CN109161703A - A kind of method of ion type rareearth mine mother liquor concentrations - Google Patents
A kind of method of ion type rareearth mine mother liquor concentrations Download PDFInfo
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- CN109161703A CN109161703A CN201811082812.XA CN201811082812A CN109161703A CN 109161703 A CN109161703 A CN 109161703A CN 201811082812 A CN201811082812 A CN 201811082812A CN 109161703 A CN109161703 A CN 109161703A
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- adsorption
- mother liquor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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 present invention relates to a kind of method of ion type rareearth mine mother liquor concentrations, steps are as follows: (1) ion type rareearth ore is filled into immersion liquid column, elutes the Rare Earth Mine in immersion liquid column with the ammonium sulfate that concentration is 2% (weight), obtains re dip solution；(2) re dip solution is adsorbed with the adsorption column that the flow velocity of 18m/h flows through adsorbent equipment, and adsorption temp is 0~50 DEG C；(3) parsed after the completion of adsorbing using 1N hydrochloric acid, 0~50 DEG C of resolution temperature, obtain pure rare earth concentrate.The adsorbent of adsorption column filling is silica gel-polyethyleneimine anionic heavy-metal adsorption material.The present invention makees adsorbent in conjunction with continuous adsorption plant using silica gel-polyethyleneimine material, mine mother liquor concentrations dedoping step is optimized, mine mother liquor concentrations process flow is shortened, is conducive to the quality for promoting rare earth concentrate, the discharge for reducing ammonia nitrogen waste water, reduces cost.
Description
Technical field
The invention belongs to Rare Earth Production technical fields, are related to the removal of impurities enrichment of rare earth mother solution, and in particular to a kind of ionic
The method of Rare-earth Mine mother liquor concentrations.
Background technique
Southern ion type rareearth ore grade increasingly dilution, rare earth concentration is lower in leachate, and containing a large amount of impurity from
Son, such as Al3+、Fe3+、Ca2+、Mg2+、Mn2+And Cu2+Deng.For extraction process, such leachate rare earth concentration is too low,
Water phase is compared too high with organic phase, and the presence of a large amount of foreign ion deteriorates extraction conditions, generates emulsion, and split-phase is tired
Difficulty, while partial impurities ion is extracted into organic phase, influences product purity, so must be carried out to leachate before entering extraction dense
Contracting and removal of impurities.
Concentration at present and removal of impurities mainly use the precipitation method.Oxalate precipitation process be from leach liquid enrichment rare earth and rare earth with it is miscellaneous
The effective ways that matter is separated can both separate with most of non-rare earth metal elements, and can also remove the acid group in earth solution
Ion.But oxalic acid is toxic, influences the health of operator, excessive oxalic acid must carry out harmless treatment, give wastewater treatment
Increase difficulty.The solubility product of carbonate precipitation method lower production costs, carbonated rare earth is smaller compared with rare earth oxalate, it is easier to heavy
It forms sediment, rare-earth precipitation rate is high and nontoxic, does not pollute the environment.But it is difficult that ammonium hydrogen carbonate can also be produced with the partial impurities in leachate
Dissolved salt class influences the quality of rare-earth products.
Publication No. CN106544507A patent application publication " a kind of rare earth leaching mother liquor concentrations process of enriching, including step
It is rapid: (1) to be passed through cleaner neutralization into concentration < 1g/L leaching at low-concentration mother liquor and remove removing aluminum impurity；(2) will lead to except aluminium post mother liquor
Enter to carry out the absorption enrichment of rare earth ion in ion exchange column, then parsed with acid, obtains liquid rare-earth products.The patent Shen
Please be better than " solid-state " rare-earth products produced with prior art processes, but carry out except aluminium process, up for being further simplified
Process.
Summary of the invention
The object of the present invention is to provide a kind of methods of ion type rareearth mine mother liquor concentrations, optimize mine mother liquor concentrations and remove
Miscellaneous process effectively solves the problems, such as the removal of impurities of current ionic mine mother liquor and concentration, shortens the concentration technology process of mother liquor, promoted
Into the quality of the concentrate of extraction, the discharge of ammonia nitrogen waste water is reduced, reduces production cost.
The technical scheme is that the method for ion type rareearth mine mother liquor concentrations, includes the following steps:
(1) ion type rareearth ore is filled into immersion liquid column, is eluted in immersion liquid column with the ammonium sulfate that concentration is 2% (weight)
Rare Earth Mine, obtain re dip solution；
(2) re dip solution is adsorbed with the adsorption column that the flow velocity of 15~2.0m/h flows through adsorbent equipment, and adsorption temp is
0~50 DEG C；
(3) parsed after the completion of adsorbing using 1N~3N hydrochloric acid, 0-50 DEG C of resolution temperature, obtain pure rare earth concentrate.
