CN113149075A - Method for preparing niobium pentoxide from low-grade niobium ore - Google Patents
Method for preparing niobium pentoxide from low-grade niobium ore Download PDFInfo
- Publication number
- CN113149075A CN113149075A CN202110431837.1A CN202110431837A CN113149075A CN 113149075 A CN113149075 A CN 113149075A CN 202110431837 A CN202110431837 A CN 202110431837A CN 113149075 A CN113149075 A CN 113149075A
- Authority
- CN
- China
- Prior art keywords
- niobium
- ore
- low
- grade
- pentoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 99
- 239000010955 niobium Substances 0.000 title claims abstract description 99
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 65
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000002386 leaching Methods 0.000 claims abstract description 49
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012141 concentrate Substances 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 19
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 230000001180 sulfating effect Effects 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004094 preconcentration Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 10
- 239000011707 mineral Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QDJUIVJLUBDARU-UHFFFAOYSA-H [Ca++].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [Ca++].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O QDJUIVJLUBDARU-UHFFFAOYSA-H 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001729 niobium mineral Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019714 Nb2O3 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052949 galena Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052923 celestite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- YIIYNAOHYJJBHT-UHFFFAOYSA-N uranium;dihydrate Chemical compound O.O.[U] YIIYNAOHYJJBHT-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of preparation of niobium pentoxide, and particularly relates to a method for preparing niobium pentoxide from low-grade niobium ore. The method comprises the following steps: 1) crushing niobium ore, and performing preselection and tailing discarding through a dense medium cyclone to obtain preselection concentrate; 2) carrying out sulfating roasting and sulfuric acid leaching on the pre-selected concentrate to obtain a leaching solution; 3) and heating and pressing the leachate to precipitate niobium, carrying out hot melting on the obtained niobium precipitate by oxalic acid to remove impurities, crystallizing to obtain niobium oxalate crystals, and calcining the niobium oxalate crystals to obtain niobium pentoxide. Compared with the processes such as the prior combined ore dressing process, the high-temperature acid decomposition extraction process and the like, the method for preparing the niobium pentoxide from the low-grade niobium ore has the advantages of simple process, short process, high niobium ore recovery rate, relatively low production cost and contribution to development and utilization of mineral resources.
Description
Technical Field
The invention belongs to the field of preparation of niobium pentoxide, and particularly relates to a method for preparing niobium pentoxide from low-grade niobium ore.
Background
Niobium belongs to a high-melting-point rare metal and is an important strategic metal which is in shortage in China, has excellent performances of high temperature resistance, corrosion resistance, wear resistance, good mechanical property and the like, and is widely applied to high-tech fields of steel, alloy, superconductivity, electronics, aerospace, atomic energy, biomedicine and the like. With the development of world science and technology and the continuous increase of electronic product consumption, the demand of niobium is increased dramatically. Niobium resources in China are rich, but most of niobium resources belong to multi-metal associated ore deposits, and the ore has complex property and composition, fine embedded particle size, low grade and great difficulty in dressing and smelting.
The beneficiation method of niobium ore mainly comprises gravity separation, magnetic separation, flotation, electric separation, chemical beneficiation and the like, and the combined flow of several processes of gravity flotation and electrification is mostly adopted in beneficiation practice so as to realize efficient and comprehensive utilization of resources. The extraction of niobium mostly adopts a hydrometallurgical process, firstly, niobium minerals are decomposed to convert niobium into soluble salts, niobium is leached to enter a solution, and then, the niobium is separated and extracted from the solution. The niobium mineral decomposition process mainly adopts an alkali decomposition method, an acid decomposition method and a chlorination decomposition method. The alkali decomposition method is the earliest adopted industrial method, and mainly adopts a crystallization method to separate and extract niobium, but due to the improvement of an extraction separation technology, the hydrofluoric acid decomposition method shows obvious superiority, and the alkali decomposition method is gradually eliminated. The acid decomposition method comprises hydrofluoric acid decomposition and sulfuric acid decomposition, the hydrofluoric acid decomposition method can be used for treating various niobium concentrates, and the sulfuric acid decomposition method can be used for low-grade niobium raw materials. The hydrofluoric acid decomposition method is the current main industrial decomposition method, is a single hydrofluoric acid decomposition leaching method which is mostly used abroad, and is generally adopted at home; extracting the leaching solution by adopting solvent extraction or ion exchange purification separation to extract niobium, and then further preparing a niobium pentoxide product by precipitation, filtration, drying and calcination. The niobium decomposition by hydrofluoric acid has strong superiority, but hydrofluoric acid has strong corrosivity and is harmful to human bodies and the environment. The chlorination decomposition method is suitable for treating niobium ore or low-grade middling and niobium-containing metallurgical slag with complex components.
The large low-grade niobium ore deposit contains 0.02-0.04% of niobium, has various mineral types, complex embedding relation and high dressing and smelting difficulty, and cannot be economically and effectively developed and utilized all the time. In earlier research work, conventional mineral separation process combined flows such as 'heavy-magnetic-floating', 'heavy-magnetic-floating-heavy', 'heavy-floating-magnetic-anti-floating' and the like are adopted, so that the technical problems of complex process, long flow and low recovery rate of useful minerals exist, the energy consumption of ore grinding operation is high, a large amount of fine-grained tailings generated by flotation operation need to be stored and treated in a large-capacity tailing pond, and the problems of difficult wastewater treatment and reuse and the like exist; conventional hydrometallurgical leaching technology processes such as high-temperature and high-pressure roasting, pressurized acid leaching, extraction and precipitation are also provided, and the conventional hydrometallurgical leaching technology is suitable for leaching high-grade ores and is used for solving the problems of high cost, high acid consumption, high cost, large environmental pollution and the like of low-grade ores; in addition, conventional alkaline leaching, acid-mixed curing leaching, microbial leaching and other processes are tried, and the problem of low leaching rate exists.
Disclosure of Invention
The invention aims to provide a method for preparing niobium pentoxide from low-grade niobium ore, which has higher recovery rate of niobium ore.
In order to achieve the purpose, the technical scheme of the method for preparing the niobium pentoxide from the low-grade niobium ore comprises the following steps:
a method for preparing niobium pentoxide from low-grade niobium ore comprises the following steps:
1) crushing niobium ore, and performing preselection and tailing discarding through a dense medium cyclone to obtain preselection concentrate;
2) carrying out sulfating roasting and sulfuric acid leaching on the pre-selected concentrate to obtain a leaching solution;
3) and heating and pressing the leachate to precipitate niobium, carrying out hot melting on the obtained niobium precipitate by oxalic acid to remove impurities, crystallizing to obtain niobium oxalate crystals, and calcining the niobium oxalate crystals to obtain niobium pentoxide.
Compared with the processes such as the prior combined ore dressing process, the high-temperature acid decomposition extraction process and the like, the method for preparing the niobium pentoxide from the low-grade niobium ore has the advantages of simple process, short process, high niobium ore recovery rate, relatively low production cost and contribution to development and utilization of mineral resources.
Preferably, when the heavy medium cyclone preselecting and tailing discarding in the step 1), the lower limit of the granularity of the selected ore is 0.1-1 mm, and the upper limit of the granularity is 1-6 mm; the tail throwing amount of the pre-selected tail throwing is more than 90%. The tailing discarding amount is preferably 90-95%.
More preferably, in step 1), the niobium ore is crushed to a particle size of 0.5 to 3 mm.
Preferably, in the step 1), when the heavy medium cyclone is used for preselecting and discarding the tailings, the medium density is 2.0-2.8 g/cm3The working pressure is 0.1-0.2 MPa.
The heavy medium cyclone can adopt a non-pressure two-product heavy medium cyclone, the heavy medium cyclone is used as low-grade complex niobium ore preselection equipment, the tailing discarding amount is more than 90%, the argillization of useful minerals is effectively avoided, the recovery rate of the useful minerals is guaranteed, the tailing discarding effect is very good, the treatment capacity of subsequent operation is greatly reduced, energy is saved, consumption is reduced, and the cost is reduced.
Preferably, in the step 2), the sulfating roasting is performed by mixing and roasting concentrated sulfuric acid and the pre-selected concentrate, the use amount of the concentrated sulfuric acid is 20-100% of the weight of the pre-selected concentrate, and the roasting temperature is 150-240 ℃. The roasting time is 30-240 minutes. To further improve the effect of the bulk roasting, it is preferred that the pre-selected concentrate has a particle size of no more than 0.074 mm.
Preferably, in the step 2), the sulfuric acid leaching is performed by using sulfuric acid and ore for mixed leaching, the concentration of the sulfuric acid is 1-3 mol/L, and the volume mass ratio of the sulfuric acid to the ore is (3-5) L: 1kg, and the leaching temperature is 40-100 ℃. The mixed leaching can adopt a stirring leaching mode.
The sulfating roasting leaching process is adopted, so that the decomposition and leaching rate of the niobium mineral are improved, and the harm of a hydrofluoric acid leaching method to human bodies and the environment is avoided.
Preferably, in the step 3), the heating temperature of the heating and autoclaving niobium precipitation is 100-200 ℃. The heating time is 30-90 minutes. Niobium is precipitated by high-temperature autoclaving at the temperature of 100-200 ℃, the niobium precipitation rate is high, and the niobium precipitation rate is not influenced by acidity (the concentration of sulfuric acid can be adjusted within a large range), so that subsequent impurity removal is facilitated; the niobium extraction process has a long process flow, and the raffinate containing heavy metal ions needs to be treated.
Preferably, in the step 3), the temperature for removing the impurities by the oxalic acid through hot melting is 60-90 ℃.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention for producing niobium pentoxide from low grade niobium ore.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
The invention aims at the low-grade complex niobium ore which comprises the following main components in percentage by mass: 0.2-0.3% of uraninite, 0.3-0.4% of galena, 0.4-0.6% of galena, 1-2% of celestite, 2-3% of barite, 2-3% of magnetite, 10-12% of calcite, 10-14% of albite, 24-28% of potassium feldspar, 34-38% of quartz, 2-3% of amphibole and 1-2% of mica; wherein the niobium content is about 0.02-0.04%, and a small amount of lead beta-spar may be contained in addition to the above main components.
The process flow diagram of the method for preparing niobium pentoxide from low-grade niobium ore of the invention is shown in figure 1, wherein the chemical reactions involved in the main treatment steps are as follows:
sulfating roasting and high-temperature peracid leaching (sulfuric acid leaching):
(Ca,U)2(Ti,Nb)2O6(OH)+H2SO4→CaSO4+U4++TiO2++Nb2O3(SO4)2+H2O
Nb2O5+2H2SO4＝Nb2O3(SO4)2+2H2O
and (3) high-temperature pressing and boiling to precipitate niobium: nb2O3(SO4)2+7H2O＝2Nb(OH)5↓+2H2SO4
Hot melting of oxalic acid: nb (OH)5+3H2C2O4＝H3[NbO(C2O4)3]+4H2O
And (3) calcining: 2H3[NbO(C2O4)3]+3O2＝Nb2O5+12CO2+3H2O
And (2) carrying out high-temperature pressure boiling on the sulfuric acid leaching solution to produce niobium precipitate, dissolving the niobium precipitate by oxalic acid to obtain a niobium oxalate solution, converting impurity calcium (titanium) into calcium (titanium) oxalate with lower solubility, remaining the calcium (titanium) oxalate with lower solubility in a slag phase, filtering to remove solid impurities, evaporating and crystallizing the filtrate to obtain niobium oxalate crystals, carrying out secondary dissolution, impurity removal and crystallization on the niobium oxalate crystals to obtain qualified niobium oxalate crystals, and calcining the niobium oxalate crystals at high temperature to obtain a niobium pentoxide product.
First, the specific embodiment of the method for preparing niobium pentoxide from low-grade niobium ore of the invention
Example 1
The process flow diagram of the method for preparing niobium pentoxide from low-grade niobium ore of the embodiment is shown in fig. 1, and comprises the following steps:
1) crushing the niobium ore to 0.5-3mm, and performing pre-selection and tailing discarding through a non-pressure two-product heavy medium cyclone to obtain pre-selected concentrate; the medium density of the heavy medium cyclone is 2.45g/cm3The medium is a suspension of ferrosilicon powder and water, and the working pressure (medium inlet pressure) is 0.15 MPa.
2) Finely grinding the pre-selected concentrate until the concentration of the pre-selected concentrate is 100% and less than 0.074mm, and performing sulfating roasting and sulfuric acid leaching;
the sulfating roasting is to mix and roast the pre-selected fine ground concentrate and concentrated sulfuric acid, the dosage of the concentrated sulfuric acid is 50 percent of the weight of the ore, the roasting temperature is 210 ℃, and the roasting time is 120 min.
The sulfuric acid leaching is to stir and leach the sulfated and roasted ore and sulfuric acid, wherein the concentration of the sulfuric acid used for stirring and leaching is 2mol/L, the volume-mass ratio of the sulfuric acid to the ore is 4:1 (L: kg), the leaching temperature is 60 ℃, the leaching time is 60min, and leaching residues are filtered and separated after leaching (the leaching residues are subjected to harmless treatment), so that a leaching solution is obtained.
In other embodiments, a substantially equivalent treatment effect can be obtained by adjusting the volume-to-mass ratio of sulfuric acid to ore to 3:1 or 5: 1.
3) Performing high-temperature pressure boiling on the leaching solution to precipitate niobium, performing hot melting impurity removal on the obtained niobium precipitate by oxalic acid, performing solid-liquid separation to remove leaching residues, performing chemical impurity removal on the residual liquid part, performing evaporative crystallization and secondary crystallization on the obtained impurity-removed liquid to obtain qualified niobium oxalate crystals, calcining the niobium oxalate crystals at high temperature to obtain niobium pentoxide products,
the temperature for high-temperature autoclaving and niobium precipitation is 150 ℃, and the time is 30 min. The pressure is 0.4-0.5MPa (vapor pressure generated by the solution itself at high temperature).
The treatment temperature for removing impurities by oxalic acid hot melting is 70 ℃. The treatment time was 30 min. The used treating agent is oxalic acid solution with the mass fraction of 40% (generally 30-50%). Specifically, the sulfuric acid leaching solution is subjected to high-temperature autoclaving to produce niobium precipitate, the niobium precipitate is dissolved by oxalic acid solution to obtain niobium oxalate solution, calcium (titanium) impurities are converted into calcium (titanium) oxalate with lower solubility and are left in a slag phase, solid impurities are removed by filtration, filtrate is evaporated and crystallized to obtain niobium oxalate crystals, the niobium oxalate crystals are subjected to secondary dissolution (oxalic acid solution), impurity removal and crystallization to obtain qualified niobium oxalate crystals, and the niobium oxalate crystals are subjected to high-temperature calcination to obtain niobium pentoxide products.
The temperature of the high-temperature calcination was 500 ℃.
Examples 2 to 3
The processes for producing niobium pentoxide from low grade niobium ores of examples 2-3 were substantially the same as in example 1, and the differences in the specific process parameters are shown in table 1.
TABLE 1 Process parameters for the methods of examples 2-3
Second, Experimental example
The experimental results of the method of the present invention are described in the examples 1 to 3, and are specifically shown in tables 2 to 4.
Table 2 test results of the method of example 1
The test results show that: the raw ore adopts the process flow of crushing, heavy medium cyclone preselection, sulfating roasting, leaching, high temperature pressure boiling and niobium precipitation, oxalic acid hot melting, chemical impurity removal, crystallization decomposition and refining of niobium pentoxide products, the heavy medium cyclone preselection tailing discarding amount is 93.76%, the useful mineral niobium recovery rate is 78.94%, and the tailing discarding effect is very ideal; pre-selecting concentrate, sulfating, roasting, leaching, and high-temperature pressing, boiling and precipitating niobium; the leaching rate of niobium is 90.48 percent, the niobium precipitation rate is 99.80 percent, the niobium precipitation efficiency is high, the loss rate is low, and the niobium metallurgy recovery rate is 90.30 percent; finally, the niobium pentoxide is refined through oxalic acid hot melting impurity removal, crystallization decomposition, and the product purity is 99.92%, the total recovery rate of niobium dressing is 71.28%, and the utilization rate of niobium resources is greatly improved.
Table 3 test results of the method of example 2
In the example 2, the pre-selected tailing discarding amount of the dense medium cyclone is 90.74 percent, the recovery rate of useful mineral niobium is 83.56 percent, and the tailing discarding effect is ideal; pre-selecting concentrate, sulfating, roasting, leaching, and high-temperature pressing, boiling and precipitating niobium; the leaching rate of niobium is 89.67 percent, the precipitation rate of niobium is 99.86 percent, the precipitation efficiency of niobium is high, the loss rate is low, and the recovery rate of niobium metallurgy is 89.54 percent; finally, the niobium pentoxide is refined through oxalic acid hot melting impurity removal, crystallization decomposition, and the product purity is 99.91%, the total recovery rate of niobium dressing is 74.82%, and the utilization rate of niobium resources is greatly improved.
Table 4 test results of the method of example 3
In example 3, the heavy medium cyclone preselects the tailing discarding amount of 94.39 percent, the useful mineral niobium recovery rate is 76.13 percent, and the tailing discarding effect is very ideal; pre-selecting concentrate, sulfating, roasting, leaching, and high-temperature pressing, boiling and precipitating niobium; the leaching rate of niobium is 90.87 percent, the precipitation rate of niobium is 99.89 percent, the precipitation efficiency of niobium is high, the loss rate is low, and the metallurgical recovery rate of niobium is 90.77 percent; finally, the niobium pentoxide is refined through oxalic acid hot melting impurity removal, crystallization decomposition, and the product purity is 99.93%, the total recovery rate of niobium dressing is 69.10%, and the utilization rate of niobium resources is greatly improved.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that there are objectively infinite specific structures due to the limited character expressions, and it will be apparent to those skilled in the art that a plurality of modifications, decorations or changes may be made without departing from the principle of the present invention, and the technical features described above may be combined in a suitable manner; such modifications, variations, combinations, or adaptations of the invention using its spirit and scope, as defined by the claims, may be directed to other uses and embodiments.
Claims (9)
1. A method for preparing niobium pentoxide from low-grade niobium ore is characterized by comprising the following steps:
1) crushing niobium ore, and performing preselection and tailing discarding through a dense medium cyclone to obtain preselection concentrate;
2) carrying out sulfating roasting and sulfuric acid leaching on the pre-selected concentrate to obtain a leaching solution;
3) and heating and pressing the leachate to precipitate niobium, carrying out hot melting on the obtained niobium precipitate by oxalic acid to remove impurities, crystallizing to obtain niobium oxalate crystals, and calcining the niobium oxalate crystals to obtain niobium pentoxide.
2. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in claim 1, wherein, in the step 1), when heavy medium cyclone is used for pre-selection and tailing discarding, the lower particle size limit of the selected ore is 0.1-1 mm, and the upper particle size limit is 1-6 mm; the tail throwing amount of the pre-selected tail throwing is more than 90%.
3. The method for producing niobium pentoxide from low-grade niobium ore as claimed in claim 2, wherein in step 1), the niobium ore is crushed to a particle size of 0.5 to 3 mm.
4. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in any one of claims 1 to 3, wherein in the step 1), the medium density at the time of pre-concentration of tailings by using a dense medium cyclone is 2.0-2.8 g/cm3The working pressure is 0.1-0.2 MPa.
5. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in claim 1, wherein in step 2), the sulfating roasting is performed by mixing concentrated sulfuric acid and the pre-selected concentrate, the concentrated sulfuric acid is used in an amount of 20-100% by weight of the pre-selected concentrate, and the roasting temperature is 150-240 ℃.
6. The method of producing niobium pentoxide from low grade niobium ore as claimed in claim 5, wherein in step 2), the pre-selected concentrate has a particle size of not more than 0.074 mm.
7. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in claim 1, 5 or 6, wherein in step 2), the sulfuric acid leaching is carried out by using sulfuric acid and ore in a mixed leaching manner, wherein the concentration of the sulfuric acid is 1-3 mol/L, and the volume mass ratio of the sulfuric acid to the ore is (3-5) L: 1kg, and the leaching temperature is 40-100 ℃.
8. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in claim 1, wherein in the step 3), the heating temperature of the heat-pressure-cooking-precipitating niobium is 100 to 200 ℃.
9. The method for preparing niobium pentoxide from low-grade niobium ore as claimed in claim 1 or 8, wherein in step 3), the temperature for hot melting and impurity removal of oxalic acid is 60-90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110431837.1A CN113149075A (en) | 2021-04-21 | 2021-04-21 | Method for preparing niobium pentoxide from low-grade niobium ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110431837.1A CN113149075A (en) | 2021-04-21 | 2021-04-21 | Method for preparing niobium pentoxide from low-grade niobium ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113149075A true CN113149075A (en) | 2021-07-23 |
Family
ID=76869380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110431837.1A Pending CN113149075A (en) | 2021-04-21 | 2021-04-21 | Method for preparing niobium pentoxide from low-grade niobium ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149075A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322087A (en) * | 2022-07-22 | 2022-11-11 | 承德莹科精细化工股份有限公司 | Method for extracting high-purity niobium oxalate and niobium pentoxide from waste niobium-containing glass |
| CN115390460A (en) * | 2022-10-28 | 2022-11-25 | 四川节之源环保工程有限公司 | Control system of heavy-medium cyclone |
| CN115893490A (en) * | 2022-11-23 | 2023-04-04 | 郑州大学 | Method for comprehensively extracting niobium, titanium and rare earth from pyrochlore ore |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5787332A (en) * | 1996-09-26 | 1998-07-28 | Fansteel Inc. | Process for recovering tantalum and/or niobium compounds from composites containing a variety of metal compounds |
| US20090202405A1 (en) * | 2005-02-03 | 2009-08-13 | Alexander Krupin | Chemical Beneficiation of Raw Material Containing Tantalum-Niobium |
| CN101955228A (en) * | 2009-07-17 | 2011-01-26 | 中国科学院过程工程研究所 | Method for separating tantalum and niobium |
| CN102230082A (en) * | 2011-07-01 | 2011-11-02 | 广州有色金属研究院 | Method for recovering rare earth and niobium from rare metallic ores |
| CN102703697A (en) * | 2012-06-29 | 2012-10-03 | 广州有色金属研究院 | Method for recovering rare earth-niobium-ferrum paragenic ore |
| CN105331811A (en) * | 2014-08-06 | 2016-02-17 | 北京有色金属研究总院 | Method for extracting tantalum, niobium and rare earth elements in multi-metal associated tantalum-niobium ores |
| CN106636691A (en) * | 2016-12-28 | 2017-05-10 | 核工业北京化工冶金研究院 | Method used for extracting uranium and niobium from low-grade ore |
| CN111020186A (en) * | 2019-12-10 | 2020-04-17 | 核工业北京化工冶金研究院 | Method for comprehensively recycling uranium, niobium and titanium from uranium-niobium-titanium ore |
| CN111876598A (en) * | 2019-12-10 | 2020-11-03 | 核工业北京化工冶金研究院 | Method for separating uranium and niobium through co-extraction |
-
2021
- 2021-04-21 CN CN202110431837.1A patent/CN113149075A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5787332A (en) * | 1996-09-26 | 1998-07-28 | Fansteel Inc. | Process for recovering tantalum and/or niobium compounds from composites containing a variety of metal compounds |
| US20090202405A1 (en) * | 2005-02-03 | 2009-08-13 | Alexander Krupin | Chemical Beneficiation of Raw Material Containing Tantalum-Niobium |
| CN101955228A (en) * | 2009-07-17 | 2011-01-26 | 中国科学院过程工程研究所 | Method for separating tantalum and niobium |
| CN102230082A (en) * | 2011-07-01 | 2011-11-02 | 广州有色金属研究院 | Method for recovering rare earth and niobium from rare metallic ores |
| CN102703697A (en) * | 2012-06-29 | 2012-10-03 | 广州有色金属研究院 | Method for recovering rare earth-niobium-ferrum paragenic ore |
| CN105331811A (en) * | 2014-08-06 | 2016-02-17 | 北京有色金属研究总院 | Method for extracting tantalum, niobium and rare earth elements in multi-metal associated tantalum-niobium ores |
| CN106636691A (en) * | 2016-12-28 | 2017-05-10 | 核工业北京化工冶金研究院 | Method used for extracting uranium and niobium from low-grade ore |
| CN111020186A (en) * | 2019-12-10 | 2020-04-17 | 核工业北京化工冶金研究院 | Method for comprehensively recycling uranium, niobium and titanium from uranium-niobium-titanium ore |
| CN111876598A (en) * | 2019-12-10 | 2020-11-03 | 核工业北京化工冶金研究院 | Method for separating uranium and niobium through co-extraction |
Non-Patent Citations (2)
| Title |
|---|
| 杨秀丽 等: ""低品位铌矿硫酸焙烧-草酸浸出回收铌"", 《有色金属工程》 * |
| 长沙工业高等专科学校 刘常诗: "《选矿厂设计》", 30 June 1994, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322087A (en) * | 2022-07-22 | 2022-11-11 | 承德莹科精细化工股份有限公司 | Method for extracting high-purity niobium oxalate and niobium pentoxide from waste niobium-containing glass |
| CN115322087B (en) * | 2022-07-22 | 2023-10-03 | 承德莹科精细化工股份有限公司 | Method for extracting high-purity niobium pentoxide from waste niobium-containing glass |
| CN115390460A (en) * | 2022-10-28 | 2022-11-25 | 四川节之源环保工程有限公司 | Control system of heavy-medium cyclone |
| CN115390460B (en) * | 2022-10-28 | 2023-01-10 | 四川节之源环保工程有限公司 | Control system of heavy-medium cyclone |
| CN115893490A (en) * | 2022-11-23 | 2023-04-04 | 郑州大学 | Method for comprehensively extracting niobium, titanium and rare earth from pyrochlore ore |
| CN115893490B (en) * | 2022-11-23 | 2024-06-04 | 郑州大学 | Method for comprehensively extracting niobium, titanium and rare earth from pyrochlore ore |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113149075A (en) | Method for preparing niobium pentoxide from low-grade niobium ore | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN106868307B (en) | A kind of comprehensive utilization process of pyrite cinder arsenic removal enrichment gold and silver | |
| CN105296744B (en) | A kind of method of lateritic nickel ore recycling treatment and comprehensive reutilization | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| Liu et al. | A new process of extracting vanadium from stone coal | |
| CN101058852A (en) | Multistage counter current acid leaching process containing nickel serpentine ore | |
| WO2012171481A1 (en) | Hydrometallurgical process for complete and comprehensive recovery with substantially no wastes and zero emissions | |
| CN110963515B (en) | Method for recovering alumina from fly ash | |
| CN115140777B (en) | Method for producing ferromanganese composite material for soft magnetic by utilizing ocean manganese nodule | |
| CN105439192A (en) | Comprehensive utilization method for zinc oxide ore | |
| CN103805789B (en) | A kind of method of comprehensively recovering valuable metal of copper nickel slag | |
| CN113846214B (en) | Method for treating zinc-containing material in zinc hydrometallurgy production | |
| CN101760652B (en) | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process | |
| CN105110300A (en) | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide | |
| CN102154546A (en) | Method for smelting molybdenum-nickel mineral association by wet process | |
| CN115893490B (en) | Method for comprehensively extracting niobium, titanium and rare earth from pyrochlore ore | |
| CN110396610B (en) | Method for treating titanium minerals and metal silicate minerals through ammonium salt pressure pyrolysis | |
| CN104402062A (en) | Method for preparing ferric chloride from pyrite cinder | |
| KR101031985B1 (en) | Method for manufacturing high purity metal compounds using the hydrometallurgical process from the tantalum ore | |
| CN104445105B (en) | Method for enriching and recovering tellurium dioxide from tellurium-containing soda residue | |
| CN109777972B (en) | Method for extracting scandium from coal gangue through concentrated sulfuric acid activated leaching | |
| CN114959309A (en) | Method for forcibly leaching vanadium from vanadium titano-magnetite | |
| CN103773953A (en) | Method for gathering eluate with low rare earth concentration by adopting ionic exchange method | |
| CN110117721B (en) | Method for extracting valuable metals from sulfuric acid residue by phosphoric acid leaching-extraction |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210723 |