CN103233134A - Recycling method of organic phase used for extracting scandium - Google Patents
Recycling method of organic phase used for extracting scandium Download PDFInfo
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- CN103233134A CN103233134A CN2013101729122A CN201310172912A CN103233134A CN 103233134 A CN103233134 A CN 103233134A CN 2013101729122 A CN2013101729122 A CN 2013101729122A CN 201310172912 A CN201310172912 A CN 201310172912A CN 103233134 A CN103233134 A CN 103233134A
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- organic phase
- sodium sulfide
- scandium
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Abstract
The invention relates to a recycling method of an organic phase used for extracting scandium. The method comprises the following steps of: adding a sodium sulfide solution into the organic phase and mixing; performing phase splitting; discharging a water phase; adding a sulfuric acid solution into the rest of organic phase; washing the acidified organic phase with water; and using the acidified organic phase to extract scandium. The organic phase treated by using the method can be recycled, the subsequent efficiencies of titanium washing and reverse extraction processes also can be improved, most of titanium impurities can be washed off from the organic phase, and the efficiency of reverse extraction can be obviously improved; and the organic phase can be totally reversely extracted by using 3mol/L of industrial alkali, the phase splitting efficiency is rapid, and the scandium content of an obtained alkali cake is high.
Description
Technical field
The present invention is about a kind of recycle method of processing aid, especially in regard to a kind of recycle method of the organic phase that extracting scandium uses from the titanium dioxide hydrolysis mother liquor.
Background technology
In the existing technology, adopt the organic phase that contains extraction agent P204 to reclaim scandium usually from titanium dioxide wastewater liquid, the organic phase that contains scandium directly enters following operation, for example reclaims scandium through after washing operations such as titanium, back extraction, press filtration.Utilize organic phase from the titanium dioxide hydrolysis mother liquor during extracting scandium, when scandium is extracted, other impurity, nickel ion for example, lead ion, zine ion, cupric ions etc. also are extracted in the organic phase, but impurity is difficult for being come out by back extraction during with sodium hydroxide or other solution back extraction, in the course of time, the enrichment in organic phase of these impurity is more and more, these foreign ions occupy the position in the organic molecule, thereby cause organic extractant phase efficient to reduce greatly, can't continue to use, the percentage extraction that is in particular in scandium reduces, the follow-up sulfuric acid of using, the process operations difficulty of hydrogen peroxide complexing titanium, titanium and other impurity are difficult to wash, during back extraction, need the industrial soda of high density can back extraction to come out reluctantly, but the content of scandium is low in its back extraction thing that obtains, and needs in the industrial production often to change fresh organic phase effectively scandium is extracted from the titanium dioxide hydrolysis mother liquor.Certainly will cause the waste of organic phase like this, improve production cost.
Therefore, in fact be necessary to develop a kind of can be so that the employed organic phase of this extracting scandium be able to cyclic utilization method.Thereby need not often to change organic phase in industrial production, the save operation program reduces production costs simultaneously, enhances productivity.
Summary of the invention
In view of existing problem in the above-mentioned prior art, the present invention is somebody's turn to do the employed organic phase of extracting scandium from the titanium dioxide hydrolysis mother liquor by adopting sodium sulphite to handle, and reaches the purification organic phase, recovers organic performance, prolongs the purpose in the cycle that recycles.
In order to realize the foregoing invention purpose, the technique means that the present invention takes is to provide the recycle method of the employed organic phase of a kind of extracting scandium, it comprises the steps: to add sodium sulfide solution in described organic phase, mix, after the phase-splitting, discharge water, in the residue organic phase, add sulphuric acid soln, after the organic phase after the acidifying washes with water, use it for extracting scandium again.In an embodiment, described sodium sulfide solution processing washes with water to for example water lotion pH value through the organic phase behind the sulfuric acid acidation then again and collects organic phase for behind the 6.5-7.5, and the organic phase reusable edible of this collection is in the extraction process of scandium.
Unexpectedly, the contriver finds the organic phase after above-mentioned sodium sulphite processing, acidifying, washing is put into production use, and can improve the extracting power of organic phase, prolongs the life cycle of organic phase.And, also can improve the follow-up efficient of washing titanium, back extraction operation, improve the purity of scandium in reclaiming product.
Preferably, the concentration of described sodium sulfide solution is 0.1-1 weight %, is preferably 0.3 weight % especially.
Preferably, the volume ratio of described organic phase and sodium sulfide solution is 1:0.1-1:10.
Preferably, described organic phase and sodium sulfide solution mixing time are 10-60 minute, are preferably 30-60 minute especially.
In a specific embodiment of the present invention, described sodium sulfide solution can be freshly prepared.In another preferred embodiment of the present invention, described sodium sulfide solution is industrial sodium sulfide waste water, the sodium sulphite waste water that for example from the present invention relates to art production process, produces, through after the recycle repeatedly, the ability of sodium sulfide solution purifying organic phase can descend, at this moment, can be according to the demand of actual production, replenish an amount of sodium sulphite solid or the sodium sulfide solution of high density, can effectively remove the impurity in the organic phase, keep the scandium in the organic phase simultaneously.For this sodium sulphite waste water, before being added to described organic phase, earlier through ageing 8-72 hour, be preferably 24 hours, the ageing temperature is room temperature, for example can be 20-30 ℃.By recycle sodium sulphite waste water, reduce trade effluent, exhaust gas discharging amount thereby reach, reach the purpose of reasonable resources utilization and environment protection.
Because sodium sulfide solution is under acidity, can form sodium sulphite gas, therefore, can be by organic phase be remained alkalescence before sodium sulfide solution adds described organic phase, for example the pH value is 7.0-14, thereby avoid sodium sulphite in organic phase, to form hydrogen sulfide, environment and the mankind are caused damage, and reduce sodium sulfide solution to the purification process ability of this organic phase.
Preferably, the concentration of described sulphuric acid soln is 1-10mol/L.
Preferably, the volume ratio of described residue organic phase and sulphuric acid soln is 1:0.1-1:10.
The obtainable useful technique effect of the present invention comprises at least:
1. the organic phase after sodium sulphite is handled, extraction ability improves greatly, even can match in excellence or beauty with the organic phase of new preparation, has prolonged the cycle that recycles of organic phase;
2. the organic phase after the method for the application of the invention is handled not only can be recycled, also can improve the follow-up efficient of washing titanium, back extraction operation, can not only from organic phase, wash most of titanium impurity to come, and stripping efficiency can be improved significantly, can be with its complete back extraction with relatively low industrial soda, divide phase effect rapid, the alkali cake scandium content height that obtains;
3. adopt the inventive method to handle organic phase and used a large amount of sodium sulfide solutions, because sodium sulphite waste water is difficult for handling, can satisfy the demand of recycle sodium sulphite through the sodium sulfide solution of ageing processing, thereby reach the minimizing trade effluent, the exhaust gas discharging amount, the purpose of more reasonably utilizing resource and protecting environment;
4. greatly reduce production cost when having improved the production production capacity.
Embodiment
Below cooperate specific embodiments of the invention, further setting forth the present invention is to reach the technique means that predetermined goal of the invention is taked.
For detecting the effect of extracting of the organic phase of handling through sodium sulphite, comparative study of the present invention handle and the organic phase of uncured sodium processing is respectively applied to extract → wash effect in titanium → back extraction → press filtration whole process flow through sodium sulphite, analyzed the percentage extraction of scandium, wash the titanium effect, the back extraction effect obtains the content of scandium in the filter cake after the press filtration.
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment, these embodiment only play the illustrative effect, are not limited to range of application of the present invention, NM concrete experimental technique carries out according to the normal experiment method usually in the following example.
Embodiment 1: the preparation of the organic phase of handling through sodium sulfide solution
1, sodium sulfide solution
Solid sodium sulfide and distilled water is mixed with by weight 0.3% sodium sulfide solution.
2, organic phase
Organic phase comprises extraction agent P204, i.e. two (2-ethylhexyl phosphoric acid) and diluent kerosenes, and wherein the volume ratio of P204 and kerosene is 1:5.This organic phase is used for behind the titanium dioxide wastewater extracting scandium, in this organic phase except containing the scandium that extraction obtains to some extent, also contain other impurity, therefore, need handle the organic phase after this utilization, simultaneously, keep this pending organic phase to be alkalescence, for example the pH value is 8.0, in addition, keeps the ventilation effect of operating environment.
By aforesaid operations, can avoid sodium sulfide solution to add organic phase after, be combined with hydrogen ion and form hydrogen sulfide, thereby cause environment and the mankind are damaged.
3, utilize the pending organic phase of above-mentioned sodium sulfide solution purifying
With 0.3% the sodium sulfide solution that prepared and pending organic phase 1:1 mixing by volume stir about 30min, leave standstill phase-splitting after, the lower floor's water of draining; The sulfuric acid that adds 3mol/L in the residue organic phase, described sulfuric acid with remain organic phase by volume 1:1 mix, after the acidifying, behind the water of draining, wash organic phase with water three times, be washed till the water pH that discharges near 7.0, thereby can wash H as far as possible off
+And other dissociated ion, collect organic phase, standby.
Embodiment 2: the preparation of the organic phase of handling through sodium sulfide solution
1, sodium sulfide solution
Collection, namely under the room temperature condition, is left standstill sodium sulphite waste water 24 hours through ageing through embodiment 1 used sodium sulphite waste water, gets supernatant liquor, adds an amount of sodium sulphite solid, is made into the sodium sulfide solution of 1.0 weight %.
2, organic phase
Organic phase comprises extraction agent P204, i.e. two (2-ethylhexyl phosphoric acid) and diluent kerosenes, and wherein the volume ratio of P204 and kerosene is 1:5.This organic phase is used for discharging water behind the titanium dioxide wastewater extracting scandium, collects organic phase, the organic phase that this is pending transfers to alkalescence, and for example the pH value is 9.0.
3, utilize the pending organic phase of above-mentioned sodium sulfide solution purifying
With 0.3% the sodium sulfide solution that prepared and pending organic phase 1:1 mixing by volume stir about 30min, leave standstill phase-splitting after, the lower floor's water of draining; The sulfuric acid that adds 3mol/L in the residue organic phase, described sulfuric acid and residue organic phase 1:1 by volume mix, after the acidifying, behind the water of draining, wash organic phase with water three times, and the water pH that the system of washing is discharged is near 7.0, and the collection organic phase is standby.
Embodiment 3: the organic phase of embodiment 1,2 gained organic phases and the processing of uncured sodium, acidifying, washing is used for reclaiming comparative study the technology of scandium from titanium dioxide wastewater
Handle and the organic phase of uncured sodium processing is respectively applied to extract → wash effect in titanium → back extraction → press filtration whole process flow through sodium sulphite by comparative study, analyzed and utilized different organic phases for the percentage extraction of scandium, wash the titanium effect, the back extraction effect obtains the difference of the content of scandium in the filter cake after the press filtration.
Wherein: described extraction process, organic phase is used in operation routinely, and for example the scandium in P204 and the kerosene extraction titanium dioxide wastewater liquid gets water and residue organic phase.
The described titanium operation of washing comprises:
Configuration three-phase mixed solution, be organic phase: the 7.5mol/L sulphuric acid soln: 27.5wt% hydrogen peroxide solution=1:0.9:0.4, use this three-phase mixed solution that the water that extracts gained is carried out single-stage and wash titanium 6 times, survey the content of titanium in the 6th surplus liquid, the volume ratio of at every turn washing the used three-phase mixed solution of titanium operation and water is 1:1.
Described back extraction operation comprises:
Use certain density alkali lye, for example in the residue organic phase of sodium hydroxide solution gained from extraction process with the scandium back extraction to alkali lye, concentration of lye is smooth can guarantee back extraction, phase-splitting is rapid, no three-phase is standard.
Described press filtration operation comprises:
Adopting model is the press filtration of XYMZB60/1000-1k Reinforced Polypropylene chamber filter press.
According to extraction recited above → wash titanium → back extraction → press filtration operation, the organic phase that adopts uncured sodium to handle reclaims scandium from titanium dioxide wastewater earlier, then, adopt similarity condition, with the organic phase after handling through sodium sulfide solution, for example the organic phase of the alternative uncured sodium solution processing of the organic phase of embodiment 1 or embodiment 2 gained repeats above-mentioned technology.Repeat respectively 3 times, average, concrete outcome sees Table 1.
The effect comparison of organic phase in the scandium extraction process that table 1 warp or uncured sodium are handled
As seen from the above table, after employing the inventive method was handled, namely organic phase was handled through sodium sulfide solution, and after acidifying, washing, the percentage extraction of scandium improves greatly, has improved about 35%; The elute effect of titanium is more abundant, and titanium content reduces greatly in the raffinate; The concentration of used alkali lye reduces in the back extraction operation, and phase-splitting is easier to be faster, and the back extraction thing reduces, and product purity improves; Obtain after the press filtration that the content of scandium improves greatly in the filter cake, bring up to 4.0wt% from 0.3wt%.This shows, adopt the recycle method of the employed organic phase of extracting scandium of the present invention, can improve organic performance of described organic phase, prolong it and recycle the cycle, not only saved the production time, also reduced manufacturing cost.
The above only is the preferred embodiments of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in the scope that does not break away from technical solution of the present invention, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (10)
1. the recycle method of the employed organic phase of extracting scandium, it is characterized in that, this method comprises the steps: to add sodium sulfide solution in described organic phase, mix, after the phase-splitting, discharge water, in the residue organic phase, add sulphuric acid soln, after the organic phase after the acidifying washes with water, use it for extracting scandium again.
2. method according to claim 1 is characterized in that, the concentration of described sodium sulfide solution is 0.1-1 weight %.
3. method according to claim 1 is characterized in that, the volume ratio of described organic phase and sodium sulfide solution is 1:0.1-1:10.
4. method according to claim 1 is characterized in that, described organic phase and sodium sulfide solution mixing time are 10-60 minute.
5. method according to claim 1 is characterized in that, described sodium sulfide solution is before being added to described organic phase, earlier through ageing 8-72 hour.
6. method according to claim 5 is characterized in that, described digestion time is 24 hours.
7. method according to claim 6 is characterized in that, described ageing temperature is room temperature.
8. method according to claim 1 is characterized in that, also comprises the steps: before described sodium sulfide solution is added to described organic phase, and keeping organic phase is alkalescence.
9. method according to claim 1 is characterized in that, the concentration of described sulphuric acid soln is 1-10mol/L.
10. method according to claim 1 is characterized in that, the volume ratio of described residue organic phase and sulphuric acid soln is 1:0.1-1:10.
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| CN105502551A (en) * | 2016-01-12 | 2016-04-20 | 四川天齐锂业股份有限公司 | Technology for recycling lithium from industrial wastewater |
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