CN102443700B - Method for recovering nickel from nickel-laterite leaching solution and device - Google Patents
Method for recovering nickel from nickel-laterite leaching solution and device Download PDFInfo
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- CN102443700B CN102443700B CN201110412104XA CN201110412104A CN102443700B CN 102443700 B CN102443700 B CN 102443700B CN 201110412104X A CN201110412104X A CN 201110412104XA CN 201110412104 A CN201110412104 A CN 201110412104A CN 102443700 B CN102443700 B CN 102443700B
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Abstract
Relating to the chemical field, the invention specifically relates to a method for recovering nickel from a nickel-laterite leaching solution and a device. The method comprises: A. treating a nickel-laterite ore leaching solution with limestone, and neutralizing the sulfuric acid in the leaching solution by a chemical reaction; B. conducting centrifugal extraction above grade one to the neutralizing solution obtained in step A with dialkyl phosphoric acid and separating nickel and metallic impurities in the leaching solution; C. treating the extracting solution obtained in step B, and further separating nickel and metallic impurities in the extracting solution through a chemical reaction, subjecting the extracting solution that has the nickel and metallic impurities removed to saponification treatment, and returning the saponified solution to step B to serve as an extracting agent; D. carrying out swirling electrolysis to the raffinate obtained in step B and extracting nickel. The metallic impurities include one or more of iron, cobalt, manganese and aluminum. The method and the device of the invention can reduce production cost.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of method and apparatus that reclaims nickel from the nickel laterite leaching solution.
Background technology
At present, for the purification process technique of nickel laterite sulfuric acid leaching solution, mainly contain hydrolytic precipitation method, solvent extration, sulfurization-precipitation method etc.For example certain nickel laterite treatment plant of Australia adopts the technique of Wingdale neutralization-hydrogen sulfide precipitate and separate nickel cobalt to be settled out nickel cobalt sulfide concentrate from nickel laterite sulfuric acid pressure leaching liquid, again nickel cobalt sulfide collective concentrate is carried out oxygen and press leaching, the leach liquor that obtains adopts Acidic phosphates (C272) extracting and separating nickel cobalt, raffinate is pure nickel sulfate solution, obtain high-purity nickel powder through hydrogen reduction, and the cobalt sulfate solution direct electrowinning that reverse extraction (back extraction) obtains is produced cobalt metal.Another treatment plant of family of Australia then adopts the art breading nickel laterite sulfuric acid pressure leaching liquid of Wingdale neutralized ex iron-magnesium oxide neutralization precipitation nickel cobalt, the nickel cobalt hydroxide mixture that obtains carries out ammonia again and soaks, further except impurity such as de-iron, manganese, calcium, magnesium, the nickel that obtains, cobalt ammonia solution, then use the LIX84-I extraction of nickel, reverse extraction (back extraction) liquid send nickel electrodeposition to produce cathode nickel.Philippines nickel industry company then adopts the art breading nickel laterite sulfuric acid pressure leaching liquid of Wingdale neutralized ex iron aluminium-hydrogen sulfide coprecipitated nickel hydroxide cobalt, and the nickel cobalt sulfide that obtains adopts chlorination refining explained hereafter nickel cobalt again.In addition, some nickel laterite treatment plant adopts direct C272 extraction process, direct Extraction of Cobalt from the leach liquor that contains a large amount of impurity, and the cobalt strip liquor carries out sulfide precipitation and obtains the CoS concentrate, then produces the negative electrode cobalt by refining.Raffinate behind the extraction cobalt send nickel electrodeposition to produce cathode nickel with a kind of carboxylic acid extraction agent-Versaticl0 extraction of nickel, back extraction nickel sulfate solution.Because the nickel laterite grade is low, it is low to cause leach liquor to contain nickel concentration, need to carry out the secondary enrichment, thereby causes processing technological flow length, scale of investment and running cost higher.On the whole, the shortcoming of prior art is: because technical process is long, process is complicated; Adopt conventional chamber type extraction apparatus, extraction system is large, and the disposable Meteorological of extraction agent is high, and simultaneously, in the production run process, the consumption of extraction agent is large, causes production cost high; Adopt conventional electrorefining technique, the low levels nickel solution needs the secondary enrichment, cause production cost to increase, thereby the integral production cost is higher.
Summary of the invention
The invention provides a kind of method and apparatus from nickel laterite leaching solution recovery nickel, can reduce production costs.
The invention provides a kind of method that from the nickel laterite leach liquor, reclaims nickel, it is characterized in that, comprising:
A. adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
B. the neutralization solution that with Acidic phosphates the A step is obtained carries out the Centrifugical extraction more than the one-level, and the nickel in the described leach liquor is separated with metallic impurity;
C. the extraction liquid that the B step is obtained is processed, utilize chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process, the solution after the saponification is turned back to the B step use as extraction agent;
D. the raffinate that the B step is obtained carries out cyclone electrolytic cell, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium.
