CN100357464C - Technology of preparing fluorine less niobium oxide by oxalic acid system extraction method - Google Patents

Technology of preparing fluorine less niobium oxide by oxalic acid system extraction method Download PDF

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CN100357464C
CN100357464C CNB2006101066783A CN200610106678A CN100357464C CN 100357464 C CN100357464 C CN 100357464C CN B2006101066783 A CNB2006101066783 A CN B2006101066783A CN 200610106678 A CN200610106678 A CN 200610106678A CN 100357464 C CN100357464 C CN 100357464C
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niobium
extraction
oxalic acid
raw
grade
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CNB2006101066783A
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CN1904097A (en
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郭青蔚
曹万里
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郭青蔚
曹万里
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Abstract

The present invention relates to a process for preparing fluorine-free niobium oxide by using oxalic acid system extraction method. It is applicable to niobium-rich raw material whose niobium/tantalum ratio is above 200. Its raw material includes various low-grade niobium-bearing materials including iron/steel metallurgical slag containing niobium and high-grade niobium-bearing pyrochlorite concentrate. Its preparation process includes the following several steps: raw material treatment, mineral decomposition, water-washing, leaching-out, extraction, back-extracting niobium, strip liquor treatment and crystal calcinations. Its extraction process adopts solvent extraction method to extract niobium and separate impurity.

Description

Technology of preparing fluorine less niobium oxide by oxalic acid system extraction method

Technical field

The invention belongs to the hydrometallurgy scope, relate to a kind of processing method that is used for manufacture level and high-purity grade of floride-free Niobium Pentxoxide product, especially a kind of technology of preparing fluorine less niobium oxide by oxalic acid system extraction method.

Background technology

The energy, information and material are three big pillars of modern civilization.Now, novel material is regarded as the basis and the guide of new technology revolution.Niobium is that a kind of rare refractory metal and tungsten, molybdenum, tantalum are called as four large space metals together.Niobium is special functional materials, is again good structured material.Along with niobium compound monocrystalline Surface Acoustic Wave Filter increasing rapidly in the application of electronic applications such as colour television set, video recorder, mobile communication, along with containing of the continuous expansion of niobium special optical glass at photographic camera, pick up camera and other opticinstrument application quantities, along with developing rapidly of new and high technologies such as infrared, laser and Military Application, along with household electrical appliance production and electronic industry fast development, make the demand of high purity niobium oxide day by day increase.Consume at present about 1000~1500 tons of high purity niobium oxide (annotate: 500 tons are Japanese consumption) whole world year approximately, and be the continuation rising tendency.When consumption increased, more and more higher to the specification of quality of high purity niobium oxide, particularly the content control to colour developing elements such as residual amount fluorine and iron required more and more stricter.Though the discovery of niobium has 200 years history the sixth of the twelve Earthly Branches, using also has nearly 70 years history, but because the high corrosion resistance of niobium, etching acid one sulfuric acid system that has only of wet production niobium oxides extracts a method in the world at present, and domestic all niobium tantalum factories also all adopt this method.It is big and loading capacity is big, advantages such as technical maturity that this method has a niobium Lip river degree of separating.But the problem that has 4 aspects:

(1) etching acid is the strongest acid of corrodibility in all mineral acids, and the main body production unit requires to adopt special corrosion-resistant material, the cost of equipment height, and the life-span is short;

(2) the production safety problem is many.Etching acid exists the serious contact injury of consequence, serious threat staff's personnel safety to production operator.The staff will wear a complete set of safety appliance and operate when producing;

(3) environmental pollution is serious, and difficulty of governance is big.Etching acid is the easy volatile material, and the severe contamination air not only forms threat to personal security, and causes production site farmland pollution on every side, causes trees death.In addition, have a large amount of peracid waste water in the production, its acidity reaches 3-4molHF+8mol H 2SO 4, difficulty of governance is big, the expense height, and be difficult to thoroughly radical cure;

(4) HF process requires to use high-grade concentrate, contains niobium oxides mostly at 50%-60%, and low grade also needs>30%.

Summary of the invention

Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of wet production niobium oxides technology is provided, this technology should have product free-floride, quality height, characteristics that production cost is lower, be applicable to niobium/tantalum than at the rich niobium raw material more than 200, and the production safety and the problem of environmental pollution that do not have HF process and had.

The technical solution used in the present invention is: a kind of oxalic acid system extraction process is produced technical grade and high-purity grade of fluorine less niobium oxide technology, its raw material object applicatory is various low-grade niobium material and the high-grade pyrrhite niobium concentrate of containing that comprises the ferrous metallurgy slag that contains niobium, and its technological process comprises following raw material processing, mineral decomposition, washing, leaching, extraction and reextraction niobium, anti-stripping agent processing and crystal calcination process successively:

It is to carry out fragmentation and ball milling earlier with containing niobium raw material that described raw material is handled, and it is reached<100 order granularities;

It is that the niobium raw material that will handle well carries out sulfuric acid baking and decomposes mineral that described mineral decompose, and the ingredients by weight of sulfuric acid baking is than being that the ratio that contains the niobium raw material and the vitriol oil is 1: 1~1.3; 180~230 ℃ of maturing temperatures, time 30~60min;

Described washing is that the grog after the roasting is washed, so that the sulfuric acid oxygen niobium generation hydrolysis that generates during roasting generates niobium hydroxide and removes partly impurity such as de-iron, manganese; The solid-liquid weight ratio of washing is 1: 10; 90 ℃ of washing temperature, time 20~30min; Washing after-filtration, filter cake send oxalic acid to leach niobium;

Described leaching is to adopt the oxalic acid of technical grade to leach niobium, so that fresh niobium hydroxide and oxalic acid effect generate water-soluble niobium oxalate complex; The concentration that adopts leach liquor during leaching is 20%~25% oxalic acid, according to the niobium situation that contains in the raw material, and solid (in the raw material weight) during leaching: liquid=1: 5~15; 75~80 ℃ of extraction temperatures, time 40~60min; The oxalic acid leach liquor is treated next step processing;

Described extraction process is to adopt solvent extration to extract niobium and separating impurity, the extraction agent that is adopted is the tertiary amine-type organic reagent, comprise N-235, tri-n-octyl amine N204, Alaimine 300, Alamine 360, Alamine 304, the thinner that adopts is two octanols, kerosene, the mixture of the thinner that consists of 30%~50% extraction agent adding 70%~50% of organic phase;

Described extraction process is to carry out in mixer-settler extractor or extraction tower, and technological process comprises organic phase acidifying, niobium extraction and niobium reextraction; Adopt 0.5mol/L H during acidifying 2SO 4Solution, compare: organic phase: water=1: 1; Being in a ratio of during extraction: organic phase: water=1: 1~2; Extraction gained load organic phases is carried out the reextraction of niobium, and strippant consists of 0.5mol/L nitric acid+2mol/L ammonium nitrate, being in a ratio of of reextraction: organic phase: water=4~6: 1;

It is to take the vacuum concentration method to concentrate reextraction gained solution that described anti-stripping agent is handled, and carries out reduction vaporization when concentrated, and 50~75 ℃ of vaporization temperatures after it separates out the niobium oxalate crystal, are separated the niobium oxalate crystal through centrifugal filter again with mother liquor;

Described crystal calcination process is that the niobium oxalate crystal is calcined in common aluminum oxide container, and the crystal calcining temperature promptly gets the niobium oxides product for 350~500 ℃.

When handling, described raw material to carry out the magnetic separation deferrization earlier for the higher raw material of iron content; Be lower than 10% raw material for the niobium oxides grade, carry out acid treatment, the niobium oxides grade is reached more than 25%.

The vitriol oil that sulfuric acid baking decomposes the mineral employing is the industrial vitriol oil, and it is technical grade oxalic acid that oxalic acid leaches the oxalic acid that niobium adopted, and what the reextraction niobium adopted is technical grade nitric acid and technical grade ammonium nitrate.

Adopt extraction process extraction of Nb and separating impurity, the tertiary amine-type compound that described extraction agent adopts comprises N-235, tri-n-octyl amine N204, Alaimine 300, Alamine 360, Alamine 304; Described thinner is two octanols and kerosene.

The strippant that adopts during reextraction is the mix reagent of nitric acid and ammonium nitrate.

The extraction equipment that adopts during extraction is mixer-settler or extraction tower, and when using mixer-settler, 2 grades of pickling extract 8 grades, strip 6 grades.

Anti-stripping agent is treated as niobium oxalate xln with repurity effect.

A crystal that is obtained can obtain secondary niobium oxalate crystal through the recrystallize purifying; Control 80~90 ℃ of heavy solubility temperatures during recrystallize, every 3Kg niobium oxalate crystal adds deionized water 1L; Adopt whizzer to filter to isolate the niobium oxalate crystal after the crystallization.

The niobium oxalate crystal decomposes can expensive platinum matter container, but carries out 350~500 ℃ of decomposition temperatures in alumina container; Adopt extraction to add the dual means of purification of crystalline on the technology, can produce the technical grade niobium oxides, also can produce high purity niobium oxide; Got rid of the use fluorine-containing reagent in the process system fully, niobium oxides is the product of floride-free character.

Because the double purifying technique of extractive crystallization is adopted in this technical process, not only can guarantee the high purity of product, and can all adopt under the situation of technical grade reagent, obtain high purity product, can also on same flow process of employing and same equipment, obtain multiple grade product (technical grade is to high-purity grade of niobium oxides) and multiple series products (niobium oxides, niobium oxalate) simultaneously.

Processing method provided by the invention has following characteristics:

(1) oxalic acid is organic acid, and acidity is very weak, and is non-volatile, and personnel are not had the contact injury problem that etching acid has, and is safer to operator, and equipment is easily gone.

(2) main reagent oxalic acid is more cheap and easy to get than etching acid in the processing method.Oxalic acid is solid acid, be easy to transportation, and etching acid is a liquid, has the strong acid of heavy corrosion, and the transportation trouble is many.

(3) this technology can both have been produced usual production on same flow process and same equipment, also can produce high purity product (>99.99%).And can under the condition that all adopts industrial reagent, produce high purity product.Fluorine hydrogen method is produced high purity product must use high purity reagent, and the price of high purity reagent generally is that industrial reagent is more than 10 times.

(4) Oxalic Acid Method both can be used the higher-grade raw material, also can use low-grade raw material, as once trying out the slag raw material that packet header only contains 20% niobium oxides.

Adopt the product of product that processing method of the present invention produces and produced in conventional processes more also to have the characteristics of chemical quality and physical properties two aspects.

1, product chemical quality

(1) Oxalic Acid Method does not adopt fluorine-containing reagent fully in producing, so the niobium oxides product is not fluorine-containing fully.Then there is fluorine-containing problem in HF process product niobium oxides, and residual fluorine can't thoroughly remove, and influences product application.For a long time, residual fluorine problem does not solve in the HF process niobium oxides.And fluorine is totally unfavorable to product application.Fall as, fluorine can cause the monocrystalline cracking when being used to draw lithium niobate monocrystal, causes the decrease in yield of product.In order to reduce fluorine in the product, manufacturing enterprise has taked the defluorinate measure of multiple complexity: one, high-temperature steam defluorinate method, but need expensive equipment.Two, washing defluorinate method, washing time reaches 3-4 order of classes or grades at school.Three, calcining defluorinate method will be in calcining under 800-900 ℃ the high temperature more than 10 hours.These measures still can not be taken off fluorine fully, and fluorine content can not solve the molten problem of fluorine fully still in the 50-100ppm level in the product.

(2) silicon in the niobium oxides also is to influence monocrystalline rimose important factor.Be easy to generate silicon fluoride (SiF because of silicon in the HF process with the fluorine effect 4), the silica removal difficulty is big, is difficult to reach the requirement of the national standard Si<10ppm of national regulation, does not have fluorine pasc reaction problem in the Oxalic Acid Method, and silicone content is extremely low in the product.

2, product physical properties

(1) fine size: the HF process product is aqua oxidation niobium [Nb (OH) 5.H 2O] the high-temperature calcination gained, granularity is thicker, only can reach<80 orders.The Oxalic Acid Method product is to decompose gained, fine size,<1u by crystal.

(2) no igloss: HF process niobium oxides product has big igloss (being generally 0.2%), and Oxalic Acid Method niobium oxides product is that crystal decomposes gained, and no igloss helps the accurate feed proportioning of product when using.

(3) nonhygroscopic: the easy moisture absorption of HF process product, change of moisture content is big when depositing; The Oxalic Acid Method product is nonhygroscopic fully, can long-term storage.

(4) chemically reactive is good: the HF process product is a high temperature 800-900 ℃ of long-time calcining gained, Niobium Pentxoxide active relatively poor, and the Oxalic Acid Method product is a 350-500 ℃ of low-temperature decomposition gained, chemically reactive is good.

(5) good fluidity: ammonia hydracid method product is because of reasons such as moisture-sensitive, and is mobile relatively poor.Oxalic Acid Method product drying, tiny, mobile splendid, even batch mixing during favourable product application.

The present invention has broken through the etching acid that generally adopts at present-sulfuric acid system extraction traditional processing technology, not only can reduce the production cost of niobium, improve the quality of products, and can fundamentally solve serious safety and the problem of environmental pollution that exists in the existing processing method.

Main drawback of the present invention is that loading capacity is lower than etching acid, and niobium solubleness is littler than etching acid, and treatment capacity is bigger when being used for low grade material.

Description of drawings

Accompanying drawing is a process flow diagram of the present invention.

Embodiment

Technology of preparing fluorine less niobium oxide by oxalic acid system extraction method, adopt the oxalic acid solution extracting process to extract in containing niobium raw material and purifying production niobium oxalate technical grade and high-purity grade of niobium oxides product, its technological process comprises raw material processing, mineral decomposition, washing and leaching, extraction, anti-stripping agent processing and crystal calcination process.This method applicable raw materials object is various low-grade niobium material and high-grade pyrrhite concentrate etc. of containing.

The concrete technological process of production is as follows:

(1) raw material is handled

Contain niobium raw material and carry out fragmentation and ball milling earlier, granularity<100 orders, the raw material higher for iron content carries out the magnetic separation deferrization earlier.Be lower than 10% raw material for the niobium oxides grade, carry out acid treatment the niobium oxides grade is reached more than 25%.Niobium oxides content directly carries out roasting greater than 30% raw material.Magnetic separation deferrization and acid treatment are existing common process.

(2) mineral decompose

The niobium raw material of handling well is carried out sulfuric acid baking.The roasting purpose is decomposing ore.Adopt the industrial vitriol oil decomposing ore during roasting.180~230 ℃ of maturing temperatures, time 30-60min; The density of used industrial sulphuric acid is 1.84g/cm 3, sulfuric acid content 95%, boiling point 297 " C.The sulfuric acid baking ratio of components determines that according to the raw material composition weight ratio that contains the niobium raw material and the vitriol oil is 1: 1~1.3; Niobium mainly generates sulfuric acid oxygen niobium during roasting, reacts to be:

Nb 2O 5+2H 2SO 4=Nb 2O 3(SO 4)2+2H 2O

(3) washing and leaching

1, washing

Grog after the roasting carries out water logging and washes; Above-mentioned sulfuric acid oxygen niobium generation hydrolysis during washing generates niobium hydroxide, reacts to be

Nb 2O 3(SO 4) 2+5H 2O=2NbO(OH) 3+2H 2SO 4

Can remove simultaneously the metallic impurity (containing the niobium converter slag with Baotou Iron and Steel Company is example, can remove 30% titanium and 80% iron and manganese during washing) of some amount during washing.90~95 ℃ of washing temperature, time 20-30min, Gu: liquid=1: 10.Contain niobium oxides<0.5g/L in the pickle solution, washing after-filtration, filter cake send oxalic acid to leach niobium;

2, leach

Leach niobium and adopt technical grade oxalic acid, niobium hydroxide and oxalic acid effect fresh during leaching generate water-soluble niobium oxalate complex, react to be:

NbO(OH) 3+H 2C 2O 4=H 3[NbO(C 2O 4) 3]+3H 2O

Leaching condition: 75~80 ℃ of extraction temperatures, time 40~60min; Because the easy crystallization of oxalic acid is separated out, leach the back and adjust niobium concentration, carry out heat preservation hot immediately and filter; Industrial ethanedioic acid consumption during leaching determines that according to niobium in the raw material and metals content impurity consolidating when generally leaching: the liquid weight ratio is 1: 5~15, and the concentration of oxalic acid is 15%~25%.With Baotou Iron and Steel Company's converter slag is that example (contains Nb in the slag 2O 5Be 5.9~6.2%), adopt industrial ethanedioic acid total concn 20% during leaching.Because the production of this processing method is the sealing flow process, quite partly oxalic acid can recycle, the reagent ratio of components when following table is leaching:

The name of an article New oxalic acid Reclaim oxalic acid Reclaim ammonium oxalate Remain ammonium oxalate in the raffinate Add up to Concentration (%) ????10 ????4 ????3 ????3 ??20

Leach filtration back gained niobium oxalate leach liquor and be cooled to room temperature in advance, the oxalic acid crystal of separating out returns leaching, contains the niobium leach liquor and send extraction process to extract niobium.

(4) extraction

Adopt solvent extration to extract niobium and separating impurity, niobium extraction agent organic phase can adopt tertiary amine-type compound (R 3N), as tri-n-octyl amine N204, TOA (Alamine 300, and Alamine 360), tridodecylamine (Alamine 304), N-235 etc.Wherein homemade tertiary amine-type extraction agent N-235 better performances.N-235 is a kind of mixed alkyl tertiary amine (N[C nH 2n+1] 3, R=8~12, molecular weight 387, density 0.8153g/cm 3).Thinner adopts industrial two octanols.Organic phase consists of: 30~50% N-235 and 70~50% two octanols.When using steel-making converter slag raw material, contain Nb in the leach liquor 2O 5About 25g/L, the extraction agent capacity is 25g/L, compare during extraction and be: organic phase: water (oxalic acid leach liquor)=1: 1~2, organic phase is carried out the organic phase acidification with the 0.5mol/L sulphuric acid soln earlier before the extraction, is in a ratio of organic phase: water (pickle solution)=1: 1.Reaction mechanism is:

Acidifying:

Extraction: 3 (R 3NH) ++ [NbO (C 2O 4) 3] 3-=(R 3NH) 3[NbO (C 2O 4) 3]

(R 3NH) ++[NbO(C 2O 4) 2] -=R 3NH[NbO(C 2O 4) 2]

Extraction back niobium load organic phases is directly stripped; Raffinate contains Nb 2O 5<0.2g/L deals with in addition.Strippant consists of and contains 0.5mol/L HNO during reextraction 3+ 2mol/L (NH) 4NO 3Solution.Nitric acid and ammonium nitrate all can be used technical grade reagent.During reextraction, strippant and niobium load organic phases be in a ratio of 1: 4~6; The reaction of stripping is:

(R 3NH) 3[NbO(C 2O 4)3]+3HNO 3=H 3[NbO(C 2O 4) 3]+3R 3NH +NO 3 -

Anti-stripping agent is further handled and is produced the niobium oxalate crystal; Organic phase is then carried out ammonia treatment regeneration, reclaims ammonium nitrate simultaneously, and the organic phase after the processing is returned acidifying groove (being reused for extraction).

Organic phase acidifying, extraction and reextraction are carried out in mixer-settler or in extraction tower; When using mixer-settler, 2 grades of pickling extract 8 grades, strip 6 grades.

(5) anti-stripping agent is handled

It is dense that reextraction gained solution contains niobium, general all (Nb more than 70g/L 2O 5Meter), the concentrated a little niobium oxalate crystal (in fact, reextraction finishes, and just has a little crystal to separate out in the solution) of just can separating out.Take the vacuum concentration method to concentrate reextraction gained solution, make it separate out the niobium oxalate crystal, through centrifugal filter crystal is separated with mother liquor again.Common once concentration gained crystal, warp sateen burns the qualified niobium oxides product that can obtain based on very high purity.The crystal that obtains after repeatedly concentrating is handled through the dissolving recrystallize, also obtains high purity product easily.

(6) crystal calcining

The niobium oxalate crystal has been a kind of intermediates, and is the unique soluble solids Industrial products of niobium.Produce Niobium Pentxoxide by the niobium oxalate crystal and can use calcination method, the also available precipitator method.

The niobium oxalate crystal can get active good Niobium Pentxoxide product through calcining.Slough crystal water during the crystal calcining in the time of 100 ℃, begin in the time of 180 ℃ to decompose, 350-500 ℃ is decomposed generation no igloss (anhydrous) niobium oxides product fully.Because floride-free, calcining can be carried out, need not to use expensive platinum matter container in common alumina crucible or pottery crucible.

Embodiment:

In conjunction with the accompanying drawings, raw material adopts Chinese packet header Bayan Obo iron rare earth niobium polymetallic ore in the present embodiment, obtains a kind of converter slag that contains niobium through iron and steel flow process enrichment (niobium enters molten iron when promptly smelting iron, and the niobium oxidation enters the steel-making slag during steel-making), and its major ingredient is:

Sort The sampling number Nb 2O 5(%) ??Fe(%) ??Mnof(%) Former slag Former slag 1 ????6.16 ??30.4 ????35.4 Former slag 1 ????5.9 ??25.0 ????34.9 Slag after the magnetic separation Magnetic slag 1 ????6.0 ??19.6 ????42.5 Magnetic slag 1 ????6.0 ??15.8 ????41.7 Magnetic slag 1 ????6.1 ??18.1 ????40.3

This magnetic separation slag obtains the pickling slag of following composition after the overpickling enrichment is handled, extract the raw material of niobium as this processing method:

Pickling slag essentially consist table

Batch Sample number Nb 2O 5(%) ??Fe(%) ??Mnof(%) Second batch Pickling 1 ????25.5 ????15.3 ????25.2 Pickling 1 ????24.0 ????14.0 ????23.4 Pickling 1 ????24.0 ????14.6 ????23.1 The 6th batch Pickling 1 ????26.5 ????15.6 ????25.1 Pickling 1 ????24.1 ????14.5 ????24.6 Pickling 1 ????24.5 ????15.1 ????20.1

Do raw material with pickling slag in the table, carry out sulfuric acid baking, parameter is: the pickling slag: the vitriol oil=1: 1.3,200 ℃ of temperature (± 15 ℃), insulation 40min.Grog after roasting water while hot embathes, and condition is for solid: liquid=1: 10,, stir 30min, the washing after-filtration by 90~95 ℃.Through roasting one washing, can remove 20-30%Ti, 80% iron and manganese.Filter cake send oxalic acid to leach niobium.Extraction temperature 75-80 ℃, stir 1h, the total concentration of oxalic acid 20% of industry, gained leach liquor main component is listed in the table below:

The sampling number Second batch feeds intake The 6th batch feeds intake ??Nb 2O 5(g/L) ???Fe(g/L) ??Mn0(g/L) ??Nb 2O 5g/L) ??Fe(g/L) ??Mn0(g/L) ??1 ??24.9 ???4.1 ??2.9 ??25.6 ??4.6 ??3.1 ??2 ??26.0 ???4.1 ??3.4 ??23.1 ??3.7 ??3.0 ??3 ??22.1 ???3.0 ??3.1 ??25.3 ??4.7 ??3.7

Extraction: extraction is carried out in mixer-settler, every grade of cell body size 140 * 207 * 700mm, and the clarifying chamber is 4: 1 to the mixing section volume ratio.It is 30%N-235+70% two octanols that grade phase composite is arranged.

Organic phase is used earlier 0.1mol H 2SO 4Acidifying, 2 grades of acidifyings extract 8 grades.

Contain Nb in the extracting phase after the extraction 2O 5<0.1g/L, the percentage extraction of niobium 97% one 98%.

Strip: the extraction gained contains niobium load organic phases 0.5mol HNO 3+ 2mol NH 4NO 3Strippant reextraction niobium.Strip 6 grades, comparing is organic phase: water (strippant solution)=4: 1.Contain Nb in the gained anti-stripping agent 2O 560-70g/L, the stripping rate 99%-100% of niobium.

Anti-stripping agent is handled: anti-stripping agent is checked earlier and is removed by filter remaining organic phase, (pressure can the be determined as required) evaporation of reducing pressure then, 50~70 ℃ of vaporization temperatures (being no more than 75 ℃); Niobium solution after the evaporation concentration is cooled to room temperature, makes to separate out the niobium oxalate crystal.This crystal through calcining get final product qualified technical grade niobium oxides (foreign matter content is lower than the standard-required of GB GB3627-83).A crystal is through recrystallize, secondary niobium oxalate crystal, secondary crystal through calcining get final product qualified high-purity grade of niobium oxides (wherein band such as iron, manganese look constituent content is better than GB GB10578-89 standard).Control 80~90 ℃ of heavy solubility temperatures during recrystallize, every 3Kg niobium oxalate crystal adds deionized water 1L.All adopt whizzer to filter to isolate the niobium oxalate crystal after the crystallization.The crystallization and the recrystallize rate of recovery 90%~95%.

The niobium oxalate crystal is handled: niobium oxalate crystal the sixth of the twelve Earthly Branches itself is a kind of solubility intermediates, as synthetic other niobium compounds (as niobium catalytic).The niobium oxalate crystal promptly gets the Niobium Pentxoxide product 350~500 ℃ of temperature lower calcinations decomposition.The niobium oxalate crystal decomposes can expensive platinum matter container, but carries out in alumina container.

This technology is suitable for handling Chinese packet header product and contains niobium slag and state's pyrrhite concentrate such as Brazil, Canada, can obtain high purity product under the situation of whole industrial reagent.

Claims (6)

1, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method, its raw material object applicatory is various low-grade niobium material and the high-grade pyrrhite niobium concentrate of containing that comprises the ferrous metallurgy slag that contains niobium, and its technological process comprises following raw material processing, mineral decomposition, washing, leaching, extraction and reextraction niobium, anti-stripping agent processing and crystal calcination process successively:
It is to carry out fragmentation and ball milling earlier with containing niobium raw material that described raw material is handled, and it is reached<100 order granularities;
It is that the niobium raw material that will handle well carries out sulfuric acid baking and decomposes mineral that described mineral decompose, and the ingredients by weight of sulfuric acid baking is than being that the ratio that contains the niobium raw material and the vitriol oil is 1: 1~1.3; 180~230 ℃ of maturing temperatures, time 30~60min;
Described washing is that the grog after the roasting is washed, so that the sulfuric acid oxygen niobium generation hydrolysis that generates during roasting generates niobium hydroxide and removes de-iron, manganese partial impurities; The solid-liquid weight ratio of washing is 1: 10; 90 ℃ of washing temperature, time 20~30min; Washing after-filtration, filter cake send oxalic acid to leach niobium;
Described leaching is to adopt the oxalic acid of technical grade to leach niobium, so that fresh niobium hydroxide and oxalic acid effect generate water-soluble niobium oxalate complex; The concentration that adopts leach liquor during leaching is 20%~25% oxalic acid, and according to the niobium situation that contains in the raw material, the solid-liquid weight ratio during leaching is 1: 5~15; 75~80 ℃ of extraction temperatures, time 40~60min; The oxalic acid leach liquor is treated next step processing;
Described extraction process is to adopt solvent extration to extract niobium and separating impurity, the extraction agent that is adopted is the tertiary amine-type organic reagent, comprise N-235, tri-n-octyl amine N204, Alaimine 300, Alamine 360, Alamine 304, the thinner that adopts is two octanols, kerosene, the mixture of the thinner that consists of 30%~50% extraction agent adding 70%~50% of organic phase;
Described extraction process is to carry out in mixer-settler extractor or extraction tower, and technological process comprises organic phase acidifying, niobium extraction and niobium reextraction; Adopt 0.5mol/L H during acidifying 2SO 4Solution, compare: organic phase: water=1: 1; Being in a ratio of during extraction: organic phase: water=1: 1~2; Extraction gained load organic phases is carried out the reextraction of niobium, and strippant consists of 0.5mol/L nitric acid+2mol/L ammonium nitrate, being in a ratio of of reextraction: organic phase: water=4~6: 1;
It is to take the vacuum concentration method to concentrate reextraction gained solution that described anti-stripping agent is handled, and carries out reduction vaporization when concentrated, and 50~75 ℃ of vaporization temperatures after it separates out the niobium oxalate crystal, are separated the niobium oxalate crystal through centrifugal filter again with mother liquor;
Described crystal calcination process is that the niobium oxalate crystal is calcined in common aluminum oxide container, and the crystal calcining temperature promptly gets the niobium oxides product for 350~500 ℃.
2, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method according to claim 1 will carry out the magnetic separation deferrization earlier for the higher raw material of iron content when it is characterized in that described raw material is handled; Be lower than 10% raw material for the niobium oxides grade, carry out acid treatment, the niobium oxides grade is reached more than 25%.
3, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method according to claim 1 and 2, it is characterized in that the vitriol oil that sulfuric acid baking decomposition mineral adopt is the industrial vitriol oil, it is technical grade oxalic acid that oxalic acid leaches the oxalic acid that niobium adopted, and what the reextraction niobium adopted is technical grade nitric acid and technical grade ammonium nitrate.
4, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method according to claim 3, when the extraction equipment that adopts when it is characterized in that extracting was mixer-settler, 2 grades of pickling extracted 8 grades, strip 6 grades.
5, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method according to claim 4 is characterized in that anti-stripping agent is treated as the niobium oxalate xln with repurity effect.
6, technology of preparing fluorine less niobium oxide by oxalic acid system extraction method according to claim 5 is characterized in that a crystal that is obtained can obtain secondary niobium oxalate crystal through the recrystallize purifying; Control 80~90 ℃ of heavy solubility temperatures during recrystallize, every 3Kg niobium oxalate crystal adds deionized water 1L; Adopt whizzer to filter to isolate the niobium oxalate crystal after the crystallization.
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