CN103721710B - A kind of supported Pt catalysts and its preparation method and application - Google Patents
A kind of supported Pt catalysts and its preparation method and application Download PDFInfo
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- CN103721710B CN103721710B CN201410006189.5A CN201410006189A CN103721710B CN 103721710 B CN103721710 B CN 103721710B CN 201410006189 A CN201410006189 A CN 201410006189A CN 103721710 B CN103721710 B CN 103721710B
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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
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The present invention relates to a kind of supported Pt catalysts and its preparation method and application.First Pt nanometer particle load had the TiO of light absorption
2conductor oxidate carrier and low-temperature catalytic activity and the strong CeO of oxygen storage capacity
2on, obtained supported Pt catalysts, then introduces ultraviolet lighting again in the reaction system of this catalyst CO/NO.Compared with the heat catalysis of routine (without ultraviolet lighting), ultraviolet lighting significantly can promote the performance of Pt support type thermocatalyst catalytic elimination CO/NO.This photo-thermal coupling process greatly reduces the serviceability temperature of catalyst, and its method is simple, is conducive to removing in NO and CO in purifying vehicle exhaust being applied.
Description
Technical field
The invention belongs to catalytic elimination CO/NO and react field, specifically relate to a kind of method being improved Pt catalyst removal CO/NO performance by photo-thermal coupling.
Background technology
Along with increasing sharply of city automobile, motor vehicle exhaust emission has become one of main air pollution source in city.The discharge of vehicle exhaust not only gives our life, environment causes great harm, is also a kind of very important injury to the health of human body simultaneously.Air oneself detergent power can not have been degraded vehicle exhaust, so solve automobile exhaust pollution, the environment that also mankind one are clean has been extremely urgent.
Scientific analysis shows, containing hundreds of different compound in vehicle exhaust, pollutant wherein has solid aerosol, carbon monoxide, carbon dioxide, hydrocarbon, oxynitrides, lead and oxygen sulfur compound etc.For the control of vehicle exhaust discharge quantity, the policy of various countries experienced by a series of change, from the initial discharge only limiting CO, to restriction CO, HCs of being discharged into last integration of CO and HCs and the discharge of nitrogen oxide NO; Simultaneously in scientific research, people attempt always chemically each side such as fuel, engine combustion efficiency, catalyst to control the especially content carbon monoxide CO of gas more serious to atmosphere pollution in vehicle exhaust, hydrocarbon HCs and nitrogen oxide NOx.
The technological means of administering automobile gas emission pollution mainly can be divided three classes: one is emission controls by improving combustion technology; as fuel qualities is improved. PCV system; EVAP recovery system; the transformation of combustion system, oil supply system and ignition system; EGR; auxiliary air is sprayed, high-energy ignition and lean burn etc. in blast pipe; Two is external purifications; mainly carry out in some processing to reach the object reducing motor vehicle exhaust emission external the carrying out of engine; with regard to the development of current external purification technology; the direction of main research is that the arrangement for catalytic purification of the research vehicle exhaust of the catalytic purification to vehicle exhaust is generally mounted in automobile exhaust system; adopt Catalysis Principles to carry out the exhaust gas processing device of the harmful substance such as carbon monoxide, oxynitrides, hydrocarbon in purifying automobile tail gas, this is a kind of device that can carry out integrated treatment on the whole to vehicle exhaust; Three is use clean alternative fuel, as natural gas, liquefied petroleum gas or electric energy etc.
Run into bottleneck and green energy resource temporarily can not replace fossil fuel now at emission controls by improving combustion technical research, cleaning catalyst for tail gases of automobiles is just obtaining increasingly extensive application as environmental protection catalyst.Three-way catalyst is the catalyst used in vehicle exhaust three-way catalytic converter, it has high activity, high selectivity, high thermal stability, good physical behavior, can remove the pollutants such as CO, HC and the NOx in vehicle exhaust, be ideal auto-exhaust catalyst simultaneously.Three-way catalyst mainly comprises carrier and active component, and carrier is generally cellular an aromatic plant metioned in ancient books green stone, and active component research more be precious metals pt, Pd, Rh.
The main chemical reactions of three-way catalyst
Oxidation reaction CO+1/2 O of CO, HC
2→ CO
2
CxHy+（x+1/2y）O
2→xCO
2+ 1/2yH
2O
Reduction reaction NO+CO → the 1/2N of NO
2+ CO
2
Especially be difficult to carry out with the reduction reaction of NO, this is also a difficult point in three-way catalyst research.
About the research catalytic elimination CO/NO of three-way catalyst reaches its maturity, wherein Pt, Pd, Rh are the active metal components studying at most, particularly about the catalyst of Pt has occurred that more patent emerges in an endless stream especially, but also it should be noted that thermocatalytic removes some limitation of CO/NO: three-way catalyst poison deactivation, the inactivation main Types of three-way catalyst has: mechanical inactivation, heat inactivation and chemical inactivation simultaneously; Life-span is short, operation temperature area is narrow; Precious Metals Resources is deficient, cost is high; Nitrous oxides selectivity under lean-burn condition.
Therefore, the conversion ratio that low temperature removes CO/NO reactivity, CO and NO how is improved, N
2selective purifying vehicle exhaust to be had great significance.
Summary of the invention
The invention provides and improve by photo-thermal coupling the method that Pt catalyst removes CO/NO performance, its object is to overcome the deficiency that above-mentioned simple thermocatalytic removes CO/NO, improve low temperature active and the N of this type of catalyst
2selective.The present invention is directed to conventional Pt loaded catalyst need at relatively high temperatures could catalysis CO and N
2selective low problem, the conductor oxidate selecting there is optical excitation activity as carrier to prepare Pt loaded catalyst, and add the strong Ce of oxygen storage capacity according to NO+CO reaction characteristics, strengthen contacting between Pt and carrier, in course of reaction, introduce ultraviolet lighting, thus significantly improve the performance of its catalytic elimination CO/NO, greatly reduce the reaction 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 Pt catalysts, then introduces ultraviolet lighting in the reaction system of supported Pt catalysts catalysis CO/NO.
Above-mentioned reaction system is normal pressure continuous-flow device, this normal pressure continuous-flow device comprises with air inlet and the quartz glass reactor of gas outlet and the thermocouple interface of detected temperatures, the inner chamber of described quartz glass reactor is filled with supported Pt catalysts, described quartz glass reactor week, side was provided with heater and the UV-light luminous device for exciting the catalyst carrier of supported Pt catalysts to produce photoresponse, and the ultraviolet light that described UV-light luminous device sends can arrive supported Pt catalysts surface through quartz glass reactor.
Described supported Pt catalysts is with TiO
2and the CeO that oxygen storage capacity is strong
2for the high-dispersion loading type catalyst that carrier, Pt nano particle are active component, and in described supported Pt catalysts, the content of active component Pt is 0.2-2.0wt%, CeO
2for 5-20wt%, all the other are TiO
2carrier.Concrete preparation process is as follows:
Step (1): add acetone and deionized water after ethylene glycol and tetra-n-butyl titanate react 5-10h, obtain be deposited in 60-80 DEG C at dry, then add the CeCl of proportional quantity
3and urea to be transferred in water heating kettle hydro-thermal 4-10h at 150-180 DEG C and is obtained TiO
2-CeO
2carrier;
Step (2): the carrier obtained in step (1) adds H
2ptCl
6solution, stirs 30min-1h, ultrasonic 15-30min, adds the NaBH containing NaOH at turbid solution
4in solution, stirred at ambient temperature 2 ~ 6h, centrifugal, after deionized water washes away excess ions, vacuum drying at 60-80 DEG C, obtained Pt loaded catalyst;
Wherein, H
2ptCl
6molar concentration containing Pt in solution is 0.01-0.1mol/L, the described NaBH containing NaOH
4in solution, NaBH
4the concentration of solution is the concentration of 0.01-0.1mol/L, NaOH is 0.01-0.1mol/L.
Described supported Pt catalysts is used for the conversion of the NO+CO of vehicle exhaust and fuel vent.
