CN103708639A - Metal waste liquid recovery treatment method - Google Patents

Metal waste liquid recovery treatment method Download PDF

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Publication number
CN103708639A
CN103708639A CN201210393855.6A CN201210393855A CN103708639A CN 103708639 A CN103708639 A CN 103708639A CN 201210393855 A CN201210393855 A CN 201210393855A CN 103708639 A CN103708639 A CN 103708639A
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China
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waste liquid
ozone
mixed solution
metal waste
metal
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CN201210393855.6A
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杨聪仁
吴俊彦
林文桔
詹惠琦
游智胜
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Ya Chung Industrial Co ltd
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Ya Chung Industrial Co ltd
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Abstract

A metal waste liquid recovery treatment method comprises the following steps: adding an alkaline chemical to the metal waste liquid to form a mixed liquid; preparing an ozone microbubble device which comprises an ozone generator and a microbubble generator connected with the ozone generator; introducing ozone into the mixed solution to obtain mixed solution containing ozone bubbles, then pushing the mixed solution to the micro-bubble generator, refining the ozone bubbles by using the micro-bubble generator, fully mixing the ozone bubbles with the mixed solution, and oxidizing and decomposing organic compounds in the mixed solution to form reaction generated solution; adding an alkaline chemical into the reaction product solution, and filtering to obtain a waste solution. The ozone bubbles are refined by the micro-bubble generator so as to increase the contact area and the detention time of the ozone bubbles and the mixed liquid, thereby effectively reducing the metal content in the metal waste liquid.

Description

Metal waste liquid recovery and treatment method
Technical field
The present invention relates to a kind of metal waste liquid recovery and treatment method, particularly relate to a kind of metal waste liquid recovery and treatment method that can reach discharge water standard.
Background technology
Electroless plating (Electroless plating) is to utilize autocatalysis principle at the process of surface treatment of matrix surface deposit alloy, is the technology that development is at present quick and have wide range of applications.And chemical nickel plating because have corrosion-resistant, surface hardness is high, chemical stability advantages of higher, so become in electroless plating with fastest developing speed a kind of.But because the processing procedure of electroless plating can produce metal waste liquid, if deal with improperly, easily environmental ecology is caused to serious harm and pollution.Therefore, how effectively processing the metal waste liquid that electroless plating produces is the direction that the art dealer actively makes great efforts.
Mainly to process by the precipitator method metal waste liquid producing after electroless plating processing procedure at present, the precipitator method are to utilize interpolation precipitation agent to make the precipitation by metallic ion in this metal waste liquid, although this method can be removed the metal ion in this metal waste liquid effectively, but not only can produce cannot recycling heavy metal sewage sludge, also can cause the waste of metals resources.In addition, because the organic compound existing in this metal waste liquid, the metal ion of meeting covered section, make the metal ion in this metal waste liquid precipitate completely, therefore, the simple discharge water standard of adding this metal waste liquid after precipitation agent is processed and cannot reach environmental regulation, for example, so must (: clorox add again oxygenant after adding precipitation agent, chlorine etc.) organic compound described in oxygenolysis, the metal ion that order is coated by this organic compound exposes, could further reduce again the metal content in this metal waste liquid, make this metal waste liquid meet discharge water standard.
Yet, the oxygenant that the aforementioned precipitator method are used, because toxicity/pungency is stronger, the strong toxicity of chlorine for example, therefore in operation, have the doubt of security, moreover, as what select is liquid oxygenant, have the problem residuing in this metal waste liquid, must through extra processing, could discharge again.
Summary of the invention
The object of the present invention is to provide a kind of metal waste liquid recovery and treatment method that can make metal content in metal waste liquid meet discharge water standard.
So metal waste liquid recovery and treatment method of the present invention comprises the following step:
(i) provide a kind of metal waste liquid;
(ii) in this metal waste liquid, add a kind of the first alkaline chemical, form a kind of pH value and be not less than 12 mixed solution;
(iii) prepare an ozone micro bubble apparatus, comprise an ozone generation device, and a microbubble generator being connected with this ozone generation device;
(iv) ozone that this ozone generation device produces is certainly passed into this mixed solution, obtain the mixed solution that contains ozone bubbles, the mixed solution that again this is contained to ozone bubbles pushes to this microbubble generator, utilize this microbubble generator to make this ozone bubbles refinement, make this ozone bubbles and this mixed solution fully mix and this mixed solution of oxygenolysis in organic compound, to form a kind of reaction solution;
(v) in this reaction solution, add a kind of the second alkaline chemical, form a kind of end reaction and generate liquid;
(vi) this end reaction is generated to liquid and filter, obtain a kind of waste liquid, and the metal content of this waste liquid is not more than 1ppm.
Metal waste liquid recovery and treatment method of the present invention, in this step (i), this metal waste liquid is nickel metal waste liquid.
Metal waste liquid recovery and treatment method of the present invention, this first alkaline chemical and this second alkaline chemical are selected from respectively sodium hydroxide, potassium hydroxide, calcium hydroxide, and the alkaline chemical of alkali gold alkaline earths, and this first alkaline chemical and this second alkaline chemical are identical or different.
Metal waste liquid recovery and treatment method of the present invention, in this step (iv), the temperature of this mixed solution maintains 50 ° of C to 90 ° of C.
Metal waste liquid recovery and treatment method of the present invention, preferably, in this step (vi), the metal content of this waste liquid is not more than 0.5ppm.
Beneficial effect of the present invention is: utilize this microbubble generator to make this ozone bubbles pulverize and form ultramicrofine ozone bubbles, and then make this ozone bubbles can fully mix with this mixed solution and this mixed solution of oxygenolysis in organic compound.
Accompanying drawing explanation
Fig. 1 is a schema, and a preferred embodiment of metal waste liquid recovery and treatment method of the present invention is described;
Fig. 2 be one for implementing the formation picture of device of metal waste liquid recovery and treatment method of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Consult Fig. 1, a preferred embodiment of metal waste liquid recovery and treatment method of the present invention comprises the following step:
Step 11, provides the metal waste liquid producing after a kind of electroless plating processing procedure.