In the described steps A and after the pH of solution be preferably 4.0-5.5; Preferred, pH is 4.0-4.5;
And/or,
Described steps A neutral temperature is preferably 70 ℃-90 ℃, preferred, neutral temperature is 75 ℃-85 ℃;
And/or,
Be preferably 1-3 hour with the time in the described steps A; Preferred, in and the time be 1-2 hour.
Before step B, described method is preferably further and comprises: Acidic phosphates is dissolved in kerosene; Preferred, the volume ratio that Acidic phosphates accounts for Acidic phosphates and kerosene mixed solution is preferably 5%-15%; More preferably, the volume ratio that Acidic phosphates accounts for Acidic phosphates and kerosene mixed solution is preferably 8%-10%;
Then,
Among the step B, the described neutralization solution that the A step is obtained with Acidic phosphates carries out Centrifugical extraction more than the one-level and is preferably further and comprises: the neutralization solution that the A step is obtained with the mixed solution of Acidic phosphates and kerosene carries out the Centrifugical extraction more than the one-level; Preferred, the neutralization solution that the A step is obtained with the mixed solution of Acidic phosphates and kerosene is preferably and carries out 3 grades of Centrifugical extractions.
The described extraction liquid that the B step is obtained is processed to be preferably and is comprised:
A. the nickel of washing that one-level is above is processed, and utilizes chemical reaction that the nickel in the extraction liquid is further extracted, and the nickel that extracts is turned back in the B step as treating that extracting substance uses; Preferred, two-stage is washed nickel and is processed;
B. the above reverse extraction treatment of one-level is utilized chemical reaction, by sulfuric acid the reverse extraction of metallic impurity is extracted, and the metallic impurity that reverse extraction is extracted are collected; Preferred, 3 grades of reverse extraction treatment;
C. the above organic regenerative of one-level is processed, and utilizes chemical reaction, by hydrochloric acid metallic impurity are extracted, and the metallic impurity that the recovery organic regenerative is extracted is collected; Preferred, 2 grades of organic regenerative are processed;
And/or,
Described to the extraction liquid of removing described nickel and described metallic impurity carry out saponification process described in saponification process to be preferably and comprise: carry out saponification with NaOH and process; Preferred, saponification degree is 35-50%, more preferably, saponification degree is 40-45%.
In the described D step, the current density of described electrolysis is preferably 200-800A/m
2, electrolyte temperature is preferably 45-85 ℃, electrolyte ph and is preferably 2.0-5.5, in the situation of electrolysis 1Kg nickel, the raffinate circular flow is preferably 200-600L/ hour; Preferred, the current density of described electrolysis is preferably 300-500A/m
2, electrolyte temperature is preferably 50-75 ℃, electrolyte ph and is preferably 2.5-3.5, in the situation of electrolysis 1Kg nickel, the raffinate circular flow is preferably 300-400L/ hour.
The present invention also provides a kind of device that reclaims nickel from the nickel laterite leach liquor that utilizes aforesaid method, comprising:
Neutralising arrangement be used for to adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
Centrifugal extraction apparatus is used for carrying out Centrifugical extraction more than the one-level with the neutralization solution that Acidic phosphates obtains the neutralization device, and the nickel in the described leach liquor is separated with metallic impurity;
The extraction liquid treatment unit is used for the extraction liquid that centrifugal extraction apparatus obtains is processed, and utilizes chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process;
Send-back device uses as extraction agent for the solution after the saponification of described extraction liquid treatment unit is transmitted back in the centrifugal extraction apparatus;
The raffinate treatment unit, the raffinate that is used for centrifugal extraction apparatus is obtained carries out electrolysis, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium.
Described neutralising arrangement is preferably and is provided with temperature measuring equipment, pH value metering facility;
Described temperature measuring equipment is preferably the temperature for the reaction solution of measuring neutralization reaction;
Described pH value metering facility is preferably for the pH value of measuring neutralization reaction.
Described device is preferably further and comprises: mixing equipment;
Described mixing equipment is preferably for mixing by Acidic phosphates and the kerosene of setting the volume ratio weighing;
Then,
Described mixing equipment is preferably by the extraction agent transport pipe and is connected with described centrifugal extraction apparatus, preferred, described centrifugal extraction apparatus is preferably and comprises the 3 cover centrifugal extraction equipments that link to each other successively.
