CN110438338B - Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid - Google Patents

Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid Download PDF

Info

Publication number
CN110438338B
CN110438338B CN201910766110.1A CN201910766110A CN110438338B CN 110438338 B CN110438338 B CN 110438338B CN 201910766110 A CN201910766110 A CN 201910766110A CN 110438338 B CN110438338 B CN 110438338B
Authority
CN
China
Prior art keywords
cobalt
nickel
magnesium
magnesium oxide
separation
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.)
Active
Application number
CN201910766110.1A
Other languages
Chinese (zh)
Other versions
CN110438338A (en
Inventor
钟宏
曹占芳
王帅
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.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201910766110.1A priority Critical patent/CN110438338B/en
Publication of CN110438338A publication Critical patent/CN110438338A/en
Application granted granted Critical
Publication of CN110438338B publication Critical patent/CN110438338B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • 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
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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

Landscapes

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

Abstract

The invention provides a device and a method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide. The method comprises the following steps: firstly, separating and recovering nickel and cobalt from a nickel-cobalt-magnesium waste liquid by an extraction method or a sulfide precipitation method to obtain a magnesium-containing solution; then adding bicarbonate and ammonia water into the magnesium-containing solution, stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; drying and roasting the basic magnesium carbonate in an atmosphere to obtain high-purity magnesium oxide; and finally crushing the high-purity magnesium oxide to obtain a silicon steel magnesium oxide product. The invention realizes the high-efficiency separation of nickel and cobalt and the low-cost preparation of high-purity magnesium oxide products through the innovative design, combination and accurate regulation and control of equipment, realizes the economic and high-efficiency utilization of nickel-cobalt-magnesium waste liquid resources, and has very wide market prospect.

