CN102694186B - 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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- CN102694186B CN102694186B CN201210177928.8A CN201210177928A CN102694186B CN 102694186 B CN102694186 B CN 102694186B CN 201210177928 A CN201210177928 A CN 201210177928A CN 102694186 B CN102694186 B CN 102694186B
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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 being improved Ru catalyst CO methanation performance by photo-thermal coupling.
Background technology
Fuel cell has caused as a kind of efficient, clean energy sources that directly chemical energy can be converted to electrochemical energy and has paid close attention to widely.Thermal loss in changing owing to not having internal combustion energy caused by mechanical movement, so relative to the power source of routine, as 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) to start and the advantage such as higher conversion efficiency has attracted numerous attentivenesss in the supply of electric motor car and house power with its higher energy density, fast.The hydrogen source of Proton Exchange Membrane Fuel Cells is by the obtained hydrogen rich gas of methane vapor reforming, and wherein approximately contain the CO of 10%, carry out removing of CO subsequently, comprise superheated vapor transformationreation and low temperature water gas shift reation, the concentration of CO reduces to about 1%.But the Pt electrode of PEMFC has high sensitiveness for CO, the CO of minute quantity also can produce very high overpotential thus cause platinum electrode poisoning.Therefore, it be prevented poisoning, must by the CO deep removal in reformed gas to below 10ppm, even if the alloy electrode of resistance to CO, the concentration of CO still needs to be down to below 100ppm.
At present, the removal method of CO mainly contains physics removal method and chemical stripping method: 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 from technological operation, the most complex process of physics removal method, bulky, generally should not adopt, study widely so chemical stripping method obtains.
For steam conversion reaction, owing to limiting by dynamics, the concentration of CO is difficult to be down to below 10ppm.Selective oxidation method is considered to more effective CO minimizing technology usually, but this method additionally need lead to people's air or pure oxygen as oxidant in reaction system, and due to the selectivity of catalyst limited, often easily cause a large amount of H
2by simultaneous oxidation.By contrast, methanation is without the need to adding reactant in addition, and flow process is simple, for the reformed gas containing trace amounts of CO, consumes H
2amount in fact only account for H
2the part that total amount is little.
The research of involving methane catalyst reaches its maturity, and wherein Ni, Ru, Fe are the active metal components studying at most, and particularly about more patent has appearred in the catalyst of Ru, the methanation of Ni-Cu alloy as catalyst also once had report.But methanation reaction still has its limitation: even if (1) in laboratory scale, the temperature range with higher CO conversion ratio is still narrower; (2) reaction temperature is still relatively high, and this can cause the generation of the back reaction of steam conversion reaction; (3), if temperature control is improper, CO can be there is
2methanation reaction, and this can consume H in a large number
2; (4) the CO concentration of air inlet is sufficiently low, and this just needs a large amount of steam conversion catalysts.Therefore, the low temperature active and the CO methanation selectivity that how to improve this type of catalyst are significant.
Summary of the invention
The invention provides the method being improved Ru catalyst CO methanation performance by photo-thermal coupling, its object is to the deficiency overcoming above-mentioned simple thermocatalytic CO methanation, improve low temperature active and the CO methanation selectivity of this type of catalyst.The present invention is directed to that conventional Ru loaded catalyst needs at relatively high temperatures could the problem of catalysis CO methanation, the conductor oxidate selecting there is optical excitation activity as carrier to prepare Ru loaded catalyst, ultraviolet lighting is introduced in course of reaction, thus significantly improve the performance of its catalysis CO methanation, greatly reduce the serviceability temperature of catalyst, reduce energy consumption, and this method for preparing catalyst is simple, is conducive to applying.
The present invention implements by following technical solution: first obtained supported Ru catalysts, then in the reaction system of supported Ru catalysts catalysis CO methanation, introduces ultraviolet lighting.
Above-mentioned reaction system is normal pressure continuous flow device, this normal pressure continuous flow device comprises the quartz glass reactor with air inlet and gas outlet, the inner chamber of described quartz glass reactor is filled with supported Ru catalysts, described quartz glass reactor week, side was provided with heater and the UV-light luminous device for exciting the catalyst carrier of supported Ru catalysts to produce photoresponse, and the ultraviolet light that described UV-light luminous device sends can arrive supported Ru catalysts surface through quartz glass reactor.
Above-mentioned supported Ru catalysts is with TiO
2for the high-dispersion loading type catalyst that carrier, Ru nano particle are active component, and in described supported Ru catalysts, the content of active component Ru is 0.2 ~ 5.0wt%, and all the other are TiO
2carrier.Concrete preparation process is as follows:
Step (1): by TiO 2 sol (by patent: 98115808.0 preparations), ultrasonic disperse 5min ~ 10min, stirred at ambient temperature 10 ~ 24h, dry at 60 ~ 120 DEG C, the solid gel obtained heat treatment about 3h at a certain temperature, and grinding, obtains TiO
2carrier.
Step (2): the carrier that step (1) is obtained is placed in a certain amount of RuCl
3in solution, dipping 2 ~ 12h, dries at 60 ~ 120 DEG C, gained drying object is placed in the NaBH containing NaOH
4in solution, stirred at ambient temperature 2 ~ 6h, centrifugal, after deionized water washes away excess ions, vacuumize at 50 ~ 80 DEG C, obtained Ru loaded catalyst.
Wherein, RuCl
3mass concentration containing Ru in solution is 0.01 ~ 1g/ml, the described NaBH containing NaOH
4in solution, NaBH
4the concentration of solution is the concentration of 0.05 ~ 0.25mol/L, NaOH is 0.05 ~ 0.25mol/L.
The method of raising Ru catalyst CO methanation performance of the present invention can be used for CO in the removal of CO under hydrogen rich gas atmosphere in fuel cell and air
2conversion.
The invention has the advantages that: (1) the present invention is with TiO
2conductor oxidate is as carrier, take full advantage of semiconductor and can excite the feature producing electron hole pair under the illumination of certain wavelength, when Ru is carried on this based semiconductor, light induced electron can be transferred to the low Ru metal of Fermi level from the semiconductor that Fermi level is high, thus improve the electric surface density of active metal Ru, be beneficial to CO or CO
2absorption and activation, and then promote the methanation of CO.Compared with simple heat catalysis, photo-thermal coupled reaction of the present invention can reduce reaction temperature, thus has and reduces energy consumption effect.
(2) preparation method of the present invention and application operating method simple, be conducive to applying.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained 1wt%Ru/TiO
2scanning electron microscope (SEM) 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-diffuse spectrogram.
Fig. 5 is reaction system sketch of the present invention.
Accompanying drawing illustrates: as can be seen from Fig. 1 and Fig. 2, and the Ru particle dispersion of about 5 nm is at the TiO of about 20 nm in the catalyst
2carrier surface; As can be seen from Figure 3, because Ru content is low, in the XRD spectra of catalyst, only there is TiO
2diffraction cutting edge of a knife or a sword, this also illustrates being uniformly dispersed of Ru particle in catalyst; As can be seen from Figure 4, except there is TiO in this catalyst
2light absorption outside, also there is the light absorption of Ru particle; In Fig. 5: be 1. air inlet, 2. be gas outlet, 3. be heater, 4. be quartz reactor, 5. being catalyst granules, is 6. ultraviolet source), reactor feed gas by 1. enter catalyst granules is housed reactor 4. in, 3. provide temperature required to reactor by the heater controlled by temperature programming temperature controller, and 6. ultraviolet lighting is imposed to reactor.
Embodiment
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below, and coordinate accompanying drawing, be described in detail below, but the present invention is not limited to this.
Embodiment 1
Ru/TiO
2the preparation of catalyst
By the titanium glue (patent No.: 98115808.0) dry at 80 DEG C, the solid gel obtained heat treatment about 3h at 450 DEG C, grinding is sieved, and obtains TiO
2carrier.Take 1g TiO
2(granular size is 60 ~ 80 orders) is placed in beaker, and adding 1ml containing Ru concentration is the RuCl of 0.005g/ml
3solution (1g RuCl
3hCL solution constant volume with 100ml 0.1mol/ml), shake up, hold over night, 80 DEG C of oven for drying.Take out, the concentration dropwise dripping the NaOH containing 0.1mol/L now joined is the NaBH of 0.1mol/L
4solution (being placed in ice-water bath), the vibration of dropping limit, limit, until upper solution is limpid, is filtered, is washed away the excess ions be attached in precipitation with distilled water.Gained is deposited in ambient temperature in vacuum to dry, obtains the Ru/TiO of 0.5 wt%
2catalyst.
According to above-mentioned steps, by changing RuCl
3the concentration of solution, the respectively Ru/TiO of obtained 0.25 wt%, 1.0 wt%, 1.5wt% and 2.0 wt%
2catalyst.