The adsorbent of adsorption column filling is silica gel-polyethyleneimine amine type heavy-metal adsorption material, adsorbent material inorganic matter-
Carrier (framework material) of the silica gel as heavy-metal adsorption material, the organic/inorganic that skeleton is formed through processing coupling grafting are multiple
Condensation material, Authorization Notice No. are that the patent of invention of CN1242932C discloses the preparation method of adsorbent material.To absorption after parsing
Adsorbent is regenerated in column, and regenerative agent uses the ammonium hydroxide of 1N~3N, and primary recycling agent dosage is 2~5 times for adsorbing column volume,
Flow velocity is 50~150ml/min；Water purification detergent is used after regeneration, removes the remaining ammonium hydroxide of material void.(2) step is adsorbed after
Adsorption tail liquid return step (1) leach process and make leacheate.
Adsorbent equipment is equipped at least 1 group of adsorption column, and every group includes No. 1 adsorption column, No. 2 adsorption columns, mother liquor pipeline, absorption tail
Liquid pipeline and parsing regeneration pipeline.Entrance of the mother liquor piping connection to No. 1 adsorption column and No. 2 adsorption columns, parsing regeneration pipeline company
It is connected to the outlet of No. 1 adsorption column and No. 2 adsorption columns.The outlet of No. 1 adsorption column and No. 2 adsorption columns is connected to adsorption tail liquid pipeline, and 1
The outlet of number adsorption column is connected to the entrance of No. 2 adsorption columns by bypass, and the outlet of No. 2 adsorption columns is connected to No. 1 by bypass
The entrance of adsorption column.
No. 1 adsorption column and No. 2 absorption column diameters are 42mm, and high-order 600mm, mother liquor pipeline, adsorption tail liquid pipeline, parsing are again
Raw pipeline and bypass are the silicone tube that diameter is 10~20mm.
The adsorbent material filled in adsorption column of the invention has for what silica gel obtained after pickling-hydration-alkylation-grafting
Machine/inorganic composite materials is different from prior art ion exchange organic resin.Its advantage is that: 1. have to rare earth ion very strong
Adsorption capacity, 1 gram of adsorbent can adsorb 0.1 gram of rare earth；2. having good separating effect to foreign ions such as aluminium, silicon, calcium, magnesium；
3. sulfuric acid rare earth solubility is small, existing extraction and separation are operated in hydrochloric acid system, after material adsorbs rare earth, with resolving hydrochloric acid,
Switch to rare earth chloride；4. it is low to parse acidity, in conjunction with continuous adsorption plant, the pH of desorbed solution can reach 3~5, and low using acidity
The characteristics of, desorbed solution can supplement concentrated hydrochloric acid circulation parsing, and rare earth concentration in desorbed solution is made to reach 100 grams per liters or more.
Adsorbent material uses the rare earth proprietary material that upper unique function group is grafted using silica gel as carrier, and the material is in silica gel table
It is shallow that face is formed by absorption duct, is diffused into rare earth ion easily in hole, completes absorption of the material to rare earth ion,
Short time can reach balance.Performance caused by the unique functional group of material, can be by technology controlling and process in absorption rare earth
Efficiently separated the alkali or alkaline earth metals such as calcium, magnesium, potassium, sodium while valuable metal.The material has intensity simultaneously
The characteristics of height, no expansion, is applicable in large size adsorption plant actual production operation.Adsorbent material has extremely strong choosing to heavy metal ion
Selecting property adsorption capacity does not adsorb alkali metal, alkaline-earth metal, light metal and anion.Silica Surface grafted functional group, structure are steady
Fixed, high temperature resistant, anti-radiation, shock resistance, volume is almost without expansion.It is shallow due to being formed by adsorbent material duct in Silica Surface,
Heavy metal ion is easily diffused into hole, completes absorption of the material to heavy metal ion, and the short time can reach flat
Weighing apparatus has quick absorption/analysis feature.
