
1st, nickel nitrate is dissolved in 1.82g water；It is other consistent with step 1 in embodiment 1.
2nd, it is identical with the step 2 of embodiment 1.
3rd, it is identical with the step 3 of embodiment 1.
4th, the sample obtained in 0.1g steps 3 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 64.97%, 78.23%；H2, CO highest selectivity be 89.98%, 96.28% respectively.
Embodiment 3
1st, TEOS is dissolved in 0.85g dust technologies (material concentration 0.080mol/L) and 1.25g ethanol；Other and embodiment
Step 1 is consistent in 1.
2nd, it is identical with the step 2 of embodiment 1.
3rd, it is identical with the step 3 of embodiment 1.
4th, the sample obtained in 0.1g steps 3 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 60.56%, 75.37%；H2, CO highest selectivity be 87.32%, 95.42% respectively.
Embodiment 4
1st, 0.69g nickel acetates are weighed, nickel acetate is dissolved in 5.32g ethanol；It is other consistent with step 1 in embodiment 1.
2nd, it is identical with the step 2 of embodiment 1.
3rd, it is identical with the step 3 of embodiment 1.
4th, the sample obtained in 0.1g steps 3 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 61.14%, 74.77%；H2, CO highest selectivity be 87.87%, 91.45% respectively.
Embodiment 5
1st, PVP dissolves in 6.62g DMFs (DMF)；It is other consistent with step 1 in embodiment 1.
2nd, it is identical with the step 2 of embodiment 1.
3rd, it is identical with the step 3 of embodiment 1.
4th, the sample obtained in 0.1g steps 3 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 64.46%, 77.98%；H2, CO highest selectivity be 89.57%, 93.05% respectively.
Comparative example 1
1st, 2.55g commercialization silica is weighed respectively (Sigma-Aldrich companies, powder, 0.007 μm of particle diameter, compares table
Area 375m2/ g) and 2.2296g nickel nitrates, Ni/SiO is prepared using equi-volume impregnating load Ni2Catalyst.
2nd, 120 DEG C of the sample dry 16h, 700 DEG C of roasting 6h that will be obtained in 1.
3rd, the sample obtained in 0.1g steps 2 is taken to be placed in quartz ampoule, after 600 DEG C of reduction, at a temperature of 700 DEG C, by flow
Than 1:1:2 ventilating methanes, carbon dioxide and argon gas are reacted, and evaluating catalyst the results are shown in Table 1.CH4、CO2Maximum conversion point
It is not 58.29%, 64.87%；H2, CO highest selectivity be 81.81%, 87.43% respectively.
The performance evaluation of the methane carbon dioxide reformation catalyst of table 1.
Example in contrast table 1, the results showed that methane titanium dioxide prepared by the carrier loaded nickel of commercialization SiO 2 powder
Carbon reforming catalyst, CH4、CO2Initial activity it is relatively low, rapid catalyst deactivation.The present invention is prepared using electrostatic spinning technique
The methane carbon dioxide reformation catalyst of silica nano fibrous nickel-loaded, CH4、CO2Initial activity it is all very high, have simultaneously
There is good stability.It is clear that the made catalyst of the present invention is used for the anti-of methane and carbon dioxide catalytic reforming preparing synthetic gas
Ying Zhong, there is the advantages that catalytic activity is high, and anti-carbon performance is good, good stability.
Claims (6)
1. a kind of catalytic activity is high, anti-carbon performance is good, good stability methane carbon dioxide reformation Ni/SiO2The system of catalyst
Preparation Method, it is characterised in that the scattered Ni nano particles of silica nano fibrous upper load；Using electrostatic spinning technique system
Standby, step includes as follows：
(1) spinning precursor liquid is configured：Mass ratio is weighed as 1:(0.15-0.48):The tetraethyl orthosilicate of (0.02-0.48)
(TEOS), polyvinylpyrrolidone (PVP) and nickel salt, TEOS is then dissolved in mass ratio as 1:The diluted acid of (0.13-2.5) and
In alcohol mixeding liquid, PVP is dissolved in DMF (DMF) or is dissolved in mass ratio as 1:The DMF of (0.21-1)
In dimethyl sulfoxide (DMSO) (DMSO) mixed liquor, nickel salt is then dissolved in ethanol or/and water；After being completely dissolved, by these three solution point
Do not stir 8-14h at the uniform velocity, 0.5-2.5h is stirred after finally three solution are sufficiently mixed, obtain spinning precursor liquid；
(2) electrostatic spinning：The spinning precursor liquid of step (1) is fitted into syringe, then syringe is loaded on pusher,
Layer of metal paper tinsel is sticked on receiver, and rotating speed is 50-550r/min, voltage is adjusted to 12-28kV, and spinning solution push speed is
0.1-5ml/h, start spinning；
(3) 80-150 DEG C of the spinning dry 6-24h, 350-900 DEG C of roasting 2-8h for being collected into step (2) in metal foil；Roasting
After the completion of, collect sample；
When TEOS is dissolved in diluted acid and ethanol, TEOS mass percent concentrations 56.46-77.55%；PVP is dissolved in N, N- bis-
When in NMF (DMF) or in DMF (DMF) and dimethyl sulfoxide (DMSO) (DMSO), PVP mass percents
Concentration 8.56-45.25%；When nickel salt is then dissolved in ethanol or/and water, nickel salt mass percent concentration 5.16-73.32%；
Silica nano fibrous, average diameter 100-500nm, length is 0.1-500 μm, specific surface area 50-500m2/g。
2. according to the method for claim 1, it is characterised in that the nickel salt described in step (1) is nickel nitrate, nickel chloride or acetic acid
Nickel.
3. according to the method for claim 1, it is characterised in that the diluted acid described in step (1) is watery hydrochloric acid, dust technology or dilute sulphur
Acid；Its concentration is 0.055-0.184mol/L.
4. the high-efficiency methane CO 2 reformation Ni/SiO obtained according to any one of claim 1-3 preparation method2Catalyst, its
It is characterised by, the weight/mass percentage compositions of Ni in the catalyst are 3%-15%.
5. the high-efficiency methane CO 2 reformation Ni/SiO obtained according to any one of claim 1-3 preparation method2Catalyst is answered
With, it is characterised in that for methane reforming with carbon dioxide.
6. the high-efficiency methane CO 2 reformation Ni/SiO obtained according to any one of claim 1-3 preparation method2Catalyst is answered
With, it is characterised in that catalyst sample is placed in quartz ampoule, in hydrogen atmosphere after 300-1000 DEG C of reduction, at 600-1000 DEG C
At a temperature of, flow-rate ratio is passed through as 1:1:2 methane, carbon dioxide and argon gas, carry out methane carbon dioxide reformation.
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| CN105561999A (en) * | 2015-12-11 | 2016-05-11 | 北京化工大学 | Preparation method of Al2O3 fiber-loaded nickel-based catalyst |
| CN106391029B (en) * | 2016-10-21 | 2018-12-28 | 东南大学 | A kind of preparation method and application of carbon nano-fiber-double-metal composite catalyst |
| US20220220639A1 (en) | 2019-06-13 | 2022-07-14 | Forschungszentrum Jülich GmbH | Process for producing carbon fiber materials for separating co2 or nh3 from gas mixtures, carbon fiber materials and its use |
| CN113351239A (en) * | 2020-03-05 | 2021-09-07 | 华东理工大学 | Nickel-based pure silicon type molecular sieve catalyst and preparation method and application thereof |
| CN111346649B (en) * | 2020-04-30 | 2021-01-08 | 荷氢新能源科技(山东)有限公司 | Pd @ Ni-SNT/graphene hydrogen evolution catalyst and preparation method and application thereof |
| CN113351217B (en) * | 2021-07-05 | 2022-07-01 | 济南大学 | Preparation method and application of fluorite support body loaded Ni-based fiber catalyst |
| CN115155599B (en) * | 2022-04-11 | 2023-07-25 | 浙江氢邦科技有限公司 | Ni-in@SiO coated 2 -Al 2 O 3 Hollow mesoporous nano catalyst as well as preparation method and application thereof |
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