Description

Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid
Technical Field
The invention relates to the technical field of chemical industry, in particular to a device and a method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide.
Background
In recent years, the demand and the capacity of the ternary lithium battery anode material are increasing. In the production or recovery process of the ternary precursor, a large amount of waste liquid mainly containing metal ions of nickel, cobalt and magnesium is usually produced as a byproduct, wherein the metal ions of nickel, cobalt and magnesium have high recovery value. However, the prior art generally only focuses on the recovery of nickel and cobalt, and rarely focuses on the recovery of a large amount of magnesium resources enriched therein, which causes serious waste of magnesium resources. Meanwhile, the supply of high-purity magnesium oxide in China is seriously short. Currently, dolomite, serpentine, brine and the like are generally used as raw materials to produce magnesium oxide products. However, the prior art has the disadvantages of low separation efficiency, high production cost and the like, and is difficult to meet the requirement of high-purity magnesium oxide production. Patent CN101804998A discloses a method for producing high-purity magnesia by using dolomite, patent CN104016393A discloses a method for preparing light calcium carbonate and magnesia by using dolomite, and patent CN101030487A discloses a new process for pyrolyzing high-purity magnesia at low temperature by normal-temperature carbonization. Patent CN105271845A discloses a method for preparing magnesia for high-performance silicon steel from dolomite. The literature (M.Zaki Mubarok, Christian Adi Kurnia wan. Synthesis of magnesia powder from East Java domicile through leiching, precipitation and catalysis. advanced Materials Research,2015,1112: 550) describes a process for obtaining magnesium oxide by dissolution with hydrochloric acid, calcium separation with a precipitant and calcination. A process for preparing heavy magnesium oxide by direct precipitation of bittern and mixed alkali is disclosed in Zhao Na, Zhang Zhai, Huangchunhui, Zong Jun, bittern-mixed alkali, 2015(8), 22-26. At present, the production of magnesium oxide in China still stays at a low-level stage, most of the magnesium oxide is in a rough-forming stage of magnesium compound products, and the problems of few magnesium oxide products with high added values, unstable product quality, overhigh production cost, environmental pollution and the like still exist.
In summary, there is no related efficient separation and recovery apparatus or method for the large amount of mixed liquid of nickel, cobalt and magnesium by-produced in the production process of the ternary precursor. Therefore, it is necessary to develop a new technology and a production device for co-producing high-purity magnesium oxide in the process of efficiently recovering nickel and cobalt from the nickel-cobalt-magnesium waste liquid.
Disclosure of Invention
The invention provides a device and a method for recovering nickel and cobalt from a nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide, and aims to realize high-efficiency separation of nickel and cobalt in the nickel-cobalt-magnesium waste liquid and low-cost preparation of a high-purity magnesium oxide product, so that the nickel-cobalt-magnesium waste liquid is maximally and economically utilized.
In order to achieve the above object, an embodiment of the present invention provides the following solutions:
a device for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid comprises a nickel-cobalt separation and recovery system, a magnesium combination separation and recovery system, an atmosphere roasting furnace and a crusher which are sequentially connected;
the nickel-cobalt separation and recovery system is a nickel-cobalt extraction separation device or a nickel-cobalt combination separation device;
the magnesium compound separation and recovery system comprises a magnesium compound separator and a filtering system; the nickel-cobalt separation and recovery system is connected with the filtering system through a magnesium combination separator; the magnesium compound separator is connected with the atmosphere roasting furnace through a filtering system;
the nickel and cobalt extraction separation device comprises an extraction tank and a back extraction tank, wherein one end of the extraction tank is connected with the back extraction tank, and the other end of the extraction tank is connected with the magnesium combination separator;
the nickel-cobalt combination separation device comprises a nickel-cobalt combination separator and a nickel-cobalt filtering system, and the nickel-cobalt combination separator is connected with the magnesium combination separator through the nickel-cobalt filtering system.
Preferably, the nickel cobalt filtering system comprises a coarse filtering device and a fine filtering device; the coarse filtering device is a plate and frame filter; the fine filtering device is a ceramic membrane filter, and the membrane aperture of the ceramic membrane filter is 10-100 nm.
The invention also provides a method for recovering nickel and cobalt from the nickel-cobalt-magnesium waste liquid and coproducing magnesium oxide, which comprises the following steps:
(1) separating and recovering nickel and cobalt from the nickel, cobalt and magnesium waste liquid by an extraction method or a sulfide precipitation method to obtain a magnesium-containing solution;
(2) adding bicarbonate and ammonia water into the magnesium-containing solution obtained in the step (1), and stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; wherein the molar ratio of the bicarbonate to the magnesium ions is 1.1-1.5; the volume ratio of the ammonia water to the magnesium carbonate solution is 2-5: 100;
(3) drying and roasting the basic magnesium carbonate obtained in the step (2) in an atmosphere to obtain high-purity magnesium oxide;
(4) and (4) crushing the high-purity magnesium oxide obtained in the step (3) to obtain a silicon steel magnesium oxide product with the average particle size of 3-5 microns.
Preferably, the nickel content in the nickel-cobalt-magnesium waste liquid is 0.1-18 g/L; the cobalt content is 0.1-10 g/L; the magnesium content is 0.1-50 g/L.
Preferably, the extraction method in the step (1) is specifically that nickel-cobalt extraction separation is carried out on the nickel-cobalt-magnesium waste liquid to obtain a nickel-cobalt-containing solution and a magnesium-containing solution; carrying out back extraction on the obtained nickel-cobalt-containing solution to recover nickel and cobalt; the resultant magnesium-containing solution is subjected to step (2).
Preferably, the sulfidation precipitation method in the step (1) is to adjust the pH value of the nickel-cobalt-magnesium waste liquid to 6-8; then adding a vulcanization precipitator according to the amount which is 1.2-1.6 times of the total amount of nickel and cobalt to obtain nickel-cobalt precipitation slurry; finally, filtering the obtained nickel-cobalt precipitation slurry by a plate filter and a ceramic membrane filter to obtain a nickel-cobalt byproduct and a magnesium-containing filtrate; and (3) feeding the obtained magnesium-containing filtrate into the step (2).
More preferably, the sulphiding precipitant comprises one or more of ammonium sulphide, sodium fermet and ethidium nitrate.
Preferably, the bicarbonate in step (2) is one or more of ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, the heating temperature in the step (2) is 70-95 ℃; the heat preservation time is 40-60 min.
Preferably, the atmosphere roasting in the step (3) comprises a temperature rising stage, a heat preservation stage and a cooling stage; wherein the heat preservation temperature is 900-1200 ℃, and the heat preservation time is 1-3 h; and introducing inert gas for protection in the cooling stage.
The method aims at the efficient recycling of the waste liquid by-product in the production or recycling process of the ternary precursor, and the waste liquid mainly contains nickel, cobalt and magnesium ions, wherein the content of Ni is 0.1-18 g/L, the content of Co is 0.1-10 g/L, and the content of Mg is 0.1-50 g/L.
The scheme of the invention has the following beneficial effects:
(1) the invention discloses a production device for efficiently separating nickel and cobalt and producing high-purity silicon steel grade magnesium oxide in parallel, which consists of a nickel and cobalt separation and recovery system, a magnesium combination separation and recovery system, a drying and calcining system, a depolymerization and crushing system and the like, and the device can accurately regulate and control the extraction temperature, the combination temperature and the pH value and realize the efficient separation of nickel, cobalt and magnesium ions; particularly, the magnesium oxide product obtained by the invention is a silicon steel grade magnesium oxide product with higher added value, has extremely high economic value, and simultaneously has the advantages of simple process flow, lower cost and the like.
(2) Based on the performance difference of nickel, cobalt and magnesium ions, after nickel and cobalt are efficiently separated by an extraction or precipitation technology, bicarbonate and ammonia water in a certain proportion are innovatively added, and further, the efficient precipitation separation of the magnesium ions and the regulation and control of the physical and chemical properties of a product are realized by regulating and controlling the combination temperature and the pH value. According to the invention, through the combined use of the bicarbonate and the ammonia water, on one hand, the high-efficiency separation of magnesium is realized, and the magnesium oxide product with the purity of more than 99% is obtained, on the other hand, the physical and chemical properties of the magnesium oxide product, such as the bulk density, the suspension property and the like, are greatly improved, and the suspension property is reduced from more than 10mm to 1-7 mm, so that the index requirement of the silicon steel grade magnesium oxide product is met and better than that of the silicon steel grade magnesium oxide product.
(3) The nickel-cobalt combination separation device provided by the invention has the advantages that the nickel and cobalt precipitation slurry is subjected to a coarse filtration and a fine filtration mode, particularly, the removal of nano-sized nickel and cobalt precipitation fine particles is realized by adopting a ceramic membrane fine filtration operation, and the quality of a magnesium oxide product is favorably ensured.
(4) In the invention, depolymerization crushing equipment such as a honeycomb mill is introduced in the step 4, compared with the conventional calcined magnesia product, the average particle size of the obtained magnesia product is smaller, the stacking density and the suspension property are better, the performance requirements of the silicon steel grade magnesia product can be met, and the magnesium resource value is greatly improved.
In conclusion, the invention realizes the high-efficiency separation of nickel and cobalt and the low-cost preparation of high-purity magnesium oxide products through the innovative design, combination and accurate regulation of equipment, realizes the economic and high-efficiency utilization of nickel-cobalt-magnesium waste liquid resources, and has very wide market prospect.
Drawings
FIG. 1 is a schematic structural view of an apparatus according to embodiment 1 of the present invention;
FIG. 2 is a schematic structural diagram of an apparatus according to embodiment 2 of the present invention;
FIG. 3 is a process flow diagram of example 3 of the present invention;
FIG. 4 is a process flow diagram of example 4 of the present invention;
FIG. 5 is an XRD pattern of a grade of silicon steel magnesium oxide product obtained in example 4 of the present invention;
FIG. 6 is an SEM image of a grade magnesium oxide product made of Si-steel obtained in example 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description will be made with reference to specific drawings and embodiments.
In order to solve the problems of low utilization rate of magnesium resources, low quality of byproducts and the like in the recycling process of the existing nickel, cobalt and magnesium mixed waste liquid, the invention realizes low-cost co-production of high-purity magnesium oxide and nickel and cobalt products by design, accurate regulation and combination innovation of equipment such as extraction, combination, precipitation, separation and the like, so that the nickel, cobalt and magnesium mixed waste liquid is economically utilized to the maximum extent.
The equipment connection mode and the use method of each system of the magnesium compound separator provided by the invention are as follows:
(1) nickel cobalt separation recovery system
The nickel and cobalt separation and recovery system can adopt an extraction separation device and can also adopt a chemical combination precipitation separation related device.
The nickel and cobalt are recovered by adopting an extraction separation technology, and the upper part of the extraction tank is communicated with the upper part of the back extraction tank through a pipeline or a pumping device; the lower part of the extraction tank is communicated with the upper part of the magnesium combination separator through a pipeline or a pumping device; and directly feeding the magnesium-containing solution after nickel and cobalt extraction and separation into a magnesium combination separator.
Nickel and cobalt are recovered by a chemical combination precipitation technology, the nickel and cobalt chemical combination separator has the functions of stirring, accurate temperature control, pH monitoring and the like, is connected with a coarse filtration system, the coarse filtration system adopts a plate-and-frame filter and other devices, the obtained filtrate is communicated with a fine filtration system through a pipeline or a pumping device, the fine filtration system adopts a ceramic membrane filter, the obtained filtrate is communicated with the upper part of a magnesium chemical combination separation reactor through a pipeline or a pumping device, and magnesium-containing feed liquid after the separation of the nickel and cobalt chemical combination precipitation is directly sent into the magnesium chemical combination separator.
(2) Magnesium separation and recovery system
The upper part of the magnesium combination separator is connected with the extraction tank of the nickel-cobalt separation system or the ceramic membrane filter through a pipeline or a pumping device, the lower part of the magnesium combination separator is connected with a filtering system through a pipeline and a pumping device, and the filtering system adopts a plate-and-frame filter and other devices; the magnesium compound separator has the functions of stirring, accurate temperature control, pH monitoring and the like.
(3) Drying and calcining system
Connecting a filtering device in a magnesium separation and recovery system with an atmosphere roasting furnace through a belt and the like, and conveying the obtained basic magnesium carbonate product into the atmosphere roasting furnace for drying and roasting to obtain a high-purity magnesium oxide product; the atmosphere roasting furnace is divided into a heating and drying section, a heat preservation and calcination section and a cooling section, wherein a gas one-way recovery device (the recovered gas can be communicated with the lower part of the magnesium combination separator through a pipeline or can be directly discharged to the air) is arranged at the upper part of the heating, drying and heat preservation section, and inert gas is introduced into the cooling section for protection.
(4) Depolymerization crushing system
And connecting a discharge port of a cooling section of the roasting furnace with depolymerization crushing equipment such as a honeycomb mill and the like, so as to realize effective control on the granularity of the high-purity magnesium oxide product, and finally preparing the silicon steel magnesium oxide product meeting the requirements. By adopting equipment such as a honeycomb mill, magnesium oxide products with the particle size of 5-20 mu m can be depolymerized and crushed to 3-5 mu m, and the index requirements of silicon steel magnesium oxide related particle size and the like are met.
The volume capacity of the extraction tank is 30-50 m3V (ton of magnesium oxide); the back extraction tank has a volume capacity of 20-35 m3V (ton of magnesium oxide); the volume capacity of the magnesium combination precipitation reactor is 25-35 m3V (ton of magnesium oxide); the fine filtering equipment in the nickel-cobalt separation system adopts a ceramic membrane filter, and the membrane aperture is 10-100 nm. In the invention, most of nickel and cobalt precipitation byproducts are separated and recovered in a nickel and cobalt separation system through a coarse filtration system; in order to avoid the influence of nickel-cobalt precipitates of fine particles on the purity of subsequent magnesium products, a ceramic membrane fine filtration system is innovatively introduced, the purity of the subsequent magnesium oxide products can be effectively improved, and the magnesium oxide products with the purity of over 99.5 percent can be prepared by adopting the device system disclosed by the invention. By applying the ceramic membrane filtration equipment, the purity of the magnesium oxide product is improved by more than 1 percent, which is very key and necessary for preparing high-purity magnesium oxide.
The atmosphere roasting furnace is mainly divided into a drying and heating section, a heat preservation and roasting section and a cooling and cooling section. Obtained in the production processThe basic magnesium carbonate product can release a large amount of water vapor and CO in the calcining process2Therefore, gas one-way valves are required to be arranged in the temperature rising section and the heat preservation section, and gas is discharged through the one-way valves or is introduced into the magnesium combination precipitation reactor through a recovery pipeline in the drying and calcining processes; in the cooling process, in order to avoid the magnesium oxide product with higher activity and water vapor or CO2The re-reaction requires the protection of inert gas, and the gas to be introduced can be one of inert gases such as nitrogen, argon and the like.
The method for recovering nickel and cobalt and co-producing magnesium oxide from the nickel-cobalt-magnesium waste liquid comprises the following steps:
step 1: and separating and recycling nickel and cobalt. Selectively separating and recovering nickel and cobalt from an acidic solution containing nickel, cobalt and magnesium by one of extraction or sulfide precipitation methods, and simultaneously obtaining a magnesium-containing solution for subsequent separation and recovery of magnesium and preparation of high-purity magnesium oxide; when a nickel-cobalt extraction process is adopted, a nickel-cobalt-loaded extractant is subjected to back extraction operation and recovered to obtain nickel-cobalt; when a nickel-cobalt precipitation separation process is adopted, firstly, the pH value of a raw material solution is adjusted to 6-8, then a precipitator which is 1.2-1.6 times (the amount of substances) the total amount of nickel and cobalt is added to separate nickel and cobalt, and after complete precipitation, the precipitation slag is filtered (plate-frame filtration and ceramic fine filtration system) and dried to obtain a nickel-cobalt byproduct;
step 2: magnesium separation and basic magnesium carbonate preparation. Adding a certain amount of bicarbonate and ammonia water into the extracted or fine-filtered magnesium-containing solution according to the content of magnesium ions, stirring for a certain time, heating to 70-95 ℃, preserving heat for a certain time, and filtering to obtain a basic magnesium carbonate product; wherein the bicarbonate is one or more of ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate, and the addition amount of the bicarbonate is 1.1-1.5 times of the amount of the magnesium ion substance; the volume ratio of the addition amount of the ammonia water to the magnesium-containing solution is as follows: 2-5: 100;
and step 3: and (4) preparing high-purity magnesium oxide. Drying the basic magnesium carbonate product obtained in the step (2), and calcining the product at a high temperature in an atmosphere roasting furnace to obtain a high-purity magnesium oxide product with MgO of more than 99.5 percent;
and 4, step 4: and preparing silicon steel grade magnesium oxide. And (4) depolymerizing and crushing the high-purity magnesium oxide product prepared in the step (3) by adopting equipment such as a honeycomb mill and the like until the average particle size is 3-5 mu m, so as to obtain the silicon steel magnesium oxide product.
The extraction operation in the step 1 can be continuous countercurrent (concurrent) flow operation or intermittent countercurrent (concurrent) flow operation; after the pH value of the feed liquid in the step 1 needs to be adjusted to 6-8, nickel and cobalt combination precipitation operation is carried out, so that the generation of hydrogen sulfide gas can be effectively avoided; after stirring in the step 2, the pyrolysis temperature is 70-95 ℃, and the reaction time is 40-60 min; the roasting conditions in the atmosphere furnace in the step 4 are as follows: 900-1200 ℃ for 1-3 h.
The extracting agent used by the extracting device can be one or more of substances such as bis- (2,4, 4-trimethylpentyl) phosphonic acid, P204, P507 and the like; extracting an organic phase: 1: 1-5 of feed liquid; loading an organic phase: the stripping agent is 1-5: 1.
Example 1
The device for recovering nickel and cobalt from the nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide provided by the embodiment comprises a nickel-cobalt separation and recovery system, a magnesium combination separation and recovery system, an atmosphere roasting furnace and a depolymerization crusher which are sequentially connected.
The nickel-cobalt separation and recovery system is a nickel-cobalt extraction and separation device; the magnesium compound separation and recovery system comprises a magnesium compound separator and a filtering system; the nickel-cobalt separation and recovery system is connected with the filtering system through a magnesium combination separator; the magnesium compound separator is connected with the atmosphere roasting furnace through a filtering system; the nickel cobalt extraction and separation device comprises an extraction tank and a back extraction tank, wherein one end of the extraction tank is connected with the back extraction tank, and the other end of the extraction tank is connected with the magnesium combination separator.
Wherein, the extraction tank is 200L (50 × 50 × 80cm), 2; 2 stripping tanks 200L (50X 80 cm); the extraction and back-extraction tanks are connected in a two-stage countercurrent mode; the capacity of the magnesium compound separation reactor is 100L (the diameter is 40 cm); the atmosphere roasting furnace is a high-temperature program box-type atmosphere furnace: the working temperature is less than or equal to 1300 ℃, and the ventilation atmosphere is as follows: nitrogen, furnace size: 400X 300X 250 mm; the filtering area of the plate and frame filter is 0.3m2(ii) a The treatment capacity is 50L/h; the depolymerization crusher is a honeycomb mill: the power is 2kW, and the average grain diameter of the classified discharged materials is 3-5 mu m. The equipment set up connection is shown in figure 1.
Example 2
The device for recovering nickel and cobalt from the nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide provided by the embodiment comprises a nickel-cobalt separation and recovery system, a magnesium combination separation and recovery system, an atmosphere roasting furnace and a depolymerization crusher which are sequentially connected.
The nickel-cobalt separation and recovery system is a nickel-cobalt combination separation device; the magnesium compound separation and recovery system comprises a magnesium compound separator and a filtering system; the nickel-cobalt separation and recovery system is connected with the filtering system through a magnesium combination separator; the magnesium compound separator is connected with the atmosphere roasting furnace through a filtering system; the nickel-cobalt combination separation device comprises a nickel-cobalt combination separator and a nickel-cobalt filtering system, and the nickel-cobalt combination separator is connected with the magnesium combination separator through the nickel-cobalt filtering system. The nickel-cobalt filtering system comprises a coarse filtering device and a fine filtering device; the coarse filtering device is a plate and frame filter; the fine filtering device is a ceramic membrane filter.
Wherein the capacity of the nickel-cobalt chemical combination separator is 100L (the diameter is 40 cm); the capacity of the magnesium compound separator is 100L (the diameter is 40 cm); the atmosphere roasting furnace is a high-temperature program box-type atmosphere furnace: the working temperature is less than or equal to 1300 ℃, and the ventilation atmosphere is as follows: nitrogen, furnace size: 400X 300X 250 mm; the filtering area of the plate and frame filter is 0.3m2(ii) a Ceramic membrane filter: the membrane aperture is 50nm, and the treatment capacity is 50L/h; the power of the depolymerization crusher is 2kW, and the average grain size of the classified discharged material is 3-5 μm. The equipment set up connection is shown in figure 2.
Example 3
The method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide provided by this embodiment, as shown in fig. 3, specifically includes the following steps:
(1) nickel cobalt extraction and separation: 100L of mixed waste liquid (pH value) containing 23g/L Mg, 1.808g/L Co and 8.34g/L Ni<2) Performing nickel-cobalt extraction separation with 50L of organic phase containing 10% of bis- (2,4, 4-trimethylpentyl) phosphonic acid in an extraction tank, and after the extraction is finished, carrying out 250g/L H on the loaded organic phase2SO4Carrying out back extraction to recover nickel and cobalt to obtain a nickel and cobalt containing solution and a magnesium containing solution, wherein the recovery rates of nickel and cobalt are both more than 96%;
(2) conveying the magnesium-containing solution obtained in the step (1) to a magnesium combination separation reactor, adjusting the pH value of the magnesium combination separation reactor to about 7, measuring the content of Mg ions in the solution to be 22.5g/L, adding ammonium bicarbonate with the amount being 1.3 times that of magnesium ions and 3L of 25% ammonia water based on the content of the magnesium ions, stirring for 30min, raising the temperature of the feed liquid in the magnesium combination separation reactor to 90 ℃, preserving heat for 50min under the stirring condition, and stirring at the rotating speed of 500 r/min;
(3) conveying the mixed slurry after the pyrolysis in the step 2 to a plate and frame filter and filtering to obtain a basic magnesium carbonate product;
(4) after drying the basic magnesium carbonate product obtained in the step 3, calcining the product for 2 hours at 1100 ℃ by using an atmosphere roaster to obtain a high-purity magnesium oxide product, wherein the purity of the magnesium oxide is 99.95%, the recovery rate of the magnesium oxide is 95.27%, and the median particle size of the product is 8.96 mu m; the high-purity magnesium oxide product is sent into a honeycomb mill to be ground and classified, the median particle size is 3.68 mu m, the bulk density is 0.09g/ml, the suspension property is 2mm, the analysis result of the main performance index of the product is shown in table 1, the XRD analysis result is shown in fig. 5, and the SEM analysis result is shown in fig. 6. As can be seen from Table 1, the indexes of the magnesium oxide product produced by the device and the method are far better than the indexes of the silicon steel magnesium oxide product (HG/T2573-2006).
Table 1 example 3 product index analysis results
Figure BDA0002171988500000091
Example 4
The method for recovering nickel and cobalt from the nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide, as shown in fig. 4, specifically includes the following steps:
(1) nickel and cobalt precipitation separation: taking 100L of mixed waste liquid (pH is less than 2) containing 23g/L of Mg, 1.808g/L of Co and 8.34g/L of Ni, adjusting the pH of the solution to about 8, adding ammonium sulfide with the amount of 1.6 times of the total substances of nickel and cobalt, and stirring for 30 min; sequentially conveying the magnesium alloy to a plate-and-frame filter and a ceramic filter to separate nickel and cobalt precipitates to obtain a magnesium-containing solution and a nickel and cobalt byproduct with high quality; wherein the mass fraction of Ni, Co and Mg in the slag is 33.26%, 8.78% and 4.06%; the recovery rates of Ni and Co are both more than 99 percent;
(2) conveying the magnesium-containing solution obtained in the step (2) to a magnesium combination separation reactor, measuring the content of Mg ions in the solution to be 18.7g/L, adding ammonium bicarbonate with the amount being 1.3 times that of magnesium ions and 3L of 25% ammonia water based on the content of the magnesium ions, stirring for 30min, raising the temperature of feed liquid in the magnesium combination separation reactor to 90 ℃, preserving the heat for 50min under the stirring condition, and stirring at the rotating speed of 500 r/min;
(3) conveying the mixed slurry after the pyrolysis in the step 2 to a plate and frame filter and separating to obtain a basic magnesium carbonate product;
(4) after drying the basic magnesium carbonate product obtained in the step 3, calcining the product for 2 hours at 1100 ℃ by using an atmosphere roaster to obtain a high-purity magnesium oxide product, wherein the purity of the magnesium oxide is 99.79%, the recovery rate of the magnesium oxide is 90.16%, and the median particle size of the intermediate product is 9.17 mu m; the high-purity magnesium oxide product is sent into a honeycomb mill to be ground and classified, the median particle size is 3.61 mu m, the bulk density is 0.10g/ml, the suspension property is 2mm, and the analysis result of the main performance index of the product is shown in Table 2.
Table 2 example 4 product index analysis results
Figure BDA0002171988500000092
Figure BDA0002171988500000101
Example 5:
a production device for co-producing high-purity magnesium oxide in the process of recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and an application method thereof. The experimental apparatus and the connection method are the same as those in example 4, in this example, sodium sulfide is used as the nickel-cobalt compound separating agent:
(1) nickel and cobalt precipitation separation: taking 100L of mixed waste liquid (pH is less than 2) containing 23g/L of Mg, 1.808g/L of Co and 8.34g/L of Ni, adjusting the pH of the solution to about 8, adding sodium sulfide with the amount of 1.6 times of the total substances of nickel and cobalt, and stirring for 30 min; sequentially conveying the magnesium alloy to a plate-and-frame filter and a ceramic filter to separate nickel and cobalt precipitates to obtain a magnesium-containing solution and a nickel and cobalt byproduct with high quality; wherein the mass fraction of Ni, Co and Mg in the slag is 31.88%, 9.02% and 3.66%;
(2) conveying the magnesium-containing solution obtained in the step (2) to a magnesium combination separation reactor, measuring the content of Mg ions in the solution to be 18.7g/L, adding ammonium bicarbonate with the amount being 1.3 times that of magnesium ions and 3L of 25% ammonia water based on the content of the magnesium ions, stirring for 30min, raising the temperature of feed liquid in the magnesium combination separation reactor to 90 ℃, preserving the heat for 50min under the stirring condition, and stirring at the rotating speed of 500 r/min;
(3) conveying the mixed slurry after the pyrolysis in the step 2 to a plate and frame filter and separating to obtain a basic magnesium carbonate product;
(4) after drying the basic magnesium carbonate product obtained in the step 3, calcining the product for 2 hours at 1100 ℃ by using an atmosphere roaster to obtain a high-purity magnesium oxide product, wherein the purity of the magnesium oxide is 99.70%, the recovery rate of the magnesium oxide is 91.04%, and the median particle size of the intermediate product is 8.26 m; and (3) feeding the high-purity magnesium oxide product into a honeycomb mill for grinding and grading, wherein the median particle size is 3.97 mu m, the bulk density is 0.09g/ml, and the suspension property is 2.8 mm.
Comparative example 1
The experimental apparatus and connection mode of comparative example 1 are the same as example 3, and the nickel cobalt is separated by extraction. Comparative example 1 differs from example 3 in that: the separation of magnesium ions in comparative example 1 was performed only by precipitation with ammonia water. The method specifically comprises the following steps:
(1) nickel cobalt extraction and separation: 100L of mixed waste liquid (pH value) containing 23g/L Mg, 1.808g/L Co and 8.34g/L Ni<2) Performing nickel-cobalt extraction separation with 50L of organic phase containing 10% of bis- (2,4, 4-trimethylpentyl) phosphonic acid in an extraction tank, and after the extraction is finished, carrying out 250g/L H on the loaded organic phase2SO4Carrying out back extraction to recover nickel and cobalt to obtain a nickel and cobalt containing solution and a magnesium containing solution;
(1) conveying the magnesium-containing solution obtained in the step (1) to a magnesium combination separation reactor, adjusting the pH value of the magnesium-containing solution to about 7, measuring the content of Mg ions in the solution to be 22.5g/L, adding 5L 25% ammonia water based on the content of the magnesium ions, stirring for 30min at the feed liquid pH value of 10.5, and recovering magnesium precipitates in the process, wherein the stirring speed is 500 r/min;
(2) conveying the mixed slurry after the precipitation in the step 2 to a plate and frame filter and separating to obtain a magnesium hydroxide product;
(3) and (3) drying the magnesium hydroxide product obtained in the step (3), and calcining for 2h at 1100 ℃ by using an atmosphere roaster to obtain a magnesium oxide product, wherein the purity of the magnesium oxide is 93.06%, the recovery rate of the magnesium oxide is 96.11%, and the median particle size of the intermediate product is 13.25 mu m. And (3) feeding the magnesium oxide product into a honeycomb mill for grinding and grading, wherein the median particle size is 3.72 mu m, the bulk density is 0.53g/ml, and the suspension property is 12 mm.
Comparative example 2
The experimental device and connection mode of the comparative example 2 are the same as those of the example 4, and the nickel cobalt is separated by adopting a vulcanization precipitation mode. Comparative example 2 differs from example 4 in that: the separation of magnesium ions in comparative example 2 was performed only by precipitation with ammonia water. The method specifically comprises the following steps:
(1) nickel and cobalt precipitation separation: taking 100L of mixed waste liquid (pH is less than 2) containing 23g/L of Mg, 1.808g/L of Co and 8.34g/L of Ni, adjusting the pH of the solution to about 8, adding ammonium sulfide with the amount of 1.6 times of the total substances of nickel and cobalt, and stirring for 30 min; sequentially conveying the magnesium alloy to a plate-and-frame filter and a ceramic filter to separate nickel and cobalt precipitates to obtain a magnesium-containing solution and a nickel and cobalt byproduct with high quality; wherein the mass fraction of Ni, Co and Mg in the slag is 33.26%, 8.78% and 4.06%;
(2) conveying the magnesium-containing solution obtained in the step (1) to a magnesium combination separation reactor, measuring the content of Mg ions in the solution to be 18.7g/L, adding 5L of 25% ammonia water, stirring for 30min at the feed liquid pH value of 10.3, and recovering magnesium precipitates in the process;
(3) conveying the mixed slurry obtained in the step (2) after magnesium precipitation is finished to a plate-and-frame filter and separating to obtain a magnesium hydroxide product;
(4) and (3) drying the magnesium hydroxide product obtained in the step (3), and calcining for 2h at 1100 ℃ by using an atmosphere roaster to obtain a magnesium oxide product, wherein the purity of the magnesium oxide is 96.49%, the recovery rate of the magnesium oxide is 94.57%, and the median particle size of the intermediate product is 15.45 mu m. And (3) feeding the magnesium oxide product into a honeycomb mill for grinding and grading, wherein the median particle size is 3.94 mu m, the bulk density is 0.48g/ml, and the suspension property is 11 mm.
Comparative example 3
The experimental device and connection mode of the comparative example 3 are the same as those of the example 4, and the nickel cobalt is separated by adopting a vulcanization precipitation mode. Comparative example 3 differs from example 4 in that: in comparative example 3, the separation of magnesium ions was performed by NaOH precipitation. The method specifically comprises the following steps:
(1) nickel and cobalt precipitation separation: taking 100L of mixed waste liquid (pH is less than 2) containing 23g/L of Mg, 1.808g/L of Co and 8.34g/L of Ni, adjusting the pH of the solution to about 8, adding ammonium sulfide with the amount of 1.6 times of the total substances of nickel and cobalt, and stirring for 30 min; the nickel and cobalt are sequentially conveyed to a plate-and-frame filter and a ceramic filter to be precipitated and separated to obtain a magnesium-containing solution and a nickel and cobalt byproduct with high quality, wherein the mass fraction of Ni in the slag is 33.26%, the mass fraction of Co in the slag is 8.78%, and the mass fraction of Mg in the slag is 4.06%;
(2) conveying the magnesium-containing solution obtained in the step (1) to a magnesium combination separation reactor, measuring the content of Mg ions in the solution to be 18.7g/L, adding a certain amount of NaOH to adjust the pH value of the feed liquid to be 11, stirring for 30min at the stirring speed of 500r/min, and recovering magnesium precipitates in the process;
(3) conveying the mixed slurry obtained in the step (2) after magnesium precipitation is finished to a plate-and-frame filter and separating to obtain a magnesium hydroxide product;
(4) and (4) drying the magnesium hydroxide product obtained in the step (3), and calcining for 2h at 1100 ℃ by using an atmosphere roaster to obtain a magnesium oxide product, wherein the purity of the magnesium oxide is 95.98%, the recovery rate of the magnesium oxide is 92.84%, and the median particle size of the intermediate product is 14.77 mu m. And (3) feeding the magnesium oxide product into a honeycomb mill for grinding and grading, wherein the median particle size is 3.77 mu m, the bulk density is 0.55g/ml, and the suspension property is 13 mm.
Comparative example 4
The experimental device and connection mode of the comparative example 4 are the same as those of the example 4, and the nickel cobalt is separated by adopting a vulcanization precipitation mode. Comparative example 4 differs from example 4 in that: the ceramic membrane polishing system was removed in comparative example 4. The method specifically comprises the following steps:
(1) nickel and cobalt precipitation separation: taking 100L of mixed waste liquid (pH is less than 2) containing 23g/L of Mg, 1.808g/L of Co and 8.34g/L of Ni, adjusting the pH of the solution to about 8, adding ammonium sulfide with the amount of 1.6 times of the total substances of nickel and cobalt, and stirring for 30 min; conveying the mixture to a plate and frame filter to separate nickel and cobalt precipitates to obtain a magnesium-containing solution and a nickel and cobalt byproduct with high quality, wherein the mass fraction of Ni in the slag is 33.31%, the mass fraction of Co in the slag is 8.72%, and the mass fraction of Mg in the slag is 3.99%; the recovery rates of Ni and Co are both more than 99 percent;
(2) conveying the magnesium-containing solution obtained in the step (2) to a magnesium combination separation reactor, measuring the content of Mg ions in the solution to be 18.8g/L, adding ammonium bicarbonate with the amount being 1.3 times that of magnesium ions and 3L of 25% ammonia water based on the content of the magnesium ions, stirring for 30min, raising the temperature of feed liquid in the magnesium combination separation reactor to 90 ℃, preserving the heat for 50min under the stirring condition, and stirring at the rotating speed of 500 r/min;
(3) conveying the mixed slurry after the pyrolysis in the step 2 to a plate and frame filter and separating to obtain a basic magnesium carbonate product;
(4) after drying the basic magnesium carbonate product obtained in the step 3, calcining the product for 2 hours at 1100 ℃ by using an atmosphere roaster to obtain a high-purity magnesium oxide product, wherein the purity of the magnesium oxide is 98.23%, the recovery rate of the magnesium oxide is 89.77%, and the median particle size of the intermediate product is 8.46 mu m; and (3) feeding the magnesium oxide product into a honeycomb mill for grinding and grading, wherein the median particle size is 3.58 mu m, the bulk density is 0.08g/ml, and the suspension property is 3 mm.
From the examples 3 and 4 and the comparative examples 1, 2, 3 and 4, the invention adopts extraction or sulfidation precipitation, and can realize the high-efficiency separation and recovery of nickel and cobalt; then, through the accurate addition of temperature, pH and bicarbonate and ammonia water, high-purity magnesium oxide and silicon steel grade magnesium oxide products with very high quality can be prepared while efficiently recovering magnesium, and the product quality far exceeds the requirement of the silicon steel magnesium oxide index; comparative examples 1, 2 and 3 show that if the magnesium is directly recovered by ammonia water or sodium hydroxide, the quality of the obtained magnesium oxide is not high. On one hand, the adoption of ammonia water or sodium hydroxide is not beneficial to improving the purity of magnesium oxide, so that the magnesium oxide product with the purity more than 97 percent is difficult to prepare, and the purity requirement of silicon steel grade magnesium oxide products is difficult to meet; on the other hand, compared with the product obtained by the method, the bulk density of the obtained product is greatly increased and exceeds the limit value of 0.15g/ml of the silicon steel grade product, and meanwhile, the requirement of the silicon steel grade magnesium oxide on the suspension property of 1-7 mm (20 ℃, standing for 1h) is difficult to meet. Comparative example 4 shows that the introduction of the nickel-cobalt combination separation system and the ceramic membrane fine filtration system can effectively improve the purity of the magnesium oxide product, and the mass fraction of the magnesium oxide can be improved by more than 1%, which is very critical for high-quality magnesium oxide products.
The invention greatly improves the utilization value of magnesium resources and has very obvious economic benefit and environmental protection benefit.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. A device for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid is characterized by comprising a nickel-cobalt separation and recovery system, a magnesium combination separation and recovery system, an atmosphere roasting furnace and a depolymerization crusher which are sequentially connected;
the nickel-cobalt separation and recovery system is a nickel-cobalt extraction separation device or a nickel-cobalt combination separation device;
the magnesium compound separation and recovery system comprises a magnesium compound separator and a filtering system; the nickel-cobalt separation and recovery system is connected with the filtering system through a magnesium combination separator; the magnesium compound separator is connected with the atmosphere roasting furnace through a filtering system;
the nickel and cobalt extraction separation device comprises an extraction tank and a back extraction tank, wherein one end of the extraction tank is connected with the back extraction tank, and the other end of the extraction tank is connected with the magnesium combination separator;
the nickel-cobalt combination separation device comprises a nickel-cobalt combination separator and a nickel-cobalt filtering system, and the nickel-cobalt combination separator is connected with the magnesium combination separator through the nickel-cobalt filtering system;
the nickel-cobalt filtering system comprises a coarse filtering device and a fine filtering device; the coarse filtering device is a plate and frame filter; the fine filtering device is a ceramic membrane filter, and the membrane aperture of the ceramic membrane filter is 10-100 nm;
the method comprises the following steps:
(1) separating and recovering nickel and cobalt from the nickel, cobalt and magnesium waste liquid by an extraction method or a sulfide precipitation method to obtain a magnesium-containing solution;
the extraction method specifically comprises the steps of firstly carrying out nickel-cobalt extraction separation on the nickel-cobalt-magnesium waste liquid to obtain a nickel-cobalt-containing solution and a magnesium-containing solution; carrying out back extraction on the obtained nickel-cobalt-containing solution to recover nickel and cobalt; the obtained magnesium-containing solution enters the step (2);
extracting an organic phase: 1: 1-5 of feed liquid; loading an organic phase: stripping agent is 1-5: 1;
the sulfuration precipitator comprises one or more of ammonium sulfide, sodium ferbamate and ethion;
(2) adding bicarbonate and ammonia water into the magnesium-containing solution obtained in the step (1), and stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; wherein the molar ratio of the bicarbonate to the magnesium ions is 1.1-1.5; the volume ratio of the ammonia water to the magnesium carbonate solution is 2-5: 100;
(3) drying and roasting the basic magnesium carbonate obtained in the step (2) in an atmosphere to obtain high-purity magnesium oxide;
(4) and (4) depolymerizing and crushing the high-purity magnesium oxide obtained in the step (3) to obtain a silicon steel magnesium oxide product with the average particle size of 3-5 microns.
2. A method for recovering nickel and cobalt from nickel-cobalt-magnesium waste liquid and co-producing magnesium oxide is characterized by comprising the following steps:
(1) separating and recovering nickel and cobalt from the nickel, cobalt and magnesium waste liquid by an extraction method or a sulfide precipitation method to obtain a magnesium-containing solution;
the extraction method specifically comprises the steps of firstly carrying out nickel-cobalt extraction separation on the nickel-cobalt-magnesium waste liquid to obtain a nickel-cobalt-containing solution and a magnesium-containing solution; carrying out back extraction on the obtained nickel-cobalt-containing solution to recover nickel and cobalt; the obtained magnesium-containing solution enters the step (2);
extracting an organic phase: 1: 1-5 of feed liquid; loading an organic phase: stripping agent is 1-5: 1;
the sulfuration precipitator comprises one or more of ammonium sulfide, sodium ferbamate and ethion;
(2) adding bicarbonate and ammonia water into the magnesium-containing solution obtained in the step (1), and stirring, heating, preserving heat and filtering to obtain basic magnesium carbonate; wherein the molar ratio of the bicarbonate to the magnesium ions is 1.1-1.5; the volume ratio of the ammonia water to the magnesium carbonate solution is 2-5: 100;
(3) drying and roasting the basic magnesium carbonate obtained in the step (2) in an atmosphere to obtain high-purity magnesium oxide;
(4) depolymerizing and crushing the high-purity magnesium oxide obtained in the step (3) to obtain a silicon steel magnesium oxide product with the average particle size of 3-5 microns;
the sulfide precipitation method in the step (1) is specifically that the pH value of the nickel-cobalt-magnesium waste liquid is adjusted to 6-8; then adding a vulcanization precipitator according to the amount which is 1.2-1.6 times of the total amount of nickel and cobalt to obtain nickel-cobalt precipitation slurry; finally, filtering the obtained nickel-cobalt precipitation slurry by a plate filter and a ceramic membrane filter to obtain a nickel-cobalt byproduct and a magnesium-containing filtrate; and (3) feeding the obtained magnesium-containing filtrate into the step (2).
3. The method according to claim 2, wherein the nickel content in the nickel-cobalt-magnesium waste liquid is 0.1-18 g/L; the cobalt content is 0.1-10 g/L; the magnesium content is 0.1-50 g/L.
4. The method of claim 2, wherein the bicarbonate in step (2) is one or more of ammonium bicarbonate, sodium bicarbonate, and potassium bicarbonate.
5. The method according to claim 2, wherein the heating temperature in the step (2) is 70 to 95 ℃; the heat preservation time is 40-60 min.
6. The method of claim 2, wherein the atmosphere roasting in step (3) comprises a temperature raising stage, a temperature holding stage and a cooling stage; wherein the heat preservation temperature is 900-1200 ℃, and the heat preservation time is 1-3 h; and introducing inert gas for protection in the cooling stage.
CN201910766110.1A 2019-08-19 2019-08-19 Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid Active CN110438338B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910766110.1A CN110438338B (en) 2019-08-19 2019-08-19 Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910766110.1A CN110438338B (en) 2019-08-19 2019-08-19 Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid

Publications (2)

Publication Number Publication Date
CN110438338A CN110438338A (en) 2019-11-12
CN110438338B true CN110438338B (en) 2021-07-30

Family

ID=68436476

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910766110.1A Active CN110438338B (en) 2019-08-19 2019-08-19 Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid

Country Status (1)

Country Link
CN (1) CN110438338B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111036161B (en) * 2019-12-27 2022-04-15 中冶瑞木新能源科技有限公司 System and method for preparing ternary precursor with narrow particle size distribution
CN114686686B (en) * 2020-12-30 2024-01-02 北京博萃循环科技有限公司 Three-outlet extraction method and system device for separating nickel salt solution and nickel cobalt solution
CN114702051B (en) * 2022-06-06 2022-08-30 潍坊泽隆新材料有限公司 Method for producing superfine high-activity magnesium oxide by using by-product magnesium carbonate filter cake
CN115286021B (en) * 2022-08-11 2024-05-03 衢州华友钴新材料有限公司 Method for recovering magnesium oxide from nickel cobalt intermediate leaching solution

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101389A (en) * 2018-02-12 2018-06-01 沈阳鑫博工业技术股份有限公司 A kind of device and method that silicon-steel grade magnesium oxide is prepared using dolomite

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101389A (en) * 2018-02-12 2018-06-01 沈阳鑫博工业技术股份有限公司 A kind of device and method that silicon-steel grade magnesium oxide is prepared using dolomite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
以硫酸镁废液为原料制备硅钢级氧化镁;马力言;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120515(第5期);第25-27、38、40、49页 *

Also Published As

Publication number Publication date
CN110438338A (en) 2019-11-12

Similar Documents

Publication Publication Date Title
CN110438338B (en) Device and method for recovering nickel and cobalt and co-producing magnesium oxide from nickel-cobalt-magnesium waste liquid
CN111206148B (en) Method for recycling and preparing ternary cathode material by using waste ternary lithium battery
CN102531002B (en) Method for purifying lithium carbonate
KR101682217B1 (en) A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery
CN110885090A (en) Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method
CN109777960B (en) Method for separating and recovering lithium and aluminum from fly ash
CN108963371B (en) Method for recovering valuable metals from waste lithium ion batteries
CN102560100B (en) Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy
CN112322909B (en) Method for extracting valuable metal elements from laterite-nickel ore by sulfuric acid leaching method and acid-base regeneration circulation
CN113651342A (en) Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method
CN111268706A (en) Method for producing high-purity magnesium hydroxide, high-purity magnesium oxide and high-purity magnesite serial magnesium products by using salt lake brine
CN102304620A (en) Comprehensive recovery and treatment method of waste nickel-hydrogen battery
CN110963515A (en) Method for recovering alumina from fly ash
CN114132951B (en) Method for extracting lithium from waste lithium battery black powder by pressure roasting and fluorine fixing
CN109721081B (en) Method for extracting lithium from lithium-rich fly ash alkaline mother liquor
CN115074540A (en) Comprehensive recovery method for valuable components of waste power battery
CN112758964A (en) Process for producing lithium carbonate by mixing spodumene and salt lake ore
CN116995327A (en) Method for recycling lithium from ternary positive electrode waste
CN116216797A (en) Method for preparing lithium ion battery anode material by recycling waste lithium battery dismantling black powder and anode powder
CN116259874A (en) System and method for preferentially extracting lithium from waste lithium ion battery black powder
CN111170359A (en) Device and process for preparing red lead from desulfurized lead
CN114655970A (en) Method for preparing lithium carbonate from scale evaporation mother liquor
CN102774863B (en) Method of using dolomite to produce magnesium chloride hexahydrate and coproduce calcium carbonate products
CN112125325A (en) Process for producing alumina by aluminosilicate mineral acid method
CN110563009A (en) Method for preparing battery-grade lithium carbonate from fly ash by carbonization decomposition method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant