CN102694186A - Method for improving catalytic performance of Ru catalyst to CO methanation - Google Patents
Method for improving catalytic performance of Ru catalyst to CO methanation Download PDFInfo
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- CN102694186A CN102694186A CN2012101779288A CN201210177928A CN102694186A CN 102694186 A CN102694186 A CN 102694186A CN 2012101779288 A CN2012101779288 A CN 2012101779288A CN 201210177928 A CN201210177928 A CN 201210177928A CN 102694186 A CN102694186 A CN 102694186A
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- methanation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a method for improving the catalytic performance of Ru catalyst to CO methanation. The method comprises the following steps: Ru nano particles are loaded on a TiO2 semi-conductor oxide carrier with a light absorption function at first to manufacture a load-type Ru catalyst and then ultraviolet light is led into a reaction system in which the catalyst catalyzes CO methanation. Compared with conventional thermal catalytic reaction (without ultraviolet light), the ultraviolet light can remarkably promote the catalytic performance of the Ru load-type thermal catalyst to CO methanation. The photo-thermal coupling method greatly lowers the service temperature of the catalyst, is simple and feasible, and facilitates removing CO and converting CO2 in a fuel cell under the hydrogen-rich atmosphere.
Description
Technical field
The invention belongs to catalysis CO methanation reaction field, specifically relate to a kind of method that improves Ru catalyst CO methanation performance through the photo-thermal coupling.
Background technology
Fuel cell has caused widely as a kind of energy sources efficient, cleaning that can be directly converts chemical energy into electrochemical energy to be paid close attention to.Owing to there is not a caused thermal loss of mechanical movement in the internal combustion engine power conversion, so with respect to the power source of routine, like fuel gas generation, steam turbine power generation and diesel power generation, the energy conversion efficiency of fuel cell is up to 90%.Fuel cell mainly comprises alkali formula fuel cell, Proton Exchange Membrane Fuel Cells, phosphoric acid fuel cell, molten carbonate fuel cell and solid oxidation polymer fuel cell.In these batteries, Proton Exchange Membrane Fuel Cells (PEMFC) with its higher energy density, start fast and higher advantages such as conversion efficiency have attracted numerous attentivenesss in the supply of electric motor car and dwelling house electric power.The hydrogen source of Proton Exchange Membrane Fuel Cells is the hydrogen rich gas that makes through methane vapor reforming, wherein approximately contains 10% CO, carries out removing of CO subsequently, comprises superheated vapor transformationreation and low temperature water gas shift reation, and the concentration of CO is reduced to about 1%.Yet the Pt electrode of PEMFC has high sensitiveness for CO, causes platinum electrode to be poisoned thereby the CO of minute quantity also can produce very high overpotential.Therefore, prevent it and poison, must be to 10ppm with the CO deep removal in the reformation gas, even if the alloy electrode of anti-CO, the concentration of CO still need be reduced to below the 100ppm.
At present, the removal method of CO mainly contains physics removal method and chemical stripping method: the physics removal method mainly comprises pressure swing adsorption method, membrane separation process and solvent absorption; Chemical stripping method mainly comprises steam conversion reaction, methanation reaction and CO selective oxidation reaction.Consider that from technological operation the most complex process of physics removal method, bulky generally should not adopt, so chemical stripping method has obtained research widely.
For the steam conversion reaction, owing to receive kinetic limitation, the concentration of CO is difficult to reduce to below the 10ppm.The selective oxidation method is considered to more effective CO removal method usually, but this method needs in reaction system extra logical people's air or pure oxygen as oxidant, and because selection of catalysts property is limited, often causes a large amount of H easily
2By simultaneous oxidation.By contrast, the methanation method need not to add in addition reactant, and flow process is simple, for the reformation gas that contains trace amounts of CO, consumes H
2Amount in fact only account for H
2A total amount part seldom.
The research of relevant methanation catalyst reaches its maturity, and wherein Ni, Ru, Fe are the active metal components of studying at most, and particularly more patent has appearred in the catalyst of relevant Ru, and the methanation of Ni-Cu alloy as catalyst also once had report.Yet methanation reaction still has its limitation: still narrower even if ⑴ in laboratory scale, has the temperature range of higher CO conversion ratio; ⑵ reaction temperature is still higher relatively, and this can cause the generation of the back reaction of steam conversion reaction; ⑶ if temperature control is improper CO can take place
2Methanation reaction, and this can lot of consumption H
2⑷ the CO concentration of air inlet must be enough low, and this just needs a large amount of steam conversion catalysts.Therefore, it is significant how to improve the low temperature active and the CO methanation selectivity of this type of catalyst.
Summary of the invention
The present invention provides the method that improves Ru catalyst CO methanation performance through the photo-thermal coupling, and its purpose is to overcome the deficiency of above-mentioned simple thermocatalytic CO methanation, improves the low temperature active and the CO methanation selectivity of this type of catalyst.The Ru loaded catalyst that the present invention is directed to routine needs the problem of ability catalysis CO methanation under higher temperature; Selection has the active conductor oxidate of optical excitation and prepares the Ru loaded catalyst as carrier, in course of reaction, introduces ultraviolet lighting, thereby significantly improves the performance of its catalysis CO methanation; Greatly reduce the serviceability temperature of catalyst; Reduced energy consumption, and this method for preparing catalyst is simple, helps applying.
The present invention implements through following technical scheme: make support type Ru catalyst earlier, then in the reaction system of support type Ru catalyst CO methanation, introduce ultraviolet lighting.
Above-mentioned reaction system is a normal pressure continuous flow device; This normal pressure continuous flow device comprises the quartz glass reactor that has air inlet and gas outlet; The inner chamber of said quartz glass reactor is filled with support type Ru catalyst; The all sides of said quartz glass reactor are provided with heater and are used to excite the catalyst carrier of support type Ru catalyst to produce the UV-light luminous device of photoresponse, and the ultraviolet light that said UV-light luminous device sends can see through quartz glass reactor and arrive support type Ru catalyst surface.
Above-mentioned support type Ru catalyst is with TiO
2For carrier, Ru nano particle are the high-dispersion loading type catalyst of active component, and the content of active component Ru is 0.2 ~ 5.0wt% in the said support type Ru catalyst, and all the other are TiO
2Carrier.Concrete preparation process is following:
Step (1): (press patent: 98115808.0 preparations), ultrasonic dispersion 5min～10min stirs 10～24h under the room temperature, dries down for 60～120 ℃, and the solid gel that obtains about heat treatment 3h, grinds at a certain temperature, promptly gets TiO with TiO 2 sol
2Carrier.
Step (2): the carrier that step (1) is made places a certain amount of RuCl
3In the solution, dipping 2 ~ 12h, 60～120 ℃ of oven dry are down dried thing with gained and are placed the NaBH that contains NaOH
4In the solution, stir 2 ~ 6h under the room temperature, centrifugal, behind the unnecessary ion of deionized water flush away, 50 ~ 80 ℃ of following vacuumizes make the Ru loaded catalyst.
Wherein, RuCl
3The mass concentration that contains Ru in the solution is 0.01 ~ 1g/ml, the described NaBH that contains NaOH
4In the solution, NaBH
4The concentration of solution is 0.05 ~ 0.25mol/L, and the concentration of NaOH is 0.05 ~ 0.25mol/L.
The method of raising of the present invention Ru catalyst CO methanation performance can be used in the fuel cell under the hydrogen rich gas atmosphere CO in the removal of CO and atmosphere
2Conversion.
The invention has the advantages that: (1) the present invention is with TiO
2Conductor oxidate is as carrier; Make full use of semiconductor and under the illumination of certain wavelength, can excite the characteristic that produces electron hole pair; When Ru is carried on this based semiconductor; Light induced electron can be transferred on the low Ru metal of Fermi level from the high semiconductor of Fermi level, thereby improves the electric surface density of reactive metal Ru, is beneficial to CO or CO
2Absorption and activation, and then promote the methanation of CO.Compare with simple heat catalysis, photo-thermal coupled reaction of the present invention can reduce reaction temperature, thereby has the effect of the energy consumption of minimizing.
(2) preparation method of the present invention and application operating method are simple, help applying.
Description of drawings
Fig. 1 is embodiment 1 gained 1wt%Ru/TiO
2Sem photograph.
Fig. 2 is embodiment 1 gained 1wt%Ru/TiO
2Transmission electron microscope picture.
Fig. 3 is embodiment 1 gained TiO
2And 1wt%Ru/TiO
2XRD figure.
Fig. 4 is embodiment 1 gained 1wt%Ru/TiO
2Ultraviolet-spectrogram diffuses.
Fig. 5 is a reaction system sketch of the present invention.
Description of drawings: can find out that from Fig. 1 and Fig. 2 the Ru particle in catalyst about 5 nm is dispersed in the TiO about 20 nm
2Carrier surface; As can be seen from Figure 3, because Ru content is low, TiO has only appearred in the XRD spectra of catalyst
2The diffraction cutting edge of a knife or a sword, this has explained that also the Ru dispersion of nano-particles is even in the catalyst; As can be seen from Figure 4, this catalyst is except existing TiO
2Light absorption outside, also have the light absorption of Ru particle; Among Fig. 5: 1. being air inlet, 2. is the gas outlet, 3. is heater; 4. be quartz reactor; 5. being catalyst granules, 6. is ultraviolet source), reactor feed gas by 1. get into catalyst granules is housed reactor 4. in; 3. heater through by the control of temperature programming temperature controller provides temperature required to reactor, and 6. reactor is imposed ultraviolet lighting.
Embodiment
For letting the above-mentioned feature and advantage of the present invention can be more obviously understandable, hereinafter is special lifts embodiment, and conjunction with figs., elaborate as follows, but the present invention is not limited to this.
Embodiment 1
Ru/TiO
2Preparation of catalysts
(patent No.: 98115808.0) 80 ℃ of oven dry down, the solid gel that obtains is about 450 ℃ of following heat treatment 3h, and grinding is sieved, and promptly gets TiO with titanium glue
2Carrier.Take by weighing 1g TiO
2(granular size is 60 ~ 80 orders) places beaker, adds 1ml and contains the RuCl that Ru concentration is 0.005g/ml
3Solution (1g RuCl
3HCL solution constant volume with 100ml 0.1mol/ml), shakes up hold over night, 80 ℃ of oven for drying.Take out, the concentration that dropwise drips the NaOH that contains 0.1mol/L that at present joins is the NaBH of 0.1mol/L
4Solution (placing ice-water bath), it is limpid until upper solution to vibrate while dripping, and filters, and is attached to the unnecessary ion on the deposition with the distilled water flush away.Gained is deposited in vacuum drying under the room temperature, promptly gets the Ru/TiO of 0.5 wt%
2Catalyst.
According to above-mentioned steps, through changing RuCl
3The concentration of solution makes the Ru/TiO of 0.25 wt%, 1.0 wt%, 1.5wt% and 2.0 wt% respectively
2Catalyst.
The performance evaluation of catalyst
The performance evaluation of embodiment 1 prepared catalyst CO methanation is carried out on the normal pressure continuous flow reaction unit of the band panel heater that designs voluntarily.About 0.6g catalyst loading is in the dull and stereotyped reactor of quartz (long 30mm * wide 15mm * high 1mm), and catalyst particle size is about 0.2 ~ 0.3mm (60 ~ 80 order), CO and H in the reaction gas
2Content be fixed as 1V% and 50V% respectively, He gas replenishes gas, the about 100mL/min of reaction gas overall flow rate as balance.Reaction temperature is regulated and control by the temperature programming temperature controller.Adopt CO, CH in the Agilent 4890D type gas chromatograph timing on-line analysis atmosphere
4, CO
2And H
2Concentration, detector is TCD and FID, packed column is TDX-01, negate answers 2 hours result to calculate CO conversion ratio and CH
4Selectivity.
The CO conversion ratio calculates with formula: C=(V
InCO-V
OutCO)/V
InCO* 100%
CH
4The selective use formula is calculated: S=V
OutCH4/ (V
InCO-V
OutCO) * 100%
In the formula, C is the conversion ratio of CO, and S is CH
4Selectivity; V
InCOAnd V
OutCOBe respectively air inlet and give vent to anger in CO content (V%), V
OutCH4Be the CH in the effluent gases
4Content (V%).
In this way, estimated the performance of the catalysis CO methanation of various catalyst respectively, its result is as shown in the table:
Show that by result in the last table for each catalyst, than the reaction condition of pure heat, under the photo-thermal coupling, the conversion ratio of CO all has raising in various degree, and the selectivity under the also purer thermal rection condition of the selectivity of CO methanation is high.It is thus clear that the illumination effect can improve the CO methanation activity and the methanation selectivity of this type of catalyst.
Claims (8)
1. a method that improves Ru catalyst CO methanation performance comprises and makes support type Ru catalyst, it is characterized in that: in the reaction system of support type Ru catalyst CO methanation, introduce ultraviolet lighting.
2. the method for raising Ru catalyst CO methanation performance according to claim 1; It is characterized in that: said reaction system is a normal pressure continuous flow device; This normal pressure continuous flow device comprises the quartz glass reactor that has air inlet and gas outlet; The inner chamber of said quartz glass reactor is filled with support type Ru catalyst; The all sides of said quartz glass reactor are provided with heater and are used to excite the catalyst carrier of support type Ru catalyst to produce the UV-light luminous device of photoresponse, and the ultraviolet light that said UV-light luminous device sends can see through quartz glass reactor and arrive support type Ru catalyst surface.
3. the method for raising Ru catalyst CO methanation performance according to claim 1, it is characterized in that: said support type Ru catalyst is with TiO
2For carrier, Ru nano particle is the high-dispersion loading type catalyst of active component.
4. according to the method for claim 1,2 or 3 described raising Ru catalyst CO methanation performances, it is characterized in that: the content of active component Ru is 0.2 ~ 5.0wt% in the said support type Ru catalyst, and all the other are TiO
2Carrier.
5. the method for raising Ru catalyst CO methanation performance according to claim 4, it is characterized in that: said support type Ru Preparation of catalysts step was divided into for two steps, and step (1) utilizes sol-gal process to make TiO
2Carrier; The TiO that step (2) utilizes deposition-precipitation method to make in step (1)
2Load active component Ru makes TiO on the carrier
2Support type Ru catalyst.
6. the method for raising Ru catalyst CO methanation performance according to claim 5, it is characterized in that: said step (2) is: with the TiO of moulding
2Carrier places a certain amount of RuCl3 solution, dipping 2～12h, and 60～120 ℃ of oven dry are down dried thing with gained and are placed the NaBH that contains NaOH
4In the solution, stir 2～6h under the room temperature, centrifugal, behind the unnecessary ion of deionized water flush away, 50～80 ℃ of following vacuumizes make TiO
2Support type Ru catalyst.
7. the method for raising Ru catalyst CO methanation performance according to claim 6 is characterized in that: described RuCl
3The mass concentration that contains Ru in the solution is 0.01～1g/ml, the described NaBH that contains NaOH
4In the solution, NaBH
4The concentration of solution is 0.05～0.25mol/L, and the concentration of NaOH is 0.05～0.5mol/L.
8. according to claim 1,2,3,5,6 and 7 described raising Ru catalyst CO methanation performance methodology, it is characterized in that: the method for described raising Ru catalyst CO methanation is applied to the removal of CO under the hydrogen rich gas atmosphere in the fuel cell.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013477A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院过程工程研究所 | Mixed phase titanium dioxide loaded ruthenium catalyst for catalyzing and oxidizing VOCs, preparation method therefor and uses thereof |
| CN107519867A (en) * | 2017-09-14 | 2017-12-29 | 江西省科学院应用化学研究所 | A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane |
| CN110624557A (en) * | 2019-10-21 | 2019-12-31 | 福州大学 | Co-based catalyst for photo-thermal coupling catalysis of CO methanation |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN112619644A (en) * | 2021-01-14 | 2021-04-09 | 福州大学 | Ru-based catalyst with tetragonal barium titanate as carrier and preparation and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013477A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院过程工程研究所 | Mixed phase titanium dioxide loaded ruthenium catalyst for catalyzing and oxidizing VOCs, preparation method therefor and uses thereof |
| CN107519867A (en) * | 2017-09-14 | 2017-12-29 | 江西省科学院应用化学研究所 | A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane |
| CN107519867B (en) * | 2017-09-14 | 2020-05-15 | 江西省科学院应用化学研究所 | Preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene |
| CN110624557A (en) * | 2019-10-21 | 2019-12-31 | 福州大学 | Co-based catalyst for photo-thermal coupling catalysis of CO methanation |
| CN110624557B (en) * | 2019-10-21 | 2021-09-24 | 福州大学 | Co-based catalyst for photo-thermal coupling catalysis of CO methanation |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN112117020B (en) * | 2020-09-09 | 2022-11-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN112619644A (en) * | 2021-01-14 | 2021-04-09 | 福州大学 | Ru-based catalyst with tetragonal barium titanate as carrier and preparation and application thereof |
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