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
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/01—Preparation or separation involving a liquid-liquid extraction, an adsorption or an ion-exchange
• • 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
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
  • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
  • C22B3/383—Tervalent phosphorus oxyacids, esters 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
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
  • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
  • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
  • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
• • 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
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
  • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
  • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
  • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • 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 present solution relates to an industrial process for obtaining highly concentrated and purified solutions of nickel(II) nitrate(V) from waste solutions of nickel containing sulphate and/or chlorides.
• Multicomponent solutions, containing nickel, directed into the process according to the present invention may be of varying origin, from solutions from liming primary (ores, concentrates, smelting products) and secondary materials (scrap, recycled materials - batteries, catalytic converters) to waste solutions from technological processes (post-rinsing liquid, post-crystallization bases and others).
• nickel nitrate obtained according to the present invention are a desirable resource for the chemical industry.
• the main use of nickel nitrate is the production of catalysts particularly sensitive to sulphur compounds, as well as in the production of nickel-cadmium batteries. It is also used in the manufacturing of products used in the initial processing of metals prior to painting and cold-shaping. In most industrial uses of nickel nitrate, it is inadmissible for it to be contaminated with other metals or salts, particularly sulphates or chlorides.
• nickel nitrate is obtained by dissolving metallic nickel in nitric acid.
• the reaction is performed in a sealed, stainless steel or glass reactor. NO and N02 are released during the reaction. These are removed from the gas stream by rinsing with water in a column forming nitric acid that returns to the process, or catalytically. Solid nickel nitrate is obtained from the solution by concentrating it.
• the apparatus is cleaned with water, and the effluent is directed to the municipal sewage system.
• Patent PL86221 describes a method of reclaiming nickel from waste baths and sediments in the form of nickel sulphate solutions with a stable pH that ensures the removal of iron, aluminum, chromium, copper and zinc, characterised in that the acidic solution containing nickel sulphate, iron, aluminum, chromium, copper and zinc or acid is put into contact with a suspension of hydroxides, carbonates or basic carbonates of these metals obtained possibly from waste nitrate baths for the electrolytic removal of faulty coatings or passed through a layer formed therefrom.
• Patent PL 129 135 describes the reclamation of copper and nickel from acidic solutions, particularly electrolytes taken out of copper electrorefinement.
• the known method is based on the fact that the acidic solution containing copper and nickel is put into contact with crushed rock containing magnesium and preferably nickel minerals, meaning serpentinite and/or magnesium, in a multi-stage countercurrent system, and between the stages of this contact as well as after its completion copper is extracted using organic compounds or mixtures containing hydroxyl and oxime functional groups.
• the aqueous solution obtained following the extraction of copper, containing amongst others nickel sulphate and contaminates from both the initial solution as well as those from the digestion of the rock is neutralised to a solution pH of 3-4 in order to precipitate metal hydroxides, except nickel hydroxide.
• Nickel is extracted from the purified solution in several steps of a countercurrent system using a 30% 2-hydroxy-5-nonylbenzophone oxime solution in a crude oil fraction. Nickel extraction is conducted by adding ammonia at each stage of the extraction such that the pH of the solution is no lower than 6, such that as the concentration of nickel in the aqueous solutions drops in consecutive stages of the extraction, the pH increases stepwise to 8.5.
• the organic phase is re-extracted with sulphuric acid solutions in three steps such that the post-extraction pH is above 2.5. Nickel is isolated from such a sulphate solution through electrolysis.
• the known methods produce possibly initially purified solutions of nickel sulphate. These are not nickel nitrate sources for industrial use, particularly due to the insufficient degree of purity and highly undesirable sulphate content.
• Patent US 6733564 describes a method of reclaiming nickel from used up catalysts. Likewise, this process only results in a purified solution of nickel sulphate.
• the subject of the present invention is a method of industrially obtaining purified and concentrated solutions of nickel(II) nitrate(V) from waste solutions of nickel containing sulphates and/or chlorides by way of solvent extraction, encompassing cationic ion exchange extraction, characterised in that a waste aqueous solution with a nickel content from 1 to 10 %, by mass, preferably initially heated with active carbon and then filtered, is subjected to extraction with a solution of liquid cationite in heavy dearomatised white spirits, wherein, during the extraction, the ratio of solutions of nickel to cationite solution varies in the range from 0.25 to 2.5, the emulsion pH is maintained in the range from 3.5 to 4.5 and the temperature is from 30 to 50°C, then the organic and aqueous phases are separated, and nickel extraction is performed into solutions of higher aliphatic acids selected from a group encompassing: di-2-ethylhexylphosphoric acid, di(2,4,4-trimethylpentyl)phospho
• the resulting method facilitates the production of highly pure nickel nitrate from various sources that currently constitute industrial waste with a high nickel content.
• these may be: solid or liquid galvanic wastes, nickel sulphate from copper production, expired solutions of nickel salts in solid and liquid form, all manner of solid nickel waste (cakes, slag) from various branches of industry or nickel alloy scrap.
• solid waste it is desirable to initially process them to obtain initial solutions containing nickel sulphate or chloride. These may be obtained using any known simple methods, such as elution with sulphuric or hydrochloric acid solutions.
• Nickel solutions with a nickel content from 1 to 10 %, by mass and containing sulphate and/or chlorides are filtered following heating with activated carbon.
• the four-stage extraction cascade is loaded with a filtered solution of nickel and a liquid cationite solution in heavy dearomatised white spirits.
• the ratio of nickel solution to cationite solution varies in the range from 0.25 to 2.5.
• the emulsion pH is controlled and corrected if needed using alkali solutions to 3.5 to 4.5.
• the extraction process is conducted at a temperature of 30 to 50°C.
• the post-extraction nickel solution is centrifuged (to remove organic phase residues) and introduced into a periodic reactor in which nickel is extracted by higher aliphatic acids, selected from a group encompassing: di-2-ethylhexylphosphoric acid, di(2,4,4-trimethylpentyl)phosphonic acid and mono-2-ethylhexyl ester 2-ethylhexylphosphorous acid, dissolved in heavy dearomatised white spirits.
• a mono-2-ethylhexyl ester 2-ethylhexylphosphorous acid solution in heavy dearomatised white spirits.
• This process is meant to separate anions from the nickel (in particular: sulphates, chlorides phosphates and other anions).
• phase separation aqueous phase/organic phase
• organic phase is rinsed with deionised water, until anions and alkali metal ions are rinsed out.
• nickel is extracted from the organic phase with a nitric acid solution with a concentration of 20- 35 %.
• nickel nitrate solution with a concentration of 10-11 % per 100% nickel.
• common knowledge means i.e. encompassing the following sequence of stages: heating - filtration - concentration - crystallization - centrifugation).
• a method according to the present invention encompasses two extraction stages:
• the method according to the present invention is the effect of multi-stage experimentation, meant to design optimal parameters for the process that are of particular significance for industrial processes.
• Solvent optimization consisted of selecting an industrial solvent so as to meet several criteria
• DEHPA constituted di-2-ethylhexylphosphoric acid (CAS No 298-07-7), Cyanex 272 to di(2,4,4-trimethylpentyl)phosphonic acid (CAS No 83411-71-6), a P 507 to mono-2- ethylhexyl ester 2-ethylhexylphosphorous acid (CAS No 3658-48-8).
• Exxol D80 due to its higher ignition temperature (for white spirits > 27 °C and for Exxol D80 > 70 °C). Since the process can be conducted at a temperature of up to 50 °C, for safety reasons it becomes necessary to use a solvent with a higher ignition temperature.
• An extractor was loaded with 250 cm3 of nickel solution containing 5.9 % nickel at pH 4,0 and heated to 60 °C and then we added 250 cm3 of extractant solution with a content of 10 % [V/V]. During mixing, the solution pH dropped to 1.5 to 2.5. We supplemented the solution portion-wise with 30 % sodium hydroxide until the pH was stable at a level of 4 +/-0.1 and after this we continued to mix the mixture for 5 minutes while controlling the pH. After this time, the mixture was settled for 60 minutes to separate. The nickel solution after separation was separated again as described above. The nickel solution was extracted thrice.
• Iron content 0,08 % 0, 190 % 0,0006 % 0,00095 °A 200 99,5

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
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• Environmental & Geological Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Geology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Extraction Or Liquid Replacement (AREA)

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Citations (6)

• 2013
  • 2013-05-31 PL PL40417213A patent/PL404172A1/pl unknown
• 2014
  • 2014-05-31 WO PCT/PL2014/050033 patent/WO2014193253A1/en not_active Ceased

Patent Citations (6)

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