阅读说明：本技术 一种从废旧钽靶材中回收制备高纯钽氧化物的方法 (A method of recycling prepares high-purity tantalum pentoxide from waste and old tantalum target ) 是由 行卫东 陈小浪 朱刘 于 2019-09-18 设计创作，主要内容包括：本发明涉及一种从废旧钽靶材中回收制备高纯钽氧化物的方法,包括以下步骤：(1)将废旧钽靶材进行酸浸处理,得到富集钽渣；(2)混酸浸出,得到浸出液,混酸为硫酸、硝酸、盐酸、氢氟酸中的两种或三种；(3)进行萃取分离,得到有机相萃取液；(4)经过酸洗、氟化铵反萃,得到反萃液,调节反萃液pH得到钽沉淀,再将钽沉淀煅烧,即得高纯钽氧化物。本发明的回收方法没有废渣产生,预处理酸浸过程中的铬可作为氢氧化铬沉淀回收,溶液中铬浓度小于1mg/L,钽氧化物纯度可达4N+,回收率达97％以上,同时萃余液中的钛可作为副产物氟钛酸钾回收；整个流程操作简单,设备投资低,无废气废水排放,达到金属的高效回收利用。(The present invention relates to a kind of to recycle the method for preparing high-purity tantalum pentoxide from waste and old tantalum target, comprising the following steps: (1) waste and old tantalum target is carried out acidleach processing, obtain enrichment tantalum slag；(2) nitration mixture leaches, and obtains leachate, and nitration mixture is sulfuric acid, nitric acid, hydrochloric acid, two or three in hydrofluoric acid；(3) extraction and separation are carried out, organic extractant phase liquid is obtained；(4) it is stripped through overpickling, ammonium fluoride, obtains strip liquor, adjusted strip liquor pH and obtain tantalum precipitating, then by tantalum precipitating calcining to get high-purity tantalum pentoxide.Recovery method of the invention does not have waste residue generation, chromium during pretreatment acidleach can be used as chromium hydroxide precipitation recycling, and chromium concn is less than 1mg/L in solution, and tantalum pentoxide purity is up to 4N+, the rate of recovery is up to 97% or more, while the titanium in raffinate can be used as the recycling of by-product potassium fluotitanate；Whole flow process is easy to operate, and equipment investment is low, no exhaust gas discharge of wastewater, and the high efficiente callback for reaching metal utilizes.)

1. a kind of recycle the method for preparing high-purity tantalum pentoxide from waste and old tantalum target, which comprises the following steps:

(1) waste and old tantalum target is subjected to acidleach processing, obtains enrichment tantalum slag；

(2) the resulting enrichment tantalum slag of step (1) is subjected to nitration mixture leaching, obtains leachate, nitration mixture is sulfuric acid, nitric acid, hydrochloric acid, hydrogen Two or three in fluoric acid；

(3) the resulting leachate of step (2) is subjected to extraction and separation, obtains organic extractant phase liquid；

(4) the resulting organic extractant phase liquid of step (3) is stripped through overpickling, ammonium fluoride, obtains strip liquor, adjusts strip liquor pH Tantalum precipitating is obtained, then by tantalum precipitating calcining to get high-purity tantalum pentoxide.

2. the method as described in claim 1, which is characterized in that in the step (1), acid that acidleach uses for sulfuric acid, nitric acid, One or both of hydrochloric acid, the concentration for the acid that acidleach uses is sour containing 100~300g in every liter of water, sour and waste and old tantalum target Liquid-solid ratio be (5~20): 1.

3. the method as described in claim 1, which is characterized in that in the step (1), leaching time is 1~5h, mixing speed For 100~300rpm, acidleach temperature is 75~95 DEG C.

4. method according to claim 2, which is characterized in that the mass fraction of the sulfuric acid is 98%, the matter of the nitric acid Measuring score is 65%, and the mass fraction of the hydrochloric acid is 35%.

5. the method as described in claim 1, which is characterized in that in the step (2), every kind of sour concentration is every liter in nitration mixture Containing 120~200g acid in water, nitration mixture and the liquid-solid ratio for being enriched with tantalum slag are (3~5): 1.

6. the method as described in claim 1, which is characterized in that in the step (2), extraction time is 1.5~2.5h, stirring Speed is 100~250rpm, and extraction temperature is 75~90 DEG C.

7. the method as described in claim 1, which is characterized in that in the step (2), the mass fraction of the sulfuric acid is 98%, the mass fraction of the nitric acid is 65%, and the mass fraction of the hydrochloric acid is 35%, and the mass fraction of the hydrofluoric acid is 40%.

8. the method as described in claim 1, which is characterized in that in the step (3), extractant be hexone, One or both of tributyl phosphate, sec-octyl alcohol, extractant are with industrial sulfonated kerosene dilution, the volume fraction of extractant 15%~85%, extraction time is 3~8min, and the volume ratio of extractant and leachate is (1~3): 1.

9. the method as described in claim 1, which is characterized in that in the step (4), acid that pickling uses for sulfuric acid, nitric acid, The concentration of one of hydrochloric acid, the acid that pickling uses is sour to contain 50~400g in every liter of water, the sour body with organic extractant phase liquid Product is than being (1~2): 1, pickling number is 2~4 times；The concentration of ammonium fluoride is to contain 50~250g ammonium fluoride in every liter of water, fluorination The volume ratio of organic extractant phase liquid after ammonium and pickling is (1~5): 1, Stripping times are 5~8min；It is adjusted and is stripped using ammonium hydroxide Liquid pH is 8~9.

10. method as claimed in claim 9, which is characterized in that the mass fraction of the sulfuric acid is 98%, the matter of the nitric acid Measuring score is 65%, and the mass fraction of the hydrochloric acid is 35%, and the mass fraction of the ammonium fluoride is 96%, the matter of the ammonium hydroxide Measuring score is 28%.

Technical field

The present invention relates to a kind of to recycle the method for preparing high-purity tantalum pentoxide from waste and old tantalum target, belongs to non-ferrous metal smelting Golden collar domain.

Background technique

Tantalum alloy recovery process is mainly the following method at present: hydrofluoric acid leaching-extraction separation method, hydrofluoric acid and sulphur Acid-mixed Ore Leaching-extraction separation method, alkali fusion roasting method etc..

Zhang Busheng recycles tantalum in " non-ferrous metal (Smelting Part) " the 9th interim disclose in 2014 from tantalum alloy slag charge Method, wherein raw material contains the metal impurities such as tantalum 34%, niobium 17%, titanium 17% and tungsten nickel chromium triangle.Using hydrofluoric acid leaching-MIBK Extraction and separation-ammonia precipitation process method obtain 99% or more tantalum purity, 90% or more overall recovery.The technique uses simple hydrogen fluorine Ore Leaching, hydrofluoric acid is volatile, and dosage is larger.

Wang Zhijun is disclosed using oxidation acid leaching-alkali burning-water logging " non-ferrous metal (Smelting Part) " 2014 the 6th is interim Process waste high-temperature alloy powder obtains tantalum, niobium, zirconium enrichment slag, using substep leaching-MIBK extraction and separation-ion Exchange removal of impurities-sodium hydroxide pellets produce tantalum pentoxide.During oxidation acid leaching, niobium tantalum leaching rate is less than 3.5%, extraction point It is O/A=5:1 counter-current extraction from process, tantalum extraction yield is 98%, back extraction ratio 99.83%.The technique extraction process compares Greatly, the loss of tantalum niobium is larger, reduces the rate of recovery.

The patent of Publication No. CN106048231B discloses a kind of recycles tantalum silver nickel and iron from waste and old tantalum capacitor Method, wherein material passes through Mechanical Crushing, magnetic separation, electron-beam smelting-evaporation-condensation separation of Silver, and remaining slag charge passes through magnesium heat also Original prepares high-purity tantalum powder, and the purity for obtaining tantalum is 99.99%.The process process equipment is more demanding, and tantalum loses during magnetic separation It is larger.

