CN1935687A - Method for treating chlorophenol pollutant by catalytic oxidation - Google Patents
Method for treating chlorophenol pollutant by catalytic oxidation Download PDFInfo
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- CN1935687A CN1935687A CN 200510047251 CN200510047251A CN1935687A CN 1935687 A CN1935687 A CN 1935687A CN 200510047251 CN200510047251 CN 200510047251 CN 200510047251 A CN200510047251 A CN 200510047251A CN 1935687 A CN1935687 A CN 1935687A
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Abstract
The invention relates to oxidation removal of chlophenol compounds, concretely a method of processing chlophenol organic pollutants by catalytic wet oxidation, loading organic pollutant-containing waste water solution into a reaction kettle, adding catalyst into the liquid phase system, then charging pure oxygen or air, and oxidize-removing the organic pollutants on blending condition, where the reaction temperature is 30-300 deg.C, the reaction pressure is 0.1-10MPa, and the oxygen partial pressure is 0.1-5.0MPa; the catalyst is soluble salt with K, Na, Mg, Ca, Ba and/or Al as active cation components; the molar concentration of cations in the added catalyst is 0.01-10 times as high as that of organic pollutants in the waste water. And the advantages: high catalytic activity, and moderate reacting conditions; low processing cost and large industrializable prospect; large application range; and environment-friendly.
Description
Technical field
The present invention relates to the oxidation removal of chlorophenols compound, specifically a kind of catalytic wet air oxidation is handled the method for chlorophenols organic pollutant.
Background technology
Since the thirties in 20th century, chlorophenols compound (CPs) is widely used as wood preservative, rust-preventive agent, sterilant and weedicide etc., and in paper pulp bleaching process, also can produce the waste water of a large amount of chlorophenols, in the Asia, Africa and South America also is used for the control of schistosomicide, and is therefore very huge in the industrial scale of many industrialized country CPs.Simultaneously, 2-chlorophenol, 2,4-two chlorophenols, 2,4,6-trichlorophenol and Pentachlorophenol all are the very high materials of toxicity, are listed in the Black List of priority pollutants by U.S. EPA.A large amount of uses of chlorophenols compound make a large amount of CPs pollutents enter environment, cause very big harm to physical environment.Therefore, this compounds of removing in the environment is a major challenge that the mankind face.
The method of handling chloride phenols wastewater at present is a lot, and method commonly used is biological degradation method, absorption method, extraction process, liquid membrane separation method.But the time that biological process needs is long especially, and inapplicable for the processing of high density chlorophenol waste water.In addition, biological degradation chlorophenols waste water also can the bigger dioxin pollution thing of toxigenicity.(L. G. Oeberg, Chemosphere, 1992) high-level oxidation technology is the technology of the organic pollutant of the processing difficult degradation that grows up the eighties in 20th century, its principal feature is to produce hydroxyl radical free radical by chemical reaction, make organic pollutant be degraded into water effectively, carbonic acid gas and mineral ion; Mainly comprise ozone oxidation, photochemical catalytic oxidation, wet oxidation, H2O2/UV, Fenton, methods such as O3/UV.Handle in the method for chlorophenol at advanced oxidation processes, the catalytic oxidation system of Meunier (Science 1996) is an oxygenant with hydrogen peroxide, iron-phthalocyanine is a catalyzer, handle the chlorophenols organic pollutant, the mineralization rate of carbon is 14% in the Trichlorophenol, and the mineralization rate of chlorine is 70%.Metal phthalocyanine catalyst has been invented in world patent application (S.Muriel, WO0059836,2000), is oxygenant with hydrogen peroxide, is used for handling Trichlorophenol waste water.In (Science 2002), be catalyzer with tetramino iron macrocylc compound in the catalyst system of Collins, hydrogen peroxide is an oxygenant, and the mineralization rate of Trichlorophenol is 35%, and the mineralization rate of chlorine is 83%.The problem that exists mainly is used oxygenant such as H at present
2O
2And O
3Cost an arm and a leg, make processing cost higher relatively, and in catalytic oxidation process, the synthetic cost of iron-phthalocyanine catalyzer etc. is also higher relatively, in addition, and some transition-metal catalyst instabilities, easy inactivation, but the existence of these problems is feasible very little for the processing industrial prospect of chlorophenols waste water.
Summary of the invention
The object of the present invention is to provide a kind of catalytic activity height, treatment effect is good, the reaction conditions gentleness, and processing cost is low, but the method for the big catalyzing oxidizing degrading chlorophenol pollutant of industrial applications prospect.
For achieving the above object, the technical solution used in the present invention is:
The waste water solution that fills the chlorophenols organic pollutant is packed in (stainless steel) reactor that has liner, in liquid-phase system, add catalyzer, charge into air in certain amount or oxygen (or ultrapure oxygen) then, oxidation removal organic pollutant under the agitation condition of in middle gentleness, pressing; Temperature of reaction is 30～300 ℃, and reaction pressure is 0.1～10Mpa, and wherein oxygen partial pressure is 0.1～5.0Mpa;
Described catalyzer is to be the soluble salt of active cation component with metal K, Na, Mg, Ca, Ba and/or Al etc.; Cationic volumetric molar concentration is 0.01～10 times of required removal organic pollutant volumetric molar concentration in the waste water in the catalyzer that is added.
Catalyzer in the reaction system is the salts solution of nontransition metal, and the soluble salt of catalyzer is with NO
3 -, NO
2 -, SO
4 2-, SO
3 2-Or CO
3 2-Deng being the active anion component.
Stirring velocity is generally 100rpm～1000rpm.
Reaction times of the present invention generally is no more than 4 hours, common reaction times 〉=5 minute, and the reaction times is preferably 0.5～4 hour; Temperature and pressure also is the important factor of influence reaction, in reaction, and 10 ℃ of the every risings of temperature, speed of reaction just increases by 2～4 times, but temperature is too high, also can increase energy expenditure, temperature of reaction is generally 30～300 ℃, is preferably 60～200 ℃, is preferably 90～150 ℃.
In reaction system, oxygen partial pressure also is the principal element of influence reaction, oxygen partial pressure increases, help the dissolving of oxygen in water, thereby help the carrying out that react, but system pressure is too high, material to reaction requires high, simultaneously, it is very little to the raising degree of reaction to increase oxygen partial pressure after oxygen partial pressure reaches certain value again, therefore must select suitable temperature and pressure; Reaction pressure is preferably 0.1～5Mpa; Oxygen partial pressure can be 0.1～5.0Mpa, is generally 0.2～3Mpa, is preferably 0.2～1.5Mpa, and the best is 0.5～1.0Mpa.
The organic pollutant structural formula of the described common oxidized removal of need is as follows:
n＝1～5。
The present invention has following advantage:
1. catalytic activity height, the reaction conditions gentleness.The present invention is in having the stainless steel cauldron of liner, is oxygenant with the air or oxygen, is catalyzer with the salts solution of nontransition metal, the chlorophenols organic pollutant is oxidized to carbonic acid gas, carbon monoxide, water and the small molecules carboxylic acid that some are nontoxic.Can reach 100% removal for chlorophenol pollutant, the mineralising efficient of carbon can reach 80%, and the mineralization rate of chlorine can reach 96%.
2. processing cost is low, but industrial prospect is big.Because used oxygenant and the catalyzer of the present invention cheaply is easy to get, treating processes is easy, and the pilot scale reaction has also obtained the good treatment effect, but therefore catalytic oxidation of the present invention has the application prospect of industrial treatment chlorophenol pollutant.
3. environmental friendliness.Reaction system of the present invention is simple, and is convenient and practical, and catalyzer cheaply is easy to get, and the reactive behavior height is thorough to the removal of pollutent.Catalyzer can not cause secondary pollution to environment in used concentration range.
4. applied widely.The present invention is applicable to the processing of chlorophenol pollutant waste liquid, and the processed organic pollutant structural formula of common need is expressed as follows:
n＝1～5。
Embodiment
Embodiment 1
With 20ml concentration is that the waste water solution of the chlorophenols organic pollutant of 100mg/L～400mg/L is packed into and had in the teflon-lined reactor, in system, add catalyzer, charge into the ultrapure oxygen or the air of certain pressure then, warming while stirring is to assigned temperature, speed stirring reaction solution with 100～1000 rev/mins, reacted 1～4 hour, the clearance of reaction back chlorophenols compound sees Table 1.
Table 1 catalytic wet air oxidation is handled the preferable result of chlorophenols waste water
| The chlorophenol compound | Catalyzer | Reaction total pressure MPa | Reaction oxygen partial pressure MPa | Temperature of reaction (℃) | The clearance of chlorophenol (%) | The mineralization rate of carbon (%) | The mineralization rate of chlorine (%) |
| Para-chlorophenol | KNO 3 | ?1.0 | ?0.5 | ?90 | ?70 | ?40 | ?80 |
| Trichlorophenol | NaNO 3/NaNO 2 | ?0.8 | ?0.4 | ?150 | ?99 | ?80 | ?96 |
| Pentachlorophenol | MgSO 4 | ?1.0 | ?0.6 | ?200 | ?80 | ?45 | ?85 |
Embodiment 2
According to the operation steps of the foregoing description 1, handle various chlorophenols organic pollutants with other catalyzer and reaction conditions, the results are shown in Table 2.
Table 2 catalytic wet air oxidation is handled the comparative result of chlorophenols waste water
| The chlorophenol compound | Catalyzer | Reaction total pressure MPa | Reaction oxygen partial pressure MPa | Temperature of reaction (℃) | The clearance of chlorophenol (%) | The mineralization rate of carbon (%) | The mineralization rate of chlorine (%) |
| Para-chlorophenol | KNO 3 | ?1.0 | ?0.5 | ?60 | ?40 | ?20 | ?30 |
| Para-chlorophenol | Na 2SO 3 | ?1.5 | ?1.0 | ?120 | ?50 | ?20 | ?20 |
| Chlorophenesic acid | NaNO 2/K 2SO 4 | ?5 | ?1.5 | ?200 | ?70 | ?30 | ?10 |
| Chlorophenesic acid | Al(NO 3) 3 | ?1.0 | ?0.4 | ?180 | ?90 | ?70 | ?90 |
| Trichlorophenol | NaNO 2 | ?1.0 | ?0.2 | ?100 | ?40 | ?20 | ?30 |
| Trichlorophenol | Na 2SO 3 | ?2.5 | ?1.5 | ?170 | ?99 | ?30 | ?50 |
| Chlorophenosic acid | Na 2SO 3/K 2SO 4 | ?3.5 | ?1.2 | ?90 | ?75 | ?55 | ?68 |
| Pentachlorophenol | MgSO 4 | ?1.0 | ?0.6 | ?200 | ?80 | ?45 | ?85 |
| Pentachlorophenol | NaNO 2 | ?1.0 | ?0.5 | ?90 | ?2 | ?0 | ?0 |
| Pentachlorophenol | Na 2SO 3/K 2SO 4 | ?1.5 | ?0.8 | ?150 | ?10 | ?2 | ?4 |
Claims (7)
1. the method for a treating chlorophenol pollutant by catalytic oxidation, it is characterized in that: the waste water solution that will fill organic pollutant is packed in the reactor, in liquid-phase system, add catalyzer, charge into pure oxygen or air then, oxidation removal organic pollutant under the agitation condition; Temperature of reaction is 30～300 ℃, and reaction pressure is 0.1～10Mpa, and wherein oxygen partial pressure is 0.1～5.0Mpa;
Described catalyzer is to be the soluble salt of active cation component with metal K, Na, Mg, Ca, Ba and/or Al; Cationic volumetric molar concentration is 0.01～10 times of required removal organic pollutant volumetric molar concentration in the waste water in the catalyzer that is added.
2. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: the soluble salt of described catalyzer is with NO
3 -, NO
2 -, SO
4 2-, SO
3 2-Or CO
3 2-Be the active anion component.
3. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: described temperature of reaction is 60～200 ℃; Reaction pressure is 0.1～5Mpa; Oxygen partial pressure is 0.2～3Mpa; Stirring velocity is 100rpm～1000rpm.
4. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: described temperature of reaction is 90～150 ℃; Oxygen partial pressure is 0.2～1.5Mpa.
5. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: described oxygen partial pressure is for being 0.5～1.0Mpa; Reaction times 〉=5 minute.
6. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: the reaction times is 0.5～4 hour.
7. according to the method for the described treating chlorophenol pollutant by catalytic oxidation of claim 1, it is characterized in that: the organic pollutant structural formula of described oxidation removal is as follows,
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289244B (en) * | 2007-04-20 | 2011-04-20 | 中国科学院大连化学物理研究所 | Process for degrading chlorophenol-like pollutants by natural light catalysis |
| CN102276046A (en) * | 2011-05-18 | 2011-12-14 | 华东理工大学 | Method for treating various organic pollutants in industrial wastewater through green wet oxidation method |
| CN102039128B (en) * | 2009-10-13 | 2013-01-09 | 中国石油化工股份有限公司 | Catalytic wet oxidation catalyst for wastewater and preparation method thereof |
| CN103991942A (en) * | 2014-04-14 | 2014-08-20 | 苏州科技学院 | Treatment method for chlorophenol micropollutants in water body |
| CN104118928A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for catalytic degradation of trichlorophenol organic pollutants by mixed mode |
| CN107721081A (en) * | 2017-11-22 | 2018-02-23 | 江苏省环境科学研究院 | A kind of innocuity disposal system and method for chlorophenols waste water |
| CN110894097A (en) * | 2019-12-12 | 2020-03-20 | 山东理工大学 | Deep oxidation treatment method for waste water containing tertiary butanol |
| CN110894119A (en) * | 2019-12-12 | 2020-03-20 | 山东理工大学 | Treatment method of chlorine salt-containing organic wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1028508C (en) * | 1988-09-06 | 1995-05-24 | 厦门大学 | Process of photocatalysis treatment of waste water |
| DE10114177A1 (en) * | 2001-03-23 | 2002-09-26 | Degussa | Process for the treatment of polluted water |
| CN1569676A (en) * | 2003-07-25 | 2005-01-26 | 中国科学院大连化学物理研究所 | Method for eliminating aqueous solution pollution from halo-phenol compounds |
| DE10341194A1 (en) * | 2003-09-06 | 2005-03-31 | Hermsdorfer Institut Für Technische Keramik E.V. | Wastewater purification by wet oxidation using catalyst comprising active components incorporated into porous inorganic solid with partially hydrophilized surface |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289244B (en) * | 2007-04-20 | 2011-04-20 | 中国科学院大连化学物理研究所 | Process for degrading chlorophenol-like pollutants by natural light catalysis |
| CN102039128B (en) * | 2009-10-13 | 2013-01-09 | 中国石油化工股份有限公司 | Catalytic wet oxidation catalyst for wastewater and preparation method thereof |
| CN102276046A (en) * | 2011-05-18 | 2011-12-14 | 华东理工大学 | Method for treating various organic pollutants in industrial wastewater through green wet oxidation method |
| CN104118928A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for catalytic degradation of trichlorophenol organic pollutants by mixed mode |
| CN103991942A (en) * | 2014-04-14 | 2014-08-20 | 苏州科技学院 | Treatment method for chlorophenol micropollutants in water body |
| CN107721081A (en) * | 2017-11-22 | 2018-02-23 | 江苏省环境科学研究院 | A kind of innocuity disposal system and method for chlorophenols waste water |
| CN110894097A (en) * | 2019-12-12 | 2020-03-20 | 山东理工大学 | Deep oxidation treatment method for waste water containing tertiary butanol |
| CN110894119A (en) * | 2019-12-12 | 2020-03-20 | 山东理工大学 | Treatment method of chlorine salt-containing organic wastewater |
| CN110894119B (en) * | 2019-12-12 | 2022-04-12 | 山东理工大学 | Treatment method of chlorine salt-containing organic wastewater |
| CN110894097B (en) * | 2019-12-12 | 2022-04-12 | 山东理工大学 | Deep oxidation treatment method for waste water containing tertiary butanol |
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Assignee: Jiangsu Huangma Agrochemicals Co., Ltd. Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2011320000337 Denomination of invention: Method for treating chlorophenol pollutant by catalytic oxidation Granted publication date: 20080514 License type: Exclusive License Open date: 20070328 Record date: 20110321 |
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