CN103614560B - Method of recycling scandium in titanium white waste acid - Google Patents

Method of recycling scandium in titanium white waste acid Download PDF

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CN103614560B
CN103614560B CN201310600227.5A CN201310600227A CN103614560B CN 103614560 B CN103614560 B CN 103614560B CN 201310600227 A CN201310600227 A CN 201310600227A CN 103614560 B CN103614560 B CN 103614560B
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scandium
solution
titanium white
acid
white waste
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CN103614560A (en
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官长平
但召贵
邓星星
汤小军
冯虎成
郝旭
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SICHUAN YOUSE JINSHA BENEFICIATION PHARMACY Co Ltd
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SICHUAN YOUSE JINSHA BENEFICIATION PHARMACY Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a method of recycling titanium white waste acid, particularly relates to a method of recycling scandium in titanium white waste acid, and belongs to the technical field of titanium chemical industry. The key point of the method of recycling scandium in the titanium white waste acid is that the method comprises the following steps of: extracting scandium ion; pickling impurities ions such as iron, manganese and titanium loaded with an organic phase; further reversely extracting the scandium ion to generate hydroxide precipitate; precipitating with oxalic acid after reacting with acid for purifying, and roasting. The method of recycling scandium in the titanium white waste acid disclosed by the invention overcomes the problems that the titanium white waste acid is low in scandium ion content, high in content of titanium, iron and manganese impurities, and difficult to extract and separate, so that scandium in the titanium white waste acid can be effectively recycled. Moreover, the method has the advantages that recovery rate is high, and obtained product has less other metal impurities, so that recycling of the titanium white waste liquor is promoted.

Description

The method of scandium is reclaimed in a kind of titanium white waste acid
Technical field
The present invention relates to a kind of titanium white waste acid recoverying and utilizing method, reclaim the method for scandium in especially a kind of titanium white waste acid, belong to titanium chemical technology field.
Background technology
Scandium and compound thereof have multiple high-performance.Scandium is widely used in the fields such as national defence, chemical industry, metallurgy, glass, space flight, nuclear technique, electronics, laser, superconduction, computer power supply and medical treatment.
Titanium white waste acid is the spent acid produced during sulfuric acid method titanium pigment is produced, wherein contain and scandium, iron, titanium, manganese etc., the present China Panxi Diqu that particularly vanadium and titanium resources is abundant, if titanium white waste acid can not be made well to be utilized, be not only the waste bringing resource, more can cause serious environmental pollution.Although the scandium content content in titanium white waste acid is very low, its annual output is large, and raw material is simple and easy to get, and production cost is low, and well solves the process problem of titanium white waste acid.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, provides a kind of method reclaiming scandium from titanium white waste acid, promotes the recycling of scandium resource in spent acid.
The technical solution used in the present invention is as follows:
Reclaim a method for scandium in titanium white waste acid, comprise following steps: (1) is with P 204-TBP-sulfonated kerosene is that extraction agent adds in titanium white waste acid, and extraction obtains the load organic phases containing scandium ion and other foreign metal ions; (2) add by H in step 1 gained load organic phases 2o 2, H 2sO 4, H 2the pickle solution of O composition, most foreign metal ion in pickling removing load organic phases; (3) in the organic phase after step 2 pickling, add alkaline solution and make Sc3 +and OH -reaction generates Sc (OH) 3precipitation; (4) in step 3 gained precipitation, acid dissolve Sc (OH) is added 3precipitation; (5) by step 4 reacting liquid filtering, add oxalic acid to gained filtrate and obtain oxalic acid scandium precipitation, gained oxalic acid scandium sedimentation and filtration also calcining obtains Sc 2o 3powder.
In described step 1, each component of extraction agent with volume percentage, P 204be 20%, TBP is 7%, sulfonated kerosene is 73%.
In described step 2, each component of pickle solution with volume basis, H 2o 2: H 2sO 4: H 2o is 1:3:8.5, described H 2o 2concentration is 27.5%, H 2sO 4concentration is 93%.
In described step 3, alkaline solution is one in NaOH solution, KOH solution or mixing.
Also add containing Cl in described alkaline solution -solution.
Described containing Cl -solution is one in NaCl solution, KCl solution or mixing.
In described step 4, acid solution is HCl solution, and the pH value of reaction system is 2-2.5.
In described step 5, in the reaction of oxalic scandium precipitation, the pH value of reaction system is 4.
A kind of Sc adopting the method reclaiming scandium in described titanium white waste acid to obtain 2o 3.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows: the method reclaiming scandium in described titanium white waste acid, overcome scandium ion content in titanium white waste acid low, titanium, iron, manganese foreign matter content are high, a difficult problem for extracting and separating difficulty, can effectively be reclaimed by the scandium in titanium white waste acid, and there is the advantage that the rate of recovery is high, other metallic impurity of products obtained therefrom are few, facilitate the cycling and reutilization of titanium white acid solution.
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Reclaim the method for scandium in a kind of titanium white waste acid of the present invention, comprise following steps: (1) is with P 204-TBP-sulfonated kerosene is that extraction agent adds in titanium white waste acid, and extraction obtains the load organic phases containing scandium ion and other foreign metal ions; (2) add by H in step 1 gained load organic phases 2o 2, H 2sO 4, H 2the pickle solution of O composition, most foreign metal ion in pickling removing load organic phases; (3) in the organic phase after step 2 pickling, add alkali and make Sc3 +and OH -reaction generates Sc (OH) 3precipitation; (4) in step 3 gained precipitation, acid dissolve Sc (OH) is added 3precipitation; (5) by step 4 reacting liquid filtering, add oxalic acid to gained filtrate and obtain oxalic acid scandium precipitation, gained oxalic acid scandium sedimentation and filtration also calcining obtains Sc 2o 3powder.
The method of scandium is reclaimed in titanium white waste acid of the present invention, by extracting scandium ion, pickling load organic phases again containing iron, manganese, the foreign ions such as titanium, again by the precipitation of hydroxide of further scandium ion, purification is reached again with acid-respons, it is the key point reclaiming scandium in titanium white waste acid, overcome scandium ion content in titanium white waste acid low, titanium, iron, manganese foreign matter content is high, a difficult problem for extracting and separating difficulty, effectively the scandium in titanium white waste acid can be reclaimed, and it is high to have the rate of recovery, the advantage that other metallic impurity of products obtained therefrom are few, facilitate the cycling and reutilization of titanium white acid solution.P 204(di-(2-ethylhexyl)phosphoric acid) has very strong extracting power, selectivity is strong, separation factor is large, good separating effect, and extracting and washing progression is few, Hui Cui ratio, back scrubbing are than little, the advantages such as chemical materials consumption is few, can by matrix element mainly Ti and Sc extracted in a large number, and after extraction completes, the disengaging time of organic phase and aqueous phase is fast, and layering is obvious; TBP is as the extraction agent of domestic normal employing, also be widely used in the extraction of scandium, because TBP must exist and extracting scandium under highly acidity or high Cl-concentration at non-iron-ion, but iron ion content is high in titanium white waste acid system, and almost there is no chlorion, this can not meet the extraction conditions of TBP, but P 204after the extractive reaction occurred with scandium, the Sc (HA of generation 2) 3.xH 2o energy and TBP continue reaction, generate Sc (HA 2) 3.xTBP, due to the self-characteristic of spent acid, so adopt the mode of synergistic extraction, to strengthen its extracting power, two kinds of reactions cooperatively interact, and extractive reaction can be made continuously to carry out, and sulfonated kerosene plays the work of membrane solvent in order to improve the percentage extraction of efficiency and the scandium ion extracted simultaneously; And based on the effect of each component in extraction agent, further adopt 20%P 204the proportioning of this organic phase of+7%TBP+73% sulfonated kerosene, the separation factor of scandium and titanium, and the separation factor of scandium and manganese can reach very high level.
The H that the present invention adopts 2o 2, H 2sO 4, H 2the pickle solution of O composition, the principle of pickling is: scandium is insoluble in the acid mutually of high density, and the impurity contained in organic phase is Fe 2+, Fe 3+, Mn 4+, Ti 3+and Ti 4+deng, what be in these impurity is in high-valence state, and what have is in lower valency, and the metal ion of high-valence state, easier and organic extractant departs from, and is more easily dissolved in the acid of high density.Wherein, the H in pickle solution 2o 2low price ion-oxygen wherein can be changed into high-valence state, and scandium is in+3 valencys always, so, just remain the scandium in organic phase, and gone out most of impurity wherein, but the titanium that should be in organic phase is too much, so also remained a part of titanium in organic phase, then by removing in follow-up step.
In described step 1, each component of extraction agent with volume percentage, P 204be 20%, TBP is 7%, sulfonated kerosene is 73%, compare preferably V (O): V (A)=1:25 in extraction, make the separation factor of scandium and titanium, and the separation factor of scandium and manganese all can reach very high level.
In described step 2, each component of pickle solution with volume basis, H 2o 2: H 2sO 4: H 2o is 1:3:8.5, described H 2o 2concentration is 27.5%, H 2sO 4concentration is 93%, the effect of well removing foreign ion can be reached, the volume ratio of preferred organic phase and pickle solution is 1:1.5, although also remained a part of titanium in the load organic phases after pickling, but the clearance of foreign metal ion is respectively: Mn 95%, Ti 80%, Fe 93%, the rate of loss of scandium is about 5%, by such pickle solution proportioning and acid cleaning process, removal impurity can be reached, the good result of scandium-enriched.
In described step 3, alkaline solution is one in NaOH solution, KOH solution or mixing, preferred NaOH solution or KOH solution concentration are 2 mol/L, preferably under the condition comparing V (O): V (A)=1:1, single-stage back extraction ratio can reach 97%, and point phase velocity is fast, wall is without adhesion phenomenon; Also add containing Cl in described alkaline solution -solution; Described containing Cl -solution is one in NaCl solution, KCl solution or mixing, is because for increase back extraction ratio further, and accelerates to divide phase velocity after extraction, avoids out an emulsification and bonding phenomenon, containing Cl -helping of solution extracts agent in stripping process, coordination Cl -with Sc 3+hydrolysate Sc (OH) 3, Sc (OH) 2+, Sc (OH) +form complex compound, and reduce extraction agent and its complex ability, thus reach better back extraction effect, and preferred NaCl solution or KCl strength of solution be 1.5mol/L are the best.
In described step 4, acid solution is HCl solution, and the pH value of reaction system is 2-2.5, under this pH value condition, makes Sc (OH) 3while carrying out reacting, avoid titanium to carry out reacting and the reaction solution obtaining titanium ion, further ensure the purity of scandium ion in solution, reaction process can be undertaken by the mode of heated and boiled 5-15 minute, in this hydrolysis dedoping step, hydrolysis removes titanium rate can reach more than 90%, and demanganization rate is 53%, deironing rate is 18%, and the rate of loss of scandium is 4%.
In described step 5, in the reaction of oxalic scandium precipitation, the pH value of reaction system is 4, can be good at the generation avoiding contamination precipitation, preferred sedimentation time is 4 hours, in steps of 5, also preferably adopt the oxalic acid that scandium ionic weight concentration is suitable, consumption of oxalic acid is 110% of step 5 reaction solution simultaneously, after oxalic acid scandium precipitation generates, put it in retort furnace, at 800 DEG C, calcine 1.5-3 hour, obtain purity higher than 95% Sc 2o 3powder.
The present invention will be described further by specific embodiment.
embodiment 1
Spent acid is left standstill 24 hours, with remove wherein can sedimented particle; Get the spent acid of 100ml again, by ICT analytical method, detect scandium content wherein, to detect the percentage extraction to scandium in subsequent step, in titanium white waste acid, sulfuric acid concentration is high, PH is less than 1 can meet extraction requirement, and the leaching process of scandium clicks step to carry out: (1) gets the spent acid of 2000ml in the beaker of 5000ml, with 20%P by volume 204, 7%TBP, 73% sulfonated kerosene configuration organic extractant, get described organic extractant 80ml join in beaker according to comparing V (O): V (A)=1:25, stir with reinforcement electric mixer, the rotating speed of agitator is 450 revs/min, after 10 minutes, divide four times by the spent acid after organic phase and extraction, join in separating funnel, leave standstill 5 minutes, isolate the organic phase that load has scandium ion and other foreign ions; (2) volume ratio of gained load organic phases and pickle solution is that 1:1.5 (namely pickle solution adds 120ml) joins in extraction flask, again extraction flask is installed in vibrator, vibrate 10 minutes, then leave standstill and carry out layering in 5 minutes, then lower floor's aqueous phase is bled off, carry out 3 times altogether, observe the color of the pickle solution after third time pickling, to determine whether to reach requirement, it judges whether to reach the required standards: the color of observing organic phase, the redness of organic phase is almost taken off, and just prove the requirement reaching pickling, described pickle solution compares for H with specific volume 2o 2: H 2sO 4: H 2o=1:3:8.5 configuration forms, described H 2o 2concentration is 27.5%, H 2sO 4concentration is 93%, H 2o is deionized water; (3) add the NaOH of the 2mol/L of 80ml after getting pickling in organic phase, utilize its hydroxide ion back extraction to go out scandium, in the precipitation formed, have Sc (OH) 3precipitation and other contamination precipitation, add organic phase in separating funnel, is separated organic phase and precipitation; (4) precipitation separated is carried out suction filtration and obtain filter cake, be transferred to again in the beaker of 400ml, then appropriate hydrochloric acid is added, by the pH regulator of system to 2-2.5, again precipitation is proceeded in round-bottomed flask together with its solution, then heat, be heated to boiling, and take out flask after maintaining 5-15 minute, carry out filtering separation infusible precipitate after cooling; (5) last in the filtrate of step 4 gained by adding appropriate NaOH solution, the pH of regulation system, to 4, produces if any impurity and then filters; Precipitate 4h when system PH is 4 with the oxalic acid little over amount and obtain oxalic acid scandium precipitation, oxalic acid scandium precipitation is put into retort furnace, regulate temperature to 800 DEG C of calcining 2h, because product is attached in wall of container after roasting, soak with distilled water or diluted acid, filter, dry and obtain Sc 2o 3product.
By gained Sc 2o 3product detects, and its purity is 99.78%, and the rate of recovery of raw material titanium white acid scandium is about 70%.
embodiment 2
The present embodiment process and raw material substantially the same manner as Example 1, institute's difference is: in described step (3), the NaCl solution also adding isopyknic 1.5mol/L with NaOH precipitates as Sc (OH) 3 promotor generated, to weaken the complex ability generating precipitation and extraction agent.
By gained Sc 2o 3product detects, and its purity is 98.92%, and the rate of recovery of raw material titanium white acid scandium is about 76%.
In the various embodiments described above, NaOH solution can be conventional KOH solution of replacing, and NaCl solution can be the conventional KCl solution replaced, and can reach identical technique effect.
The method of scandium is reclaimed in titanium white waste acid of the present invention, overcome scandium ion content in titanium white waste acid low, titanium, iron, manganese foreign matter content are high, a difficult problem for extracting and separating difficulty, effectively the scandium in titanium white waste acid can be reclaimed, and there is the advantage that the rate of recovery is high, other metallic impurity of products obtained therefrom are few, facilitate the cycling and reutilization of titanium white acid solution.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.

Claims (5)

1. reclaim a method for scandium in titanium white waste acid, it is characterized in that: comprise following steps: (1) is with P 204-TBP-sulfonated kerosene is that extraction agent adds in titanium white waste acid, and extraction obtains the load organic phases containing scandium ion and other foreign metal ions, each component of described extraction agent with volume percentage, P 204be 20%, TBP is 7%, sulfonated kerosene is 73%; (2) add by H in step 1 gained load organic phases 2o 2, H 2sO 4, H 2the pickle solution of O composition, most foreign metal ion in pickling removing load organic phases; (3) in the organic phase after step 2 pickling, add alkaline solution and make Sc 3+and OH -reaction generates Sc (OH) 3precipitation, also adds containing Cl in described alkaline solution -solution; (4) Sc (OH) is dissolved to acid supplemented solution in step 3 gained precipitation 3precipitation, the pH value of reaction system is 2-2.5; (5) by step 4 reacting liquid filtering, add oxalic acid to gained filtrate and obtain oxalic acid scandium precipitation, the pH value of reaction system is 4, and gained oxalic acid scandium sedimentation and filtration also calcining obtains Sc 2o 3powder.
2. reclaim the method for scandium in titanium white waste acid as claimed in claim 1, it is characterized in that: in described step 2, each component of pickle solution with volume basis, H 2o 2: H 2sO 4: H 2o is 1:3:8.5, described H 2o 2concentration is 27.5%, H 2sO 4concentration is 93%.
3. reclaim the method for scandium in titanium white waste acid as claimed in claim 1, it is characterized in that: in described step 3, alkaline solution is one in NaOH solution, KOH solution or mixing.
4. reclaim the method for scandium in titanium white waste acid as claimed in claim 1, it is characterized in that: described containing Cl -solution is one in NaCl solution, KCl solution or mixing.
5. reclaim the method for scandium in titanium white waste acid as claimed in claim 1, it is characterized in that: in described step 4, acid solution is HCl solution, and the pH value of reaction system is 2-2.5.
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CN104178632B (en) * 2014-08-12 2016-06-22 东北大学 A kind of method of titanium white waste acid comprehensive utilization
CN105200248B (en) * 2015-09-30 2017-06-16 中铝广西国盛稀土开发有限公司 A kind of step of utilization carbide slag one neutralizes the method that titanium white waste acid prepares high-purity scandium
CN106591581A (en) * 2016-11-07 2017-04-26 中铝广西有色稀土开发有限公司 Purification method of titanium oxide waste water regeneration scandium
CN108504866A (en) * 2018-04-03 2018-09-07 东北大学 A method of using slag processing titanium white waste acid and extracting valuable constituent element
CN108277355A (en) * 2018-04-03 2018-07-13 东北大学 A kind of step extraction of titanium white waste acid valuable metal and method of comprehensive utilization

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CN102127641B (en) * 2010-07-20 2012-09-12 湖南稀土技术开发有限公司 Method for recovering scandium and titanium in titanium white wastewater
CN102690962A (en) * 2012-06-18 2012-09-26 湖南宝盈新材料有限公司 Method for recovering scandium in waste acidic water from titanium dioxide production
CN103060581A (en) * 2013-01-11 2013-04-24 湖南宝盈新材料有限公司 Method for extracting and recycling scandium in waste acid in titanium white production

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