CN100385025C - Method of coproducing modified polyiron from copper extracted PCB acid etching waste liquid - Google Patents
Method of coproducing modified polyiron from copper extracted PCB acid etching waste liquid Download PDFInfo
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- CN100385025C CN100385025C CNB2006101220729A CN200610122072A CN100385025C CN 100385025 C CN100385025 C CN 100385025C CN B2006101220729 A CNB2006101220729 A CN B2006101220729A CN 200610122072 A CN200610122072 A CN 200610122072A CN 100385025 C CN100385025 C CN 100385025C
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Abstract
The invention relates the method for treating and utilizing PCB acid etching waste liquid. The method has the advantages of saving resource and protecting the environment. The method comprises the following steps: using iron as raw material, extracting copper from PCB acid etching waste liquid, using ferric salt, ferrous salt or water to adjust the iron content, using inorganic acid or organic acid to adjust the acid content, oxygenizing, hydrolyzing, polymerizing, modifying, and getting the modified iron product. The extraction rate of copper is 99%, and rate of finished products of iron is 100%.
Description
Technical field
The present invention relates to the processing and the method for comprehensive utilization of printing electronic circuit (being abbreviated as PCB) acidic etching waste liquid, more precisely, relate to the method that a kind of PCB acidic etching waste liquid is carried copper coproduction modified polyiron.
Technical background
IT industry is the important mainstay industry of China, but flourishing emergence along with IT industry, produced a large amount of poisonous and hazardous industrial sewages, deal with improperly very easily threaten and endanger around ecotope, wherein the PCB acidic etching waste liquid is to have the danger wastes that very big recycling is worth.
China is the populous nation of a shortage of resources, environment fragility, water resources and to pollute situation very severe, and low-cost resource and environmental capacity when not had developed country's industrialization are unable to undergo resource consumption and environmental pollution that the traditional economy development pattern brings.Recycling by industrialization means realization PCB etching waste liquor economizes on resources, and the protection environment is realized the Sustainable development of IT industry, is a major issue with strategic importance.
At the PCB acidic etching waste liquid, the general both at home and abroad at present technologies such as neutralization precipitation, electrolysis enrichment, solvent extraction, reduction separation that adopt can only manage to extract copper wherein, and other components are all carried out harmless treatment as refuse.The direct result that adopts these traditional technologys is the cost recovery height of copper, and other useful components are not only wasted resource but also needed expensive processing costs, and very easily cause serious secondary pollution and potential safety hazard by harmless treatment in a large number.
We have retrieved the nearest 6 years patent application gazette of the U.S., only find a relevant U.S. patent of invention " Method of recovering copper " (2004), this patent disclosure put forward the method for copper from spent etching solution, be to utilize alkaline matter precipitation copper hydroxide earlier, waste water is discharging after sodium sulphite, polymer etc. are handled.Domestic relevant 1 patent of invention, 2 achievements in research and the 7 pieces of academic papers of new (nearest 14 years) discovery of looking into, as Chinese invention patent publication number CN1278564A, open day 01 month 03 day calendar year 2001, patentee Sipray Co (U.S.), denomination of invention is " method and system that reclaims and remove copper from fluid ", this patent disclosure advocate to adopt electrolysis process, separate anode and negative electrode comes enrichment, extracts electrolytic copper by the cupric ion permeable membrane.Not only one-time investment is big for this method, cost is high, and the rate of recovery of copper depends on the performance of cupric ion permeable membrane consumingly, and does not consider that the resource utilization of other compositions effectively utilizes.CSTAD (CSTAD), project year numbers: 93218496, the achievement in research of Northwestern Polytechnical University " iron trichloride corrosion liquid waste treatment system ", advocate earlier with alkali precipitation iron mud, isolating iron mud is by hydrochloric acid, the renewable iron trichloride of chlorine leach, mother liquor then further precipitates by sodium sulphite carries copper, final waste water qualified discharge after advanced treatment.The treatment process of this method is numerous and diverse, and cost is too high, needs to consume a large amount of caustic soda, hydrochloric acid, chlorine, sodium sulphite etc., produces a large amount of high-salt wastewaters, acid mist and mud simultaneously, and secondary pollution is extremely serious, is difficult to obtain industrialization promotion for over ten years always and uses.Other research reports, also all with target tightening in the extraction of copper, all the other effective constituents are all carried out harmless treatment as Hazardous wastes, not only wasted resource, processing costs height, and secondary pollution are serious.
The comprehensive research and development situation in nearly twenty year both at home and abroad, because industry transfer and development in science and technology are maked rapid progress, China has in fact become main production, the research and development base of World PCB and equipment thereof, has represented international highest level substantially, especially is embodied in the recycling of downstream refuse.
The PCB acidic etching waste liquid mainly comprises mantoquita, free acid and oxygenant etc., these components have very big recycling as resource and are worth, then belong to the high density Hazardous wastes as pollutent, need high processing costs, and have secondary pollution and potential safety hazard.
Summary of the invention
Technical problem to be solved: the present invention is directed to the prior art deficiency; provide a kind of PCB acidic etching waste liquid to put forward the method for copper coproduction modified polyiron, realize whole recyclings of PCB acidic etching waste liquid effective constituent, economize on resources; the protection environment is realized the Sustainable development of IT industry.
Technical scheme: a kind of PCB acidic etching waste liquid is put forward the method for copper coproduction modified polyiron, is raw material with iron, extracts copper from the PCB acidic etching waste liquid, and the remaining waste liquid that comprises a large amount of iron and acid is used to prepare modified polyiron.
The present invention is as follows from the method technology for preparing modified polyiron after the PCB acidic etching waste liquid extracts copper and extracts copper:
With 20～30m
3The PCB etching waste liquor imports in the etching waste liquor Buffer Pool 1, and contact reactor 4 is filled up with iron plate, iron mud, iron powder or iron plane flower, start acid-resistant ceramic pump 2 then and make the PCB etching waste liquor constantly contact, react, separate out copper sponge, circulation with iron, copper sponge is discharged continuously by solid-liquid separator 3; Operating process needs regularly to add iron to contact reactor 4, and during less than 0.05g/L, copper-extracting process finishes, and closes down acid-resistant ceramic pump 2 up to extraneous copper content; By the copper sponge that solid-liquid separator 3 obtains continuously, after draining away the water,, thereby can obtain the high purity copper cake through reducing roasting;
After fully carrying copper, comprise a large amount of iron and acid remaining waste liquid be extracted into polymerization reactor 5, again with molysite, ferrous salt, water, mineral acid or organic acid allotment iron level and acid content, through oxidation, hydrolysis, polymerization, reaction such as composite modified, can synthesize modified polyiron.
PCB acidic etching waste liquid of the present invention can be any acidic etching waste liquid of producing PCB, or any mixing of multiple PCB etching waste liquor, or mixes with any of unclassified stores.
The iron that the present invention is used for carrying from the PCB acidic etching waste liquid copper can be all kinds of iron products, iron-bearing material or scrap iron; The scrap iron skin that preferably specific surface area is bigger.
The present invention is through after carrying copper, and the remaining waste liquid that comprises a large amount of iron and acid can be directly used in the preparation modified polyiron.
The present invention is through after carrying copper, and the remaining waste liquid that comprises a large amount of iron and acid also can customize modified polyiron by the content of further allotment iron and acid." further allocate the content of iron and acid " and comprise the content that increases or reduce iron and acid; But the content that increases iron and acid more helps preparing the high density modified polyiron.
The present invention can allocate iron level with molysite, ferrous salt or water.
The present invention is used to allocate the molysite or the ferrous salt of iron level, can be ferrous sulfate, iron protochloride, iron trichloride or their any mixing, preferably ferrous sulfate.
The present invention can allocate acid content with mineral acid or organic acid or their mixture.
The present invention is used to allocate mineral acid, the organic acid of acid content can use sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, citric acid or their any mixing, preferably sulfuric acid.
Production method of the present invention is at the PCB acidic etching waste liquid, be earlier that raw material extracts the copper in the PCB acidic etching waste liquid with iron, the remaining waste liquid that comprises a large amount of iron and acid is again by molysite, ferrous salt, water, mineral acid or organic acid allotment iron level and acid content, can prepare the efficient water-purifying agent modified polymeric-iron production with certain iron level and basicity through oxidation, hydrolysis, polymerization, reaction such as composite modified.
The present invention makes that each effective constituent all gets utilization in the PCB acidic etching waste liquid, and wherein the extraction yield of copper can reach 99%, and the yield rate 100% of modified polyiron does not have the three wastes to produce and effluxes.
The present invention compared with prior art has following advantage:
1, extract copper sponge by the metal replacement method from the PCB acidic etching waste liquid, the rate of recovery of copper can reach more than 99%; And traditional technology is mainly produced copper sulfate or cupric chloride, and the rate of recovery of copper only is 80～96%, and the unit cost recovery of traditional technology is higher more than 1 times than the present invention.
But 2,10～20 tons of modified polyirons of 1 ton of copper coproduction of the every extraction of the technology of the present invention are equivalent to newly-increased value 0.8～1.6 ten thousand yuan; And 1 ton of copper of the every extraction of traditional technology (converting according to copper sulfate or cupric chloride), need efflux 30～90 tons of poisonous waste water of high density approximately, these waste water of harmless treatment need about 0.3～1.0 ten thousand yuan of additional cost, efflux 1～3 ton of soluble compounds (inorganic salt etc.) and volatile gases (acid mist, ammonia etc.) simultaneously, its pollution and harm to ecotope is still very surprising.
3, the present invention will extract the remaining waste liquid behind the copper sponge, through oxidation, hydrolysis, polymerization, composite modifiedly can directly prepare modified polyiron, also can customize modified polyiron, the yield rate 100% of modified polyiron by the content of further allotment iron and acid; This production method has realized whole recyclings of PCB acidic etching waste liquid effective constituent; Not only itself produces and effluxes without any the three wastes, has realized zero release, and can produce environmental protection medicament---the efficient water-purifying agent modified polyiron of purifying treatment such as being applicable to trade effluent and municipal effluent in a large number.The composite wastewater of IT industry discharging mainly comprises pollutents such as heavy metal and COD, and purifying treatment need consume a large amount of water purification agents.According to preresearch estimates, China is annual to need all kinds of water purification agents more than 1,000 ten thousand tons, current main employing aluminium series water purifier, but the aluminium series water purifier is relatively poor to the removal effect of COD, and the aluminium poison manifests day by day to the potential threat of human body.Iron series water purifier is nontoxic with it, low production cost and superior product performance, is subjected to environmentalist's attention just day by day, will become the main flow of water purification agent, especially in the IT industry.Modified polyiron belongs to iron series water purifier, and utilizes the remaining waste liquid preparation after the PCB acidic etching waste liquid is carried copper, and its market outlook are finer naturally, and it is back to the IT industry, are major actions that realizes the Sustainable development of IT industry.And traditional technology is after extracting copper sulfate or cupric chloride, must poisonous waste water of a large amount of high densitys of harmless treatment and volatile gases, there be quite serious secondary pollution and potential safety hazard.
Description of drawings
Fig. 1 is the concise and to the point process flow sheet that the PCB acidic etching waste liquid extracts copper sponge;
Fig. 2 is the polymerization reactor structural representation.
Embodiment
Make below in conjunction with accompanying drawing 1, accompanying drawing 2 and 1～9 couple of the present invention of embodiment and to further specify.
Production method of the present invention is at the PCB acidic etching waste liquid, be earlier that raw material extracts the copper in the PCB acidic etching waste liquid with iron, the remaining waste liquid that comprises a large amount of iron and acid is again by molysite, ferrous salt, water, mineral acid or organic acid allotment iron level and acid content, can obtain a kind of efficient water-purifying agent---modified polymeric-iron production through oxidation, hydrolysis, polymerization, reaction such as composite modified.
The PCB acidic etching waste liquid is carried copper coproduction modified polyiron and is mainly realized by two steps: (A) extract copper sponge with substitution method; (B) will carry the raffinate that comprises a large amount of iron and acid behind the copper, through oxidation, hydrolysis, polymerization, the composite modified modified polyiron that obtains.Specific as follows:
(A) copper-extracting process: as Fig. 1, with 20～30m
3The PCB etching waste liquor imports 30m
3In the etching waste liquor Buffer Pool 1, and with iron plate, iron powder or iron plane flower with 8m
3Contact reactor 4 fills up, and starts 20m then
3/ h acid-resistant ceramic pump 2 makes the PCB etching waste liquor constantly contact, react, separate out copper sponge, circulation with iron, and copper sponge is discharged continuously by solid-liquid separator 3.
Operating process needs regularly to add iron to contact reactor 4, and the extraneous copper content of close attention cycle P CB etching waste liquor, up to extraneous copper content during less than 0.05g/L, copper-extracting process finishes, close down acid-resistant ceramic pump 2, the remaining waste liquid that will comprise a large amount of iron and acid with submersible pump 6 is extracted into polymerization reactor shown in Figure 25 by etching waste liquor Buffer Pool 1.
And will wait to carry 20～30m of copper
3New PCB etching waste liquor imports in the etching waste liquor Buffer Pool 1 ... so move in circles.
Following chemical reaction mainly takes place in copper-extracting process:
Cu
2++Fe＝Cu+Fe
2+
Under or the situation about exhausting not enough at copper, following side reaction will take place:
Fe+2H
+＝Fe
2++H
2↑
Therefore, judge whether copper-extracting process should finish, both can whether produce bubble through the observation system again and show according to the extraneous copper content of continuous monitoring PCB etching waste liquor.
By the copper sponge that solid-liquid separator 3 obtains continuously, after draining away the water, through reducing roasting, impurity wherein is easy to drive away with gas and scum silica frost (FeO) form, thereby can obtain the high purity copper cake.Specifically comprise following chemical reaction:
Fe+Cu
2O＝2Cu+FeO↑↑
Fe+CuO＝Cu+FeO↑↑
2Fe+O
2＝2FeO↑↑
(B) coproduction modified polyiron: as Fig. 2, after fully carrying copper, comprise a large amount of iron and acid remaining waste liquid be extracted into polymerization reactor 5, earlier through adjusting iron, acid content, and then according to existing maturation process (as Chinese invention patent publication number CN1156127A, CN1109027A and CN1101896A technology or the like), through oxidation, hydrolysis, polymerization, reaction such as composite modified, can synthesize the efficient water-purifying agent modified polyiron in about 1～2 hour.
Embodiment 1
As shown in Figure 1.With copper content is that 89.68g/L, density are 1215kg/m
3PCB etching waste liquor 20m
3Import in the etching waste liquor Buffer Pool 1, with the 1000kg left and right sides iron plate contact reactor 4 is filled up, start acid-resistant ceramic pump 2 then and make the PCB etching waste liquor constantly contact, react, separate out copper sponge, circulation with iron, copper sponge is discharged continuously by solid-liquid separator 3.Per half an hour is added iron plate one time to contact reactor 4 in operating process, and pays close attention to the extraneous copper content of cycle P CB etching waste liquor.React after 8～8.5 hours, extraneous copper content is promptly closed down acid-resistant ceramic pump 2 less than 0.05g/L in the waste liquid, with submersible pump 6 remaining waste liquid is transferred to polymerization reactor shown in Figure 25.At this moment, the total flow of iron plate is 2170kg, the copper sponge of results through drain, reducing roasting, obtain content and be 95.34% copper cake 1876kg, the rate of recovery of copper reaches 99.72%.After fully carrying copper, the remaining waste liquid that comprises a large amount of iron and acid, do not do any adjustment, directly according to Chinese invention patent notification number CN1101896A technology, can make about 25000kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 110.2g/L, basicity 18.33%, density is 1263kg/m
3
Embodiment 2
Production method is with embodiment 1, and the copper content of PCB soda acid mixing etching waste liquor is that 142.5g/L, density are 1318kg/m
3Utilize the useless technique of activated ferrous powder with displacement of iron level 49.37%, the total flow of useless technique of activated ferrous powder with is 7100kg; The gained copper sponge through drain, reducing roasting, obtain content and be 93.43% copper cake 3047kg, the rate of recovery of copper reaches 99.89%.Remaining waste liquid after fully carrying copper, add the 100kg citric acid and adjust iron level and acid content, according to Chinese invention patent notification number CN1101896A technology, can make about 29300kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 178.2g/L, basicity 16.98%, density are 1490kg/m
3
Embodiment 3
Production method is with embodiment 1, and the copper content of PCB etching waste liquor is that 116.4g/L, density are 1293kg/m
3Utilize the reduced iron powder displacement, the total flow of iron powder is 2996kg; The gained copper sponge through drain, reducing roasting, obtain content and be 95.03% copper cake 2442kg, the rate of recovery of copper reaches 99.69%.Remaining waste liquid after fully carrying copper, add 2000kg iron trichloride, 12500kg ferrous sulfate, 6000kg iron protochloride, 1500kg vitriol oil adjustment iron level and acid content, press Chinese invention patent publication number CN1101896A technology, through oxidation, hydrolysis, polymerization, reaction such as composite modified, can make about 47300kg modified polyiron, its iron level 238.2g/L, basicity 17.91%, density is 1653kg/m
3
Embodiment 4
Production method is with embodiment 1, and the copper content of PCB etching waste liquor is that 59.84g/L, density are 1155kg/m
3Utilize the displacement of iron plane flower, iron plane flower total burn-off 1450kg; The gained copper sponge through drain, reducing roasting, content is 95.20% copper cake 1253kg, the rate of recovery 99.67% of copper.Remaining waste liquid after fully carrying copper, add 15000kg ferrous sulfate, the 1000kg vitriol oil and 1000kg regenerating acid and adjust iron level and acid content, according to Chinese invention patent publication number CN1101896A technology, through oxidation, hydrolysis, polymerization, reaction such as composite modified, can make about 40300kg modified polyiron, its iron level 163.2g/L, basicity 16.94%, density is 1457kg/m
3
Production method is with embodiment 1, and the mixture of carbide slag and PCB etching waste liquor, its copper content are that 136.2g/L, density are 1321kg/m
3Utilize useless assorted iron displacement such as scrap iron nail, iron plate, iron wire, aluminium, the total flow of useless assorted iron is 2900kg; The gained copper sponge through drain, reducing roasting, obtain content and be 94.24% copper cake 2870kg, the rate of recovery of copper reaches 99.29%.Remaining waste liquid after fully carrying copper, add 100kg water, 500kg hydrochloric acid adjustment iron level and acid content, press Chinese invention patent publication number CN1101896A technology, can make about 26000kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 168.7g/L, basicity 10.33%, density are 1479kg/m
3
Production method is with embodiment 1 and micro-etching solution blended PCB etching waste liquor, and its copper content is that 75.36g/L, density are 1189kg/m
3Utilize the scrap iron mud displacement of iron content 88%, the total flow of scrap iron mud is 1946kg; The gained copper sponge through drain, reducing roasting, obtain content and be 92.62% copper cake 1611kg, the rate of recovery of copper reaches 99.01%.Remaining waste liquid after fully carrying copper, add 900kg iron protochloride, 300kg nitric acid adjustment iron level and acid content, press Chinese invention patent publication number CN1101896A technology, can make about 26000kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 103.6g/L, basicity 9.853%, density are 1258kg/m
3
Embodiment 7
Production method is with embodiment 1, and through water-reducible PCB etching waste liquor, its copper content is that 98.01g/L, density are 1223kg/m
3Utilize the displacement of scrap iron sheet and wood shavings iron, the total flow of iron is 2190kg; The gained copper sponge through drain, reducing roasting, obtain content and be 95.21% copper cake 2043kg, the rate of recovery of copper reaches 99.23%.Remaining waste liquid after fully carrying copper, add 1800kg iron trichloride, 50kg phosphoric acid adjustment iron level and acid content, press Chinese invention patent publication number CN1109027A technology, can make about 26000kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 161.8g/L, basicity 9.017%, density are 1437kg/m
3
Embodiment 8
Production method is with embodiment 1, and with regenerating acid blended PCB etching waste liquor, its copper content is that 86.77g/L, density are 1204kg/m
3Utilize waste and old iron sheet displacement, the total flow of waste and old iron sheet is 2150kg; The gained copper sponge through drain, reducing roasting, obtain content and be 96.45% copper cake 1788kg, the rate of recovery of copper reaches 99.37%.Remaining waste liquid after fully carrying copper, add 10000kg iron protochloride, 2500kg sulfuric acid, 200kg hydrochloric acid, 300kg nitric acid, 500kg phosphoric acid, 100kg citric acid adjustment iron level and acid content, press Chinese invention patent publication number CN1101896A technology, can make about 37700kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 189.9g/L, basicity 7.696%, density are 1553kg/m
3
Embodiment 9
Production method is with embodiment 1, and the mixture of PCB etching waste liquor, its copper content are that 64.82g/L, density are 1154kg/m
3The steel ring displacement is scrapped in utilization, and the total flow of scrapping steel ring is 1505kg; The gained copper sponge through drain, reducing roasting, obtain content and be 93.23% copper cake 1377kg, the rate of recovery of copper reaches 99.03%.Remaining waste liquid after fully carrying copper, add 100kg iron trichloride, 850kg ferrous sulfate, 50kg iron protochloride, 70kg sulfuric acid, 5kg hydrochloric acid, 10kg nitric acid, 10kg phosphoric acid, 5kg citric acid adjustment iron level and acid content, press Chinese invention patent publication number CN1156127A technology, can make about 23900kg modified polyiron through oxidation, hydrolysis, polymerization, reaction such as composite modified, its iron level 65.32g/L, basicity 15.73%, density are 1109kg/m
3
The technology of the present invention is converted into copper and modified polyiron with the PCB acidic etching waste liquid, has realized whole recyclings of PCB acidic etching waste liquid effective constituent, does not have the three wastes to produce and effluxes.
Copper is China's important non-ferrous metal in short supply, and all need spend a large amount of foreign exchange imports every year, and often is subjected to coercing or extorting under false pretense of international speculation fund.High efficiency extraction copper from the PCB acidic etching waste liquid, except economy, environmental protection factor, all significant to industry, the social safety of safeguarding China.
Modified polyiron is a kind of important environmental protection medicament, and belonging to iron is inorganic high molecular water purifier, has vast market prospect and economic worth in China.
The modified polyiron of the technology of the present invention coproduction has distinguished water purification performance, is applied in numerous sewage treatment projects.As two representative instances wherein, in the purifying treatment of municipal effluent and IT industry composite wastewater, its industrialization contrast and experiment as shown in Table 1 and Table 2.
The purifying treatment result of table 1 municipal effluent
The water quality and the water yield: pH7.12, turbidity 350NTU, COD=139mg/L, Q=20000m
3/ d;
Treatment process: adopt tube settling, settling tank mean residence time 4.2h;
Former with medicament: liquid aluminium polychloride, Al
2O
3Content 10.35%, basicity 60.49%, 800 yuan/ton of unit prices;
The modified polyiron of existing with medicament: embodiment 1,2,3,4,5,6,7,8,9 coproduction;
The polymer coagulant aids: nonionic PAM, molecular weight 1,800 ten thousand, CIBA produce.
The purifying treatment result of table 2 IT industry composite wastewater
The water quality and the water yield: pH3～4, turbidity 560NTU, COD=366mg/L, Q=6000m
3/ d;
Treatment process: adopt flat flow air supporting, reaction times 6min, the residence time 10min of separate chamber, molten gas is than 30%;
Former with medicament: bodied ferric sulfate, Fe
3+Content 28～30%, basicity 9～12%, 2100 yuan/ton of unit prices;
The modified polyiron of existing with medicament: embodiment 1,2,3,4,5,6,7,8,9 coproduction;
Alkaline agent and polymer coagulant aids: solid piece alkali, sloid alcali sulphide are industrial first grade; Cationic PAM, molecular weight 1,200 ten thousand, CIBA produce.
The data presentation of table 1 and table 2, with the modified polyiron excellent property of the inventive method coproduction, its purifying water effect obviously is better than existing flocculant poly ferric sulfate and polymerize aluminum chloride, can replace the like product of producing with industrial raw material fully, make a silk purse out of a sow's ear, benefit the common people.
Claims (11)
1. a PCB acidic etching waste liquid is put forward the method for copper coproduction modified polyiron, it is characterized in that with iron being raw material, extracts copper from the PCB acidic etching waste liquid, and the remaining waste liquid that comprises iron and acid is used to prepare modified polyiron.
2. PCB acidic etching waste liquid according to claim 1 is put forward the method for copper coproduction modified polyiron, it is characterized in that the method technology from preparing modified polyiron after the PCB acidic etching waste liquid extracts copper and extracts copper is as follows:
With 20m
3The PCB etching waste liquor imports in the etching waste liquor Buffer Pool (1), and contact reactor (4) is filled up with iron plate, iron mud, iron powder or iron plane flower, start acid-resistant ceramic pump (2) then and make the PCB etching waste liquor constantly contact, react, separate out copper sponge, circulation with iron, copper sponge is discharged continuously by solid-liquid separator (3); Operating process needs regularly to add iron to contact reactor (4), and during less than 0.05g/L, copper-extracting process finishes, and closes down acid-resistant ceramic pump (2) up to extraneous copper content; Copper sponge by solid-liquid separator (3) obtains continuously after draining away the water, through reducing roasting, thereby obtains copper cake;
After fully carrying copper, the remaining waste liquid that comprises iron and acid is extracted into polymerization reactor (5), with molysite, ferrous salt, water, mineral acid or organic acid allotment iron level and acid content, through oxidation, hydrolysis, polymerization, composite modified reaction, synthesizes modified polyiron again.
3. PCB acidic etching waste liquid according to claim 1 and 2 is put forward the method for copper coproduction modified polyiron, it is characterized in that the PCB acidic etching waste liquid that is adopted is any acidic etching waste liquid of producing PCB, or any mixing of multiple PCB etching waste liquor, or mix with any of unclassified stores.
4. PCB acidic etching waste liquid according to claim 1 is put forward the method for copper coproduction modified polyiron, it is characterized in that the iron that is adopted is all kinds of iron products, iron-bearing material or scrap iron.
5. PCB acidic etching waste liquid according to claim 1 is put forward the method for copper coproduction modified polyiron, it is characterized in that through after carrying copper, the remaining waste liquid that comprises iron and acid is directly used in the preparation modified polyiron.
6. PCB acidic etching waste liquid according to claim 1 is put forward the method for copper coproduction modified polyiron, it is characterized in that through after carrying copper, and the remaining waste liquid that comprises iron and acid customizes modified polyiron by further allotment iron and sour content.
7. PCB acidic etching waste liquid according to claim 6 is put forward the method for copper coproduction modified polyiron, it is characterized in that " further allocating the content of iron and acid " comprises the content that increases or reduce iron and acid.
8. PCB acidic etching waste liquid according to claim 6 is put forward the method for copper coproduction modified polyiron, it is characterized in that molysite, ferrous salt or water allocates iron level.
9. PCB acidic etching waste liquid according to claim 8 is put forward the method for copper coproduction modified polyiron, it is characterized in that being used to allocate the molysite or the ferrous salt of iron level, is ferrous sulfate, iron protochloride or iron trichloride.
10. PCB acidic etching waste liquid according to claim 6 is put forward the method for copper coproduction modified polyiron, it is characterized in that mineral acid or organic acid or their mixture allocate acid content.
11. PCB acidic etching waste liquid according to claim 10 is put forward the method for copper coproduction modified polyiron, it is characterized in that being used to allocate mineral acid or organic acid sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or the citric acid of acid content.
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| CN102115890B (en) * | 2011-01-04 | 2012-12-05 | 华南理工大学 | Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103864153B (en) * | 2014-03-12 | 2016-11-09 | 红板（江西）有限公司 | PCB factory acidic etching liquid replacement extraction copper and the method preparing poly-ferric chloride |
| CN106044868A (en) * | 2016-05-27 | 2016-10-26 | 上海绿澄环保科技有限公司 | Technological method and device for preparing ferrous sulfate crystals by aid of copper sulfate waste liquor |
| CN106086460A (en) * | 2016-07-20 | 2016-11-09 | 中南大学 | A kind of from acid CuCl2the method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor |
| CN108751326A (en) * | 2018-06-08 | 2018-11-06 | 闽南师范大学 | It is a kind of using steel pickling waste liquor modified alta-mud to the processing method of phosphorus-containing wastewater |
| CN110282715B (en) * | 2019-07-16 | 2021-08-31 | 闽江学院 | Preparation and application of polyquaternium in-situ composite modified polymeric ferric sulfate |
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| US4378270A (en) * | 1981-10-29 | 1983-03-29 | Learonal, Inc. | Method of etching circuit boards and recovering copper from the spent etch solutions |
| CN1824835A (en) * | 2006-01-24 | 2006-08-30 | 苏州市环境工程有限责任公司 | Method for recovering hydrochloric acid and copper sulfate from acidic etching liquid |
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