CN103739105B - The method of dioxin, treatment system and purposes is removed from etching waste liquor - Google Patents
The method of dioxin, treatment system and purposes is removed from etching waste liquor Download PDFInfo
- Publication number
- CN103739105B CN103739105B CN201310520218.5A CN201310520218A CN103739105B CN 103739105 B CN103739105 B CN 103739105B CN 201310520218 A CN201310520218 A CN 201310520218A CN 103739105 B CN103739105 B CN 103739105B
- Authority
- CN
- China
- Prior art keywords
- stage
- container
- waste liquor
- etching waste
- secondary filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
From etching waste liquor, remove a method for dioxin, comprising: etching waste liquor is loaded in hold-up vessel, etching waste liquor in hold-up vessel is pumped to successively by being equipped with the first step secondary filter container of first step precision Filter element, the second stage secondary filter container of second stage precision Filter element is housed, the charcoal absorption container of gac is housed, in the third stage secondary filter container that third stage precision Filter element is housed and reaction vessel, the first step precision Filter element of etching waste liquor in hold-up vessel successively in first step secondary filter container, second stage precision Filter element in second stage secondary filter container, arrive in reaction vessel after third stage precision Filter element process in gac in charcoal absorption container and third stage secondary filter container, just obtain the etching waste liquor after removing dioxin.The inventive method has the advantages such as efficient, pollution-free, simple to operate and running cost is low, is applicable to the Chu dioxin process to waste printed circuit board etching liquid in enormous quantities.
Description
[
technical field]
The present invention relates in waste water the process removing specific solute, in particular to the method for waste printed circuit board etching liquid removing dioxin, particularly relate to the method for the waste printed circuit board etching liquid removing dioxin for the production of basic copper chloride or copper sulfate, the invention still further relates to the purposes for the treatment of system and the removing dioxin after etching waste liquid removing dioxin from etching waste liquor.
[
background technology]
Dioxin (Dioxin) is also known as dioxa glutinous rehmannia, it is a kind of colorless and odorless, the lipid-soluble substance that toxicity is serious, what dioxin referred to is not a kind of one matter, it is all very similar two large class organic compound comprising numerous congener or isomer of structures and characteristics: the general designation of Duo chlorodiphenyl Bing dioxin (being called for short PCDDs) and polychlorinated dibenzo (abbreviation PCDFs), hydrogen atom on each phenyl ring can be replaced by 1 ~ 4 chlorine atom, because the difference of the position of substitution and quantity can form 210 kinds of isomer, wherein PCDDs has 75 kinds of isomer, PCDFs has 135 kinds of isomer.Because co-polar polychlorinated biphenyls (Co2PCBs), polybromodiphenyl ether compounds (PBDEs) are similar with the chemical structure of dioxin, " Convention of Stockholm about persistence organic pollutant " (abbreviation Convention of Stockholm) contracting states first time conference that in May, 2005 holds in Uruguay supplements Co2PCBs, PBDEs and PCDDs, PCDFs is referred to as dioxin-like compound.
The current World Health Organization (WHO) adopts toxic equivalency factor (TEF) to evaluate the bio-toxicity of dioxin-like compound, due to the strongest with 2,3,7,8 tetrachloro dibenzo Dui dioxin (TCDD) toxicity in dioxin-like compound, the World Health Organization (WHO) is using the toxicity of TCDD as reference standard value 1, and other dioxin-like compounds TEF converts as standard.Total toxicity of such sample Zhong dioxin-like compound just can be expressed as the summation that in sample, each homologue concentration and its toxic equivalency factor amass, and is called toxic equivalent (TEQ).
Dioxin has strong carinogenicity, causes that liver cancer dosage is low reaches per kilogram of body weight 10 nanogram (part per billion gram).IARC of the World Health Organization in 1997 to come up one-level carcinogens (to people's carcinogens certainly) Jiang dioxin from the secondary carcinogens of carcinogens list.Nineteen ninety-five, point out during the revaluation result of Dui dioxin that USEPA announces, it not only has carinogenicity, also has genotoxicity, Endocrine toxicity and immunotoxicity, and its toxicity is equivalent to 50 ~ 100 times of deadly poisonous compound potassium cyanide.Due to dioxin, there is chemical stability and be easy to be absorbed by fatty tissue, therefore once enter human body, will put aside in vivo for a long time.And in physical environment, microorganism and hydrolytic action affect less on the molecular structure of dioxin, therefore, in physical environment, dioxin is also difficult to natural degradation elimination.So dioxin is called by the World Health Organization " dangerous chemicals of persistence organic pollutant ".Toxicity due to dioxin is so high, and the intake of human body per kilogram of body weight permission every day was reduced to (1 pik is equivalent to trillionth gram) in 1 to 4 picogram region from 10 piks in 1998 by the World Health Organization.Dioxin generally enters animal food by the mode such as environment, feed.
European Union is to the maximum residue limit(MRL) standard of trace quantity mineral fodder additives: dioxin (PCCDs+PCDFs): TEQ (ND=DL)≤1.0ppt(ng/L, receives grams per liter; Or pg/ml, pg/ml); Dioxin (PCCDs+PCDFs)+PCBs:TEQ (ND=DL)≤1.5ppt.