Remarkable advantage of the present invention is:
(1) the present invention is with TiO
2-CeO
2oxide, as carrier, has not only played CeO
2the feature that cryogenic effect is strong and oxygen storage capacity is large in vehicle maintenance service, more take full advantage of semiconductor and can excite the feature producing electron hole pair under the illumination of certain wavelength, when Pt is carried in examples of such carriers, light induced electron can be transferred to the low Pt metal of fermi level from the semiconductor that fermi level is high, thus improve the electric surface density of active metal Pt, CeO simultaneously
2and TiO
2between interaction improve the efficiency in active component Pt transmission electronic and hole, be beneficial to absorption and the activation of CO and NO, and then promote the carrying out of CO/NO reaction, CO conversion ratio and N
2selective all very high.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%Pt/CeO
2-TiO
2scanning electron microscope (SEM) photograph.
Fig. 2 is embodiment 1 gained 1wt%Pt/CeO
2-TiO
2bET figure.
Fig. 3 is embodiment 1 gained 1wt%Pt/CeO
2-TiO
2xRD figure.
Fig. 4 is embodiment 1 gained 1wt%Pt/CeO
2-TiO
2ultraviolet-diffuse spectrogram.
Fig. 5 is catalyst performance evaluation reaction system sketch.1. being air inlet, is 2. gas outlet, is 3. heater, is 4. quartz reactor, is 5. catalyst granules, is 6. ultraviolet source.
Detailed description of the invention
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
Pt/CeO
2-TiO
2the preparation of catalyst
By 200mL ethylene glycol and 8 mL tetra-n-butyl titanate mix and blend 6h, then add 300mL acetone and 8mL deionized water, continue to stir 1h to be precipitated completely after centrifugal, the rear 80 DEG C of dry TiO of deionized water washing
2presoma.At TiO
20.2gCeCl is added in presoma
3with 1g urea, and add 60mL deionized water, at being transferred to water heating kettle 150 DEG C, hydro-thermal reaction 10h obtains TiO
2-CeO
2carrier.Take 1.0g TiO
2-CeO
2carrier, measuring 8 mL concentration is H between 0.05mol/L
2ptCl
6solution joins in carrier, and introduces 100mL deionized water, stirs 30min, ultrasonic 15min, about regulating the pH value to 10 of solution, slowly drips the NaBH containing 0.1mol/L
4can be reduced completely to the excessive Pt made from the solution of 0.1mol/L NaOH, centrifugal, deionized water is washed to ion concentration lower than 11ppm, dries, obtain Pt content and be about 1wt%, CeO at 80 DEG C
2content is about the Pt/CeO of 10wt%
2-TiO
2catalyst.
Embodiment 2
The performance evaluation of catalyst
The performance evaluation that catalyst obtained by embodiment 1 removes CO/NO is carried out on the normal pressure continuous-flow reaction unit of a band panel heater.About 0.6g Catalyst packing is in quartzy stacked rectangular capsules (long 30mm* wide 15mm* height 1mm), catalyst particle size is about 0.2 ~ 0.3mm(60 ~ 80 order), in reaction gas, the content of CO and NO is fixed as 0.5V% and 0.5V% respectively, He gas supplements gas as balance, and reaction gas overall flow rate is about 100mL/min.Reaction temperature is regulated and controled by temperature programming temperature controller.Adopt CO, NO, CO in AIDE-OW/AI300 on-line analysis atmosphere
2concentration, the result that negate is answered 2 hours calculates CO conversion ratio and N
2selective.
The following formulae discovery of CO conversion ratio: C1=(V
inCO-V
outCO)/V
inCO× 100%
The following formulae discovery of NO conversion ratio: C2=
(v
inNO-V
outNO )/ V
inNO× 100%
N
2the following formulae discovery of selective use: S=2V
outN2/ (V
inNO-V
outNO) × 100%
In formula, C1 is the conversion ratio of CO, and C2 is the conversion ratio of NO, and S is N
2selective; V
inCOand V
outCObe respectively air inlet and the CO content (V%) in giving vent to anger, V
inNOand V
outNObe respectively air inlet and the NO content (V%) in giving vent to anger, V
outN2for the N in effluent gases
2content (V%).
In this way, have rated the performance of the catalytic elimination CO/NO of various catalyst respectively, its result is as shown in the table:
Pt/CeO before and after table 1 ultraviolet lighting
2-TiO
2the performance of catalytic elimination CO/NO
Shown by result in upper table, for each catalyst, compared to the reaction condition of pure heat, under light+heat effect, the conversion ratio of CO all improves a lot, and N
2selective also purer thermal rection condition under selective height.Visible, illumination effect can improve performance and the N of the catalytic elimination CO/NO of this type of catalyst
2selective.
