CN105645626B - Wastewater treatment method - Google Patents
Wastewater treatment method Download PDFInfo
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- CN105645626B CN105645626B CN201410709482.8A CN201410709482A CN105645626B CN 105645626 B CN105645626 B CN 105645626B CN 201410709482 A CN201410709482 A CN 201410709482A CN 105645626 B CN105645626 B CN 105645626B
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Abstract
In wastewater treatment method of the invention, comprising: collect the composite waste of copper-containing wastewater, fluoride waste in the first reactive tank, contain copper complex in the composite waste, the pH value for adjusting the composite waste is the first setting value；Contact break agent is added into first reactive tank, the contact break agent carries out contact break with the copper complex and reacts, and the composite waste after processing injects in the second reactive tank；The pH value for adjusting the composite waste in second reactive tank is the second setting value, and fluorine ion coagulant is added, for precipitating the fluorine ion in composite waste；By treated, composite waste injects in the 4th reactive tank, and flocculant is added in the 4th reactive tank of Xiang Suoshu, carries out flocculation reaction, is precipitated later.In the present invention, copper-containing wastewater and fluoride waste are handled simultaneously in a reaction system, contact break agent, which is added, to be precipitated after copper complex contact break, while guaranteeing the precipitating of fluorine ion, so that copper ion, fluorinion concentration reach discharge standard.
Description
Technical field
The present invention relates to the technical field of waste water processing in semiconductor manufacturing industry, more particularly to a kind of wastewater treatment side
Method.
Background technique
In the manufacturing process of semiconductor devices, a large amount of waste liquid, such as copper-containing wastewater, fluoride waste etc. can be generated, is given up
Liquid such as direct emission will cause the pollution of environment, so being recycled.Currently, the cupric generated in semiconductors manufacture is useless
Liquid is general to be recycled by the way of commission processing.The content of copper is lower in the copper-containing wastewater generally directly generated, reaches
Less than the requirement of recycling, need individually to build processing system processing.
However, the discharge amount of copper-containing wastewater constantly rises, also, contains with the development of the current advanced chip technology in the country
Copper complex is up to 70% or more in copper waste water, so that copper is difficult to precipitate, the cost for individually building processing system is again very high.Tradition
Pretreating process there is no good treatment effect to the waste water so that the risk of exceeding criterion of copper content is very in waste discharge
It is high.
Therefore, how a kind of wastewater treatment method is provided, disadvantages mentioned above can be overcome, it has also become those skilled in the art need
It solves the problems, such as.
Summary of the invention
The object of the present invention is to provide a kind of wastewater treatment methods, by copper-containing wastewater and fluoride waste in a system
In handled, save cost.
In order to solve the above technical problems, the present invention provides a kind of wastewater treatment method, comprising:
The composite waste of copper-containing wastewater, fluoride waste is collected in the first reactive tank, contains copper network in the composite waste
Object is closed, the pH value for adjusting the composite waste is the first setting value；
Contact break agent is added into first reactive tank, the contact break agent carries out contact break with the copper complex and reacts, will
The composite waste after processed injects in the second reactive tank；
The pH value for adjusting the composite waste in second reactive tank is the second setting value, and fluorine ion coagulant is added,
For precipitating the fluorine ion in composite waste；
By treated, composite waste injects in the 4th reactive tank, and flocculant is added in the 4th reactive tank of Xiang Suoshu, carries out
Flocculation reaction is precipitated later.
Optionally, the copper complex includes cupric ammine complex and copper chloro-complex.
Optionally, the contact break agent is iron chloride.
Optionally, the time for carrying out contact break reaction is 30min-60min.
Optionally, first setting value is 3-5,
Optionally, second setting value is 8-10.
Optionally, the sodium hydroxide that the pH adjusting agent that adjusting composite waste pH value uses is 30% for mass percent concentration
Solution.
Optionally, the fluorine ion coagulant is calcium chloride, and the time that fluorine ion coagulant is reacted is 30min-
60min。
Optionally, the flocculant is the polyacrylamide solution that mass percent concentration is 2 ‰, and the flocculant is added
The time reacted is 20min-30min.
It optionally, further include that composite waste is injected into a third reactive tank after the fluorine ion coagulant is added
In, process that composite waste is stirred.
Optionally, further include after precipitating, by clear liquid discharging, sludge press filtration at mud cake process.
Compared with prior art, wastewater treatment method of the present invention has the advantage that
In wastewater treatment method provided by the invention, comprising: collect copper-containing wastewater, fluoride waste in the first reactive tank
Composite waste contains copper complex in the composite waste, and the pH value for adjusting the composite waste is the first setting value；To described
Contact break agent is added in first reactive tank, the contact break agent and the copper complex carry out contact break and react, after processing described in
Composite waste injects in the second reactive tank；The pH value for adjusting the composite waste in second reactive tank is the second setting value, and
Fluorine ion coagulant is added, for precipitating the fluorine ion in composite waste；By treated, composite waste injects the 4th reactive tank
In, flocculant is added in the 4th reactive tank of Xiang Suoshu, carries out flocculation reaction, is precipitated later.In the present invention, by copper-containing wastewater
It is handled simultaneously in a reaction system with fluoride waste, contact break agent, which is added, to be precipitated after copper complex contact break, simultaneously
The precipitating for guaranteeing fluorine ion, so that copper ion, fluorinion concentration reach discharge standard.
Detailed description of the invention
Fig. 1 is the flow chart of wastewater treatment method in one embodiment of the invention；
Fig. 2 is waste water process schematic in one embodiment of the invention.
Specific embodiment
Wastewater treatment method of the invention is described in more detail below in conjunction with schematic diagram, which show this hairs
Bright preferred embodiment, it should be appreciated that those skilled in the art can modify invention described herein, and still realize this hair
Bright advantageous effects.Therefore, following description should be understood as the widely known of those skilled in the art, and be not intended as
Limitation of the present invention.
The present invention is more specifically described by way of example referring to attached drawing in the following passage.It is wanted according to following explanation and right
Book is sought, advantages and features of the invention will become apparent from.It should be noted that attached drawing is all made of very simplified form and using non-
Accurately ratio, only for the purpose of facilitating and clarifying the purpose of the embodiments of the invention.
Core of the invention thought is, in the wastewater treatment method provided, comprising: collects cupric in the first reactive tank
The composite waste of waste water, fluoride waste contains copper complex in the composite waste, and the pH value for adjusting the composite waste is the
One setting value；Contact break agent is added into first reactive tank, the contact break agent carries out contact break with the copper complex and reacts, will
The composite waste after processed injects in the second reactive tank；The pH value for adjusting the composite waste in second reactive tank is
Second setting value, and fluorine ion coagulant is added, for precipitating the fluorine ion in composite waste；By treated, composite waste is infused
Enter in the 4th reactive tank, flocculant is added in the 4th reactive tank of Xiang Suoshu, carries out flocculation reaction, precipitated later.The present invention
In, copper-containing wastewater and fluoride waste are handled simultaneously in a reaction system, contact break agent is added by copper complex contact break
It precipitates later, while guaranteeing the precipitating of fluorine ion, so that copper ion, fluorinion concentration reach discharge standard.
Specifically, the flow chart of wastewater treatment method of the invention is refering to what is shown in Fig. 1, and tie in conjunction with above-mentioned core concept
Fig. 2 is closed to be specifically described.
Firstly, executing step S1, the composite waste of fluoride waste and copper-containing wastewater is injected in the first reactive tank 10, generally
, there are ammonia radical ions in fluoride waste, and wherein concentration is 50-100mg/L.There is also there is chloride ion in composite waste, however,
Ammonia radical ion and chloride ion occur complex reaction with copper ion and form cupric ammine complex and copper chloro-complex, reaction equation are as follows:
Cu2++NH3→[Cu(NH3)4]2+
Cu2++2Cl2→[Cu(Cl)4]2+
The pH value in the first reactive tank 10 obtained according to measurement determines the pH adjusting agent being added in the first reactive tank 10
Type and concentration, so that the pH value in the first reactive tank 10 reaches one first setting value, in general first reactive tank 10 just
The pH value of beginning is 1-2, and the pH value in the first reactive tank 10 is adjusted to the first setting value 3-5 by setting.In the present embodiment, pH is adjusted
The regulator of sodium hydroxide solution, determining addition as needed that the pH adjusting agent that value uses is 30% for mass percent concentration
Concentration.In the present embodiment, the pH adjusting agent used can also be potassium hydroxide solution, as long as may be implemented to adjust pH value
Effect, also within the thought range that the present invention protects.
Then, step S2 is executed, contact break agent is added in first reactive tank 10, for carrying out contact break with copper complex
Reaction.In the present invention, the iron chloride that the contact break agent uses, the amount of the iron chloride of addition determine as needed.Due to first
PH environment in reactive tank 10 is acidic environment, so that iron ion therein exists usually in the form of divalent, i.e. Fe2+.?
In one reactive tank 10.Ferrous iron can be by the cupric ammine complex ([Cu (NH in composite waste3)4]2+), copper chloro-complex ([Cu
(Cl)4]2+) contact break reaction is carried out, generate univalent copper ion.Chemical equation therein is as follows:
[Cu(NH3)4]2++Fe2+→Cu++Fe3++4NH3
[Cu(Cl)4]2++Fe2+→Cu++Fe3++4Cl-
The time reacted in the first reactive tank 10 is 60min-90min, i.e. the time of contact break reaction is 60min-
Composite waste in first reactive tank 10 is injected into the second reactive tank 20 by 90min later, the reaction after carrying out.
In the present invention, the contact break agent is not limited to iron chloride, can also be other molysite, such as ferric sulfate, only
Contact break reaction of the invention may be implemented, also within the thought range that the present invention protects.
Step S3 is executed, likewise, more accurate adjusting is carried out to the pH value in the second reactive tank 20, so that the second reaction
In slot 20 pH value of composite waste be the second setting value, second setting value be 8-10, the type of the pH adjusting agent of use and
Concentration is selected as needed, this is identical as the method that pH is adjusted in the first reactive tank 10, and details are not described herein.Second
Fluorine ion coagulant is added in reactive tank 20, for precipitating the fluorine ion in composite waste.The amount of the calcium chloride of addition is according to need
It determines.In the present invention, the fluorine ion coagulant uses calcium chloride.In the processing method of various fluoride wastes, calcium salt
For the precipitation method due to having many advantages, such as that inexpensive, easy to operate, the reaction time is short and widely used, principle is to be added in waste water
A certain amount of calcium salt is reacted using calcium ion with the fluorine ion in waste water, and to form the sediment of calcirm-fluoride, reaction equation is such as
Under:
Ca2++2F-→CaF2
Meanwhile univalent copper ion is unstable, easily reacts with hydroxyl and generates cuprous hydroxide, cuprous hydroxide is dehydrated
Copper oxidule precipitation is generated, reaction equation is as follows:
Cu++OH-→Cu2O↓+H2O
In the present invention, iron chloride is ionic state in acidic environment, and can hydrolyze generation iron hydroxide under alkaline condition,
Reaction equation is as follows:
Fe3++H2O→Fe(OH)3↓+H+
In the present invention, the fluorine ion coagulant is not limited to calcium chloride, can also be other soluble calcium salts, as long as
Fluorine ion can be precipitated, also within the thought range that the present invention protects.
Preferably, step S3 is executed, composite waste is injected into third reactive tank 30 by the second reactive tank 20.In third
In reactive tank 30, composite waste is carried out the operating process such as to be mixed, so that reaction is more abundant, in the present embodiment,
Reaction time in third reactive tank 30 is 60min-90min, while a small amount of hydrogen-oxygen can also be added in third reactive tank 30
Change sodium solution, so that calcium ion reacts sufficiently with fluorine ion, while copper ion and iron ion is precipitated.
Later, step S4 is executed, processed composite waste is injected into the 4th reactive tank 40 by third reactive tank 30,
Also, flocculant is added in the 4th reactive tank 40.In the present invention, the flocculant used is 2 ‰ for mass percent concentration
Polyacrylamide solution, the processing system for composite waste include a data acquisition and supervisor control
(Supervisory Control And Data Acquisition, SCADA), data acquisition can be with supervisor control
To composite waste with detecting, for controlling the injection rate of flocculant.In the present embodiment, be added flocculant reacted when
Between be 20min-30min, the flocculant can be reacted with copper ion, generate the compound precipitates of copper.The precipitating of copper
Conjunction object is little particle.
Later, processed composite waste is injected into sedimentation basin 50 by the 4th reactive tank 40 and is precipitated, realize mud
Water separation, separates the sludge and supernatant of the compound precipitates of copper and the sediment of fluorine.Copper-containing wastewater is passing through this implementation
After the wastewater treatment method processing of example, the removal rate of copper can achieve 74% or more, it is ensured that the qualified discharge of copper.By precipitating
After the separation of pond, supernatant is neutralized, the concentration of the copper ion and fluorine ion in composite waste after processing
The discharge standard for having reached country, can be discharged.And separate the dirt of the compound precipitates of copper and the sediment of fluorine
Mud can enter sludge concentration tank by pressure pump and be carried out dehydrating, and can both be returned in a manner of entrusting processing after dehydration
Receipts processing or other modes are handled.
In conclusion in the wastewater treatment method of present invention offer, comprising: it is useless to collect cupric in the first reactive tank
The composite waste of water, fluoride waste contains copper complex in the composite waste, and the pH value for adjusting the composite waste is first
Setting value；Contact break agent is added into first reactive tank, the contact break agent carries out contact break with the copper complex and reacts, will locate
The composite waste after reason injects in the second reactive tank；The pH value for adjusting the composite waste in second reactive tank is the
Two setting values, and fluorine ion coagulant is added, for precipitating the fluorine ion in composite waste；By treated, composite waste injects
In 4th reactive tank, flocculant is added in the 4th reactive tank of Xiang Suoshu, carries out flocculation reaction, is precipitated later.In the present invention,
Copper-containing wastewater and fluoride waste are handled simultaneously in a reaction system, contact break agent is added will be after copper complex contact break
Precipitating, while guaranteeing the precipitating of fluorine ion, so that copper ion, fluorinion concentration reach discharge standard.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (6)
1. a kind of wastewater treatment method characterized by comprising
The composite waste of copper-containing wastewater, fluoride waste is collected in the first reactive tank, contains copper complex in the composite waste,
The pH value for adjusting the composite waste is the first setting value；
Be added contact break agent into first reactive tank, the contact break agent and the copper complex carry out contact break react generation copper from
Son, the composite waste after processing inject in the second reactive tank；
The pH value for adjusting the composite waste in second reactive tank is the second setting value, and fluorine ion coagulant is added, and is used for
The fluorine ion in composite waste is precipitated, and second setting value is 8-10, so that copper ion precipitates；
After the fluorine ion coagulant is added, composite waste is injected into a third reactive tank, and to composite waste into
Row stirring, and sodium hydroxide solution is added in the third reactive tank, so that fluorine ion coagulant and fluorine ion are sufficiently anti-
It answers, while copper ion is deposited；
By treated, composite waste injects in the 4th reactive tank, and flocculant is added in the 4th reactive tank of Xiang Suoshu, flocculates
Reaction, is precipitated later.
2. wastewater treatment method as described in claim 1, which is characterized in that the copper complex includes cupric ammine complex and copper
Chloro-complex.
3. wastewater treatment method as described in claim 1, which is characterized in that first setting value is 3-5.
4. wastewater treatment method as claimed in claim 3, which is characterized in that adjust the pH adjusting agent that composite waste pH value uses
The sodium hydroxide solution for being 30% for mass percent concentration.
5. wastewater treatment method as described in claim 1, which is characterized in that the fluorine ion coagulant be calcium chloride, fluorine from
The time that sub- coagulant is reacted is 30min-60min.
6. wastewater treatment method as described in claim 1, which is characterized in that the flocculant is that mass percent concentration is
2 ‰ polyacrylamide solution, it is 20min-30min that the time that the flocculant is reacted, which is added,.
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| CN201410709482.8A CN105645626B (en) | 2014-11-28 | 2014-11-28 | Wastewater treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410709482.8A CN105645626B (en) | 2014-11-28 | 2014-11-28 | Wastewater treatment method |
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| CN105645626A CN105645626A (en) | 2016-06-08 |
| CN105645626B true CN105645626B (en) | 2019-04-19 |
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| JP4016564B2 (en) * | 2000-02-24 | 2007-12-05 | 住友金属鉱山株式会社 | Treatment method for fluorine-containing wastewater |
| US20030136742A1 (en) * | 2002-01-23 | 2003-07-24 | Bersbach Ann Nahed | Wastewater treatment process using 8856 (A&B) to remove metals from wastewater |
| JP4809080B2 (en) * | 2006-03-08 | 2011-11-02 | 協和化学工業株式会社 | Waste water treatment method and waste water treatment agent containing fluorine ions |
| CN1948190B (en) * | 2006-11-07 | 2012-07-25 | 南京大学 | Treatment method of waste water in fluorofen production |
| CN203768158U (en) * | 2014-03-28 | 2014-08-13 | 中芯国际集成电路制造(北京)有限公司 | Copper-containing wastewater treatment system |
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