Waste printed circuit board etching liquid (also claiming PCB etching waste liquor) comprises alkaline etching waste liquid for producing and acidic etching waste liquid.In etching process, etching solution contacts with organism such as the base material on wiring board, ink and easily produces dioxin, this kind of etching waste liquor is as caused serious environmental pollution and great economic waste without dealing carefully with utilization, domestic common treatment process is: extract the copper in acidic and alkaline waste etching solution, produces the products such as basic copper chloride, copper sulfate, cupric oxide or organic copper.Usually, etching waste liquor Zhong content of dioxin up to tens pg/ml(pg/ml, 1pg/ml=1ppt), use the product content of dioxin such as the basic copper chloride of this raw material production or copper sulfate higher, higher than European Union's maximum residue limit(MRL) standard, and produce food health safety problem.The content of the basic copper chloride produced by waste printed circuit board etching liquid or copper sulfate Dui dioxin has strict demand content of dioxin more low better, generally before producing basic copper chloride or copper sulfate with waste printed circuit board etching liquid, need the process in early stage waste printed circuit board etching liquid being carried out to Chu dioxin.
Prior art Chinese invention patent ZL201010567599.9, November 30 2010 applying date, disclose one and " from printed circuit board etching waste solution, remove method and the purposes of dioxin ", the method comprises: a, by metal intermediate oxide, gac and water by weight 1 ~ 10: 1 ~ 10: 1 ~ 40 add band stir reaction vessel in, be uniformly mixed, form absorption slurry; B, in reaction vessel, add acid copper-containing etching waste solution that volume is 65 ~ 80% of reaction vessel volume and stir, with ammoniacal liquor adjust ph to 3 ~ 5, then the slurry prepared by step (a) is added, the slurry added and the volume ratio of etching waste liquor are 1 ~ 10:800 ~ 1200, continue stirring after 10 ~ 60 minutes with Filter Press, metal intermediate oxide is separated with gac from etching waste liquor, obtains the copper-containing etching waste solution through absorption removing dioxin.The raw material of preparation feed grade basic copper chloride and copper sulfate is used as by the copper-containing etching waste solution of the preparation-obtained removing dioxin of the method.The prior art " removes method and the purposes of dioxin " from printed circuit board etching waste solution following weak point:
One, because needs add metal intermediate oxide, can other metallic impurity be incorporated in etching waste liquor, the purity of producing basic copper chloride or copper sulfate product can be reduced;
Two, owing to can produce precipitation in treating processes, can cause the loss of copper content in etching waste liquor on the one hand, precipitation is more difficult on the other hand, and can cause environmental pollution.
Therefore the method and the treatment system that how to find a kind of efficient, pollution-free, simple to operate and removal dioxin that running cost is low are the problems that the art technology person of appointing needs to solve.
[
summary of the invention]
The technical problem to be solved in the present invention is avoid above-mentioned the deficiencies in the prior art part and propose a kind of method removing dioxin from etching waste liquor, there is the advantages such as efficient, pollution-free, simple to operate and running cost is low, be applicable to the Chu dioxin process to waste printed circuit board etching liquid in enormous quantities.The invention allows for a kind of from etching waste liquor, remove dioxin treatment system and the purposes of removing dioxin after etching waste liquid.
The technical scheme that the present invention solve the technical problem employing is:
From etching waste liquor, remove a method for dioxin, being the treating processes in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor, in turn including the following steps:
A, etching waste liquor is loaded in hold-up vessel;
B, etching waste liquor in described hold-up vessel is pumped to successively by being equipped with the first step secondary filter container of first step precision Filter element, the second stage secondary filter container of second stage precision Filter element is housed, the charcoal absorption container of gac is housed, in the third stage secondary filter container that third stage precision Filter element is housed and reaction vessel, the first step precision Filter element of etching waste liquor in described hold-up vessel successively in described first step secondary filter container, second stage precision Filter element in second stage secondary filter container, arrive in described reaction vessel after third stage precision Filter element process in gac in charcoal absorption container and third stage secondary filter container, just obtain the etching waste liquor after removing dioxin.
Described first step precision Filter element is the filter core of 10 microns; Described second stage precision Filter element is the filter core of 5 microns; Described third stage precision Filter element is also the filter core of 5 microns.
The abbreviation of the material of described first step precision Filter element, second stage precision Filter element and third stage precision Filter element to be all PP(be English Polypropylene, Chinese is polypropylene) plastics.
In stepb, controlling flow when the etching waste liquor in described hold-up vessel is pumped in described first step secondary filter container is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h.
In stepb, controlling flow when the etching waste liquor after the process of described first step precision Filter element is pumped in described second stage secondary filter container is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h.
In stepb, controlling flow when the etching waste liquor after the precision Filter element process of the described second stage is pumped in described charcoal absorption container is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h.
In stepb, controlling flow when the etching waste liquor after described activated carbon treatment is pumped in described third stage secondary filter container is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h.
In stepb, controlling flow when the etching waste liquor after the process of described third stage precision Filter element is pumped in described reaction vessel is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h.
The invention allows for a kind for the treatment of system removing dioxin from etching waste liquor, is the treatment system in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor; The described treatment system removing dioxin from etching waste liquor comprises the hold-up vessel storing etching waste liquor, the first step secondary filter container that first step precision Filter element is housed, the second stage secondary filter container that second stage precision Filter element is housed, the charcoal absorption container that gac is housed, the third stage secondary filter container that third stage precision Filter element is housed and reaction vessel, and is arranged on the fresh feed pump between the outlet of described hold-up vessel and first step secondary filter container entrance.Pending etching waste liquor to be pumped into by described fresh feed pump from the outlet of described hold-up vessel and arrives in described reaction vessel after the first step precision Filter element in described first step secondary filter container, the second stage precision Filter element in second stage secondary filter container, the gac in charcoal absorption container and the third stage precision Filter element process in third stage secondary filter container successively, and the etching waste liquor in this reaction vessel is exactly the etching waste liquor after removing dioxin.
Described fresh feed pump is impeller pump; Described first step precision Filter element is the PP filter core of 10 microns; Described second stage precision Filter element is the PP filter core of 5 microns; Described third stage precision Filter element is also the PP filter core of 5 microns.
Described hold-up vessel, first step secondary filter container, second stage secondary filter container, charcoal absorption container, third stage secondary filter container and reaction vessel are all the containers of acid resistance and alkalescence.
The described treatment system removing dioxin from etching waste liquor also comprises the first tensimeter be arranged between the outlet of described fresh feed pump and first step secondary filter container entrance, be arranged on the second tensimeter between described first step secondary filter container outlet and second stage secondary filter container entrance, be arranged on the 3rd tensimeter between described second stage secondary filter container outlet and charcoal absorption container entrance, be arranged on the 4th tensimeter between described charcoal absorption container outlet and third stage secondary filter container entrance, be arranged on the 5th tensimeter between described third stage secondary filter container outlet and reaction vessel entrance.
The described treatment system removing dioxin from etching waste liquor also comprises the first inlet control valve be arranged between the outlet of described fresh feed pump and first step secondary filter container entrance, be arranged on the second inlet control valve between described first step secondary filter container outlet and second stage secondary filter container entrance, be arranged on the 3rd inlet control valve between described second stage secondary filter container outlet and charcoal absorption container entrance, be arranged on the 4th inlet control valve between described charcoal absorption container outlet and third stage secondary filter container entrance, be arranged on the 5th inlet control valve between described third stage secondary filter container outlet and reaction vessel entrance.
The present invention also been proposed a kind of purposes removing dioxin after etching waste liquid, namely the etching waste liquor after the removing dioxin that the present invention obtains is for the preparation of the raw material of feed grade basic copper chloride, copper sulfate, cupric oxide or organic copper, products obtained therefrom basic copper chloride, copper sulfate, cupric oxide or organic copper content of dioxin are very low, the technological standard conformed with the regulations.
Compared with the existing technology comparatively, the beneficial effect that the present invention removes the method for dioxin, treatment system and purposes from etching waste liquor is:
1, use range is wide, and etching waste liquor before treatment does not need to do process in early stage, can directly use;
2, do not need to add other material, the etching waste liquor after process can not introduce other impurity;
3, the clearance of dioxin is high;
4, the loss of copper content in etching waste liquor can not be caused during process;
5, without any pollution, protection of the environment is conducive to;
6, the operating process of whole Chu dioxin is simple, and effective, easy to control, running cost is low, is applicable to the Chu dioxin process to etching waste liquor in enormous quantities.
[
accompanying drawing explanation]
Fig. 1 is the rough schematic view that the present invention removes the treatment system of dioxin from etching waste liquor, and the arrow in figure represents the direction that etching waste liquor flows.
[embodiment]
Below in conjunction with each accompanying drawing, the present invention is described in further detail.
See Fig. 1, a kind of method removing dioxin from etching waste liquor, being the treating processes in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor, in turn including the following steps:
A, etching waste liquor is loaded in hold-up vessel 10; Etching waste liquor comprises alkaline etching waste liquid for producing and acidic etching waste liquid, and alkaline etching waste liquid for producing and acidic etching waste liquid are separately stored in hold-up vessel 10 at normal temperatures, does not generally need to do any pre-treatment in early stage.
B, etching waste liquor in described hold-up vessel 10 is pumped to successively by being equipped with the first step secondary filter container 20 of first step precision Filter element, the second stage secondary filter container 30 of second stage precision Filter element is housed, the charcoal absorption container 40 of gac is housed, in the third stage secondary filter container 50 that third stage precision Filter element is housed and reaction vessel 60, the first step precision Filter element of etching waste liquor in described hold-up vessel 10 successively in described first step secondary filter container 20, second stage precision Filter element in second stage secondary filter container 30, arrive in described reaction vessel 60 after third stage precision Filter element process in gac in charcoal absorption container 40 and third stage secondary filter container 50, just obtain the etching waste liquor after removing dioxin.