As can be seen from Fig. 1 and Fig. 2, Pt/CeO
2-TiO2 catalyst has unique nucleocapsid solid microsphere structure to allow it have larger specific area, and larger hole is melted and less aperture, is adsorbed with very large facilitation for NO and CO; As can be seen from Figure 3, because Pt 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 Pt particle in catalyst; As can be seen from Figure 4, except there is TiO in this catalyst
2light absorption outside, become wider at whole light absorption wave band absorption region, be conducive to the absorption for light, play the short effect of better light; In Fig. 5 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 imposed to reactor.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (3)
1. a preparation method for supported Pt catalysts, is characterized in that: described supported Pt catalysts is with CeO
2-TiO
2for carrier, Pt nano particle is the high-dispersion loading type catalyst of active component;
In described supported Pt catalysts, the content of active component Pt is 0.2-2.0wt%, CeO
2content 5-20wt%, all the other are TiO
2carrier;
With CeCl
37H
2o and butyl titanate are presoma, and centrifugal after 150-180 DEG C of common hydro-thermal 4-10h, deionized water is washed, and 60-80 DEG C of dry 6-10h obtains CeO
2-TiO
2carrier; At obtained CeO
2-TiO
2h is added in carrier
2ptCl
6solution and deionized water, stir 30min-1h, ultrasonic 15-30min, add the NaBH containing NaOH
4solution, stirred at ambient temperature 2-5h, centrifugal, deionized water is washed, 60 ~ 80 DEG C of vacuum drying, obtained CeO
2-TiO
2supported Pt catalysts.
2. method according to claim 1, is characterized in that: described H
2ptCl
6the concentration of solution is 0.01-0.1mol/L, the described NaBH containing NaOH
4in solution, NaBH
4the concentration of solution is the concentration of 0.01-0.1mol/L, NaOH is 0.01-0.1mol/L.
3. the application of supported Pt catalysts that obtains of the method for claim 1, it is characterized in that: described supported Pt catalysts is applied to the removal of CO and NO in vehicle exhaust, in the reaction system of supported Pt catalysts catalysis CO/NO, introduce ultraviolet lighting.
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| CN103721710B true CN103721710B (en) | 2015-08-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107020138B (en) * | 2017-05-09 | 2019-06-07 | 福州大学 | A kind of Supported Pd-Catalyst and its preparation method and application |
| CN113786842B (en) * | 2021-09-13 | 2023-08-04 | 福州大学 | Catalyst for synthesizing ammonia from NO oxide, preparation method and application thereof |
| CN114950402A (en) * | 2022-06-28 | 2022-08-30 | 苏州金宏气体股份有限公司 | TiO 2 /CeO 2 Heterojunction photocatalyst and preparation method thereof |
| CN116510510B (en) * | 2023-06-11 | 2023-09-26 | 连云港中星能源有限公司 | Efficient energy-saving denitration process based on electric heating assistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1053778A1 (en) * | 1999-05-19 | 2000-11-22 | Ford Global Technologies, Inc. | Method for manufacturing a three-way catalyst |
| CN101574648A (en) * | 2009-05-18 | 2009-11-11 | 刘光文 | Rare transition-metal catalyst for catalytic purification of CO, Nox and HC |
-
2014
- 2014-01-07 CN CN201410006189.5A patent/CN103721710B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1053778A1 (en) * | 1999-05-19 | 2000-11-22 | Ford Global Technologies, Inc. | Method for manufacturing a three-way catalyst |
| CN101574648A (en) * | 2009-05-18 | 2009-11-11 | 刘光文 | Rare transition-metal catalyst for catalytic purification of CO, Nox and HC |
Non-Patent Citations (2)
| Title |
|---|
| Controlled Hydrogenation of Acetophenone Pt/CeO2-MOx Over (M =Si, Ti, Al, and Zr) Catalysts;Benjaram M. Reddy et al.;《Catal. Lett. 》;20090327;第131卷;"2.1 Catalyst Preparation"和表1 * |
| 纳米TiO2的负载化及其在环境光催化中的应用;卢晓平 等;《应用化学》;20041130;第21卷(第11期);第1088-1092页 * |
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