CN106076375B - A kind of titanium dichloride load noble metal catalyst of Fluorin doped and the preparation method and application thereof - Google Patents
A kind of titanium dichloride load noble metal catalyst of Fluorin doped and the preparation method and application thereof Download PDFInfo
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- CN106076375B CN106076375B CN201610401670.3A CN201610401670A CN106076375B CN 106076375 B CN106076375 B CN 106076375B CN 201610401670 A CN201610401670 A CN 201610401670A CN 106076375 B CN106076375 B CN 106076375B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/70—Non-metallic catalysts, additives or dopants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses titanium dichloride load noble metal catalysts of a kind of Fluorin doped and the preparation method and application thereof.It is made of titania powder carrier, doping F and noble metal M；It is in terms of 100% by the weight of catalyst, noble metal M is based on precious metal element weight, and the weight percent that the weight percent of noble metal M is 0.05% ~ 10%, F is 0.1% ~ 10%, and surplus is titania powder.The titanium dichloride load noble metal catalyst of Fluorin doped of the invention, preparation method is easy, is convenient for large-scale industrial application；Noble metal granule can be optimized in TiO by the doping of fluorine2The interaction between dispersibility and metal and carrier on carrier is finally obtained the performance of excellent catalytic purification low concentration VOCs exhaust gas.
Description
Technical field
The invention belongs to environmental protection technical fields, specifically, a kind of expensive gold of the titanium dichloride load for being related to Fluorin doped
Metal catalyst and the preparation method and application thereof.
Background technique
Volatile organic compounds (VOCs) mainly includes aldehydes, ketone and hydrocarbon of other low molecular weights etc.,
It is a kind of important air pollutants.This kind of compound vapour pressure with higher at normal temperature is easy evaporation and is diffused into big
In gas, health and environment to human body can all cause very big harm.Production by Catalytic Combustion Process based on loaded noble metal catalyst
It is one of the effective means of purifying low-concentration VOCs.The catalytic perfomance of loaded noble metal catalyst and point of active component
The interaction (SMSI) dissipated between performance and carrier and active component is closely related.
In VOCs catalytic purification field, TiO2It is a kind of common catalyst carrier.TiO2In oxygen migration it is very capable,
The Surface Oxygen crystal vacancy position for having absorption and activation to oxygen can be provided, while between the noble metal and titania support loaded
Also it is proved that there is stronger interaction forces.TiO2Supported precious metal catalyst catalytic perfomance and its carried noble metal
Dispersion performance it is related to SMSI intensity.In order to improve the organic exhaust gas performances such as its catalysis oxidation VOCs, Chinese patent
CN103736484A discloses the performance and application of a kind of Nano tube array of titanium dioxide supported precious metal catalyst, utilizes nanometer
Pipe array confinement disperses supported noble metals particle, obtains the dispersibility and SMSI performance of preferable noble metal granule, and final
Obtain excellent formaldehyde catalytic purification performance.But it since Nano tube array of titanium dioxide class material preparation cost is higher, still needs to
Developing can be in general T iO2Dispersibility, SMSI performance and the catalytic perfomance of carried noble metal particle are controlled on nano particle
New method and technique.
Summary of the invention
For the above-mentioned TiO for VOCs catalytic purification2Supported precious metal catalyst problem encountered, mesh of the invention
Be difficult in order to solve in traditional titanium dichloride load noble metal catalyst interaction and dispersion performance between metal and carrier
In control and catalyticing purifying effect are still undesirable the problems such as, provide a kind of Fluorin doped titanium dichloride load noble metal catalyst and
Preparation method and the application in VOCs catalytic purification.
To realize the above-mentioned technical purpose, the technical solution adopted by the present invention are as follows:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, by titania powder carrier, doping F and noble metal
M composition；It is in terms of 100% by the weight of catalyst, based on precious metal element weight, the weight percent of noble metal M is noble metal M
The weight percent of 0.05% ~ 10%, F are 0.1% ~ 10%, and surplus is titania powder.
In above-mentioned catalyst, the titania powder is that anatase, rutile or rutile and anatase are compound
One of mineral phase structure.
