CN115870018A - Regeneration method of neutral ground impregnating resin - Google Patents

Regeneration method of neutral ground impregnating resin Download PDF

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Publication number
CN115870018A
CN115870018A CN202111140043.6A CN202111140043A CN115870018A CN 115870018 A CN115870018 A CN 115870018A CN 202111140043 A CN202111140043 A CN 202111140043A CN 115870018 A CN115870018 A CN 115870018A
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resin
concentration
regenerating
treating
neutrally
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封宇
许影
廖文胜
王亮
王立民
丁叶
闻振乾
汤义伟
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China Nuclear Mining Technology Group Co ltd
Beijing Research Institute of Chemical Engineering and Metallurgy of CNNC
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China Nuclear Mining Technology Group Co ltd
Beijing Research Institute of Chemical Engineering and Metallurgy of CNNC
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The invention relates to the technical field of uranium hydrometallurgy, and particularly discloses a regeneration method of neutral ground impregnated resin, which comprises the steps of firstly, backwashing the resin in a resin tower by using water to wash out macromolecular suspended matters and ultrafine clay particle sediments on the surface of the resin and in gaps among the resin; then, treating the resin by using a low-concentration acidic regenerated liquid containing an oxidant to degrade macromolecular organic matters adsorbed on the resin; then, treating the resin by using a low-acid regenerated liquid containing a stabilizer, and eluting inorganic salt sediments such as iron, aluminum, calcium and the like in the resin; and finally, treating the resin by using an alkaline regeneration liquid, and eluting silicon and degraded organic matters deposited on the surface of the resin. The method can efficiently elute the pollutants on the resin, and remarkably reduce the water consumption in the resin recovery process while recovering the adsorption capacity of the resin.

Description

Regeneration method of neutral ground impregnating resin
Technical Field
The invention belongs to the technical field of uranium hydrometallurgy, and particularly relates to a regeneration method of neutral ground impregnating resin.
Background
In the prior art of in-situ leaching uranium mining in China, ion exchange is mainly adopted for recycling uranium. In a certain neutral in-situ uranium leaching process, with the development of an ion exchange uranium extraction process, the phenomenon that the exchange capacity of anion exchange resin is reduced, even resin poisoning occurs. Factors causing neutral resin leaching poisoning are complex, and the factors causing resin poisoning are mainly silicon and macromolecular organic matters, colloid sediment of iron and aluminum, and inorganic salt sediment of calcium, magnesium and the like on the surface of resin as can be known from analysis of impurity ion components in leaching solution components and neutral resin.
The recovery of poisoning by neutral immersion of anion exchange resins usually uses sodium hydroxide solution, or adds a small amount of oxidant in alkaline solution. Experimental data show that the alkaline solution can only elute silicon and organic matters deposited on the resin; the acidic solution can elute inorganic salt deposits such as ferrum, aluminum, calcium and the like on the resin, and has limited elution to silicon and organic matters, namely, the toxic resin is difficult to be completely regenerated by adopting a single alkali liquor to treat the resin. However, the resin is treated by alternately using acid and alkali, although the regeneration effect is good, more water is needed to wash the resin to be neutral after each time of resin treatment, the water consumption is large, and the required time is long.
In order to increase the regeneration rate of resin and reduce the damage to the resin structure in the regeneration process, a new method for regenerating neutral impregnated resin is needed.
Disclosure of Invention
The invention aims to provide a regeneration method of neutral impregnated resin, which can efficiently elute pollutants on the resin and improve the regeneration rate of the resin.
The technical scheme of the invention is as follows:
a regeneration method of neutral impregnated resin, firstly, the resin in a resin tower is back flushed by water, and the deposits of macromolecular suspended matters and ultrafine clay particles on the surface of the resin and in resin gaps are washed away;
then, treating the resin by using low-concentration acid washing liquid containing an oxidant to degrade macromolecular organic matters adsorbed on the resin;
then, treating the resin by using low-concentration acidic washing liquor containing a stabilizing agent, and eluting inorganic salt sediments such as iron, aluminum, calcium and the like in the resin;
and finally, treating the resin by adopting an alkaline solution to elute silicon and degraded organic matters deposited on the surface of the resin.
The method specifically comprises the following steps:
step 1: injecting clear water into the ion exchange tower to perform back flushing on the resin;
and 2, step: firstly, treating the resin by using a low-concentration acidic washing solution containing an oxidant, and then treating the resin by using a low-concentration acidic washing solution containing a stabilizer;
the low-concentration acidic washing solution is 0.5-2% of HCl;
and 3, step 3: washing the resin with 2-3 times volume of water;
and 4, step 4: treating the resin with an alkaline solution;
and 5: washing the resin with water until the pH is neutral;
step 6: the resin was transformed with sodium bicarbonate solution.
In the step 2, the volume ratio of the low-concentration acidic washing liquid containing the oxidant to the resin is 1-3:1, and the contact time is 30-50min.
In the step 2, the oxidant is hydrogen peroxide or sodium hypochlorite with the concentration of 0.3-1%.
In the step 2, the volume ratio of the low-concentration acidic washing liquid containing the stabilizer to the resin is 1-3:1, and the contact time is 30-50min.
In the step 2, the stabilizing agent is one or more of citric acid, sulfamic acid and glycolic acid with the concentration of 0.3-1%.
In step 4, in the alkaline solution, the concentration of sodium hydroxide is 4-10% and the concentration of sodium chloride is 5-9%.
In the step 4, the ratio of the volume of the alkaline solution to the volume of the resin is 2-6:1, and the contact time is 30-50min.
In step 6, the concentration of the sodium bicarbonate solution is 20-45g/L.
In step 6, the volume ratio of the sodium bicarbonate solution to the resin is 2-6:1, and the contact time is 40-60min.
The invention has the following remarkable effects:
(1) The method of the invention is adopted to regenerate neutral leaching poisoning resin, which can effectively improve the adsorption performance of the resin, and the adsorption capacity after the resin regeneration can be improved from 50-60mg/mL to more than 95 mg/mL.
(2) The regeneration method of neutral impregnated resin can efficiently elute pollutants on the resin, and remarkably reduce water consumption in the recovery process of the resin while recovering the adsorption capacity of the resin.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
A regeneration method of neutral immersion resin is provided, aiming at neutral immersion poisoning resin with high impurity content of silicon, organic matter, iron, aluminum, calcium and the like, firstly, the resin in a resin tower is back flushed by water, and deposits of macromolecular suspended matters and ultrafine clay particles on the surface of the resin and in gaps of the resin are washed away;
then, treating the resin by using low-concentration acidic regenerated liquid containing an oxidant, and degrading macromolecular organic matters adsorbed on the resin;
then, treating the resin by using a low-acid regenerated liquid containing a stabilizer, and eluting inorganic salt sediments such as iron, aluminum, calcium and the like in the resin;
and finally, treating the resin by using an alkaline regeneration liquid, and eluting silicon and degraded organic matters deposited on the surface of the resin.
The method specifically comprises the following steps:
step 1: injecting clear water into the ion exchange tower to perform back flushing on the resin;
step 2: two low-acid pickling solutions are respectively adopted to treat the resin:
firstly, treating the resin by using a low-concentration acidic washing solution containing an oxidant, wherein the volume ratio of the washing solution to the resin is 1-3:1, and the contact time is 30-50min; the oxidant is hydrogen peroxide or sodium hypochlorite with the concentration of 0.3-1%;
then treating the resin by using low-concentration acidic washing liquid containing a stabilizer, wherein the volume ratio of the washing liquid to the resin is 1-3:1, and the contact time is 30-50min; the stabilizer is one or more of citric acid, sulfamic acid and glycolic acid with the concentration of 0.3-1%;
the low-concentration acidic washing solution is 0.5-2% of HCl;
and step 3: washing the resin with 2-3 times volume of water;
and 4, step 4: treating the resin with alkaline solution, wherein the volume ratio of the washing liquid to the resin is 2-6:1, and the contact time is 30-50min;
in the alkaline solution, the concentration of sodium hydroxide is 4-10%, and the concentration of sodium chloride is 5-9%;
and 5: washing the resin with water until the pH is neutral;
step 6: transforming the resin with 20-45g/L sodium bicarbonate solution, wherein the volume ratio of the transformation solution to the resin is 2-6:1, and the contact time is 40-60min.
Example 1
The uranium concentration in neutral leachate of a uranium ore hydrometallurgy plant in Xinjiang is 55.0mg/L, and the content of other non-uranium elements is shown in the following table 1; the adsorption capacity of the poisoning resin is 55.4mg/mL, and the content of pollutants in the poisoning resin is shown in Table 1.
TABLE 1 leachate and resin non-uranium element chemical composition
Figure BDA0003283470980000041
The resin was first back flushed with water at a volume ratio of 1:1.
Two low-acid pickling solutions are respectively adopted to treat the resin: (1) the concentration of hydrogen peroxide in the oxidant-containing low-acid solution is 0.5 percent, the concentration of HCl is 2 percent, the volume ratio of the regenerated liquid to the resin is 2:1, and the contact time is 30min; (2) the concentration of citric acid in the stabilizer-containing low-acid solution is 0.5 percent, the concentration of HCl is 2 percent, the volume ratio of the regenerated liquid to the resin is 2:1, and the contact time is 30min.
The resin was washed free of acid with water, at a water to resin volume ratio of 1:1.
Regenerating the resin by using an alkaline solution with the concentration of 10 percent of sodium hydroxide and the concentration of 8 percent of sodium chloride, wherein the volume ratio of the washing liquid to the resin is 2:1, and the contact time is 30min.
Washing the resin with water until the pH value is neutral;
the resin was transformed with 30g/L sodium bicarbonate solution, the volume ratio of the transformed solution to the resin was 4:1, and the contact time was 40min.
The regenerated resin is subjected to an adsorption test by using the leaching solution, and the adsorption capacity of the regenerated resin is improved from 55.4mg/mL to 100.1mg/mL.
Example 2
The uranium concentration in the leaching solution of a uranium endomeng hydrometallurgy plant is 48.0mg/L, and the contents of other non-uranium elements are shown in the following table 1; the adsorption capacity of the poisoned resin is 59.3mg/mL, and the content of the pollutants in the poisoned resin is shown in the table 2.
TABLE 2 leachate and chemical composition of non-uranium elements of resin
Figure BDA0003283470980000051
The resin was first back-flushed with water at a volume ratio of 1:1.
Two low-acid pickling solutions are respectively adopted to treat the resin: (1) the concentration of sodium hypochlorite in the oxidant-containing low-acid solution is 0.5 percent, the concentration of HCl is 1.5 percent, the volume ratio of the regenerated liquid to the resin is 3:1, and the contact time is 40min; (2) the concentration of the glycolic acid in the stabilizer-containing low-acid solution is 0.5 percent, the concentration of HCl is 1.5 percent, the volume ratio of the regenerated liquid to the resin is 3:1, and the contact time is 40min.
The resin was washed free of acid with water at a water to resin volume ratio of 1:1.
Regenerating the resin by using an alkaline solution with the concentration of 8 percent of sodium hydroxide and the concentration of 6 percent of sodium chloride, wherein the volume ratio of the washing liquid to the resin is 3:1, and the contact time is 40min.
Washing the resin with water until the pH is neutral;
the resin was transformed with 35g/L sodium bicarbonate solution at a ratio of the volume of the transformation solution to the volume of the resin of 4:1 for a contact time of 50min.
The regenerated resin is subjected to an adsorption test by using the leaching solution, and the adsorption capacity of the regenerated resin is improved from 59.3mg/mL to 95.5mg/mL.
In the hydrometallurgy process of neutral leaching uranium, the anion exchange resin has a poisoning phenomenon due to the existence of pollutants such as silicon, organic matters, iron, aluminum, calcium, clay and the like in the leaching solution. The invention provides a regeneration method of neutral impregnated resin, which can efficiently elute pollutants on the resin, and remarkably reduce water consumption in the recovery process of the resin while recovering the adsorption capacity of the resin.

Claims (10)

1. A method for regenerating a neutrally impregnated resin, comprising: firstly, resin in a resin tower is back-flushed by water, and macromolecular suspended matters and sediments of ultrafine clay particles in the surface of the resin and resin gaps are washed away;
then, treating the resin by using a low-concentration acidic washing solution containing an oxidant to degrade macromolecular organic matters adsorbed on the resin;
then, treating the resin by using low-concentration acidic washing liquor containing a stabilizing agent, and eluting inorganic salt sediments such as iron, aluminum, calcium and the like in the resin;
and finally, treating the resin by using an alkaline solution to elute silicon and degraded organic matters deposited on the surface of the resin.
2. A method of regenerating neutrally impregnated resin according to claim 1 wherein: the method specifically comprises the following steps:
step 1: injecting clear water into the ion exchange tower to perform back flushing on the resin;
step 2: firstly, treating the resin by using a low-concentration acidic washing solution containing an oxidant, and then treating the resin by using a low-concentration acidic washing solution containing a stabilizer;
the low-concentration acidic washing solution is 0.5-2% of HCl;
and step 3: washing the resin with 2-3 times volume of water;
and 4, step 4: treating the resin with an alkaline solution;
and 5: washing the resin with water until the pH is neutral;
step 6: the resin was transformed with sodium bicarbonate solution.
3. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in the step 2, the volume ratio of the low-concentration acidic washing liquid containing the oxidant to the resin is 1-3:1, and the contact time is 30-50min.
4. A method of regenerating neutrally impregnated resin according to claim 2 wherein: in the step 2, the oxidant is hydrogen peroxide or sodium hypochlorite with the concentration of 0.3-1%.
5. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in the step 2, the volume ratio of the low-concentration acid washing solution containing the stabilizer to the resin is 1-3:1, and the contact time is 30-50min.
6. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in the step 2, the stabilizing agent is one or more of citric acid, sulfamic acid and glycolic acid with the concentration of 0.3-1%.
7. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in the step 4, in the alkaline solution, the concentration of sodium hydroxide is 4-10%, and the concentration of sodium chloride is 5-9%.
8. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in the step 4, the ratio of the volume of the alkaline solution to the volume of the resin is 2-6:1, and the contact time is 30-50min.
9. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in step 6, the concentration of the sodium bicarbonate solution is 20-45g/L.
10. A method of regenerating a neutrally impregnated resin as claimed in claim 2 wherein: in step 6, the volume ratio of the sodium bicarbonate solution to the resin is 2-6:1, and the contact time is 40-60min.
CN202111140043.6A 2021-09-28 2021-09-28 Regeneration method of neutral ground impregnating resin Pending CN115870018A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117467862A (en) * 2023-12-22 2024-01-30 核工业北京化工冶金研究院 Method for preventing resin organic matter poisoning in neutral leaching uranium mining hydrometallurgy process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1051670A (en) * 1973-12-27 1979-04-03 Rohm And Haas Company Method of recovering uranium from aqueous solution
AU1058783A (en) * 1983-01-19 1984-07-26 Mobil Oil Corp. Regenerating ion-exchangers used in uranium recovery
JPH0760135A (en) * 1993-08-26 1995-03-07 Sumitomo Metal Mining Co Ltd Method for regenerating anion exchange resin for adsorbing rhenium
CN1724167A (en) * 2005-05-27 2006-01-25 哈尔滨工业大学 Process for reactivating gel type strong base negative resin of polluted in industrial water treatment
CN103464224A (en) * 2013-08-19 2013-12-25 西安通鑫半导体辅料有限公司 Method for recycling exhausted exchange resin during recovering process of silicon wafer wire cutting liquid
CN108786933A (en) * 2018-06-19 2018-11-13 中盐金坛盐化有限责任公司 A kind of low sodium type cation resin regeneration agent and its preparation method and application
CN112495453A (en) * 2020-12-20 2021-03-16 衢州巨化锦纶有限责任公司 Regeneration method of ion exchange resin for refining caprolactam

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1051670A (en) * 1973-12-27 1979-04-03 Rohm And Haas Company Method of recovering uranium from aqueous solution
AU1058783A (en) * 1983-01-19 1984-07-26 Mobil Oil Corp. Regenerating ion-exchangers used in uranium recovery
JPH0760135A (en) * 1993-08-26 1995-03-07 Sumitomo Metal Mining Co Ltd Method for regenerating anion exchange resin for adsorbing rhenium
CN1724167A (en) * 2005-05-27 2006-01-25 哈尔滨工业大学 Process for reactivating gel type strong base negative resin of polluted in industrial water treatment
CN103464224A (en) * 2013-08-19 2013-12-25 西安通鑫半导体辅料有限公司 Method for recycling exhausted exchange resin during recovering process of silicon wafer wire cutting liquid
CN108786933A (en) * 2018-06-19 2018-11-13 中盐金坛盐化有限责任公司 A kind of low sodium type cation resin regeneration agent and its preparation method and application
CN112495453A (en) * 2020-12-20 2021-03-16 衢州巨化锦纶有限责任公司 Regeneration method of ion exchange resin for refining caprolactam

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117467862A (en) * 2023-12-22 2024-01-30 核工业北京化工冶金研究院 Method for preventing resin organic matter poisoning in neutral leaching uranium mining hydrometallurgy process
CN117467862B (en) * 2023-12-22 2024-03-29 核工业北京化工冶金研究院 Method for preventing resin organic matter poisoning in neutral leaching uranium mining hydrometallurgy process

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