CN102976525B - Method for treating and recycling rare earth oxalate precipitation mother solution - Google Patents
Method for treating and recycling rare earth oxalate precipitation mother solution Download PDFInfo
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- CN102976525B CN102976525B CN2012105323096A CN201210532309A CN102976525B CN 102976525 B CN102976525 B CN 102976525B CN 2012105323096 A CN2012105323096 A CN 2012105323096A CN 201210532309 A CN201210532309 A CN 201210532309A CN 102976525 B CN102976525 B CN 102976525B
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Abstract
The invention discloses a method for treating and recycling a rare earth oxalate precipitation mother solution. The method comprises the steps of: adding a corresponding high-purity rare earth solution or high-purity rare earth carbonate into the precipitation mother solution to separate oxalic acid out in the form of rare earth oxalate precipitates, wherein the filtered mother solution can be directly used for preparing hydrochloric acid solutions of different concentrations to serve as refluxing acid or washing acid for extraction separation of rare earth elements, so that water and hydrochloric acid in the mother solution can be recycled totally; and returning the filtered rare earth oxalate precipitates to a rare earth precipitation process to serve as crystal seeds which can be added in a refined oxalic acid dissolution process or in a precipitation barrel before precipitation starts respectively, and ageing, washing, filtering and calcining the precipitates to obtain a high-purity rare earth product, thereby recycling originally non-precipitated rare earth and subsequently added rare earth completely. According to the invention, the comprehensive recycling problem of the rare earth oxalate precipitation mother solution of a rare earth separation plant is solved, and the method is simple and feasible, is suitable for recycling all rare earth oxalate precipitation mother solutions, and has a wide application prospect.
Description
Technical field
The invention belongs to rare-earth wet method metallurgy and Industrial Wastewater Treatment field, mainly solve rare-earth products, especially high-purity rare-earth is produced the recycle problem of mesoxalic acid rare-earth precipitation mother liquor, in can making mother liquor under the prerequisite that guarantees the high purity rare-earth products quality of production, most water, oxalic acid, hydrochloric acid and rare earths obtains recycle, not only saved cost but also reduced wastewater discharge.
Technical background
Rare earth feed liquid after rare earth extraction separates adopts the precipitator method to make it to separate with acid with a large amount of inorganic salt with water usually.Be settled out rare earth element and generally all adopt oxalate precipitation method from high purity single rare earth solution.In the rare earth oxalate precipitation process,, for the deposition rate that guarantees rare earth with to the separation selectivity of foreign ion, need to add excessive oxalic acid.Therefore, mainly contain excessive oxalic acid and the hydrochloric acid of higher concentration (1-3mol/L) in precipitation waste water, do not precipitate on a small quantity in addition rare earth element completely.Therefore, a large amount of oxalic acid precipitation waste water be can produce in high purity rare-earth products production process, considerable oxalic acid and hydrochloric acid wherein contained, and a small amount of rare earth.Let alone discharging and not only wasted industrial chemicals, and pollute the environment.Early stage treatment process is generally to make unprecipitated rare earth continue form precipitation with oxalic acid and be recycled with the alkali neutralization, and remaining acid and water discharge after being neutralized to neutrality, and wastewater discharge is large, and acid and water are not utilized effectively.In recent years, country pays much attention to the environment protection of Rare Earth Production enterprise, and each research unit has has also in succession researched and developed some and processed the method for comprehensive utilization of oxalic acid precipitation waste water.Representative technology comprises extraction process, membrane separation process, ion exchange method and distillation under vacuum.These methods respectively have advantages and disadvantages separately, for example:, although adopt neutralization method can eliminate the impact of acid on environment, consumed alkali, also will discharge a large amount of brine wastes.Adopt extraction process, can extract oxalic acid, but under acidic conditions, the extraction efficiency of oxalic acid is low, but also will consider with suitable reagent, the oxalic acid of extraction to be got off from the organic phase back extraction, the process more complicated.Distillation or distillation under vacuum can reclaim acid, water and rare earth wherein, but energy consumption is large, and be also high to equipment requirements.The present invention proposes a kind ofly with the simple precipitation method, to process precipitation waste water in rare earth oxalate precipitation waste water, especially high purity Rare Earth Production process, to reach the purpose that all elements can fine recycling.
Summary of the invention
The present invention be directed to the state of prior art, a kind of simple rare earth oxalate precipitation wastewater treatment recovery method is provided, can fully reclaim all substances in waste water, make it to obtain recycle.The method has not only been considered the recovery of resource, but also makes it as far as possible the high-purity rare-earth production process for requirements at the higher level.
Processing step of the present invention is as follows:
Return oxalate in heavy waste water with corresponding high purity rare earth feed liquid or carbonated rare earth, the amount of substance of the rare earth that adds be the solution mesoxalic acid amount of substance 0.3-0.8 doubly, with the concentration of oxalic acid in mother liquor after guaranteeing to process not higher than 0.04mol/L; With the suspended substance filtering separation, after filtering, the rare earth oxalate of gained enters into the oxalic acid solution of normal rare earth oxalate precipitation operation or the bed material that precipitates with dilute hydrochloric acid mixed preparing rare earth oxalate, is recycled utilization in the post precipitation operation, produces high pure rare earth product; Through rare-earth precipitation and the mother liquor after filtering add concentrated hydrochloric acid and be used for the back extraction of corresponding rare earth element extracted organic phase, the required hydrochloric acid content that adds so that the concentration of hydrochloric acid of solution be as the criterion at 3-5.5 mol/L.Described high purity rare earth feed liquid or carbonated rare earth can be high-purity yttrium feed liquid or high purity carbonic acid yttrium solid.
The invention has the beneficial effects as follows: present method is simple, most materials in mother liquor of precipitation of ammonium is fully utilized and do not affect the production of high purity rare earth, and economic and social benefit is remarkable.
Description of drawings
Fig. 1 is the process flow sheet of invention.
Embodiment
Embodiment 1:
Get respectively the supernatant liquor after 100ml high-purity yttrium oxalic acid precipitation, add the high-purity yttrium feed liquid (Y of different volumes
2O
3/ REO 〉=99.999%, 5NY), have obvious white precipitate to produce, and stirs the ageing certain hour, filters, and gets filtrate and analyze, according to residual rate or the clearance of the oxalate cubage oxalate in solution before and after precipitation.The results are shown in Table 1.
From the results shown in Table 1, along with the increase of 5NY feed liquid consumption, the precipitation capacity of the yttrium oxalate of generation increases, the corresponding minimizing of solution oxalate content, and the clearance of oxalate increases.During beginning, the oxalic acid clearance that causes that adds of every milliliter of feed liquid increases comparatively fast, less to 6 milliliters of later increasing degrees, clearance is more than 70%, oxalate concentration can be reduced to below 0.05 mol/L substantially, when reinforced to 9 milliliters, oxalate concentration can be reduced to below 0.04 mol/L substantially, is 0.034 mol/L.At this moment, the add-on of yttrium is 0.64 (theoretical ratio is 0.67) with the ratio of the amount of substance of initial mother liquor mesoxalic acid amount.
The membership that adds of feed liquid makes the decline to some extent of acidity, but sour total amount is constant.Major impurity content has rising by a small margin, and reason is also to contain these impurity in the 5NY feed liquid.Therefore, the membership that adds of 5NY feed liquid increases the content of impurity in solution, but does not affect the subsequent applications requirement., such as iron level, to pass through iron removal step as the rare earth feed liquid after sour regurgitation back extraction rare earth, on the not impact of back precipitation.Rare earth in solution together enters strip liquor, is recovered together in subsequent process.
The dosage of table 1 yttrium feed liquid and mother liquor of precipitation of ammonium mesoxalic acid are removed the relation of efficiency and foreign matter content
| V 5NY(ml) | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| [H +](mol/L) | 1.825 | 1.845 | 1.823 | 1.810 | 1.728 | 1.777 | 1.741 | 1.718 | 1.691 |
| [C 2O 4 2-](mol/L) | 0.125 | 0.117 | 0.095 | 0.076 | 0.052 | 0.047 | 0.400 | 0.034 | 0.027 |
| Oxalic acid clearance (%) | 24.76 | 29.64 | 42.71 | 54.04 | 68.61 | 71.63 | 75.90 | 79.8 | 83.6 |
| Fe 2O 3(mg/L) | ? | 0.9 | ? | 1.55 | ? | 1.40 | ? | 1.65 | ? |
| SiO 2(mg/L) | ? | 1.9 | ? | 2.70 | ? | 2.20 | ? | 3.45 | ? |
| CaO(mg/L) | ? | 3.8 | ? | 9.3 | ? | 8.45 | ? | 11.35 | ? |
| Al 2O 3(mg/L) | ? | 0.20 | ? | 1.25 | ? | 0.85 | ? | 0.90 | ? |
| Y 2O 3(mg/L) | ? | 465.7 | ? | 939.5 | ? | 2453 | ? | 3483 | ? |
Annotate: acidity standard base (SB) titration measuring, oxalate adopts the potassium permanganate volumetry, other ultimate analysis using plasma spectroscopic analysis (ICP), the concentration of 5NY feed liquid is 1.2mol/L, the concentration of oxalic acid in initial mother liquor is 0.166mol/L: acidity is 1.893mol/L.
Embodiment 2:
Carry out back extraction experiment through processing in various degree the solution preparation back extraction acid (hydrochloric acid soln of 5mol/l) of the different oxalic acid content (concentration is from 0.027-0.16mol/l) that obtain with the P507-kerosene organic phase of load high-purity yttrium with above-mentioned, be in a ratio of O/W=1:4.Result shows, although the hydrochloric acid of untreated oxalic acid precipitation mother liquor preparation can not produce obvious white precipitate while being directly used in yttrium in back extraction P507-kerosene organic phase, but the rare earth analysis in solution is affected, during with the EDTA titration, the terminal hangover is serious, and the also obviously minimizing of the concentration of oxalic acid of aqueous phase, generally below 0.04mol/l.Back extraction exerts an influence to rare earth in the existence meeting of proof oxalic acid, and a part of oxalic acid can enter into organic phase and affect the later use of organic phase.Along with the increase of oxalic acid clearance, this impact reduces.While arriving residual concentration of oxalic acid lower than 0.05mol/l, this impact disappears substantially.Therefore,, if will prepare sour regurgitation with mother liquor of precipitation of ammonium, need in advance oxalic acid wherein be reduced to below finite concentration.According to the above results, the acid solution mesoxalic acid concentration after we determine to process preferably can be lower than 0.04mol/L.
Embodiment 3:
Get respectively the supernatant liquor after 100ml high-purity yttrium oxalic acid precipitation, add the high purity carbonic acid yttrium solid (Y of Different Weight
2O
3/ REO 〉=99.999%, contain yttrium oxide 40% left and right, by 5NY feed liquid and reaction of sodium bicarbonate, generate the yttrium carbonate precipitation, filter after aging crystallization, oven dry under 50 ℃), both contact yttrium carbonates dissolve immediately, produce carbon dioxide, along with the increase of meltage, solution starts to occur muddy, forms the yttrium oxalate precipitation.Filter after the ageing certain hour, analyze filtrate.Residual rate or clearance according to the oxalate cubage oxalate in solution before and after precipitation, the results are shown in Table 2.Along with the increase of yttrium carbonate consumption, the precipitation capacity of the yttrium oxalate of generation is along with increase, the corresponding minimizing of solution oxalate content, and acidity also reduces thereupon.But concentration reduces and is not obvious, still can keep the above acidity of 1 mol/L; Major impurity content does not have wide variation; But when the oxalate clearance reached 90%, the removal effect to oxalate that adds that continues of yttrium carbonate started to reduce, and the ascensional range of clearance tends towards stability.
Table 2 yttrium carbonate dissolving precipitated method is removed the oxalate interpretation
| W 5NYCO3(g) | 0.5 | 1 | 2 | 3 | 4 |
| [H +](mol/L) | 1.6711 | 1.6521 | 1.4967 | 1.3279 | 1.2345 |
| [C 2O 4 2-](mol/L) | 0.1222 | 0.0911 | 0.0340 | 0.0183 | 0.0152 |
| Oxalic acid clearance (%) | 26.39 | 45.12 | 79.52 | 88.98 | 90.84 |
| Fe 2O 3(mg/L) | 1.2 | 1.1 | 1.0 | 1.25 | 1.35 |
| SiO 2(mg/L) | 1.8 | 3.2 | 2.0 | 1.65 | 2.00 |
| CaO(mg/L) | 13.6 | 13.1 | 13.1 | 22.2 | 16.1 |
| Al 2O 3(mg/L) | 0.20 | ? | ? | 0.45 | 0.34 |
| Y 2O 3(mg/L) | 303 | 479 | 1518.3 | 4802 | 10100 |
As can be seen from Table 2, the oxalic acid content in solution is dropped to below 0.04 mol/L, the add-on of yttrium carbonate is 2 grams (approximately 0.007 moles).With the ratio of the amount of substance of initial oxalic acid amount in solution be 0.42, the yttrium concentration in balanced solution is in 1500 mg/L left and right.Compare with the treatment effect with pure feed liquid, little, the residual rare earth content of the consumption of yttrium is also little, proves that it removes the better effects if of oxalic acid.But the concentration of hydrochloric acid has some declines.
Embodiment 4:
Get the supernatant liquor after 800ml high-purity yttrium oxalic acid precipitation, add the high-purity yttrium feed liquid (Y of 80ml
2O
3/ REO 〉=99.999%, 5NY), produce white yttrium oxalate precipitation, stirs the ageing certain hour, filter, collecting precipitation, natural air drying is to constant weight, precipitation is loaded in crucible, in 850 ℃ of lower calcinations, is cooled to room temperature after one hour, the oxide compound after calcination is weighed and mass analysis.Result is: burn mistake rate 63.9%, chloride content 981.7 ug/g, 7.59 microns of meta particle diameters.As seen high-purity yttrium removes that oxalic acid obtains, and to be deposited in unwashed situation chloride content higher, burns the mistake rate normal, and granularity is compared also larger with the product on production line, badly directly as product, sells.
Embodiment 5:
Get the supernatant liquor after 800ml high-purity yttrium oxalic acid precipitation, slowly add the high purity carbonic acid yttrium solid (Y of 33.5g under agitation condition
2O
3/ REO 〉=99.999%, contain yttrium oxide 40% left and right, by 5NY feed liquid and reaction of sodium bicarbonate, generate the yttrium carbonate precipitation, filter after aging crystallization, oven dry under 50 ℃), both contact yttrium carbonates dissolve immediately, produce carbon dioxide, along with the increase of meltage, solution starts to occur muddy, forms the yttrium oxalate precipitation.Filter after the ageing certain hour, collecting precipitation, natural air drying, to constant weight, are loaded on precipitation in crucible, and the insulation calcination is cooled to room temperature after one hour under 850 ℃, and the oxide compound after calcination is weighed and mass analysis.Result is: burn mistake rate 63.9%, chloride content 309.7 ug/g, 5.32 microns of meta particle diameters.As seen the precipitation burning mistake rate of yttrium carbonate removal oxalic acid is normal, and chloride content is not high in unwashed situation, and granularity is little than the precipitation of high-purity yttrium removal oxalic acid, and is close with the granularity of Industrial products.But do not reach the specification of quality of direct marketing yet.
Embodiment 6:
Take 20g oxalic acid with 80 ℃ of lower hot water dissolvings of 100ml, add the air-dry high-purity yttrium to constant weight of 0.3g to remove the crystal seed of the yttrium oxalate precipitation of oxalic acid as precipitation, under agitation, slowly add the approximately high-purity yttrium (Y of 1mol/L of 100ml
2O
3/ REO 〉=99.999%, 5NY), stir ageing, filters, and with deionized water washing and precipitating to filtrate, with silver nitrate solution, checks without till muddy the appearance.Collecting precipitation, natural air drying, to constant weight, are loaded on precipitation in crucible, in 850 ℃ of lower insulation calcinations, are cooled to room temperature after one hour, and the oxide compound after calcination is weighed and mass analysis.Result is: burn mistake rate 53.3%, chloride content 60.1 ug/g, 4.87 microns of meta particle diameters.As seen burn the mistake rate less, chloride content is low, and granularity and Industrial products are close, and therefore, the yttrium oxalate precipitation that high-purity yttrium removal oxalic acid obtains can be used as the crystal seed of yttrium oxalate precipitation, and can not exert an influence to end product quality, can return to use.
Embodiment 7:
Take 20g oxalic acid with 80 ℃ of hot water dissolvings of 100ml, add the air-dry yttrium carbonate to constant weight of 0.3g to remove the crystal seed of the yttrium oxalate precipitation of oxalic acid as precipitation, under agitation, add the approximately high-purity yttrium (Y of 1mol/L of 100ml
2O
3/ REO 〉=99.999%, 5NY), stir ageing, filters, and with deionized water washing and precipitating to filtrate, with silver nitrate solution, checks without till muddy the appearance.Collecting precipitation, natural air drying, to constant weight, are loaded on precipitation in crucible, and the insulation calcination is cooled to room temperature after one hour under 850 ℃, and the oxide compound after calcination is weighed and mass analysis.Result is: burn mistake rate 53.3%, chloride content 78.98 ug/g, 4.50 microns of meta particle diameters.As seen burn the mistake rate less, chloride content is low, and granularity and Industrial products are close, and therefore, the yttrium oxalate precipitation that yttrium carbonate removal oxalic acid obtains can be used as the crystal seed of yttrium oxalate precipitation.
Claims (1)
1. a rare earth oxalate mother liquor of precipitation of ammonium is processed recovery method, it is characterized in that:
Return oxalate in heavy mother liquor with high-purity yttrium feed liquid or high purity carbonic acid yttrium solid, the amount of substance of the rare earth that adds be the solution mesoxalic acid amount of substance 0.3-0.8 doubly, with the concentration of oxalic acid in mother liquor after guaranteeing to process not higher than 0.04mol/L; With the suspended substance filtering separation, after filtering, the rare earth oxalate of gained enters into the oxalic acid solution of normal rare earth oxalate precipitation operation or the bed material that precipitates with dilute hydrochloric acid mixed preparing rare earth oxalate, is recycled utilization in the post precipitation operation, produces high pure rare earth product; Through rare-earth precipitation and the mother liquor after filtering add concentrated hydrochloric acid and be used for the back extraction of corresponding rare earth element extracted organic phase, the required hydrochloric acid content that adds so that the concentration of hydrochloric acid of solution be as the criterion at 3-5.5 mol/L;
The purity of described high-purity yttrium feed liquid is Y
2O
3/ REO 〉=99.999%;
Described high purity carbonic acid yttrium solid obtains by following technique: above-mentioned high-purity yttrium feed liquid added reaction of sodium bicarbonate, generates the yttrium carbonate precipitation, filter after aging crystallization, and oven dry under 50 ℃, purity is Y
2O
3/ REO 〉=99.999%, contain yttrium oxide 40% left and right.
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| CN103408091B (en) * | 2013-07-19 | 2015-02-04 | 广州有色金属研究院 | Recovery method of rare earth oxalate precipitation wastewater |
| CN105624403B (en) * | 2014-11-24 | 2018-08-24 | 赣州力赛科新技术有限公司 | A kind of method of comprehensive utilization of spent acid |
| CN105886764B (en) * | 2016-04-15 | 2018-02-06 | 内蒙古科技大学 | From containing ZnCl2SmCl3Solution mesoxalic acid precipitation prepares Sm2O3Method |
| CN106119541B (en) * | 2016-06-23 | 2018-03-27 | 五矿（北京）稀土研究院有限公司 | A kind of method of oxalic acid precipitation rare earth |
| CN106336036A (en) * | 2016-08-29 | 2017-01-18 | 江西稀有金属钨业控股集团有限公司 | Method for recycling oxalic acid and hydrochloric acid in oxalic acid mother liquor |
| CN108342574B (en) * | 2018-04-27 | 2023-08-29 | 广东省富远稀土有限公司 | Countercurrent washing device for rare earth precipitation and method for recycling rare earth oxalic acid precipitation mother liquor and washing liquor by using countercurrent washing device |
| CN109252058A (en) * | 2018-10-19 | 2019-01-22 | 中铝广西国盛稀土开发有限公司 | A kind of method that oxalic acid precipitation RE waste water recycles |
| CN113428962A (en) * | 2021-06-23 | 2021-09-24 | 中国北方稀土（集团）高科技股份有限公司 | Method for removing fluorine and oxalate in ammonium sulfate wastewater |
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| JPH0832554B2 (en) * | 1989-06-16 | 1996-03-29 | 信越化学工業株式会社 | Method for producing rare earth oxide powder |
| CN1016679B (en) * | 1989-12-23 | 1992-05-20 | 江西省科学院 | Extraction of rare-earth elements by circulating oxalic acid |
| CN101723527B (en) * | 2009-11-05 | 2011-08-24 | 漳州师范学院 | recycling method of oxalic acid and hydrochloric acid from hydrochloric acid waste liquid produced by mining rare-earth metal |
| CN101935762A (en) * | 2010-08-25 | 2011-01-05 | 江西明达功能材料有限责任公司 | Method for comprehensively recycling rare earth oxalate precipitate waste liquid |
| CN101979336B (en) * | 2010-09-03 | 2012-03-28 | 江西明达功能材料有限责任公司 | Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant |
| CN102225789A (en) * | 2011-04-15 | 2011-10-26 | 五矿（北京）稀土研究院有限公司 | Washing method of oxalic acid precipitation |
| CN102676853B (en) * | 2012-05-28 | 2013-11-20 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
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