The fresh feed pump 91 in Fig. 1 can be adopted to be pumped into successively by the etching waste liquor in hold-up vessel 10 in first step secondary filter container 20, second stage secondary filter container 30, charcoal absorption container 40, third stage secondary filter container 50 and reaction vessel 60.
Controlling flow when etching waste liquor in described hold-up vessel 10 is pumped in described first step secondary filter container 20 is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h; The first inlet control valve 81 in Fig. 1 can control flow when described etching waste liquor pumps into, and then the velocity of flow of described etching waste liquor in described first step secondary filter container 20 can be controlled, usually described etching waste liquor in described first step secondary filter container 20 through the time of first step precision Filter element process at 25 ~ 35 minutes, the such as treatment time is 30 minutes.
As shown in Figure 1, when the force value that the first tensimeter 71 shows is greater than the force value 0.1 ~ 0.2Mpa of the second tensimeter 72 display, the filtration capacity of first step precision Filter element reaches capacity, first step precision Filter element can block, then described first step precision Filter element needs to change, when the force value that the applicant generally shows at the first tensimeter 71 is greater than about the force value 0.15Mpa of the second tensimeter 72 display, described first step precision Filter element is changed.Or, there is no tensimeter, if the present invention removes treatment system non-stop run every day 8 hours of dioxin from etching waste liquor, then the filtration capacity of general work about ten days first step precision Filter elements will reach capacity substantially, and described first step precision Filter element is changed with regard to needs.
Described first step precision Filter element is the filter core of 10 microns; Described first step precision Filter element is PP plastics; The kind of described first step precision Filter element is Wound-rotor type filter core.
Controlling flow when etching waste liquor after the process of described first step precision Filter element is pumped in described second stage secondary filter container 30 is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h; The second inlet control valve 82 in Fig. 1 can control flow when described etching waste liquor pumps into, and then the velocity of flow of described etching waste liquor in described second stage secondary filter container 30 can be controlled, usually described etching waste liquor in described second stage secondary filter container 30 through the time of second stage precision Filter element process at 25 ~ 35 minutes, the such as treatment time is 30 minutes.
As shown in Figure 1, when the force value that the second tensimeter 72 shows is greater than the force value 0.1 ~ 0.2Mpa of the 3rd tensimeter 73 display, the filtration capacity of second stage precision Filter element reaches capacity, second stage precision Filter element can block, then described second stage precision Filter element needs to change, when the force value that the applicant generally shows at the second tensimeter 72 is greater than about the force value 0.15Mpa of the 3rd tensimeter 73 display, described second stage precision Filter element is changed.Or, there is no tensimeter, if the present invention removes treatment system non-stop run every day 8 hours of dioxin from etching waste liquor, then the filtration capacity of general work about 25 days second stage precision Filter elements will reach capacity substantially, and described second stage precision Filter element is changed with regard to needs.
Described second stage precision Filter element is the filter core of 5 microns; Described second stage precision Filter element is also PP plastics; The kind of described second stage precision Filter element is also Wound-rotor type filter core.
Controlling flow when etching waste liquor after the precision Filter element process of the described second stage is pumped in described charcoal absorption container 40 is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h; The 3rd inlet control valve 83 in Fig. 1 can control flow when described etching waste liquor pumps into, and then the velocity of flow of described etching waste liquor in described charcoal absorption container 40 can be controlled, usually described etching waste liquor in described charcoal absorption container 40 through the time of activated carbon treatment at 50 ~ 70 minutes, the such as treatment time is 60 minutes; The time ratio stopped in charcoal absorption container 40 due to etching waste liquor is long at first step secondary filter container 20, second stage secondary filter container 30 and third stage secondary filter container 50, so the volume of the volumetric ratio first step secondary filter container 20 of charcoal absorption container 40, second stage secondary filter container 30 and third stage secondary filter container 50 wants large.
As shown in Figure 1, when the force value that the 3rd tensimeter 73 shows is greater than the force value 0.1 ~ 0.2Mpa of the 4th tensimeter 74 display, the adsorptive power of gac reaches capacity, then described gac needs to change, when the force value that the applicant generally shows at the 3rd tensimeter 73 is greater than about the force value 0.15Mpa of the 4th tensimeter 74 display, described gac is changed.Or do not have tensimeter, if the present invention removes treatment system non-stop run every day 8 hours of dioxin from etching waste liquor, then the adsorptive power of general work about 1 year gac will reach capacity substantially, and described gac is changed with regard to needs.
The volume of the described charcoal absorption container 40 that the applicant adopts can hold the gac of 450 kilograms.
The kind of described gac is wood activated charcoal, and profile is indefinite form particle, and particle diameter size is 0.5 ~ 1.0 millimeter.
Controlling flow when etching waste liquor after described activated carbon treatment is pumped in described third stage secondary filter container 50 is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h; The 4th inlet control valve 84 in Fig. 1 can control flow when described etching waste liquor pumps into, and then the velocity of flow of described etching waste liquor in described third stage secondary filter container 50 can be controlled, usually described etching waste liquor in described third stage secondary filter container 50 through the time of third stage precision Filter element process at 25 ~ 35 minutes, the such as treatment time is 30 minutes.
As shown in Figure 1, when the force value that the 4th tensimeter 74 shows is greater than the force value 0.1 ~ 0.2Mpa of the 5th tensimeter 75 display, the filtration capacity of third stage precision Filter element reaches capacity, third stage precision Filter element can block, then described third stage precision Filter element needs to change, when the force value that the applicant generally shows at the 4th tensimeter 74 is greater than about the force value 0.15Mpa of the 5th tensimeter 75 display, described third stage precision Filter element is changed.Or, there is no tensimeter, if the present invention removes treatment system non-stop run every day 8 hours of dioxin from etching waste liquor, then the filtration capacity of general work about 1 year third stage precision Filter element will reach capacity substantially, and described third stage precision Filter element is changed with regard to needs.
Described third stage precision Filter element is the filter core of 5 microns; Described third stage precision Filter element is also PP plastics; The kind of described third stage precision Filter element is also Wound-rotor type filter core.
Controlling flow when etching waste liquor after the process of described third stage precision Filter element is pumped in described reaction vessel 60 is 8 ~ 17 cubes ms/h, such as, control flow and be 15 cubes ms/h; The 5th inlet control valve 85 in Fig. 1 can control flow when described etching waste liquor pumps into.Etching waste liquor in reaction vessel 60 is exactly the etching waste liquor after removing dioxin, and the etching waste liquor of this removing dioxin is as the raw materials for production of basic copper chloride, copper sulfate, cupric oxide or organic copper.
See Fig. 1, a kind for the treatment of system removing dioxin from etching waste liquor is the treatment system in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor; The described treatment system removing dioxin from etching waste liquor comprises and stores the hold-up vessel 10 of etching waste liquor, the first step secondary filter container 20 that first step precision Filter element is housed, the second stage secondary filter container 30 that second stage precision Filter element is housed, the charcoal absorption container 40 that gac is housed, the third stage secondary filter container 50 that third stage precision Filter element is housed and reaction vessel 60, and is arranged on described hold-up vessel 10 and exports fresh feed pump 91 between 12 and first step secondary filter container 20 entrance 21.
Pending etching waste liquor to be pumped into by described fresh feed pump 91 from the outlet 12 of described hold-up vessel 10 and arrives in described reaction vessel 60 after the first step precision Filter element in described first step secondary filter container 20, the second stage precision Filter element in second stage secondary filter container 30, the gac in charcoal absorption container 40 and the third stage precision Filter element process in third stage secondary filter container 50 successively, and the etching waste liquor in this reaction vessel 60 is exactly the etching waste liquor after removing dioxin.That is each connecting tube is successively by described hold-up vessel 10, fresh feed pump 91, first step secondary filter container 20, second stage secondary filter container 30, charcoal absorption container 40, third stage secondary filter container 50 is communicated with reaction vessel 60, pending etching waste liquor is made to be pumped into first step precision Filter element successively in described first step secondary filter container 20 from described hold-up vessel 10 by described fresh feed pump 91, second stage precision Filter element in second stage secondary filter container 30, third stage precision Filter element process in gac in charcoal absorption container 40 and third stage secondary filter container 50, finally arrive in described reaction vessel 60, etching waste liquor in this reaction vessel 60 is exactly the etching waste liquor after removing dioxin.
Described fresh feed pump 91 is impeller pump; Described first step precision Filter element is the PP filter core of 10 microns; Described second stage precision Filter element is the PP filter core of 5 microns; Described third stage precision Filter element is also the PP filter core of 5 microns.
Described hold-up vessel 10, first step secondary filter container 20, second stage secondary filter container 30, charcoal absorption container 40, third stage secondary filter container 50 and reaction vessel 60 are all the containers of acid resistance and alkalescence.Such as described hold-up vessel 10, first step secondary filter container 20, second stage secondary filter container 30, charcoal absorption container 40, third stage secondary filter container 50 and reaction vessel 60 all can adopt bilayer structure, the material of layer structure adopts general carbon steel, the material of endothecium structure adopts the abbreviation of the English polyethylene of engineering plastics PE(, and Chinese is meant to polyethylene).Described hold-up vessel 10, first step secondary filter container 20, second stage secondary filter container 30, charcoal absorption container 40, third stage secondary filter container 50 and reaction vessel 60 also all resistance to malleation and negative pressure, the highest to allow to bear pressure be 0.8Mpa.
See Fig. 1, the described treatment system removing dioxin from etching waste liquor also comprises and is arranged on described fresh feed pump 91 and exports the first tensimeter 71 between first step secondary filter container 20 entrance 21, be arranged on described first step secondary filter container 20 and export the second tensimeter 72 between 22 and second stage secondary filter container 30 entrance 31, be arranged on described second stage secondary filter container 30 and export the 3rd tensimeter 73 between 32 and charcoal absorption container 40 entrance 41, be arranged on described charcoal absorption container 40 and export the 4th tensimeter 74 between 42 and third stage secondary filter container 50 entrance 51, be arranged on described third stage secondary filter container 50 and export the 5th tensimeter 75 between 52 and reaction vessel 60 entrance 61.Each manometric effect is set mainly in order to change first step precision Filter element, second stage precision Filter element, gac and third stage precision Filter element.
See Fig. 1, in order to control flow, the described treatment system removing dioxin from etching waste liquor also comprises and is arranged on described fresh feed pump 91 and exports the first inlet control valve 81 between first step secondary filter container 20 entrance 21, be arranged on described first step secondary filter container 20 and export the second inlet control valve 82 between 22 and second stage secondary filter container 30 entrance 31, be arranged on described second stage secondary filter container 30 and export the 3rd inlet control valve 83 between 32 and charcoal absorption container 40 entrance 41, be arranged on described charcoal absorption container 40 and export the 4th inlet control valve 84 between 42 and third stage secondary filter container 50 entrance 51, be arranged on described third stage secondary filter container 50 and export the 5th inlet control valve 85 between 52 and reaction vessel 60 entrance 61.
See Fig. 1, the pipeline annexation of a most preferred embodiment of the present invention is: hold-up vessel 10, fresh feed pump 91, first tensimeter 71, first inlet control valve 81, first step secondary filter container 20, second tensimeter 72, second inlet control valve 82, second stage secondary filter container the 30, the 3rd tensimeter 73, the 3rd inlet control valve 83, charcoal absorption container 40, the 4th tensimeter 74, the 4th inlet control valve 84, third stage secondary filter container the 50, the 5th tensimeter 75, the 5th inlet control valve 85 are communicated with reaction vessel 60 by each connecting tube successively.
The purposes of the etching waste liquor after the inventive method removing dioxin is the raw material for the preparation of feed grade basic copper chloride, copper sulfate, cupric oxide or organic copper, products obtained therefrom basic copper chloride, copper sulfate, cupric oxide or organic copper content of dioxin are very low, the technological standard conformed with the regulations.The etching waste liquor such as using the inventive method to remove dioxin for raw material by crystallization, centrifugal and dry can production feed grade basic copper chloride; Feed grade basic copper chloride generates cupric oxide after adding alkali dechlorination; Cupric oxide again with sulfuric acid reaction, can be made into the copper sulfate of high-purity, feed grade and food additive grade.
Etching waste liquor after the inventive method removing dioxin detects content of dioxin through authoritative institution, and its detected result is as follows:
1. the acidic etching waste liquid content of dioxin without the process of Chu dioxin is: PCCDs+PCDFs=8.61pg/mL, PCBs=4.46pg/mL, PCCDs+PCDFs+PCBs=13.07pg/mL;
2. the acidic etching waste liquid content of dioxin through the process of Chu dioxin is: PCCDs+PCDFs=0.04pg/mL, PCBs=0.05pg/mL, PCCDs+PCDFs+PCBs=0.09pg/mL;
③ dioxin clearance is: (13.07-0.09)/13.07=99.3%.
The basic copper chloride content of dioxin that to use without the etching waste liquor of Chu dioxin process be raw material production is: PCCDs+PCDFs=2.79pg/mL, PCBs=0.686pg/mL, PCCDs+PCDFs+PCBs=3.476pg/mL;
The basic copper chloride content of dioxin that to use through the etching waste liquor of Chu dioxin process be raw material production is: PCCDs+PCDFs=0.16pg/mL, PCBs=0.048pg/mL, PCCDs+PCDFs+PCBs=0.208pg/mL.
Etching waste liquor dioxin clearance after the inventive method process, up to more than 95%, even reaches more than 99%; Use the basic copper chloride content of dioxin of this raw material production lower than European Union's maximum residue limit(MRL) standard, stop dioxins materials and enter animal food by feed, ensure the safety of animal food from source.
The above embodiment only have expressed the preferred embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention; Therefore, all equivalents of doing with the claims in the present invention scope and modification, all should belong to the covering scope of the claims in the present invention.
Claims (9)
1. from etching waste liquor, remove a method for dioxin, being the treating processes in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor, in turn including the following steps:
A, etching waste liquor is loaded in hold-up vessel (10);
B, etching waste liquor in described hold-up vessel (10) is pumped to successively by being equipped with the first step secondary filter container (20) of first step precision Filter element, the second stage secondary filter container (30) of second stage precision Filter element is housed, the charcoal absorption container (40) of gac is housed, in the third stage secondary filter container (50) that third stage precision Filter element is housed and reaction vessel (60), the first step precision Filter element of etching waste liquor in described hold-up vessel (10) successively in described first step secondary filter container (20), second stage precision Filter element in second stage secondary filter container (30), arrive in described reaction vessel (60) after third stage precision Filter element process in gac in charcoal absorption container (40) and third stage secondary filter container (50), just obtain the etching waste liquor after removing dioxin.
2. the method removing dioxin from etching waste liquor according to claim 1, is characterized in that:
Described first step precision Filter element is the filter core of 10 microns; Described second stage precision Filter element is the filter core of 5 microns; Described third stage precision Filter element is also the filter core of 5 microns.
3. the method removing dioxin from etching waste liquor according to claim 2, is characterized in that:
The material of described first step precision Filter element, second stage precision Filter element and third stage precision Filter element is all PP plastics.
4. the method removing dioxin from etching waste liquor according to any one of claims 1 to 3, is characterized in that:
In stepb, the etching waste liquor in described hold-up vessel (10) be pumped into described first step secondary filter container (20) interior time control flow be 8 ~ 17 cubes ms/h;
In stepb, controlling flow when the etching waste liquor after the process of described first step precision Filter element is pumped in described second stage secondary filter container (30) is 8 ~ 17 cubes ms/h;
In stepb, controlling flow when the etching waste liquor after the precision Filter element process of the described second stage is pumped in described charcoal absorption container (40) is 8 ~ 17 cubes ms/h;
In stepb, controlling flow when the etching waste liquor after described activated carbon treatment is pumped in described third stage secondary filter container (50) is 8 ~ 17 cubes ms/h;
In stepb, controlling flow when the etching waste liquor after the process of described third stage precision Filter element is pumped in described reaction vessel (60) is 8 ~ 17 cubes ms/h.
5. the method removing dioxin from etching waste liquor according to claim 4, is characterized in that:
Etching waste liquor in described hold-up vessel (10) be pumped into described first step secondary filter container (20) interior time control flow be 15 cubes ms/h;
Control flow when etching waste liquor after the process of described first step precision Filter element is pumped in described second stage secondary filter container (30) and be 15 cubes ms/h;
Control flow when etching waste liquor after the precision Filter element process of the described second stage is pumped in described charcoal absorption container (40) and be 15 cubes ms/h;
Control flow when etching waste liquor after described activated carbon treatment is pumped in described third stage secondary filter container (50) and be 15 cubes ms/h;
Control flow when etching waste liquor after the process of described third stage precision Filter element is pumped in described reaction vessel (60) and be 15 cubes ms/h.
6. from etching waste liquor, remove a treatment system for dioxin, be the treatment system in early stage for producing basic copper chloride, copper sulfate, cupric oxide or organic copper from etching waste liquor; It is characterized in that:
Comprise the hold-up vessel (10) storing etching waste liquor, the first step secondary filter container (20) that first step precision Filter element is housed, the second stage secondary filter container (30) that second stage precision Filter element is housed, the charcoal absorption container (40) that gac is housed, the third stage secondary filter container (50) that third stage precision Filter element is housed and reaction vessel (60), and be arranged on the fresh feed pump (91) between described hold-up vessel (10) outlet (12) and first step secondary filter container (20) entrance (21);
Pending etching waste liquor to be pumped into by described fresh feed pump (91) from the outlet (12) of described hold-up vessel (10) and arrives in described reaction vessel (60) after the gac in the first step precision Filter element in described first step secondary filter container (20), the second stage precision Filter element in second stage secondary filter container (30), charcoal absorption container (40) and the third stage precision Filter element process in third stage secondary filter container (50) successively, and the etching waste liquor in this reaction vessel (60) is exactly the etching waste liquor after removing dioxin.
7. the treatment system removing dioxin from etching waste liquor according to claim 6, is characterized in that:
Described fresh feed pump (91) is impeller pump; Described first step precision Filter element is the PP filter core of 10 microns; Described second stage precision Filter element is the PP filter core of 5 microns; Described third stage precision Filter element is also the PP filter core of 5 microns; Described hold-up vessel (10), first step secondary filter container (20), second stage secondary filter container (30), charcoal absorption container (40), third stage secondary filter container (50) and reaction vessel (60) are all the containers of acid resistance and alkalescence.
8. the treatment system removing dioxin from etching waste liquor according to claim 6, is characterized in that:
Also comprise the first tensimeter (71) be arranged between described fresh feed pump (91) outlet and first step secondary filter container (20) entrance (21), be arranged on the second tensimeter (72) between the outlet of described first step secondary filter container (20) and second stage secondary filter container (30) entrance (31), be arranged on the 3rd tensimeter (73) between the outlet of described second stage secondary filter container (30) and charcoal absorption container (40) entrance (41), be arranged on the 4th tensimeter (74) between the outlet of described charcoal absorption container (40) and third stage secondary filter container (50) entrance (51), be arranged on the 5th tensimeter (75) between the outlet of described third stage secondary filter container (50) and reaction vessel (60) entrance (61).
9. the treatment system removing dioxin from etching waste liquor according to any one of claim 6 to 8, is characterized in that:
Also comprise the first inlet control valve (81) be arranged between described fresh feed pump (91) outlet and first step secondary filter container (20) entrance (21), be arranged on the second inlet control valve (82) between the outlet of described first step secondary filter container (20) and second stage secondary filter container (30) entrance (31), be arranged on the 3rd inlet control valve (83) between the outlet of described second stage secondary filter container (30) and charcoal absorption container (40) entrance (41), be arranged on the 4th inlet control valve (84) between the outlet of described charcoal absorption container (40) and third stage secondary filter container (50) entrance (51), be arranged on the 5th inlet control valve (85) between the outlet of described third stage secondary filter container (50) and reaction vessel (60) entrance (61).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310520218.5A CN103739105B (en) | 2013-10-30 | 2013-10-30 | The method of dioxin, treatment system and purposes is removed from etching waste liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310520218.5A CN103739105B (en) | 2013-10-30 | 2013-10-30 | The method of dioxin, treatment system and purposes is removed from etching waste liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103739105A CN103739105A (en) | 2014-04-23 |
| CN103739105B true CN103739105B (en) | 2016-01-20 |
Family
ID=50496198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310520218.5A Active CN103739105B (en) | 2013-10-30 | 2013-10-30 | The method of dioxin, treatment system and purposes is removed from etching waste liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103739105B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738670A (en) * | 2003-01-16 | 2006-02-22 | 日生生物股份有限公司 | Method of concentrating and removing harmful substance using double-stranded DNA and adsorbent and apparatus therefor |
| CN101223109A (en) * | 2005-07-14 | 2008-07-16 | 出光兴产株式会社 | Method for treating water containing hardly decomposable substance |
| CN202054659U (en) * | 2011-03-30 | 2011-11-30 | 宁波表面工程研究中心 | Sewage treatment device with agitating vanes |
| CN102745696A (en) * | 2011-04-19 | 2012-10-24 | 哈尔滨工业大学 | Preparation method of hydrophobic silica fiber film and use of the hydrophobic silica fiber film in removal of organic pollutants |
-
2013
- 2013-10-30 CN CN201310520218.5A patent/CN103739105B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738670A (en) * | 2003-01-16 | 2006-02-22 | 日生生物股份有限公司 | Method of concentrating and removing harmful substance using double-stranded DNA and adsorbent and apparatus therefor |
| CN101223109A (en) * | 2005-07-14 | 2008-07-16 | 出光兴产株式会社 | Method for treating water containing hardly decomposable substance |
| CN202054659U (en) * | 2011-03-30 | 2011-11-30 | 宁波表面工程研究中心 | Sewage treatment device with agitating vanes |
| CN102745696A (en) * | 2011-04-19 | 2012-10-24 | 哈尔滨工业大学 | Preparation method of hydrophobic silica fiber film and use of the hydrophobic silica fiber film in removal of organic pollutants |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103739105A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104926018A (en) | Resourceful treatment process for alkali-minimization waste water | |
| CN103848468B (en) | The extraction agent of Treatment of Wastewater in Coking | |
| CN104445711A (en) | Treatment method for aniline wastewater | |
| CN103601315B (en) | A kind of method utilizing useless tea to consider process mining and metallurgy heavy metal wastewater thereby to be worth doing | |
| CN203212413U (en) | Coking wastewater advanced treatment system | |
| CN113880347B (en) | Method for treating wastewater from 4, 4-dinitrodiphenyl ether production | |
| CN201424419Y (en) | High-concentration fluorine-containing wastewater treatment system | |
| CN110655253A (en) | Full-quantitative treatment system and method for aged refuse landfill leachate | |
| CN103739105B (en) | The method of dioxin, treatment system and purposes is removed from etching waste liquor | |
| CN105384292B (en) | A kind of H acid production process for treating industrial waste water | |
| CN209974468U (en) | Full-scale treatment device for landfill leachate | |
| CN105036493A (en) | Sewage treatment method | |
| CN203545813U (en) | Treatment system for removing dioxin from waste etching solution | |
| CN105326055B (en) | A kind of plum halogen essence functional food rich in aldehydes matter and organic acid and preparation method thereof | |
| CN104828925B (en) | Solid-state heavy metal containing wastewater treatment agent and using method | |
| CN206204081U (en) | A kind of phenmethylol produces the circulation production device of wastewater utilization | |
| Al Sakiti et al. | Removal of di-2-ethyl hexyl phthalates by membrane bioreactor | |
| CN103754958A (en) | Process for preparing black iron oxide by utilizing wastewater generated in production of chlorinated benzene | |
| CN107619072B (en) | Curing agent for treating high-COD and high-salinity wastewater and using method | |
| CN101904368A (en) | Lycopene health-care oil and production method thereof | |
| CN105331820B (en) | From mine containing the method that copper is reclaimed in Effluent of cuprous cyanide | |
| CN101700447B (en) | Filtering foam and production method thereof | |
| CN212425682U (en) | Cyaniding cadmium plating electroplating wastewater treatment system | |
| CN103011326B (en) | A kind of method of organic matter in reduction amantadine production wastewater | |
| CN102583630A (en) | Method for treating antimony-containing waste water by modified bentonite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 518104 Dongjiang Environmental Protection Workshop, Gonghe Fifth Industrial Zone, Shajing Street, Baoan District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Dongjiang Feed Additives Co., Ltd. Address before: 518104 Dongjiang Environmental Protection Workshop, Gonghe Fifth Industrial Zone, Shajing Street, Baoan District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Dongjiang Huarui Technology Co.,Ltd. |