CN102285712A - Method for removing micro pollutants from water by oxidization of potassium permanganate with ruthenium as catalyst - Google Patents
Method for removing micro pollutants from water by oxidization of potassium permanganate with ruthenium as catalyst Download PDFInfo
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- CN102285712A CN102285712A CN 201110150251 CN201110150251A CN102285712A CN 102285712 A CN102285712 A CN 102285712A CN 201110150251 CN201110150251 CN 201110150251 CN 201110150251 A CN201110150251 A CN 201110150251A CN 102285712 A CN102285712 A CN 102285712A
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Abstract
The invention belongs to the technical field of water treatment and discloses a method for removing micro pollutants from water by oxidization of potassium permanganate with ruthenium as catalyst. The method comprises the following steps: adding potassium permanganate at a concentration of 0.5 to 5.0 mg/L and the ruthenium catalyst at a concentration of 0.5 to 5.0mg/L into the water containing the micro pollutants in certain sequence; and treating the water sample for 5 to 40 minutes. The method has high selectivity and can effectively remove micro pollutants in water with low medicine consumption.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to the method that a kind of ruthenium catalysis potassium permanganate oxidation is removed Micropollutants in the water.
Background technology
Along with the quickening of process of industrialization, problem of environmental pollution is more and more serious, and water pollution problems causes that increasing people pays close attention to.Micro quantity organic pollutant in the water, though it is less as personal care articles such as phenols, phenyl amines, endocrine disrupter content in water, but they are accumulation and concentrated gradually, and can interact between the multiple pollutent, forms very complicated combined pollution trend.Micro quantity organic pollutant in the water, particularly high stability, poisonous, deleterious organic pollutant can accumulate in the municipal water working cycle gradually, and water quality is constituted very big threat.Therefore, China's up-to-date " drinking water sanitary standard " (GB 5749-2006) increases to 53 with the kind of the organic pollutant controlled in the tap water by 5.But conventional drinking water treatment technology is difficult to satisfy people to requirements in water quality, experimental study both domestic and external and actual production result show, contaminated water source water can only be removed 20%～30% of personal care articles such as phenols, phenyl amines, endocrine disrupter in the water usually through conventional coagulation, precipitation, filtration, sterilization process.Therefore, this just need introduce pre-oxidation process in water treatment procedure.
The discharging of industrial sewage and sanitary sewage is the main source that causes Micropollutants in the water surrounding, even in developed country, also usually detects multiple priority pollutants in the water outlet of sewage work and the mud.Part Study person finds that the content of pollutents such as personal care articles, endocrine disrupter such as these environment phenols, phenyl amines is than industrial sewage water outlet height in the sanitary sewage disposal plant effluent.Estrogen substance in the water surrounding is mainly derived from the municipal effluent plant effluent, and its content depends on the emission behaviour of estrogenic degraded situation and treat effluent.Conventional sewage second-level treatment process can not well be removed personal care articles, endocrine disrupters etc. such as phenols in the water, phenyl amines, and the accumulation and the conversion that can produce multiple toxic substance.Therefore, need increase green effective advanced treatment process in the later stage of conventional sewage treatment process.
Potassium permanganate is applied to water treatment and has easy transportation, stores, adds conveniently, characteristics such as price is low, treatment effect good, non-toxic by-products generation.Potassium permanganate oxidation capacity in common water treatment pH scope is stronger, and oxidising process is subjected to the influence of pH little.That potassium permanganate can not produce in oxidative degradation organism process is poisonous, harmful halo by product, and its final reduzate is insoluble eco-friendly Manganse Dioxide, is easy to separate from solution.In addition, reduzate Manganse Dioxide can also be by absorption, oxidation, help effect such as coagulate to work in coordination with depollution with potassium permanganate.Simultaneously, potassium permanganate has good selectivity to phenols and the organic oxidation of phenyl amines.Therefore, potassium permanganate is a kind of green and effectively remove the oxygenant of micro quantity organic pollutant in the water.
At present, mainly contain chlorine, dioxide peroxide, ozone and potassium permanganate etc. for oxygenant commonly used in the water treatment, under nearly neutrallty condition, potassium permanganate is lower than the speed of Micropollutants in ozone, chlorine and the dioxide peroxide oxidizing water, and this is the weak point of potassium permanganate in practical engineering application.Because the organic speed of potassium permanganate oxidation is slower, obtain the removal effect identical with chlorine, dioxide peroxide or ozone then needs longer oxidization time and bigger pharmaceutical quantities, and this will certainly increase the capital cost and the working cost of engineering.
Ruthenium is widely used in multiple catalyzed reaction as a kind of transition metal, all shows good catalytic activity.Aspect organic synthesis, ruthenium catalyst is mainly used in the hydrogenation reaction of catalysis phenyl ring, ethyl lactate, glucose, pyridine and quinoline etc.; Inorganic catalysis aspect, ruthenium catalyst is widely used in the preparation of synthetic ammonia catalyst.In recent years, part Study person began ruthenium catalyst is applied in strong basicity or the strongly-acid potassium permanganate oxidation reduction system, and ruthenium comes the catalytic oxidation-reduction reaction as a kind of high activated catalyst, improves speed of reaction, strengthens the organic removal of high-concentration hardly-degradable.At present, still there are not research or invention to relate to the application of ruthenium catalyst in neutral or nearly neutral water surrounding.
Summary of the invention
Oxidation rate is slow and remove inefficient deficiency when remedying the independent oxidation of potassium permanganate, the purpose of this invention is to provide a kind of ruthenium catalysis potassium permanganate oxidation and remove the method for Micropollutants in the water, by adding ruthenium catalyst, can improve speed of reaction, intensifying treatment effect; This method can be used as the pre-oxidation treatment of drinking water sources such as referring to river water, lake water and underground water, and the advanced treatment of the black water that contains Micropollutants of life and industrial discharge.
Technical scheme of the present invention is as follows:
The invention provides a kind of ruthenium catalysis potassium permanganate oxidation and remove the method for Micropollutants in the water, this method may further comprise the steps: in the water that contains Micropollutants, adding potassium permanganate and the concentration that concentration is 0.5～5.0mg/L according to a definite sequence is the ruthenium catalyst of 0.5～5.0mg/L, water sample is handled 5～40min get final product.
Described Micropollutants are meant personal care articles or endocrine disrupters such as phenols, phenyl amines.
A kind of in the waste water that contains Micropollutants of river water, lake water, underground water, life or industrial discharge or sewage of described wet concentration.
Described ruthenium catalyst is liquid catalyst or solid catalyst, is selected from one or more the mixture in ruthenium trichloride, ruthenium sulfate or the ruthenium hydrochloride ammonium.
Describedly add potassium permanganate and ruthenium catalyst according to a definite sequence, this be meant in proper order add earlier ruthenium catalyst add again potassium permanganate, simultaneously add potassium permanganate and ruthenium catalyst, before the water absorption tube of source water water pump, add ruthenium catalyst and add potassium permanganate again, before the water absorption tube of source water water pump, add potassium permanganate and ruthenium catalyst simultaneously, add potassium permanganate again or before coagulation process, add potassium permanganate and ruthenium catalyst simultaneously adding ruthenium catalyst before the coagulation process.
Ruthenium catalyst can be mixed with certain solution and add, and also can utilize dried equipment directly to add.According to the situation of water pollution, the dosage of potassium permanganate is controlled at 0.5～5.0mg/L, and the dosage of catalyzer is controlled at 0.5～5.0mg/L.After potassium permanganate and ruthenium catalyst are added in the water, utilize follow-up coagulation or filtration process that remaining organic pollution materials, ruthenium catalyst and reduzate Manganse Dioxide are removed synchronously.
The present invention is primarily aimed at the advanced treatment process exploitation of Micropollutants pre-oxidation treatment technology and sewage or waste water in the drinking water source.Ultimate principle of the present invention is in water treatment technological process, and a spot of potassium permanganate and ruthenium catalyst are added in water to be clean, make it with water in organism effect for some time, thereby reach the purpose of decomposing or removing organic pollutant in the water.
The present invention compares with prior art, has following advantage and beneficial effect:
1, the inventive method and traditional chlorine, hypochlorous acid or emerging ozone oxidation are compared, and potassium permanganate can not produce poisonous and hazardous by product as a kind of oxygenant of green safety.Reduzate Manganse Dioxide can also be by absorption, oxidation, help effect such as coagulate to work in coordination with depollution with potassium permanganate.
2, the inventive method is compared with traditional chlorine, hypochlorous acid or new ozone oxidation of rising, potassium permanganate has good selectivity to phenols and the organic oxidation of phenyl amines, therefore can more effectively remove the personal care articles and the endocrine disrupter of phenols and phenyl amines in the water, and the pharmaceutical quantities that consumes is less.
3, the inventive method is compared with traditional potassium permanganate oxidation, and rate of oxidation improves a lot, and the removal effect of micro-content organism is also had very big enhancing, so the ruthenium catalyst mechanism has been brought into play very significant effect in whole oxidation system.
4, ruthenium catalyst is compared with other transition-metal catalysts (as the oxidation of osmium or osmium), and (at present, the Shang Weiyou report is mentioned it the intoxicating effect to have nontoxic feature.USEPA is announced drinks the pollutant in water list and law is not clearly all mentioned ruthenium in the potentially contaminated material list of regulation; In the 20th edition tap water of being united announcement by APHA and U.S. water treatment association and sewage standard detecting method, ruthenium is spelt out without any known intoxicating effect).This Secure Application for ruthenium catalyst provides guarantee.
5, in the former studies, ruthenium catalyst is used the catalyzed reaction of organic solvent as matrix more; In the recent period, ruthenium catalyst also begins to be applied to the catalyzed reaction of strong basicity or strongly acidic aqueous solution.And the application conditions of above those ruthenium catalysts is all very harsh, the present invention studies at the catalyzed reaction of neutral or nearly neutral aqueous solution first, obtained breakthrough, this has expanded the application category of ruthenium catalyst greatly, and provides theoretical direction for its application in actual water body.
Description of drawings
Fig. 1 is the removal effect figure of 1 pair of Micropollutants of embodiment.
Fig. 2 is the removal effect figure of 2 pairs of Micropollutants of embodiment.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
Embodiment 1
Get river water (taking from Song Hua River, the Harbin) 200mL of personal care articles such as containing Micropollutants-phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium trichloride (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 0.5mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 5.0mg/L, water sample is handled 40min, and the clearance of Micropollutants can reach 75%～90%.
Fig. 1 is the removal effect figure of present embodiment to Micropollutants, Micropollutants are taken internal secretion Interferon, rabbit---dihydroxyphenyl propane,-zero-expression ruthenium catalyst catalysis potassium permanganate is removed the clearance curve of dihydroxyphenyl propane among the figure ,-●-expression adopts potassium permanganate to remove the clearance curve of dihydroxyphenyl propane separately.Present embodiment improves 50%～300% to the clearance of micro quantity organic pollutant, and speed of reaction has improved 2～4 times.To containing starting point concentration is that the water of 1.14mg/L dihydroxyphenyl propane, pH=6～8 is handled 20min, compares with independent potassium permanganate oxidation, and the clearance of the dihydroxyphenyl propane of present embodiment method can improve 200%.
Embodiment 2
Get and contain Micropollutants---sanitary sewage (taking from Wenchang, the Harbin Sewage Plant) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium trichloride (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 2.0mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 1.6mg/L, water sample is handled 20min, and the clearance of Micropollutants can reach 80%～90%.
Fig. 2 is the removal effect figure of present embodiment to Micropollutants, Micropollutants are taken internal secretion Interferon, rabbit---dihydroxyphenyl propane,-zero-expression ruthenium catalyst catalysis potassium permanganate is removed the clearance curve of dihydroxyphenyl propane among the figure ,-●-expression adopts potassium permanganate to remove the clearance curve of phenol separately.Present embodiment improves 50%～400% to the clearance of micro quantity organic pollutant, and speed of reaction has improved 3～5 times.To containing starting point concentration is that the water of 1.14mg/L dihydroxyphenyl propane, pH=6～8 is handled 20min, compares with independent potassium permanganate oxidation, and the clearance of the dihydroxyphenyl propane of present embodiment method can improve 350%.
Embodiment 3
Get and contain Micropollutants---trade effluent (the taking from Harbin Pharmaceutical Factory) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, add ruthenium trichloride (described ruthenium catalyst be liquid catalyst and solid catalyst all can) and potassium permanganate medicament simultaneously, the dosage of control ruthenium trichloride is 5.0mg/L, the dosage of potassium permanganate is 1.6mg/L, adopt the magnetic stirring apparatus vigorous stirring, water sample is handled 10min, and the clearance of Micropollutants can reach more than 90%.
Embodiment 4
Get and contain Micropollutants---lake water (the taking from Harbin) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium sulfate (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 2.5mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 1.9mg/L, water sample is handled 10min, and the clearance of Micropollutants can reach 70%～90%.
Get and contain Micropollutants---underground water (the taking from Harbin) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, add ruthenium sulfate (described ruthenium catalyst be liquid catalyst and solid catalyst all can) and potassium permanganate medicament simultaneously, the dosage of control ruthenium sulfate is 0.5mg/L, the dosage of potassium permanganate is 5.0mg/L, adopt the magnetic stirring apparatus vigorous stirring, water sample is handled 40min, and the clearance of Micropollutants can reach 60%～80%.
Embodiment 6
Get and contain Micropollutants---river water (taking from Song Hua River, the Harbin) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium sulfate (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 2.0mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 1.6mg/L, water sample is handled 20min, and the clearance of Micropollutants can reach 75%～85%.
Embodiment 7
Get and contain Micropollutants---underground water (the taking from Harbin) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium hydrochloride ammonium (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 1.0mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 3.0mg/L, water sample is handled 20min, and the clearance of Micropollutants can reach 70%～90%.
Embodiment 8
Get and contain Micropollutants---sanitary sewage (taking from Wenchang, the Harbin Sewage Plant) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, add ruthenium sulfate (described ruthenium catalyst be liquid catalyst and solid catalyst all can) and potassium permanganate medicament simultaneously, the dosage of control ruthenium sulfate is 0.5mg/L, the dosage of potassium permanganate is 1.6mg/L, adopt the magnetic stirring apparatus vigorous stirring, water sample is handled 30min, and the clearance of Micropollutants can reach 65%～80%.
Embodiment 9
Get and contain Micropollutants---water sample trade effluent (the taking from Harbin Pharmaceutical Factory) 200mL of personal care articles such as phenols, phenyl amines, endocrine disrupter, the dosage of control ruthenium hydrochloride ammonium (described ruthenium catalyst be liquid catalyst and solid catalyst all can) is 2.0mg/L, after adopting magnetic stirring apparatus vigorous stirring 10min, add potassium permanganate, the dosage of potassium permanganate is 4.0mg/L, water sample is handled 40min, and the clearance of Micropollutants can reach 85%～95%.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (6)
1. a ruthenium catalysis potassium permanganate oxidation is removed the method for Micropollutants in the water, it is characterized in that: this method may further comprise the steps: in the water that contains Micropollutants, adding potassium permanganate and the concentration that concentration is 0.5～5.0mg/L according to a definite sequence is the ruthenium catalyst of 0.5～5.0mg/L, water sample is handled 5～40min get final product.
2. ruthenium catalysis potassium permanganate oxidation according to claim 1 is removed the method for Micropollutants in the water, and it is characterized in that: described Micropollutants are meant phenols, phenyl amines or endocrine disrupter.
3. ruthenium catalysis potassium permanganate oxidation according to claim 1 is removed the method for Micropollutants in the water, it is characterized in that: a kind of in the waste water that contains Micropollutants of river water, lake water, underground water, life or industrial discharge or sewage of described wet concentration.
4. ruthenium catalysis potassium permanganate oxidation according to claim 1 is removed the method for Micropollutants in the water, and it is characterized in that: described ruthenium catalyst is liquid catalyst or solid catalyst.
5. ruthenium catalysis potassium permanganate oxidation according to claim 4 is removed the method for Micropollutants in the water, it is characterized in that: described ruthenium catalyst is selected from one or more the mixture in ruthenium trichloride, ruthenium sulfate or the ruthenium hydrochloride ammonium.
6. ruthenium catalysis potassium permanganate oxidation according to claim 1 is removed the method for Micropollutants in the water, it is characterized in that: describedly add potassium permanganate and ruthenium catalyst according to a definite sequence, this is meant that in proper order adding ruthenium catalyst earlier adds potassium permanganate again, add potassium permanganate and ruthenium catalyst simultaneously, before the water absorption tube of source water water pump, add ruthenium catalyst and add potassium permanganate again, before the water absorption tube of source water water pump, add potassium permanganate and ruthenium catalyst simultaneously, add potassium permanganate again or before coagulation process, add potassium permanganate and ruthenium catalyst simultaneously adding ruthenium catalyst before the coagulation process.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659206A (en) * | 2012-04-10 | 2012-09-12 | 大连理工大学 | Method for processing micro-pollutants in water based on cyclodextrin polymer material adsorption-KMnO4 oxidation coupling |
| CN102874914A (en) * | 2012-10-10 | 2013-01-16 | 同济大学 | Method for removing pollutants from drinking water by using supported ruthenium catalyst |
| CN109160589A (en) * | 2018-09-13 | 2019-01-08 | 天津大学 | A kind of method of aniline in degrading waste water |
| CN110255693A (en) * | 2019-07-05 | 2019-09-20 | 重庆大学 | A kind of method of Native Oxide reduction mediator activation potassium permanganate degradation organic pollutants |
| CN115536520A (en) * | 2022-11-02 | 2022-12-30 | 金川集团股份有限公司 | Preparation method of ruthenium acetate |
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| CN1557736A (en) * | 2004-01-14 | 2004-12-29 | 哈尔滨工业大学 | Oxidation coagulation aiding method using ozone and potassium permanganate |
| CN1803672A (en) * | 2005-12-20 | 2006-07-19 | 沈阳建筑大学 | Method for treating micro-polluted source water |
| CN101254986A (en) * | 2007-05-09 | 2008-09-03 | 兰州理工大学 | System and method for treating micro-polluted source water |
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2011
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Patent Citations (4)
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| JP2001187391A (en) * | 1999-12-28 | 2001-07-10 | Ebara Corp | Method for removing manganese ion in iron(iii) salt aqueous solution |
| CN1557736A (en) * | 2004-01-14 | 2004-12-29 | 哈尔滨工业大学 | Oxidation coagulation aiding method using ozone and potassium permanganate |
| CN1803672A (en) * | 2005-12-20 | 2006-07-19 | 沈阳建筑大学 | Method for treating micro-polluted source water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659206A (en) * | 2012-04-10 | 2012-09-12 | 大连理工大学 | Method for processing micro-pollutants in water based on cyclodextrin polymer material adsorption-KMnO4 oxidation coupling |
| CN102874914A (en) * | 2012-10-10 | 2013-01-16 | 同济大学 | Method for removing pollutants from drinking water by using supported ruthenium catalyst |
| CN109160589A (en) * | 2018-09-13 | 2019-01-08 | 天津大学 | A kind of method of aniline in degrading waste water |
| CN110255693A (en) * | 2019-07-05 | 2019-09-20 | 重庆大学 | A kind of method of Native Oxide reduction mediator activation potassium permanganate degradation organic pollutants |
| CN110255693B (en) * | 2019-07-05 | 2022-05-03 | 重庆大学 | Method for degrading organic pollutants in water by activating potassium permanganate through natural redox mediator |
| CN115536520A (en) * | 2022-11-02 | 2022-12-30 | 金川集团股份有限公司 | Preparation method of ruthenium acetate |
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