CN100584760C - Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor - Google Patents
Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor Download PDFInfo
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- CN100584760C CN100584760C CN200710076208A CN200710076208A CN100584760C CN 100584760 C CN100584760 C CN 100584760C CN 200710076208 A CN200710076208 A CN 200710076208A CN 200710076208 A CN200710076208 A CN 200710076208A CN 100584760 C CN100584760 C CN 100584760C
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Abstract
The invention discloses a method and devices thereof for recycling waste etching solution of circuit board to prepare copper oxide/copper sulfate. A sequencing batch reacting method is adopted to add alkali waste solution with copper for etching circuit board into a reactor; copper oxide can be prepared then by adding sodium hydroxide, absorbing ammonia in constant temperature and a centrifugal separation method or the waste solution can also be added with sulfuric acid after absorbing ammonia in constant temperature to prepare copper sulfate. The acidic circuit board etching waste solution is required to be prepared into cuprammonia solution with ammonia solution firstly for preparation of the copper oxide or copper sulfate with the same method as an alkali solution treatment method. The devices comprise a reactor (1), an ammonia recycling system (2), a combination high level tank (3) and a combination low level tank (4). The inner wall of the reactor (1) is of a layer of modified furan epoxy resin glass FRP, therefore, the invention solves the method and configuration problems of recycling waste etching solution of circuit board to prepare copper oxide/copper sulfate, has the advantages of advanced preparation technique, safety, environment protective and good technical effect, and the wide application in the recycling waste etching solution of circuit board to prepare copper oxide/copper sulfate.
Description
Technical field
The present invention relates to a kind of waste liquid and reclaim method and the device of producing cupric oxide/cupric sulfate, more particularly, relate to a kind of method and device of preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor.
Background technology
As everyone knows, the etch process of wiring board has with ammonia to be the alkali etching of etching reagent and to be two kinds of the acid etching technologies of etching reagent with hydrochloric acid, so its waste liquid also has two kinds of alkaline waste liquor and acid waste liquids, comprise that the method that adds alkali, heating and negative pressure reclaims ammonia and produces cupric oxide owing to reclaim technology, and will add sulfuric acid, thereby the alternately variation repeatedly of necessary corrosion-resistant, anti-positive negative pressure of equipment and heatproof degree with cooling acquisition cupric sulphate crystal.
In the prior art, owing to do not have advanced reactor and corresponding auxiliary facility, its flow process complexity, technology is various and have a large amount of safety and environmental protection problems, and the plant area area is big.In addition, the existing material that meets this technology only has Hastelloy-B, but its price is stainless tens times, is difficult to popularize be used for this technology.
At present, comparatively Xian Jin ammonia reclaiming process is three grades of recovery technologies, each level reclaims all to be made up of resorber, cooling tank, ammoniacal liquor storage tank, recycle pump and pipeline, because 12 kinds of equipment of three grades of recovery are separately independently, so have that occupation area of equipment is big, leakage point is many, be difficult to realize shortcoming such as automatic control.
Summary of the invention
The object of the present invention is to provide a kind of method and this method corresponding device thereof of preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor.