Embodiment 2
The performance evaluation of catalyst
The performance evaluation of the catalyst CO methanation obtained by embodiment 1 is carried out on the normal pressure continuous flow reaction unit of the band panel heater of designed, designed.About 0.6g Catalyst packing is in quartzy stacked rectangular capsules (long 30mm × wide 15mm × high 1mm), and catalyst particle size is about 0.2 ~ 0.3mm(60 ~ 80 order), CO and H in reaction gas
2content be fixed as 1V% and 50V% respectively, He gas as balance supplement gas, reaction gas overall flow rate is about 100mL/min.Reaction temperature is regulated and controled by temperature programming temperature controller.Adopt CO, CH in Agilent 4890D type gas chromatograph timing on-line analysis atmosphere
4, CO
2and H
2concentration, detector is TCD and FID, and packed column is TDX-01, and the result that negate is answered 2 hours calculates CO conversion ratio and CH
4selectivity.
The following formulae discovery of CO conversion ratio: C=(V
inCO-V
outCO)/V
inCO× 100%
CH
4the following formulae discovery of selective use: S=V
outCH4/ (V
inCO-V
outCO) × 100%
In formula, C is the conversion ratio of CO, and S is CH
4selectivity; V
inCOand V
outCObe respectively air inlet and the CO content (V%) in giving vent to anger, V
outCH4for the CH in effluent gases
4content (V%).
In this way, have rated the performance of the catalysis CO methanation of various catalyst respectively, its result is as shown in the table:
Shown by result in upper table, for each catalyst, compared to the reaction condition of pure heat, under photo-thermal coupling, the conversion ratio of CO has raising in various degree, and the selectivity of the selectivity of CO methanation also under purer thermal rection condition is high.Visible, illumination effect can improve CO methanation activity and the methanation selectivity of this type of catalyst.
Claims (3)
1. improve a method for Ru catalyst CO methanation performance, comprise making supported Ru catalysts, it is characterized in that: in the reaction system of supported Ru catalysts catalysis CO methanation, introduce ultraviolet lighting;
Described supported Ru catalysts is with TiO
2for the high-dispersion loading type catalyst that carrier, Ru nano particle are active component;
In described supported Ru catalysts, the content of active component Ru is 0.5-2.0wt%, and all the other are TiO
2carrier;
The preparation process of described supported Ru catalysts is divided into two steps, and step (1) utilizes sol-gal process to obtain TiO
2carrier; The TiO that step (2) utilizes immersion reduction method to obtain in step (1)
2supported on carriers active component Ru, obtained TiO
2supported Ru catalysts;
Described step (2) is: by shaping TiO
2carrier is placed in RuCl
3in solution, dipping 2 ~ 12h, dries at 60 ~ 120 DEG C, gained drying object is placed in the NaBH containing NaOH
4in solution, stirred at ambient temperature 2 ~ 6h, centrifugal, after deionized water washes away excess ions, vacuumize at 50 ~ 80 DEG C, obtained TiO
2supported Ru catalysts;
Described RuCl
3mass concentration containing Ru in solution is 0.01 ~ 1g/mL, the described NaBH containing NaOH
4in solution, NaBH
4the concentration of solution is the concentration of 0.05 ~ 0.25mol/L, NaOH is 0.05 ~ 0.5mol/L.
2. the method for raising Ru catalyst CO methanation performance according to claim 1, it is characterized in that: reaction system is reacted in normal pressure continuous flow device, this normal pressure continuous flow device comprises the quartz glass reactor with air inlet and gas outlet, the inner chamber of described quartz glass reactor is filled with supported Ru catalysts, the all sides of described quartz glass reactor are provided with heater and the UV-light luminous device for exciting the catalyst carrier of supported Ru catalysts to produce photoresponse, the ultraviolet light that described UV-light luminous device sends can arrive supported Ru catalysts surface through quartz glass reactor.
3. the method for raising Ru catalyst CO methanation performance according to claim 1, is characterized in that: the method for described raising Ru catalyst CO methanation is applied to the removal of CO under hydrogen rich gas atmosphere in fuel cell.
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| CN105013477B (en) * | 2015-07-03 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of catalysis oxidation VOCs mixed phase titanium dioxide loaded ruthenium catalyst, preparation method and its usage |
| 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 |
| CN110624557B (en) * | 2019-10-21 | 2021-09-24 | 福州大学 | Co-based catalyst for photo-thermal coupling catalysis of CO methanation |
| 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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