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WO2025000369A1 - Procédé d'élimination de silicium et procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte - Google Patents

Procédé d'élimination de silicium et procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte Download PDF

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Publication number
WO2025000369A1
WO2025000369A1 PCT/CN2023/104003 CN2023104003W WO2025000369A1 WO 2025000369 A1 WO2025000369 A1 WO 2025000369A1 CN 2023104003 W CN2023104003 W CN 2023104003W WO 2025000369 A1 WO2025000369 A1 WO 2025000369A1
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WO
WIPO (PCT)
Prior art keywords
leaching
nickel
acid
silicon
leaching process
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2023/104003
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English (en)
Chinese (zh)
Inventor
许开华
杨健
张坤
彭亚光
金国泉
刘文泽
许鹏云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
Original Assignee
Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
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Publication date
Application filed by Pt Gem Indonesia New Energy Materials, Pt Qmb New Energy Materials, GEM Co Ltd Korea filed Critical Pt Gem Indonesia New Energy Materials
Priority to PCT/CN2023/104003 priority Critical patent/WO2025000369A1/fr
Priority to CN202380010003.0A priority patent/CN117083402B/zh
Publication of WO2025000369A1 publication Critical patent/WO2025000369A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • 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

  • Nickel cobalt hydroxide is an intermediate product of laterite nickel ore hydrometallurgy. Since laterite nickel ore contains a large amount of silicon, some silicon will inevitably be introduced into the nickel cobalt hydroxide product during the hydrometallurgical treatment process. In the subsequent acid leaching process, the silicon entrained in nickel cobalt hydroxide will be leached into the leachate, so effective means are needed to remove it.
  • the existing process for removing silicon from nickel-cobalt hydroxide leachate is mainly to remove it by forming silicic acid or silicate precipitation.
  • Existing silicon removal technologies can effectively remove silicon from the solution, but there is also the problem that silicic acid or silicates are difficult to filter, resulting in a large amount of nickel and cobalt being entrained and lost, reducing the effective utilization rate of nickel and cobalt, and significantly prolonging the processing time of the entire process.
  • the purpose of the present invention is to overcome the above-mentioned technical deficiencies and propose a method for desiliconization and silicon recycling in the process of nickel cobalt hydroxide leaching, so as to solve the technical problems in the prior art that the silicon removal technology of nickel cobalt hydroxide leaching is difficult to filter, easily leads to a large amount of nickel and cobalt loss, and has a high silicon residue in the liquid after silicon removal.
  • the present invention provides a method for desiliconization during nickel cobalt hydroxide leaching, comprising the following steps: leaching nickel cobalt hydroxide with low acid and high pressure, filtering to obtain a first filter residue and a first filtrate; wherein, during the low acid and high pressure leaching, the pH value during the leaching process is controlled to be maintained at 0.8-2.2, and the leaching temperature is 150-350°C.
  • the present invention provides a method for recycling silicon in a nickel-cobalt hydroxide leaching process.
  • the method comprises the following steps: mixing the first filter residue obtained by leaching nickel cobalt hydroxide with low acid and high pressure, further leaching the second filter residue obtained by leaching with high acid and normal pressure with a lithium source, and then calcining at high temperature to obtain a porous CaO ⁇ Li 4 SiO 4 adsorbent.
  • the beneficial effects of the present invention include:
  • the present invention converts silicic acid, which is difficult to filter, into silicon dioxide, which is easy to filter, by converting silicic acid into silicon dioxide under high temperature and high pressure, and greatly improves the filtering performance of impure silicon precipitation, thereby solving the current situation that this process causes a bottleneck in the entire production process.
  • the content of nickel and cobalt entrained in the filter residue is significantly reduced, and the silicon concentration in the leaching solution can reach less than 1ppm, which is much better than the current situation that the residual silicon in the solution is still more than 50ppm when using silicic acid to filter.
  • the nickel-cobalt hydroxide desiliconized slag obtained by high-acid and normal-pressure leaching has a high purity, and the content of entrained nickel and cobalt is less than 0.01%, which can be used as one of the synthetic materials for CO2 capture agent.
  • the present invention further synthesizes CaO ⁇ Li4SiO4 capture agent based on this, realizing the high-value utilization of silicon slag.
  • FIG1 is a process flow chart of an embodiment of a method for desiliconization and silicon recycling in a nickel-cobalt hydroxide leaching process provided by the present invention.
  • the present invention provides a method for desiliconization in the process of nickel cobalt hydroxide leaching, comprising the following steps: low acid high pressure leaching: nickel cobalt hydroxide is leached by low acid high pressure, and filtered to obtain a first filter residue and a first filtrate. The first filtrate is a nickel cobalt solution.
  • low acid high pressure leaching process is carried out in a high pressure reactor.
  • the pH value during the leaching process is controlled to be maintained at 0.8-2.2, including but not limited to 0.8, 1, 1.2, 1.3, 1.5, 1.7, 1.8, 2, 2.2, etc., preferably 1.3-2.2;
  • the leaching temperature is 150-350°C, including but not limited to 150°C, 180°C, 200°C, 250°C, 300°C, 350°C, etc., preferably 180-350°C;
  • the leaching time is 0.5-5h, including but not limited to 0.5h, 1h, 2h, 3h, 4h, 5h, etc.
  • the leaching solid-liquid ratio is controlled at 50-200g/L, Including but not limited to 50g/L, 100g/L, 150g/L, 200g/L, etc. If the solid-liquid ratio is too low, the processing volume will be affected; if the solid-liquid ratio is too high, the slurry viscosity will be too high to affect the leaching process; acid or alkali is used to adjust the pH, the acid used is a common inorganic acid, and the alkali used is calcium oxide or calcium carbonate slurry.
  • the present invention converts silicic acid into silicon dioxide under high temperature and high pressure, so that the difficult-to-filter silicic acid is transformed into easy-to-filter silicon dioxide, thereby solving the problem that this process causes a bottleneck in the entire production process.
