CN108341424A - The production method of copper sulphate - Google Patents
The production method of copper sulphate Download PDFInfo
- Publication number
- CN108341424A CN108341424A CN201810273907.3A CN201810273907A CN108341424A CN 108341424 A CN108341424 A CN 108341424A CN 201810273907 A CN201810273907 A CN 201810273907A CN 108341424 A CN108341424 A CN 108341424A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- etching waste
- copper
- impurities
- removal
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention discloses a kind of production method of copper sulphate, includes the following steps：Oxidant is added into acidic etching waste liquid to aoxidize cuprous ion and ferrous ion therein, then pH value is adjusted to 1.7~1.9 and to be stirred to react, activated carbon is added, takes supernatant to be filtered processing after sedimentation is layered, the acidic etching waste liquid after being cleaned；Soluble magnesium salt is added into alkaline etching waste liquid for producing and is stirred to react, takes supernatant to be filtered processing after sedimentation is layered, the alkaline etching waste liquid for producing after must cleaning；By the acidic etching waste liquid and alkaline etching waste liquid for producing hybrid reaction after removal of impurities, basic copper chloride is obtained；By the reincarnation of basic copper chloride ammonia at Kocide SD, then filtering, wash water purification, mashing；It is 0.5~1.0 to add sulfuric acid and be acidified to pH, then carries out heat filtering, crystallisation by cooling, separation of solid and liquid, drying and processing, obtains copper sulphate.The copper sulphate of this method production gained can reach plating grade standard, and in etching waste liquor copper the rate of recovery it is high.
Description
Technical field
The present invention relates to a kind of production methods of copper sulphate, belong to copper sulphate technical field of producing.
Background technology
Etching waste liquor is to dissolve copper during institute by chemical corrosion method in printed wiring board (PCB) etching work procedure
It generates, two kinds of acidic etching waste liquid and alkaline etching waste liquid for producing, copper in acidic etching waste liquid can be further divided by its acid-base property
Content be about 30g/L~160g/L, the content of copper is about 40g/L~170g/L in alkaline etching waste liquid for producing.
As electronics industry is grown rapidly, China all generates etching waste liquor of the number in terms of ten thousand tons, these etching waste liquors every year
Such as without deal carefully with using serious environmental pollution and great economic waste can be caused.Domestic common processing method
It is：Copper in extraction acid, alkaline etching waste liquid, the products such as production basic copper chloride, copper sulphate and copper oxide.
Currently, the cupric sulfate purified as electroplating additive is given birth to by raw material of wiring board copper-containing etching waste solution
Production, however copper sulphate crude product quality made from the production technology of traditional copper sulphate is not up to standard, contains more impurity and metal
Ion does not meet the plating grade standard of copper sulphate.
Invention content
Based on this, it is necessary to provide a kind of method of copper sulphate production, plating grade mark can be reached by producing the copper sulphate of gained
It is accurate.
A kind of production method of copper sulphate, includes the following steps：
Oxidant is added into acidic etching waste liquid with aoxidize the cuprous ion in the acidic etching waste liquid and it is ferrous from
Then son adjusts pH value and to 1.7~1.9 and is stirred to react, add activated carbon, takes supernatant to be filtered after sedimentation is layered
Processing, the acidic etching waste liquid after being cleaned；
Soluble magnesium salt is added into alkaline etching waste liquid for producing and is stirred to react, takes supernatant to be filtered after sedimentation is layered
Processing, the alkaline etching waste liquid for producing after must cleaning；
By the acidic etching waste liquid after the removal of impurities and the alkaline etching waste liquid for producing hybrid reaction after the removal of impurities, alkali formula is obtained
Copper chloride；
The basic copper chloride is reacted to generation precipitation with ammonium hydroxide, filters to obtain filter residue, through wash water purification plus water mashing, is obtained
Kocide SD slurry；
Sulfuric acid is added into the Kocide SD slurry and adjusts the pH value of the Kocide SD slurry to 0.5~1.0, then
Heat filtering processing is carried out, the mixed liquor of sulfur acid copper is obtained；The mixed liquor of the sulfur acid copper is subjected to crystallisation by cooling, solid-liquid point
Copper sulfate crystal, drying are obtained from after.
It is ammonium hydroxide to adjust pH value to the reagent used in 1.7~1.9 in one of the embodiments,.PH value is adjusted with ammonium hydroxide
To 1.7~1.9, copper sludge (Cu (OH) on the one hand can be generated2·CuCl2), it is easy to adsorb the precipitations such as ferric arsenate generation co-sedimentation,
It on the other hand can be to avoid bringing other impurities into.
The dosage of the activated carbon and the mass volume ratio of the acidic etching waste liquid are in one of the embodiments,
(0.2~0.3) g:1L.The dosage of activated carbon is mainly determined according to the amount of the volume of acidic etching waste liquid and wherein organic impurities
Fixed, the standard that 0.2~0.3g activated carbons are added according to 1L acidic etching waste liquids carries out, you can effectively removes in acidic etching waste liquid
Organic impurities.
The Baume degrees of the acidic etching waste liquid after the removal of impurities is 24Be °~30Be ° in one of the embodiments, pH
Value is 1.0~1.5.
The Baume degrees of the alkaline etching waste liquid for producing after the removal of impurities is 12Be °~20Be ° in one of the embodiments, pH
Value is 8.0~9.0.
In the step of basic copper chloride to be reacted to generation precipitation with ammonium hydroxide in one of the embodiments, ammonia used
The envelope-bulk to weight ratio of a concentration of 20wt% of water, the dosage of the ammonium hydroxide and the basic copper chloride is (1.2~1.3) L:1Kg.
The ammonium hydroxide for being 20% with mass concentration, which react with basic copper chloride, carries out ammonia turn, according to every 1Kg basic copper chlorides and match 1.2L~
1.3L ammonium hydroxide is reacted, you can is fully converted to Kocide SD.
The concentration of the sulfuric acid is more than or equal to 98wt% in one of the embodiments,.Kocide SD is starched with the concentrated sulfuric acid
Material carries out generating amount of heat during acidification reaction, and with the progress of acidification, the temperature of reaction system is higher and higher, sulfuric acid
The solubility of copper wherein is increasing, in this way, to acidification completely be reaction system pH value be 0.5~1.0 when, reaction system
Temperature reach 100 DEG C or so, heat can be provided for the crystallization reaction of subsequent sulphuric acid copper.
The acidic etching waste liquid after the removal of impurities and the alkali etching after the removal of impurities are given up in one of the embodiments,
Liquid hybrid reaction, the step of obtaining basic copper chloride, specifically comprise the following steps：
The acidic etching waste liquid after the removal of impurities and the alkaline etching waste liquid for producing after the removal of impurities are first preheated to 43 DEG C respectively
~55 DEG C, mixed under the conditions of existing for basic copper chloride crystal seed, and in 68 DEG C~72 DEG C, speed of agitator be 65r/min~
The condition of 85r/min reacts, and obtains basic copper chloride.In this way, by strictly controlling reaction condition, make basic copper chloride knot
It is brilliant very fast, production efficiency is improved, while the basic copper chloride crystal grain of gained is uniform, good fluidity is easy to press filtration, and wherein
The impurity adulterated is few.
The acidic etching waste liquid after removal of impurities and the alkaline etching waste liquid for producing after removal of impurities occur anti-in one of the embodiments,
During answering, the alkaline etching waste liquid for producing after being continuously added into acidic etching waste liquid and removal of impurities after removal of impurities and preheating and preheating makes acid
Property pH value when reacting of etching waste liquor and alkaline etching waste liquid for producing be 4.30~5.00.In this way, by controlling reaction system
PH value can improve the rate of recovery of copper in etching waste liquor between 4.30~5.00, while the impurity in basic copper chloride being made to contain
It measures low.
The acidic etching waste liquid being continuously added into after preheating and the alkali etching after preheating in one of the embodiments,
The flow control of waste liquid is at 2 cubic meters/hour~6 cubic meters/hour.In this way, useless by controlling acidic etching waste liquid and alkali etching
Liquid enters the flow in reactor within the scope of 2 cubic meters/hour~6 cubic meters/hour, and the pH that can preferably adjust reaction system is
4.30~5.00, and other pH adjusting agents need not be added, program is simplified, is also avoided due to the use of other pH adjusting agents and band
Enter other ionic impurities.And cuprammonium chlorine network in the copper ion, chlorion and alkaline etching waste liquid for producing of acidic etching waste liquid can be made
Close object, ammonium hydroxide reacts to obtain the preferable basic copper chloride crystal of crystal form.
The above method of the present invention removes erosion by carrying out removal of impurities processing respectively to acidic etching waste liquid and alkaline etching waste liquid for producing
Carve the water insoluble matters such as metal ions and arsenic and organic impurities such as iron, the aluminium in waste liquid, and stringent control in process of production
Each reaction condition, and by intermediate products carry out the processing such as wash water purification remove respectively chlorion, ammonia salt and sulfate radical from
Son etc. makes the copper sulphate that production obtains reach plating grade standard.
Further, in acidic etching waste liquid and alkaline etching waste liquid for producing neutralization reaction step, by being lost respectively to acidity
It carves waste liquid and alkaline etching waste liquid for producing is preheating to 43 DEG C~55 DEG C, to reduce the temperature spread between raw material and crystallization reaction, avoid
It reacts unstable, and basic copper chloride crystal seed is added, crystallization is promoted to be formed, control suitable reaction temperature, pH and mixing speed,
Not only basic copper chloride crystallization is fast, and the purity of the basic copper chloride produced is high, particle flow is good, is easy to filter, and right
The rate of recovery of copper is also high in etching waste liquor.
The basic copper chloride of high-purity is reacted to the Kocide SD generated conducive to filtering, wash water purification, mashing with ammonium hydroxide again
Precipitation removes chlorion and ammonium salt through wash water purification, obtains the Kocide SD slurry of high-purity, thus the follow-up acidification of guarantee,
The purity that crystallization generates copper sulphate can reach the requirement that grade is electroplated.
Description of the drawings
Fig. 1 is the production technological process of an embodiment of the present invention copper sulphate.
Specific implementation mode
To facilitate the understanding of the present invention, below with reference to relevant drawings to invention is more fully described.In attached drawing
Give presently preferred embodiments of the present invention.But the present invention can realize in many different forms, however it is not limited to this paper institutes
The embodiment of description.Keep the understanding to the disclosure more thorough on the contrary, purpose of providing these embodiments is
Comprehensively.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention
The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the Listed Items of pass.
As shown in Figure 1, the production method of the copper sulphate of an embodiment of the present invention, includes the following steps：
S1, oxidant is added into acidic etching waste liquid to aoxidize the cuprous ion and ferrous iron in the acidic etching waste liquid
Then ion adjusts pH value and to 1.7~1.9 and is stirred to react, add activated carbon, takes supernatant to carry out after sedimentation is layered
Filter is handled, the acidic etching waste liquid after being cleaned.
Specifically, it is oxidation terminal, acidity erosion in green, penetrating shape that oxidant is added into acidic etching waste liquid to solution
Carve waste liquid in cuprous ion be oxidized to bivalent cupric ion, ferrous ions at ferric ion, meanwhile, arsenous anion oxidation
At arsenate.Arsenate reacts with iron ion, the aluminium ion etc. in acidic etching waste liquid and generates stable ferric arsenate, arsenic acid
Aluminum precipitation.If the color of acidic etching waste liquid be black non transparent, need to continuously add oxidant, until solution in green,
Penetrating shape.It is appreciated that can also be determined whether to reach oxidation terminal with the wherein cuprous and ferrous method of such as sample detecting.
Further, by adjusting acidic etching waste liquid pH value, and pH value will be strict controlled between 1.7~1.9, and be stirred
Mix reaction 0.5~3 hour.A small amount of bivalent cupric ion in acidic etching waste liquid is converted into copper sludge, and adsorbs ferric arsenate and arsenic acid
Aluminium is co-precipitated.Then the organic impurities in proper amount of active carbon absorption acidic etching waste liquid are added, by standing 10 hours
Left and right, sedimentation layering are filtered to remove the water-insolubles such as ferric arsenate, al arsenate, copper sludge and organic impurities, obtain meeting plating
The acidic etching waste liquid of grade bluestone production requirement.It is appreciated that being to meet etching quality and performance in PCB etching work procedures
It is required that, it will usually organic compound is added in etching solution to further increase etching quality and rate, gives up so as to cause etching
Contain organic compound in liquid, and these organic additives are often difficult to detach, and therefore, to ensure the purity of copper sulphate, pass through
Suitable activated carbon with strong adsorption capacity is added and carries out adsorption-edulcoration, to remove the organic impurities in etching waste liquor.
Oxidant is selected from least one of sodium chlorate, hydrogen peroxide and potassium chlorate in one of the embodiments,.
Oxidant is sodium chlorate in one of the embodiments,.Further, with the chlorine of a concentration of 0.2g/L~0.3g/L
Acid sodium solution makees oxidant.In this way, cuprous in acidic etching waste liquid is converted into cupric：6Cu++ClO3-+6H+→6Cu2++
3H2O+Cl-；Ferrous iron is converted into ferric iron：6Fe2++ClO3-+6H+→6Fe3++3H2O+Cl-；Arsenous anion is converted into arsenate：
AsO3 3-+ClO3-+4H+→AsO4 3-+Cl-+2H2O。
PH is adjusted to 1.7~1.9 with ammonium hydroxide in one of the embodiments, and is stirred to react 2 hours or so, so that sour
Co-sedimentation occurs together with copper sludge for the precipitated ferric arsenate in property etching waste liquor.
Iron ion in acidic etching waste liquid is reacted with arsenate generates ferric arsenate：Fe3++AsO4 3-→FeAsO4↓, it is acid
Aluminium ion in etching waste liquor is reacted with arsenate generates al arsenate：Al3++AsO4 3-→AlAsO4↓.By will be acid with ammonium hydroxide
The pH of etching waste liquor is adjusted to 1.7~1.9, and a small amount of chlorion in acidic etching waste liquid, copper ion and ammonium hydroxide reaction is made to generate
Copper sludge：2CuCl2+2NH3·H2O→Cu(OH)2·CuCl2↓+2NH4Cl, copper sludge adsorbs ferric arsenate, al arsenate, and occurs together
Co-precipitation, to remove the impurity such as arsenic, iron, aluminium.Meanwhile with ammonium hydroxide tune pH, new impurity will not be introduced, basic copper chloride is subsequently generated
The basic copper chloride mother liquor generated in step is convenient for circulating and recovering, and can further reduce treatment pressure of sewage.
During the test, inventor has found, when adding ammonium hydroxide that acidic etching waste liquid pH value is adjusted to 2.5 or more, altogether
The production quantity of precipitation obviously increases, and illustrates that a large amount of copper ions are reacted with ammonium hydroxide and generates copper sludge, this will lead to copper in etching waste liquor
The rate of recovery substantially reduce.
The dosage of activated carbon and the w/v for the acidic etching waste liquid that will be handled are in one of the embodiments,
(0.2~0.3) g:1L.It is appreciated that 0.2g~0.3g activated carbons are added according to every 1 liter of acidic etching waste liquid, can effectively adsorb
Organic impurities in etching waste liquor achievees the effect that remove organic impurities.
The Baume degrees of acidic etching waste liquid after cleaning in one of the embodiments, is 24Be °~30Be °, and pH value is
1.0~1.5.
The mesh number for being filtered the filter screen of processing to supernatant in one of the embodiments, is 2500 mesh.In this way, energy
The sediment and remaining fine impurities in solution are more effectively removed, the effect of filtration, purification is improved.
Sedimentation mud ammonia solvent of the acidic etching waste liquid after sedimentation is layered generates cuprammonium in one of the embodiments,
Liquid can be used for reproduction, achieve the effect that recycle.Specifically, when sedimentation mud and ammonium hydroxide mix, first plus after ammonium hydroxide plus settle
Mud, intersection feed intake, and the pH of the cuprammonia after the reaction was complete is 8.8 or so, you can.
S2, soluble magnesium salt is added into alkaline etching waste liquid for producing and is stirred to react, take supernatant to carry out after sedimentation is layered
Filtration treatment, the alkaline etching waste liquid for producing after must cleaning.It is appreciated that soluble magnesium salt is selected from magnesium chloride, magnesium sulfate and magnesium nitrate
At least one of Deng.
Preferably, magnesium chloride is selected.Specifically, Magnesium dichloride hexahydrate solution is added into alkaline etching waste liquid for producing, stirring is anti-
It answers 0.5~2 hour, in this way, magnesium ion reacts generation precipitation with arsenic acid radical ion or arsenite ion：3Mg2++2AsO4 3-=
Mg3(AsO4)2↓、3Mg2++2AsO3 3-=Mg3(AsO3)2↓.Then it is layered by standing sedimentation, supernatant is taken to be filtered processing,
Be removed the alkaline etching waste liquid for producing of the impurity such as arsenic, water-insoluble.
Further, the addition weight of Magnesium dichloride hexahydrate and the volume ratio of alkaline etching waste liquid for producing are 2g/L~2.5g/
L.Specifically, first 400Kg Magnesium dichloride hexahydrates are added in 4m3 water, stir, it is molten to be configured to Magnesium dichloride hexahydrate
Then liquid takes 0.5m3~0.6m3 six to be hydrated chlorine magnesium solution and is added in 25m3 alkaline etching waste liquid for producing, it is small to be stirred to react 0.5~2
When.
The Baume degrees of alkaline etching waste liquid for producing after cleaning in one of the embodiments, is 12Be °~20Be °, and pH value is
8.0~9.0.
It should be understood that step S1 and S2 do not have specific sequencing, the two that can be carried out at the same time.If acid etching
Contain the solid impurities such as sandstone in waste liquid or alkaline etching waste liquid for producing, it is also necessary to filtering and impurity removing processing is first carried out to etching waste liquor, with
It filters out the solid particle polluters such as the sandstone in etching waste liquor, improves subsequent purification effect and efficiency, it is on the contrary then the mistake can be saved
Filter step.
S3, by the acidic etching waste liquid after removal of impurities and the alkaline etching waste liquid for producing hybrid reaction after removal of impurities, obtain alkali formula chlorination
Copper.
Specifically, by the acidic etching waste liquid after step S1 removal of impurities and the alkaline etching waste liquid for producing point after step S2 removal of impurities
It is not preheated to 43 DEG C~55 DEG C, is mixed under the conditions of existing for basic copper chloride crystal seed, and in 68 DEG C~72 DEG C, speed of agitator
It reacts for the condition of 65r/min~85r/min, then carries out press filtration, collect solid, obtain basic copper chloride.
Further, the additive amount of basic copper chloride crystal seed is 70Kg/15m3~100Kg/15m3.It is appreciated that being added
The ratio of the weight of basic copper chloride crystal seed and the sum of the volume of acidic etching waste liquid and alkaline etching waste liquid for producing is 70Kg/15m3~
100Kg/15m3。
By before reactions by acidic etching waste liquid and alkaline etching waste liquid for producing be preheated to respectively 43 DEG C of suitable temperature~
It 55 DEG C, to reduce the temperature spread between raw material and crystallization reaction, avoids reacting unstable, and crystal seed is added and promotes crystalline
At controlling suitable reaction temperature and mixing speed, improve the recycling of copper in the formation efficiency and etching waste liquor of basic copper chloride
Rate.It finds in process of production, when mixing speed is adjusted to 90r/min, the grain size of the basic copper chloride of generation is less than 30 μm, sticks
It is attached to together, it is difficult to washing and filtering, and filter cake moisture content is high, is unfavorable for industrialized production.
Basic copper chloride crystal seed is to be scattered in basic copper chloride saturated aqueous solution or contain alkali in one of the embodiments,
Form in the dispersion liquid of the mixed liquor filtering gained filtrate of formula copper chloride is added.
Specifically, water or basic copper chloride mother liquor are added into reactor, after being stirred and heated to 68 DEG C~72 DEG C, it is added
Basic copper chloride crystal seed.Wherein, basic copper chloride mother liquor is the filter that the mixed liquor filtering containing basic copper chloride generates in step S3
Liquid.
The acidic etching waste liquid after removal of impurities and the alkaline etching waste liquid for producing after removal of impurities occur anti-in one of the embodiments,
During answering, the alkaline etching waste liquid for producing after being continuously added into acidic etching waste liquid and removal of impurities after removal of impurities and preheating and preheating makes acid
Property pH value when reacting of etching waste liquor and alkaline etching waste liquid for producing be 4.30~5.00.
Further, flow control when alkaline etching waste liquid for producing is added after the acidic etching waste liquid after removal of impurities and removal of impurities is 2
Cubic meter/hour~6 cubic meters/hour。It is useless by strictly controlling the acidic etching waste liquid after cleaning in reaction process and alkali etching
The flow of liquid keeps reaction more abundant between the pH convenient for adjusting reaction system maintains 4.30~5.00, improves production efficiency,
Promote the recycling of copper in etching waste liquor simultaneously, the purity in gained basic copper chloride is high.
S4, it step S3 is obtained to basic copper chloride and ammonium hydroxide carries out reacting generation precipitation, filter to obtain filter residue, it is net through wash water
Change plus water is beaten, obtains Kocide SD slurry.
Specifically, fully being reacted with the ammonium hydroxide of a concentration of 20wt% with the basic copper chloride that step S3 is prepared, generate
Kocide SD：Cu2(OH)3Cl+4NH3·H2O→Cu(OH)2↓+[Cu(NH3)4]2+Then+Cl- carries out press filtration, gained filter cake warp
After wash water purification, tap water is added and is beaten, Kocide SD slurry is obtained.
Further, according to the ratio of 20wt% ammonium hydroxide of the 1Kg basic copper chlorides with 1.2L~1.3L, by ammonium hydroxide and alkali formula
Copper chloride hybrid reaction.By controlling the proportioning of ammonium hydroxide and basic copper chloride, basic copper chloride is made adequately to be converted to hydroxide
Copper, the filter cake after press filtration are effectively removed remaining chlorion and ammonia salt in filter cake through wash water purification.
S5, sulfuric acid is added into the Kocide SD slurry that step S4 is obtained and adjusts the pH value of Kocide SD slurry to 0.5
~1.0, then heat filtering processing is carried out, obtain the mixed liquor of sulfur acid copper；By the mixed liquor progress crystallisation by cooling of sulfur acid copper, admittedly
Filter residue and filtrate are obtained after liquid separation, filter residue obtains copper sulphate after drying.
It is acidified specifically, the concentrated sulfuric acid that mass percent is 98% is added into Kocide SD slurry, generates sulfuric acid
Copper：Cu(OH)2+H2SO4=CuSO4+2H20.As the pH value of the addition mixed system of the concentrated sulfuric acid continuously decreases, when pH value is down to
It is acidified and completes when 0.5~1.0.Due to the concentrated sulfuric acid and Kocide SD, water hybrid reaction, a large amount of heat is generated, or even can allow solution
Local boiling, the temperature of reaction system reaches 100 DEG C or so when acidification is completed；Then reaction system is subjected to hot pressing filter, obtained
The mixed liquor of sulfur acid copper；The mixed liquor of sulfur acid copper is cooled to 45 DEG C hereinafter, cupric sulphate crystal precipitation, passes through separation of solid and liquid
Copper sulfate crystal and filtrate are obtained afterwards, and copper sulfate crystal obtains sulfuric acid copper products (CuSO after drying4·5H20), gained copper sulphate
The impurity content of production is low, reaches plating grade standard.
In one of the embodiments, the mixed liquor of sulfur acid copper after crystallisation by cooling, filtering gained filtrate cycle extremely
Kocide SD slurry is acidified instead of the part concentrated sulfuric acid in step S5.In this way, can be with the dosage of the effectively save concentrated sulfuric acid, section
About cost, meanwhile, mitigate the pressure and cost of liquid waste processing.
It is specific embodiment below
Embodiment 1
1, acidic etching waste liquid cleans：
5m3 tap water is added in sodium chlorate dispensing canister, 2 tons of solid sodium chlorate are then added, stirs evenly and is configured to chlorine
Acid sodium solution.
Start acidic etching waste liquid elevator pump, start press filtration, the filtrate overflow of generation is passed through to acidic etching waste liquid press filtration slot
Filtrate is promoted in acidic etching waste liquid purification pot and carries out purified treatment by press filtration slot elevator pump.
Blender is opened, sodium chlorate solution is added into acidic etching waste liquid purification pot by the Cu in acidic etching waste liquid+、
Fe2+It is oxidized to Cu2+、Fe3+, oxidation terminal is judged according to the color of acidic etching waste liquid, when acidic etching waste liquid is in green, logical
Saturating shape is to aoxidize terminal, does not have to continue chlorination acid sodium solution；Otherwise continue chlorination acid sodium solution until in the penetrating shape of green.It is past
Ammonium hydroxide is added in purification pot, adjusts the pH value of acidic etching waste liquid to 1.8, reacts 2 hours or so, then stop stirring.
In terms of the ratio of the weight of activated carbon and acidic etching waste liquid volume, by 5Kg/20m3~6Kg/20m3Toward acid etching
Activated carbon is added in effluent purifying tank, for adsorbing the organic impurities such as petroleum-type.It is then allowed to stand sedimentation 10 hours or so, precipitation
It is layered with supernatant, supernatant is filtered through accurate filter and is promoted to acidic etching waste liquid work tank, for use.
To cleaning, front and back acidic etching waste liquid is detected, and the result is shown in the following table 1, and the Baume degrees after removal of impurities is 29Be °.
Table 1 cleans the index of front and back acidic etching waste liquid
| Index | PH value | Cu2+(g/L) | Fe(ppm) | Al(ppm) | As(ppm) | Organic impurities |
| Before removal of impurities | -1 | 110 | 35 | 7 | 2 | On a small quantity |
| After removal of impurities | 1.5 | 100 | 20 | 5 | 0.3 | Nothing |
2, alkaline etching waste liquid for producing cleans
Toward 25m3A concentration of 0.1Kg/L Magnesium dichloride hexahydrates solution 0.6m is added in alkaline etching waste liquid for producing3, stir 45 minutes
Left and right stands to remove the arsenic in alkaline etching waste liquid for producing and carries out within 10 hours or so sedimentation layering, supernatant through accurate filter into
Row filtration treatment, filtrate are promoted to alkaline etching waste liquid for producing work tank, for use.
To cleaning, front and back alkaline etching waste liquid for producing is detected, and the result is shown in the following table 2, and the Baume degrees after removal of impurities is 27Be °.
Table 2 cleans the index of front and back alkaline etching waste liquid for producing
| Index | PH value | Cu(g/L) | As(ppm) | Organic impurities |
| Before removal of impurities | 8 | 100 | 9 | On a small quantity |
| After removal of impurities | 8.5 | 90 | 0.1 | Nothing |
3, neutralization reaction produces basic copper chloride
1) crystal seed prepares
Into crystallizing tank plus tap water direct is to designated position, i.e., the jet chimney in just dipped crystallizing tank.To crystallization
Retort starts crystallizing tank blender, mixing speed 75r/min during being pumped into tap water, and opens following certainly for crystallizing tank
Ring.
It opens steam and heats valve, temperature of charge in crystallizing tank is increased to 70 ± 2 DEG C, after temperature reaches, steam off
Heat valve.80Kg basic copper chloride crystal seeds are added into crystallizing tank.
2) raw material preheating
Start acidic etching waste liquid transfusion self-control device, toward acidic etching waste liquid preheating can charging, opens steam, be warming up to
45℃。
Start alkaline etching waste liquid for producing transfusion self-control device, toward alkaline etching waste liquid for producing preheating can charging, opens steam, be warming up to
45℃。
3), production is driven
When the temperature of charge in crystallizing tank reaches 70 ± 2 DEG C, the temperature of charge in preheating can reaches 45 DEG C, it is respectively started
Acidic etching waste liquid and alkaline etching waste liquid for producing feed pump are fed to crystallizing tank.
During producing driving, ensure that the temperature of reactive crystallization in crystallizing tank is stirred in 68 DEG C~72 DEG C, crystallization
Rotating speed 75r/min.Inlet amount is gradually tuned up from small, and 6000L/h is gradually increased to from 1100L/h, the pH value of material in crystallizing tank
It is 4.30~5.0 to be down to pH by 7, slowly adjusts pH, until basic copper chloride production is normal.
4) it, after basic copper chloride production is normal, and when liquid level is reached from tank deck 30cm~50cm in crystallizing tank, will tie
Basic copper chloride slurry in brilliant tank is pumped into filter press and carries out filter-press dehydration, and filtrate, that is, basic copper chloride mother liquor flows into settling tank,
And crystalline mother solution pond is entered by settling tank overflow；Filter cake is basic copper chloride.
4, basic copper chloride chlorine turns
The good basic copper chloride of press filtration goes to ammonia and turns tank, matches 1.2 side's 20wt% ammonium hydroxide according to 1 ton of basic copper chloride, is pumped into
Ammonium hydroxide is reacted, and 0.5 hour or so rear generation Kocide SD is reacted.
5, Kocide SD wash water is beaten
Ammonia is turned into the Kocide SD in tank and is pumped into the progress press filtration of Kocide SD filter press, after filter cake carries out wash water purification, by
Kocide SD is discharged in Kocide SD mashing tank, and tap water is added and is beaten, Kocide SD slurry is obtained.
6, sulfuric acid is acidified
The slurry that Kocide SD is beaten in tank is pumped into souring tank, after having pumped, is initially added into 98% concentrated sulfuric acid, the end of acidification
Point pH is 0.8, and temperature is 100 DEG C or so, and after the completion of acidification, the hot material being acidified carries out filter press filtering, and filtrate enters crystallization
Tank is opened crystallizing tank cooling water and is cooled down, and slurry is centrifuged, washed, centrifuged, dry, packed after being cooled to 45 DEG C or less,
Obtain sulfuric acid copper products.
7, it detects
The sulfuric acid copper products of production gained are detected, testing result see the table below 3.
The Testing index of 3 sulfuric acid copper products of table
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that, with the basic copper chloride mother liquor generated in embodiment 1
Instead of the tap water in embodiment 1.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 2, the difference is that the following aspects：
1), in acidic etching waste liquid removal step, ammonium hydroxide is added into purification pot by the adjusting of acidic etching waste liquid
PH value is different, and the pH of embodiment 2 is 1.8, and the pH value of embodiment 3 is 1.9.
2) raw material is different, specially：
Baume degrees before acidic etching waste liquid removal of impurities is 27Be °, and pH value is -0.5, and the Baume degrees after removal of impurities is 26Be °, pH
Value is 1.5；
Baume degrees before alkaline etching waste liquid for producing removal of impurities is 16Be °, pH value 10.5, and the Baume degrees after removal of impurities is 15Be °, pH
Value is 9.0.
3) preheating temperature is different, specially：The preheating temperature of embodiment 2 is 45 DEG C, and the preheating temperature of embodiment 3 is 48
℃。
Embodiment 4
Embodiment 4 is substantially the same manner as Example 2, the difference is that the following aspects：
1), in acidic etching waste liquid removal step, ammonium hydroxide is added into purification pot by the adjusting of acidic etching waste liquid
PH value is different, and the pH of embodiment 2 is 1.8, and the pH value of embodiment 4 is 1.7.
2) raw material is different, specially：
Baume degrees before acidic etching waste liquid removal of impurities is 25Be °, and pH value is -0.8, and the Baume degrees after removal of impurities is 24Be °, pH
Value is 1.2；
Baume degrees before alkaline etching waste liquid for producing removal of impurities is 13Be °, pH value 9, and the Baume degrees after removal of impurities is 12Be °, pH value
It is 8.5.
3) preheating temperature is different, specially：The preheating temperature of embodiment 2 is 45 DEG C, and the preheating temperature of embodiment 4 is 55
℃。
Detection is sampled to the sulfuric acid copper products of 2~4 gained of embodiment, statistical analysis according to testing result is shown, real
The copper sulphate product quality for applying 2~4 gained of example meets the standard of the following table 4, reaches the requirement of cupric sulfate purified.
4 copper sulphate product testing index of table
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that, ammonium hydroxide is being added into purification pot by acid etching
The pH value of the adjusting of waste liquid and the pH value for adjusting the Kocide SD slurry are different, and embodiment 1 adjusts the pH of acidic etching waste liquid
For value to 1.8, comparative example 1 adjusts the pH value of acidic etching waste liquid to 1.2.Embodiment 1 adjusts the pH to 0.8 of Kocide SD slurry,
Comparative example 1 adjusts the pH value of Kocide SD slurry to 1.5.
Production gained sulfuric acid copper products are detected, as a result see the table below 5.
5 comparative example of table, 1 copper sulphate product testing index
As upper table 5 as can be seen that sulfuric acid copper products obtained by the production of comparative example 1 do not meet plating grade standard.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 2, the difference is that the following aspects：
1) different from the reagent that basic copper chloride reaction is added in step 4, the addition of embodiment 2 is 20wt% ammonium hydroxide, right
The sodium hydroxide solution that it is 20wt% that ratio 2, which is added, correspondingly, the precipitation of reaction rear generation in 0.5 hour or so is also different, it is real
It is the cotton-shaped Kocide SD precipitation of blue to apply example 2, and comparative example 2 is that the copper oxide of brownish black sheet precipitates.
2) operation of step 5 copper oxide wash water mashing is same as Example 2, the difference is that, the operation pair of embodiment 2
As being copper oxide for the operation object of Kocide SD, comparative example 2, what is obtained is oxidation copper slurry.
3) operation that sulfuric acid is acidified in step 6 is same as Example 2, the difference is that, the sulfuric acid acidification pair of embodiment 2
As being copper oxide for the acidification object of Kocide SD, comparative example 2.
Production gained sulfuric acid copper products are detected, as a result see the table below 6.
6 comparative example of table, 2 copper sulphate product testing index
It finds in operation, since the copper oxide in comparative example 2 is precipitated as sheet, is separated by filtration relatively more tired with wash water purification
It is difficult.
Containing for grade standard, especially chloride is electroplated as can be seen that not met in the production of 2 copper sulphate of comparative example from upper table 6
Amount substantially exceeds plating grade standard.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of production method of copper sulphate, which is characterized in that include the following steps：
Oxidant is added into acidic etching waste liquid to aoxidize the cuprous ion and ferrous ion in the acidic etching waste liquid, so
PH value is adjusted afterwards to 1.7~1.9 and to be stirred to react, adds activated carbon, takes supernatant to be filtered processing after sedimentation is layered,
Acidic etching waste liquid after being cleaned；
Soluble magnesium salt is added into alkaline etching waste liquid for producing to be reacted, takes supernatant to be filtered processing after sedimentation is layered,
Alkaline etching waste liquid for producing after must cleaning；
By the acidic etching waste liquid after the removal of impurities and the alkaline etching waste liquid for producing hybrid reaction after the removal of impurities, alkali formula chlorination is obtained
Copper；
The basic copper chloride is reacted to generation precipitation with ammonium hydroxide, filters to obtain filter residue, through wash water purification plus water mashing, obtains hydrogen-oxygen
Change copper slurry；
It is 0.5~1.0 that sulfuric acid is added into the Kocide SD slurry and adjusts the pH value of the Kocide SD slurry, then is carried out
Heat filtering processing, obtains the mixed liquor of sulfur acid copper；After the mixed liquor of the sulfur acid copper is carried out crystallisation by cooling, separation of solid and liquid
Obtain copper sulfate crystal, drying.
2. the production method of copper sulphate according to claim 1, which is characterized in that used in adjusting pH value to 1.7~1.9
Reagent is ammonium hydroxide.
3. the production method of copper sulphate according to claim 1, which is characterized in that the activated carbon and the acid etching
The mass volume ratio of waste liquid is (0.2~0.3) g:1L.
4. the production method of copper sulphate according to claim 1, which is characterized in that the acidic etching waste liquid after the removal of impurities
Baume degrees be 24Be °~30Be °, pH value be 1.0~1.5.
5. the production method of copper sulphate according to claim 1, which is characterized in that the alkaline etching waste liquid for producing after the removal of impurities
Baume degrees be 12Be °~20Be °, pH value be 8.0~9.0.
6. according to the production method of Claims 1 to 5 any one of them copper sulphate, which is characterized in that by the alkali formula chlorination
Copper was reacted with ammonium hydroxide in the step of generation precipitation, a concentration of 20wt% of ammonium hydroxide used, the ammonium hydroxide and the basic copper chloride
Envelope-bulk to weight ratio be (1.2~1.3) L:1Kg.
7. according to the production method of Claims 1 to 5 any one of them copper sulphate, which is characterized in that the concentration of the sulfuric acid
To be more than or equal to 98wt%.
8. according to the production method of Claims 1 to 5 any one of them copper sulphate, which is characterized in that after the removal of impurities
Alkaline etching waste liquid for producing hybrid reaction after acidic etching waste liquid and the removal of impurities, the step of obtaining basic copper chloride specifically include as
Lower step：
The acidic etching waste liquid after the removal of impurities and the alkaline etching waste liquid for producing after the removal of impurities are first preheated to 43 DEG C~55 respectively
DEG C, mixed under the conditions of existing for basic copper chloride crystal seed, and in 68 DEG C~72 DEG C, speed of agitator be 65r/min~85r/
The condition of min reacts, and obtains the basic copper chloride.
9. the production method of copper sulphate according to claim 8, which is characterized in that acidic etching waste liquid after removal of impurities and
During alkaline etching waste liquid for producing after removal of impurities reacts, acidic etching waste liquid and removal of impurities after being continuously added into removal of impurities and preheating are simultaneously
Alkaline etching waste liquid for producing after preheating, pH value when acidic etching waste liquid and alkaline etching waste liquid for producing being made to react is 4.30~
5.00。
10. the production method of copper sulphate according to claim 9, which is characterized in that the acid being continuously added into after preheating
Property etching waste liquor and preheating after alkaline etching waste liquid for producing flow control at 2 cubic meters/hour~6 cubic meters/hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810273907.3A CN108341424B (en) | 2018-03-29 | 2018-03-29 | Method for producing copper sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810273907.3A CN108341424B (en) | 2018-03-29 | 2018-03-29 | Method for producing copper sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108341424A true CN108341424A (en) | 2018-07-31 |
| CN108341424B CN108341424B (en) | 2020-02-18 |
Family
ID=62957251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810273907.3A Active CN108341424B (en) | 2018-03-29 | 2018-03-29 | Method for producing copper sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108341424B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534384A (en) * | 2019-01-24 | 2019-03-29 | 苏州华锋环保技术有限公司 | High purity copper sulfate production line |
| CN110158089A (en) * | 2019-05-29 | 2019-08-23 | 惠州大亚湾亿田环保技术有限公司 | The alkalinity erosion copper waste liquor recovery process method of zero-emission |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN111908498A (en) * | 2019-12-27 | 2020-11-10 | 深圳市宝安东江环保技术有限公司 | Method for producing copper oxide by using printed circuit board etching waste liquid and electric suction filtration device |
| CN111943423A (en) * | 2020-07-10 | 2020-11-17 | 山东东顺环保科技有限公司 | Method and system for treating acidic copper-containing etching liquid |
| CN112813489A (en) * | 2020-12-30 | 2021-05-18 | 广东臻鼎环境科技有限公司 | Preparation method of reagent-grade copper chloride dihydrate crystal |
| CN112850778A (en) * | 2020-11-19 | 2021-05-28 | 吴江市威士达铜业科技有限公司 | Preparation method of basic copper chloride |
| CN114031105A (en) * | 2021-11-30 | 2022-02-11 | 中南大学 | Treatment method of copper-containing etching waste liquid |
| CN114195315A (en) * | 2021-12-30 | 2022-03-18 | 江苏维达环保科技有限公司 | Method for combined treatment of acidic and non-acidic copper-containing etching waste liquid, tin stripping waste liquid and copper nitrate waste liquid |
| CN114314637A (en) * | 2021-12-31 | 2022-04-12 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| CN114684847A (en) * | 2020-12-25 | 2022-07-01 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
| US20230166979A1 (en) * | 2021-11-30 | 2023-06-01 | Central South University | Method for treating copper-containing waste etching solution |
| WO2023123362A1 (en) * | 2021-12-31 | 2023-07-06 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| CN117247124A (en) * | 2023-11-10 | 2023-12-19 | 中山火炬环保新材料有限公司 | Intelligent treatment method and treatment system for copper-containing etching waste liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391800A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN105129838A (en) * | 2015-07-02 | 2015-12-09 | 清远市新绿环境技术有限公司 | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant |
| CN106348334A (en) * | 2016-11-18 | 2017-01-25 | 东莞市新意工业废物处理有限公司 | Feed-level copper sulfate and production technology thereof |
| CN106495205A (en) * | 2016-11-18 | 2017-03-15 | 东莞市新意工业废物处理有限公司 | A kind of cupric sulfate purified and its production technology |
| CN106976902A (en) * | 2016-11-30 | 2017-07-25 | 佛山市兴华源机械设备有限公司 | A kind of method for preparing basic copper carbonate using industrial copper-containing etching waste solution |
-
2018
- 2018-03-29 CN CN201810273907.3A patent/CN108341424B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391800A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN105129838A (en) * | 2015-07-02 | 2015-12-09 | 清远市新绿环境技术有限公司 | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant |
| CN106348334A (en) * | 2016-11-18 | 2017-01-25 | 东莞市新意工业废物处理有限公司 | Feed-level copper sulfate and production technology thereof |
| CN106495205A (en) * | 2016-11-18 | 2017-03-15 | 东莞市新意工业废物处理有限公司 | A kind of cupric sulfate purified and its production technology |
| CN106976902A (en) * | 2016-11-30 | 2017-07-25 | 佛山市兴华源机械设备有限公司 | A kind of method for preparing basic copper carbonate using industrial copper-containing etching waste solution |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534384A (en) * | 2019-01-24 | 2019-03-29 | 苏州华锋环保技术有限公司 | High purity copper sulfate production line |
| CN110158089A (en) * | 2019-05-29 | 2019-08-23 | 惠州大亚湾亿田环保技术有限公司 | The alkalinity erosion copper waste liquor recovery process method of zero-emission |
| CN111908498A (en) * | 2019-12-27 | 2020-11-10 | 深圳市宝安东江环保技术有限公司 | Method for producing copper oxide by using printed circuit board etching waste liquid and electric suction filtration device |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN111943423A (en) * | 2020-07-10 | 2020-11-17 | 山东东顺环保科技有限公司 | Method and system for treating acidic copper-containing etching liquid |
| CN112850778A (en) * | 2020-11-19 | 2021-05-28 | 吴江市威士达铜业科技有限公司 | Preparation method of basic copper chloride |
| CN114684847A (en) * | 2020-12-25 | 2022-07-01 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN114684847B (en) * | 2020-12-25 | 2023-11-10 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN112813489A (en) * | 2020-12-30 | 2021-05-18 | 广东臻鼎环境科技有限公司 | Preparation method of reagent-grade copper chloride dihydrate crystal |
| CN114031105B (en) * | 2021-11-30 | 2022-11-29 | 中南大学 | Treatment method of copper-containing etching waste liquid |
| US20230166979A1 (en) * | 2021-11-30 | 2023-06-01 | Central South University | Method for treating copper-containing waste etching solution |
| CN114031105A (en) * | 2021-11-30 | 2022-02-11 | 中南大学 | Treatment method of copper-containing etching waste liquid |
| US11939229B2 (en) * | 2021-11-30 | 2024-03-26 | Central South University | Method for treating copper-containing waste etching solution |
| CN114195315A (en) * | 2021-12-30 | 2022-03-18 | 江苏维达环保科技有限公司 | Method for combined treatment of acidic and non-acidic copper-containing etching waste liquid, tin stripping waste liquid and copper nitrate waste liquid |
| CN114314637A (en) * | 2021-12-31 | 2022-04-12 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| WO2023123362A1 (en) * | 2021-12-31 | 2023-07-06 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
| CN117247124A (en) * | 2023-11-10 | 2023-12-19 | 中山火炬环保新材料有限公司 | Intelligent treatment method and treatment system for copper-containing etching waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108341424B (en) | 2020-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108341424A (en) | The production method of copper sulphate | |
| US9963762B2 (en) | Scandium recovery method | |
| CN102070198B (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN103922416B (en) | A kind of method of Separation and Recovery iron from red mud | |
| CN104152687B (en) | Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale | |
| CN100572286C (en) | Utilize arsenic-containing waste water to prepare the method for white arsenic | |
| CN108423704B (en) | Method for producing basic copper chloride | |
| CN104229906B (en) | The method and apparatus of the nickel-containing waste water preparation plating level single nickel salt utilizing surface treatment process to produce | |
| CN109626420A (en) | A method of titanium dioxide and iron oxide are prepared using fluoride purification ferrotianium material | |
| CN105296753A (en) | Method for separating cobalt, nickel and magnesium from nickel oxide ore pickle liquor | |
| CN108950219A (en) | A kind of the step extraction and method of comprehensive utilization of titanium white waste acid valuable metal | |
| CN102557212A (en) | Method for treating and recycling molybdenum calcine water-washing waste water | |
| CN107429320A (en) | Scandium recovery method | |
| CN113088702B (en) | Method for recovering valuable elements from acid leaching solution of roasting slag of gold-containing sulfur concentrate | |
| CN101134566B (en) | Process for preparing amino-sulfonic acid nickel by nickel sulfide concentrate | |
| CN108862370A (en) | A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude | |
| CN113430370A (en) | Method for selectively extracting cobalt and nickel from nickel sulfide concentrate | |
| CN106148702A (en) | A kind of method separating copper arsenic from black copper mud | |
| US3687828A (en) | Recovery of metal values | |
| CN115679128B (en) | Method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag | |
| CN110453096A (en) | A kind of method that the Whote-wet method smelting molybdenum concentrate of environment-friendly type prepares high-purity ammonium heptamolybdate | |
| WO2011120093A1 (en) | Recovering metals from pickle liquor | |
| CN108622927A (en) | A method of producing nano zine oxide using containing zinc ore crude | |
| CN108754140A (en) | A method of it is produced containing zinc complexes using containing zinc ore crude | |
| US2902345A (en) | Separate recovery of nickel and cobalt from mixed compounds containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |