CN101831543B - Process for precipitating rare earth continuously - Google Patents
Process for precipitating rare earth continuously Download PDFInfo
- Publication number
- CN101831543B CN101831543B CN2010101780163A CN201010178016A CN101831543B CN 101831543 B CN101831543 B CN 101831543B CN 2010101780163 A CN2010101780163 A CN 2010101780163A CN 201010178016 A CN201010178016 A CN 201010178016A CN 101831543 B CN101831543 B CN 101831543B
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- rare earth
- surge tank
- reactor drum
- feed
- oxalic acid
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a process for precipitating rare earth continuously. The process for precipitating the rare earth continuously is characterized by comprising the following steps of: continuously filling material liquid and oxalic acid solution precipitator into a reactor in a co-current way; introducing a product generated in the reactor into one of two buffer tanks first, and when the buffer tank is full, introducing the product generated in the reactor into the other buffer tank and absorbing water in the former buffer tank; alternately using the two buffer tanks till the amount of a solid product in one buffer tank is enough, cleaning the buffer tank and drying the buffer tank by pumping to obtain the solid product finally when the other buffer tank continuously receives the product output from the reactor, and thus, realizing the continuous production. In the whole reaction process, the concentration, acidity and temperature of the rare earth at different time stages are basically unchanged, so oxalic acid rare earth with uniform D50 and the ignition rare earth oxide of the oxalic acid rare earth can be obtained. The whole production is a continuous, dynamic and energy-saving flow line process and the production efficiency is high.
Description
Technical field
The present invention relates to a kind of depositing technology of rare earth, belong to hydrometallurgy (hydrometallurgy) technical field.
Background technology
At present traditional rare earth traditional rare earth depositing technology adopts homogeneous phase intermittent type intermediate processing, the degree of supersaturation through control oxalic acid water, the concentration of feed liquid and acidity, and the conditions such as temperature of reaction produce and conform with the rare earth compound that rerum natura requires.But because its production process is in periodical operation, need to begin to heat up in reaction, the reaction end needs cooling, saves the energy inadequately, and takies the PT, and production efficiency is very low.And material moment reaction density and acidity change in the reactor drum are very big, cause size-grade distribution undesirable.Because relative concentration is along with the carrying out of precipitin reaction in the reactor drum, its concentration is more and more lower, and acidity is increasingly high.At the precipitation from homogeneous solution(PFHS) initial stage, because relative concentration is higher, it's the end is past relative acidity, nucleus formation speed is too fast during reaction, and nucleus growth speed is slow excessively, is prone to form too much fine particle this moment and also is prone to form aggregated particle; And precipitation from homogeneous solution(PFHS) latter stage, relative acidity is too high because relative concentration is lower, and nucleus is prone to growth, and it is sub to form too much macrobead.From the deposition angle, traditional rare-earth precipitation has very big defective.
Summary of the invention
The object of the invention is exactly the deficiency to above-mentioned prior art, but provides a kind of production epigranular consistent, energy-conservation, process for precipitating rare earth continuously efficiently.
The technical scheme that the present invention adopts is following:
A kind of process for precipitating rare earth continuously is characterized in that including two surge tanks, and feed liquid, the continuous cocurrent flow of precipitation agent are entered in the reactor drum; The product that generates in the reactor drum is introduced into wherein to said two surge tanks, when this surge tank do full after, the product that reactor drum is generated is connected to another surge tank; And draw the water in the last surge tank, the using by turns of two surge tanks is when solid phase prod is enough measured in surge tank wherein; This surge tank is cleaned; Drain, get final solid phase prod, when a surge tank is cleaned, drains; The product that comes out in the lasting reception of the another surge tank reactor drum is realized uninterrupted continuous production.
The feed acidity of said feed liquid is 0.25～1.25mol/L; Feed concentration is 0.2～1.0mol/L; The oxalic acid solution mass concentration is 10～20%, and the reactor drum interior reaction temperature is 10～90 ℃, and mixing speed is 4～20Hz; The additive volume that adds is 0～5% of a material liquid volume, and the residence time of feed liquid in reactor drum is 0.5～25min.
The feed acidity 0.6mol/l of said feed liquid, feed concentration are 0.8mol/L, material liquid volume 30000L, and 25～35 ℃ of temperature, the additive volume of interpolation is 2% of a material liquid volume.Put no salt solution 150L in the reactor drum earlier, 50～55 ℃ of temperature.The oxalic acid solution mass concentration is 20%, its volume 30000L, 70～80 ℃ of temperature.
Said additive is a polyoxyethylene glycol.
Said feed liquid is rare earth chloride or rare earth nitrate solution.
Said precipitation agent is an oxalic acid aqueous solution.
Beneficial effect of the present invention has:
Adopt the continous way depositing technology: certain feed concentration, acidity, temperature are equal to the degree of supersaturation oxalic acid water of certain temperature and flow in the reactor drum.In the entire reaction course, different time stage concentration, acidity, temperature are constant basically, can produce D
50The relatively rare earth oxalate of uniformity and its calcination thing rare earth oxide, whole production are successive, dynamic, energy-conservation inline process process, and be highly efficient in productivity.According to different parameter, also can produce different rerum natura specification (D
50: product 2～18 μ m).
Embodiment
Below in conjunction with specific embodiment the present invention is done explanation further:
Continuous precipitation device control D
50Method, mainly,, select and control D according to orthogonal experiment design method according to acidity, concentration, oxalic acid degree of supersaturation, temperature of reaction, stirring velocity, precipitation additives dosage and the big controlling factors of the residence time seven of feed liquid
50Parameters optimization.
Embodiment 1:
Common Y+Eu production technique deposition condition:
Feed concentration 0.8mol/L, feed acidity 0.6mol/l, material liquid volume 30000L, 25～35 ℃ of temperature, doping 2%.Put no salt solution 150L in the reactor drum earlier, 50～55 ℃ of temperature.Oxalic acid solution mass concentration 20%, its volume 30000L, 70～80 ℃ of temperature.Mixing speed is 8Hz.
Operating process:
Open oxalic acid water earlier, drive the feed liquid valve again, residence time 18min in the reactor drum, 3000～3500 minutes whole charging time.Make full surge tank earlier, make another surge tank again, when intermittence, draw the water in first surge tank.Thresh and accomplish to have in the surge tank about folding product (REO) 120Kg always, carry out Xian clearly again, drain.
Under this condition, after the oxalate calcination, medium particle diameter D
50=4.8 μ m; Granularity D＜3 μ m account for＜and 5%; Granularity D＞10 μ m account for＜and 1.5%; (D
75-D
25)≤2 μ m, the pine dress compares B.D=0.68g/cm
3, size-grade distribution Q.D=0.25 is normal distribution, specific surface SW=6800cm
2/ g.
And with traditional intermittent type deposition, under identical deposition condition, result: medium particle diameter D
50=4.9 μ m; Granularity D＜3 μ m account for＜and 10%; Granularity D＞10 μ m account for＜and 3%; (D75-D25)≤3.2 μ m, size-grade distribution Q.D=0.35, not really desirable, specific surface SW=6000cm
2/ g.
Embodiment 2:
Y+Eu production technique deposition condition:
Feed concentration 0.8mol/L, feed acidity 1.0mol/l, material liquid volume 30000L, 25～35 ℃ of temperature, doping 1.5%.Put no salt solution 150L in the reactor drum earlier, 55～60 ℃ of temperature.Oxalic acid solution mass concentration 20%, its volume 30000L, 70～80 ℃ of temperature.Mixing speed is 6Hz.
Operating process:
Oxalic acid water, feed liquid valve are opened simultaneously, residence time 18min in the reactor drum, 3000～3500 minutes whole charging time.Make full surge tank earlier, make another surge tank again, when intermittence, draw the water in first surge tank.Thresh and accomplish to have in the surge tank about folding product (REO) 120Kg always, carry out Xian clearly again, drain.
Under this condition, after the oxalate calcination, medium particle diameter D
50=5.2 μ m; Granularity D＜3 μ m account for＜and 5%; Granularity D＞10 μ m account for＜and 1.5%; (D
75-D
25)≤2.2 μ m, loose specific weight B.D=0.70g/cm
3, size-grade distribution Q.D=0.28 is normal distribution, specific surface SW=6650cm
2/ g.
Embodiment 3:
Fine particle Y+Eu production technique deposition condition:
Feed concentration 1.0mol/L, feed acidity 0.25mol/l, doping 4.5%, material liquid volume 30000L, 20～25 ℃ of temperature.Put no salt solution 150L in the reactor drum earlier, 20～25 ℃ of temperature.Oxalic acid solution mass concentration 20%, its volume 45000L, 50～55 ℃ of temperature.Mixing speed is 20Hz.
Operating process:
Open oxalic acid water earlier, drive the feed liquid valve again, no brine valve, residence time 0.5min in the reactor drum, 2600～3000 minutes whole charging time.Make full surge tank earlier, make another surge tank again, when intermittence, draw the water in first surge tank.Thresh and accomplish to have in the surge tank about folding product (REO) 120Kg always, carry out Xian clearly again, drain.
Under this condition, after the oxalate calcination, medium particle diameter D
50=3.0 μ m; Granularity D＜0.8 μ m accounts for＜and 10%; Granularity D＞4.0 μ m account for＜and 10%; (D
75-D
25)≤3.2 μ m.
Embodiment 4:
Coarse particles Y
2O
3The production technique deposition condition:
Feed concentration 0.6mol/L, feed acidity 1.25mol/l, material liquid volume 30000L, 90 ℃ of temperature, not doping.Put no salt solution 250L in the reactor drum earlier, 90 ℃ of temperature.Oxalic acid solution mass concentration 15%, its volume 30000L, 90 ℃ of temperature.Mixing speed is 4Hz.
Operating process:
Drive the feed liquid valve earlier, drive the oxalic acid water valve again, residence time 25min in the reactor drum, 1500～2000 minutes whole charging time.Make full surge tank earlier, make another surge tank again, when intermittence, draw the water in first surge tank.Thresh and accomplish to have in the surge tank about folding product (REO) 100Kg always, carry out Xian clearly again, drain.
Under this condition, after the oxalate calcination, medium particle diameter D
50=16.8 μ m; Granularity D＜12 μ m account for＜and 10%; Granularity D＞20m accounts for＜and 10%; (D
75-D
25)≤3.8 μ m.
Other undeclared part of the present invention is identical with prior art.
Claims (2)
1. a process for precipitating rare earth continuously is characterized in that including two surge tanks, and feed liquid, the continuous cocurrent flow of oxalic acid solution precipitation agent are entered in the reactor drum, and the product that generates in the reactor drum is introduced into wherein to said two surge tanks; After this surge tank was done completely, the product that reactor drum is generated was connected to another surge tank, and draws the water in the last surge tank; Using by turns of two surge tanks when solid phase prod is enough measured in surge tank wherein, cleaned this surge tank; Drain, get final solid phase prod, when a surge tank is cleaned, drains; The product that comes out in the lasting reception of the another surge tank reactor drum is realized uninterrupted continuous production, and the feed acidity of said feed liquid is 0.25～1.25mol/L; Feed concentration is 0.2～1.0mol/L, and the oxalic acid solution mass concentration is 10～20%, and the reactor drum interior reaction temperature is 10～90 ℃; Mixing speed is 4～20Hz, adds additive in the said feed liquid in advance, and the additive volume of adding is 0～5% of a material liquid volume; The residence time of feed liquid in reactor drum is 0.5～25min, and said additive is a polyoxyethylene glycol, and said feed liquid is rare earth chloride or rare earth nitrate solution.
2. process for precipitating rare earth continuously according to claim 1 is characterized in that the feed acidity 0.6mol/l of said feed liquid, and feed concentration is 0.8mol/L; Material liquid volume 30000L, 25～35 ℃ of temperature, the additive volume of interpolation is 2% of a material liquid volume; Put no salt solution 150L in the reactor drum earlier, 50～55 ℃ of temperature, oxalic acid solution mass concentration are 20%; Its volume 30000L, 70～80 ℃ of temperature.
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|---|---|---|---|
| CN2010101780163A CN101831543B (en) | 2010-05-20 | 2010-05-20 | Process for precipitating rare earth continuously |
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|---|---|---|---|
| CN2010101780163A CN101831543B (en) | 2010-05-20 | 2010-05-20 | Process for precipitating rare earth continuously |
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|---|---|
| CN101831543A CN101831543A (en) | 2010-09-15 |
| CN101831543B true CN101831543B (en) | 2012-09-26 |
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| CN111392761B (en) * | 2020-04-20 | 2021-05-14 | 中稀(宜兴)稀土新材料有限公司 | Rare earth solution preparation process capable of quickly and efficiently dispelling acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5961938A (en) * | 1996-02-13 | 1999-10-05 | Santoku Metal Industry Co., Ltd | Method for recovering reusable elements from rare earth-iron alloy |
| US6133194A (en) * | 1997-04-21 | 2000-10-17 | Rhodia Rare Earths Inc. | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
| CN1847153A (en) * | 2005-04-05 | 2006-10-18 | 内蒙古包钢稀土高科技股份有限公司 | RE salt preparing process and apparatus |
-
2010
- 2010-05-20 CN CN2010101780163A patent/CN101831543B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5961938A (en) * | 1996-02-13 | 1999-10-05 | Santoku Metal Industry Co., Ltd | Method for recovering reusable elements from rare earth-iron alloy |
| US6133194A (en) * | 1997-04-21 | 2000-10-17 | Rhodia Rare Earths Inc. | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
| CN1847153A (en) * | 2005-04-05 | 2006-10-18 | 内蒙古包钢稀土高科技股份有限公司 | RE salt preparing process and apparatus |
Non-Patent Citations (1)
| Title |
|---|
| 李梅.铈基稀土化合物的物性控制及应用研究.《中国博士学位论文全文数据库》.2008,(第11期), * |
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Owner name: CHINALCO RARE EARTH (YIXING) CO., LTD. Free format text: FORMER OWNER: YIXING CHANGJIANG RARE EARTH SMELTERY Effective date: 20131127 |
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Effective date of registration: 20131127 Address after: 214216, Wuxi Town, Yixing City, Jiangsu Province Patentee after: Chinalco rare earth (Yixing) Co., Ltd. Address before: 214216 Jiangsu city of Yixing province and the town of neem in Hong Kong Patentee before: Yixing Changjiang Rare Earth Smeltery |
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Granted publication date: 20120926 Termination date: 20140520 |