CN104404276A - Method utilizing NaY molecular sieve to recycle rare earth from low concentration rare earth solution - Google Patents
Method utilizing NaY molecular sieve to recycle rare earth from low concentration rare earth solution Download PDFInfo
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- CN104404276A CN104404276A CN201410626314.2A CN201410626314A CN104404276A CN 104404276 A CN104404276 A CN 104404276A CN 201410626314 A CN201410626314 A CN 201410626314A CN 104404276 A CN104404276 A CN 104404276A
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- rare earth
- molecular sieve
- nay molecular
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method utilizing a NaY molecular sieve to recycle rare earth from a low concentration rare earth solution. The method comprises the following steps: (1) weighing a certain amount of NaY molecular sieve, adding the NaY molecular sieve into a rare earth solution, wherein the mass ratio of the NaY molecular sieve to the rare earth ions in the rare earth solution is 12:1-14:1, and then carrying out absorption under the following conditions: an absorption temperature of 25 to 45 DEG C, a pH value of 3-5, and a vibration absorption time of 50 to 70 minutes; (2) utilizing a diluted acid or a NaCl solution to perform desorption on the NaY molecular sieves, which are obtained in the step (1) and carry rare earth ions, wherein the concentration of the diluted acid is 1 to 5 mol/L, and the rare earth is recycled from the rare earth desorption solution through a precipitation method. The absorption rate of the provided method on rare earth ions such as lanthanum, yttrium, and gadolinium can reach 96% or more, the desorption rate can reach 95% or more, the regenerative property is good, the recycling rate is high, and the method is pollution-free to the environment.
Description
Technical field
The invention belongs to hydrometallurgy and technical field of waste water processing.
Background technology
Rare earth has penetrated into national economy every field, becomes " auxiliary agent " that many industries are indispensable, is called " VITAMIN of modern industry " by people's reputation.Rare earth recovery technology in the high efficiency rare-earth extractive technique of low-quality rare-earth mineral and the low concentration of rare earth waste water that produces in Rare Earth Production process is obtained in recent years and pays close attention to widely.General method of wastewater treatment has: chemical precipitation method, electrolytic process, oxidation reduction process, ion exchange method and absorption method etc.The present invention adopt be that ion exchange method processes low concentration of rare earth waste water, the method simple to operate easy to control, flow process is short, renewable, purification of waste water can be made to arrive higher degree.
The RE waste water of the large volume low-concentration produced in the recovery process of southern ion type rareearth resource, if do not reclaimed, affect ecological safety, rare earth, once entered environment, enters human body, causes various disease, is detrimental to health.The prevention and protection of visible ecotope will be the huge challenge that China's rare-earth trade faces, and is also to drop into the instant task of a large amount of manpower and materials for a long time.
Summary of the invention
The object of this invention is to provide a kind of method that NaY molecular sieve reclaims soil from low concentration of rare earth solution, effective enrichment rare earth ion also reclaims.
The present invention is achieved through the following technical solutions.
The present invention includes following steps.
(1) take a certain amount of NaY molecular sieve, join in earth solution, the mass ratio of NaY molecular sieve and earth solution Rare Earth Ion is 12:1-14:1, adsorption temp be 25-45 DEG C, pH be 3-5, vibration adsorption time be 50-70min condition under adsorb.
The optimum condition of step of the present invention (1) is: the mass ratio 13:1 of NaY molecular sieve and earth solution Rare Earth Ion, and adsorption temp is 25 DEG C, pH is 5, vibration adsorption time is adsorb under 50min condition.
(2) by the NaY molecular sieve being adsorbed with rare earth ion in diluted acid or NaCl solution desorption procedure (1), rare earth is desorbed, and then reaching the object of recovery, the concentration of dilute acid soln is at 1-5mol/L, and the rare earth stripping liquid of gained can with recovering rare earths such as the precipitator method.
Described diluted acid is dilute hydrochloric acid or citric acid.
The present invention all can reach more than 96% to the adsorption rate of rare earth ion lanthanum, yttrium, gadolinium, and desorption efficiency is more than 95%, and reproducibility is good, and the rate of recovery is high, environmentally safe.
Accompanying drawing explanation
Fig. 1 starting point concentration of the present invention is to the graph of relation of loading capacity.
Fig. 2 sorbent material add-on of the present invention is to the graph of relation of adsorption rate.
Fig. 3 adsorption time of the present invention is to the graph of relation of adsorption rate.
Fig. 4 pH of the present invention is to the graph of relation of adsorption efficiency.
Fig. 5 adsorption temp of the present invention is to the graph of relation of adsorption rate.
The desorb graph of relation of Fig. 6 sorbent material of the present invention.
The regeneration of Fig. 7 sorbent material of the present invention uses graph of relation.
Specific embodiments
The present invention will be described further by following examples.
Embodiment 1.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) take NaY molecular sieve 40mg, be added to containing Gd respectively
3+, Y
3+, La
3+in RE waste water (ion starting point concentration different), adsorption time be 70min, pH=3, V=30ml, 25 DEG C time, get filtrate after suction filtration, (survey absorbancy, according to Gd with rare earth ion content residual in arsenazo Ⅲ determination of color solution
3+, Y
3+, La
3+typical curve calculate not by each ionic weight adsorbed), then to be drawn by the ionic weight adsorbed by minusing.As seen from Figure 1, quantity of sorbent one timing, the adsorptive capacity of NaY molecular sieve increases with the increase of rare earth ion concentration, until adsorption equilibrium, NaY molecular sieve is to the Gd of rare earth ion
3+, Y
3+, La
3+saturated extent of adsorption is respectively 71.3,69.8,67mg.g
-1.
Embodiment 2.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) at rare earth ion (Gd
3+, Y
3+, La
3+) initial mass concentration is 100mg/L, adsorption time is 60min, pH=4, V=30mL, 45 DEG C time, NaY molecular sieve adsorbent amount is on the impact of the adsorption efficiency of rare earth ion, strength of solution is measured by the arsenazo method in embodiment 1, draw by the ionic weight adsorbed, as seen from Figure 2, along with the increase of quantity of sorbent, adsorption rate also increases; After sorbent material add-on is greater than 40mg, adsorption efficiency increase amplitude is very little, and tend to be steady, this is because when NaY molecular sieve add-on is many, adsorption site can increase, and exchange capacity increases, and adsorption rate increases, and after exchange capacity reaches capacity, clearance can tend to be steady.
Embodiment 3.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) at rare earth ion (Gd
3+, Y
3+, La
3+) initial mass concentration is 100mg/L, sorbent material add-on is 40mg, pH=3, V=30ml, 35 DEG C time, adsorption time is on the impact of adsorption efficiency, strength of solution is measured by the arsenazo method in embodiment 1, draw by the ionic weight adsorbed, as seen from Figure 3, time is between 0 ~ 50min, adsorption rate increases gradually, when adsorption time is at 50min, this sorbent material of 40mg reaches saturated extent of adsorption, and adsorption rate is maximum, reach 95%, after 50min, adsorption rate is substantially constant, and the optimal adsorption time is 50min.
Embodiment 4.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) NaY molecular sieve 40mg, joins containing Gd
3+, Y
3+, La
3+in RE waste water in (initial mass concentration is 100mg/L), adsorption temp be 35 DEG C, pH value is 1 ~ 7, V=30ml, vibration adsorption time are 60min, strength of solution is measured by the arsenazo method in embodiment 1, draw by the ionic weight adsorbed, as seen from Figure 4, pH<5, the adsorption rate of NaY molecular sieve to rare earth ion increases with the increase of pH, when pH is 5, adsorption rate reaches maximum, when 5≤pH≤7, adsorption rate is substantially constant, when pH value of solution is lower, and H
+concentration is higher, there is competitive adsorption with rare earth ion, and the competitive capacity of rare earth ion is less than H
+; When pH value of solution is higher, H
+concentration reduce, the competition of rare earth ion is reduced, is conducive to the Na in rare earth ion and NaY molecular sieve
+there is ion exchange.Because NaY molecular sieve itself has certain basicity, the Na in molecular sieve
+with the H in water
+carry out ion-exchange, also can increase the pH of solution, cause the wastewater pH processed all to be greater than initial pH, and rare-earth precipitation gets off by the too high meeting of pH, determines that Optimal pH is 5.
Embodiment 5.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) at rare earth ion (Gd
3+, Y
3+, La
3+) initial mass concentration is 100mg/L, sorbent material add-on is 40mg, adsorption time is 50min, pH=5, V=30mL, under differing temps, NaY molecular sieve is on the impact of the adsorption rate of rare earth ion, strength of solution is measured by the arsenazo method in embodiment 1, draw by the ionic weight adsorbed, found out by Fig. 5, under the condition that ambient conditions is constant, when only changing temperature, NaY molecular sieve reduces the rising of the adsorption efficiency of rare earth ion with temperature.Namely adsorption temp raises, and adsorption efficiency declines.Because fix when temperature, absorption is generally spontaneous carrying out, the Gibbs function Δ G < 0 of primary sorption, and after material adsorbed, its degree of freedom declines, so the entropy Δ S < 0 in adsorption process.According to Δ G=Δ H-T Δ S, adsorption process is exothermic process.Therefore, temperature raises and is unfavorable for absorption.So temperature raises, adsorption efficiency slows down.
Embodiment 6.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) take NaY molecular sieve 40mg, process is the Gd of 100mg/L to containing concentration respectively
3+, Y
3+, La
3+in RE waste water, adsorption temp be 35 DEG C, pH value is 4, vibration adsorption time is 50min, measure strength of solution by the arsenazo method in embodiment 1, draw by the ionic weight adsorbed.
(3) have the NaY molecular sieve 50min of rare earth ion with the hydrochloric acid desorption absorption of 1mol/L, desorbed by rare earth, the same method records rare earth content contained in solution after often kind of ion desorb.As can be seen from Figure 6, this sorbent material is to Gd
3+, Y
3+, La
3+have superpower adsorption effect, and available diluted acid gets off the rare earth ion desorb of adsorbing on the sorbent, desorption efficiency is up to more than 95%.
Embodiment 7.
(1) SiO
2: Al
2o
3: Na
2o:H
20 mol ratio is under the condition of 7:1:12:420, and vigorous stirring obtains even colloidal sol, proceeds to and pour in stainless steel cauldron that liner is tetrafluoroethylene after half an hour, takes out reactors in 100 DEG C of reaction 10h, and sample is taken out in cooling dries, and is NaY molecular sieve.
(2) take NaY molecular sieve 40mg, process is the Gd of 100mg/L to containing concentration respectively
3+, Y
3+, La
3+in RE waste water, adsorption temp be 25 DEG C, pH value is 3, vibration adsorption time is 70min, measure strength of solution by the arsenazo method in embodiment 1, draw by the rare earth content adsorbed.
(3) the NaY molecular sieve 50min of rare earth ion is had with the hydrochloric acid desorption absorption of 1mol/L, rare earth is desorbed, sorbent material solution be drawn through is dried, repeating step (2), record 3 kinds of ions respectively again by the rare earth content adsorbed, when as can be seen from Figure 7 reusing this sorbent material to the adsorption rate of three kinds of rare earth ions all more than 90%.
Claims (3)
1., by the method for NaY molecular sieve recovering rare earth from low concentration of rare earth solution, it is characterized in that comprising the following steps:
(1) take a certain amount of NaY molecular sieve, join in earth solution, the mass ratio of NaY molecular sieve and earth solution Rare Earth Ion is 12:1-14:1, adsorption temp be 25-45 DEG C, pH be 3-5, vibration adsorption time be 50-70min condition under adsorb;
(2) by the NaY molecular sieve being adsorbed with rare earth ion in diluted acid or NaCl solution desorption procedure (1), the concentration of dilute acid soln is at 1-5mol/L, and the rare earth solution of gained smokes precipitator method recovering rare earth.
2. the method for recovering rare earth according to claim 1, it is characterized in that the mass ratio 13:1 of NaY molecular sieve and earth solution Rare Earth Ion in step (1), adsorption temp is 25 DEG C, pH is 5, the adsorption time that vibrates is adsorb under 50min condition.
3. the method for recovering rare earth according to claim 1, is characterized in that the diluted acid described in step (2) is dilute hydrochloric acid or citric acid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088613A (en) * | 2006-06-14 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of REY molecular sieve |
| CN103695654A (en) * | 2014-01-03 | 2014-04-02 | 南昌大学 | Method for recovering rare earth from low-concentration rare-earth solution by using loaded chitosan |
-
2014
- 2014-11-10 CN CN201410626314.2A patent/CN104404276A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088613A (en) * | 2006-06-14 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of REY molecular sieve |
| CN103695654A (en) * | 2014-01-03 | 2014-04-02 | 南昌大学 | Method for recovering rare earth from low-concentration rare-earth solution by using loaded chitosan |
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Application publication date: 20150311 |