In above-mentioned catalyst, the noble metal M is the mixing of one of Pt, Rh, Pd, Au, Ag or at least two
Object.
The preparation method of above-mentioned catalyst, includes the following steps:
(1) according to formula rate, preparing the precursor solution containing F using titania powder as carrier, it is molten will to contain F
Liquid prepares modified titanium dioxide powder carrier, and carry out calcination process to the carrier by the method dip loading of dipping；
(2) according to formula rate, the precursor solution containing noble metal M is prepared；In a manner of dipping, noble metal M is born
It is loaded on modified titanium dioxide powder carrier, using equi-volume impregnating, then by sample drying, the roasting after dipping；
(3) it dries after being restored by the catalyst after roasting in hydrogen atmosphere or with reducing solution, or directly dries
It is dry, obtain a kind of titanium dichloride load noble metal catalyst of Fluorin doped.
In the above preparation method, in step (1), the precursor solution of the F is the aqueous solution of HF or NaF；Described
Maturing temperature for roasting the carrier after impregnating fluorine-containing solution is 200 ~ 700 DEG C.
In the above preparation method, in step (2), the roasting of the sample being used to roast after dipping precious metal solution
Temperature is 200 ~ 700 DEG C.
In the above preparation method, in step (3), the hydrogen reducing temperature is 300 ~ 600 DEG C, and the reproducibility is molten
Liquid is one of sodium borohydride, potassium borohydride or formalin or a variety of, the molar ratio of the additive amount and noble metal M of reducing agent
For 10 ~ 1000:1.
Application of the titanium dichloride load noble metal catalyst of above-mentioned Fluorin doped in VOCs catalytic purification.
In the above preparation method, the selection of the noble metal active component presoma can be according to being finally prepared
Noble metal active component selection, such as noble metal active component is palladium, noble metal active component presoma can choose palladium chloride；
The noble metal active component is platinum, and noble metal active component presoma can choose chloroplatinic acid.Illustrative noble metal active
Component presoma is for example: Ag (acac), AgNO3、H2AuCI4、Pd(acac)2、Pt(acac)2、Rh(acac)2、H2PtC16·
6H2O、Pt(NO2)2(NH3)2、Pd(Ac)2、Pd(NO3)2、Rh(NO3)2, platinum chloride, palladium chloride, chlorauride, silver chlorate or chlorination
Rhodium.Above-mentioned noble metal active component presoma can be used alone, and can also be used in mixed way.
Compared with prior art, the invention has the following beneficial effects:
The titanium dichloride load noble metal catalyst of Fluorin doped of the invention, preparation method is easy, is convenient for large-scale industry
Using；Noble metal granule can be optimized in TiO by the doping of fluorine2It is mutual between dispersibility and metal and carrier on carrier
Effect, is finally obtained the performance of excellent catalytic purification low concentration VOCs exhaust gas.
Specific embodiment
Embodiment 1:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, by the anatase structured titania powder carrier of titanium,
F and active component Pt composition is adulterated, is in terms of 100% by the weight of catalyst, the weight percent of fluorine is 1.0%, the weight hundred of platinum
Divide than being 0.4%, surplus is titania powder.The preparation method is as follows: taking titania support to dry at 80 DEG C first, together
When prepare 4% hydrofluoric acid solution as maceration extract；Using equi-volume impregnating, hydrofluoric acid is impregnated into TiO2On dust carrier,
5h is calcined at 400 DEG C after drying at 80 DEG C, the TiO of F doping is made2Carrier.And then equi-volume impregnating is used, by phase
It answers the chloroplatinic acid precursor solution of content to be impregnated on carrier, is calcined 4 hours at 400 DEG C after dry at 80 DEG C.Finally will
Prepared catalyst is in H2It in atmosphere and is restored 3 hours at 300 DEG C, the carried noble metal for VOCs catalytic purification is made
Catalyst.
Embodiment 2:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, the mixed phase being made of titanium anatase and Rutile Type
Structure titanium dioxide P25 dust carrier, doping F and active component Pt composition are the weight of fluorine in terms of 100% by the weight of catalyst
Percentage is 0.5%, and the weight percent of platinum is 1%, and surplus is titania powder.The preparation method is as follows: taking titanium dioxide first
Titanium carrier is dried at 80 DEG C, while the hydrofluoric acid solution of preparation 4% is as maceration extract；Using equi-volume impregnating, by hydrofluoric acid
It is impregnated into TiO2The TiO that F doping is made in 5h is calcined on dust carrier, after drying at 80 DEG C at 500 DEG C2Carrier.And then it adopts
With equi-volume impregnating, the chloroplatinic acid precursor solution of corresponding content is impregnated on carrier, in 500 DEG C after drying at 80 DEG C
Lower calcining 4 hours.Finally by prepared catalyst in H2It in atmosphere and is restored 3 hours at 400 DEG C, is made and is catalyzed for VOCs
The loaded noble metal catalyst of purification.
Embodiment 3:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, by titanium rutile titanium dioxide powder carrier, doping F
It is formed with active component Pt, is in terms of 100% by the weight of catalyst, the weight percent of fluorine is 5%, and the weight percent of platinum is
0.4%, surplus is titania powder.The preparation method is as follows: titania support is taken to dry at 80 DEG C first, prepare simultaneously
4% Fluorinse is as maceration extract；Using equi-volume impregnating, fluorine is impregnated into TiO2On dust carrier, dried at 80 DEG C
The TiO that F doping is made in 5h is calcined after dry at 500 DEG C2Carrier.And then equi-volume impregnating is used, by the chlorine of corresponding content
Platinic acid precursor solution is impregnated on carrier, is calcined 4 hours at 400 DEG C after dry at 80 DEG C.Finally prepared is urged
Agent NaBH4It is dry after solution reduction, the loaded noble metal catalyst for VOCs catalytic purification is made.
Embodiment 4:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, by titanium rutile titanium dioxide powder carrier, doping F
It is formed with active component Pd, is in terms of 100% by the weight of catalyst, the weight percent of fluorine is 1%, and the weight percent of palladium is
0.4%, surplus is titania powder.The preparation method is as follows: titania support is taken to dry at 80 DEG C first, prepare simultaneously
4% hydrofluoric acid solution is as maceration extract；Using equi-volume impregnating, hydrofluoric acid is impregnated into TiO2On dust carrier, 80 DEG C
The TiO that F doping is made in 5h is calcined after lower drying at 500 DEG C2Carrier.And then equi-volume impregnating is used, by corresponding content
Palladium nitrate precursor solution be impregnated on carrier, calcine 4 hours, be made for VOCs at 400 DEG C after dry at 80 DEG C
The loaded noble metal catalyst of catalytic purification.
Embodiment 5:
A kind of titanium dichloride load noble metal catalyst of Fluorin doped, by the mixing being made of titanium anatase and Rutile Type
Phase structure titanium dioxide P25 dust carrier, doping F and active component Pd composition are the weight of fluorine in terms of 100% by the weight of catalyst
Measuring percentage is 2%, and the weight percent of palladium is 1%, and surplus is titania powder.The preparation method is as follows: taking titanium dioxide first
Titanium carrier is dried at 80 DEG C, while the hydrofluoric acid solution of preparation 4% is as maceration extract；Using equi-volume impregnating, by hydrofluoric acid
It is impregnated into TiO2The TiO that F doping is made in 5h is calcined on dust carrier, after drying at 80 DEG C at 500 DEG C2Carrier.And then it adopts
With equi-volume impregnating, the palladium nitrate precursor solution of corresponding content is impregnated on carrier, in 500 DEG C after drying at 80 DEG C
Lower calcining 2 hours, is made the loaded noble metal catalyst for VOCs catalytic purification.
Embodiment 6:
It selects toluene waste gas to represent as typical VOCs, evaluates the purification of catalyst prepared by embodiment 1-5
The performance of VOCs.Catalyst described in 200 mg embodiment 1-5 is taken respectively, is placed in tubular fixed-bed reactor and is tested,
Experiment condition is as follows: 20 mL/min of air inlet nitrogen, 80 mL/min of Charge-Air Oxygen, and toluene gas is blasted with Bubbling method, reactor
Imported toluene concentration is ~ 500 ppm, and air speed is 30000 ml g-1 h-1, embodiment 1-2 reaction temperature is 190 DEG C, is implemented
The reaction temperature of example 3-5 is 250 DEG C, and Activity evaluation is as shown in table 1.
1 catalyst activity evaluation result of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Toluene conversion (%) | >99 | >99 | >99 | >99 | >99 |
| Carbon dioxide selectivity (%) | 100 | 100 | 100 | 100 | 100 |
Claims (1)
1. application of the titanium dichloride load noble metal catalyst of Fluorin doped in VOCs catalytic purification, it is characterised in that described to urge
Change purification be Production by Catalytic Combustion Process, the titanium dichloride load noble metal catalyst of the Fluorin doped by titania powder carrier, mix
Miscellaneous F and noble metal M composition；It is in terms of 100% by the weight of catalyst, noble metal M is based on precious metal element weight, the weight of noble metal M
Measuring the weight percent that percentage is 0.05% ~ 10%, F is 0.1% ~ 10%, and surplus is titania powder；Titania powder is
One of anatase, rutile or rutile and the compound mineral phase structure of anatase；Noble metal M is in Pt, Rh, Pd, Au, Ag
One kind or at least two mixture；
The preparation method of catalyst includes the following steps:
(1) according to formula rate, F solution will be contained and be led to using titania powder as carrier by preparing the precursor solution containing F
The method dip loading for crossing dipping prepares modified titanium dioxide powder carrier, and carries out calcination process to the carrier；
(2) according to formula rate, the precursor solution containing noble metal M is prepared；In a manner of dipping, noble metal M is carried on
On modified titanium dioxide powder carrier, using equi-volume impregnating, then by sample drying, the roasting after dipping；
(3) it dries after being restored by the catalyst after roasting in hydrogen atmosphere or with reducing solution, or directly dries, obtain
To a kind of titanium dichloride load noble metal catalyst of Fluorin doped；
In step (1), the precursor solution of the F is the aqueous solution of HF or NaF；It is described for after roasting and impregnating fluorine-containing solution
Carrier maturing temperature be 200 ~ 700 DEG C；
In step (2), the maturing temperature for roasting the sample after impregnating precious metal solution is 200 ~ 700 DEG C；
In step (3), the hydrogen reducing temperature is 300 ~ 600 DEG C, and the reducing solution is sodium borohydride, potassium borohydride
Or one of formalin or a variety of, the additive amount of reducing agent and the molar ratio of noble metal M are 10 ~ 1000:1.
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| CN114272941B (en) * | 2020-09-27 | 2022-12-27 | 宁波方太厨具有限公司 | Catalyst for removing formaldehyde and carbon monoxide by catalysis and preparation method thereof |
| CN112246254B (en) * | 2020-10-23 | 2023-05-16 | 南京国豪环保材料科技有限公司 | Efficient room-temperature formaldehyde decomposition supported metal catalyst and preparation method thereof |
| CN112742417B (en) * | 2021-01-15 | 2022-08-09 | 华东理工大学 | Noble metal catalyst and preparation method and application thereof |
| CN113522311B (en) * | 2021-08-06 | 2022-05-27 | 华东理工大学 | Chlorine-doped catalyst and preparation method and application thereof |
| CN114220979B (en) * | 2021-11-13 | 2024-04-16 | 深圳信息职业技术学院 | Catalyst carrier, preparation method thereof, catalyst and fuel cell |
| CN114941157B (en) * | 2022-05-30 | 2023-11-28 | 安徽工业大学 | Electrocatalyst material and preparation method thereof |
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| US3711399A (en) * | 1970-12-24 | 1973-01-16 | Texaco Inc | Selective hydrocracking and isomerization of paraffin hydrocarbons |
| CN1555920A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Fluorine adulterated photocatalytic multicrystal material possessing photocatalytic performance under visible light |
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