CN102730892A - Method for cyclically utilizing nitric acid in wet process of surface treatment - Google Patents
Method for cyclically utilizing nitric acid in wet process of surface treatment Download PDFInfo
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- CN102730892A CN102730892A CN2012102740800A CN201210274080A CN102730892A CN 102730892 A CN102730892 A CN 102730892A CN 2012102740800 A CN2012102740800 A CN 2012102740800A CN 201210274080 A CN201210274080 A CN 201210274080A CN 102730892 A CN102730892 A CN 102730892A
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Abstract
The invention discloses a method for cyclically utilizing nitric acid in a wet process of surface treatment. The method comprises the following procedures of: collection treatment: collecting treating fluid in a collecting and storing groove so as to form a storing fluid; filtering treatment: receiving the storing fluid and filtering nitrates with a large grain diameter, so as to form a filtered fluid without the nitrates and concentrated fluid containing the nitrates; and sending the filtered fluid back to the collecting and storing groove; distillation treatment: heating water with a low boiling point and the nitric acid in the concentrated fluid to form nitric acid mixed vapor, and remaining a solution with a high boiling point; condensation treatment: cooling the nitric acid mixed vapor to form a nitric acid solution, and sending the nitric acid solution back to the collecting and storing groove; and electro-deposition treatment: reducing metallic ions in the high-boiling point solution to be at a metal state by using electric power, so as to remain a sulfuric acid solution; and sending the sulfuric acid solution back to a distiller. Therefore, with the adoption of the method provided by the invention, the nitric acid is recycled and the purpose of zero discharge can be realized.
Description
Technical field
The present invention be more particularly directed to the recycle method of nitric acid in a kind of surface treatment wet process, it utilizes nanofiltration, distillation and electrodeposition process to realize the recycle of nitric acid.
Background technology
In general surface treatment wet process; Wet process such as liquid crystal panel, semiconductor element or printed substrate (PCB); Usually the mix acid liquor that uses acetic acid, nitric acid or fluoric acid to be carrying out etch processes, thereby in processing procedure, can produce the waste liquid that contains acetic acid, nitric acid or fluoric acid in a large number.And under the required standard that is emitted on environmental regulation of waste liquid, the dealer must carry out proper process to reduce the wherein concentration of acid solution.Because the processing of waste liquid needs quite complicated equipment unit and operative technique, therefore, most wet process dealer after the waste liquid of all processing procedures is concentrated, transfers to the specialized vendor on behalf of processing.
Yet the shortcoming of prior art is, not only increases wet process dealer's running cost; And the various acid solutions in the waste liquid are recyclable in fact and utilize, cause the waste of valuable resource, especially nitric acid in the waste liquid; Be to use acid solution very widely, can be used as solvent or lotion and use.In addition, the heavy metal that is comprised in the waste liquid has fearful negative impact for environment, also is the resource that can utilize again simultaneously, should carry out suitable recycling.
Therefore; The recycle method that needs nitric acid in a kind of surface treatment wet process; Utilize collection and treatment, filtration treatment, distillation processing, condensation process and electrodeposition process and form the liquid waste disposal mode of closed circulation; Recycle nitric acid, and separate sulfuric acid and heavy metal, to solve the problem of above-mentioned located by prior art.
Summary of the invention
Main purpose of the present invention provides the recycle method of nitric acid in a kind of surface treatment wet process; Comprise collection and treatment, filtration treatment, distillation processing, condensation process and the electrodeposition process operation of carrying out successively; In order to the nitric acid that treatment solution comprised in the recycle surface treatment wet process; And treatment solution further comprises water, sulfuric acid and metallic impurity, wherein:
Collection and treatment is collected in the collection storage tanks treatment solution to form storage liquid;
Filtration treatment; Receive storage liquid and utilize the nanofiltration film to form filtered liq and liquid concentrator with nitrate salt bigger in the filtering separation storage liquid; Wherein the nanofiltration film can constitute by gathering the human relations vinyl fluoride; And filtered liq does not contain nitrate salt, and liquid concentrator contains nitrate salt, and filtered liq is recycled to the collection storage tanks simultaneously;
Distillation is handled, and utilizes distiller that lower boiling water and nitric acid in the liquid concentrator are added thermosetting nitric acid mixed vapour, and stays by metallic impurity and the formed high boiling point solution of high boiling sulfuric acid;
Condensation process is that the cooling of nitric acid mixed vapour is formed salpeter solution, and is recycled to the collection storage tanks, to circulate and to utilize; And
Electrodeposition process is utilized electric power that high boiling point solution metal impurity is reduced into metallic state and is separated out, and stays sulphuric acid soln, and sulphuric acid soln further is recycled to distiller.
Therefore; Method of the present invention can effectively be recycled the nitric acid in the treatment solution, and makes wherein that sulphuric acid soln circulates in closed path, simultaneously the metallic impurity that comprised in the treatment solution is separated out with metallic state; Specifically realize the recovery of nitric acid, and reach the target of zero release and zero mud.
Description of drawings
Fig. 1 is the treatment scheme synoptic diagram of the recycle method of nitric acid in the surface treatment wet process of the present invention;
Main nomenclature: S10 collection and treatment, S20 filtration treatment, S30 distillation processing, S40 condensation process, S50 electrodeposition process.
Embodiment
Below cooperate graphic and component symbol is done more detailed explanation to implementation method formula of the present invention, have the knack of this art and after studying this specification sheets carefully, can implement according to this in order to do making.
Consult Fig. 1; The recycle method of nitric acid comprises step S10, S20, S30, S40 and the S50 that carries out in regular turn in the surface treatment wet process of the present invention; In order to the nitric acid that treatment solution comprised in the recycle surface treatment wet process; And this treatment solution further comprises water, sulfuric acid and metallic impurity, and wherein metallic impurity can comprise any one in nickel, copper, cobalt and the neodymium at least.
At first, the recycle method of nitric acid is to be begun to carry out collection and treatment by step S10 in the surface treatment wet process of the present invention, is to utilize to collect storage tanks with collection and treatment liquid, forms storage liquid.
Then in step S20, carry out filtration treatment; In order to be received in the storage liquid of collecting in the storage tanks; And utilize the nanofiltration membrane filtration to separate nitrate salt any in the storage liquid or vitriol and form filtered liq and liquid concentrator; Wherein filtered liq penetrated the nanofiltration film, and liquid concentrator is not penetrate the nanofiltration film.Filtered liq does not contain nitrate salt or vitriol, and filtered liq is recycled to the collection storage tanks, and liquid concentrator contains nitrate salt or vitriol.The volume ratio of filtered liq and this liquid concentrator can be 5:100 to 15:100.The nanofiltration film can (Polyvinylidene Fluoride PVDF) constitutes, and the nanofiltration film has a plurality of nano level holes, and the effective pore radius size of nano level hole is 12 to 25 nanometers by gathering the human relations vinyl fluoride.
In step S30; Utilize distiller to distill processing; Be that liquid concentrator is heated to a certain distillation temperature and makes more lower boiling nitric acid and the formation of water partly nitric acid mixed vapour in the liquid concentrator; And stay by the formed high boiling point solution of the sulfuric acid of metallic impurity and higher, and distillation temperature is between 115 ℃ to 125 ℃.
Get into step S40 then and carry out condensation process, with the cooling of nitric acid mixed vapour that step S30 produced and form salpeter solution,, and salpeter solution is recycled to the collection storage tanks such as prolong capable of using.
At last; In step S50, carry out electrodeposition process, the high boiling point solution metal impurity that utilizes electric power that step S40 is produced is reduced into metallic state and separates out, and stays sulphuric acid soln; And further residual sulphuric acid soln is recycled to distiller, uses the formation closed circulation.
In addition, above-mentioned treatment solution can further comprise Hydrocerol A, and this Hydrocerol A system is through the liquid concentrator of step S20 and the high boiling point solution of step S30, and in step S50, is recycled to distiller with sulphuric acid soln, forms closed circulation.
Characteristics of the present invention are; Utilize distillation processing and electrodeposition process to separate nitric acid, sulfuric acid and metallic impurity; And then realize to nitric acid utilize function again, form enclosed no blowdown circulation simultaneously, sulfuric acid and Hydrocerol A are stayed in the closed circulation; And metallic impurity are to separate out with solid-state pure metal, improve the accessibility and the industrial value that utilize again.Therefore; Method of the present invention can directly apply in the surface treatment wet process to improve waste water treatment efficiency; Nitric acid contained in the treatment solution is isolated and the metallic impurity in the treatment solution is separated out with metallic state, required to provide surface treatment wet process or other to handle processing procedure.
It is to be noted; The above person is merely in order to explain preferred embodiment of the present invention; Be not that attempt is done any formal restriction to the present invention according to this; Be with, all have in that identical invention spirit is following do relevant any modification of the present invention or change, all must be included in the category that the invention is intended to protect.
Claims (6)
1. the recycle method of nitric acid in the surface treatment wet process; Be to handle water, nitric acid, sulfuric acid and the metallic impurity that treatment solution comprised in the wet process in order to release surface; And this nitric acid of recycle; It is characterized in that the recycle method of nitric acid comprises the steps: in the described surface treatment wet process
Collection and treatment is collected in one with this treatment solution and collects in the storage tanks, to form storage liquid;
Filtration treatment; Receive storage liquid; And utilize the nanofiltration membrane filtration to separate nitrate salt any in the storage liquid or vitriol and filtered liq that penetrated this nanofiltration film that forms and the liquid concentrator that did not penetrate this nanofiltration film; Wherein filtered liq does not contain nitrate salt or vitriol, and filtered liq is recycled to the collection storage tanks, and liquid concentrator contains nitrate salt or vitriol;
Distillation is handled, and utilizes a distiller under being heated to a distillation temperature, the water of more lower boiling nitric acid in this liquid concentrator and part to be formed the nitric acid mixed vapour, and stays by the formed high boiling point solution of the sulfuric acid of these metallic impurity and higher;
Condensation process forms salpeter solution with this nitric acid mixed vapour cooling, and this salpeter solution is recycled to this collection storage tanks; And
Electrodeposition process is utilized electric power that this high boiling point solution metal impurity is reduced into solid metal and is separated out, and stays sulphuric acid soln, and this sulphuric acid soln that stays further is recycled to this distiller.
2. the recycle method of nitric acid is characterized in that in the surface treatment wet process according to claim 1, and described metallic impurity comprise any one in nickel, copper, cobalt and the neodymium at least.
3. the recycle method of nitric acid in the surface treatment wet process according to claim 1; It is characterized in that; Described nanofiltration film is by gathering human relations vinyl fluoride (Polyvinylidene Fluoride; PVDF) formation, and this nanofiltration film has a plurality of nano level holes, and the effective pore radius size of this nano level hole is 12 to 25 nanometers.
4. the recycle method of nitric acid is characterized in that in the surface treatment wet process according to claim 1, and the volume ratio of described this filtered liq and liquid concentrator is 5:100 to 15:100.
5. the recycle method of nitric acid is characterized in that in the surface treatment wet process according to claim 1, and described distillation temperature is between 115 ℃ to 125 ℃.
6. the recycle method of nitric acid in the surface treatment wet process according to claim 1; It is characterized in that; Described treatment solution further comprises Hydrocerol A, and this Hydrocerol A system is through this liquid concentrator and this high boiling point solution, and after this electrodeposition process, circulates with this sulphuric acid soln.
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| CN2012102740800A CN102730892A (en) | 2012-08-02 | 2012-08-02 | Method for cyclically utilizing nitric acid in wet process of surface treatment |
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| CN2012102740800A CN102730892A (en) | 2012-08-02 | 2012-08-02 | Method for cyclically utilizing nitric acid in wet process of surface treatment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016184248A1 (en) * | 2015-05-21 | 2016-11-24 | 成都虹华环保科技股份有限公司 | Nitric acid stripping liquid treatment system |
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| KR100742088B1 (en) * | 2005-11-03 | 2007-07-23 | 재단법인 포항산업과학연구원 | Recycling method of copper nitrate waste generated from etching process with etching liquid and electrolytic copper |
| CN101125719A (en) * | 2007-07-13 | 2008-02-20 | 深圳市中冠环保科技有限公司 | Method for reclaiming hydrochloric acid and metal copper from printed circuit acidic etching waste liquid |
| CN101353727A (en) * | 2008-09-18 | 2009-01-28 | 西部金属材料股份有限公司 | Method for reclaiming silver and copper in silver-copper alloy scrap |
| CN101402496A (en) * | 2008-10-15 | 2009-04-08 | 江南大学 | Clean production process for treating electroplating poaching water with nona-filtering method |
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Patent Citations (4)
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| KR100742088B1 (en) * | 2005-11-03 | 2007-07-23 | 재단법인 포항산업과학연구원 | Recycling method of copper nitrate waste generated from etching process with etching liquid and electrolytic copper |
| CN101125719A (en) * | 2007-07-13 | 2008-02-20 | 深圳市中冠环保科技有限公司 | Method for reclaiming hydrochloric acid and metal copper from printed circuit acidic etching waste liquid |
| CN101353727A (en) * | 2008-09-18 | 2009-01-28 | 西部金属材料股份有限公司 | Method for reclaiming silver and copper in silver-copper alloy scrap |
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| WO2016184248A1 (en) * | 2015-05-21 | 2016-11-24 | 成都虹华环保科技股份有限公司 | Nitric acid stripping liquid treatment system |
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Application publication date: 20121017 |