WO2019174103A1 - Method for producing nickel sulfate and cobaltous sulfate by purification of laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin - Google Patents

Method for producing nickel sulfate and cobaltous sulfate by purification of laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin Download PDF

Info

Publication number
WO2019174103A1
WO2019174103A1 PCT/CN2018/083897 CN2018083897W WO2019174103A1 WO 2019174103 A1 WO2019174103 A1 WO 2019174103A1 CN 2018083897 W CN2018083897 W CN 2018083897W WO 2019174103 A1 WO2019174103 A1 WO 2019174103A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin column
column
resin
leaching
nickel
Prior art date
Application number
PCT/CN2018/083897
Other languages
French (fr)
Chinese (zh)
Inventor
李宾
Original Assignee
李宾
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 李宾 filed Critical 李宾
Publication of WO2019174103A1 publication Critical patent/WO2019174103A1/en

Links

Images

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
    • 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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/005—Pretreatment specially adapted for magnetic separation
    • B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
    • 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
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • 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
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the field of hydrometallurgy and relates to a method for producing nickel-cobalt from laterite nickel ore, in particular to a method for producing nickel sulfate cobalt by a laterite nickel ore leaching solution and a silica gel chelating resin.
  • Laterite nickel ore resources are surface weathering crust deposits formed by weathering-leaching-sedimentation of nickel sulfide ore bodies.
  • the world's laterite nickel ore is distributed in tropical countries within 30 degrees north and south of the equator line, concentrated in the tropical-subtropical zone of the Pacific Rim. The regions are mainly: Cuba, Brazil in the Americas, Indonesia and the Philippines in Southeast Asia, Australia, New Caledonia and Papua New Guinea in Oceania. 70% of China's nickel ore reserves are concentrated in Gansu, followed by Xinjiang, Yunnan, Jilin, Sichuan, Shaanxi, Qinghai and Hubei provinces. The total reserves account for 27% of the country's total nickel resources.
  • the upper part of the nickel oxide deposit is a brown iron type laterite ore, which is suitable for the wet process; the lower part is a magnesia nickel silicate (mainly serpentine), which is suitable for the fire process.
  • the intermediate transition section is suitable for both methods. It is estimated that the laterite nickel ore reserves (limonite, nontronite, montmorillonite) suitable for wet treatment are more than twice as suitable for the fire method (silica-magnesium ore, humus).
  • wet type mainly distributed in the near equator, such as New Caledonia, Indonesia.
  • the Philippines, Papua New Guinea and the Caribbean have higher grades, less clay and are easier to handle.
  • dry mainly distributed in the southern hemisphere continent far from the equator, with complex composition and high clay content. Not easy to handle.
  • laterite nickel ore has different types, they generally have the following characteristics:
  • composition content fluctuates greatly, not only the content of valuable elements such as nickel varies greatly, but also the gangue components such as SiO 2 , MgO, Fe 2 O 3 , Al 2 O 3 and water fluctuate greatly, even in the same deposit.
  • the composition of laterite ore Ni, Co, Fe, MgO, etc. also varies with the depth of different layers.
  • the reduction roasting-ammonia immersion process invented by Professor Caron is also called the Caron method.
  • the Nicaror Nickel Plant in Cuba has treated the high-magnesia laterite nickel ore by reduction roasting-ammonia leaching for more than half a century.
  • the typical composition of the ore that is suitable for treatment with this ammonia-alkali leaching method is 1.4% Ni, 8% MgO, 14 % SiO 2 .
  • the basic procedure is that the ore having a particle size of less than 74 ⁇ m is placed in a multi-hearth furnace for reduction roasting.
  • Nickel and cobalt in the laterite ore are substantially in the form of ferrite, and after reduction and calcination, nickel and cobalt are converted into metals or alloys.
  • the calcination is leached with ammonia-ammonium carbonate mixed solution, treated by a thickener, overflowed into a rich liquid, purified and evaporated to produce a nickel carbonate slurry, which is dried and calcined by a rotary kiln to obtain a nickel oxide product and magnetically selected.
  • the method selects iron concentrate from the leaching slag. For this reason, in the reduction calcination, it is necessary to sufficiently reduce the nickel and cobalt combined with iron, and to prevent excessive reduction of iron.
  • the US Bureau of Minerals has developed a new process for the reduction roasting-ammonia leaching process for laterite ore, referred to as the USBM method.
  • the main point of this method is the addition of pyrite (FeS 2 ) for granulation before reduction roasting, and the use of pure carbon monoxide for reduction.
  • the leachate uses Lix64-N as an extractant to separate cobalt and nickel.
  • the whole system is a closed loop, which effectively utilizes resources. According to reports, when this method is used to treat laterite ore containing 1% nickel and 0.2% cobalt, the recovery rates of nickel and cobalt are 90% and 85%, respectively.
  • Outokumpu-Lurgi is developing a process for calcination and fluidized bed pre-reduction of limonite or humus ore, which is used in the subsequent Caron process.
  • the reduction roasting-ammonia leaching process produces sintered nickel oxide (99%), nickel, nickel or nickel.
  • the sulfuric acid pressure acid leaching process is suitable for treating limonite type laterite ore with low magnesium oxide.
  • the biggest advantage of this process is that the recovery rate of metal can reach more than 90%.
  • the technology began in the 1950s and was first used in the Moa Bay mine in Cuba, called A-MAX-PAL technology. Since then, in the 1970s, Australia's QNI Corporation built the Yabula nickel plant, acid-leaching red clay-type nickel mines in New Caledonia, Indonesia and Queensland, Australia. In the second half of 1998, Australia's Murrin Murrin, Cawse and Bulong developed a laterite mining development project using a new process of pressurized acid leaching, which attracted a lot of attention.
  • the acid pressure leaching technology in these three processes is similar to that used in Cuba Moo's production, except that the vertical autoclave has replaced the Moo company's vertical autoclave. However, the recycling step has the following differences:
  • the mixed hydroxide is precipitated from the high pressure leaching solution, and then leached with ammonia, followed by solvent extraction and electrowinning.
  • the mixed sulfide is precipitated from the high pressure leaching solution by H 2 S, and then the sulfide is leached under aerobic conditions, followed by solvent extraction, hydrogen reduction, tableting, and the like.
  • the high pressure leaching solution is directly subjected to solvent extraction and electrowinning.
  • SGS Lakefileld has developed a high-pressure acid leaching scheme characterized by the addition of elemental sulfur and oxygen to the autoclave to produce sulfuric acid in situ. This makes it unnecessary to preheat the slurry before it enters the autoclave, thereby significantly saving equipment costs.
  • Atmospheric pressure leaching suitable for the treatment of lateritic nickel ore with low iron content and high magnesium content.
  • Skye Resources is researching the atmospheric pressure leaching method for the development of the Guatemala laterite deposit, which uses the residual acid after leaching of limonite and the acid released by precipitation in the form of goethite for leaching a large amount of humus Share.
  • Heap leaching mainly suitable for humus ore.
  • a large number of research results show that with heap leaching technology, the leaching rate of nickel can reach more than 75% within 3 months, and the leaching rate of cobalt can reach more than 60%.
  • European Nickel is currently conducting a large-scale dip test in Turkey and is expected to build the world's first plant to extract nickel and cobalt using heap leaching technology.
  • Microwave sintering-pressure leaching method the laterite ore is subjected to microwave sintering to destroy the mineral crystal lattice, and then subjected to pressure leaching at a low temperature to precipitate iron ions in the form of hematite to achieve enhanced leaching, lowering the high-pressure acid leaching temperature and The purpose of stress.
  • Chlorination Segregation-Ammonia Leaching Adding a certain amount of carbonaceous reducing agent and chlorinating agent (sodium chloride or calcium chloride) to the ore, heating in a neutral or weak reducing atmosphere to make valuable metals from ore The chlorination is volatilized and simultaneously reduced to metal particles on the surface of the carbon particles. The calcination is followed by direct ammonia leaching.
  • Wang Chengyan used this method to treat the Yuanjiang lean nickel oxide ore. The experimental results are as follows: the nickel leaching rate is greater than 80%, and the cobalt leaching rate is greater than 50%.
  • Bioleaching The metal is efficiently dissolved from low grade ore by microbial catalyzed oxidation-reduction.
  • Laubium-nickel ore by heterotrophic microorganisms.
  • the ore sample was taken from Acesita Mining Company of Brazil with a chemical composition of 43.2% SiO 2 and 0.09% Ni. Grinding to a particle size of 147 ⁇ m or less, five heterotrophic microorganisms were used for leaching.
  • the leaching conditions were as follows: the ore sample weighed 5 g (previously sterilized at 12 l ° C), the microbial-containing medium 1000 mL, the temperature 30 ° C, the shake flask rate 200 r / min, and the Ni leaching rate was greater than 80%.
  • pressurized acid leaching is technically and economically superior to fire and ammonia leaching.
  • this technology also has many problems, such as large investment in disposable equipment; it is only suitable for handling brown iron-type ore with low magnesium content, and has requirements for the grade of ore; the same liquid waste, polluting the environment, etc., these problems have been limited.
  • the development of the process While perfecting the pressurized acid leaching technology, people are also constantly developing new laterite nickel ore wet processes, such as atmospheric pressure leaching and bioleaching. These new processes have received much attention in recent years, and they have the following advantages compared to pressurized acid leaching processes:
  • Atmospheric leaching and bioleaching technology can treat laterite nickel ore with higher magnesium content, which is suitable for processing low grade ore.
  • Atmospheric leaching and bioleaching can be carried out under normal temperature and normal pressure conditions, with low equipment requirements, simple process and convenient operation, so the investment is low and the production cost is low.
  • Pressurized acid leaching method has many solid-liquid wastes and pollutes the environment.
  • the new process such as bioleaching, does not produce SO 2 gas, and the resulting solid-liquid waste is environmentally acceptable and environmentally friendly.
  • an object of the present invention is to provide a method for purifying nickel sulfate and cobalt sulfate by using laterite nickel ore leaching solution and silica gel chelating resin, which is characterized by excessive pressure of sulfuric acid nickel sulphate overpressure layer and limonite type sulfuric acid.
  • High-purity nickel sulfate and cobalt sulfate products can be obtained by leaching, humic layer type high temperature neutralization and impurity leaching, and leaching liquid and silica gel chelating resin purification.
  • the present invention provides a method for purifying nickel sulfate and cobalt sulfate by using a laterite nickel ore leaching solution and a silica gel chelating resin, comprising the following steps:
  • transition layer type laterite nickel ore powder is added with sulfuric acid and water according to the sulfuric acid addition amount of 900kg/t ore and the liquid-solid ratio of 4:1, and the leaching temperature is 80 ° C, the leaching time is 2.5 h, and then cooled. Up to room temperature, solid-liquid separation of leachate 1 and filter residue 1;
  • Limonite type laterite nickel ore powder is added in the autoclave according to the sulfuric acid input amount of 350kg/t ore, the ratio of liquid to solid is 3:1, sulfuric acid and leachate 1 are added, and then the temperature is raised to 240-250 ° C, and the pressure is controlled.
  • humus layer type laterite nickel ore powder is added to the leachate 2 according to the amount of 100g / L, stirring When the temperature is raised to 80 °C, 50 g / L of humus layer type laterite nickel ore powder is added, and the temperature is further increased to a hydrolysis temperature of 220 ° C, and the reaction is carried out for 2 hours, and then cooled to room temperature, and the neutralized liquid and the filter residue 3 are separated by solid-liquid separation;
  • the filtrate is enriched with nickel and cobalt through a silica gel chelating resin to obtain a nickel sulfate cobalt enrichment liquid, and the tail liquid is added with calcium oxide to remove manganese, and the tail slag is discharged;
  • the resin separation adopts a double column series connection and a single column desorption method, specifically: three resin columns are defined as No. 1 resin column, No. 2 resin column, No. 3 resin column, No. 1 resin column and No. 2
  • the resin column is connected in series, wherein the first resin column is the first column, the second resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the upper end of the No. 2 resin column is subjected to countercurrent adsorption, when the No. 1 resin column is adsorbed.
  • the No. 2 resin column and the No. 3 resin column are connected in series by the same method, the No. 2 resin column is used as the head column, the No.
  • the No. 3 resin column is used as the tail column for countercurrent adsorption, and the No. 1 resin column is regenerated, when the No. 2 resin column is used.
  • the No. 3 resin column and the No. 1 resin column are connected in series, the No. 3 resin column is used as the head column, the No. 1 resin column is used as the tail column for reverse flow adsorption, and the No. 2 resin column is subjected to regeneration treatment; when the No. 3 resin column is adsorbed and saturated Thereafter, the No. 1 resin column and the No. 2 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and thus the cycle operation is performed.
  • the resin separation adopts a double column series and double column desorption method, specifically: four resin columns are defined as No. 1 resin column, No. 2 resin column, No. 3 resin column, No. 4 resin column, No. 1
  • the resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the upper end of the No. 2 resin column is discharged for countercurrent adsorption.
  • the No. 2 resin column and the No. 3 resin column were connected in series by the same method, the No. 2 resin column was used as the head column, the No.
  • the step of the regeneration treatment is: the first cleaning: washing the saturated resin column with the tap water in and out, the cleaning volume is 6 BV; desorption: the way the desorbent is moved in and out The resin column is desorbed, the desorption volume is 1.26 BV, and the liquid is concentrated after desorption to carry out nickel and cobalt extraction; the second cleaning: the desorbed resin column is cleaned by tap water in and out, and the cleaning volume is 3 BV. After the cleaning, the resin column is regenerated, and the next adsorption can be performed.
  • the desorbent is 25-35% sulfuric acid or 15-25% hydrochloric acid.
  • the resin is an inorganic silica gel chelating ion exchange resin.
  • the inorganic silica gel chelating ion exchange resin is an SI-2 resin or an IAA-PEI-SiO 2 resin.
  • the magnetic field strength of the weak magnetic separation is 160 kA/M.
  • the condition of removing the calcium oxide is: the amount of calcium oxide added is 3% of the tail liquid, and the reaction is carried out at room temperature for 30 minutes.
  • the invention adopts the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin to purify the nickel sulfate and cobalt sulfate method, and adopts the excessive layer type laterite ore atmospheric pressure acid leaching, the limonite type high pressure acid leaching, the humus layer type neutralization and the impurity acid leaching,
  • the leachate is purified by inorganic silica gel chelating resin to produce nickel sulfate cobalt sulfate; the other solid-liquid separation processes of various leachates are solved, and the production and operation costs are greatly reduced by 40%.
  • the method for purifying nickel sulfate and cobalt sulfate by using the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin provided by the invention adopts a wet method for one-time extraction of limonite type laterite nickel ore and humus soil laterite nickel ore, and is suitable for intermediate transition soil.
  • the treatment of laterite nickel ore in the layer has high extraction efficiency of nickel and cobalt.
  • the large amount of residual free acid contained in the leachate of acid extraction of limonite type laterite nickel ore continues to be used for leaching humus layer type laterite nickel ore, which can effectively save acid. The amount of use, thereby reducing production and operating costs.
  • FIG. 1 is a flow chart of a method for purifying nickel sulfate and cobalt sulfate by using a laterite nickel ore sulfuric acid leaching solution and a silica gel chelating resin provided by the present invention.
  • nickel sulfate and cobalt sulfate are extracted by the process shown in Figure 1, and the specific process is as follows:
  • the dried limonite type laterite nickel ore, the transition layer type laterite nickel ore and the humus layer type laterite nickel ore are respectively ground to -0.15 mm and account for more than 95% of the ore powder.
  • the transition layer type laterite nickel ore powder is added with sulfuric acid and water according to the sulfuric acid addition amount of 900 kg/t ore and the liquid-solid ratio of 4:1, and the leaching temperature is 80 ° C, the leaching time is 2.5 h, and then cooled to room temperature.
  • the solid solution separates the leachate 1 and the filter residue 1.
  • the limonite type laterite nickel ore powder is added to the autoclave according to the sulfuric acid input amount of 350 kg/t ore, the liquid-solid ratio is 3:1, and the sulfuric acid and the leachate 1 are added, and then the temperature is raised to 250 ° C by stirring (70 rpm).
  • the control pressure is 4 MPa, the leaching is continued for 60 min, the temperature is lowered to room temperature, and vacuum filtration is performed to separate the leachate 2 and the filter residue 2 by solid-liquid separation.
  • the leaching rates of nickel and cobalt are both greater than 95%, and the leaching rate of iron is less than 2%.
  • the humus layer type laterite nickel ore powder is added to the leachate 2 according to the dosage of 100g/L, and the temperature is raised to 80 °C by stirring (70 rpm), and then the humus layer type laterite nickel ore powder 50g/L is added, and the continuation is continued. Heating to a hydrolysis temperature of 220 ° C, the reaction for 2h, and then cooled to room temperature, solid-liquid separation of the neutralized liquid and filter residue 3;
  • the existing neutralization efficiency can be increased from 80% to over 99% by adding humus layer type laterite nickel ore.
  • the residual Fe 2+ in the neutralization solution can be oxidized to Fe 3+ by hydrogen peroxide, and then hydrolyzed to Fe(OH) 3 for removal.
  • the iron removal rate can reach more than 99%. After the iron removal, the iron concentration in the filtrate is close to 10 ppm, and the nickel cobalt In the slag, only 0.2% of cobalt and 0.1% of nickel are contained, and the loss of nickel and cobalt is small.
  • the filtrate is enriched in nickel-cobalt by resin, and then desorbed to obtain nickel-cobalt-sulfurate enrichment liquid.
  • the tail liquid is added with 3% calcium oxide and manganese, and the reaction is carried out at room temperature for 30 min, and the tail slag is discharged to the tailings storage.
  • the resin used is inorganic silica gel chelate ion exchange resin SI-2, and the resin enriched nickel cobalt adopts double column series and single column desorption method.
  • three resin columns are defined as No. 1 resin column and No. 2 resin.
  • Column No. 3 resin column, the No. 1 resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the No. 2 resin The upper end of the column is subjected to countercurrent adsorption.
  • the No. 1 resin column is saturated and saturated
  • the No. 2 resin column and the No. 3 resin column are connected in series by the same method, and the No.
  • the step of the regeneration treatment is: the first cleaning: the resin column saturated with adsorption is washed in the manner of tap water up and down, the cleaning volume is 6 BV; desorption: 35% sulfuric acid desorbent is fed in and out The resin column is desorbed, the desorption volume is 1.26 BV, and the liquid is concentrated after desorption to carry out nickel and cobalt extraction; the second cleaning: the desorbed resin column is cleaned by tap water in and out, the cleaning volume is 3 BV, and the cleaning is performed. The post-resin column is regenerated for the next adsorption.
  • the obtained nickel cobalt cobalt-rich liquid can be prepared by a conventional method.
  • the iron content in the iron concentrate is more than 60%, and the sulfur content is below 0.2%.
  • the chemical composition of the iron concentrate completely meets the requirements of the iron concentrate in the iron ore industry.
  • the method for purifying nickel sulfate and cobalt sulfate by using the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin used in the invention can effectively enrich the nickel and cobalt in the low grade laterite nickel ore, and the normal pressure and the high pressure are
  • the combination of high-temperature leaching extraction and resin purification and enrichment solves the problem of the world's mining hydrometallurgical solid-liquid separation, reduces the use of a large number of external reagents in the traditional extraction and enrichment mode, and at the same time, streamlines the production process, and purifies the resin.
  • the two-column series, single-column or double-column desorption method is adopted in a concentrated manner, which can be continuously produced without stopping work and desorption, and achieve the production effect of improving quality and efficiency.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for producing nickel sulfate and cobaltous sulfate by purification of a laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin, comprising: 1) grinding laterite nickel ores (limonite type, transition layer type and detritus layer type) to -0.15 mm of ore powder accounting for 95% or above; 2) adding sulfuric acid and water into the ground transition layer type laterite nickel ore to carry out atmospheric pressure leaching and separate a leaching solution 1 and filter residue 1; 3) placing the limonite type laterite nickel ore into an autoclave, and adding sulfuric acid and water to carry out high pressure leaching to separate a leaching solution 2 from a filter residue 2; 4) adding the leaching solutions into the detritus layer type laterite nickel ore to carry out neutralization, impurity removal and leaching to separate a neutralization solution and a filter residue 3; 5) adding hydrogen peroxide for reaction precipitation, and performing solid-liquid separation to separate a filtrate and a filter residue 4; 5) performing silica gel chelating resin separation on the filtrate to produce nickel sulfate and cobaltous sulfate; 6) adding pulverized coal into the filter residues, conducting magnetization roasting, then conducting weak magnetic separation to separate iron ore concentrate and tailings; 7) removing manganese from a tail liquid; and 8) discharging the tailings.

Description

一种红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法Method for purifying nickel sulfate cobalt by sulfuric acid leaching solution of laterite nickel ore and silica gel chelating resin 技术领域Technical field
本发明属于湿法冶金领域，涉及一种红土镍矿生产镍钴的方法，具体涉及一种红土镍矿浸出液和硅胶螯合树脂提生产硫酸镍钴的方法。The invention belongs to the field of hydrometallurgy and relates to a method for producing nickel-cobalt from laterite nickel ore, in particular to a method for producing nickel sulfate cobalt by a laterite nickel ore leaching solution and a silica gel chelating resin.
背景技术Background technique
红土镍矿资源为硫化镍矿岩体风化-淋滤-沉积形成的地表风化壳性矿床，世界上红土镍矿分布在赤道线南北30度以内的热带国家，集中分布在环太平洋的热带-亚热带地区，主要有：美洲的古巴、巴西；东南亚的印度尼西亚、菲律宾；大洋洲的澳大利亚、新喀里多尼亚、巴布亚新几内亚等。我国镍矿资源储量中70％集中在甘肃，其次分布在新疆、云南、吉林、四川、陕西和青海和湖北7个省，合计保有储量占全国镍资源总储量的27％。Laterite nickel ore resources are surface weathering crust deposits formed by weathering-leaching-sedimentation of nickel sulfide ore bodies. The world's laterite nickel ore is distributed in tropical countries within 30 degrees north and south of the equator line, concentrated in the tropical-subtropical zone of the Pacific Rim. The regions are mainly: Cuba, Brazil in the Americas, Indonesia and the Philippines in Southeast Asia, Australia, New Caledonia and Papua New Guinea in Oceania. 70% of China's nickel ore reserves are concentrated in Gansu, followed by Xinjiang, Yunnan, Jilin, Sichuan, Shaanxi, Qinghai and Hubei provinces. The total reserves account for 27% of the country's total nickel resources.
氧化镍矿床的上部为褐铁型红土矿，适合于湿法工艺处理；下部为镁质硅酸镍矿(蛇纹岩为主)，适合用火法工艺处理。中间过渡段同时适于两种方法。据估计，适合用湿法处理的红土镍矿储量(褐铁矿、绿脱石、蒙脱石)是适合火法(硅镁镍矿、腐植矿)的两倍多。The upper part of the nickel oxide deposit is a brown iron type laterite ore, which is suitable for the wet process; the lower part is a magnesia nickel silicate (mainly serpentine), which is suitable for the fire process. The intermediate transition section is suitable for both methods. It is estimated that the laterite nickel ore reserves (limonite, nontronite, montmorillonite) suitable for wet treatment are more than twice as suitable for the fire method (silica-magnesium ore, humus).
随着红土镍矿资源的不断开发利用，人们对其利用性能和类型又有了新的认识：一类称为“湿型”，主要分布于近赤道地区，如新喀里多尼亚、印尼、菲律宾、巴布亚新几内亚和加勒比海地区，其品位较高，粘土少，易于处理；一类称为“干型”，主要分布于距赤道较远的南半球大陆，其成分复杂，粘土含量高，不易处理。With the continuous development and utilization of laterite nickel ore resources, people have a new understanding of their utilization properties and types: one is called “wet type” and is mainly distributed in the near equator, such as New Caledonia, Indonesia. The Philippines, Papua New Guinea and the Caribbean have higher grades, less clay and are easier to handle. One type is called “dry”, mainly distributed in the southern hemisphere continent far from the equator, with complex composition and high clay content. Not easy to handle.
虽然红土镍矿有不同类型之分，但从总体上来看，它们都具有以下特点：Although laterite nickel ore has different types, they generally have the following characteristics:
(一)含镍1.0～3％，品位较低且组成比硫化镍矿复杂得多，很难通过选矿获得较高(6％以上)的镍精矿，同时含镍太低也难以直接用简单的冶金工艺富集。(1) 1.0-3% nickel, the grade is lower and the composition is much more complicated than the nickel sulfide ore. It is difficult to obtain a higher (6% or more) nickel concentrate by beneficiation, and it is difficult to use the nickel directly too low. The metallurgical process is enriched.
(二)成分含量波动大，不仅镍等有价元素的含量变化大，而且脉石成分如SiO 2、MgO、Fe 2O 3、Al 2O 3和水分波动也很大，即使是在同一矿床，红土矿成分(Ni，Co，Fe和MgO等)也随着不同的矿层的深度而不断变化。 (2) The composition content fluctuates greatly, not only the content of valuable elements such as nickel varies greatly, but also the gangue components such as SiO 2 , MgO, Fe 2 O 3 , Al 2 O 3 and water fluctuate greatly, even in the same deposit. The composition of laterite ore (Ni, Co, Fe, MgO, etc.) also varies with the depth of different layers.
(三)矿石中仅伴生有少量的钴，无硫，无热值。(3) There is only a small amount of cobalt associated with the ore, no sulfur, no calorific value.
(四)矿石储量大，而且赋存于地表，易采，可露天操作，具有开发的优越条件。(4) The ore reserves are large, and they are deposited on the surface, easy to harvest, open-air operation, and have excellent conditions for development.
以新喀里多尼亚红土矿开发为标志，从红土矿中生产金属镍迄今已经有100多年的历史了。近年来，由于不锈钢行业对镍的巨大需求，很多产镍大国都积极 加大对红土矿的开发利用。较有影响的有菲律宾住友/三井公司2005年开始的Coral Bay项目；2007年Inco在新喀照多尼亚正式启动的Goro镍项目，预计年产镍5.4万t；此外，在澳大利亚、印度尼西亚、巴西等国的一些镍矿资源的开发也在实施和研究中，With the development of the red clay mine in New Caledonia as a symbol, the production of metallic nickel from laterite mines has been more than 100 years old. In recent years, due to the huge demand for nickel in the stainless steel industry, many large nickel producing countries have actively increased the development and utilization of laterite mines. More influential are the Coral Bay project started in 2005 by Sumitomo/Mitsui Corporation of the Philippines; the Goro nickel project officially launched by Inco in New Mexico in 2007, with an estimated annual production of 54,000 tons of nickel; in addition, in Australia, Indonesia, The development of some nickel ore resources in countries such as Brazil is also being implemented and researched.
红土镍矿的湿法冶金技术的现状Current Status of Hydrometallurgical Technology for Laterite Nickel Ore
(一)还原焙烧-氨浸工艺(RRAL)(1) Reduction roasting-ammonia leaching process (RRAL)
Caron教授发明的还原焙烧-氨浸工艺，所以又叫做Caron法。古巴尼加罗镍厂用还原焙烧-氨浸法处理高氧化镁红土镍矿已达半个多世纪，适合采用这种氨碱浸出方法处理的矿典型成分为1.4％Ni，8％MgO，14％SiO 2。基本流程为粒度小于74μm的矿石放在多膛炉内进行还原焙烧。红土矿中的镍和钴基本上呈铁酸盐形式存在，经还原焙烧后，镍、钴转变为金属或合金。焙砂用氨-碳酸铵混合溶液浸出，经浓密机处理，溢流为富液，净化、蒸氨后产出碳酸镍浆料，经回转窑干燥和煅烧后，得到氧化镍产品，并用磁选法从浸出渣中选出铁精矿。为此，还原焙烧时既要使与铁结合的镍和钴充分还原，又要防止铁过分还原。我国在20世纪70年代援助阿尔巴尼亚爱尔巴桑钢铁联合企业项目中，首先在世界上完成从红土矿还原焙烧-氨浸提取镍钴-浸出渣磁选-铁精矿炼钢铁的研究，并成功地应用于工业生产。 The reduction roasting-ammonia immersion process invented by Professor Caron is also called the Caron method. The Nicaror Nickel Plant in Cuba has treated the high-magnesia laterite nickel ore by reduction roasting-ammonia leaching for more than half a century. The typical composition of the ore that is suitable for treatment with this ammonia-alkali leaching method is 1.4% Ni, 8% MgO, 14 % SiO 2 . The basic procedure is that the ore having a particle size of less than 74 μm is placed in a multi-hearth furnace for reduction roasting. Nickel and cobalt in the laterite ore are substantially in the form of ferrite, and after reduction and calcination, nickel and cobalt are converted into metals or alloys. The calcination is leached with ammonia-ammonium carbonate mixed solution, treated by a thickener, overflowed into a rich liquid, purified and evaporated to produce a nickel carbonate slurry, which is dried and calcined by a rotary kiln to obtain a nickel oxide product and magnetically selected. The method selects iron concentrate from the leaching slag. For this reason, in the reduction calcination, it is necessary to sufficiently reduce the nickel and cobalt combined with iron, and to prevent excessive reduction of iron. In the 1970s, China assisted the Albanian Al Bassan Iron and Steel Joint Enterprise Project, firstly completing the research on the reduction of roasting-ammonia leaching nickel-cobalt-leaching slag magnetic separation-iron concentrate steelmaking from laterite ore in the world. Applied to industrial production.
为了提高镍钻浸出率，美国矿物局发展了还原焙烧-氨浸法处理红土矿的新流程，简称USBM法。该法的要点在于还原焙烧前加入了黄铁矿(FeS 2)进行制粒，还原时用的是纯一氧化碳。浸出液用LIX64－N作为萃取剂实现钴镍的分离，整个***为闭路循环，有效地利用了资源。据报道，用该法处理含镍1％、钴0.2％的红土矿时，镍、钴的回收率分别为90％和85％。若处理含镍0.53％和钴0.06％的低品位红土矿时，钴的回收率亦能达到76％。与原来的氨浸工艺相比较，大大提高了镍钴的回收率，降低过程的能耗。 In order to improve the leaching rate of nickel diamonds, the US Bureau of Minerals has developed a new process for the reduction roasting-ammonia leaching process for laterite ore, referred to as the USBM method. The main point of this method is the addition of pyrite (FeS 2 ) for granulation before reduction roasting, and the use of pure carbon monoxide for reduction. The leachate uses Lix64-N as an extractant to separate cobalt and nickel. The whole system is a closed loop, which effectively utilizes resources. According to reports, when this method is used to treat laterite ore containing 1% nickel and 0.2% cobalt, the recovery rates of nickel and cobalt are 90% and 85%, respectively. When processing low-grade laterite ore containing 0.53% nickel and 0.06% cobalt, the recovery of cobalt can reach 76%. Compared with the original ammonia leaching process, the recovery rate of nickel and cobalt is greatly improved, and the energy consumption of the process is reduced.
奥托昆普-鲁奇公司(Outokumpu-Lurgi)正在开发处理工艺为：焙烧和流化床预还原褐铁矿或腐殖土矿，还原后矿石分别用于后一步的Caron法处理。Outokumpu-Lurgi is developing a process for calcination and fluidized bed pre-reduction of limonite or humus ore, which is used in the subsequent Caron process.
在产品工艺方面，还原焙烧-氨浸法可产出烧结氧化镍(99％)、电镍、镍粉或镍块。In terms of product process, the reduction roasting-ammonia leaching process produces sintered nickel oxide (99%), nickel, nickel or nickel.
(二)硫酸加压酸浸工艺(HPAL)(2) Sulfuric acid pressurization acid leaching process (HPAL)
硫酸加压酸浸工艺适合处理含氧化镁低的褐铁矿型红土矿，此流程最大的优势在于金属的回收率都能达到90％以上。该技术始于20世纪50年代，首次用于古巴Moa Bay矿，称A-MAX-PAL技术。此后，70年代澳洲QNI公司建成Yabula镍厂，酸浸处理新喀里多尼亚、印尼及澳州昆士兰州的红土型镍矿。1998年下半 年澳大利亚的莫林莫林(Murrin Murrin)、科斯(Cawse)和布隆(Bulong)三个公司采用加压酸浸新工艺的红土矿开发项目陆续投入生产运营，引起很大的关注。这三个工艺中的酸性加压浸出技术与古巴莫奥公司生产中应用的工艺相近，只不过用卧式高压釜取代了莫奥公司的立式高压釜而已。然而，回收步骤却有以下区别：The sulfuric acid pressure acid leaching process is suitable for treating limonite type laterite ore with low magnesium oxide. The biggest advantage of this process is that the recovery rate of metal can reach more than 90%. The technology began in the 1950s and was first used in the Moa Bay mine in Cuba, called A-MAX-PAL technology. Since then, in the 1970s, Australia's QNI Corporation built the Yabula nickel plant, acid-leaching red clay-type nickel mines in New Caledonia, Indonesia and Queensland, Australia. In the second half of 1998, Australia's Murrin Murrin, Cawse and Bulong developed a laterite mining development project using a new process of pressurized acid leaching, which attracted a lot of attention. The acid pressure leaching technology in these three processes is similar to that used in Cuba Moo's production, except that the vertical autoclave has replaced the Moo company's vertical autoclave. However, the recycling step has the following differences:
1、在Cawse工艺中，混合氢氧化物是从高压浸出液中沉淀出来的，然后用氨浸出它们，接着再进行溶剂萃取和电积。1. In the Cawse process, the mixed hydroxide is precipitated from the high pressure leaching solution, and then leached with ammonia, followed by solvent extraction and electrowinning.
2、在Bulong工艺中，用H 2S从高压浸出液中沉淀出混合硫化物，然后在有氧条件下浸出硫化物，接着再进行溶剂萃取、氢还原、压片等作业。 2. In the Bulong process, the mixed sulfide is precipitated from the high pressure leaching solution by H 2 S, and then the sulfide is leached under aerobic conditions, followed by solvent extraction, hydrogen reduction, tableting, and the like.
3、在Murrin工艺中，直接对高压浸出液进行溶剂萃取和电积。3. In the Murrin process, the high pressure leaching solution is directly subjected to solvent extraction and electrowinning.
澳大利亚这三个红土矿HPAL项目的进程并不十分令人满意，仅Cawse达到设计产能的74％，生产成本从4.1美元/磅镍降至1.54美元/磅镍；Murrin Murrin为设计的1/3，并且是在原计划一推再推的情况下达到的，Bulong厂就因为技术和资金问题而被迫在2004年进入破产清算。The process of the three red clay mines in Australia is not very satisfactory. Only Cawse has reached 74% of the design capacity, and the production cost has dropped from 4.1 USD/lb nickel to 1.54 USD/lb nickel; Murrin Murrin is 1/3 of the design. And it was achieved with the original plan pushed forward, Bulong factory was forced to enter bankruptcy liquidation in 2004 because of technical and financial problems.
这三个项目在技术、机械设计以及成本计算上存在着不少的问题，如设备选材不当、配套脱节等等。尽管这三个项目没有达到所期望的目标，但它们的建立为今后的加压酸浸技术的发展提供了宝贵的经验。These three projects have many problems in technology, mechanical design and cost calculation, such as improper equipment selection and dislocation. Although these three projects did not achieve the desired goals, their establishment provided valuable experience for the development of pressurized acid leaching technology in the future.
由于约70％的红土矿资源是褐铁矿型的，高压酸浸技术受到了最大的关注，在技术上得到了很多的改进。从1998年以来，几家大公司，包括BHPB、巴西国有矿业公司(CVRD)、加拿大的鹰桥公司(Falcon bridge)等都进行了技术开发项目。BHPB公司和CVRD公司都倾向于用新流程生产混合硫化物或氢氧化物。Inco公司采用了两步溶剂萃取法，镍从硫酸介质转入盐酸介质，然后将溶液高温水解，得到氧化镍产品和盐酸，盐酸可循环利用。Since about 70% of the laterite resources are of limonite type, the high-pressure acid leaching technology has received the greatest attention and has been technically improved. Since 1998, several major companies, including BHPB, Brazil's state-owned mining company (CVRD), and Canada's Falcon bridge, have conducted technology development projects. Both BHPB and CVRD companies tend to use new processes to produce mixed sulfides or hydroxides. Inco uses a two-step solvent extraction method in which nickel is transferred from a sulfuric acid medium to a hydrochloric acid medium, and then the solution is hydrolyzed at a high temperature to obtain a nickel oxide product and hydrochloric acid, which can be recycled.
SGS Lakefileld公司研究出一种高压酸浸方案，其特点为：在高压釜内加入元素硫和氧，就地产生硫酸。这可使矿浆进入高压釜前的预热变得没有必要，从而显著节约设备成本。SGS Lakefileld has developed a high-pressure acid leaching scheme characterized by the addition of elemental sulfur and oxygen to the autoclave to produce sulfuric acid in situ. This makes it unnecessary to preheat the slurry before it enters the autoclave, thereby significantly saving equipment costs.
(三)其他的湿法流程(3) Other wet processes
常压浸出(AL)：适合处理那些铁含量低和镁含量高的红土型镍矿石。目前Skye资源公司正在研究用于开发危地马拉红土矿矿床的常压浸出法，该法把褐铁矿浸出后的剩余酸和以针铁矿形式沉淀后释放的酸用于浸出大量的腐殖土组份。Atmospheric pressure leaching (AL): suitable for the treatment of lateritic nickel ore with low iron content and high magnesium content. At present, Skye Resources is researching the atmospheric pressure leaching method for the development of the Guatemala laterite deposit, which uses the residual acid after leaching of limonite and the acid released by precipitation in the form of goethite for leaching a large amount of humus Share.
堆浸：主要适合于腐植土矿。大量的研究结果表明，采用堆浸技术，3个月内镍的浸出率可以达到75％以上，钴的浸出率可达到60％以上。欧洲镍公司(European Nickel)目前正在土耳其进行大规模浸试验，有望建成世界上第一座采用堆浸技术提取镍和钴的工厂。Heap leaching: mainly suitable for humus ore. A large number of research results show that with heap leaching technology, the leaching rate of nickel can reach more than 75% within 3 months, and the leaching rate of cobalt can reach more than 60%. European Nickel is currently conducting a large-scale dip test in Turkey and is expected to build the world's first plant to extract nickel and cobalt using heap leaching technology.
微波烧结-加压浸出法：将红土矿进行微波烧结以破坏矿物晶格，再在低温下加压浸出，使铁离子以赤铁矿的形式析出沉淀，达到强化浸出，降低高压酸浸温度和压力的目的。Microwave sintering-pressure leaching method: the laterite ore is subjected to microwave sintering to destroy the mineral crystal lattice, and then subjected to pressure leaching at a low temperature to precipitate iron ions in the form of hematite to achieve enhanced leaching, lowering the high-pressure acid leaching temperature and The purpose of stress.
氯化离析-氨浸：在矿石中加入一定量的碳质还原剂和氯化剂(氯化钠或氯化钙)，在中性或弱还原性的气氛下加热，使有价金属从矿石中氯化挥发，并同时在碳粒表面还原成金属颗粒。随后焙砂直接氨浸。王成彦采用此法处理元江贫氧化镍矿，实验结果为：镍浸出率大于80％，钴浸出率大于50％。Chlorination Segregation-Ammonia Leaching: Adding a certain amount of carbonaceous reducing agent and chlorinating agent (sodium chloride or calcium chloride) to the ore, heating in a neutral or weak reducing atmosphere to make valuable metals from ore The chlorination is volatilized and simultaneously reduced to metal particles on the surface of the carbon particles. The calcination is followed by direct ammonia leaching. Wang Chengyan used this method to treat the Yuanjiang lean nickel oxide ore. The experimental results are as follows: the nickel leaching rate is greater than 80%, and the cobalt leaching rate is greater than 50%.
生物浸出：通过微生物催化的氧化-还原作用能使金属从低品位矿石中有效溶解出来。Castro等研究了异养微生物从硅镁镍矿中浸出镍。矿样取自巴西Acesita矿业公司，化学成份为43.2％SiO 2、0.09％Ni。磨至粒度为147μm以下，浸矿用了5种异养微生物。浸出条件为：矿样重5g(事先在12l℃下灭菌)，含微生物的培养基1000mL，温度30℃，摇瓶速率200r/min，Ni浸出率大于80％。 Bioleaching: The metal is efficiently dissolved from low grade ore by microbial catalyzed oxidation-reduction. Castro et al. studied the leaching of nickel from silicon-magnesium-nickel ore by heterotrophic microorganisms. The ore sample was taken from Acesita Mining Company of Brazil with a chemical composition of 43.2% SiO 2 and 0.09% Ni. Grinding to a particle size of 147 μm or less, five heterotrophic microorganisms were used for leaching. The leaching conditions were as follows: the ore sample weighed 5 g (previously sterilized at 12 l ° C), the microbial-containing medium 1000 mL, the temperature 30 ° C, the shake flask rate 200 r / min, and the Ni leaching rate was greater than 80%.
传统的加压酸浸工艺越来越受重视，在未来几年新建的红土镍矿项目中，此法占了很大的比例。这是由于与火法和氨浸法相比较，加压酸浸在技术和经济上都占有优势。但是该技术也存在很多的问题，如一次性设备投入大；只适合处理含镁低的褐铁型矿石，且对矿石的品位有要求；同液废料多，污染环境等等，这些难题一直限制着该工艺的发展。人们在完善加压酸浸技术的同时也在不断地开发新的红土镍矿湿法流程，如常压浸出、生物浸出等技术。近年来这些新流程备受关注，与加压酸浸工艺相比较，它们具有以下优点：The traditional pressurized acid leaching process has received more and more attention, and this method accounts for a large proportion in the new laterite nickel ore project in the next few years. This is because pressurized acid leaching is technically and economically superior to fire and ammonia leaching. However, this technology also has many problems, such as large investment in disposable equipment; it is only suitable for handling brown iron-type ore with low magnesium content, and has requirements for the grade of ore; the same liquid waste, polluting the environment, etc., these problems have been limited. The development of the process. While perfecting the pressurized acid leaching technology, people are also constantly developing new laterite nickel ore wet processes, such as atmospheric pressure leaching and bioleaching. These new processes have received much attention in recent years, and they have the following advantages compared to pressurized acid leaching processes:
(一)常压浸出、生物浸出技术能处理含镁比较高的红土镍矿，都适合处理低品位的矿石。(1) Atmospheric leaching and bioleaching technology can treat laterite nickel ore with higher magnesium content, which is suitable for processing low grade ore.
(二)常压浸出、生物浸出可以在常温常压的条件下进行，对设备要求低、工艺简单、操作方便，因而投资少，生产成本低。(2) Atmospheric leaching and bioleaching can be carried out under normal temperature and normal pressure conditions, with low equipment requirements, simple process and convenient operation, so the investment is low and the production cost is low.
(三)加压酸浸法固液废料多，污染环境。而新的流程如生物浸出不会产生SO 2气体，产生的固液废弃物也能为环境所接受，十分环保。 (3) Pressurized acid leaching method has many solid-liquid wastes and pollutes the environment. The new process, such as bioleaching, does not produce SO 2 gas, and the resulting solid-liquid waste is environmentally acceptable and environmentally friendly.
但是这些新流程还不成熟，还存在一些技术难题，如常压浸出中浸出液固液分离困难，生物浸出也存在有机酸不能循环的问题，且从目前的报道可知，常压和生物浸出技术处理红土镍矿时镍、钴的浸出率一般都低于加压酸浸。各种方法的固液分离达不到后序提纯金属工艺的标准要求，并且成本高；因此需要研发一种新的红土镍矿提取技术以解决上述问题。However, these new processes are still immature, and there are still some technical problems. For example, the solid-liquid separation of the leachate in atmospheric leaching is difficult, and the bioleaching also has the problem that the organic acid cannot be circulated, and it is known from the current reports that atmospheric pressure and bioleaching techniques are processed. The leaching rate of nickel and cobalt in laterite nickel ore is generally lower than that of pressurized acid leaching. The solid-liquid separation of various methods can not meet the standard requirements of the post-purification metal process, and the cost is high; therefore, it is necessary to develop a new laterite nickel ore extraction technology to solve the above problems.
发明内容Summary of the invention
