CN113564383B - System and process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization - Google Patents
System and process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization Download PDFInfo
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- CN113564383B CN113564383B CN202111111466.5A CN202111111466A CN113564383B CN 113564383 B CN113564383 B CN 113564383B CN 202111111466 A CN202111111466 A CN 202111111466A CN 113564383 B CN113564383 B CN 113564383B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 287
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 173
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 68
- 239000010941 cobalt Substances 0.000 title claims abstract description 68
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 169
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 97
- 239000002253 acid Substances 0.000 claims abstract description 93
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims abstract description 55
- 239000012535 impurity Substances 0.000 claims abstract description 47
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001556 precipitation Methods 0.000 claims abstract description 25
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002918 waste heat Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 44
- 229910052742 iron Inorganic materials 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 230000003472 neutralizing effect Effects 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 23
- 239000000292 calcium oxide Substances 0.000 claims description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 16
- 230000007062 hydrolysis Effects 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002893 slag Substances 0.000 description 54
- 235000012255 calcium oxide Nutrition 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 8
- 229910017709 Ni Co Inorganic materials 0.000 description 7
- 229940037003 alum Drugs 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052595 hematite Inorganic materials 0.000 description 4
- 239000011019 hematite Substances 0.000 description 4
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910001710 laterite Inorganic materials 0.000 description 2
- 239000011504 laterite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000005020 Acaciella glauca Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- -1 compound salts Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- 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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
Abstract
The application provides a system and a process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization, and relates to the technical field of laterite-nickel ore treatment. The system comprises a high-pressure acid leaching device, a high-pressure neutralization unit, a neutralization and impurity removal unit and a nickel-cobalt precipitation unit; in the process of extracting nickel and cobalt, the ore pulp treated by the high-pressure acid leaching device is directly conveyed to a high-pressure neutralization unit, and after the ore pulp is subjected to high-pressure neutralization in cooperation with the added serpentine ore pulp, neutralization, impurity removal and nickel and cobalt precipitation treatment are carried out. The system and the process can fully utilize the waste heat after the high-pressure acid leaching treatment of the limonite, realize the enhancement of the leaching of the serpentine and promote the Al3+The further hydrolysis of the nickel and cobalt leaching agent achieves the effects of improving the leaching rate of nickel and cobalt and reducing the consumption of auxiliary materials such as alkali and the like.
Description
Technical Field
The application relates to the technical field of laterite-nickel ore treatment, in particular to a system and a process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization.
Background
The nickel in the laterite-nickel ore occupies about 70 percent of the land-based nickel reserve on the ball, and is a main ore source for extracting the metal nickel. Generally, the chemical compositions are divided into two types: one is garnierite (serpentine type), which has high contents of nickel, silicon and magnesium and low contents of iron and cobalt. The other is limonite type, the content of iron and cobalt is high, the content of magnesium is low, the nickel storage amount of the other is 70 percent of that of laterite ore, and the development and utilization of the other are concerned.
In the process of treating the laterite-nickel ore by the wet method, the serpentine ore is mainly subjected to processes of normal-pressure acid leaching, pressurization-normal-pressure combination and the like, the leaching rate of nickel and cobalt is increased in proportion with the acid-ore ratio, the leaching rate of iron is increased, the consumption of auxiliary materials is increased, and the economic benefit of the laterite-nickel ore is greatly influenced when the international nickel market price is not good. The limonite treatment process mainly comprises a high pressure acid leaching method (HPAL), such as a Guba MOA BAY plant, a Korea plant, a Murrin plant, a Redwood plant and the like, wherein the nickel-cobalt leaching rate can reach more than 95 percent. The pressure leaching process has the characteristics of high nickel and cobalt recovery rate, low iron leaching rate and strong selectivity. In recent years, the international development projects of laterite-nickel ore mostly adopt a wet process of high-pressure acid leaching, such as the project of Mizhou-smelt Ruimei, and the project of Indonesia of companies such as Mingyou, Huanyou and Glimei which are built in force, adopts the high-pressure acid leaching process.
Currently, the established or under-construction high-pressure acid leaching method is used for treating limonite type laterite-nickel ore, and the combined process of high-pressure acid leaching for limonite treatment and normal-pressure neutralization for serpentine ore is adopted without exception, the process is called high-pressure acid leaching-normal-pressure neutralization for short, and the typical process flow is shown in figure 1. The limonite is treated by high-pressure acid leaching, the nickel and cobalt are selectively leached under high temperature and high acid, most of impurity iron and aluminum exist in slag, high nickel and cobalt leaching rate can be obtained, ore pulp is subjected to flash evaporation cooling after reaction is finished, the ore pulp is added into serpentine ore pulp to neutralize residual acid in the limonite ore pulp, nickel in the serpentine is leached as far as possible, and the nickel leaching rate is about 40-60% generally. The method can leach a small amount of nickel in the serpentine, improves the resource utilization rate of the laterite-nickel ore, neutralizes the residual acid by using the serpentine, is beneficial to reducing the consumption of a neutralizer in the subsequent neutralization and impurity removal process, and has certain advantages, so that the method is greatly applied. A similar technique is also disclosed in prior art CN107250394A, which employs a combined process of high pressure treatment of limonite-atmospheric treatment of saprolite.
Aiming at the high-pressure acid leaching-normal-pressure neutralization process, the method has the following advantages that: on one hand, the high-pressure acid leaching ore pulp is cooled by adopting 3-level flash evaporation and 3-level preheating, so that the waste heat utilization rate is not high, and the energy is wasted; on the other hand, the serpentine pulp is used for normal pressure neutralization after leaching, and because the reaction is carried out under normal pressure, leached iron cannot produce hematite precipitate and releases acid, the leaching rate of nickel is very low and is only about 50-60%, and resource waste is caused; in addition, the aluminum can not be effectively removed by normal pressure neutralization, so that a large amount of neutralizing agents such as alkali are consumed to remove the aluminum during the later neutralization and impurity removal.
In the prior art, a combined process of treating limonite by normal-pressure acid leaching and treating saprolite by high-pressure neutralization is disclosed in a patent CN101001964A, and the combined process is used for treating acid leaching solution and saprolite at the temperature of 120-160 ℃ and under the condition of higher than atmospheric pressure; the method has the problems of low leaching rate of nickel and cobalt, and high cost because a large amount of neutralizing agents such as alkali and the like are required to remove aluminum, iron and the like during neutralization and impurity removal.
In patent CN104789766A published by Jinchuan group, a combined process of treating saprolite ore at normal pressure and leaching limonite under pressure is adopted; it has the problem of high acid consumption, and in the later neutralization and impurity removal, a large amount of neutralizing agent such as alkali is also needed to be consumed to remove aluminum, iron and the like, so the cost is high.
In patent CN103614571A disclosed earlier by the applicant, a combined process of atmospheric limonite leaching and serpentine ore pressure leaching is adopted, and the purposes of reducing investment, energy consumption and production cost are achieved by reducing the temperature and pressure of a pressure leaching section; however, the method has the problems of low leaching rate of nickel and cobalt, and a large amount of neutralizing agents such as alkali are consumed to remove aluminum, iron and the like during neutralization and impurity removal.
Therefore, the research on how to fully utilize the residual heat of the ore pulp in the high-pressure acid leaching process, reduce the energy consumption and simultaneously improve the leaching rate of nickel and cobalt has great significance.
Based on the thought, the invention provides a process route for treating the laterite-nickel ore by adopting a system and a method of high-pressure acid leaching-high-pressure neutralization, the limonite is treated at high pressure and high temperature, and the leached ore pulp directly enters a high-pressure neutralization unit through a pipeline instead of being subjected to flash evaporation and is added with the added ore pulpThe serpentine slurry is synergistically neutralized at high pressure, residual sulfuric acid is neutralized at a slightly low temperature and pressure by using the high-pressure acid leaching residual heat of limonite, newly generated iron is precipitated in the form of hematite to release acid, and meanwhile, the enhanced leaching of serpentine is realized, and along with the enhanced leaching of serpentine, the enhanced leaching of the serpentine can promote Al3+Further hydrolysis, and reducing the concentration of impurity Al in the neutralization solution. In the process and the system, the first-stage high-pressure acid leaching ensures the full leaching of limonite, and the second-stage high-pressure acid leaching utilizes the residual heat of the first-stage high-pressure acid leaching ore pulp to leach serpentine, so that the aims of reducing residual acid and reducing impurity aluminum are fulfilled, and the leaching rate of the serpentine type laterite-nickel ore can be greatly improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the application aims to provide a system and a process for extracting nickel and cobalt from a laterite-nickel ore by two-stage pressurization, and the system and the process realize the full utilization of the residual heat of high-pressure acid leaching ore pulp and the efficient leaching of nickel and cobalt from serpentine ore through a new concept of high-pressure acid leaching-high-pressure neutralization, reduce the energy consumption and the consumption of auxiliary materials, and realize the efficient extraction of nickel and cobalt from the laterite-nickel ore.
In a first aspect, the application provides a system for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization, which comprises:
the high-pressure acid leaching device is used for carrying out high-temperature high-pressure acid leaching on the limonite type laterite-nickel ore, and is provided with a limonite type laterite-nickel ore pulp inlet, a sulfuric acid inlet and a leached pulp outlet;
the high-pressure neutralizing unit is used for performing high-temperature and high-pressure neutralizing treatment on the ore pulp subjected to high-pressure acid leaching and is provided with a high-pressure acid leaching ore pulp inlet, a serpentine laterite-nickel ore pulp inlet, a high-pressure neutralizing liquid outlet and a high-pressure neutralizing underflow outlet;
the neutralization and impurity removal unit is used for neutralizing and impurity removal treatment of the ore pulp subjected to high-pressure neutralization treatment and is provided with a high-pressure neutralized post-liquid inlet, a neutralizer inlet, a neutralized impurity-removed post-liquid outlet and a neutralized impurity-removed bottom flow outlet;
the nickel-cobalt precipitation unit is used for carrying out precipitation treatment on the neutralized impurity-removed liquid and is provided with a neutralized impurity-removed liquid inlet, a precipitator inlet, a precipitated liquid outlet and a nickel-cobalt enriched substance outlet;
wherein, the ore pulp outlet of the high-pressure acid leaching device after leaching is directly connected with the high-pressure acid leaching ore pulp inlet of the high-pressure neutralizing device through a pipeline.
According to the system for treating the laterite-nickel ore, ore pulp treated by the high-pressure acid leaching device is directly conveyed to the high-pressure neutralization unit through a pipeline and is subjected to high-pressure neutralization in cooperation with the added serpentine ore pulp; the system can fully utilize the waste heat after the high-pressure acid leaching treatment of the limonite to realize the enhancement of the leaching of the serpentine and promote the Al3+The further hydrolysis of the nickel and cobalt leaching agent achieves the effects of improving the leaching rate of nickel and cobalt and reducing the consumption of auxiliary materials such as alkali and the like.
In one possible implementation, the high-pressure acid leaching device is a horizontal or vertical autoclave.
In one possible implementation manner, the high-pressure neutralization unit comprises a high-pressure neutralization device, a flash evaporation device and a thickening device which are connected in sequence, wherein the high-pressure neutralization device is a horizontal or vertical autoclave.
In a possible implementation manner, the neutralization and impurity removal unit comprises a neutralization and impurity removal device and a thickening device which are connected in sequence.
In one possible implementation, the nickel cobalt precipitation unit of the present application includes a nickel cobalt precipitation device, a thickening device, and a filter pressing device that are connected in sequence.
In a possible implementation mode, a pipeline for connecting an ore pulp outlet of a high-pressure acid leaching device after leaching and a high-pressure acid leaching ore pulp inlet of a high-pressure neutralizing device is a heat insulation pipeline, and the outer wall of the pipeline is further attached with a heating unit; the heating mode of the heating unit is selected from any one of resistance wire heating, electromagnetic heating and infrared heating, and aims to ensure that the waste heat of high-pressure acid leaching can be fully utilized, improve the leaching rate of nickel and cobalt and reduce the consumption of auxiliary materials such as alkali and the like.
In a possible implementation, the high-pressure neutralization device is further provided with a heating unit, so that the ore pulp can be subjected to a heating treatment when needed.
In a second aspect, the application provides a process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization, which comprises the following steps:
step one, high-pressure acid leaching: adding limonite type laterite-nickel ore and sulfuric acid solution into a high-pressure acid leaching device, controlling the liquid-solid ratio, the acid-ore ratio and the reaction conditions of the limonite type laterite-nickel ore and the sulfuric acid solution, and completing high-pressure acid leaching to obtain leached ore pulp;
step two, high-pressure neutralization: directly feeding the leached ore pulp into a high-pressure neutralization unit through a pipeline, adding serpentine-type laterite-nickel ore pulp into the high-pressure neutralization unit, carrying out high-pressure neutralization, and carrying out liquid-solid separation after the reaction is finished to obtain leachate;
step three, neutralization and impurity removal: adding a neutralizing agent into the leachate obtained in the second step, removing iron and aluminum impurities in the leachate, and carrying out liquid-solid separation after the reaction is finished to obtain a liquid after impurity removal;
step four, nickel cobalt precipitation: and D, adding a precipitator into the impurity-removed liquid obtained in the step three to precipitate nickel and cobalt, and performing liquid-solid separation and washing after the reaction is finished to obtain a nickel-cobalt concentrate and a precipitated liquid.
In one possible implementation manner, in the step one, the mineral powder granularity of the limonite type laterite-nickel ore is less than 0.074 mm; preferably, the particle size is less than 0.05 mm;
the initial acidity of the sulfuric acid solution is 100-300 g/L; specifically, the initial acidity is 100 g/L, 125 g/L, 150 g/L, 175 g/L, 200 g/L, 225 g/L, 250 g/L, 275 g/L, or 300g/L, etc.
The liquid-solid ratio is 2: 1-10: 1 mL/g; specifically, the liquid-solid ratio is 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, etc.
The acid-ore ratio is as follows: 300-390 kg/t-ore.
The reaction conditions are as follows: the leaching temperature is 200-270 ℃, the pressure is 1.55-5.5 MPa, the leaching time is 0.5-3.0 h, and the stirring speed is 200-600 rpm. Specifically, the leaching temperature is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃ or 270 ℃ and the like; the pressure is as follows: 1.55MPa, 1.91MPa, 2.32MPa, 2.80MPa, 3.34MPa, 3.97MPa, 4.69MPa, 5.5MPa and the like; the leaching time is as follows: 0.5h, 1h, 1.5h, 2h, 2.5h or 3h and the like; the stirring speed is 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, or the like.
In the high-pressure acid leaching process, metal oxides or composite salts such as nickel, cobalt, iron, aluminum, manganese and the like in the limonite directly react with sulfuric acid to be converted into metal ions which enter the solution, and the chemical reaction general formula can be expressed as follows:
Me2On(s)+2nH+ = 2Men++nH2O
wherein Me: valuable metals such as Ni, Co, Fe, Al, Mn, etc., n: the valence of the metal.
Leached Fe under high temperature and high pressure3+A strong hydrolysis occurs, forming hematite precipitate and releasing an equivalent amount of acid.
2Fe3++3H2O(1) = Fe2O3(s)+6H+
The inventor simultaneously finds that by controlling the ratio of the sulfuric acid to the limonite, under the conditions that the leaching temperature is 200-270 ℃ and the pressure is 1.55-5.5 MPa, the acid-mineral ratio is preferably as follows: 320-360 kg/t-ore, the temperature is 230-260 ℃, and the pressure is 2.8-4.69 MPa; along with the reduction of the acidity of the ore pulp, a small part of Al3+Hydrolysis can occur, forming a precipitate of grass alum or alum and liberating acid. The alum or alum is insoluble in acid at high temperature and high pressure, and precipitates into the slag, thereby making the solution Al3+The concentration is reduced. At high temperatures, the following reactions occur:
6Al3++9SO4 2-+14H2O → 2(H3O)Al3(OH)6(SO4)2(s)+10H++5SO4 2-
3Al3++2SO4 2-+M+6H2O = MAl3(SO4)2(OH)6(s)+6H+
wherein M is Na+、K+Or NH4 +。
In a possible implementation manner, in the second step, the ore pulp in the first step enters the high-pressure neutralization unit through a pipeline by gravity flow or pressure difference; the pipeline is a heat-insulating pipeline, and the outer wall of the pipeline is further attached with a heating unit; the heating mode of the heating unit is selected from any one of resistance wire heating, electromagnetic heating and infrared heating;
in the serpentine type laterite-nickel ore pulp, the granularity of mineral powder of the serpentine laterite-nickel ore is less than 0.15 mm; preferably, less than 0.1 mm.
Wherein the adding amount of the serpentine type laterite-nickel ore is 10-100% of that of the limonite type laterite-nickel ore; specifically, the amount added is 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or the like.
Reaction conditions for high pressure neutralization include: the reaction temperature is 190-250 ℃, the pressure is 1.25-3.97 MPa, the leaching time is 0.5-3.0 h, and the stirring speed is 200-600 rpm. Specifically, the reaction temperature is 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃ and the like; the pressure is as follows: 1.25MPa, 1.55MPa, 1.91MPa, 2.32MPa, 2.80MPa, 3.34MPa, 3.97MPa and the like; the leaching time is as follows: 0.5h, 1h, 1.5h, 2h, 2.5h or 3h and the like; the stirring speed is 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, or the like. The preferable reaction temperature is 200-230 ℃.
In the above implementation manner, the high-pressure acid leaching ore pulp (limonite ore pulp) directly enters the high-pressure neutralization unit through a pipeline without flash evaporation, and is subjected to high-pressure neutralization in cooperation with the added serpentine ore pulp, and the high-pressure neutralization is performed by using the waste heat of the limonite ore pulp, so that the nickel, cobalt, iron, aluminum, manganese and other metal oxides or compound salts in the serpentine directly react with the residual sulfuric acid in the limonite ore pulp to convert into metal ions which enter the solution, and the chemical reaction general formula can be expressed as follows:
Me2On(s)+2nH+ = 2Men++nH2O
wherein Me: valuable metals such as Ni, Co, Fe, Al, Mn, etc., n: the valence of the metal.