For the attainment of one's purpose, the invention provides following technical scheme: the method for inventing a kind of preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor, the reaction of employing sequence batch (, comprise following process: (1) is that 8%～14% circuit board etching alkaline waste liquor adds reactor with the weight percentage of copper, in copper: the mol ratio of sodium hydroxide is that 1: 1.0～2.2 ratio adds sodium hydrate solid or its aqueous solution, stirring at normal temperature 10～30 minutes, (2) are stirred down reactant are heated to 95 ℃～110 ℃ again, open ammonia recovery system simultaneously, constant temperature was inhaled ammonia 2～4 hours, the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 20%～25%, make cuprammonia as the etching acid waste liquid, (3) are after constant temperature is inhaled ammonia then, open the jet vacuum pump of reactor, negative pressure is cooled to 50 ℃～60 ℃, stop stirring, left standstill 10～30 minutes, allow CuO precipitate, venting is clear liquid at the middle and upper levels, open again and stir, the moisturizing washing, multiple retry 2～3 times, the clout centrifugation after (4) will wash again, obtain the cupric oxide of weight in wet base 10%～20%, drying gets moisture 2% following cupric oxide the finished product, and perhaps (5) add copper: the vitriolic mol ratio is 1: 1.0～1.1 sulfuric acid, add the water that the water yield is a copper mole number 4～6, open stirring, open jet vacuum pump, be cooled to 40 ℃～room temperature by 1～4 ℃/minute speed, left standstill 10～30 minutes, get rid of supernatant liquid, will remain material and carry out solid-liquid separation, get the finished product CuSO
4.5H
2O.The pH value of described alkaline waste liquor is generally 9～13, comes the CONTROL PROCESS index with copper content in the actually operating; Described copper: the mol ratio of sodium hydroxide, copper wherein is to exist with ionic condition, comprises monovalence copper and cupric, when the copper of circuit board etching alkaline waste liquor is monovalence copper, copper then: the mol ratio of sodium hydroxide is 1: 1.0～1.1, and promptly sodium hydroxide is excessive slightly gets final product; In like manner, when the copper of circuit board etching alkaline waste liquor was cupric, copper then: the mol ratio of sodium hydroxide was 1: 2.0～2.2, and promptly sodium hydroxide is excessive slightly gets final product; If have monovalence copper and cupric simultaneously, then determine sodium hydroxide concentration as the case may be.The ammonia concn that ammonia recovery system is produced is controlled at 20%～25%, in operation, and NH
3Emission concentration standard is 30mg/l, is discharged to neutralizing well 4-5, need not to control this index in the operation, 2～4 hours is that nature reaches as long as control constant temperature is inhaled ammonia.
In the enforcement of the present invention, when circuitboard etching waste liquid is acid waste liquid, then use copper: NH
3Mol ratio be that 1: 1.0～2.2 ammoniacal liquor is made cuprammonia, and with this cuprammonia after outer circulation is filtered, produce cupric oxide or copper sulfate by claim 1 (1)～(5) process again.
Said process is from the extremely final CuSO that makes of acidic etching liquid
45H
2The chemical equation of O is as follows:
(1) acidic etching liquid+ammoniacal liquor (ammonia alkali reaction)
HCl+NH
4OH＝NH
4Cl+H
2O+Q
Cu+2NH
4Cl+2NH
3+1/2O2＝Cu(NH
3)
4Cl
2+H
2O+Q
Cu(NH
3)
4Cl
2+Cu＝2Cu(NH
3)
2Cl-Q
(2) cuprammonia+caustic soda (heavily quaternization)
Cu(NH
3)
4Cl
2+2NaOH＝CuO+4NH
3+2NaCl+H
2O+Q
(3) acidic etching liquid+caustic soda (heavily quaternization)
CuCl
2+2NaOH＝Cu(OH)
2+2NaCl+Q
(4) copper hydroxide thermolysis (heavily quaternization)
Cu(OH)
2＝CuO+H
2O-Q
(5) cupric oxide+sulfuric acid (acidizing crystal)
CuO+H
2SO
4+4H
2O＝CuSO
4.5H
2O+Q
(6) residual acid+alkali (heavily quaternization)
HCl+NaOH＝NaCl+H
2O+Q
(7) residue alkali+acid (treatment reaction)
2NaOH+H
2SO4＝Na
2SO
4+2H
2O+Q
The present invention's technical scheme preferably is: add in claim 1 (5) and add centrifuge mother liquor in the sulfuric acid process simultaneously.Centrifuge mother liquor is from the centrifugal mother liquor that goes out of whizzer 13, is actually CuSO
4.5H
2The saturated solution of O, CuSO at this moment
4.5H
2O plays the effect of " crystal seed ", makes finished product crystalline granularity increase and even.
The apparatus system that the device that the present invention uses constitutes as multiple devices, comprise pipe arrangement and power-equipment, power-equipment comprises whizzer, pump and stirrer, this device comprises the rounded reactor of cross section 1, ammonia recovery system 2, combination header tank 3 and combination Lower tank 4, the inwall of reactor 1 is a modification furan nucleus epoxy resins frp layer, the bottom is taper, and screw-blade 6 is housed on the axis 5, and the lower end of axis 5 is positioned at exit, reactor 1 below spiral hinge dragon 7 is housed.
In the device of the present invention, reactor 1 has outer modification furans epoxy glass laminate A and internal layer modification furans epoxy glass laminate B, join together by a plurality of evenly modification furans epoxy glass laminate C spaced apart, mesh steel plate D therebetween and modification furans epoxy glass laminate A, B, C join together and constitute the compound kettle of plastic-steel.
