CN86108543A - The method of preparing optical grade niobium oxide from waste slags of niobium metallurgy - Google Patents
The method of preparing optical grade niobium oxide from waste slags of niobium metallurgy Download PDFInfo
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- CN86108543A CN86108543A CN198686108543A CN86108543A CN86108543A CN 86108543 A CN86108543 A CN 86108543A CN 198686108543 A CN198686108543 A CN 198686108543A CN 86108543 A CN86108543 A CN 86108543A CN 86108543 A CN86108543 A CN 86108543A
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Abstract
The present invention relates to a kind of preparation method of niobium oxides, particularly use the novel method of preparing optical grade niobium oxide from waste slags of niobium metallurgy.The present invention adopts chemical treatment enrichment and secondary octanol purification by liquid extraction, i.e. H
2SO
4Pickling, HF-H
2SO
4Leaching, secondary octanol extract, hang down the technical process of acid and pure water segmentation back extraction, produce the optical grade niobium oxides of purity＞99.95%.
Description
The present invention relates to a kind of preparation method of optical grade niobium oxides, be specially adapted to wet method extraction high purity niobium oxide from contain the niobium metallurgical slag.
The optical grade niobium oxides has extremely strict requirement as the important source material that draws laser crystals and special optical glass to foreign matter content.Along with developing rapidly of the top science, high purity niobium oxide all has wide future in fields such as electric material, aerospace material.
Producing of optical grade niobium oxides, it is raw material that common employing contains the higher niobium concentrate of niobium grade, the wet method mineral decompose, and in high hydrofluoric acid system, carry out purification by liquid extraction with phosphoric acid ester or ketone extraction agent.This technology is the reagent costliness not only, and the low (Nb of niobium oxides product purity
2O
5～99.9%), the foreign matter content height is difficult to satisfy the requirement of drawing laser crystals to raw material.To contain the niobium metallurgical slag is raw material, and the optical grade niobium oxides is produced in wet-process beneficiation and alcohols extraction, is not reported so far.
The purpose of this invention is to provide a kind of comprehensive utilization and contain the niobium metallurgical slag, technical process is simple, and chemical reagent is easy to solve, and with low cost, foreign matter content is few, the optical grade niobium oxides that product purity is high produce novel method.
Below in conjunction with process flow sheet the present invention is elaborated.
Figure one is the process flow sheet of chemical treatment enrichment niobium;
Figure two is process flow sheets of purification by liquid extraction niobium oxides.
Shown in figure one, the present invention contains niobium pentaoxide (Nb2O
5) 1～10% metallurgical slag is raw material, through Mechanical Crushing, the spherical abrasive grit of magnet sucking-off, wet ball-milling, obtain accounting for slag weigh 90% contain the niobium granulated slag. The granularity of granulated slag wherein accounts for more than 70% less than 360 purposes less than 80 orders. Its main chemical sees Table 1.
Granulated slag chemical analysis table 1
| Title | Nb 2O 5 | MnO | TFe | SiO 2 | CaO | P |
| Content % | 1～10 | 20～30 | 15～25 | 15～25 | 1～5 | 0.5～3 |
In order to remove impurity such as part iron, manganese, silicon in the granulated slag, contain the niobium grade with what improve granulated slag, with dilute sulphuric acid (1～3N) carries out pickling to granulated slag, and its pickling condition is:
Solid-to-liquid ratio is 1: a 10～13(weight ratio)
Pickling temperature is 80～100 ℃
Soaking time is 30～60 minutes.
Operation steps is as follows:
Add a certain amount of granulated slag in pickling tank, add a certain amount of water in proportion, size mixing, under violent stirring, add a certain amount of vitriol oil gradually, be warming up to closely and boil, be incubated 30～60 minutes,, remove supernatant liquor (recyclable manganese, iron etc.) after the clarification with the hot water dilution.Pickling slag reusable heat water washing three times filters to get filtrate and the pickling slag, and filtrate discards after treatment, and the main chemical of pickling slag sees Table 2.
Pickling dreg chemistry composition table 2
| Title | Nb 2O 5 | MnO | TFe | SiO 2 | CaO | P |
| Content % | 15～20 | 11～13 | 16～17 | 20～22 | 0.8～1.0 | 0.2～0.3 |
Niobium enters solution with fluorine niobic acid form in the slag in order to make, with the pickling slag with 40% industrial hydrofluoric acid (HF) and industrial sulphuric acid (H
2SO
4) leach, its leaching condition is:
Nitration mixture ratio: HF: H
2SO
4=1: the 1(weight ratio)
Solid-to-liquid ratio: 1: 5～9
Soaking time: more than three hours.
Operation steps is as follows:
In pickling slag input pickling tank, add hydrofluoric acid and sulfuric acid then in batches, and fully stir, insulation is more than three hours, and the acidproof filter cloth of reaction slurry body and function filters, and gets leached mud and leach liquor.Leached mud is used water wash again, and water lotion and leach liquor merging enter stock chest, add HF, H
2SO
4Acid adjustment makes total acidity reach 16～17N(H
2SO
413N, HF3～4N), be feed liquid for purification by liquid extraction.
Shown in figure two, by the chemical treatment gained contain niobium extraction feed liquid, be extraction agent with the secondary octanol of industry (proportion is 0.8429), in sulfuric acid, hydrofluoric acid mixed acid system, extract niobium oxides, its extraction conditions is:
Feed liquid total acidity: 16～17N
H
2SO
4∶HF＝13N∶3～4N
Feed concentration (contains Nb
2O
5): 15～150g/l
Be in a ratio of O/A=1: 0.2～1.0
The concrete operations step is as follows:
By comparing O/A=1: 0.2～1.0, secondary octanol of industry and extraction feed liquid are entered extraction section respectively, carry out 15～25 grades of (box mixed settler extractor) counter-current extractions, must contain niobium organic phase and raffinate, raffinate returns acidleach, organic phase enters the pickling section, carries out pickling with the 17N nitration mixture, gets elutant and organic phase.Elutant is returned the acid adjustment batching.
In extraction process, except that niobium is extracted into organic phase, various impurity also enter organic phase to some extent, for removing impurity, carry out the multi-stage countercurrent washing to containing the niobium organic phase, because the percentage extraction of niobium in sulfuric acid-hydrofluoric acid-secondary octanol system is to raise with acidity to increase, and the loss of niobium is reduced as far as possible, pickling agent acidity should be not less than the acidity of extraction feed liquid.
Acid cleaning process is the key link of decision niobium oxides quality product.Impurity contrast situation does not see Table 3 in pickling and the pickling rear oxidation niobium product.
As previously mentioned, the percentage extraction of niobium is that the increase with acidity increases, and on the contrary, if niobium back extraction from organic phase is got off, just must carry out hanging down under the acidity.Be high in view of the percentage extraction of tantalum under low acidity than niobium again, can separate better for making tantalum, thus the purity of raising niobium, the present invention takes the segmentation reverse-extraction method, promptly low sour anti-niobium and the anti-tantalum of pure water, and its back extraction condition is:
1. low sour anti-niobium: strip liquor acidity 1.5～2.0N
Be in a ratio of O/A=5: 1～5
2. the anti-tantalum of pure water: be in a ratio of O/A=5: 1～4
Operation steps is as follows:
The niobium organic phase that contains after the pickling is entered anti-niobium section,, must contain the niobium strip liquor and contain the tantalum organic phase with the back extraction of 1.5～2.0N dilute sulphuric acid.To contain the niobium strip liquor and put into acid-resistant container, and place boiling water bath to heat, and transfer about pH value to 8 with ammoniacal liquor, and make niobium be niobium hydroxide form precipitation, ageing was filtered more than three hours, sized mixing with hot water again, and repetitive scrubbing for several times.Get the throw out filter cake at last, change over to after the oven dry in platinum or the ceramic ware, place calcination in the retort furnace, the control calcination temperature is 700～900 ℃, and calcination time is 4～6 hours, can obtain qualified optical grade niobium oxides product.
To contain the tantalum organic phase and enter anti-tantalum section,, obtain anti-tantalum liquid and organic phase with pure water back extraction tantalum.Organic phase behind the anti-tantalum continues to recycle, and the anti-tantalum aqueous solution must contain tantalum oxyhydroxide through ammonia precipitation process, can be used as the raw material of comprehensive recovery tantalum.
The three wastes that produced in the technological process of the present invention (slag, water, gas), through processing reach meet the national health emission standard after, store up respectively and discharge.
The present invention has following characteristics:
1. be raw material to contain the niobium metallurgical slag, adopt pickling-nitration mixture to leach enrichment, the technical process of nitration mixture-secondary octanol system extraction, rational in infrastructure, advanced technology, the total recovery height of niobium can be produced qualified work and draw the optical grade niobium oxides that lithium niobate monocrystal is used.
2. metallurgical slag comprehensive utilization, chemical raw material are easy to solve, and be with low cost, the economic benefit height.
Be the embodiment of the inventive method below.
Get and contain Nb
2O
5100 kilograms of 5.49% bessemer furnace slags through Hubei Province formula fragmentation, pair roller fragmentation, again through the spherical abrasive grit of permanent magnet sucking-off, advance the wet-type ball mill ball milling then and become powder, get 90 kilograms and contain the niobium granulated slag.
Getting 6 kilograms of granulated slags places in the 110 liter pickling tanks, add 54 liter water, be warming up to 50 ℃, add the sulphuric acid soln of 15 liter 12.6N, to be steam heated to 80 ℃, be incubated 55 minutes, leave standstill, sucking-off supernatant liquor (being elutant), the pickling slag is added hot wash three times, filter, dry, get 1.92 kilograms of pickling slags, its Nb
2O
5Content is 17.3%.Pickling number batch granulated slag obtains containing Nb as stated above
2O
5The mixing acid washery slag of average out to 16.5%.
Get in 3.78 kilograms of input leaching vat of mixing acid washery slag, add industrial hydrofluoric acid and 13 kilograms of industrial sulphuric acids of 14.5 kilogram 40% respectively, stir, be incubated 4 hours, reaction slurry body and function nylon gauze filters, and gets leach liquor.Leached mud washes with water, and washings and leach liquor merge, and is total to such an extent that 28 liters contain Nb
2O
5The feed liquid of about 20g/l and 0.55 kilogram contain Nb
2O
50.48% leaching washing slag.
To extract the feed liquid total acidity and transfer to wherein H of 16.5～17.0N(
2SO
4Be about 13N, HF is about 3.5～4.0N), and feed concentration is for (to contain Nb
2O
5) 17.9g/l, respectively secondary octanol and extraction feed liquid are entered extraction section by comparing 1: 1.(1.5 liter plastics or the box mixed settler extractor of synthetic glass) carries out the extraction of 15 stage countercurrents.Raffinate returns acidleach.
Gained contains the niobium organic phase and carries out 18 stage countercurrent pickling with the sulphuric acid soln of 17.5N by comparing 14: 1 and entering the pickling section respectively.
Elutant is returned feed liquid acid adjustment usefulness after the pickling, contains the niobium organic phase and enters 6 grades of anti-niobium sections, and by comparing O/A=5: 2 add 1.8N sulfuric acid back extraction niobium.Organic phase behind the anti-niobium enters 4 grades of anti-tantalum sections again, and by comparing O/A=5: 2 add pure water back extraction tantalum, and the anti-tantalum aqueous solution gets rich tantalum oxyhydroxide through ammonia precipitation process, and the organic phase behind the anti-tantalum recycles.
To contain the niobium strip liquor and put into the vinyon bucket, in boiling water bath, heat, transfer about pH value to 8 with SILVER REAGENT ammoniacal liquor, ageing four hours, precipitation, filtration, with the hot water pulping, repetitive scrubbing 10 times.At last the throw out oven dry is changed in the platinum dish, place retort furnace,, promptly obtain qualified optical grade niobium oxides 800 ℃ of following calcinations five hours.Its Chemical Composition sees Table 4.
By the optical grade niobium oxides product that method of the present invention is produced, through the unit use proof of domestic drawing lithium niobate monocrystal, quality meets the requirements fully, and is respond well.
Claims (12)
1, a kind of method of producing niobium oxides is particularly produced the method for optical grade niobium oxides, it is characterized in that to contain the niobium metallurgical slag be raw material, adopts chemical treatment enrichment and solvent extraction to purify, and technical process is divided into:
1. slag → fragmentation → ball milling → pickling → acidleach → acid adjustment → feed liquid is adjusted solid-to-liquid ratio, controlling acidity, temperature and time;
2. feed liquid → extraction → washing → back extraction → precipitation → calcination → niobium oxides.Select pure kind of extractants and mixed acid system, adjust and compare O/A (being organic phase/water), controlling acidity, temperature and time.
2, method according to claim 1, it is characterized in that containing the niobium metallurgical slag is various industrial residues, niobium content is (with Nb
2O
5Meter) be 1～10%.
3, according to claim 1,2 described methods, it is characterized in that containing the niobium metallurgical slag through broken, ball milling powdering, its granularity wherein accounts for more than 70% less than 360 purposes less than 80 orders.
4, method according to claim 1 is characterized in that the pickle solution that pickling is used is the sulfuric acid of 1～3N, and the pickling solid-to-liquid ratio is 1: 10～13, and temperature is 80～100 ℃, and soaking time is 30～60 minutes.
5, method according to claim 1 is characterized in that the pickling liquor that acidleach is used is 40% industrial hydrofluoric acid (HF) and industrial sulphuric acid (H
2SO
4) nitration mixture, its proportioning is 1: the 1(weight ratio).The acidleach solid-to-liquid ratio is 1: 5～9.
6, method according to claim 1 is characterized in that said pure kind of extractants is a secondary octanol etc.
7, method according to claim 1 is characterized in that said mixed acid system is sulfuric acid and hydrofluoric acid.
8, according to claim 1,7 described methods, it is characterized in that the feed liquid total acidity is 16～17N, sulfuric acid is 13N: 3～4N with the ratio of hydrofluoric acid, feed concentration (contains Nb
2O
5) be 15～150g/l, extraction agent is secondary octanol (proportion is 0.8429), extraction section is in a ratio of O/A=1: 0.2～1.0.
9, method according to claim 1, the washing composition that it is characterized in that containing the niobium organic phase is the nitration mixture of sulfuric acid or sulfuric acid and hydrofluoric acid, its acidity is not less than the acidity of feed liquid, generally is controlled to be 16～18N.The pickling section is in a ratio of O/A=10～15: 1.
10, method according to claim 1 is characterized in that containing niobium organic phase segmentation back extraction:
1. low sour back extraction niobium, strip liquor acidity is 1.5～2.0N, is in a ratio of O/A=5: 1～5;
2. pure water back extraction tantalum is in a ratio of O/A=5: 1～4.
11, method according to claim 1 is characterized in that containing the niobium strip liquor with ammonia precipitation process, and controlling its pH value is about 8, and digestion time was greater than 3 hours.
12, method according to claim 1 is characterized in that the throw out calcination temperature is 700～900 ℃, and calcination time is 4～6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686108543A CN86108543A (en) | 1986-12-15 | 1986-12-15 | The method of preparing optical grade niobium oxide from waste slags of niobium metallurgy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686108543A CN86108543A (en) | 1986-12-15 | 1986-12-15 | The method of preparing optical grade niobium oxide from waste slags of niobium metallurgy |
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| Publication Number | Publication Date |
|---|---|
| CN86108543A true CN86108543A (en) | 1988-07-13 |
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ID=4803969
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686108543A Pending CN86108543A (en) | 1986-12-15 | 1986-12-15 | The method of preparing optical grade niobium oxide from waste slags of niobium metallurgy |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952951A (en) * | 2011-08-22 | 2013-03-06 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag |
| CN103408070A (en) * | 2013-08-09 | 2013-11-27 | 九江有色金属冶炼有限公司 | Technological method for removing antimony in preparation of high-pure niobium oxide by niobium tantalite |
| CN103936072A (en) * | 2014-04-29 | 2014-07-23 | 从化钽铌冶炼厂 | Process for directly producing crystal-level high-purity niobium oxide from decomposition supernate |
| CN106929697A (en) * | 2017-04-18 | 2017-07-07 | 江苏圣亚有色金属材料有限公司 | A kind of purifying technique of pure niobium |
| CN112010348A (en) * | 2020-09-14 | 2020-12-01 | 宁夏东方钽业股份有限公司 | Preparation method of high-purity niobium oxide for high-purity niobium sheet for irradiation monitoring tube |
-
1986
- 1986-12-15 CN CN198686108543A patent/CN86108543A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952951A (en) * | 2011-08-22 | 2013-03-06 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag |
| CN103408070A (en) * | 2013-08-09 | 2013-11-27 | 九江有色金属冶炼有限公司 | Technological method for removing antimony in preparation of high-pure niobium oxide by niobium tantalite |
| CN103408070B (en) * | 2013-08-09 | 2015-11-25 | 九江有色金属冶炼有限公司 | A kind of niobium-tantalum ore prepares high purity niobium oxide except antimony processing method |
| CN103936072A (en) * | 2014-04-29 | 2014-07-23 | 从化钽铌冶炼厂 | Process for directly producing crystal-level high-purity niobium oxide from decomposition supernate |
| CN103936072B (en) * | 2014-04-29 | 2015-08-26 | 从化钽铌冶炼厂 | A kind of directly utilization decomposes the technique that crystal level high purity niobium oxide produced by supernatant liquor |
| CN106929697A (en) * | 2017-04-18 | 2017-07-07 | 江苏圣亚有色金属材料有限公司 | A kind of purifying technique of pure niobium |
| CN112010348A (en) * | 2020-09-14 | 2020-12-01 | 宁夏东方钽业股份有限公司 | Preparation method of high-purity niobium oxide for high-purity niobium sheet for irradiation monitoring tube |
| CN112010348B (en) * | 2020-09-14 | 2022-08-19 | 宁夏东方钽业股份有限公司 | Preparation method of high-purity niobium oxide for high-purity niobium sheet for irradiation monitoring tube |
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