CN104511279A - Efficient methane and carbon dioxide reforming Ni/SiO2 catalyst and electrostatic spinning preparation method - Google Patents
Efficient methane and carbon dioxide reforming Ni/SiO2 catalyst and electrostatic spinning preparation method Download PDFInfo
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Abstract
The invention discloses an efficient methane and carbon dioxide reforming Ni/SiO2 catalyst and an electrospinning preparation method, and belongs to the technical field of catalyst preparation. Through electrospinning technique, an efficient silica nanofiber supported nickel nanoparticle catalyst can be prepared. The preparation method comprises the following steps: first preparing a spinning precursor solution, then electrospinning, and finally drying and roasting to prepare a finished product. The preparation method has the advantages of easily obtained raw materials, simple operation, and good controllability, and is conducive to industrialized enlargement. The catalyst used in reaction for preparation of synthesis gas by methane and carbon dioxide catalytic reforming, and has the advantages of high catalytic activity, good resistance to deposition of carbon, good stability and the like.
Description
Technical field
The present invention relates to a kind of methane carbon dioxide reformation Ni/SiO
2the method of catalyst preparing, adopts electrostatic spinning technique to prepare SiO
2the effective catalyst of nano-fibre supported Ni, belongs to catalyst preparation technical field.
Background technology
In recent years, the problem such as energy crisis and environmental pollution is subject to the extensive concern of society gradually.Day by day exhausted along with petroleum resources, the development and utilization of natural gas resource seems ever more important.Methane is the key component of natural gas, and its trans-utilization is mainly divided into directly conversion and indirect reformer.Direct conversion is then direct is chemical products by methane conversion, and process is simple, but implements more difficult.Methane conversion is first synthesis gas by indirect reformer, then is other chemical products by Synthetic holography, and process relative complex, but technology relative maturity, have more prospects for commercial application.Indirect reformer mainly comprises steam reformation, CO 2 reformation and partial oxidation reaction.Wherein, methane reforming with carbon dioxide can by CH
4, CO
2two kinds of main greenhouse gas are converted into the synthesis gas of applicable Fiscber-Tropscb synthesis and carbonylation synthesis, alleviation greenhouse effects while obtain alternative energy source, to promotion clean energy resource produce and protection of the environment significant.
Current most study and catalyst system and catalyzing closest to industrial applications is that nickel (Ni) is catalyst based.The unredeemed reason of economically viable industrial applications is that this reaction is strong endothermic process, must carry out at relatively high temperatures, and catalyst exists serious carbon distribution problem under corresponding reaction condition.Therefore, the key of research is that exploitation is active high under relative low temperature condition, good stability, the new and effective Ni base catalyst system and catalyzing that carbon accumulation resisting ability is strong.Research report, the use of nano-catalytic agent carrier, can improve the catalyst based anti-carbon performance of Ni (see Sizelimit of support particles in an oxide-supported metal catalyst:Nanocomposite Ni/ZrO
2for utilization of natural gas.Journal of PhysicalChemistry C, 2003, Vol.107, pp.5203-5207).Separately there is the nanometer confinement effect reported and show by phyllosilicate nanotube, can be structured in alcohol steam reformed reaction there is strong anti-sintering and strong anti-carbon performance Ni base catalyst system and catalyzing (see Sintering-resistantNi-based reforming catalysts obtained via the nanoconfinement effect.Chemical Communications, 2013, Vol.49,9383-9385.).Thus, prepare nano-carrier and confinement Ni base catalyst system and catalyzing by special preparation method to be expected to obtain new and effective methane carbon dioxide reformation catalyst.
Electrostatic spinning technique be fluid under high voltage electric field, flow and be out of shape, and then obtaining a kind of spining technology of fibrous material.Can be obtained the nanofiber of abundant species by this technology, and manufacturing installation is simple, spinning is with low cost, thus has extensive use in materials science field.But, electrostatic spinning technique is applied in the preparation of catalyst and but there is not yet wide coverage.Thus, the present invention attempts electrostatic spinning technique compared with traditional incipient impregnation method, prepares the efficient catalytic system of nanofiber confinement.Result shows, the SiO that the present invention is prepared by spining technology
2nanofiber specific area is large, high temperature resistant, mechanical strength is high, and it makes active component Ni have better dispersiveness as carrier.Ni/SiO
2nano-fiber catalyst catalytic activity in methane carbon dioxide reformation is high, and anti-carbon performance is good, good stability.
Summary of the invention
The object of the invention is to provide a kind of high-efficiency methane CO 2 reformation Ni/SiO
2the preparation method of catalyst and electrostatic spinning thereof.Make that it is high temperature resistant, mechanical strength is high, component Ni has better dispersiveness.Ni/SiO
2nano-fiber catalyst catalytic activity in methane carbon dioxide reformation is high, and anti-carbon performance is good, good stability.
For achieving the above object, technical scheme of the present invention is as follows.
A kind of high-efficiency methane CO 2 reformation Ni/SiO
2catalyst, is characterized in that, the Ni nano particle of silica nano fibrous upper load dispersion.
A kind of electrostatic spinning technique of the present invention prepares high-efficiency methane CO 2 reformation Ni/SiO
2the method of catalyst, is characterized in that, adopts electrostatic spinning technique to prepare the effective catalyst of the Ni nano particle of silica nano fibrous load dispersion.
Described catalyst preparation step comprises as follows:
(1) spinning precursor liquid is configured: taking mass ratio is 1:(0.15-0.48): the ethyl orthosilicate (TEOS) of (0.02-0.48), polyvinylpyrrolidone (PVP) and nickel salt, then TEOS being dissolved in mass ratio is 1:(0.13-2.5) diluted acid and alcohol mixeding liquid in, PVP is dissolved in N, in dinethylformamide (DMF) or to be dissolved in mass ratio be 1:(0.21-1) DMF and dimethyl sulfoxide (DMSO) (DMSO) mixed liquor in, nickel salt is then dissolved in ethanol or/and water; After dissolving completely, these three kinds of solution are at the uniform velocity stirred 8-14h respectively, stirs 0.5-2.5h after finally fully being mixed by three solution, obtain spinning precursor liquid; Aforesaid operations generally carries out at 5-60 DEG C of temperature.
(2) electrostatic spinning: the spinning precursor liquid of step (1) is loaded in syringe, again syringe is loaded on pusher, stick layer of metal paper tinsel on the receiver, and rotating speed is 50-550r/min, voltage is adjusted to 12-28kV, it is 0.1-5ml/h that spinning solution pushes speed, starts spinning;
(3) by spinning 80-150 DEG C of dry 6-24h, 350-900 DEG C of roasting 2-8h that step (2) is collected in metal forming; After roasting completes, collect sample.
Above-mentioned a kind of electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO
2the method of catalyst, the nickel salt described in preferred steps (1) is nickel nitrate, nickel chloride or nickel acetate etc.
Above-mentioned a kind of electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO
2the method of catalyst, the diluted acid described in preferred steps (1) is watery hydrochloric acid, dust technology or dilute sulfuric acid; Its concentration is generally 0.055-0.184mol/L.
When TEOS is dissolved in diluted acid and ethanol, preferred TESO mass percent concentration 56.46-77.55%; PVP be dissolved in DMF (DMF) or in DMF (DMF) and dimethyl sulfoxide (DMSO) (DMSO) time, preferred PVP mass percent concentration 8.56-45.25%; Nickel salt be then dissolved in ethanol or/and in water time, preferred nickel salt mass percent concentration 5.16-73.32%.
Above-mentioned a kind of electrostatic spinning technique is adopted to prepare high-efficiency methane CO 2 reformation Ni/SiO
2the method of catalyst, the carrier of the catalyst of preparation is silica nano fibrous, even thickness, and average diameter is 100-500nm, and length is 0.1-500 μm, and specific area is 50-500m
2/ g, there is high temperature resistant, mechanical strength advantages of higher.According to the method described above, the usage ratio of ethyl orthosilicate (TEOS), polyvinylpyrrolidone (PVP) and nickel salt is regulated, the high-efficiency methane CO 2 reformation Ni/SiO of preparation
2catalyst, preferred active component Ni mass percentage is in the catalyst 1%-30%, further preferred 3%-15%.
Above-mentioned a kind of electrostatic spinning technique prepares high-efficiency methane CO 2 reformation Ni/SiO
2the catalyst that the method for catalyst is obtained is used for methane reforming with carbon dioxide.
Get above-mentioned high-efficiency methane CO 2 reformation Ni/SiO
2catalyst sample is placed in quartz ampoule, in hydrogen atmosphere after 300-1000 DEG C of reduction, at 600-1000 DEG C of temperature, passes into methane, carbon dioxide and argon gas that flow-rate ratio is 1:1:2, carries out methane carbon dioxide reformation.
A kind of electrostatic spinning technique of the present invention prepares high-efficiency methane CO 2 reformation Ni/SiO
2the method advantage of catalyst is: method for preparing catalyst raw material is easy to get, simple to operate, and controllability is good, is beneficial to industrialization and amplifies.Silica nano fibrous carrier makes active component Ni have better dispersiveness.Catalyst is used in synthesizing gas by reforming methane with co 2 reaction, and have catalytic activity high, anti-carbon performance is good, the advantages such as good stability.
Accompanying drawing explanation
Fig. 1 is Ni/SiO prepared by the present invention
2hR-TEM figure (embodiment 1) of nano-fiber catalyst.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention, but the present invention is not limited to following examples.
Embodiment 1
1,4.7g ethyl orthosilicate (TEOS) and 1.1g polyvinylpyrrolidone (PVP) and 1.13g nickel nitrate is taken respectively, then TEOS is dissolved in 0.95g watery hydrochloric acid (material concentration 0.080mol/L) and 1.25g ethanol, PVP is then at 4.12g N, dissolve in dinethylformamide (DMF) and 2.50g dimethyl sulfoxide (DMSO) (DMSO), nickel nitrate is then dissolved in 1.82g ethanol; After dissolving completely, these three kinds of solution are placed on magnetic stirring apparatus respectively and at the uniform velocity stir 9h, finally three solution are fully mixed and be put in magnetic stirrer 0.5h, obtain spinning precursor liquid.Carry out at operating in 25 DEG C.
2, the mixed liquor obtained in 1 is loaded in syringe, then syringe is loaded on pusher, stick layer of metal paper tinsel on the receiver, and rotating speed is 80r/min.Voltage is adjusted to 12kV, and it is 1ml/h that spinning solution pushes speed, starts spinning.
3, the sample 120 DEG C of dry 16h will obtained in 2,700 DEG C of roasting 6h.
4, get the sample obtained in 0.1g step 3 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 65.34%, 79.01% respectively; H
2, CO most high selectivity be 90.36%, 98.21% respectively.
Embodiment 2
1, nickel nitrate is dissolved in 1.82g water; Other is consistent with step 1 in embodiment 1.
2, identical with embodiment 1 step 2.
3, identical with embodiment 1 step 3.
4, get the sample obtained in 0.1g step 3 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 64.97%, 78.23% respectively; H
2, CO most high selectivity be 89.98%, 96.28% respectively.
Embodiment 3
1, TEOS is dissolved in 0.85g dust technology (material concentration 0.080mol/L) and 1.25g ethanol; Other is consistent with step 1 in embodiment 1.
2, identical with embodiment 1 step 2.
3, identical with embodiment 1 step 3.
4, get the sample obtained in 0.1g step 3 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 60.56%, 75.37% respectively; H
2, CO most high selectivity be 87.32%, 95.42% respectively.
Embodiment 4
1, take 0.69g nickel acetate, nickel acetate is dissolved in 5.32g ethanol; Other is consistent with step 1 in embodiment 1.
2, identical with embodiment 1 step 2.
3, identical with embodiment 1 step 3.
4, get the sample obtained in 0.1g step 3 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 61.14%, 74.77% respectively; H
2, CO most high selectivity be 87.87%, 91.45% respectively.
Embodiment 5
1, PVP dissolves in 6.62g DMF (DMF); Other is consistent with step 1 in embodiment 1.
2, identical with embodiment 1 step 2.
3, identical with embodiment 1 step 3.
4, get the sample obtained in 0.1g step 3 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 64.46%, 77.98% respectively; H
2, CO most high selectivity be 89.57%, 93.05% respectively.
Comparative example 1
1,2.55g commercialization silica (Sigma-Aldrich company, powder, particle diameter 0.007 μm, specific area 375m is taken respectively
2/ g) and 2.2296g nickel nitrate, adopt equi-volume impregnating load Ni to prepare Ni/SiO
2catalyst.
2, the sample 120 DEG C of dry 16h will obtained in 1,700 DEG C of roasting 6h.
3, get the sample obtained in 0.1g step 2 and be placed in quartz ampoule, after 600 DEG C of reduction, at 700 DEG C of temperature, react by flow-rate ratio 1:1:2 ventilating methane, carbon dioxide and argon gas, evaluating catalyst the results are shown in Table 1.CH
4, CO
2maximum conversion be 58.29%, 64.87% respectively; H
2, CO most high selectivity be 81.81%, 87.43% respectively.
The performance evaluation of table 1. methane carbon dioxide reformation catalyst
Example in contrast table 1, result shows methane carbon dioxide reformation catalyst prepared by the carrier loaded nickel of commercialization SiO 2 powder, CH
4, CO
2initial activity lower, rapid catalyst deactivation.The present invention adopts electrostatic spinning technique to prepare the methane carbon dioxide reformation catalyst of silica nano fibrous nickel-loaded, CH
4, CO
2initial activity all very high, there is good stability simultaneously.Obviously, institute of the present invention controlling catalyst is used in the reaction of methane and carbon dioxide catalytic reforming preparing synthetic gas, and have catalytic activity high, anti-carbon performance is good, the advantages such as good stability.
Claims (10)
1. a high-efficiency methane CO 2 reformation Ni/SiO
2catalyst, is characterized in that, the Ni nano particle of silica nano fibrous upper load dispersion.
2. according to a kind of high-efficiency methane CO 2 reformation Ni/SiO of claim 1
2catalyst, is characterized in that, Ni mass percentage is in the catalyst 1%-30%.
3. according to a kind of high-efficiency methane CO 2 reformation Ni/SiO of claim 1
2catalyst, is characterized in that, Ni mass percentage is in the catalyst 3%-15%.
4. according to a kind of high-efficiency methane CO 2 reformation Ni/SiO of claim 1
2catalyst, is characterized in that, silica nano fibrous, and average diameter is 100-500nm, and length is 0.1-500 μm, and specific area is 50-500m
2/ g.
5. the method for the arbitrary catalyst of preparation described in claim 1-4, is characterized in that, adopt electrostatic spinning technique preparation, step comprises as follows:
(1) spinning precursor liquid is configured: taking mass ratio is 1:(0.15-0.48): the ethyl orthosilicate (TEOS) of (0.02-0.48), polyvinylpyrrolidone (PVP) and nickel salt, then TEOS being dissolved in mass ratio is 1:(0.13-2.5) diluted acid and alcohol mixeding liquid in, PVP is dissolved in N, in dinethylformamide (DMF) or to be dissolved in mass ratio be 1:(0.21-1) DMF and dimethyl sulfoxide (DMSO) (DMSO) mixed liquor in, nickel salt is then dissolved in ethanol or/and water; After dissolving completely, these three kinds of solution are at the uniform velocity stirred 8-14h respectively, stirs 0.5-2.5h after finally fully being mixed by three solution, obtain spinning precursor liquid;
(2) electrostatic spinning: the spinning precursor liquid of step (1) is loaded in syringe, again syringe is loaded on pusher, stick layer of metal paper tinsel on the receiver, and rotating speed is 50-550r/min, voltage is adjusted to 12-28kV, it is 0.1-5ml/h that spinning solution pushes speed, starts spinning;
(3) by spinning 80-150 DEG C of dry 6-24h, 350-900 DEG C of roasting 2-8h that step (2) is collected in metal forming; After roasting completes, collect sample.
6. according to the method for claim 5, it is characterized in that, the nickel salt described in step (1) is nickel nitrate, nickel chloride or nickel acetate.
7. according to the method for claim 5, it is characterized in that, the diluted acid described in step (1) is watery hydrochloric acid, dust technology or dilute sulfuric acid; Its concentration is 0.055-0.184mol/L.
8., according to the method for claim 5, it is characterized in that, when TEOS is dissolved in diluted acid and ethanol, TESO mass percent concentration 56.46-77.55%; PVP be dissolved in DMF (DMF) or in DMF (DMF) and dimethyl sulfoxide (DMSO) (DMSO) time, PVP mass percent concentration 8.56-45.25%; Nickel salt be then dissolved in ethanol or/and in water time, nickel salt mass percent concentration 5.16-73.32%.
9. the arbitrary catalyst described in claim 1-4 is used for methane reforming with carbon dioxide.
10. the arbitrary catalyst described in claim 1-4 is used for methane reforming with carbon dioxide, it is characterized in that, catalyst sample is placed in quartz ampoule, in hydrogen atmosphere after 300-1000 DEG C of reduction, at 600-1000 DEG C of temperature, pass into methane, carbon dioxide and argon gas that flow-rate ratio is 1:1:2, carry out methane carbon dioxide reformation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561999A (en) * | 2015-12-11 | 2016-05-11 | 北京化工大学 | Preparation method of Al2O3 fiber-loaded nickel-based catalyst |
| CN106391029A (en) * | 2016-10-21 | 2017-02-15 | 东南大学 | Preparation method and application of carbon nanofiber-bimetal composite catalyst |
| CN111346649A (en) * | 2020-04-30 | 2020-06-30 | 青岛品泰新材料技术有限责任公司 | Pd @ Ni-SNT/graphene hydrogen evolution catalyst and preparation method and application thereof |
| WO2020249441A1 (en) | 2019-06-13 | 2020-12-17 | Forschungszentrum Jülich GmbH | Production method for carbon fibre material for separating co2 or nh3 from gas mixtures, carbon fibre material, and use thereof |
| 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 |
| CN113351217A (en) * | 2021-07-05 | 2021-09-07 | 济南大学 | Preparation method and application of fluorite support body loaded Ni-based fiber catalyst |
| 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 |
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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 |
| CN106391029A (en) * | 2016-10-21 | 2017-02-15 | 东南大学 | Preparation method and application of carbon nanofiber-bimetal composite 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 |
| WO2020249441A1 (en) | 2019-06-13 | 2020-12-17 | Forschungszentrum Jülich GmbH | Production method for carbon fibre material for separating co2 or nh3 from gas mixtures, carbon fibre material, and use thereof |
| 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 |
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| 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 |
| CN113351217A (en) * | 2021-07-05 | 2021-09-07 | 济南大学 | Preparation method and application of fluorite support body loaded Ni-based fiber catalyst |
| 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 |
| 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 |
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