为了解决上述问题，本发明的目的在于提供一种红土镍矿浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法，该方法通过红土镍矿过度层型硫酸常压浸出、褐 铁矿型硫酸高压浸出、腐质层型高温中和除杂浸出，浸出液和硅胶螯合树脂提纯可以获得高纯度的硫酸镍和硫酸钴产品。In order to solve the above problems, an object of the present invention is to provide a method for purifying nickel sulfate and cobalt sulfate by using laterite nickel ore leaching solution and silica gel chelating resin, which is characterized by excessive pressure of sulfuric acid nickel sulphate overpressure layer and limonite type sulfuric acid. High-purity nickel sulfate and cobalt sulfate products can be obtained by leaching, humic layer type high temperature neutralization and impurity leaching, and leaching liquid and silica gel chelating resin purification.
为了实现上述目的，本发明提供一种红土镍矿浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法，包括如下步骤：In order to achieve the above object, the present invention provides a method for purifying nickel sulfate and cobalt sulfate by using a laterite nickel ore leaching solution and a silica gel chelating resin, comprising the following steps:
1)将干燥的褐铁矿型红土镍矿、过渡层型红土镍矿、腐植土层型红土镍矿分别磨矿至-0.15mm占95％以上的矿粉；1) grinding the dry limonite type laterite nickel ore, the transition layer type laterite nickel ore and the humus layer type lateritic nickel ore to -0.15mm and accounting for more than 95% of the ore powder;
2)将过渡层型红土镍矿矿粉按照硫酸加入量900kg/t矿、液固比4:1的比例添加硫酸和水，进行常压浸出，浸出温度80℃、浸出时间2.5h、然后冷却至室温，固液分离出浸出液1和滤渣1；2) The transition layer type laterite nickel ore powder is added with sulfuric acid and water according to the sulfuric acid addition amount of 900kg/t ore and the liquid-solid ratio of 4:1, and the leaching temperature is 80 ° C, the leaching time is 2.5 h, and then cooled. Up to room temperature, solid-liquid separation of leachate 1 and filter residue 1;
3)褐铁矿型红土镍矿矿粉在高压釜中按照硫酸投入量350kg/t矿，液固比为3:1的比例添加硫酸和浸出液1，然后搅拌升温至240-250℃，控制压力4MPa，继续搅拌浸出60min，降至室温，真空抽滤，固液分离出浸出液2和滤渣2；4)将腐植土层型红土镍矿矿粉按照100g/L的用量加入到浸出液2中，搅拌升温至80℃时再加入腐植土层型红土镍矿矿粉50g/L，继续升温至水解温度220℃，反应2h，然后冷却至室温，固液分离出中和液和滤渣3；3) Limonite type laterite nickel ore powder is added in the autoclave according to the sulfuric acid input amount of 350kg/t ore, the ratio of liquid to solid is 3:1, sulfuric acid and leachate 1 are added, and then the temperature is raised to 240-250 ° C, and the pressure is controlled. 4MPa, continue to stir and leaching for 60min, down to room temperature, vacuum filtration, solid solution separation of leachate 2 and filter residue 2; 4) humus layer type laterite nickel ore powder is added to the leachate 2 according to the amount of 100g / L, stirring When the temperature is raised to 80 °C, 50 g / L of humus layer type laterite nickel ore powder is added, and the temperature is further increased to a hydrolysis temperature of 220 ° C, and the reaction is carried out for 2 hours, and then cooled to room temperature, and the neutralized liquid and the filter residue 3 are separated by solid-liquid separation;
5)在中和液中加入双氧水除杂，添加量为Fe 2+氧化为Fe 3+的理论用量的1.2倍，然后同时滴加8mol/L氨水和浓度为10％的Ca(OH) 2，反应温度为85℃，至中和液pH恒定于3.5～4.0，然后进行固液分离，分离出滤液和滤渣4； 5) Adding hydrogen peroxide to the neutralizing solution to remove impurities, the amount of addition is 1.2 times of the theoretical amount of Fe 2+ oxidized to Fe 3+ , and then adding 8 mol/L ammonia water and 10% Ca(OH) 2 at the same time . The reaction temperature is 85 ° C, the pH of the neutralizing solution is constant at 3.5 to 4.0, and then the solid-liquid separation is carried out to separate the filtrate and the filter residue 4;
6)滤液通过硅胶螯合树脂富集镍钴，获得硫酸镍钴富集液，尾液加入氧化钙除锰，尾渣排放；6) The filtrate is enriched with nickel and cobalt through a silica gel chelating resin to obtain a nickel sulfate cobalt enrichment liquid, and the tail liquid is added with calcium oxide to remove manganese, and the tail slag is discharged;
7)将滤渣1、滤渣2、滤渣3和滤渣4混合，然后加入20％的-80目煤粉，进行磁化焙烧，焙烧温度为650-900℃，焙烧时间为45-75min，水冷却，然后进行弱磁磁选，分离出铁精矿和尾渣。7) mixing the filter residue 1, the filter residue 2, the filter residue 3 and the filter residue 4, and then adding 20% of -80 mesh coal powder for magnetization roasting, the calcination temperature is 650-900 ° C, the calcination time is 45-75 min, the water is cooled, and then Weak magnetic separation is performed to separate iron concentrate and tailings.
其中，所述树脂分离采用双柱串联、单柱解吸的方式，具体为：将三个树脂柱定义为1号树脂柱、2号树脂柱、3号树脂柱，将1号树脂柱和2号树脂柱进行串联，其中1号树脂柱为首柱，2号树脂柱为尾柱，原液从1号树脂柱的下端进液，2号树脂柱的上端出液进行逆流吸附，当1号树脂柱吸附饱和后，采用相同方法将2号树脂柱和3号树脂柱串联，以2号树脂柱为首柱，3号树脂柱为尾柱进行逆流吸附，1号树脂柱进行再生处理，当2号树脂柱吸附饱和后，将3号树脂柱和1号树脂柱串联，以3号树脂柱为首柱，1号树脂柱为尾柱进行逆流吸附，2号树脂柱进行再生处理；当3号树脂柱吸附饱和后，再将1号树脂柱和2号树脂柱串联进行逆流吸附，3号树脂柱进行再生处理，如此循环操作。Wherein, the resin separation adopts a double column series connection and a single column desorption method, specifically: three resin columns are defined as No. 1 resin column, No. 2 resin column, No. 3 resin column, No. 1 resin column and No. 2 The resin column is connected in series, wherein the first resin column is the first column, the second resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the upper end of the No. 2 resin column is subjected to countercurrent adsorption, when the No. 1 resin column is adsorbed. After saturation, the No. 2 resin column and the No. 3 resin column are connected in series by the same method, the No. 2 resin column is used as the head column, the No. 3 resin column is used as the tail column for countercurrent adsorption, and the No. 1 resin column is regenerated, when the No. 2 resin column is used. After the adsorption is saturated, the No. 3 resin column and the No. 1 resin column are connected in series, the No. 3 resin column is used as the head column, the No. 1 resin column is used as the tail column for reverse flow adsorption, and the No. 2 resin column is subjected to regeneration treatment; when the No. 3 resin column is adsorbed and saturated Thereafter, the No. 1 resin column and the No. 2 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and thus the cycle operation is performed.
或，所述树脂分离采用双柱串联、双柱解吸的方式，具体为：将四个树脂柱 定义为1号树脂柱、2号树脂柱、3号树脂柱、4号树脂柱，将1号树脂柱和2号树脂柱进行串联，其中1号树脂柱为首柱，2号树脂柱为尾柱，原液从1号树脂柱的下端进液，2号树脂柱的上端出液进行逆流吸附，当1号树脂柱吸附饱和后，采用相同方法将2号树脂柱和3号树脂柱串联，以2号树脂柱为首柱，3号树脂柱为尾柱进行逆流吸附，1号树脂柱进行再生处理，当2号树脂柱吸附饱和后，将3号树脂柱和4号树脂柱串联，以3号树脂柱为首柱，4号树脂柱为尾柱进行逆流吸附，2号树脂柱进行再生处理；当3号树脂柱吸附饱和后，再将4号树脂柱和1号树脂柱串联进行逆流吸附，3号树脂柱进行再生处理，如此循环操作。Or, the resin separation adopts a double column series and double column desorption method, specifically: four resin columns are defined as No. 1 resin column, No. 2 resin column, No. 3 resin column, No. 4 resin column, No. 1 The resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the upper end of the No. 2 resin column is discharged for countercurrent adsorption. After adsorption and saturation of the No. 1 resin column, the No. 2 resin column and the No. 3 resin column were connected in series by the same method, the No. 2 resin column was used as the head column, the No. 3 resin column was used as the tail column for countercurrent adsorption, and the No. 1 resin column was subjected to regeneration treatment. When the No. 2 resin column is saturated and saturated, the No. 3 resin column and the No. 4 resin column are connected in series, the No. 3 resin column is used as the head column, the No. 4 resin column is used as the tail column for countercurrent adsorption, and the No. 2 resin column is used for regeneration treatment; After the resin column is saturated and adsorbed, the No. 4 resin column and the No. 1 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and thus the cycle operation is performed.
更进一步地，所述再生处理的步骤为：第一次清洗：用自来水以下进上出的方式对吸附饱和的树脂柱进行清洗，清洗体积为6BV；解吸：将解吸剂以下进上出的方式对树脂柱进行解吸，解吸体积为1.26BV，解吸后液进行浓缩后进行提镍钴；第二次清洗：用自来水以下进上出的方式对解吸后的树脂柱进行清洗，清洗体积为3BV，清洗后树脂柱即获得再生，可进行下次吸附。Further, the step of the regeneration treatment is: the first cleaning: washing the saturated resin column with the tap water in and out, the cleaning volume is 6 BV; desorption: the way the desorbent is moved in and out The resin column is desorbed, the desorption volume is 1.26 BV, and the liquid is concentrated after desorption to carry out nickel and cobalt extraction; the second cleaning: the desorbed resin column is cleaned by tap water in and out, and the cleaning volume is 3 BV. After the cleaning, the resin column is regenerated, and the next adsorption can be performed.
更进一步地，所述解吸剂为25-35％的硫酸或15-25％的盐酸。Further, the desorbent is 25-35% sulfuric acid or 15-25% hydrochloric acid.
更进一步地，所述树脂为无机型硅胶螯合离子交换树脂。Further, the resin is an inorganic silica gel chelating ion exchange resin.
优选地，所述无机型硅胶螯合离子交换树脂为SI-2树脂或IAA-PEI-SiO 2树脂。 Preferably, the inorganic silica gel chelating ion exchange resin is an SI-2 resin or an IAA-PEI-SiO 2 resin.
更进一步地，所述弱磁磁选的磁场强度为160KA/M。Further, the magnetic field strength of the weak magnetic separation is 160 kA/M.
更进一步地，所述氧化钙除猛的条件为：氧化钙添加量为尾液的3％，常温反应30min。Further, the condition of removing the calcium oxide is: the amount of calcium oxide added is 3% of the tail liquid, and the reaction is carried out at room temperature for 30 minutes.
本发明采用红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴方法，采用过度层型红土矿常压酸浸、褐铁矿型高压酸浸、腐质层型中和除杂酸浸，浸出液采用无机型硅胶螯合树脂提纯生产硫酸镍钴工艺；解决了其他各种浸出液固液分离工艺，大幅降低40％生产运营成本。The invention adopts the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin to purify the nickel sulfate and cobalt sulfate method, and adopts the excessive layer type laterite ore atmospheric pressure acid leaching, the limonite type high pressure acid leaching, the humus layer type neutralization and the impurity acid leaching, The leachate is purified by inorganic silica gel chelating resin to produce nickel sulfate cobalt sulfate; the other solid-liquid separation processes of various leachates are solved, and the production and operation costs are greatly reduced by 40%.
本发明的有益效果在于：The beneficial effects of the invention are:
本发明提供的红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法，采用湿法一次性提取褐铁矿型红土镍矿及腐殖土层红土镍矿，适用于中间过渡段土层的红土镍矿的处理，镍钴提取效率高，酸法提取褐铁矿型红土镍矿的浸出液中含有的大量剩余游离酸继续用于浸出腐殖土层型红土镍矿，可以有效节省酸的使用量，从而降低生产运营成本。The method for purifying nickel sulfate and cobalt sulfate by using the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin provided by the invention adopts a wet method for one-time extraction of limonite type laterite nickel ore and humus soil laterite nickel ore, and is suitable for intermediate transition soil. The treatment of laterite nickel ore in the layer has high extraction efficiency of nickel and cobalt. The large amount of residual free acid contained in the leachate of acid extraction of limonite type laterite nickel ore continues to be used for leaching humus layer type laterite nickel ore, which can effectively save acid. The amount of use, thereby reducing production and operating costs.
附图说明DRAWINGS
图1为本发明提供的红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法流程图。1 is a flow chart of a method for purifying nickel sulfate and cobalt sulfate by using a laterite nickel ore sulfuric acid leaching solution and a silica gel chelating resin provided by the present invention.
具体实施方式detailed description
以下仅以实施例说明本发明可能的实施形式，然并非用以限制本发明所要保护的范围。The following is a description of the possible embodiments of the invention, but is not intended to limit the scope of the invention.
实施例1Example 1
以如图1所示的流程提取硫酸镍和硫酸钴，具体过程如下：The nickel sulfate and cobalt sulfate are extracted by the process shown in Figure 1, and the specific process is as follows:
所用红土镍矿样品具体成分如表1所示：The specific composition of the laterite nickel ore sample used is shown in Table 1:
表1型红土镍矿样品成分(％)Table 1 type laterite nickel ore sample composition (%)
NiNi CoCo FeFe SiO 2 SiO 2 MgOMgO
0.970.97 0.150.15 48.148.1 4.884.88 1.261.26
将干燥的褐铁矿型红土镍矿、过渡层型红土镍矿、腐植土层型红土镍矿分别磨矿至-0.15mm占95％以上的矿粉。The dried limonite type laterite nickel ore, the transition layer type laterite nickel ore and the humus layer type laterite nickel ore are respectively ground to -0.15 mm and account for more than 95% of the ore powder.
将过渡层型红土镍矿矿粉按照硫酸加入量900kg/t矿、液固比4:1的比例添加硫酸和水，进行常压浸出，浸出温度80℃、浸出时间2.5h、然后冷却至室温，固液分离出浸出液1和滤渣1。The transition layer type laterite nickel ore powder is added with sulfuric acid and water according to the sulfuric acid addition amount of 900 kg/t ore and the liquid-solid ratio of 4:1, and the leaching temperature is 80 ° C, the leaching time is 2.5 h, and then cooled to room temperature. The solid solution separates the leachate 1 and the filter residue 1.
褐铁矿型红土镍矿矿粉在高压釜中按照硫酸投入量350kg/t矿，液固比为3:1的比例添加硫酸和浸出液1，然后搅拌(70转/分)升温至250℃，控制压力4MPa，继续搅拌浸出60min，降至室温，真空抽滤，固液分离出浸出液2和滤渣2，此步骤中镍、钴浸出率均大于95％，而铁的浸出率小于2％。The limonite type laterite nickel ore powder is added to the autoclave according to the sulfuric acid input amount of 350 kg/t ore, the liquid-solid ratio is 3:1, and the sulfuric acid and the leachate 1 are added, and then the temperature is raised to 250 ° C by stirring (70 rpm). The control pressure is 4 MPa, the leaching is continued for 60 min, the temperature is lowered to room temperature, and vacuum filtration is performed to separate the leachate 2 and the filter residue 2 by solid-liquid separation. In this step, the leaching rates of nickel and cobalt are both greater than 95%, and the leaching rate of iron is less than 2%.
将腐植土层型红土镍矿矿粉按照100g/L的用量加入到浸出液2中，搅拌(70转/分)升温至80℃时再加入腐植土层型红土镍矿矿粉50g/L，继续升温至水解温度220℃，反应2h，然后冷却至室温，固液分离出中和液和滤渣3；The humus layer type laterite nickel ore powder is added to the leachate 2 according to the dosage of 100g/L, and the temperature is raised to 80 °C by stirring (70 rpm), and then the humus layer type laterite nickel ore powder 50g/L is added, and the continuation is continued. Heating to a hydrolysis temperature of 220 ° C, the reaction for 2h, and then cooled to room temperature, solid-liquid separation of the neutralized liquid and filter residue 3;
采用两次添加腐植土层型红土镍矿的方式可把现有的中和效率由80％提升到99％以上。The existing neutralization efficiency can be increased from 80% to over 99% by adding humus layer type laterite nickel ore.
在中和液中加入双氧水，添加量为Fe 2+氧化为Fe 3+的理论用量的1.2倍，然后同时滴加8mol/L氨水和浓度为10％的Ca(OH) 2，反应温度为85℃，至中和液pH恒定于3.5～4.0，然后进行固液分离，分离出滤液和滤渣4； Add hydrogen peroxide to the neutralizing solution in an amount of 1.2 times the theoretical amount of Fe 2+ oxidized to Fe 3+ , and then add 8 mol/L ammonia water and 10% Ca(OH) 2 at a reaction temperature of 85. °C, to the neutralization liquid pH is constant at 3.5 ~ 4.0, then solid-liquid separation, separation of filtrate and filter residue 4;
采用双氧水可将中和液中残余的Fe 2+氧化为Fe 3+，进而水解为Fe(OH) 3去除，铁去除率可达99％以上，除铁后滤液中铁浓度接近10ppm，而镍钴在渣中仅含钴0.2％，镍0.1％，镍钴损失很小。 The residual Fe 2+ in the neutralization solution can be oxidized to Fe 3+ by hydrogen peroxide, and then hydrolyzed to Fe(OH) 3 for removal. The iron removal rate can reach more than 99%. After the iron removal, the iron concentration in the filtrate is close to 10 ppm, and the nickel cobalt In the slag, only 0.2% of cobalt and 0.1% of nickel are contained, and the loss of nickel and cobalt is small.
滤液通过树脂富集镍钴，然后解吸获得硫酸镍钴富集液，尾液加入3％氧化钙除锰，常温反应30min，尾渣排放输送至尾矿库。The filtrate is enriched in nickel-cobalt by resin, and then desorbed to obtain nickel-cobalt-sulfurate enrichment liquid. The tail liquid is added with 3% calcium oxide and manganese, and the reaction is carried out at room temperature for 30 min, and the tail slag is discharged to the tailings storage.
所用树脂为无机型硅胶螯合离子交换树脂SI-2，树脂富集镍钴采用双柱串联、单柱解吸的方式，具体为：将三个树脂柱定义为1号树脂柱、2号树脂柱、3 号树脂柱，将1号树脂柱和2号树脂柱进行串联，其中1号树脂柱为首柱，2号树脂柱为尾柱，原液从1号树脂柱的下端进液，2号树脂柱的上端出液进行逆流吸附，当1号树脂柱吸附饱和后，采用相同方法将2号树脂柱和3号树脂柱串联，以2号树脂柱为首柱，3号树脂柱为尾柱进行逆流吸附，1号树脂柱进行再生处理，当2号树脂柱吸附饱和后，将3号树脂柱和1号树脂柱串联，以3号树脂柱为首柱，1号树脂柱为尾柱进行逆流吸附，2号树脂柱进行再生处理；当3号树脂柱吸附饱和后，再将1号树脂柱和2号树脂柱串联进行逆流吸附，3号树脂柱进行再生处理，如此循环操作。The resin used is inorganic silica gel chelate ion exchange resin SI-2, and the resin enriched nickel cobalt adopts double column series and single column desorption method. Specifically, three resin columns are defined as No. 1 resin column and No. 2 resin. Column No. 3 resin column, the No. 1 resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, the raw liquid is fed from the lower end of the No. 1 resin column, and the No. 2 resin The upper end of the column is subjected to countercurrent adsorption. When the No. 1 resin column is saturated and saturated, the No. 2 resin column and the No. 3 resin column are connected in series by the same method, and the No. 2 resin column is used as the head column, and the No. 3 resin column is used as the tail column for countercurrent flow. Adsorption, No. 1 resin column is regenerated. When the No. 2 resin column is saturated, the No. 3 resin column and the No. 1 resin column are connected in series, and the No. 3 resin column is used as the head column, and the No. 1 resin column is used as the tail column for countercurrent adsorption. The No. 2 resin column is subjected to regeneration treatment; when the No. 3 resin column is adsorbed and saturated, the No. 1 resin column and the No. 2 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and thus the cycle operation is performed.
所述再生处理的步骤为：第一次清洗：用自来水以下进上出的方式对吸附饱和的树脂柱进行清洗，清洗体积为6BV；解吸：将35％硫酸解吸剂以下进上出的方式对树脂柱进行解吸，解吸体积为1.26BV，解吸后液进行浓缩后进行提镍钴；第二次清洗：用自来水以下进上出的方式对解吸后的树脂柱进行清洗，清洗体积为3BV，清洗后树脂柱即获得再生，可进行下次吸附。The step of the regeneration treatment is: the first cleaning: the resin column saturated with adsorption is washed in the manner of tap water up and down, the cleaning volume is 6 BV; desorption: 35% sulfuric acid desorbent is fed in and out The resin column is desorbed, the desorption volume is 1.26 BV, and the liquid is concentrated after desorption to carry out nickel and cobalt extraction; the second cleaning: the desorbed resin column is cleaned by tap water in and out, the cleaning volume is 3 BV, and the cleaning is performed. The post-resin column is regenerated for the next adsorption.
获得的硫酸镍钴富集液可按常规方法制备镍钴产品。The obtained nickel cobalt cobalt-rich liquid can be prepared by a conventional method.
表2硫酸镍钴滤液及树脂富集后解吸液成分(g/L)Table 2 Dissolved liquid components (g/L) after nickel sulfate cobalt filtrate and resin enrichment
Figure PCTCN2018083897-appb-000001
Figure PCTCN2018083897-appb-000001
6)将滤渣1、滤渣2、滤渣3、滤渣4混合后加入20％的-80目煤粉，进行磁化焙烧，焙烧温度为750℃，焙烧时间为60min，水冷却，然后进行弱磁磁选，磁场强度为160KA/M，分离出铁精矿和尾渣。6) Mixing the filter residue 1, the filter residue 2, the filter residue 3, and the filter residue 4, adding 20%-80 mesh coal powder for magnetization roasting, the calcination temperature is 750 ° C, the calcination time is 60 min, the water is cooled, and then the weak magnetic separation is performed. The magnetic field strength is 160KA/M, and the iron concentrate and tailings are separated.
其中铁精矿中铁的含量达到60％以上，硫的含量达到0.2％以下，其化学成分完全达到炼铁行业对铁精矿化学成分的要求。The iron content in the iron concentrate is more than 60%, and the sulfur content is below 0.2%. The chemical composition of the iron concentrate completely meets the requirements of the iron concentrate in the iron ore industry.
从上述实施例可以看出，本发明采用的红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法，可以有效富集低品位红土镍矿中的镍钴，通过常压、高压、高温方式浸出提取与树脂提纯富集结合的方式，解决世界矿业湿法冶金固液分离的难题，减少了传统萃取富集方式中的大量外来试剂的使用，同时，精简了生产工艺，树脂提纯富集中采用了双柱串联、单柱或双柱解吸的方式，可进行连续生产，无需停工解吸，达到提质增效的生产效果。It can be seen from the above embodiments that the method for purifying nickel sulfate and cobalt sulfate by using the laterite nickel ore sulfuric acid leaching solution and the silica gel chelating resin used in the invention can effectively enrich the nickel and cobalt in the low grade laterite nickel ore, and the normal pressure and the high pressure are The combination of high-temperature leaching extraction and resin purification and enrichment solves the problem of the world's mining hydrometallurgical solid-liquid separation, reduces the use of a large number of external reagents in the traditional extraction and enrichment mode, and at the same time, streamlines the production process, and purifies the resin. The two-column series, single-column or double-column desorption method is adopted in a concentrated manner, which can be continuously produced without stopping work and desorption, and achieve the production effect of improving quality and efficiency.

Claims (10)

  1. 一种红土镍矿硫酸浸出液和硅胶螯合树脂提纯生产硫酸镍钴的方法，其特征在于，包括如下步骤：A method for purifying nickel sulfate and cobalt sulfate by using a laterite nickel ore sulfuric acid leaching solution and a silica gel chelating resin, comprising the steps of:
    1)将干燥的褐铁矿型红土镍矿、过渡层型红土镍矿、腐植土层型红土镍矿分别磨矿至-0.15mm占95％以上的矿粉；1) grinding the dry limonite type laterite nickel ore, the transition layer type laterite nickel ore and the humus layer type lateritic nickel ore to -0.15mm and accounting for more than 95% of the ore powder;
    2)将过渡层型红土镍矿矿粉按照硫酸加入量900kg/t矿、液固比4:1的比例添加硫酸和水，进行常压浸出，浸出温度80℃、浸出时间2.5h、然后冷却至室温，固液分离出浸出液1和滤渣1；2) The transition layer type laterite nickel ore powder is added with sulfuric acid and water according to the sulfuric acid addition amount of 900kg/t ore and the liquid-solid ratio of 4:1, and the leaching temperature is 80 ° C, the leaching time is 2.5 h, and then cooled. Up to room temperature, solid-liquid separation of leachate 1 and filter residue 1;
    3)褐铁矿型红土镍矿矿粉在高压釜中按照硫酸投入量350kg/t矿，液固比为3:1的比例添加硫酸和浸出液1，然后搅拌升温至240-250℃，控制压力4MPa，继续搅拌浸出60min，降至室温，真空抽滤，固液分离出浸出液2和滤渣2；3) Limonite type laterite nickel ore powder is added in the autoclave according to the sulfuric acid input amount of 350kg/t ore, the ratio of liquid to solid is 3:1, sulfuric acid and leachate 1 are added, and then the temperature is raised to 240-250 ° C, and the pressure is controlled. 4MPa, continue to stir and leaching for 60min, down to room temperature, vacuum filtration, solid solution separation of leachate 2 and filter residue 2;
    4)将腐植土层型红土镍矿矿粉按照100g/L的用量加入到浸出液2中，搅拌升温至80℃时再加入腐植土层型红土镍矿矿粉50g/L，继续升温至水解温度220℃，反应2h，然后冷却至室温，固液分离出中和液和滤渣3；4) Add the humus layer type laterite nickel ore powder to the leachate 2 according to the dosage of 100g/L, stir the temperature to 80 °C, then add the humus layer type laterite nickel ore powder 50g/L, and continue to raise the temperature to the hydrolysis temperature. 220 ° C, the reaction for 2h, then cooled to room temperature, solid-liquid separation of the neutralizing solution and filter residue 3;
    5)在中和液中加入双氧水除杂，添加量为Fe 2+氧化为Fe 3+的理论用量的1.2倍，然后同时滴加8mol/L氨水和浓度为10％的Ca(OH) 2，反应温度为85℃，至中和液pH恒定于3.5～4.0，然后进行固液分离，分离出滤液和滤渣4； 5) Adding hydrogen peroxide to the neutralizing solution to remove impurities, the amount of addition is 1.2 times of the theoretical amount of Fe 2+ oxidized to Fe 3+ , and then adding 8 mol/L ammonia water and 10% Ca(OH) 2 at the same time . The reaction temperature is 85 ° C, the pH of the neutralizing solution is constant at 3.5 to 4.0, and then the solid-liquid separation is carried out to separate the filtrate and the filter residue 4;
    6)滤液通过硅胶螯合树脂富集镍钴，获得硫酸镍钴富集液，尾液加入氧化钙除锰，尾渣排放；6) The filtrate is enriched with nickel and cobalt through a silica gel chelating resin to obtain a nickel sulfate cobalt enrichment liquid, and the tail liquid is added with calcium oxide to remove manganese, and the tail slag is discharged;
    7)将滤渣1、滤渣2、滤渣3和滤渣4混合，然后加入20％的-80目煤粉，进行磁化焙烧，焙烧温度为650-900℃，焙烧时间为45-75min，水冷却，然后进行弱磁磁选，分离出铁精矿和尾渣。7) mixing the filter residue 1, the filter residue 2, the filter residue 3 and the filter residue 4, and then adding 20% of -80 mesh coal powder for magnetization roasting, the calcination temperature is 650-900 ° C, the calcination time is 45-75 min, the water is cooled, and then Weak magnetic separation is performed to separate iron concentrate and tailings.
  2. 如权利要求1所述的方法，其特征在于，所述无机型硅胶螯合树脂分离采用双柱串联、单柱解吸的方式，具体为：将三个树脂柱定义为1号树脂柱、2号树脂柱、3号树脂柱，将1号树脂柱和2号树脂柱进行串联，其中1号树脂柱为首柱，2号树脂柱为尾柱，原液从1号树脂柱的下端进液，2号树脂柱的上端出液进行逆流吸附，当1号树脂柱吸附饱和后，采用相同方法将2号树脂柱和3号树脂柱串联，以2号树脂柱为首柱，3号树脂柱为尾柱进行逆流吸附，1号树脂柱进行再生处理，当2号树脂柱吸 附饱和后，将3号树脂柱和1号树脂柱串联，以3号树脂柱为首柱，1号树脂柱为尾柱进行逆流吸附，2号树脂柱进行再生处理；当3号树脂柱吸附饱和后，再将1号树脂柱和2号树脂柱串联进行逆流吸附，3号树脂柱进行再生处理，如此循环操作。The method according to claim 1, wherein the inorganic silica gel chelating resin is separated by a two-column series and a single column desorption method, specifically: three resin columns are defined as No. 1 resin column, 2 No. resin column, No. 3 resin column, the No. 1 resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, and the raw liquid is fed from the lower end of the No. 1 resin column, 2 The upper end of the resin column is subjected to countercurrent adsorption. When the No. 1 resin column is saturated, the No. 2 resin column and the No. 3 resin column are connected in series by the same method, and the No. 2 resin column is used as the head column, and the No. 3 resin column is the tail column. Reverse flow adsorption was carried out, and the No. 1 resin column was regenerated. When the No. 2 resin column was saturated, the No. 3 resin column and the No. 1 resin column were connected in series, and the No. 3 resin column was used as the head column, and the No. 1 resin column was used as the tail column for the reverse flow. Adsorption, No. 2 resin column for regeneration treatment; when the No. 3 resin column is saturated, the No. 1 resin column and the No. 2 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and the cycle operation is performed.
  3. 如权利要求1所述的方法，其特征在于，所述无机型硅胶螯合树脂分离采用双柱串联、双柱解吸的方式，具体为：将四个树脂柱定义为1号树脂柱、2号树脂柱、3号树脂柱、4号树脂柱，将1号树脂柱和2号树脂柱进行串联，其中1号树脂柱为首柱，2号树脂柱为尾柱，原液从1号树脂柱的下端进液，2号树脂柱的上端出液进行逆流吸附，当1号树脂柱吸附饱和后，采用相同方法将2号树脂柱和3号树脂柱串联，以2号树脂柱为首柱，3号树脂柱为尾柱进行逆流吸附，1号树脂柱进行再生处理，当2号树脂柱吸附饱和后，将3号树脂柱和4号树脂柱串联，以3号树脂柱为首柱，4号树脂柱为尾柱进行逆流吸附，2号树脂柱进行再生处理；当3号树脂柱吸附饱和后，再将4号树脂柱和1号树脂柱串联进行逆流吸附，3号树脂柱进行再生处理，如此循环操作。The method according to claim 1, wherein the inorganic silica gel chelating resin is separated by two-column series and two-column desorption, specifically: four resin columns are defined as No. 1 resin column, 2 No. resin column, No. 3 resin column, No. 4 resin column, the No. 1 resin column and the No. 2 resin column are connected in series, wherein the No. 1 resin column is the first column, the No. 2 resin column is the tail column, and the raw liquid is from the No. 1 resin column. The lower end is filled with liquid, and the upper end of the No. 2 resin column is subjected to countercurrent adsorption. When the No. 1 resin column is saturated and saturated, the No. 2 resin column and the No. 3 resin column are connected in series by the same method, and the No. 2 resin column is used as the head column, No. 3 The resin column is subjected to countercurrent adsorption for the tail column, and the No. 1 resin column is regenerated. When the No. 2 resin column is saturated, the No. 3 resin column and the No. 4 resin column are connected in series, and the No. 3 resin column is used as the head column, and the No. 4 resin column is used. The tail column is subjected to countercurrent adsorption, and the No. 2 resin column is subjected to regeneration treatment; when the No. 3 resin column is saturated and adsorbed, the No. 4 resin column and the No. 1 resin column are connected in series for countercurrent adsorption, and the No. 3 resin column is subjected to regeneration treatment, and thus the cycle is repeated. operating.
  4. 如权利要求2或3所述的方法，其特征在于，所述再生处理的步骤为：第一次清洗：用自来水以下进上出的方式对吸附饱和的树脂柱进行清洗，清洗体积为6BV；解吸：将解吸剂以下进上出的方式对树脂柱进行解吸，解吸体积为1.26BV，解吸后液进行浓缩后进行提镍钴；第二次清洗：用自来水以下进上出的方式对解吸后的树脂柱进行清洗，清洗体积为3BV，清洗后树脂柱即获得再生，可进行下次吸附。The method according to claim 2 or 3, wherein the step of regenerating is: first cleaning: washing the saturated resin column with tap water in and out, the cleaning volume is 6 BV; Desorption: desorb the resin column in the manner of the desorbent below, the desorption volume is 1.26BV, and the solution is concentrated after desorption to extract nickel and cobalt; the second cleaning: using tap water to enter and exit the desorption after desorption The resin column is cleaned, the cleaning volume is 3BV, and the resin column is regenerated after washing, and the next adsorption can be performed.
  5. 如权利要求4所述的方法，其特征在于，所述解吸剂为25-35％的硫酸或15-25％的盐酸。The method of claim 4 wherein said desorbent is 25-35% sulfuric acid or 15-25% hydrochloric acid.
  6. 如权利要求1所述的方法，其特征在于，所述树脂为无机型硅胶螯合离子交换树脂。The method of claim 1 wherein said resin is an inorganic silica gel chelating ion exchange resin.
  7. 如权利要求6所述的方法，其特征在于，所述无机型硅胶螯合离子交换树脂为SI-2树脂或IAA-PEI-SiO 2树脂。 The method of claim 6 wherein said inorganic silica gel chelating ion exchange resin is SI-2 resin or IAA-PEI-SiO 2 resin.
  8. 如权利要求1所述的方法，其特征在于，所述弱磁磁选的磁场强度为160KA/M。The method of claim 1 wherein said field weakening magnetic field strength is 160 kA/M.
  9. 如权利要求1所述的方法，其特征在于，所述氧化钙除猛的条件为：氧化钙添加量为尾液的3％，常温反应30min。The method according to claim 1, wherein the calcium oxide is pulverized under the condition that the amount of calcium oxide added is 3% of the tail liquid, and the reaction at room temperature is 30 minutes.
  10. 如权利要求1所述的方法，其特征在于，所述步骤搅拌的速度为60-80转/分。The method of claim 1 wherein said step of agitation is at a rate of from 60 to 80 rpm.
PCT/CN2018/083897 2018-03-15 2018-04-20 Method for producing nickel sulfate and cobaltous sulfate by purification of laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin WO2019174103A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810213786.3 2018-03-15
CN201810213786.3A CN108396157B (en) 2018-03-15 2018-03-15 Method for producing nickel-cobalt sulfate by purifying laterite-nickel ore sulfuric acid leaching solution and silica gel chelating resin

Publications (1)

Publication Number Publication Date
WO2019174103A1 true WO2019174103A1 (en) 2019-09-19

Family

ID=63092360

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/083897 WO2019174103A1 (en) 2018-03-15 2018-04-20 Method for producing nickel sulfate and cobaltous sulfate by purification of laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin

Country Status (2)

Country Link
CN (1) CN108396157B (en)
WO (1) WO2019174103A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699557A (en) * 2019-10-23 2020-01-17 金川集团股份有限公司 Low-cost treatment device and method for nickel hydroxide cobalt slag
CN113528808A (en) * 2021-05-24 2021-10-22 红河钢铁有限公司 Sintered ore based on high-crystal-water limonite and magnetic separation tailings and production method thereof
CN114279806A (en) * 2021-12-16 2022-04-05 浙江鑫旺钒业控股有限公司 Method for improving vanadium adsorption rate from acidic solution
WO2023010837A1 (en) * 2022-02-08 2023-02-09 陈崇学 Pyrolysis sulfurization beneficiation method for laterite-nickel ore, metal sulfide, and use
WO2023077215A1 (en) * 2021-11-05 2023-05-11 Alliance Magnesium Process of extracting nickel sulfate from asbestos mining residue

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109252056A (en) * 2018-09-25 2019-01-22 眉山顺应动力电池材料有限公司 A kind of processing method of low magnesium brown iron type nickel laterite ore
CN111004915A (en) * 2018-10-08 2020-04-14 金川集团股份有限公司 Method for extracting nickel, cobalt and iron from low-grade laterite-nickel ore
CN111004926A (en) * 2018-10-08 2020-04-14 金川集团股份有限公司 Method for extracting nickel and cobalt from low-grade laterite-nickel ore leaching solution by resin
CN110004306B (en) * 2019-03-11 2021-06-29 西安蓝晓科技新材料股份有限公司 Continuous ion exchange device and method for recovering metallic nickel from laterite-nickel ore leaching liquor
CN114645143B (en) * 2020-12-21 2023-10-20 北京博萃循环科技有限公司 Method for separating nickel, cobalt, copper and manganese from laterite-nickel ore
CN113073207B (en) * 2021-03-23 2022-07-22 中国恩菲工程技术有限公司 Method for extracting valuable metals from high-magnesium type laterite-nickel ore
CN114480877B (en) * 2021-12-16 2023-10-17 中南大学 Comprehensive resource recovery method for laterite nickel ore

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805828A (en) * 2010-04-19 2010-08-18 中南大学 Low-cost method for disposing red soil nickel ore
CN102226236A (en) * 2011-06-15 2011-10-26 王钧 Hydrometallurgical method for comprehensively recycling components in lateritic nickel ore as products
CN102268537A (en) * 2011-08-15 2011-12-07 广西银亿科技矿冶有限公司 Method for extracting cobalt and nickel from laterite-nickel ore
CN104611558A (en) * 2014-12-31 2015-05-13 金川集团股份有限公司 Method for recovering nickel, cobalt, iron and silicon from laterite-nickel ore through united leaching technology

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6379636B2 (en) * 1999-11-03 2002-04-30 Bhp Minerals International, Inc. Method for leaching nickeliferous laterite ores
CA2597440A1 (en) * 2005-02-14 2006-08-17 Bhp Billiton Ssm Technology Pty Ltd Process for enhanced acid leaching of laterite ores
BRPI0701068B1 (en) * 2007-04-12 2018-02-27 Vale S.A. NICKEL AND COBALT RECOVERY PROCESS FROM AN ELUTE USING SOLVENT EXTRACTION
CN101974685B (en) * 2010-11-05 2013-02-27 吉林吉恩镍业股份有限公司 Process for extracting nickel-cobalt from laterite by using resin-in-pulp adsorption technology
CN102212684B (en) * 2011-06-08 2013-06-12 广西银亿科技矿冶有限公司 Method for wet-leaching lateritic-nickel ore at transition layer
CN103131855A (en) * 2011-11-29 2013-06-05 沈阳有色金属研究院 Method for treating normal pressure leaching of transitional nickel laterite ore
CN102994753A (en) * 2012-12-10 2013-03-27 金川集团股份有限公司 Method for separating and enriching nickel from leach liquor used for pickling and vulcanizing tailing
CN103614571A (en) * 2013-10-09 2014-03-05 北京矿冶研究总院 Combined leaching process of laterite-nickel ore
CN104630464A (en) * 2014-12-31 2015-05-20 金川集团股份有限公司 Method for extracting nickel and cobalt from laterite-nickel ores by atmospheric-pressure acid leaching
CN105154669A (en) * 2014-12-31 2015-12-16 金川集团股份有限公司 Method for recovering Ni, Co, Fe, Si and Mg from laterite
CN104775024A (en) * 2014-12-31 2015-07-15 金川集团股份有限公司 Method for recovering nickel, cobalt and iron from laterite-nickel ore
CN104805306A (en) * 2014-12-31 2015-07-29 金川集团股份有限公司 New method for recovering nickel, cobalt and iron from low-grade laterite-nickel ore

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805828A (en) * 2010-04-19 2010-08-18 中南大学 Low-cost method for disposing red soil nickel ore
CN102226236A (en) * 2011-06-15 2011-10-26 王钧 Hydrometallurgical method for comprehensively recycling components in lateritic nickel ore as products
CN102268537A (en) * 2011-08-15 2011-12-07 广西银亿科技矿冶有限公司 Method for extracting cobalt and nickel from laterite-nickel ore
CN104611558A (en) * 2014-12-31 2015-05-13 金川集团股份有限公司 Method for recovering nickel, cobalt, iron and silicon from laterite-nickel ore through united leaching technology

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699557A (en) * 2019-10-23 2020-01-17 金川集团股份有限公司 Low-cost treatment device and method for nickel hydroxide cobalt slag
CN110699557B (en) * 2019-10-23 2023-06-27 金川集团股份有限公司 Low-cost treatment device and method for cobalt nickel hydroxide slag
CN113528808A (en) * 2021-05-24 2021-10-22 红河钢铁有限公司 Sintered ore based on high-crystal-water limonite and magnetic separation tailings and production method thereof
WO2023077215A1 (en) * 2021-11-05 2023-05-11 Alliance Magnesium Process of extracting nickel sulfate from asbestos mining residue
CN114279806A (en) * 2021-12-16 2022-04-05 浙江鑫旺钒业控股有限公司 Method for improving vanadium adsorption rate from acidic solution
CN114279806B (en) * 2021-12-16 2024-05-28 浙江鑫旺钒业控股有限公司 Method for improving vanadium adsorption rate from acid solution
WO2023010837A1 (en) * 2022-02-08 2023-02-09 陈崇学 Pyrolysis sulfurization beneficiation method for laterite-nickel ore, metal sulfide, and use

Also Published As

Publication number Publication date
CN108396157B (en) 2020-01-10
CN108396157A (en) 2018-08-14

Similar Documents

Publication Publication Date Title
WO2019174103A1 (en) Method for producing nickel sulfate and cobaltous sulfate by purification of laterite nickel ore sulfuric acid leaching solution and silica gel chelate resin
CN101509072B (en) Method for extracting valuable metals from laterite nickel mine with hydrochloric acid full-closed circulation method
CN109234522B (en) Comprehensive recovery processing method for cobalt-sulfur concentrate
AU2007288109B2 (en) Production of metallic nickel with low iron content
CN112080636B (en) Method for producing battery-grade nickel sulfate salt by using laterite-nickel ore
CN101230422A (en) Method for enriching nickel from lateritic nickel with co-production of iron-oxide red
WO2006089358A1 (en) Production of ferronickel
CN101323909B (en) Method of microwave selective reduction roasting-dilute acid leaching nickel oxide ore
CN102534206A (en) Leaching method of limonite type laterite-nickel ore
CN102286661A (en) Method for direct electrolysis of laterite nickel ore by sulfuric acid leaching
WO2017185946A1 (en) Method for processing low-grade laterite nickel ore and beneficiation method therefor
CN113897491B (en) Method for comprehensively and efficiently treating zinc leaching slag
CN102851489B (en) Method for comprehensively recovering valuable metals in limonite type laterite-nickel ore
CN101974685A (en) Process for extracting nickel-cobalt from laterite by using resin-in-pulp adsorption technology
EP2814992A1 (en) Production of high grade nickel product
WO2012171480A1 (en) Hydrometallurgical method for comprehensive recycling of lateritic nickel ore components as products
CN113846214B (en) Method for treating zinc-containing material in zinc hydrometallurgy production
CN101139656A (en) Laterite nickel ore leaching method
CN111575502A (en) Method for extracting nickel element from nickel ore
CN101798633B (en) Method for treating limonite type oxidized nickel ore by roasting and leaching
EP2829620A1 (en) Method for producing hematite for iron-making use
CN114507780A (en) Low-cost and low-acid-consumption laterite-nickel ore leaching method
CN206828600U (en) The system for handling lateritic nickel ore
CN101392321B (en) Method for treating nickel-containing laterite by microwave reducing roasting-hematite precipitation conversion method
CN109604052A (en) The processing method of lateritic nickel ore slag

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18909569

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18909569

Country of ref document: EP

Kind code of ref document: A1