CN107400788B - Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy - Google Patents
Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy Download PDFInfo
- Publication number
- CN107400788B CN107400788B CN201710587122.9A CN201710587122A CN107400788B CN 107400788 B CN107400788 B CN 107400788B CN 201710587122 A CN201710587122 A CN 201710587122A CN 107400788 B CN107400788 B CN 107400788B
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- precipitation
- underflow
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for precipitating nickel and cobalt in the hydrometallurgy of laterite-nickel ore. The method comprises the following steps: the method comprises the following steps of firstly, carrying out acid leaching on laterite-nickel ore to obtain nickel-cobalt-containing acid leaching solution, wherein the nickel-cobalt-containing acid leaching solution contains magnesium ions; performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part; step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as at least part of precipitator; and carrying out calcium-nickel separation on the second part of the nickel-cobalt deposit underflow to obtain the nickel-cobalt hydroxide. In the method, the precipitation performance of the nickel cobalt hydroxide is better, the thickening separation speed is favorably improved, the solid content of the thickened underflow is improved, and the water content of the nickel cobalt hydroxide product is reduced.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for precipitating nickel and cobalt in the hydrometallurgy of laterite nickel ore.
Background
Currently, the precipitation of nickel and cobalt in the hydrometallurgical process of laterite nickel ores generally comprises the following steps: firstly, carrying out acid leaching on laterite-nickel ore; then, precipitating nickel and cobalt in the acid leaching solution by using sodium hydroxide as a precipitator to form nickel and cobalt precipitation solution; and then carrying out thickening treatment on the nickel cobalt precipitation solution to obtain nickel hydroxide cobalt precipitate (nickel hydroxide and cobalt hydroxide).
However, when sodium hydroxide is used as a precipitant, on one hand, the cost is high, and on the other hand, due to strong alkalinity, local over-alkali is easily formed in feeding in the industrial practical operation process, so that the precipitation particle size is small, the sedimentation energy is poor, the separation speed in the concentration separation process is slow, the concentration of the concentration underflow is low, and the later separation is not facilitated. In addition, sodium hydroxide is adopted as a precipitator, and the obtained nickel cobalt hydroxide filter cake has high water content and is not beneficial to subsequent treatment.
Disclosure of Invention
The invention mainly aims to provide a method for precipitating nickel and cobalt in the laterite-nickel ore hydrometallurgy, and aims to solve the problems of high cost, poor precipitation effect and overhigh water content of a filter cake in the process of precipitating the nickel and cobalt in the laterite-nickel ore hydrometallurgy in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for precipitating nickel and cobalt in the hydrometallurgical process of lateritic nickel ores, comprising the steps of: the method comprises the following steps of firstly, carrying out acid leaching on laterite-nickel ore to obtain nickel-cobalt-containing acid leaching solution, wherein the nickel-cobalt-containing acid leaching solution contains magnesium ions; performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, and dividing the nickel and cobalt precipitation underflow into a first part and a second part; step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as at least part of precipitator; and carrying out calcium-nickel separation on the second part of the nickel-cobalt deposit underflow to obtain the nickel-cobalt hydroxide.
Further, the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of the nickel-cobalt-deposited underflow is 2-4: 1.
Furthermore, the concentration of the lime milk is 5-20 wt%.
Further, in the process of mixing the first part of the nickel and cobalt precipitation underflow with lime milk, the mixing time is 1-10 min.
Further, in the fourth step, in the process of returning the mixed ore pulp to the second step as at least part of the precipitator, the seed crystal ratio calculated by nickel hydroxide cobalt is 2-7: 1, and preferably 3-5: 1.
Furthermore, in the precipitation reaction process, the reaction temperature is 40-70 ℃, and the reaction time is 1.0-5.0 h.
Further, after the step of acid leaching the laterite-nickel ore, the step one also comprises the step of removing iron and aluminum from the nickel-cobalt-containing acid leaching solution.
Further, in the fourth step, the step of subjecting the second part of the nickel-cobalt-deposited underflow to calcium-nickel separation comprises: grading the second part of the nickel-cobalt bottom flow by using grading equipment to obtain calcium-containing slurry and nickel hydroxide cobalt slurry; and filtering the nickel cobalt hydroxide slurry to obtain the nickel cobalt hydroxide.
Further, in the first step, acid leaching is carried out on the laterite-nickel ore by adopting sulfuric acid; preferably, in the fourth step, after the calcium-containing slurry is obtained, the method further comprises the step of filtering the calcium-containing slurry to obtain gypsum.
Further, the classification equipment is a vibrating screen, a hydrocyclone, a shaker or a hydraulic separation column.
The technical scheme of the invention provides a method for precipitating nickel and cobalt in the laterite-nickel ore hydrometallurgy. The method comprises the following steps: the method comprises the following steps of firstly, carrying out acid leaching on laterite-nickel ore to obtain nickel-cobalt-containing acid leaching solution, wherein the nickel-cobalt-containing acid leaching solution contains magnesium ions; performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part; step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as at least part of precipitator; and carrying out calcium-nickel separation on the second part of the nickel-cobalt deposit underflow to obtain the nickel-cobalt hydroxide.
In the method provided by the invention, the nickel and cobalt precipitation solution is subjected to dense separation to obtain a nickel and cobalt precipitation underflow, and the mixed ore pulp of part of the nickel and cobalt precipitation underflow and lime milk is returned to the previous precipitation reaction to be used as at least part of precipitator of the fresh nickel and cobalt-containing pickle liquor to participate in the precipitation reaction. The pickle liquor of the lateritic nickel ore usually contains magnesium ions, wherein part of the magnesium ions can enter the underflow of nickel cobalt by nickel cobalt precipitation along with concentration separation. When partial nickel and cobalt precipitation underflow is mixed with lime milk, magnesium ions react with the lime milk to generate magnesium hydroxide with weaker alkalinity, and the returned mixed ore pulp contains the magnesium hydroxide and the previously generated nickel and cobalt hydroxide. When the magnesium hydroxide is used as at least part of precipitator to participate in the precipitation reaction of fresh nickel-cobalt-containing pickle liquor, on one hand, the hydration degree of newly generated nickel-cobalt hydroxide can be reduced due to weak basicity of the magnesium hydroxide; on the other hand, the nickel hydroxide cobalt added together can also be used as a seed crystal to promote the growth of newly generated nickel hydroxide cobalt and improve the particle size of the nickel hydroxide cobalt. The two reasons can obviously improve the sedimentation performance of the nickel cobalt precipitation solution, so that the nickel cobalt precipitation solution has higher separation speed in the thickening treatment process, and the concentration of the nickel cobalt precipitation underflow is higher, thereby being beneficial to the subsequent treatment. And finally, separating the nickel hydroxide cobalt in the nickel cobalt precipitation underflow through calcium-nickel separation to obtain the nickel hydroxide cobalt. Meanwhile, the hydration degree of the nickel cobalt hydroxide is reduced, so that the moisture content of the finally obtained nickel cobalt hydroxide is reduced, the subsequent treatment is facilitated, the cost of the lime milk is low, and the precipitation cost of the nickel cobalt can be greatly saved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background section, the problems of high cost, poor precipitation effect and excessive water content of filter cakes exist in the prior art when nickel and cobalt are precipitated in the laterite nickel ore hydrometallurgy.
In order to solve the problem, the invention provides a method for precipitating nickel and cobalt in the hydrometallurgy of laterite-nickel ore, which comprises the following steps: the method comprises the following steps of firstly, carrying out acid leaching on laterite-nickel ore to obtain nickel-cobalt-containing acid leaching solution, wherein the nickel-cobalt-containing acid leaching solution contains magnesium ions; performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part; step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as at least part of precipitator; and carrying out calcium-nickel separation on the second part of the nickel-cobalt deposit underflow to obtain the nickel-cobalt hydroxide.
In the method provided by the invention, the nickel and cobalt precipitation solution is subjected to dense separation to obtain a nickel and cobalt precipitation underflow, and the mixed ore pulp of part of the nickel and cobalt precipitation underflow and lime milk is returned to the previous precipitation reaction to be used as at least part of precipitator of the fresh nickel and cobalt-containing pickle liquor to participate in the precipitation reaction. The pickle liquor of the lateritic nickel ore usually contains magnesium ions, wherein part of the magnesium ions can enter the underflow of nickel cobalt by nickel cobalt precipitation along with concentration separation. When partial nickel and cobalt precipitation underflow is mixed with lime milk, magnesium ions react with the lime milk to generate magnesium hydroxide with weaker alkalinity, and the returned mixed ore pulp contains the magnesium hydroxide and the previously generated nickel and cobalt hydroxide. When the magnesium hydroxide is used as at least part of precipitator to participate in the precipitation reaction of fresh nickel-cobalt-containing pickle liquor, on one hand, the hydration degree of newly generated nickel-cobalt hydroxide can be reduced due to weak basicity of the magnesium hydroxide; on the other hand, the nickel hydroxide cobalt added together can also be used as a seed crystal to promote the growth of newly generated nickel hydroxide cobalt and improve the particle size of the nickel hydroxide cobalt. The two reasons can obviously improve the sedimentation performance of the nickel cobalt precipitation solution, so that the nickel cobalt precipitation solution has higher separation speed in the thickening treatment process, and the concentration of the nickel cobalt precipitation underflow is higher, thereby being beneficial to the subsequent treatment. And finally, separating the nickel hydroxide cobalt in the nickel cobalt precipitation underflow through calcium-nickel separation to obtain the nickel hydroxide cobalt. Meanwhile, the hydration degree of the nickel cobalt hydroxide is reduced, so that the moisture content of the finally obtained nickel cobalt hydroxide is reduced, the subsequent treatment is facilitated, the cost of the lime milk is low, and the precipitation cost of the nickel cobalt can be greatly saved.
It should be noted that the above-mentioned method treatment in the present invention is continuously performed, the nickel-cobalt-containing acid leaching solution is continuously supplemented into the precipitation reaction system, and after a part of the concentrated nickel-cobalt-containing underflow is subsequently mixed with lime milk, the formed mixed ore pulp also continuously participates in the precipitation reaction of the fresh nickel-cobalt-containing acid leaching solution as at least a part of fresh precipitator. As mentioned above, magnesium ions are continuously circulated in the process, magnesium ions are continuously formed in the precipitation reaction, and part of magnesium ions are introduced into the reaction system along with the fresh nickel-cobalt-containing pickle liquor. And a part of magnesium ions reacts with lime milk along with the underflow of nickel and cobalt precipitation to generate magnesium hydroxide, and the magnesium hydroxide participates in the precipitation reaction of fresh nickel and cobalt-containing pickle liquor again.
It should be noted that the above nickel cobalt hydroxide is a general term for nickel hydroxide and cobalt hydroxide, and the pH of the nickel cobalt precipitate is almost the same and is generally recovered at the same time, so the industry refers to this intermediate product as nickel cobalt hydroxide.
In addition, compared with the scheme of directly adding lime milk in the precipitation reaction process, partial precipitated nickel and cobalt underflow is mixed with the lime milk and then is added into the precipitation reaction system together. Therefore, on one hand, sufficient time can be provided for the generation of the magnesium hydroxide, on the other hand, the magnesium hydroxide and the nickel hydroxide cobalt carried in the nickel cobalt underflow are used as a precipitator together, and compared with the method of directly adding lime milk, the method has the advantages of better precipitation effect, better precipitation performance of the nickel hydroxide cobalt and lower water content. In addition, the method effectively utilizes magnesium ions in the laterite-nickel ore pickle liquor, and reduces the reaction cost.
According to the analysis of the invention, the amount of lime milk added can be adjusted. In a preferred embodiment, the molar ratio of hydroxide ions in the milk of lime to magnesium ions in the first portion of the nickel cobalt precipitate underflow is 2 to 4: 1. Under the condition, the magnesium ions used for returning can be more thoroughly converted into magnesium hydroxide, so that the precipitation effect in the precipitation reaction can be further improved, and the precipitation capacity of the nickel cobalt hydroxide is improved. More preferably, the concentration of the lime milk is 5-20 wt%. Under the concentration, the lime milk and the magnesium ions can be more fully reacted, and the phenomenon that excessive water is introduced to reduce the efficiency of concentration separation can be avoided. More preferably, in the process of mixing the first part of nickel-cobalt-precipitating underflow with lime milk, the mixing time is 1-10 min. Thus, the reaction degree of magnesium ions and lime milk can be further improved, and higher treatment speed is ensured.
In a preferred embodiment, in the fourth step, in the process of returning the mixed ore pulp to the second step as at least part of the precipitator, the seed crystal ratio calculated by nickel cobalt hydroxide is 2-7: 1, preferably 3-5: 1. The "seed ratio" herein refers to the weight ratio between the nickel hydroxide cobalt in the returned mixed slurry and the newly formed nickel hydroxide cobalt in the precipitation reaction, calculated as nickel hydroxide cobalt. The seed crystal ratio is controlled within the range, the particle size of nickel hydroxide cobalt precipitate formed in the precipitation reaction process is larger, and the sedimentation performance is better. In the actual production process, the lime milk is added into the nickel and cobalt precipitation underflow, not mixed with all the nickel and cobalt precipitation underflow, but mixed with part of the nickel and cobalt precipitation underflow. The volume of the partial underflow is set according to the seed crystal ratio, if the seed crystal ratio of 5:1 is needed, the solid amount of the underflow needs to be 5 times of the amount of the generated nickel cobalt hydroxide, and then the partial underflow can be known according to the concentration proportion of the ore pulp. In the process, because the total amount of magnesium hydroxide in the precipitator and nickel cobalt hydroxide which can be generated by reaction have a corresponding relation in the prior reaction, magnesium ions in the underflow and the nickel cobalt hydroxide also have a corresponding relation, the control of the seed crystal ratio is also equivalent to the control of the content of the magnesium ions in the first part of the underflow, the guarantee that the content of the magnesium returned to the liquid crystal phase is not lower than the content of the magnesium required for precipitating the nickel cobalt hydroxide is ensured, and then the use amount of lime milk is determined according to the content of the nickel cobalt ions to be precipitated, so that the magnesium ions are converted into the magnesium hydroxide to be returned to participate in the.
More preferably, in the precipitation reaction process, the reaction temperature is 40-70 ℃, and the reaction time is 1.0-5.0 h. The temperature and time of the precipitation reaction are controlled within the above ranges, and the precipitation degree of nickel cobalt ions is higher.
In a preferred embodiment, after the step of acid leaching the lateritic nickel ore, the step one further comprises the step of removing iron and aluminum from the nickel-cobalt-containing acid leaching solution. Before the precipitation reaction is carried out, iron and aluminum impurities in the pickle liquor are removed, so that the separation purity of nickel and cobalt can be further improved. The specific means of removing the aluminum iron can be in a manner common to those skilled in the art, and is preferred. And (3) carrying out iron and aluminum removal on the nickel-cobalt-containing pickle liquor by using limestone.
In a preferred embodiment, in step four, the step of subjecting the second portion of the nickel-cobalt-precipitated underflow to calcium-nickel separation comprises: grading the second part of the nickel-cobalt bottom flow by using grading equipment to obtain calcium-containing slurry and nickel hydroxide cobalt slurry; and filtering the nickel cobalt hydroxide slurry to obtain the nickel cobalt hydroxide. More preferably, in the step one, the laterite-nickel ore is subjected to acid leaching by using sulfuric acid; in the fourth step, after the calcium-containing slurry is obtained, the method further comprises the step of filtering the calcium-containing slurry to obtain gypsum. At this time, during the precipitation reaction, calcium ions and sulfate ions in the pickle liquor are reflected to form a slightly soluble calcium sulfate. Because the particle sizes of the calcium sulfate and the nickel cobalt hydroxide are obviously different, and the particle size of the calcium sulfate is far larger than that of the nickel cobalt hydroxide, the sedimentation speed of the calcium sulfate is obviously different from that of the nickel cobalt hydroxide, the calcium sulfate and the nickel cobalt hydroxide are easily separated by adopting grading equipment, and then the gypsum and the nickel cobalt hydroxide can be obtained by filtering respectively. Preferably, the classification apparatus includes, but is not limited to, a vibrating screen, a hydrocyclone, a shaker, a hydrocyclone column, or the like.
The beneficial effects of the present invention are further illustrated by the following examples:
example 1
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 16%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 10 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitated underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 5: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
The water content of the nickel hydroxide cobalt product is 56 percent through detection.
Example 2
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 12%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 10 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitated underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 3: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 58%.
Example 3
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 8%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 10 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitated underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 2: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 68%.
Example 4
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 18%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 10 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitated underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 7: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 55%.
Example 5
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 10%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of lime milk is 5 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitated underflow is 4: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 1min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 5: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 58%.
Example 6
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 12%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 20 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of the nickel-cobalt bottom flow is 3: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 10min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 3: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 60%.
Example 7
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 70 ℃, and the precipitation time is 1 h;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 15%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 8 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitation underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 5: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
The detection shows that the water content of the nickel hydroxide cobalt product is 62%.
Example 8
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 40 ℃, and the precipitation time is 5 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 13%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 7 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of nickel-cobalt-precipitation underflow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 5: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 63%.
Example 9
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 30 ℃, and the precipitation time is 0.8 h;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 7%; and the underflow of the nickel and cobalt deposition is divided into a first part and a second part;
step four, mixing the first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to be used as all precipitants; in the process, the concentration of the lime milk is 4 wt%, and the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first part of the nickel-cobalt bottom flow is 2: 1. The time for mixing the nickel cobalt bottom flow and the lime milk is 3min, and after the mixed ore pulp returns, the seed crystal ratio counted by nickel cobalt hydroxide in the precipitation reaction process is 5: 1. And screening the second part of the nickel and cobalt deposit underflow (mixed ore pulp of nickel hydroxide cobalt and gypsum) by using a vibrating screen to complete calcium and nickel separation, and then respectively filtering to obtain gypsum and nickel and cobalt hydroxide products.
Through detection, the water content of the nickel hydroxide cobalt product is 68%.
Comparative example 1
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and precipitator sodium hydroxide in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 5%;
and step four, filtering the nickel and cobalt bottom flow to obtain a nickel and cobalt hydroxide product.
Through detection, the water content of the nickel hydroxide cobalt product is 75%.
Comparative example 2
Firstly, acid leaching is carried out on laterite-nickel sulfate ore to obtain nickel-cobalt-containing acid leaching solution, and limestone is used for removing iron and aluminum; 3.5g/L of nickel and 0.3g/L of cobalt are contained in the nickel-cobalt-containing acid leaching solution after iron and aluminum are removed;
secondly, carrying out precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and precipitator lime milk in the precipitation reaction process to obtain nickel-cobalt precipitation solution; the precipitation temperature in the process is 65 ℃, and the precipitation time is 2 hours;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, wherein the solid content of the nickel and cobalt precipitation underflow is 6%;
and step four, filtering the nickel and cobalt bottom flow to obtain a nickel and cobalt hydroxide product.
The detection shows that the water content of the nickel hydroxide cobalt product is 73%.
In addition, in the production process, in the above examples 1 to 9, the sedimentation velocity in the process of thickening to obtain the nickel cobalt precipitate underflow is much higher than that in the thickening in comparative examples 1 and 2.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the method of the invention can obviously improve the sedimentation performance of the nickel cobalt precipitation solution, so that the nickel cobalt precipitation solution can be separated out more quickly in the thickening treatment process, and the obtained thickening underflow has higher solid content, thereby being beneficial to the subsequent recovery of nickel cobalt hydroxide. Meanwhile, the hydration degree of the nickel hydroxide cobalt is reduced, so that the moisture content of the finally obtained nickel hydroxide cobalt is reduced, and the subsequent treatment is facilitated. And the lime milk has lower cost, and can greatly save the precipitation cost of nickel and cobalt.
Specifically, compared with the mode of directly adding lime milk in the precipitation reaction stage in the comparative example 2 and the mode of adopting sodium hydroxide as a precipitator in the comparative example 1, the method has the advantages that the lime milk is mixed with part of the dense underflow and then added as the precipitator, the precipitation performance of the nickel hydroxide cobalt can be further improved, the solid content of the dense underflow obtained in the continuous production is higher, and the water content of the final product of the nickel hydroxide cobalt is lower; more particularly, in examples 1 to 8, the concentration of lime milk, the seed crystal ratio of the mixed slurry, the reaction temperature, the mixing time, and the like were controlled within the preferable ranges, and the settling ability of nickel hydroxide cobalt formed in the precipitation stage of nickel hydroxide cobalt could be further improved, so that the nickel hydroxide cobalt could be more sufficiently separated in the thickening treatment stage.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy is characterized by comprising the following steps:
step one, carrying out acid leaching on the laterite-nickel ore to obtain nickel-cobalt-containing acid leaching solution, wherein the nickel-cobalt-containing acid leaching solution contains magnesium ions;
performing precipitation reaction on the nickel-cobalt-containing acid leaching solution, and continuously adding fresh nickel-cobalt-containing acid leaching solution and a precipitator in the precipitation reaction process to obtain nickel-cobalt precipitation solution;
carrying out dense separation on the nickel and cobalt precipitation solution to obtain a nickel and cobalt precipitation underflow, and dividing the nickel and cobalt precipitation underflow into a first part and a second part;
step four, mixing a first part of the nickel and cobalt precipitation underflow with lime milk to form mixed ore pulp, and returning the mixed ore pulp to the step two to serve as at least part of the precipitator; carrying out calcium-nickel separation on the second part of the nickel-cobalt-deposited underflow to obtain nickel hydroxide cobalt; wherein the molar ratio of hydroxide ions in the lime milk to magnesium ions in the first portion of the nickel cobalt precipitation underflow is 2-4: 1, and the seed crystal ratio in terms of nickel cobalt hydroxide is 3-5: 1 in the process of returning the mixed ore pulp to the second step as at least a portion of the precipitant;
in the fourth step, the step of performing calcium-nickel separation on the second part of the nickel-cobalt deposit underflow comprises: grading the second part of the nickel and cobalt precipitation underflow by using grading equipment to obtain calcium-containing slurry and nickel and cobalt hydroxide slurry; filtering the nickel cobalt hydroxide slurry to obtain the nickel cobalt hydroxide;
in the first step, the laterite-nickel ore is subjected to acid leaching by adopting sulfuric acid.
2. A method according to claim 1, characterized in that the concentration of the milk of lime is 5-20 wt%.
3. The method according to claim 2, wherein in the process of mixing the first part of the nickel-cobalt-precipitating underflow with the lime milk, the mixing time is 1-10 min.
4. The method according to any one of claims 1 to 3, wherein the precipitation reaction is carried out at a reaction temperature of 40 to 70 ℃ for 1.0 to 5.0 hours.
5. The method according to any one of the claims 1 to 3, characterized in that after the step of acid leaching the lateritic nickel ore, the step one further comprises the step of removing iron and aluminium from the nickel cobalt containing acid leach solution.
6. A method according to any one of claims 1 to 3, wherein in step four, after obtaining the calcium-containing slurry, further comprising the step of filtering the calcium-containing slurry to obtain gypsum.
7. A method according to any one of claims 1 to 3, wherein the classification apparatus is a vibrating screen, a hydrocyclone, a shaker or a hydrocyclone column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710587122.9A CN107400788B (en) | 2017-07-18 | 2017-07-18 | Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710587122.9A CN107400788B (en) | 2017-07-18 | 2017-07-18 | Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107400788A CN107400788A (en) | 2017-11-28 |
| CN107400788B true CN107400788B (en) | 2020-05-22 |
Family
ID=60402134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710587122.9A Active CN107400788B (en) | 2017-07-18 | 2017-07-18 | Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107400788B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467951A (en) * | 2018-02-22 | 2018-08-31 | 中国恩菲工程技术有限公司 | The method of concentrating cobalt and nickel from nickeliferous cobalt liquor |
| CN108374089A (en) * | 2018-02-22 | 2018-08-07 | 中国恩菲工程技术有限公司 | The method of concentrating cobalt and nickel from nickeliferous cobalt liquor |
| CN108998682A (en) * | 2018-07-11 | 2018-12-14 | 中铁资源集团有限公司 | A method of the Call Provision from cobalt sulfate solution |
| CN108913883B (en) * | 2018-09-07 | 2020-07-14 | 中国恩菲工程技术有限公司 | Method for producing nickel cobalt hydroxide by laterite-nickel ore hydrometallurgy |
| AU2020239801B2 (en) * | 2019-10-28 | 2022-06-16 | China Enfi Engineering Corporation | Method for treating metal-containing solution |
| CN110714128B (en) * | 2019-10-28 | 2022-02-18 | 中国恩菲工程技术有限公司 | Method for treating cobalt precipitation solution |
| CN110747353B (en) * | 2019-10-28 | 2022-02-18 | 中国恩菲工程技术有限公司 | Method for treating nickel deposition solution |
| CN111020187A (en) * | 2019-12-10 | 2020-04-17 | 广东邦普循环科技有限公司 | Method for preparing nickel hydroxide |
| CN114427037B (en) * | 2022-01-06 | 2023-09-29 | 中国恩菲工程技术有限公司 | Method for continuously enriching nickel and cobalt from low-concentration nickel and cobalt solution |
| CN114854987B (en) * | 2022-07-11 | 2022-09-20 | 中国恩菲工程技术有限公司 | Nickel-cobalt precipitation method for removing iron-aluminum solution by acid leaching of laterite-nickel ore |
| CN117120642A (en) * | 2023-06-30 | 2023-11-24 | 青美邦新能源材料有限公司 | Method for continuously preparing cobalt nickel hydroxide by hydrometallurgy of laterite nickel ore |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPO837197A0 (en) * | 1997-08-01 | 1997-08-28 | Centaur Mining & Exploration Limited | Selective precipitation of nickel and cobalt |
| ZA987217B (en) * | 1997-08-15 | 2000-02-14 | Cominco Eng Services | Chloride assisted hydrometallurgical extraction of metal from sulphide or laterite ores. |
| CN103074493A (en) * | 2013-02-20 | 2013-05-01 | 广西银亿科技矿冶有限公司 | Application of brucite to recovery of nickel cobalt |
| CN106566934B (en) * | 2016-10-28 | 2019-02-01 | 中国恩菲工程技术有限公司 | Method of the processing except liquid after iron aluminium |
| CN106834741B (en) * | 2017-01-03 | 2019-07-12 | 中国恩菲工程技术有限公司 | The method for handling liquid after sinking nickel cobalt |
-
2017
- 2017-07-18 CN CN201710587122.9A patent/CN107400788B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107400788A (en) | 2017-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107400788B (en) | Method for precipitating nickel and cobalt in laterite-nickel ore hydrometallurgy | |
| CN108913883B (en) | Method for producing nickel cobalt hydroxide by laterite-nickel ore hydrometallurgy | |
| CN105349803B (en) | A kind of method from the phosphotungstic acid containing molybdenum/phosphotungstate solution separation tungsten | |
| CN101921001B (en) | Technology for preparing cobalt hydroxide from cobaltous sulfate solution | |
| WO2014203661A1 (en) | Hematite manufacturing method and hematite manufactured by same | |
| EP3112481B1 (en) | Method for producing hematite for iron production | |
| CN103993174B (en) | The method of mixed base coprecipitated nickel hydroxide | |
| JP2022502564A (en) | Methods for Preparing High Purity Hydrated Nickel Sulfate | |
| US2899300A (en) | Method for extracting nickel from | |
| CN101760614B (en) | Leaching method of nickel-containing ore | |
| CN106629806A (en) | Method for producing dihydrate gypsum from waste liquid in laterite nickel ore wet process | |
| CN103787396A (en) | Method for preparing high-purity potassium alum and aluminum sulfate from alunite ore | |
| CN104862503A (en) | Method for extracting scandium from nickel laterite ore | |
| CN114959302B (en) | Method for preparing nickel/cobalt sulfate by using laterite-nickel ore | |
| TWI513826B (en) | The Manufacturing Method of Hematite for Ironmaking | |
| CN106566934B (en) | Method of the processing except liquid after iron aluminium | |
| CN114314540A (en) | Method for producing magnesium hydrogen phosphate by using phosphate tailings | |
| CN108893611B (en) | Method for extracting molybdenum from molybdenum-removing slag to prepare sodium molybdate | |
| CN110714128B (en) | Method for treating cobalt precipitation solution | |
| CN110759526A (en) | Method for treating copper-containing waste liquid | |
| CN110747353B (en) | Method for treating nickel deposition solution | |
| CN115594208B (en) | Method for synchronously removing sulfur, iron and silicon in sodium aluminate solution through controllable oxidation | |
| RU2352658C2 (en) | Method of receiving lithium-bearing alumina from spodumene concentrate | |
| EP3816109B1 (en) | Method for treating metal-containing solution | |
| CN111471863B (en) | Method for step-by-step alkaline precipitation of nickel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |