CN115109925A - Method for treating transition metal oxide ore by citric acid system - Google Patents
Method for treating transition metal oxide ore by citric acid system Download PDFInfo
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- CN115109925A CN115109925A CN202210700985.3A CN202210700985A CN115109925A CN 115109925 A CN115109925 A CN 115109925A CN 202210700985 A CN202210700985 A CN 202210700985A CN 115109925 A CN115109925 A CN 115109925A
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- citric acid
- metal oxide
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 343
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims description 16
- 238000002386 leaching Methods 0.000 claims abstract description 45
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 35
- 239000011707 mineral Substances 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 238000013019 agitation Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 229910052592 oxide mineral Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- 150000002739 metals Chemical class 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
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- 235000013399 edible fruits Nutrition 0.000 description 2
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- 230000004151 fermentation Effects 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000003133 Elaeis guineensis Species 0.000 description 1
- 235000001950 Elaeis guineensis Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 citrate ions Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for treating transition metal oxidized ore by a citric acid system belongs to the technical field of oxidized mineral metal extraction, and comprises the following steps: step (1): preparing a semi-solid suspension system of citric acid; step (2): grinding the metal oxide type minerals to a certain granularity; and (3): mixing the citric acid obtained in the step (1) and the oxidized mineral powder ground in the step (2) into ore pulp in proportion; and (4): and (4) carrying out ultrasonic agitation leaching on the ore pulp mixed in the step (3) at the temperature of 30-110 ℃ for 0.5-10h to obtain a leaching solution. The invention adopts semi-solid suspended citric acid to leach metals in oxidized minerals, has short leaching time and high leaching efficiency, and the citric acid is harmless to the environment and can realize recycling.
Description
Technical Field
The invention belongs to the technical field of extraction of oxidized mineral metals, and particularly relates to a method for treating transition metal oxidized ore by using a citric acid system.
Background
There are two general categories of terrestrial available metal mineral resources: sulphide ores and oxidic ores. For example, metals such as nickel, copper, and zinc include sulfide ores and oxide ores. Sulphide ores, because valuable minerals exist in the sulphide form, can be concentrated into concentrates by a beneficiation method, and the concentrates are always main raw materials for metal production. With the exhaustion of sulfide ore resources, the utilization of oxidized ore is increasingly receiving attention.
Valuable metals (metals exist in the form of oxides or silicates) in the oxidized minerals are similar to gangue in properties, valuable elements and impurities are inlaid and coexist, the residual valence bond characteristics of interfaces are similar, and even the impurities and the valuable elements exist in the same crystal lattice, so that the valuable minerals cannot be effectively identified by the flotation agent, and the valuable minerals and the gangue can be separated even after the flotation agent is crushed to the molecular level. The existing metal oxide ore smelting method comprises two major types of fire method and wet method: the pyrometallurgical method needs smelting temperature over 1000 deg.c and certain amount of assistant to increase the flowability of the melt. Therefore, the fire process has the problems of high energy consumption and high solid waste emission all the time; the wet method is to leach metals in the oxidized minerals by adopting acid-containing solution, which usually needs to be carried out under the conditions of 240-270 ℃ and high pressure, the leaching time is long, the requirement on equipment is high, and the storage and treatment of the acid-containing waste liquid, the acid-containing leaching waste residue and the impurity-removing wet residue generated in the impurity-removing process are always difficult problems in hydrometallurgy.
Disclosure of Invention
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a method for treating transition metal oxide ore by using citric acid system, which uses semi-solid suspended citric acid to leach metals in oxidized minerals, and has the advantages of short leaching time, high leaching efficiency, no harm to environment of citric acid and realization of recycling.
In order to achieve the purpose, the invention adopts the main technical scheme that:
a method for treating transition metal oxide ores with a citric acid system, comprising the steps of:
step (1): preparing a semi-solid suspension system of citric acid;
step (2): grinding the transition metal oxidized mineral to a certain particle size;
and (3): mixing the citric acid in the step (1) and the oxidized mineral powder ground in the step (2) into ore pulp in proportion;
and (4): and (4) carrying out ultrasonic agitation leaching on the ore pulp mixed in the step (3) at the temperature of 30-110 ℃ for 0.5-10h to obtain a leaching solution of metal ions.
Further, the method also comprises the following steps:
and (5): filtering the leaching solution obtained in the step (4), leaching the filter residue with water, and obtaining a washing solution which is a citric acid solution;
and (6): cooling the filtrate obtained in the step (5) to separate out citric acid crystals, and filtering to obtain citric acid crystals; mixing the citric acid crystal obtained by filtering with the citric acid solution obtained in the step (5) to obtain a semi-solid citric acid suspension;
and (7): and (4) returning the semi-solid citric acid suspension obtained in the step (6) to the step (1) for reaction again.
Further, in the step (1), the semi-solid suspension system of citric acid is a citric acid suspension, wherein the mass ratio of the solid citric acid accounts for 10% or more of the mass of the total citric acid.
Further, in the step (1), the temperature of the semi-solid suspension system in which the citric acid is arranged is 30-110 ℃.
Further, in the step (2), the transition metal oxide type minerals are ground to particles with the particle size of less than 0.75 μm, which account for 80-95% of the total mass.
Further, in the step (3), the citric acid and the transition metal oxidized ore are mixed at a ratio V (ml)/m (g) of 1:0.1 to 1: 2.
Further, in the step (5), the temperature of the filtration and the water rinsing is 30-110 ℃.
Further, in the step (6), the filtrate is cooled to below 20 ℃.
Further, the metal-oxidized mineral is an oxidized mineral of a transition metal capable of forming a complex with a citrate ion, and specifically is one of an oxidized ore of nickel, an oxidized ore of cobalt, an oxidized ore of copper, and an oxidized ore of zinc.
Further, the frequency of the ultrasonic wave in the step (4) is more than 20 kHz.
The invention has the beneficial effects that:
1. the invention adopts ultrasonic semi-solid reaction-cooling crystallization to separate out excessive citric acid crystals, no corrosive reagent is used in the process, the time required by leaching is greatly shortened, and the leaching efficiency is greatly improved.
2. The invention uses supersaturated citric acid solution to treat oxidized ore, the reaction temperature is controlled at 30-110 ℃, excessive reagent is not added in the method, metal oxides such as nickel, iron, magnesium, copper, zinc and the like react with citric acid to generate soluble products which enter the solution after leaching, slag is only silicate which does not react with the citric acid, and the amount of the obtained slag is less than the amount of the treated raw ore.
3. And filtering the hot semi-solid citric acid suspension and the system obtained after the ultrasonic leaching of the oxidized ore, and returning the citric acid crystals separated out by cooling the filtrate to the semi-solid citric acid suspension preparation process, so that the consumption of citric acid in the process can be reduced, and the consumption of a neutralizing agent in the subsequent impurity removal process can be reduced. The citric acid can be prepared by fermenting agricultural wastes, is more environment-friendly and safer, and is a recognized environment-friendly and energy-saving production mode; the unreacted citric acid in the extraction process can be eliminated by microbial metabolism.
4. Due to the application of the semi-solid citric acid suspension and the ultrasonic auxiliary technology, the leaching efficiency is greatly improved, the leaching rate of 0.5-10h can reach more than 90%, and the leaching efficiency can meet the requirements of industrial production.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Citric Acid (CA) with molecular formula C 6 H 8 O 7 Is an organic acid. It is colorless crystal, odorless, strongly sour, and easily soluble in water. Unlike sulfuric acid and hydrochloric acid, citric acid exists in nature and is widely distributed. For example, lemon, mandarin orangeCitric acid exists in fruits of plants such as oranges, pineapples and the like and bones, muscles and blood of animals, the content of the lemon and the lime can reach 8 percent after being dried, and the content of the lemon and the lime in the fruit juice is about 47 g/L. Therefore, citric acid has great 'containing' property in nature, and is not like strong corrosivity and great harm to the environment of inorganic acids such as sulfuric acid, hydrochloric acid and the like.
In nature, citric acid is an important metabolite, and almost all microorganisms actively synthesize citric acid, except that not all microorganisms capable of producing citric acid can be used as a citric acid producing strain. Industrially, the aspergillus niger fermentation process is the main method for preparing citric acid. The method has high yield and no toxic by-product. Various agricultural products and agricultural wastes can be used as carbon sources in the fermentation process, such as pineapple peel, cane molasses, corn starch, corncobs, corn husks, coffee husks, banana peel, oil palm empty fruit clusters, cassava starch and the like. Therefore, in the process of extracting the laterite-nickel ore, citric acid is used as a reaction raw material, and compared with other inorganic acids, the laterite-nickel ore has the advantages of being non-toxic, biodegradable and capable of solving the problem of agricultural wastes.
Citric acid contains three carboxyl groups, and dissociation constants of three protons are respectively expressed as pKa at 25 DEG C 1 ＝3.13、pKa 2 4.76 and pKa 3 6.40. When the acid is completely dissociated, the formation of a complex of nickel, copper, zinc, etc. ions with the citrate ion can be expressed as
In addition to acidity, citrate forms soluble complexes with nickel, copper, zinc, etc., which is another advantage in the extraction of nickel oxide ores.
As shown in fig. 1, the present invention is a method for treating transition metal oxide ores with a citric acid system, comprising the steps of:
step (1): preparing a semi-solid suspension system of citric acid with the temperature of 30-110 ℃, namely ensuring that the mass ratio of the solid citric acid in the solution accounts for more than 10% of the mass of the total citric acid;
step (2): grinding the metal oxide mineral to 80-95% of the metal oxide mineral having a particle size of less than 0.75 μm; the metal oxidized mineral is an oxidized mineral of transition metal capable of forming a complex with citrate ions, and specifically is one of nickel oxidized ore, cobalt oxidized ore, copper oxidized ore and zinc oxidized ore.
And (3): mixing the citric acid supersaturated solution prepared in the step (1) and oxidized ore with a certain particle size into ore pulp according to a proportion, wherein the proportion V (ml)/m (g) of the citric acid to the ore is 1: 0.1-1: 2;
and (4): carrying out ultrasonic agitation leaching on the mixed ore pulp at the temperature of 30-110 ℃ for 0.5-10 h; the frequency of the ultrasonic wave is more than 20 kHz.
And (5): filtering the leaching solution obtained in the step (4), leaching the filter residue with water, and obtaining a washing solution which is a citric acid solution;
and (6): cooling the filtrate obtained in the step (5) to below 20 ℃, separating out part of citric acid crystals, and filtering to obtain citric acid crystals; mixing the citric acid crystal obtained by filtering with the citric acid solution obtained in the step (5), and obtaining semi-solid citric acid suspension again after supplementing citric acid crystals properly;
and (7): and (4) returning the semi-solid citric acid suspension obtained in the step (6) to the step (1) for reaction again.
And (4) obtaining a filtrate which is the citric acid leachate of the metal oxide ores. The leachate can be prepared into one or more metal products by adopting the existing fractional precipitation method, extraction method or electrolysis method.
Example 1
1. Preparing a citric acid solution with the concentration of 1M at room temperature;
2. mixing 1M citric acid solution with copper oxide ore, zinc oxide ore and nickel oxide ore respectively, grinding the oxide ore in advance to 80% with the granularity of less than 0.75 μ M, and mixing the citric acid solution with the minerals according to the ratio of 1:1(ml)/M (g).
3. Leaching the mixed ore pulp at room temperature for 10 hours; ultrasonic leaching with 20kHz intensity ultrasonic wave is used.
The leaching rate of the obtained leached metal is shown in table 1.
Example 2
1. Preparing a saturated citric acid solution at room temperature;
2. respectively mixing saturated citric acid solution with copper oxide ore, zinc oxide ore and nickel oxide ore, grinding the oxide ore in advance to 80% with the granularity of less than 0.75 μm, and mixing the saturated citric acid solution with the minerals according to the ratio of 1:1(ml)/m (g).
3. Leaching the mixed slurry at room temperature for 10 hours; ultrasonic leaching with 20kHz intensity ultrasonic wave is used.
The leaching rate of the obtained leached metal is shown in table 1.
Example 3
1. Preparing a saturated citric acid solution at 60 ℃;
2. respectively mixing saturated citric acid solution with copper oxide ore, zinc oxide ore and nickel oxide ore, grinding the oxide ore in advance to 80% with the granularity of less than 0.75 μm, and mixing the saturated citric acid solution with the minerals according to the ratio of 1:1(ml)/m (g).
3. Leaching the mixed ore pulp at 60 ℃ for 10 hours; ultrasonic leaching with 20kHz intensity ultrasonic wave is used.
The leaching rate of the obtained leached metal is shown in table 1.
Example 4
1. Preparing a semi-solid citric acid suspension solution at 60 ℃, wherein the mass ratio of solid citric acid accounts for 20% of the total citric acid;
2. respectively mixing supersaturated semi-solid suspension citric acid solution with copper oxide ore, zinc oxide ore and nickel oxide ore, grinding the oxide ore in advance to 80% of the particle size less than 0.75 μm, and mixing the semi-solid suspension citric acid solution and the minerals according to the proportion of 1:1(ml)/m (g).
3. Leaching the mixed ore pulp at 60 ℃ for 10 hours; ultrasonic leaching with 20kHz intensity ultrasonic wave is used.
The leaching rate of the obtained leached metal is shown in table 1.
Table 1: leaching rate table for leaching copper oxide ore, zinc oxide ore and nickel oxide ore for 10 hours in different citric acid states
As can be seen from table 1, the use of citric acid solution can leach valuable metals from minerals, but the leaching rate is low. By increasing the concentration and temperature, the leaching rate of the corresponding metal from the oxidized ore can also be increased, but the increase is limited. Such leaching rate is difficult to be industrially applied. Only when the citric acid system is a semi-solid suspension system, the extraction rate of the nonferrous metal is greatly improved. It can be seen that the "impact" of solid citric acid particles on minerals plays an important role in the extraction system of semi-solid suspended citric acid-oxidised ores. In this system, because of the cavitation effect of the ultrasonic wave, the continuous collision of citric acid particles and mineral particles is promoted, the strong interaction causes the mineral to break to generate a new surface, the contact area with citric acid in the solution is continuously increased, and the direct reaction of the citric acid and the effective components of the mineral is realized, which is the reason for improving the reaction efficiency. In this application, the citric acid solution is required to have solid citric acid, and if only the citric acid solution is used, the reaction is controlled by the diffusion process. Only solid citric acid particles exist in the solution, and the reaction is converted from diffusion control to chemical reaction control. Under the action of ultrasonic cavitation effect, citric acid particles directly impact mineral particles, and chemical reaction control becomes a control step of a system. In addition, the present invention can recover the excessive citric acid through the following cooling crystallization, so that the circulation of the reacted citric acid can be carried out.
The invention adopts ultrasonic semi-solid reaction-cooling crystallization to separate out excessive citric acid crystals, no corrosive reagent is used in the process, the time required by leaching is greatly shortened, and the leaching efficiency is greatly improved.
Although embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the scope of the present invention.
Claims (10)
1. A method for treating transition metal oxide ores by a citric acid system is characterized by comprising the following steps:
step (1): preparing a semi-solid suspension system of citric acid;
step (2): grinding the transition metal oxidized mineral to a certain particle size;
and (3): mixing the citric acid obtained in the step (1) and the oxidized mineral powder ground in the step (2) into ore pulp in proportion;
and (4): and (4) carrying out ultrasonic agitation leaching on the ore pulp mixed in the step (3) at the temperature of 30-110 ℃ for 0.5-10h to obtain a leaching solution of metal ions.
2. The method of treating transition metal oxide ores with a citric acid system as claimed in claim 1, further comprising the steps of:
and (5): filtering the leaching solution obtained in the step (4), and leaching the filter residue with water to obtain a washing solution, namely a citric acid solution;
and (6): cooling the filtrate obtained in the step (5) to separate out citric acid crystals, and filtering to obtain citric acid crystals; mixing the citric acid crystal obtained by filtering with the citric acid solution obtained in the step (5) to obtain a semi-solid citric acid suspension;
and (7): and (4) returning the semi-solid citric acid suspension obtained in the step (6) to the step (1) for reaction again.
3. The method for treating transition metal oxide ores with the citric acid system according to claim 1, wherein in the step (1), the semi-solid suspension system of the citric acid is a citric acid suspension, wherein the mass ratio of the solid citric acid is 10% or more of the mass of the total citric acid.
4. The method for treating transition metal oxide ores with a citric acid system according to claim 1, wherein the temperature of the semi-solid suspension system for preparing citric acid in the step (1) is 30-110 ℃.
5. The method for treating transition metal oxide ores with a citric acid system according to claim 1, wherein in the step (2), the metal oxide type minerals are ground to have a particle size of less than 0.75 μm, which is 80-95% of the total mass.
6. The method for treating transition metal oxide ore with citric acid system according to claim 1, wherein in the step (3), the mixing ratio is the ratio of citric acid to metal oxide ore V (ml)/m (g) is 1: 0.1-1: 2.
7. The method for treating transition metal oxide ore with citric acid system as claimed in claim 2, wherein in the step (5), the temperature of water rinsing is 30-110 ℃.
8. The method for treating transition metal oxide ore with citric acid system as claimed in claim 2, wherein in step (6), the filtrate is cooled to below 20 ℃ to precipitate citric acid crystals.
9. The method for treating the transition metal oxide ore by using the citric acid system according to claim 1, wherein the metal oxide mineral is an oxide mineral of a transition metal capable of forming a complex with a citrate ion, and is specifically one of nickel oxide ore, cobalt oxide ore, copper oxide ore and zinc oxide ore.
10. The method for treating transition metal oxide ores with the citric acid system according to claim 1, wherein the frequency of the ultrasonic waves in the step (4) is more than 20 kHz.
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