Described mesh steel plate D is praised fully to be rolled between the modification furans fiber glass epoxy, and as steel bar in reinforced concrete, the intensity height can stand-1～5kg/cm
2Pressure alternately change and stand 0～150 ℃ temperature and alternately change; This still has outstanding corrosion resistance nature, and solidity to corrosion is good in most of acid such as the hydrochloric acid of the sulfuric acid below 70%, various concentration, phosphoric acid, acetic acid.
In the reactor 1 of the present invention stabilizer shaft frame 8 is housed, stabilizer shaft frame 8 spiral hinge dragon 7 with below screw-blade 6 between and link to each other with the inwall of taper, prevent the smooth running of shaft end swing with the assurance stir shaft.
Interchanger 22 of the present invention is shell and tube heat exchanger, and interchanger 22 is installed on the middle part, case chamber of casing 23 and the front and rear panel that casing 23 is stretched out at two ends.
The case chamber of casing 23 of the present invention is separated by by mesh division board 26, and the overflow weir 29 on mesh division board 26 tops is equipped with non-return valve 27.To guarantee that ammoniacal liquor can only flow to high density case chamber by lower concentration case chamber, can close automatically when inactive.
Compared with prior art, the present invention has following tangible advantage: 1, technology is simple, easy to operate: as to carry out criticizing of preface equipment because the non-power-equipment arrangement of the class of turret vessel more than 30 in the traditional technology and reactor class is merged the technology of forming for 4～7 complete equipments such as reactor 1, ammonia recovery system 2, combination header tank 3 and combination Lower tank 4, again more than 10 ammonia recovery system in the traditional technology is merged integrated ammonia recovery unit, optimize technology greatly, simplified flow process; 2, technique effect is good: designed reactor is rational in infrastructure, and the intensity height can stand-1～5kg/cm
2Pressure alternately change, the temperature that can stand 0～150 ℃ alternately changes, and having an outstanding corrosion resistance nature, solidity to corrosion is good in most of acid such as the hydrochloric acid of the sulfuric acid below 70%, various concentration, phosphoric acid, acetic acid, and ammonia recovery can reach more than 99.5%; 3, safety and environmental protection: device of the present invention has adapted to new manufacturing technique requirent, has overcome that former technology auxiliary facility is many, flow process is complicated, technology is various, has overcome a large amount of safety and environmental protection problems simultaneously; 4, ammonia recovery system device of the present invention can be used for the recycling of wiring board spent etching solution, and Coking Plant Wastewater is handled, and rare earth element extracts, and multiple industries such as metallurgy, environmental protection, pharmacy and chemical fertilizer have dedusting, demist, Long Wen, absorb and take out effects such as negative; 5, practical: in conjunction with new production technique, construction investment saves 35%; Floor space saves 50%; Number of devices reduces 50%; Operator reduce more than 30%.
Description of drawings
It below is description of drawings of the present invention;
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the system structure of device synoptic diagram of the present invention based on reactor 1;
Fig. 3 is the F place local section structural representation of Fig. 2;
Fig. 4 is the cross-sectional view of strainer 15;
Fig. 5 is the one-piece construction synoptic diagram of ammonia recovery system 2;
Fig. 6 is the side-view of Fig. 5;
Fig. 7 is the integrated appearance structure synoptic diagram of ammonia recovery system 2;
Fig. 8 is the cross-sectional view of casing 23;
Fig. 9 is the cross-sectional view of miniature packing tower 24.
Among Fig. 1～Fig. 4,1,1-1,1-2 and 1-3 are reactors, the 2nd, and ammonia recovery system, the 3rd, the combination header tank, 3-1 is a mother liquor tank, 3-2 is a sulfuric acid tank, 3-3 inhales acid tank, and 3-4 is an ammonia vessel, and 3-5 is a dosing vessel, 3-6 is a dosing vessel, the 4th, and the combination Lower tank, 4-1 is a mother liquor tank, 4-2 is a sulfuric acid tank, and 4-3 is the acid etching liquid bath, and 4-4 is the alkali etching liquid bath, 4-5 is a neutralizing well, and 4-6 is that letdown tank 5 is axis, the 6th, and screw-blade, the 7th, spiral hinge dragon, the 8th, stabilizer shaft frame, the 9th, filter box, the 10th, sustained ring, the 11st, inhale sour venturi tube, the 12nd, inhale acid circulating pump, the 13rd, whizzer, the 14th, jet vacuum pump, the 15th, strainer, the 16th, steam inlet, the 17th, rubber gasket, the 18th, frame-type filter, the 19th, handle, the 20th, blind flange, A is outer modification furans epoxy glass laminate, B is an internal layer modification furans epoxy glass laminate, and C is a modification furans epoxy glass laminate, and D is the mesh steel plate.
In addition, a is that mother liquor reclaims pump, and b is the reuse water pump, and c is the alkali etching liquid pump, and d is the acidic etching liquid lift pump, and e is the sulfuric acid lift pump, and f is the mother liquor lift pump, g
1, g
2, g
3Be the filtration cycle pump, h
1, h
2, h
3Be the negative pressure recycle pump, i
1, i
2, i
3, i
4Be to inhale ammonia circulating pump, m is the centrifuge mother liquor accumulator tank, r be in and stirrer, s is anti-precipitating agitator.
Among Fig. 5～Fig. 9,21,21-1,21-2,21-3,21-4 are Venturi meters, 22,22-1,22-2,22-3,22-4 are interchanger, the 23rd, and casing, 23-1,23-2,23-3,23-4 are the case chambers, the 24th, miniature packing tower, the 25th, water distributor, the 26th, mesh division board, the 27th, non-return valve, the 28th, suction opening, the 29th, overflow weir, the 30th, baffling water tank cover plate, the 31st, pump entry, the 32nd, the blowdown outlet pipe, the 33rd, circulating-pump outlet, the 34th, ammoniacal liquor overflow port, 35 blow-off line mainboard faces, the 36th, filler, the 37th, support grid.
With reference to Fig. 1, be parallel with 3 reactor 1-1,1-2,1-3, share one group of ammonia and reclaim System, one group of combination head tank 3 and one group combination Lower tank 4, take use reactor 1-1 as Example is sketched process: acidic etching liquid elevator pump d loses quantitative acidic etching liquid from acidity Carve liquid bath 4-3 and deliver to reactor 1-1 liquid level, open stirring, and with quantitative ammoniacal liquor also by ammoniacal liquor Groove 3-6 puts into reactor 1-1, and both react, and becomes copper chloride network four ammonia and protochloride Copper network diamino is commonly called as cuprammonia, if adding is alkaline etching liquid, then needn't pass through this process. Cuprammonia is circulating pump g after filtration1Deliver to coupled filter 15 and carry out the outer circulation filtration only Change, return reactor 1-1, filter 15 positions are higher than reactor 1-1, can not stockpile liquid, Non-filtration time can be uncapped and be got filter residue; Add liquid caustic soda such as need, can add from dosage bunker 3-5 or 3-6 Enter reactor 1-1; When the ammonia recovery system ammonia excretion, then be discharged to neutralization chamber 4-5, when causing Reactor 1-1 low pressure is namely left the jet vacuum pump 14 that links to each other with this still; If with CuO for Finished product can enter the clout of Xian Dihou the centrifuge that installs qualified filter bag under this still 13, after the Separation of Solid and Liquid, namely obtain the finished product to be dried of water content; If with CuSO4.5H
2O for the amount finished product, then with the metering mother liquor and sulfuric acid respectively from mother liquor tank 3-1, sulfuric acid tank 3-2 put into reactor, and take the circumstances into consideration to add a certain amount of water, open stirring, Opening jet vacuum pump 14 gets final product; After the mixed thing of reactor 1-1 leaves standstill, supernatant liquor row Enter mother liquor accumulator tank m, afterwards, the residue material is entered the centrifuge that installs qualified filter bag 13 carry out Separation of Solid and Liquid. and separate among the mother liquor income mother liquor accumulator tank m, solid is namely final Products C uSO4.5H
2O。
After a collection of production is finished, namely clear up reactor 1 and carry out the next group operation.