Described extraction liquid treatment unit is preferably and comprises: what link to each other successively washes nickel treatment facility, reverse extraction treatment equipment, organic regenerative treatment facility, saponification treatment facility;
Wherein, the described nickel treatment facility of washing is preferably be used to the nickel of washing that carries out more than the one-level and processes, and utilizes chemical reaction that the nickel in the extraction liquid is further extracted; Described nickel outlet of washing the nickel treatment facility is connected with the nickel backpass ductwork, and described nickel backpass ductwork links to each other with described centrifugal extraction apparatus, is preferably for and turns back to described centrifugal extraction apparatus conduct from the nickel that described nickel outlet is discharged to treat that extracting substance uses; Preferred, the described nickel treatment facility of washing is preferably and comprises two covers and wash nickel and process subset;
Described reverse extraction treatment equipment is preferably be used to the reverse extraction treatment of carrying out more than the one-level, utilizes chemical reaction, by sulfuric acid the reverse extraction of metallic impurity is extracted, and the metallic impurity that reverse extraction is extracted are collected; Preferred, described reverse extraction treatment equipment is preferably and comprises the reverse extraction treatment subset that 3 covers link to each other successively;
Described organic regenerative treatment facility, be preferably be used to the organic regenerative of carrying out more than the one-level and process, utilize chemical reaction, by hydrochloric acid metallic impurity are extracted, its metal outlet links to each other with the metallic impurity collecting device by the metallic impurity recovery channel, and described metallic impurity collecting device is used for the metallic impurity that reclaim the organic regenerative extraction are collected; Preferred, described organic regenerative treatment facility is preferably the organic regenerative processing subset that comprises that 2 covers link to each other successively;
The saponification treatment facility is preferably for the extraction liquid of removing described nickel and described metallic impurity being carried out saponification and processes; The saponification solution outlet of described saponification treatment facility is preferably by the solution backpass ductwork and connects described centrifugal extraction apparatus, and described solution backpass ductwork is preferably for the solution after the saponification is turned back to described centrifugal extraction apparatus and uses as extraction agent.
The raffinate treatment unit is preferably and is provided with electrolytic solution temperature measuring equipment, current density operating device, electrolyte ph metering facility, raffinate flow operating device;
Wherein,
Described electrolytic solution temperature measuring equipment is preferably for the temperature of measuring electrolytic solution;
Described current density operating device is preferably for the control current density;
Described electrolyte ph metering facility is preferably for measuring electrolyte ph;
Described raffinate flow operating device is preferably for control raffinate flow.
By the invention provides a kind of method and apparatus from nickel laterite leaching solution recovery nickel, can reach following beneficial effect:
1. reduce production costs.The present invention extracts nickel to the nickel laterite leach liquor of low levels nickel, wherein replace traditional box extraction process with advanced centrifugal extracting process, greatly reduced the consumption of extraction agent, simultaneously extraction liquid is processed, the recovery extraction agent also is back to use in the Centrifugical extraction process, has also greatly reduced the consumption of extraction agent, has improved extraction efficiency, reduce extraction system, reduced input amount of extraction agent and waste.And, adopt the cyclone electrolytic cell technology to replace traditional electrolysis tech, can be from the solution of lower concentration nickel the Direct Electrolysis high-purity metal nickel product of taking advantage of the occasion, thereby shortened nickel laterite sulphuric leachate treatment scheme, by above measure, reduced extraction agent consumption, shortened technical process, thereby greatly reduce production cost.
2. simplification of flowsheet is simplified treating processes.The present invention adopts the cyclone electrolytic cell technology to replace traditional electrolysis tech, can be from the solution of lower concentration nickel the Direct Electrolysis high-purity metal nickel product of taking advantage of the occasion, thereby shortened nickel laterite sulphuric leachate treatment scheme.And the metallic nickel product purity original text of producing, technical process simple, be easy to accomplish scale production, production cost is low; and the high-efficiency cleaning of having realized low levels nickel laterite sulphuric leachate in the process that extraction liquid is processed is processed, and technique is simple, simple to operate.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, accompanying drawing in below describing only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawing illustrated embodiments other embodiment and accompanying drawing thereof.
Fig. 1 is the present invention reclaims the method for nickel from the nickel laterite leach liquor basic flow sheet.
Fig. 2 is the basic flow sheet that reclaims the method for nickel in the one embodiment of the invention from the nickel laterite leach liquor.
Fig. 3 is the basic block diagram that reclaims the device of nickel in the one embodiment of the invention from the nickel laterite leach liquor.
Embodiment
Below with reference to accompanying drawing the technical scheme of various embodiments of the present invention is carried out clear, complete description, obviously, described embodiment only is a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are resulting all other embodiment under the prerequisite of not making creative work, all belong to the scope that the present invention protects.
The invention provides a kind of method that from the nickel laterite leach liquor, reclaims nickel, such as Fig. 1, shown in, comprising:
A. adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
B. the neutralization solution that with Acidic phosphates the A step is obtained carries out the Centrifugical extraction more than the one-level, and the nickel in the described leach liquor is separated with metallic impurity;
C. the extraction liquid that the B step is obtained is processed, utilize chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process, the solution after the saponification is turned back to the B step use as extraction agent;
D. the raffinate that the B step is obtained carries out cyclone electrolytic cell, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium.
