CN1695801A - Catalyst in use for treating sewage through heterogeneous catalysis and oxidation, and preparing method - Google Patents
Catalyst in use for treating sewage through heterogeneous catalysis and oxidation, and preparing method Download PDFInfo
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- CN1695801A CN1695801A CN 200510011496 CN200510011496A CN1695801A CN 1695801 A CN1695801 A CN 1695801A CN 200510011496 CN200510011496 CN 200510011496 CN 200510011496 A CN200510011496 A CN 200510011496A CN 1695801 A CN1695801 A CN 1695801A
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- oxydation
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Abstract
A catalyst for treating sewage by multi-phase catalytic oxidizing is prepared from Fe, and one of Zn, Cu, Co and Mn through codepositing by precipitant, drying at 90-110 deg.C, and heat treating at 200-500 deg.C.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that is used for heterogeneous catalytic oxidation Treatment of Wastewater in Coking and phenol-containing wastewater.
Background technology
Coking chemical waste water is the waste water that produces in coal system coke, gas purification and the coke chemicals removal process, is subjected to all multifactor influences such as raw coal character, coke making process, coke chemicals recovery, and its complicated component is changeable, belongs to unmanageable industrial wastewater.Hardly degraded organic substance matter occupies the majority in the coking chemical waste water, mainly contain phenols, polycyclic aromatic hydrocarbon, itrogenous organic substance and heterocyclic compound, wherein the phenolic compound based on phenol accounts for total amount of organic more than 70%, these components in the coking chemical waste water have a significant impact environment, phenolic compound particularly, can make protein coagulating, the mankind, aquatic products and crops are all had very big harm.
The catalytic wet air oxidation that is used for Treatment of Wastewater in Coking at present is a kind of treatment technology (US 4699720,1987) of handling high concentration difficult for biological degradation organic wastewater that the eighties grows up in the world.It is in reactor, under catalyst action, directly the oxidation operation in the sewage is become harmless objects such as carbon dioxide, water with oxygen or air under high-temperature and high-pressure conditions, to reach the purpose of purification.So far there is multiple transition metal oxide to be considered to that wet oxidation is had catalytic activity, people such as the Du Hongzhang of DaLian, China Chemical Physics research institute, room Lian Qing are at (water technology 23 (1997, the activity of the noble metal catalyst series of 2) 83-87) mentioning is high, the life-span is long, but cost an arm and a leg, make its application be subjected to great restriction.The rare earth metal catalyst has stronger stability and adaptability, but activity remains further to be improved.The copper catalyst series is active high, cheap and easy to get, it is widely used in CWO, but there is copper ion Cu in such catalyst
2+The stripping problem is used because a large amount of consumption of catalyst have restricted its scale.Catalytic wet air oxidation is handled high concentrated organic wastewater will carry out the treatment process more complicated in high-temperature high-pressure reaction kettle.
Summary of the invention
Technical problem to be solved by this invention is: propose a kind of Catalysts and its preparation method that is used for heterogeneous catalytic oxidation Treatment of Wastewater in Coking and phenol-containing wastewater.Because this catalyst does not contain noble metal, cost is low, and the preparation method is easy, and the good stability of catalyst is to organic pollutant removal rate height.
A kind of multiphase catalysis oxydation sewage treatment catalyst that the present invention proposes, this catalyst is the primary activity component with iron Fe, a kind of among zinc Zn, copper Cu, cobalt Co or the manganese Mn is the auxiliary activity component, and the composition of catalyst calculates with the content of oxide: di-iron trioxide Fe
2O
3(60～90%), cobaltosic oxide Co
3O
4, manganese dioxide MnO
2, cupric oxide CuO or zinc oxide ZnO (10～40%).
This Preparation of catalysts method comprises following each step:
(1) the soluble-salt configuration 1.0mol/L solution that contains catalytic component, is made into mixed solution by component;
(2) mixed solution is stirred fast, slowly drip precipitating reagent and obtain sediment, the pH value of solution value is 8～9;
(3) sediment is left standstill 24 hours;
(4) isolated by filtration sediment is with distilled water flush away foreign ion, under the air atmosphere normal pressure in 90～110 ℃ of baking ovens dry 5～9 hours;
(5) drying sample places 200～500 ℃ of muffle furnaces, and air atmosphere heat treatment 1～2 hour promptly gets the multiphase catalysis oxydation sewage treatment catalyst.
Soluble-salt is ferric sulfate Fe described in the above-mentioned preparation method (1)
2(SO
4)
3, iron chloride FeCl
3, ferric nitrate Fe (NO
3)
3, zinc sulfate ZnSO
4, zinc nitrate Zn (NO
3)
2, copper nitrate Cu (NO
3)
2Or manganese chloride MnCl
2(2) the ammoniacal liquor NH of the precipitating reagent in
3H
2O, 20% sodium carbonate Na
2CO
3Or 10% NaOH NaOH.
The beneficial effect that the present invention has:
Use this catalyst through the phenol synthetic water of catalytic oxidation treatment CODcr value as 2870mg/L, handle back CODcr value less than 20mg/L, clearance is 99.3%.Catalyst of the present invention can be reduced to below the 30mg/L by 1000mg/L through catalytic oxidation treatment coking chemical waste water CODcr value, and well below discharging standards (less than 150mg/L), clearance is 97%.
Description of drawings
Fig. 1 is the ultraviolet-visible spectrogram of the simulation phenolic waste water of 2870mg/L for the CODcr value.
Fig. 2 is through the ultraviolet spectrogram after the catalytic oxidation treatment.
The specific embodiment
The multiphase catalysis oxydation sewage treatment catalyst, its composition is: the content with oxide calculates: di-iron trioxide Fe
2O
3(60～90%), cobaltosic oxide Co
3O
4, manganese dioxide MnO
2, cupric oxide CuO and zinc oxide ZnO (10～40%).
Composition and content according to its catalyst prepare catalyst.
Embodiment 1: the preparation of catalyst A
Fe with 1.0mol/L
2(SO
4)
3The ZnSO of solution 200ml and 1.0mol/L
4Solution 40ml mixes, and stirs fast with magnetic stirring apparatus, slowly drips 20% Na
2CO
3Solution to pH value of solution value is 8～9, leaves standstill 24h under normal temperature.
Adopt filtered off with suction that precipitation is separated with mother liquor,,, in 200～500 ℃ of air atmospheres, heat-treat again, obtain catalyst (A) sediment dry 5～9h in 90～110 ℃ of air atmospheres with distilled water flush away foreign ion.
Embodiment 2: the preparation of catalyst B
Fe (NO with 1.0mol/L
3)
3Cu (the NO of solution 200ml and 1.0mol/L
3)
2Solution 20ml mixes, and stirs fast with magnetic stirring apparatus, slowly drips 20% Na
2CO
3Other condition of solution is identical with embodiment 1, and heat treatment temperature is 200 ℃ and gets catalyst (B).
Embodiment 3: the preparation of catalyst C
FeCl with 1.0mol/L
3The MnCl of solution 200ml and 1.0mol/L
2Solution 60ml mixes, and stirs fast with magnetic stirring apparatus, and it is identical with embodiment 1 slowly to drip other condition of 10%NaOH solution, heat treatment temperature be 500 ℃ must catalyst (C).
Embodiment 4: the preparation of catalyst D
Fe (NO with 1.0mol/L
3)
3Mn (the NO of solution 200ml and 1.0mol/L
3)
2Solution 60ml mixes, and stirs fast with magnetic stirring apparatus, and it is identical with embodiment 1 slowly to drip other condition of 10%NaOH solution, heat treatment temperature be 500 ℃ must catalyst (D).
Fig. 1 is the ultraviolet-visible spectrogram of the simulation phenolic waste water of 2870mg/L for the CODcr value, and very strong phenol characteristic absorption peak is arranged at the 270nm place as can be seen from Figure 1;
Fig. 2 is that the characteristic absorption peak of 270nm place phenol has disappeared as can be seen from Figure 2, illustrates by catalytic oxidation constitutionally stable phenyl ring have been opened through the ultraviolet spectrogram after the catalytic oxidation treatment.
Claims (3)
1. a multiphase catalysis oxydation sewage treatment catalyst is characterized in that, is the primary activity component with iron Fe, and a kind of among zinc Zn, copper Cu, cobalt Co or the manganese Mn is the auxiliary activity component, and the composition of catalyst calculates with the content of oxide: di-iron trioxide Fe
2O
3(60～90%), cobaltosic oxide Co
3O
4, manganese dioxide MnO
2, cupric oxide CuO or zinc oxide ZnO (10～40%).
2. a multiphase catalysis oxydation sewage treatment Preparation of catalysts method is characterized in that, this method comprises following each step:
(1) soluble-salt that contains catalytic component is made into the solution of 1.0mol/L, is made into mixed solution in the component ratio;
(2) mixed solution is stirred fast, slowly drip precipitating reagent and obtain sediment, the pH value of solution value is 8～9;
(3) sediment is left standstill 24 hours;
(4) isolated by filtration sediment, with distilled water flush away foreign ion, under the air atmosphere normal pressure, drying is 5～9 hours in 90～110 ℃ of baking ovens;
(5) drying sample is placed 200～500 ℃ of muffle furnaces, air atmosphere heat treatment 1～2 hour promptly gets the multiphase catalysis oxydation sewage treatment catalyst.
3. multiphase catalysis oxydation sewage treatment Preparation of catalysts method according to claim 2 is characterized in that soluble-salt is ferric sulfate Fe
2(SO
4)
3, iron chloride FeCl
3, ferric nitrate Fe (NO
3)
3, zinc sulfate ZnSO
4, zinc nitrate Zn (NO
3)
2, copper nitrate Cu (NO
3)
2Or manganese chloride MnCl
2Precipitating reagent is ammoniacal liquor NH
3H
2O, 20% sodium carbonate Na
2CO
3Or 10% NaOH NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100114963A CN1325161C (en) | 2005-03-29 | 2005-03-29 | Catalyst in use for treating sewage through heterogeneous catalysis and oxidation, and preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100114963A CN1325161C (en) | 2005-03-29 | 2005-03-29 | Catalyst in use for treating sewage through heterogeneous catalysis and oxidation, and preparing method |
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|---|---|
| CN1695801A true CN1695801A (en) | 2005-11-16 |
| CN1325161C CN1325161C (en) | 2007-07-11 |
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ID=35348786
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395022C (en) * | 2006-07-04 | 2008-06-18 | 北京交通大学 | Activated charcoal carried copper oxide catalyst and process for preparing same |
| CN101759278B (en) * | 2010-02-04 | 2011-07-20 | 江南大学 | Ozonation water treatment method taking nanometer zinc oxide as catalyst |
| CN104148067A (en) * | 2014-03-05 | 2014-11-19 | 朱同德 | Flocculation catalyst applied to polymer-containing oilfield oil production wastewater and preparation method of catalyst |
| CN104659379A (en) * | 2015-02-13 | 2015-05-27 | 清华大学 | Nanometer iron-manganese composite oxide loaded gas diffusion electrode and preparation and application thereof |
| CN106111156A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | Efficient class Fenton magnetic catalyst based on clay mineral and preparation method and application |
| CN106622275A (en) * | 2016-11-17 | 2017-05-10 | 龙岩紫荆创新研究院 | Preparation method of manganese cobalt catalyst for ammonium bisulfate decomposition |
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| CN103373757A (en) * | 2013-07-10 | 2013-10-30 | 上海睿优环保工程技术有限公司 | Method for treating nondegradable organic wastewater by oxidation by transition metal catalyst |
| CN103623840B (en) * | 2013-11-18 | 2015-07-22 | 西南科技大学 | Low-heat degrading catalyst and preparation and usage methods thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052480C (en) * | 1996-06-28 | 2000-05-17 | 中国石油化工总公司 | Method for preparing gamma-butyl lactone by gas-phase dehydrogenation of 1, 4-butanediol |
| CN1151875C (en) * | 2001-11-16 | 2004-06-02 | 中国科学院大连化学物理研究所 | Copper base catalyst for catalyzing wet oxidation method treating industrial waste water |
-
2005
- 2005-03-29 CN CNB2005100114963A patent/CN1325161C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395022C (en) * | 2006-07-04 | 2008-06-18 | 北京交通大学 | Activated charcoal carried copper oxide catalyst and process for preparing same |
| CN101759278B (en) * | 2010-02-04 | 2011-07-20 | 江南大学 | Ozonation water treatment method taking nanometer zinc oxide as catalyst |
| CN104148067A (en) * | 2014-03-05 | 2014-11-19 | 朱同德 | Flocculation catalyst applied to polymer-containing oilfield oil production wastewater and preparation method of catalyst |
| CN104659379A (en) * | 2015-02-13 | 2015-05-27 | 清华大学 | Nanometer iron-manganese composite oxide loaded gas diffusion electrode and preparation and application thereof |
| CN106111156A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | Efficient class Fenton magnetic catalyst based on clay mineral and preparation method and application |
| CN106111156B (en) * | 2016-06-23 | 2018-09-11 | 上海交通大学 | Efficient class Fenton magnetic catalyst and preparation method based on clay mineral and application |
| CN106622275A (en) * | 2016-11-17 | 2017-05-10 | 龙岩紫荆创新研究院 | Preparation method of manganese cobalt catalyst for ammonium bisulfate decomposition |
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| Publication number | Publication date |
|---|---|
| CN1325161C (en) | 2007-07-11 |
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