With reference to Fig. 2, circuitboard etching waste liquid reclaims the device of producing cupric oxide or copper sulphate and is The apparatus system that multiple devices consist of comprises pipe arrangement and power-equipment, and power-equipment comprises centrifugal Machine, pump and mixer, this device comprise the rounded reactor of cross section 1, ammonia recovery system 2, combination head tank 3 and combination Lower tank 4, the inwall of reactor 1 is modification furans epoxy Resin glass fibre reinforced plastics layer, bottom are taper, and helical blade 6 is housed on the axis 5, axis 5 lower End is positioned at exit, reactor 1 below spiral Auger 7 is housed, and in the reactor 1 stabilizer shaft is housed Frame 8, stabilizer shaft frame 8 spiral Auger 7 and below helical blade 6 between and and taper Wall link to each other.
With reference to Fig. 3, reactor 1 has outer modification furans epoxy glass laminate A and internal layer Modification furans epoxy glass laminate B is by several even modification furans epoxies spaced apart Resin glass fibre reinforced plastics C joins together, mesh steel plate D therebetween and modification furans glass epoxy Steel A, B, C join together and consist of the compound kettle of plastic-steel.
With reference to Fig. 4, filter box 9 is housed in the filter 15, filter box 9 is positioned at frame-type filter 18 In, the periphery of filter box 9 is taken on the support ring 10 that is placed on filter 15 inwalls. Filter 15 Being another auxiliary facility of reactor 1, is with having under upper the putting down that steel and plastic composite material is made The column of cone. blue quick-actuating closure 20 and seal are managed in top, in establish handle 19, be convenient to fast Speed is removed filter residue. and frame-type filter 18 can be selected the fluoroplastics of salt tolerant acid, ammoniacal liquor.
With reference to Fig. 5～9, ammonia recovery system 2 comprises four groups of Venturi tubes that are one another in series 21, namely Venturi tube 21-1,21-2,21-3,21-4, four groups of heat exchangers 22 be heat exchanger 22-1,22-2, 22-3,22-4, one have the case chamber identical with 21 groups of numbers of Venturi tube namely four case chamber 23-1, 23, one miniature packed towers 24 of the casing of 23-2,23-3,23-4 and its water-locator 25, Venturi tube 21-1,21-2,21-3,21-4 respectively at right angle setting in the case chamber of correspondence 23-1, On 23-2,23-3, the 23-4, under the absorber portion of Venturi tube 21-1,21-2,21-3,21-4 End lays respectively at corresponding case chamber 23-1,23-2,23-3,23-4 top, Venturi tube 21-1 Air entry for reclaiming ammonia material inlet, the air entry of Venturi tube 21-2 and Venturi tube 21-1 institute The gaseous phase outlet of the case chamber 23-1 of correspondence links to each other, and the rest may be inferred by analogy for it, the identical heat exchanger 22 of group number Be that 22-1,22-2,22-3,22-4 are installed in respectively in the corresponding casing 23 casing 23 The upper space segment of last case chamber 23-4 the top directly with the bottom vertical of miniature packed tower 24 Communicate, water-locator 25 is positioned at miniature packed tower 24 superjacent air space places, heat exchanger 22-1,22-2, 22-3,22-4 all are tubular heat exchangers, be installed on respectively casing 23 case chamber 23-1,23-2, The front and rear panel of casing 23 is stretched out at 23-3,23-4 middle part and two ends.
With reference to Fig. 5,6, casing 23 of the present invention is provided with baffling water cover plate 30, at the baffling water cover The plate 30 interior lattice gusset guide cooling waters that can also be provided with are turned back circuitous mobile.
With reference to Fig. 6,7, Venturi tube 21-1,21-2,21-3,21-4 interleaved are arranged, Can effectively dwindle floor space of the present invention.
With reference to 5,8, the case chamber of casing 23 is separated by by mesh division board 26, mesh division board 26 tops Spout hole 29 is equipped with check (non-return) valve 27.
With reference to Fig. 6, heat exchanger 22 is tubular heat exchangers, and heat exchanger 22 is installed on casing 23 Case chamber middle part and the two ends front and rear panel that stretches out casing 23.
With reference to Fig. 9, the top of miniature packed tower 24 has water-locator 25, and filler is housed in it 36 Pall rings have support grid 37 below Pall ring.
By specific embodiment product technology is produced in recovery of the present invention below the embodiment and is carried out more detailed description:
(1) concentration expressed in percentage by weight of getting copper be 9%, the circuit board etching alkaline waste liquor 4.0M of pH value 11.8
3Amount to 5800 kilograms, the circuit board etching alkaline waste liquor adds reactor, and add 330 kilograms of sodium hydrate solids again, its copper: the mol ratio of sodium hydroxide is 1: 1.01, stirring at normal temperature 10 minutes, again
(2) stirring is heated to 100 ℃ with reactant down, and constant temperature was inhaled ammonia 2 hours, opens ammonia recovery system in the time of heating, and the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 20%, as etching acid waste liquid making cuprammonia, again
(3) after constant temperature is inhaled ammonia, open the jet vacuum pump of reactor ,-0.2～-0.5 kilograms per centimeter
2Negative pressure under be cooled to 50 ℃, stop stirring, left standstill 20 minutes, allow the CuO precipitation, venting is clear liquid at the middle and upper levels, open again and stir, the moisturizing washing, multiple retry 2 times, again
(4) with the clout centrifugation of Xian Dihou, obtain the cupric oxide of weight in wet base 10%, drying gets moisture 1% cupric oxide the finished product.
(1) gets and contain weight of copper 10%, proportion 1.28, the etching acid waste liquid 4M of pH value 1.5
3Amount to 5120 kilograms, in the contained copper monovalence copper and cupric 50% are arranged respectively in this etching acid waste liquid, add and contain NH
3800 kilograms of 204 kilograms ammoniacal liquor, copper: NH
3Mol ratio be 1: 1.5, make cuprammonia, and with this cuprammonia after outer circulation is filtered, add 1750 kilograms of the sodium hydroxide solutions of 40% weight concentration again, copper: the mol ratio of sodium hydroxide is 1: 2.2, stirring at normal temperature 30 minutes, again
(2) stirring is heated to 110 ℃ with reactant down, and constant temperature was inhaled ammonia 4 hours, opens ammonia recovery system in the time of heating, and the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 25%, as etching acid waste liquid making cuprammonia, then
(3) after constant temperature is inhaled ammonia, open the jet vacuum pump of reactor ,-0.2～-0.5 kilograms per centimeter
2Negative pressure under be cooled to 50 ℃, stop stirring, left standstill 15 minutes, allow the CuO precipitation, venting is clear liquid at the middle and upper levels, open again and stir, the moisturizing washing, multiple retry 3 times, again
(4) add 800 kilograms of 98% vitriol oils, at this moment copper: the vitriolic mol ratio is 1: 1.0, adds 750 kilograms of the water yields, for 5 times of copper mole numbers, adds centrifuge mother liquor 2M simultaneously
3, open stirring, open jet vacuum pump, be cooled to 40 ℃ by 2 ℃/minute speed, left standstill 30 minutes, get rid of supernatant liquid, will remain material and carry out solid-liquid separation, get the finished product CuSO of weight in wet base 4%
4.5H
2O.
Step below is concrete technical parameter with (1)～(3) of embodiment 1 and (4) of embodiment 2:
(1) the weight of copper percentage concentration be 14%, pH value 12, alkaline waste liquor 4.0M
3Amount to 6000 kilograms, the circuit board etching alkaline waste liquor adds reactor, and add 575 kilograms of sodium hydrate solids again, its copper: the mol ratio of sodium hydroxide is 1: 1.1, stirring at normal temperature 30 minutes, again
(2) reactant is heated to 95 ℃, and constant temperature was inhaled ammonia 3 hours, and the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 20%, makes cuprammonia as the etching acid waste liquid, again
(3) jet vacuum pump of reactor ,-0.2～-0.5 kilograms per centimeter
2Negative pressure under be cooled to 50 ℃, left standstill 10 minutes, CuO precipitation, multiple retry 2 times, again
1280 kilograms of (4) 98% vitriol oils, copper at this moment: the vitriolic mol ratio is 1: 1.0, adds 1400 kilograms of the water yields, is 6 times of copper mole numbers, centrifuge mother liquor 1M
3, open stirring, be cooled to 40 ℃ by 4 ℃/minute speed, left standstill 10 minutes, get the finished product CuSO of weight in wet base 4%
4.5H
2O.
Step below is concrete technical parameter with embodiment 2 (1)～(3) and embodiment 1 (4):
(1) contains weight of copper 8%, proportion 1.25, the etching acid waste liquid 4M of pH value 1.7
3Amount to 5000 kilograms, in the contained copper monovalence copper and cupric 50% are arranged respectively in this etching acid waste liquid, add and contain NH
3630 kilograms of 160 kilograms ammoniacal liquor, copper: NH
3Mol ratio be 1: 1.5, add 1250 kilograms of the sodium hydroxide solutions of 40% weight concentration again, copper: the mol ratio of sodium hydroxide is 1: 2.0, stirring at normal temperature 15 minutes, again
(2) stirring is heated to 100 ℃ with reactant down, and constant temperature was inhaled ammonia 3 hours, and the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 20%, makes cuprammonia as the etching acid waste liquid, again
(3) jet vacuum pump-0.2～-0.5 kilograms per centimeter
2Negative pressure under be cooled to 50 ℃, stop stirring, left standstill 25 minutes, allow the CuO precipitation, multiple retry 2 times, again
(4) cupric oxide of weight in wet base 10%, dry moisture 1% cupric oxide the finished product.
Claims (10)
1, a kind of method of preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor is characterized in that: adopt the sequence batch (reaction, comprise following process:
(1) be that 8%～14% circuit board etching alkaline waste liquor adds reactor with the weight percentage of copper, by copper: the mol ratio of sodium hydroxide is 1: 1.0～2.2 ratio adding sodium hydrate solid or its aqueous solution, stirring at normal temperature 10～30 minutes, again
(2) stirring is heated to 95 ℃～110 ℃ with reactant down, opens ammonia recovery system simultaneously, and constant temperature was inhaled ammonia 2～4 hours, and the ammoniacal liquor weight percent concentration that ammonia recovery system is produced is controlled at 20%～25%, makes cuprammonia as the etching acid waste liquid, again
(3) after constant temperature is inhaled ammonia, open the jet vacuum pump of reactor, negative pressure is cooled to 50 ℃～60 ℃, stops stirring, and leaves standstill 10～30 minutes, allows CuO precipitate, and venting is clear liquid at the middle and upper levels, and open again and stir, the moisturizing washing, multiple retry 2～3 times, then
(4) the clout centrifugation after will washing obtains the cupric oxide of weight in wet base 10%～20%, drying, moisture 2% following cupric oxide the finished product, perhaps
(5) add copper: the vitriolic mol ratio is 1: 1.0～1.1 sulfuric acid, adding the water yield is the water of 5～6 times of copper mole numbers, open stirring, open jet vacuum pump, be cooled to 40C °～room temperature by 1～4C °/minute speed, left standstill 10～30 minutes, get rid of supernatant liquid, to remain material and carry out solid-liquid separation, get the finished product CuSO
4.5H
2O.
2, method according to claim 1 is characterized in that: when circuitboard etching waste liquid is acid waste liquid, use copper: NH
3Mol ratio be that 1: 1.0～2.2 ammoniacal liquor is made cuprammonia, and with this cuprammonia after outer circulation is filtered, produce cupric oxide or copper sulfate by claim 1 (1)～(5) process again.
3, method according to claim 1 is characterized in that: add in claim 1 (5) and add centrifuge mother liquor in the sulfuric acid process simultaneously.
4, the device of the described method use of claim 1, apparatus system for the multiple devices formation, comprise pipe arrangement and power-equipment, power-equipment comprises whizzer, pump and stirrer, it is characterized in that: device comprises the rounded reactor of cross section (1), ammonia recovery system (2), combination header tank (3) and combination Lower tank (4), the inwall of reactor (1) is a modification furan nucleus epoxy resins frp layer, the bottom is taper, screw-blade (6) is housed on the axis (5), and the lower end of axis (5) is positioned at exit, reactor (1) below spiral hinge dragon (7) is housed.
5, device according to claim 4, it is characterized in that: reactor (1) has outer modification furans epoxy glass laminate (A) and internal layer modification furans epoxy glass laminate (B), join together by a plurality of evenly modification furans epoxy glass laminates (C) spaced apart, mesh steel plate (D) therebetween joins together with modification furans epoxy glass laminate (A), (B), (C) and constitutes the compound kettle of plastic-steel.
6, device according to claim 4 is characterized in that: stabilizer shaft frame (8) is housed in the reactor (1), and stabilizer shaft frame (8) is positioned between the screw-blade (6) of spiral hinge dragon (7) and below and with the inwall of taper and links to each other.
7, device according to claim 4, it is characterized in that: ammonia recovery system (2) comprises the interchanger (22) that one or more groups Venturi meter that is one another in series (21) is identical with quantity, casing (23) with case chamber identical with Venturi meter (21) group number, a miniature packing tower (24) and water distributor (25) thereof, Venturi meter (21) vertically is installed on the casing (23) and corresponding one group of Venturi meter (21) on each case chamber, the absorber portion lower end of Venturi meter (21) lays respectively at top, case chamber corresponding in the casing (23), the suction opening of first group of Venturi meter (21) is for reclaiming ammonia material inlet (28), suction opening and the last group of Venturi meter (21) of the one group of Venturi meter in back (21) the gaseous phase outlet of corresponding case chamber continuous, each interchanger (22) is installed in respectively in the case chamber corresponding with it of casing (23), the top of space segment directly communicates with the bottom vertical of miniature packing tower (24) on last case chamber of casing (23), and water distributor (25) is positioned at place, space, center, miniature packing tower (24) top.
8, according to claim 4 or 7 described devices, it is characterized in that: ammonia recovery system (2) comprises the interchanger (22) that four groups of Venturi meters that are one another in series (21) are identical with quantity, and case chamber that casing (23) has and their quantity adapt.
9, device according to claim 7 is characterized in that: interchanger (22) is a shell and tube heat exchanger, and interchanger (22) is installed on the middle part, case chamber and the two ends of casing (23) and stretches out the front and rear panel of casing (23).
10, device according to claim 7 is characterized in that: the case chamber of casing (23) is separated by by mesh division board (26), and the overflow weir (29) on mesh division board (26) top is equipped with non-return valve (27).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710076208A CN100584760C (en) | 2007-06-26 | 2007-06-26 | Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710076208A CN100584760C (en) | 2007-06-26 | 2007-06-26 | Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101113013A CN101113013A (en) | 2008-01-30 |
| CN100584760C true CN100584760C (en) | 2010-01-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200710076208A Expired - Fee Related CN100584760C (en) | 2007-06-26 | 2007-06-26 | Method and device for preparing cupric oxide/cupric sulfate by reclaiming wiring board etching waste liquor |
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| CN (1) | CN100584760C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792220A (en) * | 2010-03-16 | 2010-08-04 | 杭州电子科技大学 | Comprehensive treatment method of acidic etching waste liquid |
| CN101935062B (en) * | 2010-09-02 | 2012-05-30 | 昆山联鼎环保科技有限公司 | Method for preparing high-purity copper oxide by adopting acidic etching waste liquor |
| CN102786076B (en) * | 2012-08-30 | 2014-05-28 | 廖勇志 | Method for preparing high-purity copper sulfate by means of waste liquid of copper-contained circuit boards |
| CN102925704B (en) * | 2012-11-22 | 2014-10-08 | 上海绿澄环保科技有限公司 | Method and equipment for producing copper oxide and ammonia water by using alkaline copper etching liquid waste |
| CN103161046B (en) * | 2012-12-28 | 2015-04-08 | 东华大学 | Natural fiber crystal variation modified liquid medium filling and recovery system and method based on paralleled multiple buses and multiple modified kettles |
| CN103303963A (en) * | 2013-06-14 | 2013-09-18 | 同济大学 | Preparation method of copper oxide material with high sensitivity response property to hydrogen sulfide |
| CN103397341B (en) * | 2013-07-29 | 2015-10-28 | 陈飙 | A kind of method reclaiming copper from alkaline spent etching solution |
| CN106587317A (en) * | 2016-12-30 | 2017-04-26 | 江门市崖门新财富环保工业有限公司 | Concentrated acid fractional distillation treatment process for copper ammonia concentrated liquid of circuit board |
| CN109534384B (en) * | 2019-01-24 | 2020-12-25 | 苏州华锋环保技术有限公司 | High-purity copper sulfate production line |
| CN109761430B (en) * | 2019-03-11 | 2021-12-03 | 福建志坤能源科技开发有限公司 | Treatment method of alkaline etching waste liquid |
| CN111892066A (en) * | 2020-07-21 | 2020-11-06 | 湖北荣梦环保科技有限公司 | Environment-friendly treatment method and device for waste alkaline etching solution |
| CN114772628B (en) * | 2022-04-22 | 2024-02-06 | 盛隆资源再生（无锡）有限公司 | Recovery method of waste etching liquid |
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