CN107502757A - A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge - Google Patents
A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
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Abstract
The present invention relates to scrap metal processing technology field, a kind of more particularly to method of the reclaiming nickel sulfate from nickel bath slag and sludge, using nickel bath slag and sludge as raw material, dissolving leaching, press filtration separation, complexing are carried out except Fe and As, abstraction impurity removal, ultrasonic oil removing and is concentrated and dried process, composite activated carbon is added in ultrasonic oil removing process and carries out ultrasonic oil removing, composite activated carbon is that nano modification activated carbon is made through hydroxypropyl beta cyclodextrin modification, and composite activated carbon combination ultrasonic wave can effectively remove the greasy dirt in solution.Present invention process flow is simple and convenient to operate, metal recovery utilization rate is high, and discharge of wastewater is less, can reclaiming purity it is higher and meet the nickel sulfate of national standard, can be widely applied to plating, battery industry, there is preferable economic benefit.
Description
Technical field
The present invention relates to scrap metal processing technology field, more particularly to a kind of reclaiming from nickel bath slag and sludge
The method of nickel sulfate.
Background technology
Nickel sulfate is industrial important nickel compound, and generally based on nickel sulfate hexahydrate, nickel sulfate is electronickelling and change
The main nickel salt of nickel is learned, is widely used in electroplating industry, catalytic industries, pharmaceuticals industry, inorganic industrial, national defense industry and printing and dyeing
The fields such as industry, there is higher economic value.Industrial most of nickel sulfate production is to make raw material using metallic nickel, and China is
The deficient country of one nickel resources, most of nickel need import, and the cost for producing nickel sulfate is higher.
Electroplating technology plays very important role in modern industry, and it can enter to metal, non-metal material surface
Row modification, protect and it is obtained new performance, be widely applied in industrial production.Electroplating bath slag can be produced in electroplating work procedure
And sludge, containing various metals ions such as a large amount of nickel, it is necessary to could be just by harmless treatment in these electroplating bath slags and sludge
Discharge, otherwise can cause seriously to pollute, while also result in the wasting of resources to environment.It can be used according to electroplating sludge component difference steady
The method of determining/solidification method processing, pyrogenic attack and wet-treating etc., for the nickel bath slag containing valuable metals such as a large amount of nickel and dirt
Mud, reclaiming the valuable metals such as nickel with the mode of wet-treating can enable it recycle and reach innoxious purpose, simultaneously
Also the cost of production nickel sulfate can be substantially reduced, economizes on resources, reduces environmental pollution.
At present, the method that wet-treating is first soaked using acidleach and ammonia brings metal ion in aqueous phase into, then heavy by chemistry
The mode such as shallow lake or solvent extraction extracts the valuable metal that recovery needs.But waste water production in existing wet processing technique be present
Raw amount is larger, and environmental pollution is serious, and the nickel sulfate purity of regeneration is relatively low, does not meet relevant national standard.
The content of the invention
In view of this, it is an object of the invention to provide a kind of side of the reclaiming nickel sulfate from nickel bath slag and sludge
Method, discharge of wastewater is less, can reclaiming purity it is higher and meet the nickel sulfate of national standard, can be widely applied to plating,
Battery industry, there is preferable economic benefit.
The present invention solves above-mentioned technical problem by following technological means：
A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge, including following process：
S1. dissolving is leached, and nickel bath slag is added into dissolving tank and sludge adds water to carry out pulp, stirring adds sulfuric acid, drum
Enter pure air and carry out aerating oxidation 2h~3h, obtain the leaching slurry of pH=1.0~1.5.
S2. press filtration is separated, and leaching slurry is transferred into the isolated filtrate A and filter residue A of press filtration in plate and frame filter press.
S3. complexing remove Fe, As, adjusts filtrate A pH=2.5~3.2 with aqueous slkali, and the oxidizing reaction 3h of addition~
5h, it is filtered under diminished pressure to obtain liquor B and filter residue B, adds pH=3.5~3.8 of sodium carbonate regulation liquor B, precipitate 2h~3h, depressurized
Filter obtains liquor C and filter residue C.
S4. abstraction impurity removal, including one-level extraction, one-level back extraction, two level extraction and two level are stripped four steps, one-level
Extraction, the 260# solvent naphthas containing extractant P507 and the sodium carbonate liquor continuous soap in closed extraction box are added into liquor C
Change, counter-current extraction, obtain raffinate A and organic phase A；One-level is stripped, and hydrochloric acid solution is added into organic phase A and is stripped
Take, obtain organic phase B and anti-stripping agent B, organic phase B is reclaimed for one-level extraction step；Two level extracts, and adds into raffinate A
Enter the 260# solvent naphthas containing extractant P507 and sodium carbonate liquor continuous saponification process, counter-current extraction in closed extraction box, obtain
Raffinate C and organic phase C；Two level is stripped, and sulfuric acid solution is added into organic phase C and is stripped, and obtains organic phase D and anti-
Extract D, organic phase D are reclaimed for two level extraction step.
S5. ultrasonic oil removing, the ultrasonic oil removing of composite activated carbon progress is added into anti-stripping agent D, is filtrated to get refined sulfuric acid
Nickel solution；
S6. be concentrated and dried, by refined sulfuric acid nickel solution progress heating, vacuum be concentrated into concentration of nickel sulfate for 330g/L~
380g/L, decrease temperature crystalline, filtering, it is dried to obtain nickel sulfate.
Further, after the filter residue A in the S2 carries out countercurrent washing twice using 1.8mol/L sulfuric acid solution, obtain
Washery slag Water Sproading, which is used to dissolve, leaches process, and the waste residue after washing is as fixed-end forces.
Further, the aqueous slkali in the S3 processes is the sodium carbonate liquor of mass concentration 14%, and the oxidant is double
Oxygen water or sodium chlorate.
Further, in the one-level extraction and two level extraction step, the volume ratio of extractant P507 and 260# solvent naphthas is
1:5, use mass concentration to carry out homogeneous saponification for 14% sodium carbonate liquor, and saponification rate is controlled 70%, control extraction temperature
Spend for 15 DEG C~30 DEG C.
Further, composite activated carbon and the mass ratio of anti-stripping agent D mass are 0.3~0.5 in the S5 processes:1, ultrasound
Parameter is frequency 22kHz~25kHz, power 350W, temperature 45 C~55 DEG C.
Further, the composite activated carbon is that nano modification activated carbon is made through hydroxypropyl-β-cyclodextrin modification.
Further, the nano modification activated carbon is that cocoanut active charcoal carried out into acidleach, after filtration washing, adds 5mol/L
Hydrogen peroxide solution in 65 DEG C stir 5h, after filtration washing, 6h~10h is soaked in acetone solvent, takes out obtained modification
Activated carbon, be successively carbonized, be carbonized in advance, activate be made.
Further, the pre- carbonization is that modified activated carbon is put into Muffle furnace, in 350 DEG C of pre- carbonizations in air atmosphere
5h, carbonization are that the activated carbon after pre- carbonization is put into tube furnace, and be carbonized 4h under 300mL/min nitrogen atmosphere in 650 DEG C
~6h, activation are that the activated carbon after carbonization is activated into 4h in 700 DEG C~900 DEG C under 300mL/min carbon dioxide atmosphere.
Further, the specific surface area of the nano modification activated carbon is 2430m2/ g~2710m2/g。
Further, the decrease temperature crystalline in the S6 processes is that the nickel sulfate solution after concentration is transferred in crystallizing tank, in
300r/min mixing speeds are cooled to 50 DEG C~55 DEG C, continue at 100r/min mixing speeds and are cooled to 35 DEG C~40 DEG C, stop
Stirring, still aging 10h~15h.
The method of reclaiming nickel sulfate from nickel bath slag and sludge of the present invention, using nickel bath slag and sludge as raw material
Reclaiming nickel sulfate, rationally make use of resource, avoid the wasting of resources.This method is first with sulfuric acid by nickel bath slag and sludge
Dissolving metal leaching is changed into metal ion and is dissolved in solution, avoids using nitric acid or ferric trichloride pollution on the environment, and
The leaching rate of sulfuric acid is higher.In leaching process is dissolved, it can dissolve and leach a small amount of iron and arsenic, the present invention is led to using sodium carbonate liquor
Overregulate pH value to precipitate iron and arsenic, and then be removed by filtration.The present invention carries out edulcoration purification, avoiding using solvent extraction
Learn in the precipitation method and use environmental problem caused by vulcanization method, and impurity-eliminating effect is preferable.Present invention employs with compared with Large ratio surface
The composite activated carbon that long-pending nano modification activated carbon obtains after hydroxy propyl-Beta-Activated Carbon Modification, the back extraction to two level back extraction
Take liquid to carry out ultrasonic de-oiling, ultrasonic wave is a kind of compression compressional wave, can make pressure change in liquid under the use of promotion medium and
Countless slight vacuum bubbles are produced, cause void effect, when bubble compression explosion, powerful impulsive force can be produced, are surpassed simultaneously
Sound wave, which also has, emulsifies neutralization, and the greasy dirt that effectively can prevent from being cleaned out is attached on cleaned object again, composite reactive
Charcoal has stronger adsorptivity and dispersiveness, the oil in the anti-stripping agent D that can be stripped in the presence of ultrasonic wave to two level
Dirt is adsorbed completely.Contain a small amount of nickel ion in the organic phase B that one-level is stripped to obtain in the present invention, reclaim and extract for one-level
Take in step, realize the abundant recycling of nickel, avoid wasting.