The patent of Publication No. CN104164567A discloses a kind of side of enriching and recovering niobium tantalum from waste high-temperature alloy Method, the technique dust waste high-temperature alloy by melting atomization, the material obtained after nickel cobalt tungsten rhenium are leached, using alkali Molten, water logging, acid processing, obtain the oxide of the tantalum containing niobium.Tantalum niobium is enriched with very well in the technical process, but further to be separated It must also be by technical process such as acid dipping separations.

Summary of the invention

One kind is provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art to return from waste and old tantalum target The method for preparing high-purity tantalum pentoxide is received, this method is easy to operate, equipment investment is small, pollution-free.

To achieve the above object, the technical scheme adopted by the invention is as follows: one kind from waste and old tantalum target recycling prepare it is high-purity The method of tantalum pentoxide, comprising the following steps:

(1) waste and old tantalum target is subjected to acidleach processing, obtains enrichment tantalum slag；

(2) the resulting enrichment tantalum slag of step (1) is subjected to nitration mixture leaching, obtains leachate, nitration mixture is sulfuric acid, nitric acid, salt Two or three in acid, hydrofluoric acid；

(3) the resulting leachate of step (2) is subjected to extraction and separation, obtains organic extractant phase liquid；

(4) the resulting organic extractant phase liquid of step (3) is stripped through overpickling, ammonium fluoride, obtains strip liquor, adjusts back extraction Liquid pH obtains tantalum precipitating, then by tantalum precipitating calcining to get high-purity tantalum pentoxide.

As the preferred embodiment of the method for the invention, in the step (1), the acid that acidleach uses is sulfuric acid, nitre Acid, one or both of hydrochloric acid, the concentration for the acid that acidleach uses are sour containing 100~300g in every liter of water, leaching time 1 ~5h, mixing speed are 100~300rpm, and acidleach temperature is 75~95 DEG C, it is sour be with waste and old tantalum target liquid-solid ratio (5~ 20):1。

Step (1) acidleach processing, it is main to remove other a small amount of metals being mixed in most of chromium and a small amount of titanium and raw material Impurity, the main metal tantalum of Sync enrichment.After acidleach processing, the chromium in infusion solution can prepare chromium hydroxide by precipitating, in waste liquid Chromium concn is less than 1mg/L.

As the preferred embodiment of the method for the invention, the mass fraction of the sulfuric acid is 98%, the nitric acid Mass fraction is 65%, and the mass fraction of the hydrochloric acid is 35%.

As the preferred embodiment of the method for the invention, in the step (1), acidleach after treatment is enriched with tantalum Slag is washed with distilled water 3 times.

As the preferred embodiment of the method for the invention, in the step (2), every kind of sour concentration is every in nitration mixture It rises containing 120~200g acid in water, extraction time is 1.5~2.5h, and mixing speed is 100~250rpm, extraction temperature 75 ~90 DEG C, nitration mixture and the liquid-solid ratio for being enriched with tantalum slag are (3~5): 1.

Nitration mixture in step (2) is fewer with acid amount than the prior art, reduces the volatilization of hydrofluoric acid, while nitration mixture can leach entirely Portion's material, almost without slag residual.

As the preferred embodiment of the method for the invention, in the step (2), the mass fraction of the sulfuric acid is 98%, the mass fraction of the nitric acid is 65%, and the mass fraction of the hydrochloric acid is 35%, and the mass fraction of the hydrofluoric acid is 40%.

As the preferred embodiment of the method for the invention, in the step (3), extractant is methyl-isobutyl first One or both of ketone, tributyl phosphate, sec-octyl alcohol, extractant industrial sulfonated kerosene dilution, the volume fraction of extractant It is 15%~85%, extraction time is 3~8min, and the volume ratio of extractant and leachate is (1~3): 1.

Leachate in step (2) can be extracted directly, do not had to clean or adjusted pH, using hexone, phosphoric acid One or both of tributyl, sec-octyl alcohol are extracted as extractant, and tantalum extraction yield is greater than 98%.

As the preferred embodiment of the method for the invention, in the step (4), the acid that pickling uses is sulfuric acid, nitre The concentration of one of acid, hydrochloric acid, the acid that pickling uses is sour to contain 50~400g in every liter of water, acid and organic extractant phase liquid Volume ratio is (1~2): 1, pickling number is 2~4 times；The concentration of ammonium fluoride is to contain 50~250g ammonium fluoride, fluorine in every liter of water The volume ratio of organic extractant phase liquid after changing ammonium and pickling is (1~5): 1, Stripping times are 5~8min；It is adjusted using ammonium hydroxide anti- Extracting liquid pH is 8~9.

It in step (4), is stripped using ammonium fluoride, for tantalum back extraction ratio up to 99.9%, the foreign ions such as crome metal titanium are dense Degree is less than 1mg/L.The tantalum pentoxide purity prepared after tantalum precipitating calcining is up to 99.99%, and organic extractant phase liquid is through pickling When number is greater than 3 times, for tantalum pentoxide purity up to 99.999%, the tantalum rate of recovery is greater than 97%.

As the preferred embodiment of the method for the invention, the mass fraction of the sulfuric acid is 98%, the nitric acid Mass fraction is 65%, and the mass fraction of the hydrochloric acid is 35%, and the mass fraction of the ammonium fluoride is 96%, the ammonium hydroxide Mass fraction is 28%.

Compared with prior art, the invention has the benefit that

(1) it is directed to the recovery method of waste and old tantalum target, the present invention first pre-processes waste and old tantalum target and removes a large amount of metal impurities, Secondly it is leached using nitration mixture, is generated without residue；Leachate extraction process is using hexone, tributyl phosphate, secondary One or both of octanol is extracted as extractant, and up to 98% or more, chromium and titanium all stop the extraction yield of leachate In raffinate, organic extractant phase liquid improves the purity of product by pickling, and purity can reach 4N+ or more；Pickling solution can return to Stoste continues to extract, and without metal loss, the tantalum rate of recovery is up to 97% or more；It is stripped using ammonium fluoride, strip liquor pH upon mediation Metal tantalum is precipitated, finally calcining prepares high-purity tantalum pentoxide；

(2) present invention is anti-by acidleach processing, nitration mixture leaching, extraction and separation, pickling, ammonium fluoride for tantalum target waste material Extraction, precipitating calcining prepares high-purity tantalum pentoxide, present invention selection hexone, tributyl phosphate, one in sec-octyl alcohol It plants or two kinds is extracted as extractant, while ammonium fluoride being selected to be stripped, be prepared using method of the invention High-purity tantalum pentoxide rate of recovery is greater than 97%, and purity is up to 99.999%；

(3) compared with prior art, there is no waste residue generation in the technical process, the chromium during pretreatment acidleach can be used as Chromium hydroxide precipitation recycling, chromium concn is less than 1mg/L in solution, tantalum pentoxide purity up to 4N+, the rate of recovery up to 97% or more, The titanium in raffinate can be used as the recycling of by-product potassium fluotitanate simultaneously；Whole flow process is easy to operate, and equipment investment is low, and no exhaust gas is useless Water discharge, the high efficiente callback for reaching metal utilize.

Detailed description of the invention

Fig. 1 is the flow chart for the method that present invention recycling from waste and old tantalum target prepares high-purity tantalum pentoxide.

Specific embodiment

Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with the drawings and specific embodiments pair The present invention is described further.

The mass fraction of sulfuric acid used in the embodiment of the present invention is 98%, and the mass fraction of nitric acid is 65%, hydrochloric acid Mass fraction is 35%, and the mass fraction of hydrofluoric acid is 40%, and the mass fraction of ammonium fluoride is 96%, and the mass fraction of ammonium hydroxide is 28%.