CN104399460A - Catalyst for industrial wastewater treatment and preparation method of catalyst - Google Patents
Catalyst for industrial wastewater treatment and preparation method of catalyst Download PDFInfo
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- CN104399460A CN104399460A CN201410799140.XA CN201410799140A CN104399460A CN 104399460 A CN104399460 A CN 104399460A CN 201410799140 A CN201410799140 A CN 201410799140A CN 104399460 A CN104399460 A CN 104399460A
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Abstract
The invention discloses a catalyst for industrial wastewater treatment and a preparation method of the catalyst. The catalyst comprises a carrier and catalytic components loaded on the carrier, wherein the carrier adopts nanometer rare earth CeO2, the catalytic components adopt precious metal Pt and/or Ru, and the catalytic components account for 0.1%-1% of the total weight of the catalyst. The precious metal loading capacity of the catalyst is low, the dispersity is high, and the catalyst stability is good; and according to the preparation method, the synthesis technology is simple, and the cost is low.
Description
Technical field
The invention belongs to industrial waste water treatment, be specifically related to a kind of Industrial Wastewater Treatment Catalysts and its preparation method.
Background technology
Since 20 beginnings of the century, Wet Oxidation Process has been used to process the organic wastewater of poisonous, harmful, the difficult degradation in water, Organic substance in water can be oxidized to nontoxic carbon dioxide and water, when catalyst-free, temperature often needs to rise to 320 DEG C, and pressure is up to 20Mpa.In order to energy-saving and emission-reduction, reaction temperature can be down to less than 200 DEG C by adding of catalyst, and pressure can be down to below 3Mpa.At present, the catalyst used mainly is divided into two kinds: homogeneous phase and heterogeneous catalysis.The Organic substance in water although homogeneous catalyst can effectively be degraded, underwater gold belongs to ion and but needs other step to dispel.So segregative heterogeneous catalysis degraded Organic substance in water obtained people in the last few years and more paid close attention to, and heterogeneous catalysis can be divided into noble metal and transition-metal catalyst.Noble metal catalyst is higher with transition-metal catalyst phase specific catalytic activity, but cost is too high, and transition-metal catalyst exists the shortcomings such as active component easily runs off.Therefore, exploitation noble metal dosage is few, catalytic activity is high has huge industrial application value with the process industrial wastewater catalyst of good stability.
Summary of the invention
The object of the present invention is to provide a kind of Industrial Wastewater Treatment catalyst.
Another object of the present invention is to the preparation method that above-mentioned catalyst is provided.
Concrete technical scheme of the present invention is as follows:
A kind of Industrial Wastewater Treatment catalyst, comprises carrier and is in debt and the catalyst component on carrier, carrier is nano rare earth CeO
2, catalyst component is precious metals pt and/or Ru, and the amount of this catalyst component is 0.1 ~ 1wt% of described total catalyst weight.
A preparation method for above-mentioned Industrial Wastewater Treatment catalyst, comprises the steps:
(1) take cerous nitrate and NaOH by the mol ratio of 20 ~ 100:1, and add water respectively and be mixed with cerous nitrate solution and sodium hydroxide solution;
(2), after above-mentioned cerous nitrate solution and sodium hydroxide solution fully being mixed, at the temperature of 100 ~ 180 DEG C, react 10 ~ 24h, obtain support precursor solution;
(3) by support precursor solution obtained for step (2) in 80 ~ 100 DEG C of oven dry, then in air atmosphere 300 ~ 700 DEG C of roasting 2 ~ 5h, be cooled to room temperature, obtain described carrier;
(4) protective agent, reducing agent and precious metals pt and/or Ru presoma hybrid reaction are prepared precious metals pt and/or Ru nano particle, wherein the mass ratio of protective agent and described precious metals pt and/or Ru is 1 ~ 5:1, and the mol ratio of reducing agent and described precious metals pt and/or Ru is 1 ~ 10:1;
(5) after the precious metals pt prepared by step (4) and/or Ru nano particle and described carrier mix and blend 3 ~ 10h, again successively after filtration, after washing and the vacuum drying of 60 ~ 150 DEG C, obtain described Industrial Wastewater Treatment catalyst, wherein the amount of precious metals pt and/or Ru nano particle is 0.1 ~ 1wt% of described Industrial Wastewater Treatment total catalyst weight.
In a preferred embodiment of the invention, the reaction time in described step (2) is 14 ~ 24h.
In a preferred embodiment of the invention, in described step (3), the temperature of roasting is 400 ~ 600 DEG C, and roasting time is 4 ~ 5h.
In a preferred embodiment of the invention, the protective agent of described step (4) is polyvinylpyrrolidone PVP or PVAC polyvinylalcohol.
In a preferred embodiment of the invention, the reducing agent of described step (4) is sodium borohydride or hydrazine hydrate.
The invention has the beneficial effects as follows:
1, in catalyst of the present invention, noble-metal-supported amount is low, and decentralization is high, and catalyst stability is good;
2, catalyst of the present invention is applicable to difficult degradation, particularly containing in phenol organic wastewater, organic matter can be changed into less molecule or be converted into water and carbon dioxide by the method for wet oxidation.Utilize autoclave, be less than 150 DEG C in reaction temperature, within gross pressure is below 2Mpa, reaction time 3h, phenol 100% transformed, and COD (COD) is degraded more than 95%.
3, adopt this catalyst also degradable methyl alcohol or formic acid wastewater, reaction temperature is less than 50 DEG C, and gross pressure is that below 2Mpa, COD clearance is close to 100%.
4, preparation method's synthesis technique of the present invention is simple, and cost is low, by regulating ratio and the hydrothermal temperature of different cerium oxide and NaOH, synthesizes the cerium oxide with different catalytic performance.The decentralization of noble metal carrier catalyst can be improved by sol method, effectively noble metal dosage must be reduced to 0.1% ~ 1wt%.Therefore, by above method, the catalyst that catalytic activity is high, energy consumption is low and price is low can be synthesized, in the technology of CWO.
Accompanying drawing explanation
Fig. 1 is CeO prepared in the embodiment of the present invention 1 to 3
2the XRD result of carrier;
Fig. 2 is CeO prepared in the embodiment of the present invention 1 to 3
2one of transmission electron microscope picture of carrier;
Fig. 3 is CeO prepared in the embodiment of the present invention 1 to 3
2the transmission electron microscope picture two of carrier.
Detailed description of the invention
By reference to the accompanying drawings below by way of detailed description of the invention technical scheme of the present invention is further detailed and is described.
Embodiment 1: loaded noble metal catalyst prepares I (comparative example)
By 6g Ce (NO
3)
36H
2o is dissolved in after in 60mL water, adds rapidly 60mL10%NaOH solution, and stirs 18h.Filtered by sediment, wash, dry 12h in 60 DEG C of air after, in Muffle furnace, at 600 DEG C, roasting 4h, obtains CeO
2-A carrier; Get 2.2mL H
2ptCl
66H
2the aqueous solution (1g/250mL) of O, adds 0.8mL PVP protective agent (0.1M), after ultrasonic 10min, adds 2mL sodium borohydride aqueous solution (0.1M), stirs 1h.0.5g nano Ce O is added in the solution after reduction
2-A carrier, and stir 5h.In 100 DEG C of air, dry 12h after filtration, washing, obtain Pt/CeO
2-A catalyst.
Take the CeO of the above-mentioned preparation of 50mg
2-A carrier or Pt/CeO
2-A catalyst adds in 20mL wastewater containing phenol, and COD is 2500ppm, and reaction pressure is 1Mpa, and reaction temperature is 140 DEG C.After reaction 2h, CeO as shown in Table 1 and Table 2
2-A degradable 42%COD, and Pt/CeO
2the COD degradation rate of-A is close to 55%.
Embodiment 2: loaded noble metal catalyst prepares II
By 1.5g Ce (NO
3)
36H
2o adds in 10mL deionized water, and ultrasonic 20min.12.8g NaOH is dissolved in 70mL deionized water, and ultrasonic 20min.Again above two kinds of solution are mixed and stir 20min.Move to after stirring in water heating kettle, after closing, be warming up to 180 DEG C, keep 14h.Dry in 100 DEG C of air after filtration washing, in Muffle furnace, 400 DEG C of roasting 5h, obtain nano Ce O
2-B carrier; Get 2.2mL H
2ptCl
66H
2the aqueous solution (1g/250mL) of O, adds 0.8mL PVP protective agent (0.1M), after ultrasonic 10min, adds 2mL sodium borohydride aqueous solution (0.1M), stirs 1h.0.5g nano Ce O is added in the solution after reduction
2-B carrier, and stir 5h.In 100 DEG C of air, dry 12h after filtration, washing, obtain Pt/CeO
2-B catalyst.
Take the CeO of the above-mentioned preparation of 50mg
2-B carrier or Pt/CeO
2-B catalyst adds in 20mL wastewater containing phenol, and COD is 2500ppm, and reaction pressure is 1Mpa, and reaction temperature is 140 DEG C.After reaction 2h, CeO as shown in Table 1 and Table 2
2-B degradable 32%COD, and Pt/CeO
2the COD degradation rate of-B is 96%, demonstrates higher catalytic activity, and as shown in table 3, Pt/CeO
2the reaction stability of-B is good.
Embodiment 3: loaded noble metal catalyst prepares III
Similar to embodiment 2, by 1.5g Ce (NO
3)
36H
2o and 24g NaOH is dissolved in ionized water respectively, then mixes and stirs 20min.Move to after stirring in water heating kettle, after closing, be warming up to 100 DEG C, keep 24h.Dry in 100 DEG C of air after filtration, washing.In Muffle furnace, 600 DEG C of roasting 4h, obtain nano Ce O
2-C carrier; Get 1.58mLH
2ptCl
66H
2the aqueous solution (1g/250mL) of O, adds 0.9mL PVP protective agent (0.1M), after ultrasonic 10min, adds 1.38mL sodium borohydride aqueous solution (0.1M), stirs 1h.Then 0.5g nano Ce O is added
2-C carrier, and stir 5h.In 120 DEG C of air, dry 12h after filtration, washing, obtain Pt/CeO
2-C catalyst.
Experimental technique and example 1, example 2 are similar, and added by 50mg catalyst after in 20mL phenolic waste water, reaction pressure is 1Mpa, and reaction temperature is 140 DEG C.After reaction 2h, as shown in Table 1 and Table 2, Pt/CeO
2-C catalyst can transform 84%COD.
Embodiment 4: loaded noble metal catalyst prepares IV
By 1.5g Ce (NO
3)
36H
2o adds in 10mL deionized water, and ultrasonic 20min.12.8g NaOH is dissolved in 70mL deionized water, and ultrasonic 20min.Again above two kinds of solution are mixed and stir 20min.Move to after stirring in water heating kettle, after closing, be warming up to 180 DEG C, keep 14h.Dry in 100 DEG C of air after filtration washing, in Muffle furnace, 400 DEG C of roasting 5h, obtain nano Ce O
2-B carrier; Get 2.56mL RuCl
3xH
2the aqueous solution (1g/500mL) of O, adds 0.9mL PVP protective agent (0.1M), after ultrasonic 10min, adds 1.38mL sodium borohydride aqueous solution (0.1M), stirs 1h.Then 0.5g nano Ce O is added
2-C carrier, and stir 5h.In 120 DEG C of air, dry 12h after filtration, washing, obtain Ru/CeO
2-B catalyst.
Embodiment 5: loaded noble metal catalyst prepares V
By 1.5g Ce (NO
3)
36H
2o adds in 10mL deionized water, and ultrasonic 20min.12.8g NaOH is dissolved in 70mL deionized water, and ultrasonic 20min.Again above two kinds of solution are mixed and stir 20min.Move to after stirring in water heating kettle, after closing, be warming up to 180 DEG C, keep 14h.Dry in 100 DEG C of air after filtration washing, in Muffle furnace, 400 DEG C of roasting 5h, obtain nano Ce O
2-B carrier; Get 0.79mL H
2ptCl
66H
2the aqueous solution (1g/250mL) of O and 1.28mL RuCl
3xH
2the aqueous solution (1g/500mL) of O, adds 0.9mL PVP protective agent (0.1M), after ultrasonic 10min, adds 1.38mL sodium borohydride aqueous solution (0.1M), stirs 1h.Then 0.5g nano Ce O is added
2-C carrier, and stir 5h.In 120 DEG C of air, dry 12h after filtration, washing, obtain Pt/CeO
2-C catalyst.
CeO prepared by above-described embodiment 1 to 3
2as shown in Figure 1, transmission electron microscope picture as shown in Figures 2 and 3 for the XRD result of carrier.
The table 1 related in above-described embodiment, 2 and 3 specific as follows:
Each CeO in table 1 embodiment 1 to 3
2the reactivity of carrier catalysis wet oxidation phenolic waste water
Each Pt/CeO in table 2 embodiment 1 to 3
2the reactivity of catalyst wet oxidation phenolic waste water
Pt/CeO prepared by table 3 embodiment 2
2the stability of-B catalyst wet oxidation phenolic waste water
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (6)
1. an Industrial Wastewater Treatment catalyst, is characterized in that: comprise carrier and be in debt and the catalyst component on carrier, carrier is nano rare earth CeO
2, catalyst component is precious metals pt and/or Ru, and the amount of this catalyst component is 0.1 ~ 1wt% of described total catalyst weight.
2. a preparation method for Industrial Wastewater Treatment catalyst according to claim 1, is characterized in that: comprise the steps:
(1) take cerous nitrate and NaOH by the mol ratio of 20 ~ 100:1, and add water respectively and be mixed with cerous nitrate solution and sodium hydroxide solution;
(2), after above-mentioned cerous nitrate solution and sodium hydroxide solution fully being mixed, at the temperature of 100 ~ 180 DEG C, react 10 ~ 24h, obtain support precursor solution;
(3) by support precursor solution obtained for step (2) in 80 ~ 100 DEG C of oven dry, then in air atmosphere 300 ~ 700 DEG C of roasting 2 ~ 5h, be cooled to room temperature, obtain described carrier;
(4) protective agent, reducing agent and precious metals pt and/or Ru presoma hybrid reaction are prepared precious metals pt and/or Ru nano particle, wherein the mass ratio of protective agent and described precious metals pt and/or Ru is 1 ~ 5:1, and the mol ratio of reducing agent and described precious metals pt and/or Ru is 1 ~ 10:1;
(5) after the precious metals pt prepared by step (4) and/or Ru nano particle and described carrier mix and blend 3 ~ 10h, again successively after filtration, after washing and the vacuum drying of 60 ~ 150 DEG C, obtain described Industrial Wastewater Treatment catalyst, wherein the amount of precious metals pt and/or Ru nano particle is 0.1 ~ 1wt% of described Industrial Wastewater Treatment total catalyst weight.
3. preparation method as claimed in claim 2, is characterized in that: the reaction time in described step (2) is 14 ~ 24h.
4. preparation method as claimed in claim 2, is characterized in that: in described step (3), the temperature of roasting is 400 ~ 600 DEG C, and roasting time is 4 ~ 5h.
5. preparation method as claimed in claim 2, is characterized in that: the protective agent of described step (4) is polyvinylpyrrolidone PVP or PVAC polyvinylalcohol.
6. preparation method as claimed in claim 2, is characterized in that: the reducing agent of described step (4) is sodium borohydride or hydrazine hydrate.
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Cited By (5)
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| CN104549257A (en) * | 2015-01-14 | 2015-04-29 | 厦门大学 | Catalyst for treating organic small molecule wastewater and preparation method of catalyst |
| CN108736030A (en) * | 2018-05-17 | 2018-11-02 | 福州大学 | A kind of porous no C catalyst of used in proton exchange membrane fuel cell and preparation method thereof |
| CN109153588A (en) * | 2016-05-25 | 2019-01-04 | 国际壳牌研究有限公司 | The method for handling waste water |
| CN109621951A (en) * | 2018-12-31 | 2019-04-16 | 内蒙古大学 | A kind of three-way catalyst and preparation method thereof preparing glyceric acid for aoxidizing glycerol |
| CN115646511A (en) * | 2022-11-29 | 2023-01-31 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549257A (en) * | 2015-01-14 | 2015-04-29 | 厦门大学 | Catalyst for treating organic small molecule wastewater and preparation method of catalyst |
| CN109153588A (en) * | 2016-05-25 | 2019-01-04 | 国际壳牌研究有限公司 | The method for handling waste water |
| CN109153588B (en) * | 2016-05-25 | 2021-09-24 | 国际壳牌研究有限公司 | Method for treating waste water |
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| CN108736030A (en) * | 2018-05-17 | 2018-11-02 | 福州大学 | A kind of porous no C catalyst of used in proton exchange membrane fuel cell and preparation method thereof |
| CN108736030B (en) * | 2018-05-17 | 2020-12-25 | 福州大学 | Porous carbon-free catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN109621951A (en) * | 2018-12-31 | 2019-04-16 | 内蒙古大学 | A kind of three-way catalyst and preparation method thereof preparing glyceric acid for aoxidizing glycerol |
| CN115646511A (en) * | 2022-11-29 | 2023-01-31 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
| CN115646511B (en) * | 2022-11-29 | 2024-04-05 | 厦门大学 | Catalytic wet oxidation catalyst and preparation method and application thereof |
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