CN102849824B - Iron-based copper for treating organic sewage and sewage treatment method - Google Patents
Iron-based copper for treating organic sewage and sewage treatment method Download PDFInfo
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- CN102849824B CN102849824B CN201210077333.5A CN201210077333A CN102849824B CN 102849824 B CN102849824 B CN 102849824B CN 201210077333 A CN201210077333 A CN 201210077333A CN 102849824 B CN102849824 B CN 102849824B
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Abstract
The invention relates to an iron-based copper high-efficient microelectrolytic material which contains a lot of nonuniform iron-copper microelectrode primary batteries and is formed by coating copper on cast iron granular carrier surfaces in a crystal grain form by a chemical conversion method. When organic sewage flows through a fixed bed reactor formed by the material, the reaction efficiency is controlled by the flow rate. With the material and the fixed bed reaction technology, the problem of low electrochemical degradation efficiency of organic pollutant macromolecules in sewage by common granular iron-carbon microelectrolytic materials and granular iron-copper microelectrolytic materials in current sewage treatment process is solved.
Description
Technical field
The invention belongs to technical field of sewage, be specifically related to a kind of iron-based copper of processing organic sewage, and sewage water treatment method.
Background technology
Sewage disposal micro-(interior) electrolytic process is a kind of self discharge effect that utilizes some to have the microbattery forming between the material particle of Different electrodes current potential, the electrochemical method that decomposes contaminant molecule in sewage, it can be for the decontamination process of the trade effluents such as process hides, oil field, printing and dyeing, chemical industry.
In sewage disposal industry, the internal electrolysis using is at present iron-carbonaceous galvanic cell base material, and the electromotive force that microbattery two interpolars produce is less for the galvanic cell of iron/copper base, and therefore the degradation efficiency of organic pollutant molecule is lower.
Iron/copper base galvanic cell has higher electromotive force and electric discharge potential energy, therefore consequent electrochemical reaction is to impelling the decomposition of organic pollutant molecule to have more high-level efficiency.
In recent years, be involved in the patent report that adopts above-mentioned principle to dispose of sewage both at home and abroad, as:
CN1382649A discloses a kind of method for the treatment of used water difficult to degradate by catalytic internal electrolysis of iron, comprise first by good by WCu/WFe=0.1-1.0 weighing to copper and iron, and add the zeolite of 0% ~ 10% cats product modification of copper and iron gross weight according to the different situations of waste water, fully mix, put into filter tank; The pH of waste water is transferred to 4.5-11.0, the in the situation that of aeration not, is 2 by reflux ratio: 1-10: 1 abundant reaction for some time, pH is transferred to 8.0-9.0 subsequently, makes Fe
3+further generate flocculation agent Fe (OH)
3, by suspended solids, colloidalmaterial cohesion in waste water, and adsorb solubility pollutent coprecipitation, waste water is purified.
CN1915846A discloses a kind of aeration and catalyzing iron internal electrolysis reinforced sewage process for primary treatment, its step comprises: a. waste water enters electrolyzer in aeration and catalyzing iron after grid, sand setting pre-treatment, make dissolved oxygen concentration in pond at 0.1 ~ 8mg/L by the control of aeration rate, in pond, place iron copper mixed fillers, the ratio of copper and iron is WCu/WFe=0 ~ 0.5, in the time of WCu/WFe=0, require the carbon content of iron to be greater than 0.15%; B. the water outlet of electrolyzer in aeration and catalyzing iron is carried out to mud-water separation, precipitation water outlet discharge.
The common ground of above two kinds of patented technologies is: they are all respectively using the pellet of iron and copper as material, mix by a certain percentage and form micro-electrolysis reaction bed.Its defect is: this galvanic cell being made up of the different intermetallic of granule type should belong to a kind of macro cell from the strict sense, therefore the quantity that treatment system can form the microbattery of effective electrochemical degradation reaction to organic pollutant will obviously be subject to particle diameter and the number quantitative limitations of particles of material, and reaction efficiency is greatly affected.If adopt more tiny iron and the copper powder of granularity, to increase specific surface, the rate of permeation of system can reduce, and sewage disposal flow or processing efficiency be corresponding reduction also.
Summary of the invention
In view of the deficiencies in the prior art, the present invention is attached to copper the surface of cast iron bead-type substrate with crystal grain form by chemical conversion process, forms the efficient micro-electrolysis material of iron-based copper type with inhomogeneous, numerous iron/copper microelectrode galvanic cells.By this material and fixed bed reaction technique, successfully solve plain particles sections-carbon-based material in current sewage treatment process, and granule type iron/copper sill is lower to the macromolecular electrochemical degradation efficiency of dirty organic pollutants, and the higher problem of the consumable quantity of invalid copper.
Therefore, the invention provides a kind of iron-based copper of processing organic sewage, and the method that adopts this iron-based copper to dispose of sewage.
First object of the present invention is achieved in that
A kind of iron-based copper of processing organic sewage; be prepared from as follows: by cast iron filing or cast iron powder at 5-40%(w/w) soak 10-130min in alkaline solution, filter, leach thing and wash with water 2-3 time; use again 5-45%(w/w) inorganic middle strong acid solution soak 1-45min; filter, leach thing and wash with water 2-3 time, join 1-50%(w/w) copper salt solution in stir 1-50min; filter; leach thing and wash with water 2-3 time, under nitrogen protection, dry, obtain iron-based copper.
Preferably, the iron-based copper of described processing organic sewage, wherein said alkaline solution is sodium hydroxide or sodium carbonate solution.
Preferably, the iron-based copper of described processing organic sewage, wherein said inorganic middle strong acid is selected from following one or more: sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
Preferably, the iron-based copper of described processing organic sewage, wherein said mantoquita is selected from following one or more: copper sulfate, cupric chloride and cupric nitrate.
Second object of the present invention is achieved in that
Adopt above-mentioned iron-based copper to process a method for organic sewage, it is characterized in that comprising the steps:
1) insert densely in the reactor of cylindrical or rectangle iron-based copper as filler;
2) in regulating tank, regulate acidity to pH=2-6 with sulfuric acid or hydrochloric acid in sewage;
3) sour water after regulating is pumped into anti-container, the residence time of sewage in reaction bed is 10-60min, and pollutent occurs to be flowed out by the other end after electrochemical decomposition in responding layer.
The iron-based copper of the processing organic sewage the present invention relates to, can be for the industrial production that contains organic pollutant (as oil field, chemical industry, refining of petroleum, mining industry, medicine, dyestuff, weaving etc.), in the purification process technique of the waste water such as agriculture production (as livestock industry etc.) and urban life (percolate, life discharge).
Compared with prior art, the iron-based copper tool of the processing organic sewage the present invention relates to has the following advantages and is progressive significantly: iron-based copper micro-electrolysis material has higher degradation efficiency and reduction-decolor ability to organic pollutant molecule, is mainly manifested in: (1) iron/copper dipoles scatter to than iron-carbon dipole to thering is higher potential difference and reaction electromotive force; (2) adhere to unevenly after some copper on siderophore surface, the iron/copper contact surface of its generation, and the microbattery quantity forming is much bigger more than the couple utmost point galvanic cell quantity being made up of through simple mixing two kinds of metal pellets, the discharging efficiency of system obviously improves; (3) in the crystalline network of cast iron and plain carbon stool, there is a large amount of intergranular carbon, they and iron matrix have also formed iron-carbonaceous microbattery, therefore, total electrolysis usefulness of this iron-based copper micro-electrolysis material is to be superposeed by iron-carbonaceous and two kinds of coefficient usefulness of microbattery of iron/copper matter.
Embodiment
Be below specific embodiments of the invention, technical scheme of the present invention is done to further description, but protection scope of the present invention is not limited to these embodiment.Every do not deviate from the change of the present invention design or be equal to substitute include within protection scope of the present invention.
1) preparation of iron-based copper material:
A. at a certain temperature, by the mineral alkalis such as 10% sodium hydroxide for a certain amount of cast iron filing (powder), or soak in the subsalt solution such as sodium carbonate, leach.Wherein, temperature range is 0-100 DEG C; The amount of cast iron filing is to be limited by alkali lye submergence; Concentration of lye scope 5-40%; Soak reaction times 10-130min;
B. leaching thing washes with water 2-3 time.
C. to activating the cast iron filing after degreasing with immersion in inorganic middle strong acid under fixed temperature, leach.Wherein, given temperature range is 5-50 DEG C; Inorganic middle strong acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.; Acid concentration is 5-45%; The immersion reaction times is 1-45min.
D. the cast iron filing after activation washes with water 2-3 time, leaches.
E. subsequently it is joined in the copper salt solution of 1-50% and stir 1-50min.Wherein, mantoquita is copper sulfate, cupric chloride, the inorganic mantoquita such as cupric nitrate.
F. after iron-based copper washes 2-3 time with water after leaching, under nitrogen protection, dry and preserve.
2) preparation of electrochemistry fixation reaction bed
Insert densely iron-based copper products as filler and possess fixing how much plastics of external form or the shell of other acid corrosion-resistant material, and in reaction vessel with upper and lower ends inlet/outlet valve door interface.
3) technique of sewage disposal
In regulating tank before reactor with sulfuric acid or hydrochloric acid by the acidity adjustment of sewage to pH=2-6, then sour water is pumped in reactor by top or the lower port of reactor, pollutent occurs to be flowed out by the other end after electrochemical decomposition in responding layer, controls palliating degradation degree and the efficiency of pollutent by the flow velocity of valve regulated water outlet.
The processing of Application Example 1 phenolic wastewater
At 25 DEG C of temperature, 250 grams of cast iron filings, with leaching after submergence de-oiling 30min in 10% sodium hydroxide solution, are leached to thing and activate in washing the dilute sulphuric acid that devotes 5% after 3 times, after 3min, leach and wash 3 times.Cast iron filing after activation is immersed in 25% copper-bath again and reacts 30min, leach and wash 3 logical nitrogen (preventing metallic high temperature oxidation) protection oven dry afterwards, obtain iron-based copper base-material.
Above-mentioned iron-based copper base-material is poured in the glass stylostome that is provided with upper and lower gangway, after compacting, forms fixed-bed reactor.
By coking chemical waste water (being 303.73mg/L containing phenol concentration) with behind sulphur acid for adjusting pH value=3 through by conduit lentamente in inflow reactor, controls water flow is 5-7ml/min, the residence time of guarantee sewage in reaction bed is 30-35min.
Effluent quality color becomes basic water white transparency from ingress light brown, and phenol concentration degradation efficiency is 55.34-67.43%.
Claims (3)
1. process the iron-based copper of organic sewage for one kind, it is characterized in that being prepared from as follows: by cast iron filing or cast iron powder at 5-40%(w/w) soak 10-130min in alkaline solution, filter, leach thing and wash with water 2-3 time, use again 5-45%(w/w) inorganic middle strong acid solution soak 1-45min, filter, leach thing and wash with water 2-3 time, join 1-50%(w/w) copper salt solution in stir 1-50min, filter, leach thing and wash with water 2-3 time, under nitrogen protection, dry, obtain iron-based copper;
Described alkaline solution is sodium hydroxide or sodium carbonate solution; Described inorganic middle strong acid is selected from following one or more: sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
2. the iron-based copper of processing organic sewage according to claim 1, is characterized in that: described mantoquita is selected from following one or more: copper sulfate, cupric chloride and cupric nitrate.
3. adopt iron-based copper described in claim 1 or 2 to process a method for organic sewage, it is characterized in that comprising the steps:
1) insert densely in the reactor of cylindrical or rectangle iron-based copper as filler;
2) in regulating tank, regulate acidity to pH=2-6 with sulfuric acid or hydrochloric acid in sewage;
3) sour water after regulating is pumped into anti-container, the residence time of sewage in reaction bed is 10-60min, and pollutent occurs to be flowed out by the other end after electrochemical decomposition in responding layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210077333.5A CN102849824B (en) | 2012-03-22 | 2012-03-22 | Iron-based copper for treating organic sewage and sewage treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210077333.5A CN102849824B (en) | 2012-03-22 | 2012-03-22 | Iron-based copper for treating organic sewage and sewage treatment method |
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| CN102849824A CN102849824A (en) | 2013-01-02 |
| CN102849824B true CN102849824B (en) | 2014-06-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105060578B (en) * | 2015-08-11 | 2018-05-01 | 南京大学盐城环保技术与工程研究院 | It is a kind of to utilize the method for activating Special Casting Iron material process organic wastewater containing cupric ammine complex |
| CN106854030B (en) * | 2017-01-11 | 2021-02-02 | 江苏八达科技股份有限公司 | Chemical wastewater treatment process |
| CN106673370B (en) * | 2017-01-11 | 2021-02-02 | 江苏八达科技股份有限公司 | Coking sewage treatment method |
| CN106587539B (en) * | 2017-01-11 | 2021-02-02 | 江苏八达科技股份有限公司 | Treatment method of tannery wastewater |
| CN106587540B (en) * | 2017-01-11 | 2021-02-02 | 江苏八达科技股份有限公司 | Treatment process of printing and dyeing wastewater |
| CN111233107A (en) * | 2018-11-29 | 2020-06-05 | 同济大学 | Copper-plated iron, preparation method and application thereof |
| CN109911990B (en) * | 2019-03-04 | 2020-12-11 | 中国科学院过程工程研究所 | Preparation method of high-activity iron-carbon micro-electrolysis filler |
| CN114602468A (en) * | 2022-02-10 | 2022-06-10 | 中国人民解放军63605部队 | Catalyst, device and method for treating aerospace propellant production sewage through catalytic reduction |
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| CN100503486C (en) * | 2005-02-25 | 2009-06-24 | 惠州大亚湾惠绿环保服务有限公司 | Method for treating waste sludge in wiring board plant into resources |
| CN100591632C (en) * | 2008-08-07 | 2010-02-24 | 石永丰 | Advanced treatment method and device for dyeing waste water by ozone iron zinc catalysis |
| CN102219498B (en) * | 2011-03-31 | 2013-07-24 | 厦门建霖工业有限公司 | Water purification ceramic material and preparation method thereof |
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