Leached Fe under high temperature and high pressure3+A strong hydrolysis occurs, forming hematite precipitate and releasing an equivalent amount of acid.
2Fe3++3H2O(1) = Fe2O3(s)+6H+
Al3+It also mostly hydrolyzes to form grass alum or alum precipitate and release acid.
6Al3++9SO4 2-+14H2O → 2(H3O)Al3(OH)6(SO4)2(s)+10H++5SO4 2-
3Al3++2SO4 2-+M+6H2O = MAl3(SO4)2(OH)6(s)+6H+
Wherein M is Na+、K+Or NH4 +。
Thermodynamically, the above reaction is favorably caused when the temperature of the autoclave is 190 ℃ or higher and the pressure is 1.25MPa or higher, particularly when the temperature is 200 ℃ or higher and the pressure is 1.55MPa or higher. Al (Al)3+Hydrolysis is affected by environmental acidity and temperature, and high acidity inhibits Al3+Hydrolysis of (3) and increase solubility of alum, low acidity promotes Al3+The solubility of alunite is reduced by hydrolysis. Therefore, in the high-pressure acid leaching step, Al3+A small part of hydrolysis can occur, and during high-pressure neutralization, because the serpentine consumes residual acid, the acidity in the system is greatly reduced, which is beneficial to Al3+Further hydrolysis of (3), most of Al3+A hydrolysis reaction takes place. The acid released by the iron and aluminum water further promotes the leaching of the nickel and cobalt oxides or the composite salt.
NiO(s)+2H+ = Ni2++H2O(1)
CoO(s)+2H+ = Co2++H2O(1)
Different from the traditional high-pressure acid leaching-normal-pressure neutralization, the method disclosed by the invention has the advantages that the addition amount of the serpentine ore is controlled, the waste heat of the limonite is fully utilized, the high-temperature and high-pressure neutralization conditions of the reaction temperature of 190-250 ℃ and the pressure of 1.25-3.97 MPa are kept, the nickel and cobalt can be fully leached, the nickel and cobalt leaching rate can reach more than 95%, meanwhile, the iron and aluminum impurities are fully hydrolyzed under the high-temperature and high-pressure conditions of two sections, the content of the iron and aluminum impurities in the liquid after high-pressure neutralization is low, the consumption of alkali and other auxiliary materials in the subsequent neutralization and impurity removal process can be greatly reduced, and the effects of simplifying the process and reducing the cost are achieved.
In one possible implementation, in the third step, the neutralizing agent is calcium oxide and/or calcium carbonate; the reaction part for neutralization and impurity removal is as follows: the pH value is 3.8-4.5, the reaction temperature is 25-85 ℃, and the reaction time is 0.5-3.0 h. Specifically, the pH is 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5, etc.; the reaction temperature is 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃; the reaction time is 0.5h, 1h, 1.5h, 2h, 2.5h or 3h and the like.
In the above embodiment, when neutralizing to remove Fe and Al, the added neutralizing agent can decompose OH in the solution system-Or CO3 2-Neutralizing residual acid in the leaching solution to generate water, namely OH-Change of OH-With Fe3+、Al3+When the product of the concentrations reaches the solubility product of the hydroxide corresponding to the metal ions, the metal ions precipitate out, and the following reaction occurs:
Fe3++3OH-=Fe(OH)3↓
Al3++3OH-=Al(OH)3↓。
in one possible implementation manner, in the fourth step, the precipitant is one or more of sodium hydroxide, sodium carbonate and magnesium oxide; the reaction conditions for neutralization and impurity removal are as follows: the pH value is 7.0-8.5, the reaction temperature is 25-85 ℃, and the reaction time is 0.5-3.0 h. Specifically, the pH value is 7.0, 7.2, 7.5, 8.0, 8.2, 8.5, or the like; the reaction temperature is 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or 85 ℃; the reaction time is 0.5h, 1h, 1.5h, 2h, 2.5h or 3h and the like.
In the implementation mode, the nickel-cobalt precipitation principle is similar to the neutralization impurity removal principle, and the pH value of the system is adjusted by adding a precipitator to ensure that Ni2+、Co2+The hydroxide precipitates and reacts as follows:
Ni2++2OH-=Ni(OH)2↓
Co2++2OH-=Co(OH)2↓。
in a possible implementation manner, the limonite type laterite-nickel ore is high iron ore, the iron content is 35-50 wt%, and the nickel content is 0.6-2.0 wt%; specifically, the iron content is 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, or the like, and the nickel content is 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.0wt%, or the like. The serpentine type laterite-nickel ore is high-magnesium ore, the content of magnesium oxide is generally more than 20wt%, and the content of nickel is 0.6-2.0 wt%; specifically, the nickel content is 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.0wt%, or the like.
In a third aspect, the application provides an application of the system and the process for extracting nickel and cobalt from the laterite-nickel ore by two-stage pressurization in the wet extraction of nickel and cobalt from the laterite-nickel ore.
Compared with the prior art, the invention has the following beneficial effects:
according to the system provided by the application, the ore pulp treated by the high-pressure acid leaching device is directly conveyed to the high-pressure neutralization unit through a pipeline, particularly a heat-insulating pipeline, and is subjected to high-pressure neutralization in cooperation with the added serpentine ore pulp; the system can fully utilize the waste heat after the high-pressure acid leaching treatment of the limonite to realize the enhancement of the leaching of the serpentine and promote the Al3+The further hydrolysis of the nickel and cobalt leaching agent achieves the effects of improving the leaching rate of nickel and cobalt and reducing the consumption of auxiliary materials such as alkali and the like.
The method provided by the application fully utilizes the waste heat of the high-pressure acid leaching ore pulp, reduces the energy consumption in the production process, and realizes the efficient utilization of the waste heat of the high-pressure acid leaching ore pulp by continuously leaching the serpentine ore at high temperature and high pressure by utilizing the residual sulfuric acid after the limonite is leached. The conditions of reaction generation are skillfully utilized, the serpentine ore is intensively leached by adopting the high-temperature and high-pressure reaction conditions which can be maintained by the residual heat of the high-pressure acid leaching ore pulp, meanwhile, the nickel and cobalt are further leached by the acid released by hydrolysis precipitation of iron and aluminum, the high-efficiency leaching of the nickel and cobalt in the serpentine ore is realized, the leaching rate of the nickel and cobalt in the serpentine ore is improved to more than 85 percent from the traditional 40-60 percent, and the utilization rate of nickel resources is greatly improved. In addition, under the conditions of two sections of high temperature and high pressure, iron and aluminum in the leaching solution are subjected to hydrolysis precipitation reaction, and the neo-acid released by hydrolysis precipitation is used for leaching serpentine ore, so that the utilization rate of sulfuric acid is greatly improved, and the acid consumption is reduced. Meanwhile, compared with the traditional high-pressure acid leaching process, the content of iron and aluminum in the leachate is obviously reduced, the subsequent alkali consumption for neutralization is reduced, the subsequent neutralization and impurity removal procedures are greatly simplified, and the consumption of auxiliary materials is reduced.
The system and the method have no special requirements on ore grade, have wide raw material adaptability, and can efficiently and jointly treat limonite type and serpentine type laterite-nickel ore.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a typical process flow diagram of the prior art;
FIG. 2 is a schematic structural diagram of a system for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization
Fig. 3 is a process flow diagram provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Referring to fig. 2, a schematic structural diagram of a system for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization is shown.
As can be seen from fig. 2, the system for two-stage pressure extraction of nickel and cobalt from laterite-nickel ore comprises a high-pressure acid leaching device 100 for performing high-temperature high-pressure acid leaching on limonite type laterite-nickel ore, wherein the high-pressure acid leaching device 100 is provided with a limonite type laterite-nickel ore pulp inlet 101, a sulfuric acid inlet 102 and a leached pulp outlet 103;
the high-pressure neutralizing unit 200 is used for performing high-temperature and high-pressure neutralizing treatment on the ore pulp subjected to high-pressure acid leaching, and is provided with a high-pressure acid leaching ore pulp inlet 201, a serpentine type laterite-nickel ore pulp inlet 202, a high-pressure neutralized rear liquid outlet 203 and a high-pressure neutralized bottom flow outlet 204;
the neutralization and impurity removal unit 300 is used for neutralizing and impurity removal treatment of ore pulp subjected to high-pressure neutralization treatment, and the neutralization and impurity removal unit 300 is provided with a high-pressure neutralized liquid inlet 301, a neutralizer inlet 302, a neutralized impurity removal liquid outlet 303 and a neutralized impurity removal underflow outlet 304;
the nickel-cobalt precipitation unit 400 is used for carrying out precipitation treatment on the neutralized and impurity-removed liquid, and the nickel-cobalt precipitation unit 400 is provided with a neutralized and impurity-removed liquid inlet 401, a precipitator inlet 402, a precipitated liquid outlet 403 and a nickel-cobalt concentrate outlet 404;
wherein, the leached ore pulp outlet 103 of the high-pressure acid leaching device 100 is directly connected with the high-pressure acid leaching ore pulp inlet 201 of the high-pressure neutralization unit 200 through a pipeline 104.
The extraction process and the effect thereof according to the present invention will be described in detail with reference to the following examples.
In the following examples and comparative examples, some foreign laterite-nickel ore was used, the contents of its main elements being shown in table 1 below. The limonite type laterite nickel ore contains 1.01 percent of nickel and 0.076 percent of cobalt, higher iron content of 47.84 percent and 0.17 percent of magnesium, and also contains a certain amount of aluminum, silicon and chromium and a small amount of manganese, zinc and the like. The main elements of the serpentine type laterite-nickel ore are silicon, magnesium, iron and nickel, wherein the contents of nickel and cobalt are respectively 1.55 percent and 0.066 percent, the content of magnesium is 11.05 percent, the content of silicon is 16.72 percent, and the content of iron is 16.38 percent.
TABLE 1 main ingredient table of laterite-nickel ore
| Element(s) | Ni | Co | Cu | Zn | Mn | Mg | Ca | Al | Fe | Si | Cr |
| Limonite type | 1.01 | 0.076 | / | 0.27 | 0.48 | 0.17 | 0.025 | 4.16 | 47.84 | 1.75 | 1.93 |
| Serpentine type | 1.55 | 0.066 | 0.01 | 0.023 | 0.37 | 11.05 | 1.06 | 1.95 | 16.38 | 16.72 | 0.67 |
Fig. 3 is a process flow diagram of the present application, and specific relevant process parameters can be found in the following examples.
Example 1
1-1, high pressure acid leaching
Crushing and finely grinding the limonite type laterite-nickel ore, taking 100g of limonite with the ore powder granularity of 100 percent and the ore powder granularity of 0.074mm, and controlling the high-pressure acid leaching reaction conditions as follows: adding a sulfuric acid solution (the initial sulfuric acid concentration is 115 g/L), and controlling the liquid-solid ratio to be 2:1, the acid-mineral ratio: 330kg sulfuric acid/t ore, 250 deg.C, 3.97MPa, 500rpm stirring speed, and 1 h. Taking a small amount of ore pulp for liquid-solid separation, washing, drying and then sending to analysis.
And (4) analyzing results: 0.025 percent of nickel in the slag, less than 0.005 percent of cobalt in the slag, 1.89 percent of aluminum in the slag and 98.58 percent of nickel leaching rate.
1-2, high pressure neutralization
The high-pressure acid leaching pulp enters a high-pressure neutralization unit through a pipeline, and serpentine pulp with the granularity of 100 percent and the granularity of 0.15mm after being finely ground is added for high-pressure neutralization reaction. The high-pressure neutralization reaction conditions were controlled as follows: the adding amount of the serpentine type laterite-nickel ore is 25wt% of that of the limonite type laterite-nickel ore, the concentration of the serpentine ore pulp is 35wt%, the reaction temperature is 230 ℃, the pressure is 2.80MPa, the stirring speed is 500rpm, and the reaction time is 1 h. And after the reaction is finished, carrying out liquid-solid separation, washing and drying on the ore pulp, and then analyzing the ore pulp.
And (4) analyzing results: the nickel content in the slag is 0.06%, the cobalt content in the slag is less than 0.005%, the leaching rate of nickel in the section is 92.96%, and the total leaching rate of nickel in the two sections is 95.81%. The leachate components are shown in Table 1-1 below.
TABLE 1-1 table of contents of main components in the high-pressure neutralized leaching solution
| Element(s) | Fe | Ni | Co | Al |
| content/(g/L) | 0.68 | 3.09 | 0.19 | 0.53 |
Therefore, most of iron and aluminum in the nickel ore are hydrolyzed and precipitated, and less iron and aluminum exist in the solution, so that the selective leaching separation of nickel, cobalt and iron and aluminum is realized.
1-3, neutralizing and removing impurities
Taking the leachate, and using quicklime emulsion as a neutralizer to neutralize and remove impurities. The neutralization and impurity removal reaction conditions are controlled as follows: the temperature is 75 ℃, the reaction time is 2h, the concentration of the lime milk is 20%, the end point pH value is 4.2, wherein, the calcium oxide consumption: 3.06kg calcium oxide/m3A liquid; after the reaction, the liquid and solid are separated.
And (4) analyzing results: the slag amount is 5.4kg slag/m3The amount of the liquid is,the iron removal rate of the liquid meter reaches 99.03 percent, and the aluminum precipitation rate is 95.22 percent.
1-4, nickel cobalt precipitation
And taking the neutralized and impurity-removed solution, and carrying out nickel-cobalt precipitation by using sodium hydroxide as a precipitator. The nickel-cobalt precipitation reaction conditions were controlled as follows: the temperature was 70 ℃, the reaction time was 3h, and the end point pH was 7.8. After the reaction, the liquid and solid are separated.
And (4) analyzing results: the nickel precipitation rate and the cobalt precipitation rate were 96.63% and 95.86%, respectively, based on the liquid. The compositions of the nickel cobalt concentrate (nickel cobalt hydroxide intermediate) obtained are shown in tables 1-2
TABLE 1-2 tables of major constituents of nickel cobalt concentrates
| Element(s) | Ca | Co | Ni | Mg | Cr | Mn | Cu | Zn | Fe | Al |
| Content/wt% | 0.15 | 3.92 | 40.85 | 1.46 | 0.0193 | 5.25 | 0.10 | 0.73 | 0.076 | 0.24 |
Therefore, the nickel content in the nickel-cobalt concentrate is 40.85%, the cobalt content is 3.92%, and the nickel-cobalt concentrate can be used for further refining and preparing battery-grade nickel sulfate and battery-grade cobalt sulfate.
Example 2
Unlike example 1, the high pressure neutralization used in this example was carried out at 190 ℃ and 1.25MPa, and the procedure was otherwise the same as in example 1.
And (4) analyzing results: after high-pressure neutralization reaction, the nickel content in the slag is 0.08%, the cobalt content in the slag is less than 0.005%, the leaching rate of nickel in the section is 85.13%, and the total leaching rate of nickel in the two sections is 93.36%. The leachate composition is shown in table 2 below.
TABLE 2 table of contents of main components in the high-pressure neutralized leaching solution
| Element(s) | Fe | Ni | Co | Al |
| content/(g/L) | 2.48 | 3.37 | 0.22 | 2.63 |
In the neutralization impurity removal step, when the end point pH value is controlled to be 4.2, the calcium oxide is consumed: 4.71kg calcium oxide/m3The amount of liquid and slag is 23.78kg slag/m3Liquid (E).
Example 3
The high pressure acid leaching step was carried out at 225 ℃ and 2.55MPa, which is different from example 1, and the other steps were the same as example 1.
And (4) analyzing results: after high-pressure acid leaching, the nickel content of the slag is 0.09%, the cobalt content of the slag is less than 0.005%, and the leaching rate of nickel is 95.25%.
In the high-pressure neutralization step, the temperature used was 200 ℃ and the pressure used was 1.55MPa, unlike in example 1, and the other steps were the same as in example 1.
And (4) analyzing results: after high-pressure neutralization, the nickel content in the slag is 0.12 percent, the cobalt content in the slag is less than 0.005 percent, the leaching rate of nickel in the section is 88.25 percent, and the total leaching rate of nickel in the two sections is 90.64 percent. The leaching solution contains 0.52g/L of iron and 0.63g/L of aluminum.
In the neutralization impurity removal step, when the end point pH value is controlled to be 4.2, the calcium oxide is consumed: 3.35kg calcium oxide/m3Liquid, slag amount 5.82kg slag/m3Liquid (d)
Example 4
The high pressure acid leaching step was carried out at 200 ℃ and 1.55MPa, which are the same as in example 1, except that the temperature was controlled in the high pressure acid leaching step.
And (4) analyzing results: after high-pressure acid leaching, the nickel content of the slag is 0.10 percent, the cobalt content of the slag is less than 0.005 percent, and the leaching rate of the nickel is 92.33 percent.
In the high-pressure neutralization step, the temperature was 190 ℃ and the pressure was 1.25MPa, unlike in example 1, and the other steps were the same as in example 1.
And (4) analyzing results: after high-pressure neutralization, the nickel content in the slag is 0.15 percent, the cobalt content in the slag is less than 0.005 percent, the leaching rate of nickel in the section is 85.39 percent, and the total leaching rate of nickel in the two sections is 89.64 percent. The leaching solution contains 1.10g/L of iron and 1.28g/L of aluminum.
In the neutralization impurity removal step, when the end point pH value is controlled to be 4.2, the calcium oxide is consumed: 4.28kg calcium oxide/m3Liquid, slag amount is 16.25kg slag/m3Liquid (E).
Example 5
In the high-pressure acid leaching step, the temperature was controlled at 270 ℃ and the pressure was controlled at 5.5MPa, which is different from example 1, and the other steps were the same as example 1.
And (4) analyzing results: after high-pressure acid leaching, the nickel content of the slag is 0.011 percent, the cobalt content of the slag is less than 0.005 percent, and the leaching rate of the nickel is 99.11 percent.
In the high-pressure neutralization step, the temperature used was 250 ℃ and the pressure used was 3.97MPa, unlike in example 1, and the other steps were the same as in example 1.
And (4) analyzing results: after high-pressure neutralization, the nickel content in the slag is 0.026%, the cobalt content in the slag is less than 0.005%, the leaching rate of nickel in the section is 95.69%, and the total leaching rate of nickel in the two sections is 98.02%. The leaching solution contains 0.38g/L of iron and 0.23g/L of aluminum.
In the neutralization impurity removal step, when the end point pH value is controlled to be 4.2, the calcium oxide is consumed: 2.82kg calcium oxide/m3Liquid, slag amount 4.67kg slag/m3Liquid (E).
Example 7
The difference from example 1 is that the temperature used in the high pressure neutralization in this example is 180 ℃ and the pressure is 1.0MPa, and the other steps are the same as in example 1.
And (4) analyzing results: after high-pressure neutralization reaction, the nickel content in the slag is 0.12%, the cobalt content in the slag is 0.008%, the nickel leaching rate in the section is 84.64%, and the total leaching rate of two sections of nickel is 87.95%. The leachate composition is shown in table 3 below.
TABLE 3 table of contents of main components in the high-pressure neutralized leaching solution
| Element(s) | Fe | Ni | Co | Al |
| content/(g/L) | 2.67 | 3.26 | 0.19 | 2.86 |
In the neutralization impurity removal step, when the end point pH value is controlled to be 4.2, the calcium oxide is consumed: 5.67kg calcium oxide/m3Liquid, slag amount 28.13kg slag/m3Liquid (E).
From the results of the above examples, it can be seen that the nickel and cobalt are extracted by the high-pressure acid leaching-high-pressure neutralization two-stage pressurizing process, so that the nickel and cobalt leaching rate in serpentine ore is greatly improved, and the alkali consumption and slag consumption in the subsequent neutralization are reduced. Wherein, in the high-pressure neutralization step, when the temperature is 250 ℃ and the pressure is 3.97MPa, the nickel-cobalt leaching rate in the serpentine ore is the highest, and the alkali consumption for neutralization is the least; when the temperature is 180 ℃ and the pressure is 1.0MPa, the nickel and cobalt leaching rate in the serpentine ore is low, and the amount of alkali used for neutralization is large.
Comparative example 1
Unlike example 1, the high pressure acid leaching pulp is cooled and then added with serpentine ore at normal pressure for neutralization reaction. The reaction temperature is 90 ℃ and the reaction time is 4 h.
And (4) analyzing results: the slag contains 0.19 percent of nickel and 0.008 percent of cobalt, the leaching rate of nickel in the section is 55.55 percent, the total leaching rate of nickel in the two sections is 82.63 percent, and the components of the leaching solution are shown in the following table 4.
TABLE 4 table of contents of main components in the high-pressure neutralized leaching solution
| Element(s) | Fe | Ni | Co | Al |
| content/(g/L) | 1.32 | 3.62 | 0.24 | 6.53 |
And (3) neutralizing and removing impurities from the leachate, wherein the reaction conditions are the same as those in example 1, and the calcium oxide consumption: 8.70kg calcium oxide/m3Liquid (E). After the reaction, the liquid and solid are separated. The slag amount is 17.68 slag/m3Liquid (E). The iron-aluminum precipitation rate is about 95 percent.
As can be seen from the results, the traditional high-pressure acid leaching-normal-pressure neutralization process not only consumes long time for normal-pressure neutralization reaction, but also has low leaching rate of nickel in serpentine ore, which is only 55.55 percent, in addition, the leaching solution has high iron and aluminum content, and the dosage of calcium oxide and slag amount in neutralization impurity removal are greatly increased.
Comparative example 2
In contrast to example 1, the acid leaching of limonite was carried out at atmospheric pressure, with a leaching temperature of 95 ℃ and a reaction time of 6 h; and (4) analyzing results: the nickel content in the slag is 0.24 percent, the cobalt content in the slag is 0.007 percent, and the leaching rate of the nickel is 86.05 percent.
Different from the embodiment 1, in the two-stage adding serpentine type laterite-nickel ore high-pressure leaching step, the reaction temperature is 150 ℃, and the pressure is 0.48 MPa. And (4) analyzing results: the slag contains 0.21 percent of nickel, the slag contains 0.016 percent of cobalt, the leaching rate of nickel in the section is 87.50 percent, the total leaching rate of nickel in the two sections is 87.03 percent, and the components of the leaching solution are shown in the following table 5.
TABLE 5 table of contents of main components in the high-pressure neutralized leaching solution
| Element(s) | Fe | Ni | Co | Al |
| content/(g/L) | 5.32 | 4.41 | 0.18 | 4.24 |
And (3) neutralizing and removing impurities from the leachate, wherein the reaction conditions are the same as those in example 1, and the calcium oxide consumption: 6.04kg calcium oxide/m3Liquid (E). After the reaction, the liquid and solid are separated. The slag amount is 37.18kg slag/m3Liquid (E). The iron-aluminum precipitation rate is about 95 percent.
The results show that the problems of low leaching rate of nickel and cobalt, high iron and aluminum content of the leaching solution, large amount of subsequent neutralization impurity removal slag and high loss rate of nickel and cobalt exist in the normal-pressure acid leaching-high-pressure neutralization process.
Comparative example 3
Unlike comparative example 2, the acid leaching for serpentine ore was carried out at normal pressure, with a leaching temperature of 110 ℃ and a reaction time of 8 min; and (4) analyzing results: the nickel content in the slag is 0.22%, the cobalt content in the slag is 0.008%, and the nickel leaching rate is 84.46%.
Unlike comparative example 2, in the second high-pressure leaching step, limonite was added at a reaction temperature of 220 ℃ and a pressure of 2.32 MPa. And (4) analyzing results: the nickel content in the slag is 0.19 percent, the cobalt content in the slag is 0.008 percent, the leaching rate of nickel in the stage is 89.30 percent, the total leaching rate of nickel in the two stages is 86.04 percent, and the components of the leaching solution are shown in the following table 6.
TABLE 6 table of contents of main components in the high-pressure neutralized leachate
| Element(s) | Fe | Ni | Co | Al | Mg |
| content/(g/L) | 1.83 | 4.27 | 0.29 | 2.86 | 12.01 |
And (3) neutralizing and removing impurities from the leachate, wherein the reaction conditions are the same as those in example 1, and the calcium oxide consumption:5.82kg calcium oxide/m3Liquid (E). After the reaction, the liquid and solid are separated. The slag amount is 28.94kg slag/m3Liquid (E). The iron-aluminum precipitation rate is about 95 percent.
The results show that in the process of normal-pressure acid leaching of serpentine ore-high-pressure neutralization limonite, the leaching rate of nickel and cobalt is not high, the iron and aluminum content of the leaching solution is high, the subsequent neutralization impurity removal slag amount is large, and the magnesium content of the filtrate is high, so that the problem of serious equipment scaling can be caused.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. A process for extracting nickel and cobalt from laterite-nickel ore by two-stage pressurization is characterized by comprising the following steps:
step one, high-pressure acid leaching: adding limonite type laterite-nickel ore and sulfuric acid solution into a high-pressure acid leaching device, controlling the liquid-solid ratio, the acid-ore ratio and the reaction conditions of the limonite type laterite-nickel ore and the sulfuric acid solution, and completing high-pressure acid leaching to obtain leached ore pulp;
step two, high-pressure neutralization: directly feeding the leached ore pulp into a high-pressure neutralization unit through a pipeline, adding the serpentine-type laterite-nickel ore pulp into the high-pressure neutralization unit, performing high-pressure neutralization at a slightly low temperature and pressure by using the waste heat of the leached limonite ore pulp, and performing liquid-solid separation after the reaction is finished to obtain a leaching solution;
step three, neutralization and impurity removal: adding a neutralizing agent into the leachate obtained in the second step, removing iron and aluminum impurities in the leachate, and carrying out liquid-solid separation after the reaction is finished to obtain a liquid after impurity removal;
step four, nickel cobalt precipitation: adding a precipitator into the impurity-removed liquid obtained in the third step to precipitate nickel and cobalt, and performing liquid-solid separation and washing after the reaction is finished to obtain a nickel-cobalt concentrate and a precipitated liquid;
wherein:
in the first step, the initial acidity of the sulfuric acid solution is 100-300 g/L; the acid-ore ratio is as follows: 320-360 kg/t-ore; the reaction conditions are as follows: the leaching temperature is 230-260 ℃, the pressure is 3.97-4.69 MPa, the leaching time is 0.5-3.0 h, and the stirring speed is 200-600 rpm;
in the second step, the adding amount of the serpentine type laterite-nickel ore is 25-100% of that of the limonite type laterite-nickel ore, and the reaction conditions of high-pressure neutralization comprise: the reaction temperature is 210-230 ℃, the pressure is 2.8-3.34 MPa, the leaching time is 0.5-3.0 h, and the stirring speed is 200-600 rpm;
in the third step, the neutralizing agent is calcium oxide and/or calcium carbonate.
2. The process according to claim 1, characterized in that in the first step, the limonite type lateritic nickel ore has a mineral powder particle size of less than 0.074 mm;
the liquid-solid ratio is 2: 1-10: 1 mL/g.
3. The process of claim 1, wherein in step two, the slurry in step one is introduced into the high-pressure neutralization unit through a pipeline by gravity flow or pressure difference; the pipeline is a heat-insulating pipeline, and the outer wall of the pipeline is further attached with a heating unit; the heating mode of the heating unit is selected from any one of resistance wire heating, electromagnetic heating and infrared heating;
in the serpentine type laterite-nickel ore pulp, the granularity of mineral powder of the serpentine type laterite-nickel ore is less than 0.15 mm.
4. The process according to claim 1, wherein in the third step, the reaction part for neutralization and impurity removal is as follows: the pH value is 3.8-4.5, the reaction temperature is 25-85 ℃, and the reaction time is 0.5-3.0 h.
5. The process of claim 1, wherein in step four, the precipitant is one or more of sodium hydroxide, sodium carbonate and magnesium oxide; the reaction conditions of the nickel-cobalt precipitation are as follows: the pH value is 7.0-8.5, the reaction temperature is 25-85 ℃, and the reaction time is 0.5-3.0 h.
6. The process according to any one of the claims 1-5, the limonitic lateritic nickel ore being a high iron ore, with an iron content of 35-50 wt% and a nickel content of 0.6-2.0 wt%; the serpentine type laterite-nickel ore is high-magnesium ore, the content of magnesium oxide is generally more than 20wt%, and the content of nickel is 0.6-2.0 wt%.
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| US3991159A (en) * | 1975-01-09 | 1976-11-09 | Amax Inc. | High temperature neutralization of laterite leach slurry |
| US4097575A (en) * | 1976-11-05 | 1978-06-27 | Amax Inc. | Roast-neutralization-leach technique for the treatment of laterite ore |
| EP0547744A1 (en) * | 1991-10-09 | 1993-06-23 | PACIFIC METALS Co., Ltd. | Process for recovering metal from oxide ores |
| CN101899567A (en) * | 2009-12-09 | 2010-12-01 | 中国恩菲工程技术有限公司 | Ore pressure leaching process |
| CN103614571A (en) * | 2013-10-09 | 2014-03-05 | 北京矿冶研究总院 | Combined leaching process of laterite-nickel ore |
| CN203530398U (en) * | 2013-10-09 | 2014-04-09 | 北京矿冶研究总院 | Laterite-nickel ore jointly leaches system |
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| US3991159A (en) * | 1975-01-09 | 1976-11-09 | Amax Inc. | High temperature neutralization of laterite leach slurry |
| US4097575A (en) * | 1976-11-05 | 1978-06-27 | Amax Inc. | Roast-neutralization-leach technique for the treatment of laterite ore |
| EP0547744A1 (en) * | 1991-10-09 | 1993-06-23 | PACIFIC METALS Co., Ltd. | Process for recovering metal from oxide ores |
| CN101899567A (en) * | 2009-12-09 | 2010-12-01 | 中国恩菲工程技术有限公司 | Ore pressure leaching process |
| CN103614571A (en) * | 2013-10-09 | 2014-03-05 | 北京矿冶研究总院 | Combined leaching process of laterite-nickel ore |
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