  • the filtration performance of impure silicon precipitation is greatly improved, and the silicon concentration in the leachate can reach less than 1ppm, which is far better than the current situation where the residual silicon in the solution filtered by silicic acid is still more than 50ppm.
  • the nickel cobalt hydroxide is obtained by sequentially subjecting laterite nickel ore to high pressure acid leaching, neutralization and impurity removal, and neutralization and precipitation of nickel and cobalt. This is prior art and will not be elaborated in detail in the present invention.
  • the composition of nickel cobalt hydroxide is: Ni: 35-40%, Co 3-5%, Mn 5-10%, Fe ⁇ 0.1%, Al ⁇ 0.1%, Zn 0.5-1%, Si 0.1-0.3%.
  • the method for desiliconization in the above nickel-cobalt hydroxide leaching process also includes: a high-acid normal pressure leaching step.
  • the first filter residue is further leached with high acid and normal pressure, and the leaching acidity is controlled to be 0.1-1 mol/L, including but not limited to 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 1 mol/L, etc., preferably 0.2-0.5 mol/L;
  • the leaching temperature is room temperature, and the leaching time is 0.5-5h, including but not limited to 0.5h, 1h, 2h , 3h, 4h, 5h, etc.
  • the present invention provides a method for recycling silicon in the process of nickel cobalt hydroxide leaching, comprising the following steps: after uniformly mixing the second filter residue with the lithium source, high-temperature roasting is performed to obtain a porous CaO ⁇ Li 4 SiO 4 adsorbent.
  • the second filter residue can be dried;
  • the lithium source is lithium hydroxide or lithium carbonate;
  • the mass ratio of the second filter residue to the lithium source is 1: (1-5), including but not limited to 1: 1, 1: 2, 1: 3, 1: 4, 1: 5, etc.;
  • the temperature of high-temperature roasting is 800-1200°C, including but not limited to 800°C, 900°C, 1000°C, 1100°C, 1200°C, etc.;
  • the time of high-temperature roasting is 1: 1: 2, 1: 3, 1: 4, 1: 5, etc.
  • the calcination time is 1-5h, including but not limited to 1h, 2h, 3h, 4h, 5h, etc.; the calcination atmosphere is the atmospheric atmosphere, and the calcination product is crushed and sieved after the calcination is completed to obtain a CO2 capture agent with a particle size of less than 150 mesh.
  • the calcination tail gas generated in this step is absorbed by an alkaline solution, and further evaporated and crystallized to prepare an alkali metal sulfate or ammonium sulfate salt.
  • the present invention does not limit the type of alkali used, and those skilled in the art can choose according to actual conditions. For example, it can be an alkali metal hydroxide, ammonia water, etc., with a concentration of 1-3 mol/L.
  • the present invention mixes and roasts the second filter residue with a lithium source to further increase the value of SiO 2 /CaSO 4 residue and recycle it to prepare a porous CO 2 adsorbent (CaO ⁇ Li 4 SiO 4 adsorbent), which can be used to adsorb CO 2 in the air.
  • Low-acid high-pressure leaching In a high-pressure reactor, nickel cobalt hydroxide is leached at a solid-liquid ratio of 100g/L, a temperature of 180°C, and a time of 1h. The rotation speed is uniformly set to 400rpm during the leaching process. Dilute sulfuric acid/second filtrate or liquid alkali is continuously pumped in by a peristaltic pump to maintain the pH of the solution in the leaching reactor at 1.5 ⁇ 0.2. After the reaction is completed, the first filtrate is filtered to obtain a subsequent treatment process.
  • High-acid atmospheric pressure leaching The first filter residue is further subjected to high-acid atmospheric pressure leaching under the following conditions: solid-liquid ratio of 100 g/L, room temperature, acidity of 0.2 mol/L H 2 SO 4 , leaching time of 1 h, stirring speed uniformly set at 400 rpm. After the leaching is completed, the second filtrate and the second filter residue are obtained by filtration, wherein the second filtrate is returned to the low-acid high-pressure leaching process section to realize further utilization of the residual acid in the second filtrate.
  • Example 2-5 verifies the effect of pH on the silicon content in the first filtrate and the nickel and cobalt content entrained in the second filter residue in the low-acid high-pressure leaching step. Compared with Example 1, the only difference is that the pH is different in the low-acid high-pressure leaching step. The test results are shown in Table 1.
  • Examples 6-11 verify the effect of leaching temperature on the silicon content in the first filtrate and the nickel and cobalt content entrained in the second filter residue in the low-acid high-pressure leaching step. Compared with Example 1, the only difference is that the leaching temperature is different in the low-acid high-pressure leaching step.
  • the test results are shown in Table 2.
  • Examples 12-16 verify the effect of acidity on the content of nickel and cobalt entrained in the second filter residue in the high-acid and normal-pressure leaching step. Compared with Example 1, the only difference is that the acidity is different in the high-acid and normal-pressure leaching step.
  • the test results are shown in Table 3.
  • Step (1) of Comparative Example 1 is an existing low-acid atmospheric pressure leaching process, which is specifically as follows:
  • High-acid atmospheric pressure leaching The first filter residue is further subjected to high-acid atmospheric pressure leaching under the following conditions: solid-liquid ratio of 100 g/L, room temperature, acidity of 0.2 mol/L H 2 SO 4 , leaching time of 1 h, stirring speed uniformly set at 400 rpm. After the leaching is completed, the second filtrate and the second filter residue are obtained by filtration, wherein the second filtrate is returned to the low-acid high-pressure leaching process section to realize further utilization of the residual acid in the second filtrate.
  • the silicon content in the obtained first filtrate is 53 ppm
  • the nickel content entrained in the second filter residue is 0.58%
  • the cobalt content entrained in the second filter residue is 0.33%.
  • the present invention reduces the silicon concentration in the nickel cobalt hydroxide leaching solution to below 1ppm through one-step deep silicon removal, and greatly improves the filtering performance of the silicon removal slag; at the same time, the acid utilization rate of the whole process exceeds 95%, and the nickel and cobalt leaching rates exceed 99%.
  • the nickel cobalt hydroxide desiliconized slag has a high purity, and the entrained nickel and cobalt content is less than 0.01%, which can be used as one of the synthetic materials for CO2 capture agents.
  • the present invention further synthesizes CaO ⁇ Li4SiO4 capture agents based on this, realizing the high-value utilization of silicon slag.

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  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention se rapporte au domaine technique de l'hydrométallurgie. L'invention concerne un procédé d'élimination de silicium et un procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte. Le procédé d'élimination de silicium comprend : la réalisation d'une lixiviation à haute pression et à faible teneur en acide sur un précipité d'hydroxyde mixte, et la réalisation d'une filtration pour obtenir un premier résidu de filtre et un premier filtrat. Selon la présente invention, par conversion d'acide silicique en dioxyde de silicium à haute température et haute pression, l'acide silicique qui est difficile à filtrer est transformé en dioxyde de silicium qui peut être facilement filtré, de telle sorte que les performances de filtration de précipités de silicium d'impureté sont considérablement améliorées, ce qui permet de résoudre la situation actuelle selon laquelle l'ensemble du processus de production est coincé à cette étape ; en outre, la concentration de silicium dans une solution de lixiviation peut atteindre une valeur maximale de 1 ppm, et l'effet est bien supérieur à celui dans la situation actuelle selon laquelle la concentration de silicium résiduel dans une solution de filtration d'acide silicique est supérieure ou égale à 50 ppm. De plus, le laitier éliminé par silicium du précipité d'hydroxyde mixte obtenu en outre au moyen d'une lixiviation à pression normale et à haute teneur en acide a une pureté relativement élevée, et la teneur en nickel entraîné et la teneur en cobalt entraîné sont toutes deux inférieures ou égales à 0,01%, et sur cette base, un agent de piégeage de CaO·Li4SiO4 est également synthétisé dans la présente invention, ce qui permet d'obtenir une réutilisation à haute valeur de laitier de silicium.
PCT/CN2023/104003 2023-06-29 2023-06-29 Procédé d'élimination de silicium et procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte Pending WO2025000369A1 (fr)

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PCT/CN2023/104003 WO2025000369A1 (fr) 2023-06-29 2023-06-29 Procédé d'élimination de silicium et procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte
CN202380010003.0A CN117083402B (zh) 2023-06-29 2023-06-29 一种氢氧化镍钴浸出过程中脱硅及硅再利用的方法

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