CN113789443A - Resin adsorption method for nickel and cobalt in laterite-nickel ore - Google Patents
Resin adsorption method for nickel and cobalt in laterite-nickel ore Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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Abstract
The invention provides a resin adsorption method for nickel and cobalt in laterite-nickel ore, which comprises the following steps: step S1, carrying out acid leaching, neutralization and iron and aluminum removal and solid-liquid separation on the laterite-nickel ore in sequence to obtain pretreated ore pulp; step S2, carrying out nickel-cobalt adsorption on the pretreated ore pulp by using IDA chelating resin to obtain adsorption resin; step S3, desorbing the adsorption resin by using an acidic solution to obtain desorbed resin and a nickel-cobalt desorption solution; and step S4, performing saponification transformation on the desorption resin by using a sodium hydroxide aqueous solution or lime milk as a saponifying agent to obtain saponified resin, and returning to the step S2 for nickel-cobalt adsorption. The invention effectively improves the adsorption performance of the desorption resin on nickel and cobalt, so that the desorption resin can be circularly adsorbed for many times.
Description
Technical Field
The invention relates to the field of hydrometallurgy, and particularly relates to a resin adsorption method for nickel and cobalt in laterite-nickel ore.
Background
About 30 percent of global terrestrial nickel resources exist in sulphide ores, and 70 percent of global terrestrial nickel resources exist in laterite-nickel ores (nickel oxide ores). Only about 40% of the global nickel production is currently derived from lateritic nickel ores. The laterite-nickel ore has the characteristic of difficult ore dressing, and compared with nickel sulfide ore, the laterite-nickel ore has the advantages of low ore grade for smelting treatment, high smelting cost and relatively poor development economy
At present, the process for treating the laterite-nickel ore mainly comprises a fire separation process and a wet process. The fire method is mainly used for producing ferronickel by reduction smelting or producing nickel matte by reduction smelting. The wet method mainly comprises an ammonia leaching method and a high-pressure acid leaching method, wherein the high-pressure acid leaching process becomes a main method for treating the laterite-nickel ore by the wet method.
The main process flow of smelting laterite-nickel ore by high-pressure acid leaching wet method generally comprises the steps of high-pressure acid leaching, impurity removal by precipitation and preparation of nickel-cobalt intermediate product by precipitation. However, the precipitation method usually requires solid-liquid separation by using large-scale separation equipment such as CCD and the like, and has high investment and wide occupied area. The impurities such as manganese, magnesium and the like in the nickel-cobalt intermediate product obtained after preliminary impurity removal by a precipitation method are also high in content. Compared with a precipitation method, the method has the advantages of high efficiency, low equipment requirement and the like by removing impurities through resin adsorption.
US6350420B1 discloses a process for the recovery of nickel and cobalt from a nickel oxide containing ore leach slurry using ion exchange resins. The nickel-containing ore is leached with mineral acid to dissolve the metal. The obtained leached ore pulp is contacted with pyridyl ion exchange resin after the steps of pre-neutralization, neutralization for removing iron and aluminum, copper removal, reduction for hexavalent chromium and the like, and the ion exchange resin selectively loads nickel and cobalt from the ore pulp. The resin was separated by sieving and then desorbed with an acidic solution. After desorption, the resin is returned to the adsorption unit for recycling.
Chinese patent CN101974685B provides a process for extracting nickel and cobalt from laterite ore by using resin-in-pulp adsorption technology. Directly mixing the ore pulp subjected to high-pressure leaching and neutralization iron removal with a sodium type strong-acid cation exchange resin, putting the mixture into a leaching tank, adsorbing nickel and cobalt by the resin, washing the sieved resin with water to obtain slurry, desorbing by using 2-15% sulfuric acid or hydrochloric acid, and returning the desorbed resin to the adsorption process for use.
However, at present, after the high-pressure acid leaching, neutralization and iron and aluminum removal of the laterite-nickel ore pulp are subjected to resin adsorption, the resin is usually desorbed by using acid liquor for regeneration, and then the desorbed resin is directly subjected to cyclic adsorption. In fact, after acid solution desorption, the adsorption effect of the regenerated resin during cyclic adsorption is not ideal, and the conditions of low resin adsorption capacity, high concentration of residual nickel and cobalt in the liquid phase after final adsorption and the like often occur, so that the cyclic adsorption capacity of the resin is greatly limited.
Disclosure of Invention
The invention mainly aims to provide a resin adsorption method for nickel and cobalt in laterite-nickel ore, and aims to solve the problems that in the prior art, regenerated resin after acid liquor desorption is poor in adsorption performance and is not beneficial to cyclic adsorption of nickel and cobalt in laterite-nickel ore.
In order to achieve the above object, according to one aspect of the present invention, there is provided a resin adsorption method of nickel cobalt in lateritic nickel ore, comprising the steps of: step S1, carrying out acid leaching, neutralization and iron and aluminum removal and solid-liquid separation on the laterite-nickel ore in sequence to obtain pretreated ore pulp; step S2, carrying out nickel-cobalt adsorption on the pretreated ore pulp by using IDA chelating resin to obtain adsorption resin; step S3, desorbing the adsorption resin by using an acidic solution to obtain desorbed resin and a nickel-cobalt desorption solution; and step S4, performing saponification transformation on the desorption resin by using a sodium hydroxide aqueous solution or lime milk as a saponifying agent to obtain saponified resin, and returning to the step S2 for nickel-cobalt adsorption.
Furthermore, the mass concentration of the sodium hydroxide aqueous solution is 2-20%, preferably 5-10%; the mass concentration of the lime milk is 5-30%, preferably 10-20%.
Further, in step S4, the volume ratio of the saponifying agent to the desorption resin is 0.5-10: 1, and preferably, when the saponifying agent is an aqueous solution of sodium hydroxide, the volume ratio of the saponifying agent to the desorption resin is 2-10: 1; when the saponifying agent is lime milk, the volume ratio of the saponifying agent to the desorption resin is 0.5-5: 1.
Further, in step S4, mixing the saponifying agent and the desorption resin by stirring with a stirring paddle, air stirring or cross-flow through a column to perform saponification transformation; preferably, when the saponifying agent is sodium hydroxide aqueous solution, saponification transformation is carried out in an air stirring or column cross flow mode; when the saponifying agent is lime milk, saponification transformation is carried out in an air stirring mode.
Further, step S1 includes: carrying out acid leaching process on the laterite-nickel ore by adopting sulfuric acid to obtain acid leaching ore pulp; adjusting the pH value of the acid leaching ore pulp to 3.8-5 to perform a neutralization deironing process to obtain neutralized ore pulp; and carrying out solid-liquid separation on the neutralized ore pulp to filter solid particles with the particle size of more than or equal to 180 mu m to obtain the pretreated ore pulp.
Further, the temperature in the acid leaching process is 200-300 ℃, the acid-ore ratio is 250-340 kg/t, and the liquid-solid ratio is 20-30: 1.
Further, in the step S2, the volume ratio of the IDA chelating resin to the pretreated ore pulp is 1: 1-20.
Further, in step S3, the acidic solution is an aqueous sulfuric acid solution having a mass concentration of 2% or more.
Further, after the nickel-cobalt desorption solution is obtained, the method further comprises the steps of sequentially removing manganese, magnesium and nickel-cobalt.
Further, the IDA chelating resin is of type S930, M4195, IRC748, SR-5, TP207 or TP 209.
The IDA chelating resin is applied to nickel-cobalt adsorption of pretreated ore pulp obtained after acid leaching, neutralization and iron and aluminum removal and solid-liquid separation of the laterite-nickel ore, meanwhile, the sequence of IDA chelating resin on different cation affinities is considered, the bonding cation type of the IDA chelating resin after nickel-cobalt adsorption and acid desorption is fully considered, and a calcification transformation step is added after the acid desorption step. Specifically, the saponification transformation of the sodium hydroxide aqueous solution or the lime milk is carried out on the desorption resin, and the bonded cations in the desorption resin are changed into sodium ions or calcium ions, so that the affinity of the desorption resin for nickel ions and calcium ions is greatly improved, the adsorption capacity of the desorption resin for nickel and cobalt when the desorption resin returns to the nickel and cobalt adsorption step is effectively improved, and the concentration of the residual nickel and cobalt in the tailing pulp after the nickel and cobalt adsorption is obviously reduced.
In a word, the invention effectively improves the adsorption performance of the desorption resin on nickel and cobalt by saponification and transformation of the sodium hydroxide aqueous solution or the lime cream on the desorption resin, so that the desorption resin can be circularly adsorbed for many times. By utilizing the resin adsorption method, the adsorption and separation effects of nickel and cobalt in the laterite-nickel ore are effectively improved.
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.
As described in the background art, in the adsorption treatment process of the laterite-nickel ore in the prior art, the adsorption performance of the regenerated resin after acid liquor desorption is poor, which is not beneficial to the cyclic adsorption of nickel and cobalt in the laterite-nickel ore.
In order to solve the problems, the invention provides a resin adsorption method of nickel and cobalt in laterite-nickel ore, which comprises the following steps: step S1, carrying out acid leaching, neutralization and iron and aluminum removal and solid-liquid separation on the laterite-nickel ore in sequence to obtain pretreated ore pulp; step S2, carrying out nickel-cobalt adsorption on the pretreated ore pulp by using IDA chelating resin to obtain adsorption resin; step S3, desorbing the adsorption resin by using an acidic solution to obtain desorbed resin and a nickel-cobalt desorption solution; and step S4, performing saponification transformation on the desorption resin by using a sodium hydroxide aqueous solution or lime milk as a saponifying agent to obtain saponified resin, and returning to the step S2 for nickel-cobalt adsorption.
After the IDA chelating resin is desorbed by the acid solution, the bonding cation types on the resin functional groups are different, and the adsorption effect can be greatly changed when the IDA chelating resin is reapplied to the adsorption process. The bonded cation after acid solution desorption is hydrogen ion, and the affinity of the hydrogen ion and the resin is stronger than that of nickel cobalt (the affinity sequence of IDA chelating resin to the cation is H)+＞Ni2+＞Co2+＞Mn2+＞Ca2+＞Mg2+＞Na+) If the resin after acid solution desorption is directly used for nickel and cobalt re-adsorption, the conditions of low resin adsorption capacity, high concentration of residual nickel and cobalt in liquid phase after final stage adsorption and the like can occur. The invention applies IDA chelating resin to redThe nickel-cobalt adsorption of the pretreated ore pulp obtained after acid leaching, iron and aluminum removal and solid-liquid separation of the nickel-bearing laterite ore is performed, meanwhile, the sequence of the affinity of IDA chelating resin to different cations is considered, the bonding cation type of the IDA chelating resin after nickel-cobalt adsorption and acid desorption is fully considered, and a calcification transformation step is added after the acid desorption step. Specifically, the saponification transformation of the sodium hydroxide aqueous solution or the lime milk is carried out on the desorption resin, and the bonded cations in the desorption resin are changed into sodium ions or calcium ions, so that the affinity of the desorption resin for nickel ions and calcium ions is greatly improved, the adsorption capacity of the desorption resin for nickel and cobalt when the desorption resin returns to the nickel and cobalt adsorption step is effectively improved, and the concentration of the residual nickel and cobalt in the tailing pulp after the nickel and cobalt adsorption is obviously reduced.
In a word, the invention effectively improves the adsorption performance of the desorption resin on nickel and cobalt by saponification and transformation of the sodium hydroxide aqueous solution or the lime cream on the desorption resin, so that the desorption resin can be circularly adsorbed for many times. By utilizing the resin adsorption method, the adsorption and separation effects of nickel and cobalt in the laterite-nickel ore are effectively improved.
In order to perform more sufficient saponification transformation on the desorption resin, in a preferred embodiment, the mass concentration of the sodium hydroxide aqueous solution is 2 to 20%, preferably 5 to 10%; the mass concentration of the lime milk is 5-30%, preferably 10-20%. Controlling the concentration of each saponifier within the above range can more fully replace hydrogen ions on the desorption resin to complete saponification transformation to form sodium-based or calcium-based desorption resin, and is beneficial to reducing resource waste. More preferably, the volume ratio of the saponifier to the desorption resin is 0.5-10: 1.
Considering the affinity of cations and chelating resin in different saponifying agents, preferably, when the saponifying agent is sodium hydroxide aqueous solution, the volume ratio of the saponifying agent to the desorption resin is 2-10: 1; when the saponifying agent is lime milk, the volume ratio of the saponifying agent to the desorption resin is 0.5-5: 1. Thus, saponification can be more sufficiently completed. In consideration of the saponification effect, the ability of the resin to adsorb nickel and cobalt after saponification, and the cost of the material, it is preferable to use lime milk as the saponifier.
In a preferred embodiment, in step S4, the saponifying agent and the desorption resin are mixed by stirring with a stirring paddle, air stirring or cross-flow through a column to perform saponification transformation. The above forms can promote the mixing and saponification transformation of the saponifying agent and the desorption resin, and of course, considering the more suitable forms of different saponifying agents, the saponification transformation is preferably carried out in the form of air stirring or cross flow through a column when the saponifying agent is sodium hydroxide aqueous solution; when the saponifying agent is lime milk, saponification transformation is carried out in an air stirring mode.
The procedures of acid leaching, neutralization iron and aluminum removal and the like can adopt common processes in the field. In a preferred embodiment, step S1 includes: carrying out acid leaching process on the laterite-nickel ore by adopting sulfuric acid to obtain acid leaching ore pulp; adjusting the pH value of the acid leaching ore pulp to 3.8-5 to perform a neutralization deironing process to obtain neutralized ore pulp; and carrying out solid-liquid separation on the neutralized ore pulp to filter solid particles with the particle size of more than or equal to 180 mu m to obtain the pretreated ore pulp. Through the method, nickel and cobalt ions in the laterite-nickel ore can enter the pickle liquor more fully, and impurities such as iron, aluminum and the like can be removed in a neutralization mode. Specifically, the acid leaching pulp can be contacted with lime milk to adjust the pH value of the pulp to 3.8-5. Ferrous iron has far lower competitive power than ferric iron and has little influence on nickel cobalt adsorption, so that the pH is only adjusted to remove most of aluminum and ferric iron, and the traditional process of oxidizing ferrous iron into ferric iron by aeration is not needed. In addition, fine filtration equipment is needed for completely removing small particles, the investment is large, only large particles (solid particles with the particle size of more than or equal to 180 mu m) are removed, the resin is then adsorbed, and the small particles can be left in the poor ore pulp and are not treated.
In order to further improve the acid leaching effect, in a preferred embodiment, the temperature in the acid leaching process is 230-260 ℃, the acid-mineral ratio is 230-280 kg/t, and the liquid-solid ratio is 22-26. Preferably, the leaching time is 30-60 min, and sulfuric acid is adopted for acid leaching.
Preferably, in the step S2, the volume ratio of the IDA chelating resin to the pretreated ore pulp is 1: 1-20. This is favorable to further improve the nickel cobalt adsorption effect.
Preferably, in step S3, the acidic solution is an aqueous solution of sulfuric acid having a mass concentration of 2% or more. The nickel cobalt can be more sufficiently desorbed by the sulfuric acid aqueous solution. Preferably, after the nickel cobalt desorption solution is obtained, the method further comprises the steps of sequentially removing manganese, magnesium and nickel cobalt. The specific steps of manganese removal, magnesium removal, nickel-cobalt separation and the like can adopt common steps in the field, and are not described herein again.
In a preferred embodiment, the IDA chelating resin is of type S930, M4195, IRC748, SR-5, TP207 or TP 209. The IDA chelating resin has better nickel and cobalt adsorption and separation effects, and the desorption resin has stronger capacity of adsorbing nickel and cobalt again after saponification and transformation.
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.
The laterite-nickel ore mainly comprises the following components:
| Cr | Ni | Co | Mg | Mn | Fe | Al | Si | Ca | |
| content, wt% | 2.23 | 1.37 | 0.16 | 1.09 | 0.90 | 43.80 | 2.76 | 3.86 | 0.034 |
Example 1
The laterite-nickel ore is subjected to sulfuric acid leaching, and the specific process comprises the following steps: the temperature is 255 ℃, the acid-mineral ratio is 270kg/t, the liquid-solid ratio is 25.5, the leaching time is 60min, and the leached ore pulp is subjected to circulating leaching to obtain the circulating leached ore pulp.
And (3) contacting the circularly leached ore pulp with lime milk with the concentration of 10 wt%, adjusting the pH value of the ore pulp to 3.8, and neutralizing to remove most of iron and aluminum ions in the ore pulp phase to obtain neutralized ore pulp.
And (4) performing partial solid-liquid separation on the neutralized ore pulp, and filtering out solid particles with the size of more than 180 micrometers to obtain the pretreated ore pulp.
Adding fresh chelating resin TP209 to contact the pretreated ore pulp, wherein the volume ratio of the resin to the ore pulp is 1:5, the adsorption temperature is 60 ℃, the time is 9 hours, and separating the adsorbed resin from the lean ore pulp after the adsorption is finished. And (4) conveying the lean ore pulp to a tailing treatment system, and discharging the treated lean ore pulp into a tailing pond.
And mixing the adsorption resin with a sulfuric acid solution with the mass concentration of 10% for desorption to obtain desorption resin and a nickel-cobalt desorption solution. The pumping extraction process of the nickel-cobalt desorption solution sequentially carries out the processes of demanganization, demagging, nickel-cobalt separation and the like to obtain a nickel solution and a cobalt solution.
And mixing the desorption resin with a sodium hydroxide aqueous solution with the mass concentration of 5% for sodium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the sodium hydroxide aqueous solution is 1:2.5(V: V), obtaining the sodium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
Compared with the prior art that the unsaponifiable desorption resin returns to adsorb nickel and cobalt again, the adsorption capacity of the resin in the ore pulp after the secondary adsorption pretreatment of the saponified resin after saponification transformation is about 20g (Ni + Co)/L wet resin and is far higher than that of the hydrogen-based resin without sodium soap transformation (5g (Ni + Co)/L wet resin). After saponification and transformation are carried out, the concentration of nickel in tailing slurry is lower than 5mg/L, the concentration of cobalt in tailing slurry is lower than 0.5mg/L and is lower than the values (Ni-100 mg/L and Co-10 mg/L) obtained by the same process of hydrogen-based resin without sodium soap transformation after three-stage countercurrent adsorption (the saponification resin is discharged from the 1 st stage and the 3 rd stage, and the adsorption stock solution is discharged from the 3 rd stage and the 1 st stage) is carried out on the saponification and transformation.
Example 2
The only difference from example 1 is that: and mixing the desorption resin with a 10 mass percent sodium hydroxide aqueous solution for sodium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the sodium hydroxide aqueous solution is 1:2(V: V), obtaining sodium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt in the pretreated ore pulp.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 28g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 5mg/L and the cobalt concentration in tailing pulp is lower than 0.5mg/L after three-stage countercurrent adsorption.
Example 3
The only difference from example 1 is that: and mixing the desorption resin with a sodium hydroxide aqueous solution with the mass concentration of 20% for sodium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the sodium hydroxide aqueous solution is 1:2(V: V), obtaining the sodium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 36g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 2mg/L and the cobalt concentration in tailing pulp is lower than 0.2mg/L after three-stage countercurrent adsorption.
Example 4
The only difference from example 1 is that: and mixing the desorption resin with a sodium hydroxide aqueous solution with the mass concentration of 5% for sodium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the sodium hydroxide aqueous solution is 1:10(V: V), obtaining the sodium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 25g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 5mg/L and the cobalt concentration in tailing pulp is lower than 0.5mg/L after three-stage countercurrent adsorption.
Example 5
The only difference from example 1 is that: and mixing the desorption resin with a sodium hydroxide aqueous solution with the mass concentration of 2% for sodium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the sodium hydroxide aqueous solution is 1:0.5(V: V), obtaining the sodium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 12g (Ni + Co)/L of wet resin, the concentration of nickel in tailing pulp is lower than 50mg/L and the concentration of cobalt in tailing pulp is lower than 5mg/L after three-stage countercurrent adsorption.
Example 6
The process for carrying out sulfuric acid pressure acid leaching on the laterite-nickel ore comprises the following specific steps: the temperature is 255 ℃, the acid-mineral ratio is 270kg/t, the liquid-solid ratio is 25.5, the leaching time is 60min, and the leached ore pulp is subjected to circulating leaching to obtain the circulating leached ore pulp.
And (3) contacting the circularly leached ore pulp with lime milk with the concentration of 20 wt%, adjusting the pH value of the ore pulp to 4.2, and neutralizing to remove most of iron and aluminum ions in the ore pulp phase to obtain neutralized ore pulp.
And (4) performing partial solid-liquid separation on the neutralized ore pulp, and filtering out solid particles with the size of more than 180 micrometers to obtain the pretreated ore pulp.
Adding fresh S930 to contact the pretreated ore pulp, wherein the volume ratio of resin to ore pulp is 1:8, the adsorption temperature is 40 ℃, the time is 12 hours, and after the adsorption is finished, separating the adsorbed resin from the lean ore pulp. And (4) conveying the lean ore pulp to a tailing treatment system, and discharging the treated lean ore pulp into a tailing pond.
And mixing the adsorption resin with a sulfuric acid solution with the mass concentration of 10% for desorption to obtain desorption resin and a nickel-cobalt desorption solution. The pumping extraction process of the nickel-cobalt desorption solution sequentially carries out the processes of demanganization, demagging, nickel-cobalt separation and the like to obtain a nickel solution and a cobalt solution.
And mixing the desorbed resin with lime milk with the mass concentration of 20% for calcium soap transformation, wherein the stirring mode is air stirring, the proportion of the resin to the lime milk is 1:5(V: V), obtaining the calcium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
Compared with the method that the unsaponifiable desorption resin returns to adsorb nickel and cobalt again, the adsorption capacity of the resin in the secondary adsorption of the saponified resin after saponification and transformation is about 30g (Ni + Co)/L of wet resin and is much higher than that of the hydrogen-based resin without calcium soap transformation (5g (Ni + Co)/L of wet resin). After three-stage countercurrent adsorption, the concentration of nickel in tailing pulp is lower than 2mg/L, the concentration of cobalt in tailing pulp is lower than 0.2mg/L and is lower than the values (Ni-100 mg/L and Co-10 mg/L) obtained by the same process of hydrogen-based resin which is not subjected to calcium soap transformation.
Example 7
The only difference from example 5 is that: and mixing the desorbed resin with lime milk with the mass concentration of 10% to perform calcium soap transformation, wherein the stirring mode is air stirring, the proportion of the resin to the lime milk is 1:4(V: V), so as to obtain the calcium-based IDA chelate resin, and returning to the adsorption process to perform secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 25g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 5mg/L and the cobalt concentration in tailing pulp is lower than 0.5mg/L after three-stage countercurrent adsorption.
Example 8
The only difference from example 5 is that: and mixing the desorbed resin with lime milk with the mass concentration of 10% to perform calcium soap transformation, wherein the stirring mode is air stirring, the proportion of the resin to the lime milk is 1:5(V: V), so as to obtain the calcium-based IDA chelate resin, and returning to the adsorption process to perform secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 26g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 5mg/L and the cobalt concentration in tailing pulp is lower than 0.5mg/L after three-stage countercurrent adsorption.
Example 9
The only difference from example 5 is that: and mixing the desorbed resin with lime milk with the mass concentration of 30% for calcium soap transformation, wherein the stirring mode is air stirring, the proportion of the resin and the lime milk is 1:0.5(V: V), obtaining the calcium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 20g (Ni + Co)/L of wet resin, the concentration of nickel in tailing pulp is lower than 5mg/L and the concentration of cobalt in tailing pulp is lower than 0.5mg/L after three-stage countercurrent adsorption.
Example 10
The only difference from example 5 is that: and mixing the desorbed resin with lime milk with the mass concentration of 5% for calcium soap transformation, wherein the stirring mode is air stirring, the ratio of the resin to the lime milk is 1:0.5(V: V), obtaining the calcium-based IDA chelate resin, and returning to the adsorption process for secondary adsorption of nickel and cobalt.
And (3) adsorption result: the adsorption capacity of the secondary adsorption resin of the saponified resin is about 16g (Ni + Co)/L of wet resin, the nickel concentration in tailing pulp is lower than 10mg/L and the cobalt concentration in tailing pulp is lower than 1mg/L after three-stage countercurrent adsorption.
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 (10)
1. A resin adsorption method for nickel and cobalt in laterite-nickel ore is characterized by comprising the following steps:
s1, sequentially carrying out acid leaching, neutralization and iron and aluminum removal and solid-liquid separation on the laterite-nickel ore to obtain pretreated ore pulp;
step S2, carrying out nickel-cobalt adsorption on the pretreated ore pulp by IDA chelating resin to obtain adsorption resin;
step S3, desorbing the adsorption resin by using an acidic solution to obtain desorbed resin and a nickel-cobalt desorption solution;
and S4, performing saponification transformation on the desorption resin by using a sodium hydroxide aqueous solution or lime milk as a saponifying agent to obtain saponified resin, and returning to the step S2 to perform nickel-cobalt adsorption.
2. The method according to claim 1, wherein the mass concentration of the sodium hydroxide aqueous solution is 2-20%, preferably 5-10%; the mass concentration of the lime milk is 5-30%, and preferably 10-20%.
3. The method according to claim 1 or 2, wherein in the step S4, the volume ratio of the saponifying agent to the desorption resin is 0.5-10: 1, preferably,
when the saponifying agent is the sodium hydroxide aqueous solution, the volume ratio of the saponifying agent to the desorption resin is 2-10: 1;
when the saponifying agent is the lime milk, the volume ratio of the saponifying agent to the desorption resin is 0.5-5: 1.
4. The method according to any one of claims 1 to 3, wherein in the step S4, the saponifying agent and the desorption resin are mixed by stirring with a stirring paddle, stirring with air, or cross-flow through a column to perform the saponification transformation; preferably, when the saponifying agent is the sodium hydroxide aqueous solution, the saponification transformation is performed in the form of air stirring or cross-flow through a column; and when the saponifying agent is the lime milk, performing saponification and transformation in the form of air stirring.
5. The method according to any one of claims 1 to 3, wherein the step S1 includes:
carrying out the acid leaching process on the laterite-nickel ore by adopting sulfuric acid to obtain acid leaching ore pulp;
adjusting the pH value of the acid leaching ore pulp to 3.8-5 to perform the process of removing iron and aluminum in the neutralization process to obtain neutralized ore pulp;
and carrying out the solid-liquid separation process on the neutralized ore pulp to filter solid particles with the particle size of more than or equal to 180 mu m to obtain the pretreated ore pulp.
6. The method according to claim 5, wherein the temperature in the acid leaching process is 200-300 ℃, the acid-mineral ratio is 250-340 kg/t, and the liquid-solid ratio is 20-30: 1.
7. The method according to any one of the claims 1 to 3, wherein in the step S2, the volume ratio of the IDA chelating resin to the pretreated ore pulp is 1: 1-20.
8. The method according to any one of claims 1 to 3, wherein in step S3, the acidic solution is an aqueous solution of sulfuric acid having a mass concentration of 2% or more.
9. The method according to any one of claims 1 to 3, wherein after the nickel cobalt desorption solution is obtained, the method further comprises the steps of sequentially removing manganese, magnesium and nickel cobalt.
10. The method according to any one of claims 1 to 3, wherein the IDA chelating resin is of type S930, M4195, IRC748, SR-5, TP207 or TP 209.
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