Step 12 adds a kind of the first alkaline chemical in this metal waste liquid, forms a kind of pH value and is not less than 12 mixed solution.This first alkaline chemical is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and the alkaline chemical of alkali gold alkaline earths, utilizes this first alkaline chemical to react with most metal ion in this metal waste liquid, generates hydroxide precipitate.
Step 13, prepares an ozone micro bubble apparatus as shown in Figure 2, comprises a tank 2, return-flow type pump 3, an ozone generation device 4, and a microbubble generator 5; This return-flow type pump 3, this ozone generation device 4, and this microbubble generator 5 is sequentially connected with this tank 2.In addition, this ozone micro bubble apparatus also comprises a pressure detection device 6, a pressure regulator 7, an and temperature regulator 8, this pressure regulator 7 and this temperature regulator 8 are connected with this tank 2 respectively, borrow the pressure of these pressure detection device 6 these tanks 2 of detecting, and by this pressure regulator 7, controlled the pressure of these tanks 2, avoid the gas constantly producing in this metal waste liquid recycling process to cause the excessive problem of these tank 2 pressure, this temperature regulator 8, for making the liquid-retentive that is placed in this tank 2 in the temperature of setting, carries out in order to reaction.
Step 14, is placed in this tank 2 by this mixed solution, utilizes this return-flow type pump 3 that this mixed solution is carried toward this ozone generation device 4, and the ozone that order produces from this ozone generation device 4 mixes with this mixed solution, forms a kind of mixed solution that contains ozone bubbles; Then the mixed solution that again this is contained to ozone bubbles pushes to this microbubble generator 5, utilizes this microbubble generator 5 and then the ozone bubbles in this mixed solution is pulverized and formed ultramicrofine ozone bubbles.Borrow and form the contact area that ultramicrofine ozone bubbles increases those ozone bubbles and this mixed solution, and effectively the oxidation of organic compounds in this mixed solution is decomposed, the metal ion being coated is exposed, to form a kind of reaction solution by this organic compound.
Be noted that in the reaction process of this step 14, this pressure regulator 7 is to be controlled at 1.5 to 1.7 (kg/cm 2), and in order to promote the oxidative decomposition speed between ozone and this organic compound, preferably, the temperature of this mixed solution is to maintain 50 ° of C to 90 ° of C.
Step 15 then, adds a kind of the second alkaline chemical in this reaction solution, forms a kind of end reaction and generates liquid.This second alkaline chemical is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and the alkaline chemical of alkali gold alkaline earths, utilizes this second alkaline chemical further to react with the metal ion in this reaction solution, generates hydroxide precipitate.
In addition, be noted that this first alkaline chemical adding in this second alkaline chemical of adding in this step 15 and this step 12 is identical or different.
Step 16, generates liquid by this end reaction and filters, and obtain a kind of filtrate, and a kind of metal content is not more than the waste liquid of 1ppm.This filtrate of gained is washed to purifying, obtain the metal hydroxides of energy recycling, and the metal content of this waste liquid also meets the discharge water standard of environmental regulation.
The present invention puts up with following 2 concrete examples and 2 comparative examples are described further, but described concrete example is only as the purposes of explanation, should not be interpreted as restriction of the invention process.
concrete example 1:
(1-1) provide respectively 3 liters of undressedization nickel waste liquids after electroless plating processing procedure, and in this change nickel waste liquid, nickel content is 5553ppm.
(1-2) in describedization nickel waste liquid, add different alkaline chemicals respectively, this alkaline chemical is selected from sodium hydroxide, potassium hydroxide, and calcium hydroxide, take and forms respectively the mixed solution that pH value is 12.5.
(1-3) described mixed solution is placed in respectively to the tank 2 of this ozone micro bubble apparatus, and the temperature that makes described mixed solution maintains 70 ° of C, make ozone mix with described mixed solution, formation is dissolved with the mixed solution of ozone bubbles, then push to again this microbubble generator 5, make the ozone bubbles in described mixed solution pulverize the ultramicrofine ozone bubbles of formation, the reaction times is 3 hours, forms respectively reaction solution.
(1-4) in described reaction solution, add the alkaline chemical identical with step (1-2), take and form respectively the end reaction generation liquid that pH value is 12.5.
(1-5) described end reaction is generated to liquid and filter, obtain respectively nickel hydroxide precipitate thing and waste liquid.
With ozone, be used as oxygenant and participate in reaction, and utilize this microbubble generator 5 effectively to increase the contact area of ozone and this mixed solution, the difference that just adds alkaline chemical, in the described nickel hydroxide rate of recovery and described waste liquid, the analytical results of nickel content is as shown in the table:
Alkaline chemical Nickel content (ppm) The rate of recovery (%)
Sodium hydroxide 0.46 99.9917
Potassium hydroxide 0.49 99.9912
Calcium hydroxide 0.48 99.9914
concrete example 2:
(2-1) provide respectively 3 liters of undressedization nickel waste liquids after electroless plating processing procedure, and in this change nickel waste liquid, nickel content is 5553ppm.
(2-2) in describedization nickel waste liquid, add sodium hydroxide respectively, take and form respectively the mixed solution that pH value is 12.5.
(2-3) described mixed solution is placed in respectively to the tank 2 of this ozone micro bubble apparatus, and the temperature that makes described mixed solution maintains respectively 50 ° of C and 90 ° of C, make ozone mix with described mixed solution, formation is dissolved with the mixed solution of ozone bubbles, then push to again this microbubble generator 5, make the ozone bubbles in described mixed solution pulverize the ultramicrofine ozone bubbles of formation, the reaction times is 3 hours, forms respectively reaction solution.
(2-4) in described reaction solution, add sodium hydroxide, form respectively pH value and be 12.5 end reaction and generate liquid.
(2-5) described end reaction is generated to liquid and filter, obtain respectively nickel hydroxide precipitate thing and waste liquid.
With ozone, be used as oxygenant and participate in reaction, and utilize this microbubble generator 5 effectively to increase the contact area of ozone and this mixed solution, with regard to the difference of temperature of reaction, in the described nickel hydroxide rate of recovery and described waste liquid, the analytical results of nickel content is as shown in the table:
Temperature of reaction Nickel content (ppm) The rate of recovery (%)
50°C 0.48 99.9914
90°C 0.11 99.9980
comparative example 1:
(1-1) provide respectively 3 liters of undressedization nickel waste liquids after electroless plating processing procedure, and in this change nickel waste liquid, nickel content is 5553ppm.
(1-2) in describedization nickel waste liquid, add different alkaline chemicals respectively, this alkaline chemical is selected from sodium hydroxide, potassium hydroxide, and calcium hydroxide, take and forms respectively the mixed solution that pH value is 12.5.
(1-3) described mixed solution is filtered, obtain respectively nickel hydroxide precipitate thing and waste liquid.
Without adding oxygenant, participate in the difference that reaction just adds alkaline chemical, in the described nickel hydroxide rate of recovery and described waste liquid, the analytical results of nickel content is as shown in the table:
Alkaline chemical Nickel content (ppm) The rate of recovery (%)
Sodium hydroxide 651 88.2766
Potassium hydroxide 507 90.8698
Calcium hydroxide 396 92.8687
comparative example 2:
(2-1) provide respectively 3 liters of undressedization nickel waste liquids after electroless plating processing procedure, and in this change nickel waste liquid, nickel content is 5553ppm.
(2-2) in describedization nickel waste liquid, add sodium hydroxide respectively, take and form respectively the mixed solution that pH value is 12.5.
(2-3) make described mixeding liquid temperature maintain 30 ° of C, add respectively hydrogen peroxide and clorox to be used as oxygenant, the reaction times is 3 hours, forms respectively reaction solution.
(2-4) in described reaction solution, add sodium hydroxide, take and form respectively the end reaction generation liquid that pH value is 12.5.
(2-5) described end reaction is generated to liquid and filter, obtain respectively nickel hydroxide precipitate thing and waste liquid.
The difference that just adds oxygenant, in the described nickel hydroxide rate of recovery and described waste liquid, the analytical results of nickel content is as shown in the table:
Oxygenant Nickel content (ppm) The rate of recovery (%)
Hydrogen peroxide 16.30 99.7064
Clorox 10.92 99.8033
Conclusion the above results shows, for processing the metal waste liquid producing after electroless plating processing procedure, more above-mentioned concrete example and comparative example discovery, this comparative example 1 reacts without adding oxygenant, and the nickel content in described waste liquid all cannot reach the discharge water standard below 1ppm; And this comparative example 2 is used respectively hydrogen peroxide and clorox to be used as oxygenant, this changes the organic compound in nickel waste liquid oxygenolysis, by analytical results, shown, use this hydrogen peroxide and this clorox as oxygenant, although existing effect reduces this and changes the nickel content in nickel waste liquid, but cannot reach the standard of discharge water, and liquid oxygenant also can residue in this changes nickel waste liquid, must pass through extra processing again and could discharge.
Yet, this concrete example 1 and this concrete example 2 are to use ozone to participate in reaction as oxygenant, and utilize this microbubble generator 5 that ozone bubbles refinement is formed to ultramicrofine ozone bubbles, effectively increase the contact area of ozone and this mixed solution, by analytical results, shown, nickel content in this change nickel waste liquid has declined to a great extent and all below 0.5ppm, has met the discharge water standard of environmental regulation.In addition, by this concrete example 2, learnt, the increase of temperature of reaction can make the oxidative decomposition speed between ozone and this organic compound promote really, and then effectively reduces the nickel content in this change nickel waste liquid.Moreover the ozone of gaseous state can be decomposed into oxygen later using, do not there is toxicity and can not change nickel waste liquid to this yet and have any impact.
In sum, the present invention uses ozone to be used as oxygenant, and utilize this microbubble generator 5 effectively to increase contact area and the residence time of ozone and this metal waste liquid, reinforcement reaction is carried out and abundant oxygenolysis is present in the organic compound in this metal waste liquid, and then make the metal content reduction in this metal waste liquid reach the standard of discharge water, so really can reach object of the present invention.

Claims (5)

1. a metal waste liquid recovery and treatment method, comprises the following step: provide a kind of metal waste liquid; In this metal waste liquid, add a kind of the first alkaline chemical, form a kind of pH value and be not less than 12 mixed solution; Prepare an ozone micro bubble apparatus, comprise an ozone generation device, and a microbubble generator being connected with this ozone generation device; Certainly the ozone that this ozone generation device produces is passed in this mixed solution and reacted, to form a kind of reaction solution; In this reaction solution, add a kind of the second alkaline chemical, form a kind of end reaction and generate liquid, and this end reaction is generated to liquid filtration, obtain a kind of waste liquid; It is characterized in that: this mixed solution passes into after ozone, become a kind of mixed solution that contains ozone bubbles, the mixed solution that again this is contained to ozone bubbles pushes to this microbubble generator, utilize this microbubble generator to make this ozone bubbles refinement, make this ozone bubbles and this mixed solution fully mix and this mixed solution of oxygenolysis in organic compound, to form this reaction solution, whereby, make the metal content of this waste liquid be not more than 1ppm.
2. metal waste liquid recovery and treatment method according to claim 1, is characterized in that: this metal waste liquid is nickel metal waste liquid.
3. metal waste liquid recovery and treatment method according to claim 1, it is characterized in that: this first alkaline chemical and this second alkaline chemical are selected from respectively sodium hydroxide, potassium hydroxide, calcium hydroxide, and the alkaline chemical of alkali gold alkaline earths, and this first alkaline chemical and this second alkaline chemical are identical or different.
4. metal waste liquid recovery and treatment method according to claim 1, is characterized in that: the temperature of this mixed solution maintains 50 ° of C to 90 ° of C.
5. metal waste liquid recovery and treatment method according to claim 1, is characterized in that: the metal content of this waste liquid is not more than 0.5ppm.
CN201210393855.6A 2012-09-28 2012-10-17 Metal waste liquid recovery treatment method Pending CN103708639A (en)

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TW101135917A TWI535668B (en) 2012-09-28 2012-09-28 Recycling of metal waste
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110759540A (en) * 2019-11-25 2020-02-07 湖南中湘春天环保科技有限公司 Treatment method of chemical nickel plating waste liquid

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Publication number Priority date Publication date Assignee Title
KR100420561B1 (en) * 2001-05-29 2004-03-06 주식회사 탑이엔씨 Micro Dissolved Oxygen Flotation System
US20050077250A1 (en) * 2003-08-01 2005-04-14 Rohm And Haas Electronic Materials, L.L.C. Methods for recovering metals
CN101475256A (en) * 2009-01-19 2009-07-08 中南大学 Method for treating low concentration cobalt-containing wastewater by ozone dispersion oxidation
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110759540A (en) * 2019-11-25 2020-02-07 湖南中湘春天环保科技有限公司 Treatment method of chemical nickel plating waste liquid
CN110759540B (en) * 2019-11-25 2022-04-22 湖南中湘春天环保科技有限公司 Treatment method of chemical nickel plating waste liquid

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Application publication date: 20140409