A kind of method of reclaiming nickel sulfate from nickel bath slag and sludge of the present invention, technological process is simple, operation
It is convenient, metal recovery utilization rate is high, discharge of wastewater is less, can reclaiming purity it is higher and meet the sulfuric acid of national standard
Nickel, plating, battery industry are can be widely applied to, there is preferable economic benefit.
Brief description of the drawings
Fig. 1 is a kind of schematic flow sheet of the method for the reclaiming nickel sulfate from nickel bath slag and sludge of the present invention.
Embodiment
Below with reference to the drawings and specific embodiments, the present invention is described in detail：
As shown in figure 1, a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge of the present invention, includes molten
Solution leaches, press filtration separates, complexing except Fe and As, abstraction impurity removal, ultrasonic oil removing and is concentrated and dried process, is adopted in ultrasonic oil removing process
With composite activated carbon absorption anti-stripping agent D oil phase substance, reach the purpose for removing greasy dirt in nickel sulfate solution.The compound work
Property charcoal to be nano modification activated carbon modify through hydroxypropyl-β-cyclodextrin is made, nano modification activated carbon be using cocoanut active charcoal as
Raw material, it is modified by hydrogen peroxide oxidation, organic solvent immersion is carried out, pre- carbonization, carbonization, activation is made, specific as follows：
Embodiment one：It is prepared by nano modification activated carbon
Cocoanut active charcoal is added in the 6mol/L hydrochloric acid solutions of 3 times of volumes to being completely soaked, and stir 12h, filtered, used
Deionized water is washed to neutrality, is added in 5mol/L hydrogen peroxide solution, and 5h is stirred at a temperature of 65 DEG C, filtering, is spent
After ion water washing to neutrality, add in acetone solvent and soak 6h, taking-up obtains modified activated carbon, and modified activated carbon is put into horse
Not in stove, in 350 DEG C of pre- carbonization 5h in air atmosphere, then it is transferred in tube furnace, 650 DEG C is warming up to 3 DEG C/min speed,
It is carbonized under 300mL/min nitrogen atmosphere after 4h, then is warming up to 700 DEG C, is activated under 300mL/min carbon dioxide atmosphere
4h, take out, natural cooling just obtains nano modification activated carbon, and the specific surface area that detection obtains nano modification activated carbon is
2430m2/g。
Embodiment two：It is prepared by nano modification activated carbon
Cocoanut active charcoal is added in the 6mol/L hydrochloric acid solutions of 4 times of volumes to being completely soaked, and stir 12h, filtered, used
Deionized water is washed to neutrality, is added in 5mol/L hydrogen peroxide solution, and 5h is stirred at a temperature of 65 DEG C, filtering, is spent
After ion water washing to neutrality, add in acetone solvent and soak 8h, taking-up obtains modified activated carbon, and modified activated carbon is put into horse
Not in stove, in 350 DEG C of pre- carbonization 5h in air atmosphere, then it is transferred in tube furnace, 650 DEG C is warming up to 5 DEG C/min speed,
It is carbonized under 300mL/min nitrogen atmosphere after 6h, then is warming up to 850 DEG C, is activated under 300mL/min carbon dioxide atmosphere
4h, take out, natural cooling just obtains nano modification activated carbon, and the specific surface area that detection obtains nano modification activated carbon is
2710m2/g。
Embodiment three：It is prepared by nano modification activated carbon
Cocoanut active charcoal is added in the 6mol/L hydrochloric acid solutions of 3 times of volumes to being completely soaked, and stir 12h, filtered, used
Deionized water is washed to neutrality, is added in 5mol/L hydrogen peroxide solution, and 5h is stirred at a temperature of 65 DEG C, filtering, is spent
After ion water washing to neutrality, add in acetone solvent and soak 10h, taking-up obtains modified activated carbon, and modified activated carbon is put into
In Muffle furnace, in 350 DEG C of pre- carbonization 5h in air atmosphere, then it is transferred in tube furnace, 650 is warming up to 5 DEG C/min speed
DEG C, it is carbonized under 300mL/min nitrogen atmosphere after 6h, then 900 DEG C are warming up to, under 300mL/min carbon dioxide atmosphere
4h is activated, is taken out, natural cooling just obtains nano modification activated carbon, and the specific surface area that detection obtains nano modification activated carbon is
2571m2/g。
In the method for reclaiming nickel sulfate of the present invention, the suction-operated of activated carbon is mainly utilized in ultrasonic oil removing process
Oily waste degradation is carried out, and the specific surface area of activated carbon is bigger, adsorption effect is better, can more effectively remove degreasing, therefore,
It is used for oil removing after hydroxypropyl-β-cyclodextrin is modified from the nano modification activated carbon that embodiment two is prepared below.Modification
Process adds 60g nano modification activated carbons for 5g hydroxypropyl-β-cyclodextrins are dissolved in 1L deionized waters in obtained solution
Supersonic modifying 30min, stand 12h, filtering, drying to obtain composite activated carbon.In the composite activated carbon due to have hydroxy propyl-Beta-
Cyclodextrin, its dispersiveness in anti-stripping agent D can be improved, is easy to oil removing.
The method of the reclaiming nickel sulfate of the present invention is described in detail by following examples.
Example IV：The method of reclaiming nickel sulfate
The present embodiment it is a kind of from the method that nickel bath slag and sludge are raw materials recovery black sulfuric acid nickel, including following work
Sequence：
S1. dissolving is leached, and nickel bath slag and sludge are added in dissolving tank, and after adding water stirring to carry out pulp, stirring adds
Sulfuric acid, and blast air and carry out aerating oxidation 2h, obtain the pH=1.0 leaching slurry containing various metals ion, the process
The main chemical reactions of middle generation are as follows：
MeO+H2SO4=MeSO4+H2O
Me therein is soluble metal, predominantly Ni, Cu, Fe, Mn, Ca, Mg.Meeting during dissolving is leached
A small amount of sulfuric acid mist is produced, alkali spray absorber can be entered by air draft system and absorbs rear high altitude discharge up to standard.
S2. press filtration is separated, and leaching slurry is transferred into the isolated filtrate A1 and filter residue A1 of press filtration in plate and frame filter press, press filtration
Filter residue A1 is dried up with compressed air afterwards, filter residue A1 water content is reduced as far as possible.In order to improve the rate of recovery of nickel, use concentration for
1.8mol/L sulfuric acid solution carries out countercurrent washing twice to filter residue A1, fully to wash away the soluble valuable gold carried secretly in filter residue
Category, the washery slag Water Sproading of second of washing wash for first time filter residue A1, wash obtained washery slag Water Sproading for the first time and be used for
Process is leached in dissolving, the metal ion in material is reclaimed as far as possible, the filter residue A1 after washing twice is as fixed-end forces.
Detection and analysis obtain the primary metal ion content such as table 1 below in filtrate A：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 121.3 | 36.4 | 11.6 | 7.9 | 3.2 | 4.0 | 2.9 | 8.6 |
Table 1
S3. complexing removes Fe, As, adjusts filtrate A1 pH=2.5 with the sodium carbonate liquor of mass concentration 14%, adds oxidation
Agent hydrogen peroxide oxidation reaction 5h, by the oxidation of divalent iron ion in filtrate A1 into ferric ion, so as in the solution with chemical combination
Thing ferric sulfate is present, and ferric sulfate has suction-operated to arsenic, can form FeAsO4Sediment, reaction principle Fe3++AsO4 3-=
FeAsO4, it is filtered under diminished pressure to obtain liquor B 1 and filter residue B1, filter residue B1 is mainly FeAsO4Sediment, continue thereafter with removing and do not precipitate
Iron ion, add the pH=3.8 of sodium carbonate regulation liquor B 1, precipitate 2h, during this, carbonate first generates carbonic acid with acid reaction
Hydrogen radical, because now solution acidic is stronger, further reaction generation carbon dioxide, reaction are as follows with acid for bicarbonate radical：CO3 2-+2H+=CO2+H2O, therefore other materials such as Ni, Cu, Ca, Mg etc. can not generate carbonate deposition；Meanwhile Fe3+Hydrolysis and and Na+It is raw
Come out into complex compound sediment, reaction principle is as follows：
2Fe2(SO4)3+6H2O=6Fe (OH) (SO4)+3H2SO4；
2Fe(OH)(SO4)+2H2O=Fe2(OH)4(SO4)4+H2SO4；
2Fe2(OH)4(SO4)4+2Fe(OH)(SO4)+Na2SO4+2H2O=Na2Fe6(OH)12(SO4)4+H2SO4；
That is 3Fe2(SO4)3+12H2O+Na2SO4=Na2Fe6(OH)12(SO4)4↓+6H2SO4。
It is filtered under diminished pressure to obtain liquor C 1 and filter residue C1, filter residue C1 is mainly Na2Fe6(OH)12(SO4)4Sediment.
