CN108525661A - The method that hollow titanium dioxide ball embeds Pd catalyst removals 2,4-D - Google Patents
The method that hollow titanium dioxide ball embeds Pd catalyst removals 2,4-D Download PDFInfo
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- CN108525661A CN108525661A CN201810351259.9A CN201810351259A CN108525661A CN 108525661 A CN108525661 A CN 108525661A CN 201810351259 A CN201810351259 A CN 201810351259A CN 108525661 A CN108525661 A CN 108525661A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention discloses a kind of hollow titanium dioxide balls to embed the method that Pd catalyst removes 2,4 D, which is characterized in that by PdCl2With SiO2Pd/SiO is made after ball solution water bath method2；It is added into the mixed liquor of ethyl alcohol, butyl titanate and cetyl trimethylammonium bromide, Pd/SiO is obtained through drying, roasting2@TiO2；It is added into NaOH solution, agitated successively, washing, drying, H2Reduction, obtains hollow TiO2Ball embeds Pd catalyst, i.e. Pd@hTiO2；It is put into the water body containing 2,4 D, is successively passed through N2And H2Carry out catalytic hydrogenation and dechlorination reaction.The Pd@hTiO that the present invention uses2The well-regulated pore structure of catalyst, and carrier is stronger to the fixed function of active metal, has higher activity and stability in catalytic hydrogenation and dechlorination reaction, has good economy and environmental benefit.
Description
Technical field
The invention belongs to inorganic material synthesis and water technology range, more particularly to a kind of hollow titanium dioxide ball is embedded
The method that Pd catalyst removes 2,4-D.
Background technology
Chlorobenzene oxygen acid herbicides and auximone such as 4- tomatotones (4-CPA), 2,4- dichlorophenoxies
Acetic acid (2,4-D) etc., is widely used in agricultural production so that this kind of chlorinatedorganic progresses into natural water body, causes serious
Water environment pollution problem.Chlorinatedorganic usually has stronger " three cause " effect even genetoxic.Therefore, how to have
Chlorophenoxy class source water micropollutants in effect removal water body, are a problem to be solved.
The processing method of chlorobenzene oxygen acid herbicides mainly has：Absorption method, electrochemical process, photocatalytic method and reduction dechlorination
Method etc..The regenerative process of adsorbent is more complex in absorption method and adsorbate need to carry out harmless treatment to prevent secondary pollution.Electricity
Chemical method is preferable to the treatment effect of chlorobenzene oxygen acid herbicides, but the quality of electrode material performance limits pushing away for the technology
Wide application.Current catalyst is also relatively low to the response of visible light in photocatalytic method, results in lower treatment effeciency.Catalysis
Hydrogenation-dechlorination (HDC) is one kind of reduction dechlorination method, and this method can be under normal temperature and pressure conditions, and catalyst generates work using hydrogen source
Property hydrogen hydrogenolysis is carried out to the carbon in pollutant-chlorine key (C-Cl), and then the chlorine in chlorinatedorganic is removed completely, is effectively reduced
Its toxicity, and not will produce other harmful by-products is a kind of low energy consumption, environmentally protective technology.
The most commonly used is loaded noble metal catalysts in liquid phase catalytic hydrogenation dechlorination reaction, wherein metal Pd is due to having
Stronger absorption and dissociation H2Ability, be a kind of most-often used active metal.Synthesis loaded catalyst is the most frequently used at present
Method be that metal salt presoma is deposited on carrier surface and is restored, in the catalyst of synthesis metallic particles only adhere to
In carrier surface, during catalysis reaction especially recycles, since weaker Metal-Support interaction makes metal
Grain is easy to fall off, is lost in, and leads to catalyst inactivation.The method for coating active metal using carrier, metallic particles is embedded in hollow
Ball type carrier inner wall obtains metal core@carrier shell catalysts, can significantly increase fixed function of the carrier to active metal, be effective
One of the approach for the problems such as solving metallic particles in catalyst easy to fall off, loss, especially when mesoporous hollow ball material is in nanometer
When rank, the small size and outstanding dispersibility that it has can extremely efficiently reinforce the mass transfer in guest molecule portion in the inner
Rate improves catalysis reaction efficiency.Noble metal catalyst Pd@hTiO are embedded by synthesizing hollow ball2, it is compared to common table
Face loaded catalyst Pd/TiO2With higher catalytic performance, the efficiency for being catalyzed reduction greatly improves, and with good steady
It is qualitative.
Invention content
Problem to be solved by this invention is：The catalyst activity and stabilization prepared for general surface deposition-reduction method
Property relatively low disadvantage, a kind of method that carrier embeds 2,4-D in active metal material removal water body is provided.
To solve the above-mentioned problems, the present invention provides a kind of hollow titanium dioxide balls to embed Pd catalyst removal 2,4-D
Method, which is characterized in that include the following steps：
Step 1)：By PdCl2With SiO2Pd/SiO is made after water bath method for ball solution mixing2；
Step 2)：By Pd/SiO2The mixed liquor of ethyl alcohol, butyl titanate and cetyl trimethylammonium bromide, warp is added
Dry, roasting obtains Pd/SiO2@TiO2；
Step 3)：By Pd/SiO2@TiO2NaOH solution, agitated successively, washing, drying, H is added2Reduction, obtains hollow
TiO2Ball embeds Pd catalyst, i.e. Pd@hTiO2；
Step 4)：By Pd@hTiO2In water body of the input containing 2,4-D, control ph is 9~12, and in normal temperature and pressure conditions
Lower priority is passed through N2And H2Carry out catalytic hydrogenation and dechlorination reaction.
Preferably, SiO in the step 1)2The preparation method of ball is：The mixed solution of ethyl orthosilicate and ethyl alcohol is fast
Speed is added in the mixed solution of ammonium hydroxide and ethyl alcohol, after mixing, is washed repeatedly using ethyl alcohol and distilled water, in 70 DEG C of vacuum
Drying.
It is highly preferred that the volume ratio of the ethyl orthosilicate and ethyl alcohol is 1: 10；The volume ratio of ammonium hydroxide and ethyl alcohol is 1: 2.
Preferably, the SiO in the step 1)2A diameter of 360nm of nanosphere.
Preferably, SiO in the step 2)2The mass ratio of ball and butyl titanate is 1: 2~6, preferably 1: 5；SiO2Ball with
The mass ratio of cetyl trimethylammonium bromide is 2~8: 1, preferably 4: 1.
Preferably, the calcination temperature in the step 2) is 300 DEG C, roasting time 3h, and heating rate is 3 DEG C/min.
Preferably, Pd/SiO in the step 3)2@TiO2It is 1: 100 (g/mL), NaOH with NaOH solution mass/volume ratio
A concentration of 2.0~4.0mol/L of solution, preferably 2.5mol/L；The mass content of Pd is 0.5~3.0% in Pd catalyst, excellent
Select 1.5%.
Preferably, H in the step 3)2Reduction is specially：The reductase 12 h at 300 DEG C, heating rate are 10 DEG C/min, H2
Flow velocity be 40mL/min.
Preferably, the initial concentration of 2,4-D water bodys is 20~100mg/L in the step 4)；Pd@hTiO2With 2,4-D water
The mass ratio of body is 1: 2000~8000.
Preferably, the reaction temperature that catalytic hydrogenation and dechlorination reacts in the step 4) is 15~25 DEG C, preferably 20 DEG C, is reacted
Time is 40~120min；PH adjusting agent uses HCl or NaOH solution.
The present invention embeds precious metals pd@hTiO with hollow ball2For catalyst, by the method for catalytic hydrogenation and dechlorination in water
2,4- dichlorphenoxyacetic acids handled, catalysis reaction continuous batch dynamic process can be used.The polluted-water that the present invention is handled
It is initial concentration ranging from 20~100mg/L of 2, the 4-D in the micro-polluted source water polluted by 2,4-D, water body, water temperature 15
~25 DEG C.Pollutant 2 in water body is removed, the specific method of 4-D is：By Pd@hTiO2Catalyst be added to by a certain percentage containing
Pollutant 2, in 4-D micro-polluted source waters, the dosage of catalyst can be adjusted as the case may be, preferred catalyst and micro-polluted water
Mass ratio is 1: 5000, and presetting pH to 11.0 or so is continually fed into N while being vigorously stirred2(50mL/min) 30min, later
Air-flow is switched to H2(60mL/min) after reaction separates and recovers catalyst from solution, and treated, and solution is direct
Discharge, to reach the purpose of 2,4-D in removal water body.
The Pd@hTiO of the present invention2Specifically it is made by following methods：Currently, Nano-meter SiO_22The synthetic method of ball is closely ripe,
Details are not described herein again.It will advance vacuum drying Nano-meter SiO_22Ball is immersed in the PdCl weighed by 1.5% load capacity2In solution, often
Temperature, which is descended, stirs 2h, and Pd/SiO is made in 105 DEG C of dryings after 85 DEG C of water bath methods2；By 100mg Pd/SiO2Be dispersed in 40mL ethyl alcohol with
And in 0.25g cetyl trimethylammonium bromide mixed liquors, 0.5mL butyl titanates are added after mixing, are added after stirring 4h
15mL ethyl alcohol and 3mL water continue to stir 8h, centrifuge, washed respectively with deionized water and ethyl alcohol, is dried in vacuo, after grinding
300 DEG C of roasting 3h, obtain Pd/SiO2@TiO2；By Pd/SiO2@TiO2It is scattered in the NaOH solution of 2.5mol/L, stirs 8h,
Separation, is washed to neutrality, dries, 300 DEG C of H2It is restored in atmosphere, obtains Pd@hTiO2。
The present invention uses hollow mesoporous TiO2Ball coats Pd particles as catalyst, can be had to 2,4-D in water
The catalysis dechlorination of effect.With hollow mesoporous TiO2Ball coats Pd particle Pd@hTiO2As catalyst have higher specific surface area and
More regular pore structure reaches 95.3% after reaction 50min when pH value is 12 to the conversion ratio of 2,4-D, and with general commercial
TiO2For carrier, the catalyst Pd/TiO prepared using surface deposition-reduction method2It is to the conversion ratio of 2,4-D in 2h
35.1%.Compared to Pd/TiO2, on the one hand, Pd@hTiO2Middle carrier is stronger to the fixed function of metal, and catalyst is made to react
It can continue to keep higher activity in the process；On the other hand, Pd@hTiO2In pore structure strengthen it to reactant 2,4-D's
Adsorption and enrichment keeps 2,4-D higher in the adsorption concentration on active sites surface, to accelerate the progress of reaction.
Compared with prior art, the present invention having the advantages that notable.Compared to common Pd/TiO2Catalyst, Pd@hTiO2In
Carrier has stronger fixed function to active metal, improves stability of the catalyst in catalytic reaction process；In addition, comparing
In plain particles shape TiO2, the hollow TiO with nanometer spherical structure2Ball has the pore structure of larger surface area and rule, is conducive to
Enrichment concentration of the reactant near catalyst activity position, significantly improves catalysis reaction efficiency.After reaction, standing can be passed through
Or catalyst is recycled and is reused by membrane filtration separation.In addition, by catalyst Pd@hTiO2Catalytic hydrogenation for 2,4-D in water
Equipment is simple needed for dechlorination processing, and reaction condition is mild, takes short.Therefore, hollow ball is embedded noble metal catalyst by the present invention
Pd@hTiO2For removing 2,4-D in micro-polluted source water, there is good economy and environmental benefit.
Description of the drawings
Fig. 1 is SiO2The TEM collection of illustrative plates of ball；
Fig. 2 is Pd/SiO2TEM collection of illustrative plates；
Fig. 3 is Pd/SiO2@TiO2TEM collection of illustrative plates；
Fig. 4 is Pd@hTiO2TEM collection of illustrative plates.
Specific implementation mode
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Embodiment 1
A kind of method that hollow titanium dioxide ball embeds 2,4-D of Pd catalyst removals：
(1)SiO2The synthesis of ball：First prepare solution A：The concentrated ammonia liquor of 9mL 28%, 16.25mL ethyl alcohol and 24.75mL are steamed
Distilled water mixes, and stirs evenly (stir speed (S.S.) 1100rpm)；Solution B is prepared again：By the ethyl orthosilicate and 45.5mL of 4.5mL
Ethyl alcohol is uniformly mixed；Under agitation, solution B is rapidly joined in solution A, after stirring one minute, reduces mixing speed extremely
360~400rpm；Reaction bottleneck is sealed, reacts 2h at room temperature；It centrifuges, 70 DEG C of vacuum dryings after ethyl alcohol washing.
(2)Pd/SiO2Synthesis：Weigh appropriate PdCl2Nano-meter SiO_2 obtained is added in beaker in solution2Ball, under room temperature
Magnetic agitation 2h, the later water bath method at 85 DEG C, 105 DEG C of drying.
(3)Pd/SiO2@TiO2Synthesis：By the Pd/SiO of 100mg2It is scattered in 40mL ethyl alcohol and 0.25g cetyls
0.5mL butyl titanates are added dropwise in trimethylammonium bromide mixed liquor, after mixing and continue stirring 4 hours；Be added 15mL ethyl alcohol and
3mL deionized waters continue stirring 8 hours；It is centrifuged, is washed respectively with ethyl alcohol and deionized water after reaction, after
It is dried in vacuo in 65 DEG C 20 hours, 300 DEG C of roasting 3h, heating rate is 3 DEG C/min.
(4)Pd@hTiO2Preparation：By the Pd/SiO of 0.4g2@TiO2The NaOH for being scattered in a concentration of 2.5mol/L of 40mL is molten
It in liquid, centrifuges after 8h, is dried after being washed to neutrality, later the H at 300 DEG C2Reductase 12 h in atmosphere, H2Flow velocity 40mL/min.
The mesoporous hollow TiO of the present embodiment2It is 134.5m that ball, which embeds Pd specific surface area of catalyst,2/ g, TiO2The aperture of ball is
3.8nm, inductive coupling plasma emission spectrograph detection show that the content of Pd is 1.3%.SiO2Ball, Pd/SiO2、Pd/
SiO2@TiO2With Pd@hTiO2TEM collection of illustrative plates it is as shown in Figs 1-4, SiO2Ball and TiO2Hollow bulb diameter may each be about 360nm.
Embodiment 2
The Pd@hTiO synthesized with embodiment 12For catalyst, micro-polluted water of the processing containing 2,4-D：Reaction normal pressure, 20 DEG C
Under, it is carried out in tetra- mouthfuls of vials of 250ml.The mass ratio of catalyst and polluted water is 1: 5000, and pH value in reaction 11.0 is got dirty
The initial concentration for contaminating 2,4-D in water is 44.2mg/L, is vigorously stirred and is passed through N2(50mL/min), persistently by air-flow after 30min
Switch to H2(60mL/min), at timed intervals sample detection, the removal rate for reacting 2,4-D after 50min reach 100%.
Comparative example 1
With commercial TiO2(P25) it is carrier, the Pd/TiO synthesized using conventional impregnation2For catalyst, processing contains 2,4-D
Micro-polluted water：For catalytic reaction condition with embodiment 2, the removal rate for reacting 2,4-D after 50min is only 40.3%.As it can be seen that identical
Under the conditions of, Pd@hTiO2Catalytic activity be significantly higher than Pd/TiO2。
Embodiment 3
Catalytic reaction condition is 22.1mg/L with the initial concentration of embodiment 2,2,4-D, and 2 when reacting 40min, 4-D's goes
Except rate is 100%.
Embodiment 4
Catalytic reaction condition is 88.4mg/L with the initial concentration of embodiment 2,2,4-D, and 2,4-D is gone after reacting 70min
Except rate is 100%.
Embodiment 5
Catalytic reaction condition filters recycle catalyst after reaction with embodiment 2, and be recycled and reused for 2,4-D adds hydrogen
Dechlorination (the catalysis reaction time is 2h every time), after recycling 5 times, 2,4-D removal rate is 84.1%.As it can be seen that the catalysis
Agent remains to keep higher activity after a number of uses.
Claims (10)
1. a kind of hollow titanium dioxide ball embeds the method that Pd catalyst removes 2,4-D, which is characterized in that include the following steps：
Step 1)：By PdCl2With SiO2Pd/SiO is made after water bath method for ball solution mixing2；
Step 2)：By Pd/SiO2Be added ethyl alcohol, butyl titanate and cetyl trimethylammonium bromide mixed liquor, through drying,
Roasting obtains Pd/SiO2@TiO2；
Step 3)：By Pd/SiO2@TiO2NaOH solution, agitated successively, washing, drying, H is added2Reduction, obtains hollow TiO2
Ball embeds Pd catalyst, i.e. Pd@hTiO2；
Step 4)：By Pd@hTiO2In water body of the input containing 2,4-D, control ph is 9~12, and under normal temperature and pressure conditions first
After be passed through N2And H2Carry out catalytic hydrogenation and dechlorination reaction.
2. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
SiO in the step 1)2The preparation method of ball is：The mixed solution of ethyl orthosilicate and ethyl alcohol is added rapidly to ammonium hydroxide and second
It in the mixed solution of alcohol, after mixing, is washed repeatedly using ethyl alcohol and distilled water, in 70 DEG C of vacuum dryings.
3. hollow titanium dioxide ball as claimed in claim 2 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
The volume ratio of the ethyl orthosilicate and ethyl alcohol is 1: 10；The volume ratio of ammonium hydroxide and ethyl alcohol is 1: 2.
4. hollow titanium dioxide ball as claimed in claim 1 or 2 embeds the method that Pd catalyst removes 2,4-D, feature exists
In the SiO in the step 1)2A diameter of 360nm of nanosphere.
5. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
SiO in the step 2)2The mass ratio of ball and butyl titanate is 1: 2~6；SiO2Ball and cetyl trimethylammonium bromide
Mass ratio is 2~8: 1.
6. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
Calcination temperature in the step 2) is 300 DEG C, roasting time 3h, and heating rate is 3 DEG C/min.
7. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
Pd/SiO in the step 3)2@TiO2With NaOH solution mass/volume ratio be 1: 100 (g/mL), a concentration of the 2.0 of NaOH solution
~4.0mol/L；The mass content of Pd is 0.5~3.0% in Pd catalyst.
8. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
H in the step 3)2Reduction is specially：The reductase 12 h at 300 DEG C, heating rate are 10 DEG C/min, H2Flow velocity be 40mL/
min。
9. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
The initial concentration of 2,4-D water bodys is 20~100mg/L in the step 4)；Pd@hTiO2Mass ratio with 2,4-D water bodys is 1:
2000~8000.
10. hollow titanium dioxide ball as described in claim 1 embeds the method that Pd catalyst removes 2,4-D, which is characterized in that
The reaction temperature that catalytic hydrogenation and dechlorination reacts in the step 4) is 15~25 DEG C, and the reaction time is 40~120min；PH value tune
It saves agent and uses HCl or NaOH solution.
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Cited By (1)
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| CN113996290A (en) * | 2020-07-27 | 2022-02-01 | 中国科学院大连化学物理研究所 | Platinum or palladium catalyst with titanium dioxide coated metal nanoparticles, preparation and application thereof |
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Application publication date: 20180914 |