Below by a specific embodiment the method is described in detail, as shown in Figure 2:
Step 201 is soaked nickel laterite with sulfuric acid;
The nickel laterite of the present invention's design is the nickel laterite that nickel content is told somebody what one's real intentions are, and wherein, the content of nickel is substantially at 1.5% mass ratio.
Sulfuric acid soaks nickel laterite, and chemical reaction mainly occurs, and the nickel ion in the nickel laterite and sulfate ion carry out chemical reaction, generates preferably vitriol of solvability.
To be preferably 1-10g/L, iron content be 0.1-3g/L, contain cobalt is 0.2-0.5g/L, contain aluminium is 0.3-0.6g/L, contain manganese is 1-2g/L for the content of nickel in the nickel laterite leaching solution after the reaction.Wherein the content metal that has certain requirements is comprised nickel, iron, cobalt, content is unfavorable for too greatly next step processing.
Step 202 is filtered the soak solution of step 201, removes impurity and obtains leach liquor;
Step 203 utilizes Wingdale that the leach liquor that step 202 obtains is carried out neutralization reaction;
Can remove sulfuric acid excessive in the leach liquor after the neutralization reaction, be preferably by the pH value and judge whether neutralization reaction has carried out.
Wherein, neutral temperature is selected from 70 ℃-90 ℃, and is such as 70 ℃, 75 ℃, 80 ℃, 85 ℃ or the scopes of any two values wherein, preferred, 75 ℃-85 ℃, the time that neutralizes under this temperature is generally at 1-3 hour, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or the scopes of any two values wherein, and preferred 1-2 hour, the endpoint pH of neutralization reaction is 4.0-5.5, such as: 4.0,4.5,5.0,5.5 or wherein any two scopes that are worth, preferred, 4.0-4.5.
Step 204 is mixed Acidic phosphates (C272) with kerosene, form extractant mixture;
When promoting that C272 makees extraction agent, with separating of water, C272 need to be mixed with kerosene;
Wherein, to account for the volume ratio of Acidic phosphates and kerosene mixed solution be 5%-15% to Acidic phosphates; Such as: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or wherein any two scopes that are worth, the preferred 8%-10% that gets.
Step 205 is easily carried out Centrifugical extraction as extraction agent after to neutralization with the mixture of Acidic phosphates and kerosene;
It is more thorough that Centrifugical extraction can carry out extraction, and effect of extracting is better, can save extraction agent simultaneously, simultaneously, in order to reach better effect of extracting, with the nickel in the leach liquor, and other metals extract respectively, be preferably and carry out multistage centrifugal extraction (being the multistage centrifugal extraction);
Isolate organic phase and water through behind the Centrifugical extraction, wherein contain other metallic impurity (one or more in cobalt, manganese, iron, the aluminium) in the organic phase, organic phase is called again extraction liquid, and aqueous phase contains nickel, and water is called again raffinate.
Step 206 is washed nickel to extraction liquid and is processed;
In order further to reclaim the nickel that organic phase participates in, can the nickel in the extraction liquid be washed, simultaneously, for better effects if, be preferably and carry out 2 grades and wash nickel (namely washing nickel twice);
The nickel that washes out is preferably and comes back to the treating in the extracting substance of Centrifugical extraction, as a part for the treatment of extracting substance.
Step 207 is carried out reverse extraction to washing in the extraction liquid behind the nickel;
Reverse extraction is back extraction, utilizes sulfuric acid with metal extraction out, and these metals comprise one or more in cobalt, manganese, iron, the aluminium, by this step can be with above-mentioned metal recovery;
Be preferably and carry out 3 grades of reverse extractions (i.e. 3 reverse extractions) in order to reach preferably effect;
Separate after the reverse extraction, reclaim above-mentioned metal, and other the solution of extraction liquid material that will isolate metal is further processed.
Step 208 is carried out organic regenerative to the isolated solution of step 207;
Organic regenerative is further to go out metallics in the solution, and this step, the main hydrochloric acid that adopts was processed, and the metal of mainly going out is iron;
In order to reach preferably effect, be preferably and carry out 2 grades of organic regenerative (i.e. 2 organic regenerative).
This step is extracted for further metallic impurity being carried out Separation and Recovery;
Material after the organic regenerative is separated, obtain further removing the solution of ferrous metal.
Saponification can be adopted NaOH to carry out saponification and process, and saponification degree is 35-50%, the scope between being worth such as 35%, 40%, 45%, 50% or any two, preferred, 40-45%.
In the saponification hydrogen ion is removed, sodium ion is introduced, get rid of Na after the saponification
2SO
4
Step 210 is with after the saponification and remove Na
2SO
4Solution be back to use in the step 205;
After the saponification and remove Na
2SO
4Solution be back to use in the step 205 usually and again use as extraction agent, recycle and extraction agent can be recycled by this step, thereby reduced the usage quantity of extraction agent.
Step 211 is carried out cyclone electrolytic cell to raffinate, extracts nickel;
This step is adopted cyclone electrolytic cell, can realize from the solution of the nickeliferous 10g/L of being lower than, and Direct Electrolysis deposition high-purity metal nickel product, thus shorten nickel laterite sulphuric leachate treatment scheme.
The current density of described electrolysis is 200-800A/m
2, such as 200A/m
2, 300A/m
2, 400A/m
2, 500A/m
2, 600A/m
2, 700A/m
2, 800A/m
2Or the scope between any two values, preferred 300-500A/m
2Electrolyte temperature is 45-85 ℃, such as, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or any two the value between scope, preferred 50-75 ℃, electrolyte ph is 2.0-5.5, such as, 2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5 or the scope between any two values, the preferred 2.5-3.5 that gets, in the situation of electrolysis 1Kg nickel, the raffinate circular flow is 200-600L/ hour, such as, 200L/ hour, 250L/ hour, 300L/ hour, 350L/ hour, 400L/ hour, 450L/ hour, 500L/ hour, 550L/ hour, 600L/ hour or any two the value between scope; Preferred, 300-400L/ hour.
Method of the present invention; the metallic nickel product purity of producing is high, technical process is succinct, be easy to accomplish scale production, production cost is low; can realize the processing of low levels nickel laterite sulphuric leachate high-efficiency cleaning, be one and taken into account simultaneously reliability, suitability and Eco-power advanced technologies.
The present invention is optimized currently used nickel laterite sulfuric acid leaching liquor treating process, adopt advanced centrifugal extracting process to replace traditional box extraction process, greatly reduce the consumption of extraction agent, improved simultaneously extraction efficiency, thereby reduced production cost.
The present invention can also have following operation: the nickel laterite sulphuric leachate adopts direct C272 extraction process, direct Extraction of Cobalt from the leach liquor that contains a large amount of impurity, and the cobalt strip liquor carries out sulfide precipitation and obtains the CoS concentrate, then produces the negative electrode cobalt by refining.Raffinate behind the extraction cobalt send nickel electrodeposition to produce cathode nickel with a kind of carboxylic acid extraction agent-Versaticl0 extraction of nickel, back extraction nickel sulfate solution.
The present invention also provides a kind of device that reclaims nickel from the nickel laterite leach liquor that utilizes aforesaid method, such as Fig. 3, shown in, comprising:
Neutralising arrangement be used for to adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
Centrifugal extraction apparatus is used for carrying out Centrifugical extraction more than the one-level with the neutralization solution that Acidic phosphates obtains the neutralization device, and the nickel in the described leach liquor is separated with metallic impurity;
The extraction liquid treatment unit is used for the extraction liquid that centrifugal extraction apparatus obtains is processed, and utilizes chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process;
Send-back device uses as extraction agent for the solution after the saponification of described extraction liquid treatment unit is transmitted back in the centrifugal extraction apparatus;
The raffinate treatment unit, the raffinate that is used for centrifugal extraction apparatus is obtained carries out electrolysis, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium.
Described neutralising arrangement is preferably and is provided with temperature measuring equipment, pH value metering facility;
Described temperature measuring equipment is preferably the temperature for the reaction solution of measuring neutralization reaction;
Described pH value metering facility is preferably for the pH value of measuring neutralization reaction.
Described device is preferably further and comprises: mixing equipment;
Described mixing equipment is preferably for mixing by Acidic phosphates and the kerosene of setting the volume ratio weighing;
Then,
Described mixing equipment is preferably by the extraction agent transport pipe and is connected with described centrifugal extraction apparatus, preferred, described centrifugal extraction apparatus is preferably and comprises the 3 cover centrifugal extraction equipments that link to each other successively.
Described extraction liquid treatment unit is preferably and comprises: what link to each other successively washes nickel treatment facility, reverse extraction treatment equipment, organic regenerative treatment facility, saponification treatment facility;
Wherein, the described nickel treatment facility of washing is preferably be used to the nickel of washing that carries out more than the one-level and processes, and utilizes chemical reaction that the nickel in the extraction liquid is further extracted; Described nickel outlet of washing the nickel treatment facility is connected with the nickel backpass ductwork, and described nickel backpass ductwork links to each other with described centrifugal extraction apparatus, is preferably for and turns back to described centrifugal extraction apparatus conduct from the nickel that described nickel outlet is discharged to treat that extracting substance uses; Preferred, the described nickel treatment facility of washing is preferably and comprises two covers and wash nickel and process subset;
Described reverse extraction treatment equipment is preferably be used to the reverse extraction treatment of carrying out more than the one-level, utilizes chemical reaction, by sulfuric acid the reverse extraction of metallic impurity is extracted, and the metallic impurity that reverse extraction is extracted are collected; Preferred, described reverse extraction treatment equipment is preferably and comprises the reverse extraction treatment subset that 3 covers link to each other successively;
Described organic regenerative treatment facility, be preferably be used to the organic regenerative of carrying out more than the one-level and process, utilize chemical reaction, by hydrochloric acid metallic impurity are extracted, its metal outlet links to each other with the metallic impurity collecting device by the metallic impurity recovery channel, and described metallic impurity collecting device is used for the metallic impurity that reclaim the organic regenerative extraction are collected; Preferred, described organic regenerative treatment facility is preferably the organic regenerative processing subset that comprises that 2 covers link to each other successively;
The saponification treatment facility is preferably for the extraction liquid of removing described nickel and described metallic impurity being carried out saponification and processes; The saponification solution outlet of described saponification treatment facility is preferably by the solution backpass ductwork and connects described centrifugal extraction apparatus, and described solution backpass ductwork is preferably for the solution after the saponification is turned back to described centrifugal extraction apparatus and uses as extraction agent.
The raffinate treatment unit is preferably and is provided with electrolytic solution temperature measuring equipment, current density operating device, electrolyte ph metering facility, raffinate flow operating device;
Wherein,
Described electrolytic solution temperature measuring equipment is preferably for the temperature of measuring electrolytic solution;
Described current density operating device is preferably for the control current density;
Described electrolyte ph metering facility is preferably for measuring electrolyte ph;
Described raffinate flow operating device is preferably for control raffinate flow.
A kind of method and apparatus from nickel laterite leaching solution recovery nickel can reach following beneficial effect:
1. reduce production costs.The present invention extracts nickel to the nickel laterite leach liquor of low levels nickel, wherein replace traditional box extraction process with advanced centrifugal extracting process, greatly reduced the consumption of extraction agent, simultaneously extraction liquid is processed, the recovery extraction agent also is back to use in the Centrifugical extraction process, has also greatly reduced the consumption of extraction agent, has improved extraction efficiency, reduce extraction system, reduced extraction agent one-level input amount and waste.And, adopt the cyclone electrolytic cell technology to replace traditional electrolysis tech, can be from the solution of lower concentration nickel the Direct Electrolysis high-purity metal nickel product of taking advantage of the occasion, thereby shortened nickel laterite sulphuric leachate treatment scheme, by above measure, reduced extraction agent consumption, shortened technical process, thereby greatly reduce production cost.
2. simplification of flowsheet is simplified treating processes.The present invention adopts the cyclone electrolytic cell technology to replace traditional electrolysis tech, can be from the solution of lower concentration nickel the Direct Electrolysis high-purity metal nickel product of taking advantage of the occasion, thereby shortened nickel laterite sulphuric leachate treatment scheme.And the metallic nickel product purity original text of producing, technical process simple, be easy to accomplish scale production, production cost is low; and the high-efficiency cleaning of having realized low levels nickel laterite sulphuric leachate in the process that extraction liquid is processed is processed, and technique is simple, simple to operate.
Various embodiment provided by the invention can be as required in any way mutually combination, the technical scheme that obtains by this combination, also within the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification to the present invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also comprises these changes and modification interior.
Claims (17)
1. a method that reclaims nickel from the nickel laterite leach liquor is characterized in that, comprising:
A. adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
B. the neutralization solution that with Acidic phosphates the A step is obtained carries out the Centrifugical extraction more than the one-level, and the nickel in the described leach liquor is separated with metallic impurity;
C. the extraction liquid that the B step is obtained is processed, utilize chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process, the solution after the saponification is turned back to the B step use as extraction agent;
D. the raffinate that the B step is obtained carries out cyclone electrolytic cell, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium;
The described extraction liquid that the B step is obtained is processed and is comprised:
A. the nickel of washing that one-level is above is processed, and utilizes chemical reaction that the nickel in the extraction liquid is further extracted, and the nickel that extracts is turned back in the B step as treating that extracting substance uses;
B. the above reverse extraction treatment of one-level is utilized chemical reaction, by sulfuric acid the reverse extraction of metallic impurity is extracted, and the metallic impurity that reverse extraction is extracted are collected;
C. the above organic regenerative of one-level is processed, and utilizes chemical reaction, by hydrochloric acid metallic impurity are extracted, and the metallic impurity that the recovery organic regenerative is extracted is collected.
2. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 1 is characterized in that,
In the described steps A and after the pH of solution be 4.0-5.5;
And/or,
Described steps A neutral temperature is 70 ℃-90 ℃;
And/or,
In the described steps A and the time be 1-3 hour.
3. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 2 is characterized in that,
In the described steps A and after the pH of solution be 4.0-4.5;
And/or,
Described steps A neutral temperature is 75 ℃-85 ℃;
And/or,
In the described steps A and the time be 1-2 hour.
4. the method that from the nickel laterite leach liquor, reclaims nickel as claimed in claim 1, it is characterized in that, before step B, described method further comprises: Acidic phosphates is dissolved in kerosene, and the volume ratio that Acidic phosphates accounts for Acidic phosphates and kerosene mixed solution is 5%-15%;
Then,
Among the step B, the Centrifugical extraction that the described neutralization solution that the A step is obtained with Acidic phosphates carries out more than the one-level further comprises: the neutralization solution that the A step is obtained with the mixed solution of Acidic phosphates and kerosene carries out the Centrifugical extraction more than the one-level.
5. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 4 is characterized in that the volume ratio that Acidic phosphates accounts for Acidic phosphates and kerosene mixed solution is 8%-10%.
6. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 4 is characterized in that, the neutralization solution that the A step is obtained with the mixed solution of Acidic phosphates and kerosene carries out 3 grades of Centrifugical extractions.
7. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 1 is characterized in that,
The described extraction liquid that the B step is obtained is processed and is comprised:
Two-stage is washed nickel and is processed;
3 grades of reverse extraction treatment;
2 grades of organic regenerative are processed;
And/or,
Described to the extraction liquid of removing described nickel and described metallic impurity carry out saponification process described in saponification process and comprise:
Carrying out saponification with NaOH processes; Saponification degree is 35-50%.
8. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 7 is characterized in that saponification degree is 40-45%.
9. such as each described method that from the nickel laterite leach liquor, reclaims nickel of claim 1-8, it is characterized in that in the described D step, the current density of described electrolysis is 200-800A/m
2, electrolyte temperature is that 45-85 ℃, electrolyte ph are 2.0-5.5, in the situation of electrolysis 1Kg nickel, the raffinate circular flow is 200-600L/ hour.
10. the method that reclaims nickel from the nickel laterite leach liquor as claimed in claim 9 is characterized in that the current density of described electrolysis is 300-500A/m
2, electrolyte temperature is that 50-75 ℃, electrolyte ph are 2.5-3.5, in the situation of electrolysis 1Kg nickel, the raffinate circular flow is 300-400L/ hour.
11. a device that reclaims nickel from the nickel laterite leach liquor that utilizes each described method of claim 1-10 is characterized in that, comprising:
Neutralising arrangement be used for to adopt Wingdale that the nickel laterite leach liquor is processed, utilize in the chemical reaction and described leach liquor in sulfuric acid;
Centrifugal extraction apparatus is used for carrying out Centrifugical extraction more than the one-level with the neutralization solution that Acidic phosphates obtains the neutralization device, and the nickel in the described leach liquor is separated with metallic impurity;
The extraction liquid treatment unit is used for the extraction liquid that centrifugal extraction apparatus obtains is processed, and utilizes chemical reaction further the nickel in the extraction liquid to be separated with metallic impurity, the extraction liquid of removing described nickel and described metallic impurity is carried out saponification process;
Send-back device uses as extraction agent for the solution after the saponification of described extraction liquid treatment unit is transmitted back in the centrifugal extraction apparatus;
The raffinate treatment unit, the raffinate that is used for centrifugal extraction apparatus is obtained carries out electrolysis, extracts nickel;
Wherein, nickel content is 1-10g/L in the described leach liquor, and/or iron level is 0.1-3g/L, and/or cobalt contents is 0.2-0.5g/L;
Metallic impurity comprise: one or more in iron, cobalt, manganese, the aluminium.
12. the device that reclaims nickel from the nickel laterite leach liquor as claimed in claim 11 is characterized in that,
Described neutralising arrangement is provided with temperature measuring equipment, pH value metering facility;
Described temperature measuring equipment is for the temperature of the reaction solution of measuring neutralization reaction;
Described pH value metering facility is for the pH value of measuring neutralization reaction.
13. the device that reclaims nickel from the nickel laterite leach liquor as claimed in claim 11 is characterized in that,
Described device further comprises: mixing equipment;
Described mixing equipment is used for and will mixes by Acidic phosphates and the kerosene of setting the volume ratio weighing;
Then,
Described mixing equipment is connected with described centrifugal extraction apparatus by the extraction agent transport pipe.
14. the device that reclaims nickel from the nickel laterite leach liquor as claimed in claim 13 is characterized in that, described centrifugal extraction apparatus comprises the 3 cover centrifugal extraction equipments that link to each other successively.
15. the device that reclaims nickel from the nickel laterite leach liquor as claimed in claim 11 is characterized in that,
Described extraction liquid treatment unit comprises: what link to each other successively washes nickel treatment facility, reverse extraction treatment equipment, organic regenerative treatment facility, saponification treatment facility;
Wherein, the described nickel treatment facility of washing is used for carrying out the above nickel of washing of one-level and processes, and utilizes chemical reaction that the nickel in the extraction liquid is further extracted; Described nickel outlet of washing the nickel treatment facility is connected with the nickel backpass ductwork, and described nickel backpass ductwork links to each other with described centrifugal extraction apparatus, is used for turning back to from the nickel that described nickel outlet is discharged described centrifugal extraction apparatus as treating that extracting substance uses;
Described reverse extraction treatment equipment is used for carrying out the above reverse extraction treatment of one-level, utilizes chemical reaction, by sulfuric acid the reverse extraction of metallic impurity is extracted, and the metallic impurity that reverse extraction is extracted are collected;
Described organic regenerative treatment facility, being used for carrying out the above organic regenerative of one-level processes, utilize chemical reaction, by hydrochloric acid metallic impurity are extracted, its metal outlet links to each other with the metallic impurity collecting device by the metallic impurity recovery channel, and described metallic impurity collecting device is used for the metallic impurity that reclaim the organic regenerative extraction are collected;
The saponification treatment facility is used for that the extraction liquid of removing described nickel and described metallic impurity is carried out saponification and processes; The saponification solution outlet of described saponification treatment facility connects described centrifugal extraction apparatus by the solution backpass ductwork, and described solution backpass ductwork is used for that the solution after the saponification is turned back to described centrifugal extraction apparatus to be used as extraction agent.
16. the device that reclaims nickel from the nickel laterite leach liquor as claimed in claim 15 is characterized in that,
The described nickel treatment facility of washing comprises two covers and washes nickel and process subset;
Described reverse extraction treatment equipment comprises the reverse extraction treatment subset of 3 covers;
Described organic regenerative treatment facility comprises 2 cover organic regenerative processing subsets.
17. such as each described device that from the nickel laterite leach liquor, reclaims nickel of claim 11-16, it is characterized in that,
The raffinate treatment unit is provided with electrolytic solution temperature measuring equipment, current density operating device, electrolyte ph metering facility, raffinate flow operating device;
Wherein,
Described electrolytic solution temperature measuring equipment is for the temperature of measuring electrolytic solution;
Described current density operating device is used for the control current density;
Described electrolyte ph metering facility is used for measuring electrolyte ph;
Described raffinate flow operating device is used for control raffinate flow.
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| CN105734610B (en) * | 2016-03-29 | 2017-12-01 | 中南大学 | The cleaning procedure that a kind of whartonite slag increment utilizes |
| CN106893859B (en) * | 2017-02-24 | 2018-08-14 | 中南大学 | A method of processing nickel cobalt waste material |
| CN107385220A (en) * | 2017-08-04 | 2017-11-24 | 俞振元 | A kind of method of the reclaiming high purity nickel from waste nickel catalyst |
| CN107641816B (en) * | 2017-08-07 | 2020-01-24 | 凯莱英医药集团（天津）股份有限公司 | Continuous electrochemical reaction device and method for continuously oxidizing thioether substrate into sulfone |
| CN114686698B (en) * | 2020-12-30 | 2023-10-13 | 北京博萃循环科技有限公司 | Treatment method of laterite nickel ore |
| CN113061748B (en) * | 2021-03-12 | 2022-07-12 | 中国恩菲工程技术有限公司 | Laterite nickel ore leaching liquid treatment system and method |
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| CN1995414A (en) * | 2006-12-20 | 2007-07-11 | 潘继红 | Vitriol intensified leach extraction method for nickel oxide ore |
| CN101338375A (en) * | 2008-08-15 | 2009-01-07 | 中南大学 | Technological process for extracting nickel and cobalt and comprehensively developing iron and magnesium from laterite-nickel ore |
| CN101532094A (en) * | 2008-03-11 | 2009-09-16 | 江西稀有稀土金属钨业集团有限公司 | Technology for full-process extracting and separating nickel and cobalt from acid material system with high content of calcium and magnesium impurities |
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| US20090056501A1 (en) * | 2007-08-29 | 2009-03-05 | Vale Inco Limited | Hydrometallurgical process using resin-neutralized-solution of a heap leaching effluent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1995414A (en) * | 2006-12-20 | 2007-07-11 | 潘继红 | Vitriol intensified leach extraction method for nickel oxide ore |
| CN101532094A (en) * | 2008-03-11 | 2009-09-16 | 江西稀有稀土金属钨业集团有限公司 | Technology for full-process extracting and separating nickel and cobalt from acid material system with high content of calcium and magnesium impurities |
| CN101338375A (en) * | 2008-08-15 | 2009-01-07 | 中南大学 | Technological process for extracting nickel and cobalt and comprehensively developing iron and magnesium from laterite-nickel ore |
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