CN102399990A - Method for extracting niobium oxide from waste and old niobium-containing high-temperature alloy - Google Patents
Method for extracting niobium oxide from waste and old niobium-containing high-temperature alloy Download PDFInfo
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- CN102399990A CN102399990A CN2011103835095A CN201110383509A CN102399990A CN 102399990 A CN102399990 A CN 102399990A CN 2011103835095 A CN2011103835095 A CN 2011103835095A CN 201110383509 A CN201110383509 A CN 201110383509A CN 102399990 A CN102399990 A CN 102399990A
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Abstract
The invention discloses a method for extracting niobium oxide from waste and old niobium-containing high-temperature alloy, which is characterized in that copper sulfate, sulfuric acid and oxidizing agents are used for damaging and leaching soluble alloy ingredients such as iron, nickel, cobalt and the like, leaching slag is oxidized, copper is washed out by acid, in addition, the washing is carried out for many times for obtaining rich-niobium materials. Then, the rich-niobium materials are roasted by sulfuric acid, the water washing and the hot filtering are carried out, filtering slag is leached by oxalic acid, niobium oxalate is extracted by N235, nitric acid and ammonium nitrate reverse extraction is carried out, two-stage organic phase acid washing, eight-stage extraction and six-stage reverse extraction are carried out, the reverse extraction solution is subjected to primary crystallization, re-dissolution purification, secondary crystallization and centrifugal separation to obtain niobium oxalate crystals, and high-purity niobium oxide is obtained after roasting. The method is characterized in that raw materials are waste and old high-temperature alloy, the oxalic acid is cheap and is easy to obtain, the recovery process is simple and controllable, the niobium oxalate extraction and reverse extraction industrial production technology is mature, the large scale production is convenient to realize, the recovered product has good activity and high purity, the method belongs to a green path for resource cyclic utilization sustainable development, high practicability and good economic prospects are realized, and good social benefits can be generated.
Description
Technical field
The invention belongs to the hydrometallurgy field, be specifically related to a kind of from the waste and old method that contains niobium high temperature alloy extraction niobium oxides.
Background technology
The fifties in last century, the production of China's niobium oxides all is from tungsten metallurgical slag, rare-earth smelting slag and other reclaimed materials, to reclaim owing to there is not single-minded tantalum niobium concentrate, and output is minimum.Get into the sixties, China begins to have niobium tantalum ore output, and the output of niobium oxides increases to some extent.1966, chestnut tin ore rare metal smeltery, Ningxia Non-Ferrous Metal Smeltery test-manufactures operation in succession, and nineteen eighty-two, Jiujiang non-ferrous metals smelting works went into operation from changing the test manufacture of tantalum-niobium smelt factory in 1972, but until the end of the eighties, China Nb
2O
5Annual capacity is still less than 100t, and YO is less than 80t.Get into the nineties in 20th century, along with reform and opening-up and science and technology development, niobium oxides is more and more wider in the application in fields such as metallurgy, electronics, glass, has promoted China Nb
2O
5Increasing rapidly of throughput, particularly in recent years, the development of high-tech area made China tantalum niobium metallurgical industry obtain develop rapidly, and product structure obtains adjustment, and range of product constantly increases, and the quality product class is improved, and production technology makes rapid progress.The tantalum niobium industry of China is representative with Ningxia Non-Ferrous Metal Smeltery, has got into the ranks of world tantalum niobium big country, power.It is reported that China tantalum niobium producer has carried out technological transformation in various degree in succession during 80 ~ nineties of 20th century, make the annual capacity of niobium oxides surpass kiloton.Each producer according to market and requirement of client, has all carried out research, exploitation and improvement to technology and equipment when technological transformation and expanding production, thereby makes various technical process and processing unit all have large improvement and innovate.Along with the development and utilization of mineral wealth, the resource reserve exploitation time limit is to be a great problem that the whole world faces, and the main outlet that addresses this problem is to realize the recycle of limited resources and find the new low cost production thereof of being convenient to suitability for industrialized production.
Summary of the invention
Goal of the invention: to the deficiency that exists in the prior art; The purpose of this invention is to provide a kind of from the waste and old method that contains niobium high temperature alloy extraction niobium oxides, to realize resource circulation utilization, through the control and the optimization of technological process; With than lower production cost, obtain activity niobium oxides preferably.
Technical scheme: in order to realize the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of from the waste and old method that contains niobium high temperature alloy extraction niobium oxides, with 250 ℃ of sulfuric acid baking 1h of rich niobium material employing, the roasting material washing, heat filtering, filter residue oxalic acid leaches, N
235The extraction niobium oxalate, nitric acid-an ammonium nitrate back extraction, 2 grades of organic phase pickling extract 8 grades, 6 grades of back extractions, stripping workshop is processed into the primary crystallization niobium oxalate, heavily dissolves the purifying recrystallize, and spinning obtains the niobium oxalate crystal, and calcining obtains the high purity Niobium Pentxoxide.Concrete steps are following:
(1) leaches
Raw materials used for discarding the unmanageable iron nickel base superalloy that contains precious metal niobium titanium cobalt, matter is hard, corrosion such as anti-sulfuric acid, nitric acid, chloroazotic acid; Selected temperature alloy niobium content with a high standard is about 5%; The titanium of trace, other are iron-cobalt-nickel chromium, prepare to leach through simple cut.Leachings such as the iron-cobalt-nickel chromium in the alloying constituent, the niobium titanium is because of insoluble enrichment in leached mud.
Leaching begins to adopt copper sulfate to leach, and is heated to 60 ~ 85 ℃ of bulging air or oxygen agitation leachs, to contain Cu
2+Content is to add copper sulfate about 90g/L, adds capacity sulfuric acid, still remains at least about 1 ~ 2 to reacting the complete back of 50min pH, and promptly sulfuric acid is at least 1.5mol/L, and sulfuric acid adds to prevent that high temperature sulfuric acid from splashing at a lower temperature.Be warmed up to 60 ℃ and add excessive alloy, reaction process can add a small amount of VAL-DROP, accelerates speed of reaction.After treating that leached mud is copper sheet basically, and employing oxygenant drum air or bulging air (oxygenant can be a VAL-DROP, hydrogen peroxide etc., and it is faster that VAL-DROP dissolves copper speed; The hydrogen peroxide temperature is higher to be to decompose comparatively fast, and utilization ratio is low), once add sulfuric acid; Dissolved copper to enough copper ion concentrations are about 90g/L, and maintenance dissolving final pH is about 1 equally, is heated to 80 ~ 90 ℃; Add the superalloy slag, utilize waste heat to leave standstill to be leached to react completely, filter; Obtain rich niobium material, leach liquor can process according to production requirement and obtain other products, so cyclic production.
Liquid after the leaching leaves standstill, and outwells supernatant liquid, and the rich niobium material of sedimentary rich niobium material is heated to 60 ℃; Through VAL-DROP sulfuric acid oxidation copper removal, further removal of impurities enrichment, sulfuric acid, VAL-DROP can be excessive; Filter or spinning, filtrating is returned leaching process, and filter residue is washed repeatedly flush away foreign ion.
Leaching process adopts industrial sulphuric acid, technical grade VAL-DROP, and air or oxygen, low in raw material cost is easy to get, and is pollution-free, copper source reusable edible, the final rich niobium material that obtains to contain the niobium titanium, leach liquor contains iron-cobalt-nickel, makes separating treatment in addition.
(2) sulfuric acid baking
The rich niobium material niobium enrichment composition that superalloy extracts is difference to some extent with the difference of alloy species; Niobium content was about 80% after the used alloy of the present invention leached enrichment, and excess sulfuric acid is during roasting; Rich niobium material (weight): the vitriol oil (volume)=1:1 ~ 1.2; Maturing temperature can be 250 ℃ of roasting 1h, or 200 ℃ prolong roasting time to 2h, increase roasting reactivity.
(3) washing filtering
Washing while hot after the roasting, solid-to-liquid ratio is pressed 1:8 ~ 12, in 85 ~ 95 ℃ of stirring in water bath 30min, filters, and filter residue send niobium oxalate to leach, and filtrating is returned extract technology, utilizes its spent acid and ion.The roasting washing filtering can be removed 20% titanium, and other soluble ions.
(4) oxalic acid leaches and aftertreatment
Oxalic acid leaches and belongs to floride-free production technique, and oxalic acid is cheap and easy to get.And niobium oxalate extracting-back extraction industrial production technology is comparatively ripe, removes impurity purification niobium oxalates such as titanium, is convenient to production-scale expansion.
With reference to technology of preparing fluorine less niobium oxide by oxalic acid system extraction method (CN1904097A); According to material characteristic; Improve technology, extraction temperature changes 70 ~ 75 ℃ into and stirs 1h, prevents that the too high niobium oxalate of temperature is decomposed into niobic acid; The solubleness (in niobium oxides) of 70 ℃ of niobiums in oxalic acid can reach 220 ~ 230g/L, and it is enough that big like this solubleness is used for technical process.The industrial ethanedioic acid total concn is 20%, and leaching solid (rich niobium material) liquor ratio is 1:12, filters, and residue returns roasting, and filtrating gets into extraction process.
The acid extraction method is hanged down in the employing that separates of niobium and impurity (titanium, iron, cobalt, nickel etc.).With N
235Be extraction agent, two octanols or kerosene are thinner, and low acid medium (pH2.5 ~ 3) layering is fast, good separating effect.Organic phase consists of 30% ~ 50% extraction agent, adds 70% ~ 50% thinner, extracted organic phase: water=1:1.5 ~ 3.Reextraction 0.5mol/L nitric acid+2mol/L an ammonium nitrate, back extraction organic phase: water=4 ~ 6:1.Extraction tower or mixer-settler are as extractor, and 2 grades of acidifying organic phases extract 8 grades, strip 6 grades, handle obtaining a niobium oxalate crystal, and 90 ℃ are heavily molten, crystallisation by cooling, and spinning obtains the niobium oxalate crystal.
Niobium oxalate calcination process, temperature are 350 ~ 500 ℃, and calcining vessel is an aluminum oxide, finally obtains the Niobium Pentxoxide product, and fine size is nonhygroscopic and product is active better.
Beneficial effect: method of the present invention, raw material is waste and old superalloy, oxalic acid is cheap and easy to get; Removal process simple controllable, niobium oxalate extracting-back extraction industrial production technology are comparatively ripe, are convenient to scale operation; It is good to reclaim the product activity, and purity is high, is the green road of a resource circulation utilization Sustainable development; Have good practicability, good economic outlook is arranged, can produce good social benefit.
Description of drawings
Fig. 1 is a SEM photo after 700 ℃ of oxidizing roastings of the rich niobium material (titaniferous) of copper removal;
Fig. 2 is the EDS figure after 700 ℃ of oxidizing roastings of the rich niobium material (titaniferous) of copper removal;
Fig. 3 is a Niobium Pentxoxide product XRD figure spectrum.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation.
Niobium content is about 5%, the iron nickel base superalloy 300g of the titanium of trace, prepares to leach through simple cut.Leaching begins to adopt copper sulfate to leach, and adds capacity sulfuric acid 180ml, and water intaking 3L is heated to 60 ~ 85 ℃, to contain Cu
2+Content is to add copper sulfate about 90g/L, and the agitation leach of drum air or oxygen still remains on about 1 ~ 2 to reacting the complete back of 50min pH at least, is warmed up to 60 ℃ and adds alloys, and reaction process can add a small amount of VAL-DROP, accelerates speed of reaction.After treating that leached mud is copper sheet basically, adopt oxygenant drum air or do not rouse air (oxygenant is a VAL-DROP), 3L water (can sneak into the solution that contains solion, acid or oxygenant that other subsequent steps return) once adds enough sulfuric acid 180ml; Dissolved copper to enough copper ion concentrations are about 90g/L, are heated to 80 ~ 90 ℃, add the superalloy slag; Utilize waste heat to leave standstill to be leached to and react completely; Filter, obtain rich niobium material, leach liquor carries out other processing.The rich niobium material of liquid after the leaching leaves standstill, and outwells supernatant liquid, and sedimentary rich niobium material is heated to 60 ~ 85 ℃; Through VAL-DROP sulfuric acid oxidation copper removal, further removal of impurities enrichment, sulfuric acid, VAL-DROP can be excessive; Filter or spinning, filtrating is returned leaching process, and filter residue is washed repeatedly flush away foreign ion.Rich niobium material niobium content is about 80%, and excess sulfuric acid is during roasting; Rich niobium material (weight): the vitriol oil (volume)=1:1 ~ 1.2, maturing temperature can be 250 ℃ of roasting 1h, or 200 ℃ prolong roasting time to 2h; Washing while hot after the roasting, solid-to-liquid ratio is pressed 1:8 ~ 12, in 85 ~ 95 ℃ of stirring in water bath 30min; Filter, filter residue send niobium oxalate to leach, and filtrating is returned extract technology.The oxalic acid extraction temperature is 70 ~ 75 ℃ of stirring 1h, prevents that the too high niobium oxalate of temperature is decomposed into niobic acid, and the solubleness (in niobium oxides) of 70 ℃ of niobiums in oxalic acid can reach 220 ~ 230g/L, and it is enough that big like this solubleness is used for technical process.The industrial ethanedioic acid total concn is 20%, and leaching solid (rich niobium material) liquor ratio is 1:12, filters, and residue returns roasting, and filtrating gets into extraction process.With N
235Be extraction agent, two octanols or kerosene are thinner, and organic phase consists of 30% ~ 50% extraction agent, add 70% ~ 50% thinner, extracted organic phase: water=1:1.5 ~ 3.Reextraction 0.5mol/L nitric acid+2mol/L an ammonium nitrate, organic phase: water=4 ~ 6:1. back extraction.Extraction tower or mixer-settler are as extractor, and 2 grades of acidifying organic phases extract 8 grades, strip 6 grades, handle obtaining a niobium oxalate crystal, and 90 ℃ are heavily molten, crystallisation by cooling, and spinning obtains the niobium oxalate crystal.350 ~ 500 ℃ of calcinings of niobium oxalate finally obtain the Niobium Pentxoxide product.
Claims (5)
1. method of from the waste and old iron nickel base superalloy that contains niobium, extracting niobium oxides; It is characterized in that: with the waste and old iron nickel base superalloy that contains niobium is raw material, adopts sulfuric acid oxidation agent circulation to dissolve the copper extract technology and makes rich niobium material, adopts the rich niobium material of 200 ~ 250 ℃ of sulfuric acid bakings 1 ~ 2h; Washing then; Heat filtering, filter residue oxalic acid leaches, N
235The extraction niobium oxalate, nitric acid-an ammonium nitrate back extraction, stripping workshop is processed into the primary crystallization niobium oxalate, heavily dissolves the purifying recrystallize, and spinning obtains the niobium oxalate crystal, and calcining obtains Niobium Pentxoxide.
2. the method for from the waste and old iron nickel base superalloy that contains niobium, extracting niobium oxides according to claim 1, it is characterized in that: concrete steps are following:
(1) leaches
With the waste and old iron nickel base superalloy that contains niobium is raw material, adopts copper sulfate to leach, and is heated to 60 ~ 85 ℃ of bulging air or oxygen agitation leachs, to contain Cu
2+Content is that 90g/L adds copper sulfate, and pH was at least 1 ~ 2 after adding capacity sulfuric acid guaranteed to react 50min; Be heated to 80 ~ 90 ℃, adding excessive alloy, to be leached to leached mud be copper sheet, reacts completely, and filters, and obtains rich niobium material;
(2) sulfuric acid baking: 200 ~ 250 ℃ of rich niobium material of sulfuric acid baking 1 ~ 2h; The weightmeasurement ratio of the rich niobium material and the vitriol oil is 1:1 ~ 1.2;
(3) washing filtering
Roasting finishes, washing while hot, and solid-to-liquid ratio is 1:8 ~ 12, in 85 ~ 95 ℃ of stirring in water bath 30min, filters, filter residue send niobium oxalate to leach;
(4) oxalic acid leaches
Niobium oxalate leaches with reference to CN1904097A, and wherein, extraction temperature is 70 ~ 75 ℃, stirs 1h, and the leaching solid-to-liquid ratio is 1:12, filters, and residue returns roasting, and filtrating gets into extraction process;
(5) extraction
Adopt low acid extraction method to extract; With N
235Be extraction agent, two octanols or kerosene are thinner, and organic phase consists of 30% ~ 50% extraction agent, add 70% ~ 50% thinner, extracted organic phase: water=1:1.5 ~ 3; Reextraction 0.5mol/L nitric acid+2mol/L an ammonium nitrate, organic phase: water=4 ~ 6:1 back extraction; Extraction tower or mixer-settler are extractor, handle to obtain a niobium oxalate crystal, and 90 ℃ are heavily molten, crystallisation by cooling, and spinning obtains the niobium oxalate crystal;
(6) calcining: calcining niobium oxalate crystal, temperature is 350 ~ 500 ℃, calcining vessel is an aluminum oxide, finally obtains the Niobium Pentxoxide product.
3. the method for from the waste and old iron nickel base superalloy that contains niobium, extracting niobium oxides according to claim 2 is characterized in that: in the step (1), leaching process adds oxygenant chloric acid sodium or hydrogen peroxide, adopts the drum air or do not rouse air to add fast response.
4. the method for from the waste and old iron nickel base superalloy that contains niobium, extracting niobium oxides according to claim 2, it is characterized in that: the rich niobium material that step (1) is prepared, niobium content is 79 ~ 81%.
5. the method for from the waste and old iron nickel base superalloy that contains niobium, extracting niobium oxides according to claim 2, it is characterized in that: in the step (5), 2 grades of acidifying organic phases extract 8 grades, strip 6 grades.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104085921A (en) * | 2014-06-17 | 2014-10-08 | 中国科学院近代物理研究所 | Method for extracting niobium from mixed acid waste liquid obtained after chemical cleaning of superconductive niobium cavity |
| CN110629048A (en) * | 2019-11-04 | 2019-12-31 | 常州市耐欧金属材料科技有限公司 | Niobium tube production process |
| CN111607697A (en) * | 2020-06-16 | 2020-09-01 | 北京工业大学 | Method for separating niobium and tantalum and application thereof |
| CN113151695A (en) * | 2021-04-28 | 2021-07-23 | 郑州大学 | Method for decomposing low-grade tantalum-niobium resource and extracting tantalum-niobium by acid method |
| CN113308606A (en) * | 2021-06-04 | 2021-08-27 | 昆明理工大学 | Method for leaching and separating valuable metals from silver-gold-rich selenium steaming slag |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113151695A (en) * | 2021-04-28 | 2021-07-23 | 郑州大学 | Method for decomposing low-grade tantalum-niobium resource and extracting tantalum-niobium by acid method |
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| CN113308606A (en) * | 2021-06-04 | 2021-08-27 | 昆明理工大学 | Method for leaching and separating valuable metals from silver-gold-rich selenium steaming slag |
| 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 |
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Application publication date: 20120404 |