Adsorbent material combine continuous switching technology and equipment, can separate well impurity and enrichment rare earth, effectively improve from
The rate of recovery of subtype rare earth resources, economic, effective, serialization enriching and purifying rare earth from low concentration of rare earth leaching liquid, realizes nothing
Contaminated ion type rare earth leaches closed cycle
The method of ion type rareearth mine mother liquor concentrations of the present invention makees adsorbent using silica gel-polyethyleneimine material, knot
Closing continuous exchange adsorption equipment, make ion type rareearth ore through leaching ,-continuous absorption exchanges-rare earth that one-component is obtained by extraction produces
Product optimize the miscellaneous process of mine mother liquor concentrations, solve the problems, such as the removal of impurities of ionic mine mother liquor and concentration, shorten mine
Mountain mother liquor concentrations process flow is conducive to the quality for promoting rare earth concentrate, reduces the discharge of ammonia nitrogen waste water, reduction is produced into
This.
Detailed description of the invention
Fig. 1 is the flow diagram of ion type rareearth mine mother liquor concentrations of the present invention；
Fig. 2 is the flow diagram of adsorbent equipment；
Wherein；1-parsing regeneration pipeline, 2-adsorption tail liquid pipelines, 3-No. 1 adsorption column, 4-mother liquor pipelines, 5-No. 2
Adsorption column, 6-bypasses, 7-valves.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in detail.The scope of protection of the present invention is not limited to the embodiment,
Those skilled in the art make any change within the scope of the claims and also belong to the scope of protection of the invention.
The processes of ion type rareearth mine mother liquor concentrations of the present invention as shown in Figure 1, ion type rareearth mine mother liquor through immersion liquid
Column obtains leachate with the ammonium sulfate elution of 2% (weight), and the adsorption tail liquid after absorption returns to immersion liquid column and is recycled.
Leachate is adsorbed to adsorbent equipment, is parsed after adsorption saturation with 1N dilute hydrochloric acid, and rare earth concentrate, rare earth concentration are obtained
Liquid is to Rare Earth Separation factory rare-earth separating.The adsorption column of adsorbent equipment is regenerated after parsing, with water purification to absorption after regeneration
Column is washed.
As shown in Fig. 2, the adsorbent equipment that adsorption process uses includes two groups of adsorption columns, every group is equipped with No. 1 adsorption column 3,2
Adsorption column 5, mother liquor pipeline 4, adsorption tail liquid pipeline 2 and parsing regeneration pipeline 1.Mother liquor piping connection is inhaled to No. 1 adsorption column and No. 2
The entrance of attached column, parsing regeneration pipeline 1 are connected to the outlet of No. 1 adsorption column and No. 2 adsorption columns, and two groups of No. 1 adsorption column is connected to,
Two groups of No. 2 adsorption columns connection.The outlet of No. 1 adsorption column and No. 2 adsorption columns is connected to adsorption tail liquid pipeline, No. 1 adsorption column
Outlet is connected to the entrance of No. 2 adsorption columns by bypass 6, and the outlet of No. 2 adsorption columns is connected to No. 1 adsorption column by bypass 6
Entrance.Each connecting line is equipped with valve 7.It is 42mm that No. 1 adsorption column 3 and No. 2 adsorption column 5, which is diameter, high-order 600mm, female
Liquid pipeline 4, adsorption tail liquid pipeline 2, parsing regeneration pipeline 1 and bypass are the silicone tube that diameter is 15mm.
The course of work of adsorbent equipment is: mine mother liquor passes through No. 1 adsorption column 3 first and is adsorbed, when No. 1 adsorption column is worn
Before leakage, adsorption tail liquid, which directly returns, leaches column as leacheate circulation.After absorption water outlet REO leakage, the water outlet warp of No. 1 adsorption column
Bypass 6 is adsorbed again into No. 2 adsorption columns 5, and until No. 1 adsorption column adsorption saturation, mine mother liquor is directly accessed No. 2 adsorption columns
Absorption.No. 1 adsorption column enters parsing, regeneration and washing process.The hydrochloric acid solution of resolving, regenerated weak aqua ammonia and washed
The water purification of journey is entered from the outlet of No. 1 adsorption column, is discharged from entrance.Before No. 2 adsorption column leakages, adsorption tail liquid directly as
For leacheate circulation.After the absorption water outlet REO leakages of No. 2 adsorption columns, the water outlet of No. 1 adsorption column through bypass 6 enter parsing, regeneration and
No. 1 adsorption column of washing process is adsorbed, and until No. 2 adsorption column adsorption saturations, mother liquor is directly entered No. 1 adsorption column and adsorbs, and 2
Number adsorption column enters parsing, regeneration and washing process, circuits sequentially, and blocked operation is realized in the opening and closing for passing through each road valve.Parsing
When, it is connected and is parsed using the pillar of two adsorption saturations, obtain the rare earth concentrate of high concentration.When regeneration, parsed using two
Pillar series-connected regenerative, it is possible to reduce the dosage of regenerated liquid.
Embodiment
To adsorption column load silica gel-polyethyleneimine anionic heavy-metal adsorption material, and to the adsorbent material into
Row pretreatment；Saturated oxalic acid solution is configured to examine rare earth leakage；Obtain leakage data；
1. preprocessing process includes: to be cleaned after loading adsorption column with 5 times of column volume clear water, emptied after cleaning；With 2 times of cylinders
Product 1N ammonium hydroxide impregnates 1h, emptying；It is cleaned, is emptied with 10 times of column volume clear water again；
2. rare earth leakage are as follows: the solution containing rare earth is with the flow velocity of 100~150ml/min by being filled with the absorption of material
After column, absorption water outlet is titrated with saturated oxalic acid solution, and rare earth leakage is thought after there is white flock precipitate, is absorbed at this time
A small amount of rare earth (rare earths of several ppm) outflow has just been begun in water；
(2) ion type rareearth ore is filled into immersion liquid column, loads Rare Earth Mine 100kg, and compound concentration is the sulfuric acid of 2% (weight)
Ammonium salt solution elutes the Rare Earth Mine in immersion liquid column, obtains 40L re dip solution, the analysis result part table 1 of re dip solution；
(3) re dip solution is adsorbed with the adsorption column that the flow velocity of 18m/h flows through adsorbent equipment, and 25 DEG C of adsorption temp；
Adsorption tail liquid return step (2) after absorption leaches process and makees leacheate；
(4) it is parsed after the completion of adsorbing using 1N hydrochloric acid, resolution temperature is 25 DEG C, obtains pure rare earth concentrate, dilute
The analysis dataware table 2 of native concentrate；Rare earth concentrate isolates rare earth to Rare Earth Separation factory；
(5) adsorbent in adsorption column is regenerated after parsing, regenerative agent uses the ammonium hydroxide of 1N, and regeneration temperature is 30 DEG C；
Primary recycling agent dosage is 2 times for adsorbing column volume, flow velocity 100ml/min；Water purification detergent is used after regeneration, removes absorption
The ammonium hydroxide of agent voids left.
1 ion type rareearth mine mother liquor leachate analysis result of table
2 adsorption tail liquid of table and desorbed solution analyze data
Table 2 shows that the rate of recovery of rare earth resources is effectively guaranteed lower than detection limit in rare earth in the water outlet after absorption, solves
Content of rare earth is greater than 100g/L in imbibition, is enriched about 200 times, ratio about 1764:1 of the rare earth to aluminium, ratio of the rare earth to iron
About 5683:1, silica gel-polyethyleneimine adsorbent material can be very good separation impurity and be enriched with rare earth.The result shows that adsorbent
Adsorption capacity about 0.85mmol/g, about 1g silica gel-polyethyleneimine anionic heavy-metal adsorption material absorption to rare earth
The rare earth of 0.102g.The method of ion type rareearth mine mother liquor concentrations of the present invention utilizes silica gel-polyethyleneimine anionic weight
Metal-adsorbing material does not have to carry out milk of lime as adsorbent except aluminium process before being adsorbed, simplify ionic mine mother liquor concentrations
Process flow reduces ammonia nitrogen waste water, is conducive to promote rare earth concentrate quality, reduces production cost.
The present invention passes through silica gel-polyethyleneimine anionic heavy-metal adsorption material and adsorbent equipment and innovative means
Effectively combine and work continuously to the absorption of the targeting of metal target, separation and purification, overcome conventional ion switching technology absorption,
Rinse and the problem of desorption three necessary links interruption operation, realize entire technical process targeting, wide spectrum, automation,
Serialization, large-scale and low energy consumption have been really achieved the effect of " environmental protection metallurgy ".
Claims (6)
1. a kind of method of ion type rareearth mine mother liquor concentrations, it is characterized in that: the concentration step is as follows:
(1) ion type rareearth ore is filled into immersion liquid column, is eluted with the ammonium sulfate that concentration is 2% (weight) dilute in immersion liquid column
Tu Kuang obtains re dip solution；
(2) re dip solution is adsorbed with the adsorption column that the flow velocity of 15~2.0m/h flows through adsorbent equipment, adsorption temp be 0~
50℃；
(3) parsed after the completion of adsorbing using 1N~3N hydrochloric acid, 0~50 DEG C of resolution temperature, obtain pure rare earth concentrate.
2. the method for ion type rareearth mine mother liquor concentrations according to claim 1, it is characterized in that: the adsorption column is filled
Adsorbent be silica gel-polyethyleneimine anionic heavy-metal adsorption material, the adsorbent material uses silica gel as heavy metal
The carrier of adsorbent material.
3. the method for ion type rareearth mine mother liquor concentrations according to claim 2, it is characterized in that: to adsorption column after parsing
Middle adsorbent is regenerated, and regenerative agent is the ammonium hydroxide of 1N~3N, and regeneration temperature is 0~50 DEG C；Primary recycling agent dosage is absorption
2~5 times of column volume, flow velocity are 50~150ml/min；Adsorption column is washed with water purification after regeneration, it is remaining to remove material void
Ammonium hydroxide.
4. the method for ion type rareearth mine mother liquor concentrations according to claim 1, it is characterized in that: (2) the step is adsorbed
(1) adsorption tail liquid return step afterwards leaches process and makees leacheate.
5. the method for ion type rareearth mine mother liquor concentrations according to claim 1, it is characterized in that: the adsorbent equipment is set
There is at least 1 group of adsorption column, every group includes No. 1 adsorption column (3), No. 2 adsorption columns (5), mother liquor pipeline (4), adsorption tail liquid pipeline (2)
With parsing regeneration pipeline (1)；Entrance of the mother liquor piping connection to No. 1 adsorption column and No. 2 adsorption columns, the parsing regenerating tube
Road (1) is connected to the outlet of No. 1 adsorption column and No. 2 adsorption columns；The outlet of No. 1 adsorption column and No. 2 adsorption columns is connected to suction
Attached tail washings pipeline, the entrance that the outlet of No. 1 adsorption column is connected to No. 2 adsorption columns by bypassing (6), No. 2 adsorption columns
Outlet be connected to the entrance of No. 1 adsorption column by bypassing (6).
6. the method for leached ions type Rare-earth Mine mother liquor concentrations according to claim 4, it is characterized in that: No. 1 suction
It is 42mm that attached column (3) and No. 2 adsorption columns (5), which are diameter, high-order 600mm, the mother liquor pipeline (4), adsorption tail liquid pipeline
(2), it parses regeneration pipeline (1) and bypass is the silicone tube that diameter is 10~20mm.
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|---|---|---|---|---|
| CN1055203A (en) * | 1990-03-26 | 1991-10-09 | 中国科学院金属腐蚀与防护研究所 | A kind of novel process of extracting rare earth |
| CN1597553A (en) * | 2003-09-21 | 2005-03-23 | 邱建宁 | Technological method of producing highly toxic heavy metal waste water treatment agent |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
| CN102671642A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN103331144A (en) * | 2013-05-28 | 2013-10-02 | 工信华鑫科技有限公司 | Preparation method of silica gel-polyethylenepolyaminepoly(methylenephosphonic acid) and use of silica gel-polyethylenepolyaminepoly(methylenephosphonic acid) in rare earth ion adsorption |
| CN103361498A (en) * | 2013-06-20 | 2013-10-23 | 工信华鑫科技有限公司 | Method for separating impurities from rare earth in rare-earth-ore leaching solution to purify rare earth |
| CN105112692A (en) * | 2015-10-11 | 2015-12-02 | 江西理工大学 | Ore leaching method for ion-adsorbing type rare earth ore |
| CN108212225A (en) * | 2018-03-15 | 2018-06-29 | 李宾 | A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof |
-
2018
- 2018-09-17 CN CN201811082812.XA patent/CN109161703A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055203A (en) * | 1990-03-26 | 1991-10-09 | 中国科学院金属腐蚀与防护研究所 | A kind of novel process of extracting rare earth |
| CN1597553A (en) * | 2003-09-21 | 2005-03-23 | 邱建宁 | Technological method of producing highly toxic heavy metal waste water treatment agent |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
| CN102671642A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN103331144A (en) * | 2013-05-28 | 2013-10-02 | 工信华鑫科技有限公司 | Preparation method of silica gel-polyethylenepolyaminepoly(methylenephosphonic acid) and use of silica gel-polyethylenepolyaminepoly(methylenephosphonic acid) in rare earth ion adsorption |
| CN103361498A (en) * | 2013-06-20 | 2013-10-23 | 工信华鑫科技有限公司 | Method for separating impurities from rare earth in rare-earth-ore leaching solution to purify rare earth |
| CN105112692A (en) * | 2015-10-11 | 2015-12-02 | 江西理工大学 | Ore leaching method for ion-adsorbing type rare earth ore |
| CN108212225A (en) * | 2018-03-15 | 2018-06-29 | 李宾 | A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof |
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Application publication date: 20190108 |