CN100489125C

CN100489125C - Niobium purifying method

Info

Publication number: CN100489125C
Application number: CNB2004100233417A
Authority: CN
Inventors: 万明远
Original assignee: Zhuzhou Cemented Carbide Group Co Ltd
Current assignee: Zhuzhou Cemented Carbide Group Co Ltd
Priority date: 2004-06-24
Filing date: 2004-06-24
Publication date: 2009-05-20
Anticipated expiration: 2024-06-24
Also published as: CN1594611A

Abstract

A production method for niobium containing little tantalum and impurity using ordinary single extraction niobium liquid from secondary octyl alcohol as material is provided, consisting of three steps: A: extracting from single extraction using organic mixture under weak acid, then obtaining water phase little tantalum containing niobium liquid ;B: extracting tantalum from secondary extraction organic phase, obtaining little impurity niobium liquid; C: washing tantalum, recovering no-loaded organic phase and using in step A. The purifying method is simple, operate easily and reduce the material consumption.

Description

A kind of method of purification of niobium

Technical field

The present invention relates to a kind of extracting and purifying technology method of niobium, refer in particular to the method for the pure niobium of extraction from the anti-niobium liquid of the technical grade of secondary octanol single extraction system, belong to non-ferrous metal extracting process class.

Background technology

Along with the high speed development of information industry and superconductor technology, the demand of low tantalum niobium and low assorted niobium (pure niobium) is increasing.Low tantalum niobium is mainly used in makes the niobium slab, and further processing can roll into thin plate, makes product, also can be used for this field of sputter coating.Niobium film as type material is in developmental stage, and the pent-up demand amount is very big.Simultaneously, pure niobium is again a kind of superconducting material of practicality, can make the superconduction frequency cavity, A.C. losses can be reduced to 1/10.Therefore in contemporary sophisticated technology exploitation utilization, play crucial effect, for example, the large-scale positron-electron accelerator at European nuclear power center needs to make cavity with the High-purity Niobium plate, and required niobium finished weight will 1500 tons.As seen, the market outlook of low tantalum niobium and low assorted niobium are very wide.

The known processing method of producing the purification niobium has three kinds at present, the first is levigate with tantalum-niobium concentrate, decomposes with hydrofluoric acid, sulfuric acid, makes the aqueous solution or the ore pulp that contain the tantalum niobium after the acid adjustment, then use organic solvent, the fluoro complex of tantalum niobium is extracted in the organic phase as MIBK, secondary sad, N-503 etc.; And it is separated with other impurity.In order to remove the small amount of impurities element of bringing in the extraction process in the organic phase, wash organic phase with sulphuric acid soln, make small amount of impurities change aqueous phase again over to.The organic phase that contains tantalum, niobium fluoro complex after washing arrives aqueous phase with dilute sulphuric acid with the niobium back extraction.When back extraction niobium fluoro complex, a spot of tantalum fluoro complex also enters and contains the niobium aqueous phase, for this reason, uses organic extractant phase little tantalum (carrying tantalum) again, and niobium is separated with tantalum.But in the separating obtained niobium liquid of such single extraction, wherein the content of tantalum and other impurity element is also than higher.Available data shows and to show, this moment tantalum in 0.05～0.1% level, other impurity is in 0.005～0.01% level.Though the product that this technology realizes can satisfy the requirement of general industry level niobium oxides and metal niobium product, be difficult to satisfy the specification of quality of low tantalum niobium and low assorted niobium.Two kinds of backs are that present industry circle is generally acknowledged sophisticatedly puies forward blunt niobium method: the processing method of the dissolving crystallized purification niobium of reextraction and oxalic acid under the high acidity condition, these the two kinds high-purity Niobium Pentxoxides that are suitable for producing opticglass level and monocrystalline level, defective is that cost height, production scale are little, is not suitable for mass production is more of low grade than High-purity Niobium, price is low low tantalum niobium and low assorted niobium product.

Therefore it is lower to seek a kind of production cost, can be used for the production technology of low tantalum niobium of industrialized mass production and low assorted niobium, has been a kind of expectation of manufacturer and user.

Summary of the invention

The objective of the invention is to work out a kind of processing method that is suitable for producing low tantalum niobium and low assorted niobium, not only technology is simple, easy to operate, the minimizing materials consumption to wish it, simultaneously, be controlled at the cost increase minimum, and with like product relatively, the novel method that has a clear superiority in again qualitatively, novel process.

The common anti-niobium liquid of this technical grade with secondary octanol single extraction is niobium method of purification raw material, that produce low tantalum niobium and low assorted niobium, it is characterized in that it is made up of following three technological processs:

A, part reextraction; Promptly the organic liquid mixture phase of forming with 40%N-503+60% kerosene volume ratio is used 1.3-1.6moL/LH ₂SO ₄With 2-3moL/LHF solution the common niobium liquid of the technical grade of secondary octanol system is hanged down part reextraction under the sour condition, make 30～40% of niobium fluoro complex in the common niobium liquid, 80～90% of remaining tantalum fluoro complex is extracted in the organic phase, form the load organic phases mixed solution, obtain the own significantly reduced low tantalum niobium liquid of surplus tantalum content at aqueous phase.

B, the anti-niobium of secondary, carry tantalum: promptly to entering niobium and the little tantalum in the organic phase in the above-mentioned A technology during to the part reextraction, carry out the anti-niobium of secondary, carry tantalum, its method is to be incorporated in the load organic phases mixed solution with pure water earlier, once more aqueous phase is arrived in the niobium back extraction, also there is simultaneously micro-tantalum to get off with niobium back extraction together, then with unloaded N-503 organic phase the micro-tantalum in the back extraction niobium liquid is come together in the organic phase more again, the anti-niobium liquid that obtains is the higher low assorted niobium liquid of purity.

C, wash tantalum; After being the anti-niobium of secondary, to the organic phase that contains the little tantalum fluoro complex that produces, NH with 1～1.5% ₄F solution washs, and makes the tantalum back extraction to aqueous phase, and should the zero load organic phase return the A technology starting stage, participates in new reextraction and carries tantalum.

What adopted in the described technology is 6 grades of anti-niobiums of pure water.

In the described technology the low tantalum niobium liquid that obtains behind the reextraction being neutralized to pH value with ammonia respectively with low assorted niobium liquid is 9, and removes fluorine with hot pure water washing, and oven dry is after calcination promptly gets the solid oxidation niobium.

Niobium purification process of the present invention is compared with oneself purifying technique of known three kinds of niobiums, except that the normal loss of extraction agent, does not almost have other reagent consumption in actual process; And the extraction of N-503, reextraction groove just connect by secondary octanol extracts line, can see by the operative employee who sees secondary octanol line is double, need not to increase in addition operator.The characteristics that flow process is short so this processing method has, equipment is simple, consume less, cost is low.

Description of drawings

Accompanying drawing is a niobium purifying technique schema of the present invention.

Embodiment

Be described in detail the present invention below in conjunction with process flow sheet, and provide embodiment.

Embodiment:

The starting material that the present invention adopts are as follows: the anti-niobium liquid of the technical grade of secondary octanol single extraction system (the common niobium liquid of N-1): content 84.8g/L, H ₂SO ₄: 1.6moL/L, HF:2.7moL/L presses O:A=0.8:1 with the organic phase that 40%N-503+60% kerosene is formed, and 6 grades of extraction raffinates are low tantalum niobium liquid (N-2).Load organic phases is pressed O:A=1:0.6, and with 6 grades of pure water, the back extraction niobium is pressed O:A=0.8:1 again, and 6 grades of pure water are carried tantalum and got the low assorted niobium liquid of N-3.Instead finish the organic phase of niobium and propose the merging of tantalum organic phase, press O:A=1:0.6, use 1.2%NH ₄F, 6 grades of pure water are washed tantalum (TaNb) to organic phase ₂O ₅＜0.1g/L.

It is 9 that above-mentioned three kinds of niobium liquid are neutralized to PH with ammonia respectively, and fluorine is removed in the washing of heating pure water, and oven dry makes the solid oxidation niobium after the calcination again.

In above-mentioned extraction process, because the N-503+ kerosene extraction that the present invention adopts carries out under low sour condition, with this understanding, tantalum preferentially extracts, niobium partly extracts, and impurity seldom extracts; Make the impurity that carries in the organic phase behind the reextraction seldom.Therefore, for the higher low assorted niobium liquid of the anti-niobium liquid purity that obtains through the anti-niobium of secondary, after carrying tantalum, created the good technique basis.

In addition, secondary octanol tantalum niobium extraction system back extraction niobium will be used the H of 1.25-1.5moL/L ₂SO ₄Solution, the anti-niobium liquid acidity that obtains is: H ₂SO ₄1.3-1.6moL/L; HF:2-3moL/L, and N-503 tantalum niobium extraction system back extraction niobium pure water, the anti-niobium liquid acidity that obtains is 1.6-2.4moL/L, more much lower than the former. illustrate so under the anti-niobium liquid acidity condition of secondary octanol extraction system, N-503 still has certain extracting power to niobium, the present invention has utilized the difference of the two extraction and reextraction niobium condition just, with N-503 the anti-niobium liquid of secondary octanol extraction system is not added sour low acid, part reextraction.

Niobium liquid and corresponding solid sample are analyzed result such as table 1, table 2.

Table 1 liquid sample analytic result numbers the sample title

Table 2 solid sample analytical results

Claims

1, a kind of is niobium method of purification raw material, that produce low tantalum niobium and low assorted niobium with the common anti-niobium liquid of secondary octanol single extraction technical grade, it is characterized in that it is made up of following three technological processs:

A, part reextraction; Promptly the organic liquid mixture phase of forming with 40%N-503+60% kerosene volume ratio is used 1.3-1.6moL/L H ₂SO ₄With 2-3moL/LHF solution the common niobium liquid of the technical grade of secondary octanol system single extraction is hanged down part reextraction under the sour condition, make 30～40% of niobium fluoro complex in the common niobium liquid, 80～90% of remaining tantalum fluoro complex is extracted in the organic phase, form the load organic phases mixed solution, obtain the own significantly reduced low tantalum niobium liquid of surplus tantalum content at aqueous phase;

B, the anti-niobium of secondary, carry tantalum; Promptly to entering niobium and the little tantalum in the organic phase in the above-mentioned A technology during to the part reextraction, carry out the anti-niobium of secondary, carry tantalum, its method is to be incorporated in the load organic phases mixed solution with pure water earlier, once more aqueous phase is arrived in the niobium back extraction, also there is simultaneously micro-tantalum to get off with niobium back extraction together, then with unloaded N-503 organic phase the micro-tantalum in the back extraction niobium liquid is come together in the organic phase more again, obtain the higher low assorted niobium liquid of anti-niobium liquid purity;

2, the method for purification of a kind of niobium as claimed in claim 1 is characterized in that: what adopted in the described technology is 6 grades of anti-niobiums of pure water.