Detection and analysis obtain the primary metal ion content such as table 2 below in liquor C 1：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 100.6 | 26.8 | 0.095 | 5.3 | 2.1 | 2.8 | 1.8 | 0.089 |
Table 2
S4. abstraction impurity removal, including one-level extraction, one-level back extraction, two level extraction and two level are stripped four steps.One-level
Extraction, the 260# solvent naphthas containing extractant P507 and mass concentration are added into liquor C 1 as 14% sodium carbonate liquor, this
When pH=3.8, continuous saponification process, counter-current extraction in closed extraction box, wherein, extractant P507 and diluent 260# solvent naphthas
Volume ratio be 1:5, and control saponification rate 70%, it is 15 DEG C to control extraction temperature, and raffinate A1 and organic is obtained after extraction
Phase A1, most of nickel ion is split into raffinate A1 in liquor C 1, and small part is split into organic phase A1；One-level is stripped
Take, the hydrochloric acid solution that 6mol/L is added into organic phase A1 is stripped, and obtains organic phase B1 and anti-stripping agent B1, organic phase
Contain a small amount of nickel in B1, reclaim for one-level extraction step, the metallics in anti-stripping agent B1 mainly has copper, also containing a small amount of
Manganese, calcium, the metal such as zinc；Two level is extracted, and 260# solvent naphthas and sodium carbonate containing extractant P507 are added into raffinate A1
Solution continuous saponification process, counter-current extraction in closed extraction box, and saponification rate is controlled 70%, it is 15 DEG C to control extraction temperature, is obtained
To raffinate C1 and organic phase C 1, during this, because most of cation has been removed, the nickel in raffinate A1 is extracted into
In organic phase C 1, main sulfur acid sodium and a small amount of anion in raffinate C1, it is discharged into waste water processing station processing and meets national mark
Discharged after quasi- regulation；Two level is stripped, and 4mol/L sulfuric acid solutions are added into organic phase C 1 and are stripped, obtain organic phase D 1
With anti-stripping agent D1, organic phase D 1 is reclaimed for two level extraction step.The reaction equation that the process is related to is as follows：
P507 saponification：(R’O)2POOH+Na+→(R’O)2POONa；
P507 is extracted：2(R’O)2POONa+MeSO4=[(R ' O)2POO]2Me+Na2SO4；
Wherein Me is the metals such as Zn, Cu, Mn, Ca；
Sulfuric acid is stripped：2RH+CuSO4=R2Cu+H2SO4；
Wherein RH is extractant, R2Cu is the complex compound that extractant is formed with copper；
R2Cu+H2SO4=2RH+CuSO4；
Hydrochloric acid is stripped：[(R’O)2POO]2Me+2HCl=2 (R ' O)2POOH+MeCl2；
Wherein Me is the metals such as Zn, Cu, Mn, Ca, Mg.
S5. ultrasonic oil removing, composite activated carbon is added into anti-stripping agent D1 and carries out ultrasonic oil removing, composite activated carbon and back extraction
The mass ratio for taking liquid D1 mass is 0.3:1, in frequency 22kHz, power 350W, ultrasonic oil removing is carried out under the conditions of temperature 45 C
0.5h, it is filtrated to get refined sulfuric acid nickel solution.
S6. it is concentrated and dried, refined sulfuric acid nickel solution is heated, it is 330g/L to be concentrated in vacuo to concentration of nickel sulfate, will
Nickel sulfate solution after concentration is transferred in crystallizing tank, is cooled to 55 DEG C in 300r/min mixing speeds, is continued at 100r/min and stir
Mix speed and be cooled to 35 DEG C, stop stirring, still aging 10h, filtering, be dried to obtain nickel sulfate.
The product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation technique will
Ask comparison as shown in table 3.
Table 3
The present embodiment sulfuric acid that from nickel bath slag and sludge prepared by reclaiming it can be seen from the data shown by table 3
The product quality of nickel is higher than national standard《GB/T26524-2011》Technical requirements, can be widely applied to plating, battery industry.
Embodiment five：The method of reclaiming nickel sulfate
The present embodiment it is a kind of from the method that nickel bath slag and sludge are raw materials recovery black sulfuric acid nickel, including following work
Sequence：
S1. dissolving is leached, and nickel bath slag and sludge are added in dissolving tank, and after adding water stirring to carry out pulp, stirring adds
Sulfuric acid, and blast air and carry out aerating oxidation 3h, obtain the pH=1.5 leaching slurry containing various metals ion.Dissolving leaching
A small amount of sulfuric acid mist can be produced during going out, alkali spray absorber can be entered by air draft system and absorbs rear high idle discharge up to standard
Put.
S2. press filtration is separated, and leaching slurry is transferred into the isolated filtrate A2 and filter residue A2 of press filtration in plate and frame filter press, press filtration
Filter residue A2 is dried up with compressed air afterwards, filter residue A2 water content is reduced as far as possible.In order to improve the rate of recovery of nickel, use concentration for
1.8mol/L sulfuric acid solution carries out countercurrent washing twice to filter residue A2, fully to wash away the soluble valuable gold carried secretly in filter residue
Category, the washery slag Water Sproading of second of washing wash for first time filter residue A2, wash obtained washery slag Water Sproading for the first time and be used for
Process is leached in dissolving, the metal ion in material is reclaimed as far as possible, the filter residue A2 after washing twice is as fixed-end forces.
Detection and analysis obtain the primary metal ion content such as table 4 below in filtrate A：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 111.8 | 33.4 | 11.4 | 7.2 | 2.2 | 4.0 | 2.6 | 7.7 |
Table 4
S3. complexing removes Fe, As, adjusts filtrate A2 pH=3.2 with the sodium carbonate liquor of mass concentration 14%, adds oxidation
Agent sodium chlorate oxidation reaction 3h, it is filtered under diminished pressure to obtain liquor B 2 and filter residue B2, filter residue B2 is mainly FeAsO4Sediment, with follow-up
It is continuous to remove unprecipitated iron ion, add the pH=3.5 of sodium carbonate regulation liquor B 2, precipitate 3h, be filtered under diminished pressure to obtain the He of liquor C 2
Filter residue C2, filter residue C2 are mainly Na2Fe6(OH)12(SO4)4Sediment.
Detection and analysis obtain the primary metal ion content such as table 5 below in liquor C 2：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 97.8 | 30.1 | 0.087 | 5.6 | 1.7 | 3.1 | 1.9 | 0.077 |
Table 5
S4. abstraction impurity removal, including one-level extraction, one-level back extraction, two level extraction and two level are stripped four steps.One-level
Extraction, the 260# solvent naphthas containing extractant P507 and mass concentration are added into liquor C 2 as 14% sodium carbonate liquor, this
When pH=4.0, continuous saponification process, counter-current extraction in closed extraction box, wherein, extractant P507 and diluent 260# solvent naphthas
Volume ratio be 1:5, and control saponification rate 70%, it is 30 DEG C to control extraction temperature, and raffinate A2 and organic is obtained after extraction
Phase A2, most of nickel ion is split into raffinate A2 in liquor C 2, and small part is split into organic phase A2；One-level is stripped
Take, the hydrochloric acid solution that 5mol/L is added into organic phase A2 is stripped, and obtains organic phase B2 and anti-stripping agent B2, organic phase
Contain a small amount of nickel in B2, reclaim for one-level extraction step, the metallics in anti-stripping agent B2 mainly has copper, also containing a small amount of
Manganese, calcium, the metal such as zinc；Two level is extracted, and 260# solvent naphthas and sodium carbonate containing extractant P507 are added into raffinate A2
Solution continuous saponification process, counter-current extraction in closed extraction box, and saponification rate is controlled 70%, it is 30 DEG C to control extraction temperature, is obtained
To raffinate C2 and organic phase C 2, during this, because most of cation has been removed, the nickel in raffinate A2 is extracted into
In organic phase C 2, main sulfur acid sodium and a small amount of anion in raffinate C2, it is discharged into waste water processing station processing and meets national mark
Discharged after quasi- regulation；Two level is stripped, and 4mol/L sulfuric acid solutions are added into organic phase C 2 and are stripped, obtain organic phase D 2
With anti-stripping agent D2, organic phase D 2 is reclaimed for two level extraction step.
S5. ultrasonic oil removing, composite activated carbon is added into anti-stripping agent D2 and carries out ultrasonic oil removing, composite activated carbon and back extraction
The mass ratio for taking liquid D2 mass is 0.5:1, in frequency 25kHz, power 350W, ultrasonic oil removing is carried out under the conditions of 55 DEG C of temperature
0.5h, it is filtrated to get refined sulfuric acid nickel solution.
S6. it is concentrated and dried, refined sulfuric acid nickel solution is heated, it is 380g/L to be concentrated in vacuo to concentration of nickel sulfate, will
Nickel sulfate solution after concentration is transferred in crystallizing tank, is cooled to 55 DEG C in 300r/min mixing speeds, is continued at 100r/min and stir
Mix speed and be cooled to 40 DEG C, stop stirring, still aging 15h, filtering, be dried to obtain nickel sulfate.
The product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation technique will
Ask comparison as shown in table 6.
Table 6
The present embodiment sulfuric acid that from nickel bath slag and sludge prepared by reclaiming it can be seen from the data shown by table 6
The product quality of nickel is higher than national standard《GB/T26524-2011》Technical requirements, can be widely applied to plating, battery industry.
Embodiment six：The method of reclaiming nickel sulfate
The present embodiment it is a kind of from the method that nickel bath slag and sludge are raw materials recovery black sulfuric acid nickel, including following work
Sequence：
S1. dissolving is leached, and nickel bath slag and sludge are added in dissolving tank, and after adding water stirring to carry out pulp, stirring adds
Sulfuric acid, and blast air and carry out aerating oxidation 2.5h, obtain the pH=1.3 leaching slurry containing various metals ion.Dissolving
A small amount of sulfuric acid mist can be produced during leaching, alkali spray absorber can be entered by air draft system and absorbs rear high-altitude up to standard
Discharge.
S2. press filtration is separated, and leaching slurry is transferred into the isolated filtrate A3 and filter residue A3 of press filtration in plate and frame filter press, press filtration
Filter residue A3 is dried up with compressed air afterwards, filter residue A3 water content is reduced as far as possible.In order to improve the rate of recovery of nickel, use concentration for
1.8mol/L sulfuric acid solution carries out countercurrent washing twice to filter residue A3, fully to wash away the soluble valuable gold carried secretly in filter residue
Category, the washery slag Water Sproading of second of washing wash for first time filter residue A3, wash obtained washery slag Water Sproading for the first time and be used for
Process is leached in dissolving, the metal ion in material is reclaimed as far as possible, the filter residue A3 after washing twice is as fixed-end forces.
Detection and analysis obtain the primary metal ion content such as table 7 below in filtrate A：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 144.2 | 28.4 | 0.096 | 6.3 | 4.1 | 3.4 | 2.6 | 0.088 |
Table 7
S3. complexing removes Fe, As, adjusts filtrate A3 pH=3.0 with the sodium carbonate liquor of mass concentration 14%, adds oxidation
Agent hydrogen peroxide oxidation reaction 4h, by the oxidation of divalent iron ion in filtrate A3 into ferric ion, so as in the solution with chemical combination
Thing ferric sulfate is present, and ferric sulfate has suction-operated to arsenic, can form FeAsO4Sediment, it is filtered under diminished pressure to obtain liquor B 3 and filter
Slag B3, filter residue B3 are mainly FeAsO4Sediment, continue thereafter with and remove unprecipitated iron ion, add sodium carbonate regulation liquor B 3
PH=3.8,3h is precipitated, is filtered under diminished pressure to obtain liquor C 3 and filter residue C3, filter residue C3 is mainly Na2Fe6(OH)12(SO4)4Sediment.
Detection and analysis obtain the primary metal ion content such as table 8 below in liquor C 3：
| Element | Ni | Cu | Fe | Zn | Ca | Mg | Mn | As |
| Content (g/L) | 129.7 | 26.0 | 7.7 | 5.1 | 2.8 | 2.6 | 2.0 | 6.2 |
Table 8
S4. abstraction impurity removal, including one-level extraction, one-level back extraction, two level extraction and two level are stripped four steps.One-level
Extraction, the 260# solvent naphthas containing extractant P507 and mass concentration are added into liquor C 3 as 14% sodium carbonate liquor, this
When pH=4.0, continuous saponification process, counter-current extraction in closed extraction box, wherein, extractant P507 and diluent 260# solvent naphthas
Volume ratio be 1:5, and control saponification rate 70%, it is 20 DEG C to control extraction temperature, and raffinate A3 and organic is obtained after extraction
Phase A3, most of nickel ion is split into raffinate A3 in liquor C 3, and small part is split into organic phase A3；One-level is stripped
Take, the hydrochloric acid solution that 6mol/L is added into organic phase A3 is stripped, and obtains organic phase B3 and anti-stripping agent B3, organic phase
Contain a small amount of nickel in B3, reclaim for one-level extraction step, the metallics in anti-stripping agent B3 mainly has copper, also containing a small amount of
Manganese, calcium, the metal such as zinc；Two level is extracted, and 260# solvent naphthas and sodium carbonate containing extractant P507 are added into raffinate A3
Solution continuous saponification process, counter-current extraction in closed extraction box, and saponification rate is controlled 70%, it is 20 DEG C to control extraction temperature, is obtained
To raffinate C3 and organic phase C 3, during this, because most of cation has been removed, the nickel in raffinate A3 is extracted into
In organic phase C 3, main sulfur acid sodium and a small amount of anion in raffinate C3, it is discharged into waste water processing station processing and meets national mark
Discharged after quasi- regulation；Two level is stripped, and 4mol/L sulfuric acid solutions are added into organic phase C 3 and are stripped, obtain organic phase D 3
With anti-stripping agent D3, organic phase D 3 is reclaimed for two level extraction step.
S5. ultrasonic oil removing, composite activated carbon is added into anti-stripping agent D3 and carries out ultrasonic oil removing, composite activated carbon and back extraction
The mass ratio for taking liquid D3 mass is 0.4:1, in frequency 23kHz, power 350W, ultrasonic oil removing is carried out under the conditions of temperature 50 C
0.5h, it is filtrated to get refined sulfuric acid nickel solution.
S6. it is concentrated and dried, refined sulfuric acid nickel solution is heated, it is 350g/L to be concentrated in vacuo to concentration of nickel sulfate, will
Nickel sulfate solution after concentration is transferred in crystallizing tank, is cooled to 55 DEG C in 300r/min mixing speeds, is continued at 100r/min and stir
Mix speed and be cooled to 35 DEG C, stop stirring, still aging 15h, filtering, be dried to obtain nickel sulfate.
The product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation technique will
Ask comparison as shown in table 9.
Table 9
The present embodiment sulfuric acid that from nickel bath slag and sludge prepared by reclaiming it can be seen from the data shown by table 3
The product quality of nickel is higher than national standard《GB/T26524-2011》Technical requirements, can be widely applied to plating, battery industry.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferred embodiment to this hair
It is bright to be described in detail, it will be understood by those within the art that, technical scheme can be modified
Or equivalent substitution, without departing from the objective and scope of technical solution of the present invention, it all should cover the claim in the present invention
Among scope.The present invention be not described in detail technology, shape, construction part be known technology.
Claims (10)
- A kind of 1. method of the reclaiming nickel sulfate from nickel bath slag and sludge, it is characterised in that including following process：S1. dissolving is leached, and nickel bath slag is added into dissolving tank and sludge adds water to carry out pulp, stirring adds sulfuric acid, blasts sky Gas carries out aerating oxidation 2h~3h, obtains the leaching slurry of pH=1.0~1.5；S2. press filtration is separated, and leaching slurry is transferred into the isolated filtrate A and filter residue A of press filtration in plate and frame filter press；S3. complexing removes Fe, As, and filtrate A pH=2.5~3.2 are adjusted with aqueous slkali, adds oxidizing reaction 3h~5h, It is filtered under diminished pressure to obtain liquor B and filter residue B, adds pH=3.5~3.8 of sodium carbonate regulation liquor B, precipitate 2h~3h, be filtered under diminished pressure Obtain liquor C and filter residue C；S4. abstraction impurity removal, including one-level extraction, one-level back extraction, two level extraction and two level are stripped four steps, one-level extraction Take, added into liquor C the 260# solvent naphthas containing extractant P507 and sodium carbonate liquor in closed extraction box continuous saponification process, Counter-current extraction, obtain raffinate A and organic phase A；One-level is stripped, and hydrochloric acid solution is added into organic phase A and is stripped, is obtained To organic phase B and anti-stripping agent B, organic phase B is reclaimed for one-level extraction step；Two level extracts, and adds and contains into raffinate A Extractant P507 260# solvent naphthas and sodium carbonate liquor continuous saponification process, counter-current extraction in closed extraction box, obtain raffinate C And organic phase C；Two level is stripped, and sulfuric acid solution is added into organic phase C and is stripped, obtains organic phase D and anti-stripping agent D, organic phase D are reclaimed for two level extraction step；S5. ultrasonic oil removing, the ultrasonic oil removing of composite activated carbon progress is added into anti-stripping agent D, it is molten to be filtrated to get refined sulfuric acid nickel Liquid；S6. it is concentrated and dried, it is 330g/L~380g/L that refined sulfuric acid nickel solution progress heating, vacuum is concentrated into concentration of nickel sulfate, Decrease temperature crystalline, filtering, is dried to obtain nickel sulfate.
- 2. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 1, its feature exist In after the filter residue A in the S2 carries out countercurrent washing twice using 1.8mol/L sulfuric acid solution, obtained washery slag Water Sproading is used Process is leached in dissolving, the waste residue after washing is as fixed-end forces.
- 3. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 2, its feature exist In the aqueous slkali in the S3 processes is the sodium carbonate liquor of mass concentration 14%, and the oxidant is hydrogen peroxide or sodium chlorate.
- 4. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 3, its feature exist In in the one-level extraction and two level extraction step, the volume ratio of extractant P507 and 260# solvent naphthas is 1:5, using quality The sodium carbonate liquor that concentration is 14% carries out homogeneous saponification, and controls saponification rate control extraction temperature as 15 DEG C~30 70% ℃。
- 5. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 4, its feature exist In composite activated carbon and the mass ratio of anti-stripping agent D mass are 0.3~0.5 in the S5 processes:1, ultrasound parameter is frequency 22kHz~25kHz, power 350W, temperature 45 C~55 DEG C.
- 6. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 5, its feature exist In the composite activated carbon is that nano modification activated carbon is made through hydroxypropyl-β-cyclodextrin modification.
- 7. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 6, its feature exist It is that cocoanut active charcoal is subjected to acidleach in, the nano modification activated carbon, after filtration washing, with hydrogen peroxide oxidation, after diafiltration After washing, 6h~10h is soaked in acetone solvent, obtained modified activated carbon is taken out, is successively carbonized, be carbonized in advance, activating system .
- 8. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 7, its feature exist In, the pre- carbonization is that modified activated carbon is put into Muffle furnace, in 350 DEG C of pre- carbonization 5h in air atmosphere, carbonization be by Activated carbon after pre- carbonization is put into tube furnace, and be carbonized 4h~6h under 300mL/min nitrogen atmosphere in 650 DEG C, and activation is Activated carbon after carbonization is activated into 4h under 300mL/min carbon dioxide atmosphere in 700 DEG C~900 DEG C.
- 9. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 8, its feature exist In the specific surface area of the nano modification activated carbon is 2430m2/ g~2710m2/g。
- 10. a kind of method of reclaiming nickel sulfate from nickel bath slag and sludge according to claim 9, its feature exist In the decrease temperature crystalline in the S6 processes is that the nickel sulfate solution after concentration is transferred in crystallizing tank, and speed is stirred in 300r/min Degree is cooled to 50 DEG C~55 DEG C, continues at 100r/min mixing speeds and is cooled to 35 DEG C~40 DEG C, stops stirring, still aging 10h~15h.
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