CN102101715A - Treatment method of organic waste water - Google Patents
Treatment method of organic waste water Download PDFInfo
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- CN102101715A CN102101715A CN2009101177559A CN200910117755A CN102101715A CN 102101715 A CN102101715 A CN 102101715A CN 2009101177559 A CN2009101177559 A CN 2009101177559A CN 200910117755 A CN200910117755 A CN 200910117755A CN 102101715 A CN102101715 A CN 102101715A
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- waste water
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Abstract
The invention discloses a treatment method of organic waste water. In the treatment method, a supported catalyst made of carbonyl metal is used, so that the chemical oxygen demands (COD) of various high-concentration organic waste waters can be effectively reduced under the mild condition; and the catalyst is convenient for separation and can be recycled, reaction condition is mild, and the treatment method is easy to operate.
Description
Technical field
The invention provides a kind of method that can carry out the Catalytic Wet Oxidation processing to various organism in the waste water.Be to be that the supported catalyst of precursor preparation is handled organic waste water under comparatively gentle condition specifically, belong to water technology and environment functional material field with the metallic carbonyls complex compound.
Background technology
Along with the fast development of industry, the water environment pollution problem also is on the rise.Especially the development of industries such as medicine, chemical industry, dyestuff makes high concentration hard-degraded organic waste water more and more, is a big difficult point of wastewater treatment.
In recent years, developed country all attached great importance to the substitute technology of exploitation innovation in the world, to scheme to improve processing efficiency and reduction processing costs.Occur with new vitality so Catalytic Wet Oxidation is very fast, it can reduce the needed pressure and temperature of reaction, accelerates speed of reaction, thereby carries out extensive and deep research and development in states such as the U.S., Japan, the European Community.
Catalytic Wet Oxidation is the purification techniques of the processing high concentrated organic wastewater that grows up of external the eighties, can under relatively mild condition organism be degraded fully and generates micromolecular CO
2, N
2, H
2O.Catalytic Wet Oxidation is because its reaction conditions gentleness, the reaction times is short, energy consumption is little, secondary pollution is few etc., and advantage has caused people's extensive concern.The catalytic wet oxidation method all has a large amount of catalyzer patents to occur in the application that states such as Japan have obtained industrially scalable every year; Also started the research focus of Catalytic Wet Oxidation in Europe, and less relatively in the research of China's this respect.This method is used for Treatment of Cyanide-containing Wastewater, nitrogenous effluent, sulfur-containing waste water, alcohol waste water, coal gas waste, waste water from dyestuff and paper waste or the like, and effect is fine.
Though the non-precious metal catalyst in the catalytic wet air oxidation also has certain catalytic activity, the stripping of its catalyzer and coking are still unresolved so far.A large amount of precious metal catalyst series that studies show that is handled in the waste water at catalytic wet air oxidation very high activity and stability (Janez Levec, Albin Pintar, Catalysis Today 124 (2007) 172-184).The wet oxidizing catalyst that is used for wastewater treatment at present is mostly with TiO
2, ZrO
2, CeO
2Deng oxide compound or composite oxides is carrier.For example JP-A63-158189 discloses the catalyzer of metal oxides such as using titanium dioxide and precious metal combination, has obtained certain effect, but for satisfying efficient handle required high temperature, condition of high voltage, has also had facility cost problem.Also having patents such as CN101045204A, CN1498861A, US4699720 all is at TiO
2, ZrO
2Or carried noble metal on its composite oxides, and noble metal precursor all is muriate and the nitrate of Pt, Pd, Ru, Ir, Rh etc., bullion content is generally higher, the complicated process of preparation of carrier, will certainly influence its cost, and the high capacity amount of metal can produce stripping and coking to a certain extent and influence its catalytic activity and life-span.
Summary of the invention
The purpose of this invention is to provide a kind of method that can carry out the Catalytic Wet Oxidation processing to various different organism in the waste water.Catalyzer adopts simple preparation technology to prepare low charge capacity, highly active catalyzer in this method, is used for the Catalytic Wet Oxidation of waste water, can make the COD in the water reduce significantly under comparatively gentle condition.
Because organic components complexity, concentration height in the waste water, the simple catalyzer that adopts in general Catalytic Wet Oxidation process is difficult to reach high treatment efficiency, and the present invention can carry out Catalytic Wet Oxidation to various organism in the waste water and handle.
The present invention adopts the supported catalyst of metallic carbonyls preparation, can effectively reduce the COD in the various different high concentrated organic wastewaters under mild conditions, and catalyzer is convenient to separate, and reuses the gentle easy handling of reaction conditions.
A kind of treatment process of organic waste water is characterized in that this method is a catalyzer with the load metallic carbonyls, and metallic carbonyls is one or both combinations among Ru, the Co, and support of the catalyst is selected from Al
2O
3, gac, TiO
2, ZrO
2, CeO
2In at least a or their combination; The weight percentage of metal is 0.01～5% (with respect to carrier), wherein the weight percent of precious metal element (with respect to carrier) is 0.05～0.3%, with the oxygen-containing gas is oxygenant, organism in the oxidative degradation waste water, temperature of reaction is 90～250 ℃, reaction stagnation pressure 1.0～6.0MPa reacted 1～3 hour.
Organism in the described waste water comprises organism such as alcohols, phenols, aromatic hydrocarbons, carboxylic-acid and nitrogenous compound, is specially phenol, Virahol, N, dinethylformamide (DMF), acetate.
COD in the described organic wastewater is 50～50000mg/L.
Oxygen-containing gas of the present invention is an air or oxygen.
The present invention has following advantage: (1) has improved the removal efficient of COD in the high concentrated organic wastewater; (2) reaction conditions is comparatively gentle easy to control; (3) handle various different organic waste waters and all have very high COD clearance; (4) high-dispersion load metallic carbonyls catalyzer, content of metal is low, recyclable utilization.
Specific embodiments
The invention provides a kind of Catalytic Wet Oxidation and handle the method for high concentrated organic wastewater.This method is a catalyzer with the load metallic carbonyls of high dispersive, can be under comparatively gentle condition to water in different organism (for example compounds such as alcohol, phenol, aromatic hydrocarbons, carboxylic acid and itrogenous organic substance) carry out oxidative degradation.
Below by embodiment the present invention is described further.
Embodiment 1 to 4: the experimental result of different loads metallic carbonyls catalyst treatment Virahol waste water.Reaction conditions is: simulated wastewater 20ml (COD=5g/L), catalyst levels are 0.6g, and aerating oxygen, temperature of reaction kettle are 200 ℃, reaction stagnation pressure 4.0MPa, reaction times 2h.Reaction result sees Table 1.
Table 1
| The metallic carbonyls of load | Metal content (wt%) | COD clearance (%) | |
| Embodiment 1 | Co 2(CO) 8 | 5％Co/γ-Al 2O 3 | 50.8 |
| Embodiment 2 | Co 2(CO) 8 | 5％Co/Al-Ti | 55.9 |
| Embodiment 3 | Ru 3(CO) 12 | 0.3％Ru/γ-Al 2O 3 | 90.1 |
| Embodiment 4 | Ru 3(CO) 12 | 0.3％Ru/Al-Ti | 95.0 |
| Embodiment 5 | Ru 3(CO) 12 Co 2(CO) 8 | 0.2％Ru/1％Co/γ-Al 2O 3 | 93.2 |
Embodiment 6 to 9: the removal effect of different concns organic waste water.Adopt Ru
3(CO)
12The 0.3%Ru/Al-Ti catalyzer of preparation is used to handle the Virahol waste water of various concentration, and temperature of reaction is 220 ℃, and the remaining reaction condition is with embodiment 1 to 4, and reaction result sees Table 2
Table 2
| COD (g/L) in the water before the reaction | COD clearance (%) | |
| Embodiment 6 | 6 | 99.8 |
| Embodiment 7 | 10 | 98.9 |
| Embodiment 8 | 20 | 93.1 |
| Embodiment 9 | 30 | 88.0 |
Embodiment 10 to 12: the treatment effect of high concentrated organic wastewater under the differential responses temperature.Adopt Ru
3(CO)
12The 0.3%Ru/Al-Ti catalyzer of preparation is used to handle the Virahol waste water (COD=30g/L) of high density, and reaction conditions is: simulated wastewater 20ml, catalyst levels are 0.6g, aerating oxygen, reaction stagnation pressure 5.0MPa, reaction times 2h.
Table 3
| Temperature of reaction (℃) | COD clearance (%) | |
| Embodiment 10 | 200 | 85.9 |
| Embodiment 11 | 220 | 93.1 |
| Embodiment 12 | 230 | 99.0 |
Embodiment 13 to 16: to the treatment effect of different organic waste waters.Adopt Ru
3(CO)
12The 0.3%Ru/Al-Ti catalyzer of preparation is used to handle phenol, Virahol, N, the simulated wastewater of dinethylformamide (DMF) and acetate, reaction conditions is: simulated wastewater 20ml (COD is 10g/L), catalyst levels is 0.6g, aerating oxygen, the reactor total pressure is 4.0MPa, reaction times 2h.The clearance of different organism its COD under certain temperature of reaction sees Table 3, and phenol is more easily removed as can be seen, and that difficult removal is DMF.
Table 4
| Organism in the water | Temperature of reaction (℃) | COD clearance (%) | |
| Embodiment 13 | Phenol | 120 | 99.5 |
| Embodiment 14 | Virahol | 220 | 98.9 |
| Embodiment 15 | DMF | 240 | 92.1 |
| Embodiment 16 | Acetate | 210 | 98.0 |
Claims (4)
1. the treatment process of an organic waste water is characterized in that this method is a catalyzer with the load metallic carbonyls, and metallic carbonyls is one or both combinations among Ru, the Co, and support of the catalyst is selected from Al
2O
3, gac, TiO
2, ZrO
2, CeO
2In at least a or their combination; The weight percentage of metal is 0.01～5% (with respect to carrier), wherein the weight percent of precious metal element (with respect to carrier) is 0.05～0.3%, with the oxygen-containing gas is oxygenant, organism in the oxidative degradation waste water, temperature of reaction is 90～250 ℃, reaction stagnation pressure 1.0～6.0MPa reacted 1～3 hour.
2. the method for claim 1 is characterized in that the organism in the waste water is phenol, Virahol, N, dinethylformamide, acetate.
3. the method for claim 1 is characterized in that the COD in the organic wastewater is 50～50000mg/L.
4. the method for claim 1 is characterized in that oxygen-containing gas is an air or oxygen.
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|---|---|---|---|
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| CN2009101177559A CN102101715A (en) | 2009-12-18 | 2009-12-18 | Treatment method of organic waste water |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084217A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Catalyst for wet oxidation during catalysis of ammonia-nitrogen wastewater and preparation method of catalyst |
| CN104129757A (en) * | 2014-08-14 | 2014-11-05 | 昆明理工大学 | Catalytic gasification method of supercritical water system organic matter Ru/CeO2 |
| CN105236611A (en) * | 2015-09-25 | 2016-01-13 | 浙江奇彩环境科技有限公司 | Processing method of benzene waste water |
| CN105858860A (en) * | 2016-04-19 | 2016-08-17 | 中新苏州工业园区环保技术有限公司 | Efficient treatment method for phenol-containing wastewater |
| CN106268789A (en) * | 2015-09-25 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of carried noble metal ruthenium gold/mesoporous carbon catalyst and preparation method thereof and the application of catalysis Oxidation of Wastewater Containing Phenol |
-
2009
- 2009-12-18 CN CN2009101177559A patent/CN102101715A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084217A (en) * | 2014-07-17 | 2014-10-08 | 厦门大学 | Catalyst for wet oxidation during catalysis of ammonia-nitrogen wastewater and preparation method of catalyst |
| CN104084217B (en) * | 2014-07-17 | 2017-03-08 | 厦门大学 | Catalyst that a kind of ammonia nitrogen waste water CWO is processed and preparation method thereof |
| CN104129757A (en) * | 2014-08-14 | 2014-11-05 | 昆明理工大学 | Catalytic gasification method of supercritical water system organic matter Ru/CeO2 |
| CN105236611A (en) * | 2015-09-25 | 2016-01-13 | 浙江奇彩环境科技有限公司 | Processing method of benzene waste water |
| CN106268789A (en) * | 2015-09-25 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of carried noble metal ruthenium gold/mesoporous carbon catalyst and preparation method thereof and the application of catalysis Oxidation of Wastewater Containing Phenol |
| CN105858860A (en) * | 2016-04-19 | 2016-08-17 | 中新苏州工业园区环保技术有限公司 | Efficient treatment method for phenol-containing wastewater |
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Application publication date: 20110622 |