CN1706973A - Zinc powder reduction process of preparing europium-enriched solution - Google Patents
Zinc powder reduction process of preparing europium-enriched solution Download PDFInfo
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- CN1706973A CN1706973A CNA2004100596196A CN200410059619A CN1706973A CN 1706973 A CN1706973 A CN 1706973A CN A2004100596196 A CNA2004100596196 A CN A2004100596196A CN 200410059619 A CN200410059619 A CN 200410059619A CN 1706973 A CN1706973 A CN 1706973A
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Abstract
The present invention provides relates to the preparation of europium-enriched solution, and is especially zinc powder reduction-extraction process for preparing fluorescent europium oxide in wet metallurgical technology. The present invention features that 3-5 reducing reaction tanks are connected serially to form 3-5 independent and correlated continuous reaction regions, and sold-liquid countercurrent process is adopted to make excessive zinc powder and low-europium Sm-Eu-Gd solution react fully, so as to reach the aims of lowering the Zn ion content in Eu-enriching solution and the europium oxide content in Sm-Gd enriching solution, raising the yield of europium oxide, lowering the consumption of zinc powder, hydrochloric acid, etc and lowering production cost.
Description
The technical field is as follows:
the invention belongs to the field of hydrometallurgy, and relates to a zinc powder reduction method for a samarium-europium-gadolinium enriched material in a fluorescent grade europium oxide preparation process.
Secondly, the prior art:
in the process of extracting fluorescent grade europium oxide from samarium-europium-gadolinium enriched material, the key procedure is to prepare a europium-rich solution. At present, reduction-extraction methods, reduction-alkalinity methods and electrolytic reduction methods are mainly available, and the reduction-extraction method is the most widely used method. The original working procedure is that samarium europium gadolinium feed liquid, magnesium sulfate and zinc powder are mixed according to a certain proportion and are respectively added into reduction reaction tanks which independently run, and through single-stage reaction, the zinc powder reduces trivalent europium ions into divalent europium ions, and the reaction equation of the zinc powder reducing the trivalent europium ions into the divalent europium ions is carried out according to the formula (1):
the reaction of divalent europium ion with sulfate radical to produce stable europium sulfate, the reaction of divalent europium ion with sulfate radical proceeds according to the following equation (2):
after precipitation, the precipitate in each reduction reaction tank is added into a vacuum filter and filtered, and filter cakes are europium sulfate and excessive zinc powder, and the europium oxide content (Eu) in the filter cakes2O3/Σ REO) is more than or equal to 93%; the filtrate is a low europium samarium europium gadolinium solution with europium oxide content (Eu)2O3The/sigma REO) is less than or equal to 0.2 percent. In the reaction process, the ratio of the actual addition amount of zinc powder to the content of europium oxide in the rich samarium europium gadolinium is 1: 1(W/W), in order to ensure that trivalent europium ions have higher reduction rate, the addition amount of zinc powder is 2-4 times of the theoretical amount, excessive zinc powder which is not fully utilized by reaction enters a filter cake after being filtered along with the precipitation of europium sulfate, enters a dissolution reaction tank together, and also participates in the reaction in the dissolution process of hydrochloric acid and hydrogen peroxide to form ZnCI2Into a europium-rich solution.
Dissolving europium sulfate precipitate by hydrochloric acid and hydrogen peroxide according to the following reaction equation (3):
the zinc powder participates in hydrochloric acid and hydrogen peroxide to dissolve europium sulfate precipitate, and the reaction is carried out according to the following reaction equation (4):
the excessive zinc powder wastes the zinc powder, increases the consumption of hydrochloric acid and hydrogen peroxide, and increases the content of zinc ions in the europium-rich solution, thereby increasing the difficulty of the reprocessing process of the europium-rich solution and the production cost.
The flow diagram of the crude zinc powder reduction process is shown in figure 1.
Thirdly, the invention aims to:
the consumption of zinc powder is reduced, the consumption of chemical reagents such as hydrochloric acid, hydrogen peroxide and the like which are consumed by the increase of the consumption of the zinc powder is reduced, the yield of europium oxide is improved, and the production cost for preparing the europium-rich solution is reduced.
Fourthly, the technical scheme is as follows:
n (3 is less than or equal to N is less than or equal to 5) reduction reaction tanks which originally run independently are communicated in series with each other (through a pipeline and a centrifugal pump) to form a N (3 is less than or equal to N is less than or equal to 5) stage reduction reaction zone, a solid-liquid mixed phase (europium sulfate, zinc powder and low-europium samarium-europium gadolinium solution) pumped by a next stage and a liquid phase (samarium-europium-gadolinium and magnesium sulfate solution) self-fed by a previous stage are reduced in the reaction zone, so that excessive zinc powder continuously and sufficiently participates in the reaction, when europium sulfate crystals generated in the next stage of reaction zone are transferred upwards along with the solid-liquid mixed phase, the europium sulfate crystals can be used as seed crystals in the reduction reaction tank of the current stage and are subjected to reduction reaction with the liquid phase transferred in the previous stage of reaction zone, so that fine europium sulfate crystals further grow up and finally become substances convenient for realizing solid-liquid separation, and the solid-liquid content of the samarium-gadolinium solution is lower and, final content (Eu)2O3The volume of the concentrated samarium solution is less than 0.1 percent; zn in europium-rich solution+The content (Zn/Zn + REO) is less than 2 percent.
The process is realized as follows: firstly, adding samarium europium gadolinium enriched material liquid 2 and magnesium sulfate 1 in batches in a tank A of a first-stage reduction reaction zone, simultaneously adding zinc powder 3 in batches in a tank D of a last-stage reduction reaction zone, then transferring the solid-liquid mixture 4 generated in the tank B in the second-stage reduction reaction area into the tank A to be stirred and mixed with the feed liquid 2 and the magnesium sulfate 1, fully performing reduction reaction on trivalent europium in the samarium-europium-gadolinium feed liquid 2 and excessive zinc powder in the solid-liquid mixture 4 in the tank B, reacting generated divalent europium ions with the magnesium sulfate 1 to generate europium sulfate 6, precipitating and clarifying, feeding the solid-liquid mixed phase 4 into a vacuum filter E for filtering, transferring the supernatant (low-europium samarium europium gadolinium solution) 5 into the B tank to continuously react with the solid-liquid mixed phase 4 transferred from the reduction reaction tank C so as to reduce the surplus amount of zinc powder in the solid-liquid mixed phase 4 in the reduction reaction tank B; fresh zinc powder 3 added into the reduction reaction tank D and the supernatant 5 transferred from the tank C are stirred, mixed and subjected to reduction reaction, and the clarified samarium-gadolinium enriched solution 11 is transferred to the next working procedure, at which time the europium oxide content in the samarium-gadolinium enriched solution 11 can be reduced to (Eu)2O3V. REO)<0.10%. And the solid-liquid mixture 4 precipitated in the tank A is filtered by a vacuum filter E, the filtrate is a low-europium samarium europium gadolinium solution 10, the low-europium samarium europium gadolinium solution and a supernatant 5 formed in the tank A are transferred to a tank B to continuously participate in the reaction, and a filter cake is a solid phase 6 (europium sulfate precipitate and unreacted excessive zinc powder), the solid phase 6, the hydrogen peroxide 8 and industrial hydrochloric acid 7 are added into a dissolution reaction tank F together, a europium-rich solution 9 is generated after the reaction, and the next procedure is carried out for standby.
The schematic flow chart of the zinc powder reduction process after the invention is shown in figure 2.
Fifthly, accompanying drawing explanation:
FIG. 1 is a schematic diagram of a crude zinc powder reduction process flow;
FIG. 2 is a schematic process flow diagram of the present invention.
Wherein: 1: magnesium sulfate, 2: feed liquid (samarium-europium-gadolinium enriched solution), 3: zinc powder, 4: solid-liquid mixed phase, 5: supernatant (low-europium samarium europium gadolinium solution), 6: solid phase-filter cake (europium sulfate precipitate + zinc powder), 7: industrial hydrochloric acid, 8: hydrogen peroxide, 9: europium-rich solution, 10: filtrate (low europium samarium europium gadolinium solution), 11, samarium gadolinium enriched solution,
A. B, C, D … … N is the code of the reduction reaction tank,
E is the code of the vacuum filter,
F is the code of a dissolution reaction tank,
2- (c) -: a solid phase transfer route participating in the reaction,
: liquid phase transfer route participating in reaction
… - - - …: solid-liquid mixed phase transfer route participating in reaction
Sixthly, the invention has the positive effects that:
the solid-liquid separation is convenient to realize, the europium oxide content in the samarium-gadolinium solution is favorably reduced, and the yield of the europium oxide is improved. In industrial production, the rich europium solution of samarium europium gadolinium in the samarium europium gadolinium solution prepared by the technology is used for zinc powder reduction, the europium oxide content in the samarium gadolinium solution can be reduced to (Eu2O3/TREO)<0.1%, the zinc powder consumption is reduced by 65% compared with that before the technology is used, meanwhile, the consumption of chemical reagents is reduced, and a large amount of hydrochloric acid can be saved annually.
Seventhly, embodiment:
on a production line for producing 30 tons of fluorescent europium oxide in the year, four original reduction reaction tanks are sequentially connected in series through pipelines and centrifugal pumps to form a four-stage continuous reaction interval, and a solid-phase and liquid-phase countercurrent reduction reaction process is implemented.
In the first stage reduction reaction zone A tank (volume 3 m)3) Adding 2.0m3Samarium europium gadolinium enriched material liquid 2[ rare earth concentration of material liquid 100-250 g/l, acidity [ H]+]In the range of 0.2N to pH 4, europium oxide content (Eu)2O36-12% for/∑ REO)]And 50-210 kg of magnesium sulfate heptahydrate 1; then the second-stage reduction reaction zone B tank is fully reacted and precipitatedAnd transferring the solid-liquid mixed phase 4 at the bottom to a tank A in the first-stage reaction zone by using a centrifugal pump, starting a stirrer to react for 0.5-3 hours, and clarifying for 1-12 hours. Putting the europium sulfate precipitate 6 at the bottom of the tank A in the first-stage reaction zone into a vacuum filter E in a self-flowing mode, and performing vacuum filtration to obtain a filter cake for later use; transferring supernatant 5 generated in the first-stage reaction zone into a tank B of a second-stage reaction zone in a self-flowing mode, carrying out stirring reaction for 0.5-3 hours with a solid-liquid mixed phase 4 transferred from a tank C of a third-stage reaction zone by using a centrifugal pump, clarifying for 1-12 hours, and transferring the supernatant 5 in the tank B of the second-stage reaction zone into a tank C of the third-stage reaction zone; similarly, in the third-stage reaction zone tank C, the supernatant 5 transferred from the second-stage tank B and the solid-liquid mixed phase 4 transferred from the fourth-stage tank D are stirred to react for 0.5 to 3 hours, clarified for 1 to 12 hours, and transferred to the fourth-stage tank D; in the fourth stage D tank addAdding 4.2-21 kg of zinc powder 3, stirring and reacting for 0.5-3 hours, clarifying for 1-12 hours, and transferring the supernatant 5 in the tank D to the next procedure. Adding filter cake (europium sulfate precipitate and zinc powder) obtained from vacuum filter E into dissolution reaction tank F, adding industrial hydrochloric acid 7 and industrial hydrogen peroxide 8, and dissolving to obtain europium-rich solution 9 with concentration of 20-50 g/L and europium oxide content (Eu)2O3And/sigma REO) is more than or equal to 93 percent. Before the technology is implemented, the current similar prior art is adopted to carry out zinc powder reduction on the rich samarium europium gadolinium, the ratio of the addition amount of the zinc powder to the content of europium oxide in the rich samarium europium gadolinium is 1: 1, the annual consumption of the zinc powder is 30 tons, and finally the rich samarium gadolinium contains europium oxide (Eu)2O3The/sigma REO) is less than or equal to 0.2 percent, and a large amount of surplus zinc powder is not fully utilized and is dissolved by hydrochloric acid and hydrogen peroxide along with the europium sulfate precipitation, so that the zinc powder is wasted, the consumption of the hydrochloric acid and the hydrogen peroxide is increased, the content of zinc ions in the dissolved europium-rich solution is high, and the difficulty and the cost of the reprocessing of the europium-rich solution are increased. After the technology is implemented on a production line, the ratio of the addition amount of the zinc powder to the content of europium oxide in the rich samarium-europium-gadolinium product is reduced to 0.35: 1, the annual consumption of the zinc powder is only 10.5 tons, and finally the europium oxide content in the rich samarium-gadolinium product is reduced to (Eu)2O3The/sigma REO) is less than 0.1 percent, and 70 tons of hydrochloric acid are saved each year.
Claims (8)
1. A process for preparing europium-enriched solution features that the reaction regions are serially connected to form a whole, and the reduction reaction is carried out discontinuously and independently in each region and continuously step by step in multi-stage region. Solid-phase (including liquid-phase) substances and liquid-phase substances generated in each interval operate in a mutually countercurrent mass transfer mode outside the interval; adding feed liquid and chemical reagents from one end of a multi-stage reaction zone in batches according to the proportion, stirring and mixing the feed liquid and the chemical reagents with a solid-liquid mixed phase transferred from a lower-stage zone, reacting, and transferring the solid-liquid mixed phase in a reaction product to a filter; the liquid phase in the reaction product is transferred to the other end step by step, and is mixed with the solid-liquid mixed phase transferred from the next stage in each interval during the transfer and reacts; and zinc powder is added in batches from the other end according to a certain proportion, and is stirred and mixed with the liquid phase transferred from the previous stage to react, the generated solid-liquid mixed phase is transferred to the previous stage, and the supernatant is the samarium-gadolinium enriched solution and is transferred to the next process.
2. A process for preparing europium-enriched solution features that the filtrate generated by filter is added to the second-stage reaction region for further reaction.
3. The process of claim 1, wherein said plurality of stages is three, four or five stages.
4. The process of claim 1, wherein said feed solution is a rare earth enriched solution, particularly a rich samarium europium gadolinium solution.
5. The process of claim 1, wherein the chemical reagent is magnesium sulfate solution.
6. The process of claim 1, wherein said solid phase material is a mixture of europium sulfate precipitate and zinc powder, and said liquid phase material is a low europium samarium europium gadolinium solution.
7. A process according to claim 1 or claim 5, characterised in that the final europium oxide (Eu) containing solution of the samarium gadolinium concentrate2O3/∑REO)＜0.1％。
8. The process according to claim 2, characterized in that said filtrate is a low europium samarium europium gadolinium solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337405A (en) * | 2011-10-28 | 2012-02-01 | 包头市京瑞新材料有限公司 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
| CN105420493A (en) * | 2015-12-28 | 2016-03-23 | 云南云铜锌业股份有限公司 | Wet-metallurgy continuous reaction kettle equipment |
| CN107326200A (en) * | 2017-05-25 | 2017-11-07 | 广东省稀有金属研究所 | The method of europium is enriched with a kind of chloride solution from sm-eu-gd |
| WO2017181541A3 (en) * | 2016-04-20 | 2017-11-30 | 广东省稀有金属研究所 | Method for decomposing europium(ii) sulfate |
| CN115072759A (en) * | 2022-05-05 | 2022-09-20 | 龙南京利有色金属有限责任公司 | Method for recovering high-purity europium oxide from rare earth fluorescent powder waste |
-
2004
- 2004-06-12 CN CNB2004100596196A patent/CN100485056C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337405A (en) * | 2011-10-28 | 2012-02-01 | 包头市京瑞新材料有限公司 | Method for applying baotite mixed carbonate-rare earth precipitation wastewater in precipitation of europium (II) sulfate |
| CN105420493A (en) * | 2015-12-28 | 2016-03-23 | 云南云铜锌业股份有限公司 | Wet-metallurgy continuous reaction kettle equipment |
| WO2017181541A3 (en) * | 2016-04-20 | 2017-11-30 | 广东省稀有金属研究所 | Method for decomposing europium(ii) sulfate |
| CN107326200A (en) * | 2017-05-25 | 2017-11-07 | 广东省稀有金属研究所 | The method of europium is enriched with a kind of chloride solution from sm-eu-gd |
| CN107326200B (en) * | 2017-05-25 | 2019-05-31 | 广东省稀有金属研究所 | A method of it being enriched with europium from sm-eu-gd chloride solution |
| CN115072759A (en) * | 2022-05-05 | 2022-09-20 | 龙南京利有色金属有限责任公司 | Method for recovering high-purity europium oxide from rare earth fluorescent powder waste |
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| CN100485056C (en) | 2009-05-06 |
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Granted publication date: 20090506 Termination date: 20170612 |