CN106435172A - Process for performing classifying split-flow treatment on rare earth sin-situ leaching mother solution - Google Patents
Process for performing classifying split-flow treatment on rare earth sin-situ leaching mother solution Download PDFInfo
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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
- 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
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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
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
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Abstract
The invention discloses a process for performing classifying split-flow treatment on a rare earth sin-situ leaching mother solution. The method comprises introducing a purifying agent I into the medium and high concentration leaching mother solution with a concentration of being larger than or equal to 1g/L for purifying, precipitating through a precipitator after purifying, and washing with clean water and filtering and sintering to obtain a solid rare earth product, wherein the purifying agent I is a mixed solution of a sodium bicarbonate solution and a sodium carbonate solution, wherein the precipitator is a sodium bicarbonate solution; introducing a purifying agent II into a low concentration mother solution with a concentration of being smaller than 1g/L for neutralizing to remove aluminum impurity, then introducing the mother solution without aluminum into an ion exchange column for absorption and enrichment of rare earth ions, and then desorbing with acid to obtain a liquid rare earth product, wherein the purifying agent is lime milk. The mother solutions of different concentrations are subjected to split-flow treatment by the process to obtain two different types of solid and liquid rare earth products, such that exploitation of an ionic type rare earth mine enters an efficient and economic technical leading edge with a high resource use rate.
Description
Technical field
The present invention relates to mining technology technical field, and in particular to a kind of carry out classification shunting to rare earth Situ Leaching mother solution
The technique of process.
Background technology
So far, the leaching of " ion type rareearth ore " mainly has two kinds with process of enriching, and a kind of is " pond leaching ", a kind of for " original
Ground leaching ore deposit ".Because the destruction that " pond leaching " is brought on ecological environment is very big with impact, China exploits implementation to " ion type rareearth ore "
Extraction technique policy is eliminated, and now carried out is " in_situ leaching " technique.The schematic flow sheet of both excavated technologies divides
Not as depicted in figs. 1 and 2.
Typical rare earth leaches curve as shown in figure 3, from figure 3, it can be seen that with the carrying out of leaching ore deposit, soaking the ore deposit initial stage
Before leaching ore deposit, liquid rare earth concentration is relatively low, and leaching ore deposit mid-term rare earth concentration is stepped up, and (can reach several more than g/L) after reaching peak value, and
Gradually reduce, soak ore deposit later stage rare earth tail washings rare earth concentration and reach the low mark of receipts liquid of setting (such as<0.1g/L) liquid is received in cut-off afterwards.
The collection of the leaching mother solution of " ion-type " Rare-earth Mine, is all by liquid collection system, which to be collected now.Though
So most rare earth mother solution effectively can be collected by this receipts liquid mode, but the rare earth concentration that collects is low, and often average only have
0.5～1.5g/L or so.The rare earth mother solution of this concentration, as rare earth concentration is low, impurity content is high, it is impossible to directly enter groove and divide
From.Existing production technology be using carbon ammonium precipitation or oxalic acid precipitation, so as to obtain carbon ammonium rare earth or rare earth oxalate.This technique
Though can preferably precipitating rare earth, also bring a lot of problems.Such as：
(1) leaching mother liquid concentration is low, liquid measure is big, following process amount is big, processing cost is higher.
(2) ammonia nitrogen severe overweight, pollutes environment, constrains the use of technique, cause many mines to suspend operations for consolidation for many years,
So far do not reproduce.
(3) the leaching mother solution to collecting, it is impossible to accomplish reasonably, scientifically to process, only a kind of processing mode, that is, carry out
Remove impurity and precipitation, produce single solid rare earth oxide product, and product structure is single, and selectivity is little.
(4) leach that mother liquid concentration is low, impurity content is high, it is impossible to directly enter groove and separate.
(5) product of existing technique productions, need to carry out the operations such as remove impurity, precipitation, dehydration, filter pressing, calcination to leaching mother solution, obtain
Solid mixed rare-earth oxide；Solid rare earth oxide is carried out before factory's extract and separate is separated by the mine rare-earth products again
Sour molten and remove impurity, is obtained after meeting into the qualified feed liquid of groove, could enter separating and extracting process.It can be seen that, the production technology and point
From factory's subsequent process complexity, long flow path, also integrated cost height, acid mist impact problem.
(6) rare-earth products of prior art processes production, non-rare earth impurity content is higher.
Content of the invention
In view of this, it is an object of the invention to provide a kind of rare earth Situ Leaching mother solution is carried out classifying shunts the work for processing
Skill, to solving at least one technical problem present in aforementioned prior art.
To achieve these goals, the present invention provides a kind of rare earth Situ Leaching mother solution is carried out classifying and shunts the work for processing
Skill, which includes：
Cleaner I being passed through in the middle and high concentration leaching mother solution of concentration >=1g/L carries out remove impurity, heavy through precipitant after remove impurity
Forming sediment, then solid-state rare-earth products is obtained through clear water washing, filtration, calcination；Wherein, the cleaner I is sodium bicarbonate solution and carbon
The mixed liquor of acid sodium solution, the precipitant is sodium bicarbonate solution；With
To concentration<Be passed through in the leaching at low-concentration mother solution of 1g/L in cleaner II and remove removing aluminum impurity, then will be except aluminum after
Mother solution (leaching mother solution gained rare earth supernatant after except aluminum) is passed through in ion exchange column and carries out the adsorption and enrichment of rare earth ion,
Desorbing is carried out with acid again, obtain liquid rare-earth products；Wherein, the cleaner II is lime cream.
Wherein, the mother solution that leaches is the conventional implication in this area, i.e., the Rare Earth Mine for obtaining through leaching ore deposit in situ leaches mother solution.
Preferably, the leaching mother solution is obtained by following methods：Injection leaching ore deposit agent and contracting agent, original place to the inside of ore body
Leaching ore deposit in situ leaches " ion phase " and part " other phases " rare earth, obtains leaching mother solution；
Wherein, the leaching ore deposit agent is obtained by the magnesite of iron content, manganese and calcium, and the preparation process of the leaching ore deposit agent is：Ore
Sized mixing with water after crushed, be subsequently adding acid and decompose in faintly acid, obtain final product the leaching ore deposit agent of liquid；
The contracting agent is calcium chloride solution.
Preferably, ferrum in the magnesite<10%th, manganese<3%th, calcium<10%, the percentage ratio is mass percent.
Preferably, leaching ore deposit process includes to soak ore deposit agent injection stage and top water injection stage；In leaching ore deposit agent injection stage injection
Leaching ore deposit agent, in top water injection stage injection top water；
Wherein in top water injection stage, calcium chloride solution is added in the water of top as contracting agent, is injected with top water in the lump.
Wherein, during the content of rare earth in leaching mother solution is crossed peak value and is in decline, stop the agent injection of leaching ore deposit,
It is changed to injection top water (including contracting agent)；When the content of rare earth in leaching mother solution drops to 0.1 grams per liter, stop injection top water
(including contracting agent) liquid is received, terminate leaching ore deposit.It is highly preferred that crossing peak value and drop to when the content of rare earth in mother solution is leached
During (peak value) 80%～50%, stop the agent injection of leaching ore deposit, be changed to injection top water.
Wherein, described being passed through when cleaner I carries out remove impurity preferably controls pH≤5.2.
Wherein, the cleaner II is lime cream, but may be otherwise with cleaner I (i.e. sodium bicarbonate solution and carbonic acid
The mixed liquor of sodium solution) substitute lime cream carry out remove impurity.
Wherein, the preferred acrylic acid type cation exchange resin of the ion exchange column.
Compared to existing technology, the present invention has following advantages：
(1) middle and high concentration rare earth leaches mother solution, and rare earth total output can account for more than 50%, but leach the volume amount of mother solution
General not over the 1/4～1/3 of recovered liquid total amount, depositing technology facility can be substantially reduced, shorten with technical process, reduce phase
The disposable investment of pass and production cost.
(2) present invention process is larger to leachate liquid measure, account for the low concentration of rare earth mother solution of leaching mother solution amount 2/3, takes
Ion exchange absorption enrichment method process.The superiority of the method be exactly using equipment treating capacity is big, work is continuous.Such mother solution
Liquid storage tank and tail washings liquid storage tank, join liquid pool and can all reduce, reduce disposable investment.As middle and high concentration mother solution enters
Enter processing system above, it is possible thereby to design less complete set of equipments to process low concentration mother solution.This equipment is disposably thrown
After money, can reuse for a long time.
Description of the drawings
Fig. 1 is the schematic flow sheet of Rare Earth Mine " pond leaching " technique.
Fig. 2 is the schematic flow sheet of prior art Rare Earth Mine " in_situ leaching " technique.
Fig. 3 leaches curve for typical rare earth.
Fig. 4 carries out classifying to rare earth Situ Leaching mother solution for the present invention and shunts the process flow diagram for processing.
Specific embodiment
For making the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in further detail.
In this area, the preservation character of " ion-type " Rare Earth Mine rare earth, it is made up of " four phases, eight state " rare-earth mineral：1. from
Son absorption phase (ADSORPTION STATE containing interchangeability, obligate ADSORPTION STATE；2. dispersion (ADSORPTION STATE containing colloid, gel state)；3. independent
Mineral facies (state containing hypergenic minerals, residual ore body states of matter)；4. lattice impurity phase (state containing isomorph, interior dive same crystalline state).By this " four
The rare-earth mineral of eight state of phase ", that is, constituted in ion adsorption type rare earth ore, so-called " full phase " rare-earth mineral.It is related to " four phases eight
The source of its name data of state " is：《South jiangxi granite weathering crust ion adsorption type re research on mineralization》Report, south jiangxi
Geologic survey group, 1986.
In the present invention, described " other phases " rare earth is referred in ion type rareearth ore, except " ion phase " rare-earth mineral
Outside, the rare-earth mineral of remaining " phase ".
Present inventor classifies to leaching mother solution in a creative way for outstanding problem present in prior art
Shunting is processed, so as to obtain the product of different shape by different handling process.
Refer to shown in Fig. 3, which is that the present invention rare earth Situ Leaching mother solution is carried out classifying shunts the technique stream for processing
Journey schematic diagram.The technique for carrying out classification shunting process to rare earth Situ Leaching mother solution of the present invention includes：
Cleaner I being passed through in the middle and high concentration leaching mother solution of concentration >=1g/L carries out remove impurity, heavy through precipitant after remove impurity
Forming sediment, then solid-state rare-earth products is obtained through clear water washing, filtration, calcination；Wherein, the cleaner I is sodium bicarbonate solution and carbon
The mixed liquor of acid sodium solution, the precipitant is sodium bicarbonate solution；With
To concentration<Be passed through in the leaching at low-concentration mother solution of 1g/L in cleaner II and remove removing aluminum impurity, then will be except aluminum after
Mother solution (leaching mother solution gained rare earth supernatant after except aluminum) is passed through in ion exchange column and carries out the adsorption and enrichment of rare earth ion,
Desorbing is carried out with acid again, obtain liquid rare-earth products；Wherein, the cleaner II is lime cream.
Before formally starting to soak ore deposit exploitation work, in general, also include following preparation：
1st, geologic prospect is supplemented；
2nd, engineering design and construction；
3rd, major project is built：
(1) fluid injection system；
(2) water supplying system；
(3) liquid system is received on underground, ground；
(4) hydrometallurgy system；
(5) power-distribution architecture is supplied；
(6) other assistant systems；
(7) ionic adsorption remove impurity, enrichment system and storage tank (car).
Several specific embodiments of application present invention process are the following is, this is understood in detail by specific embodiment
Bright realization and its technique effect.Wherein, REO refers to rare earth oxide (rare earth oxide), and RE refers to rare earth (rare
earth).
Leaching ore deposit agent used in following embodiments is obtained by the magnesite of iron content, manganese and calcium, the preparation of the leaching ore deposit agent
Cheng Wei：Ore is sized mixing with water after crushed, is subsequently adding acid and decomposes in faintly acid, obtains final product the leaching ore deposit agent, the leaching ore deposit for obtaining
Agent contains the composite cations such as magnesium, ferrum, manganese and calcium.Wherein, ferrum in the magnesite<10%th, manganese<3%th, calcium<10%, described hundred
Divide than being mass percent.
Contracting agent used in following embodiments be by calcium chloride solution.
Embodiment 1
Ion type rareearth ore in the present embodiment comes from Ganzhou Xunwu Rare-earth Mine, sample ore main chemical compositions such as table
Shown in 1.
1 Xunwu ion type rareearth ore main component table of table
First, the preparation of early stage is carried out：
1st, geologic prospect is supplemented；
2nd, engineering design and construction；
3rd, major project is built：
(1) fluid injection system；
(2) water supplying system；
(3) liquid system is received on underground, ground；
(4) hydrometallurgy system；
(5) power-distribution architecture is supplied；
(6) other assistant systems；
(7) ionic adsorption remove impurity, enrichment system and storage tank (car).
Then, start to soak ore deposit enrichment work：
Step one：Injection leaching ore deposit agent and contracting agent to the inside of ore body, In-situ leaching ore deposit makes " ion phase " and part " other
Phase " rare earth is leached, and obtains leaching mother solution；
Step 2：Cleaner I being passed through in the middle and high concentration leaching mother solution of concentration >=1g/L carries out remove impurity, remove impurity time control
PH≤5.2 processed, precipitate through precipitant after remove impurity, then obtain solid-state rare-earth products through clear water washing, filtration, calcination；Wherein, described
Cleaner I is the mixed liquor of sodium bicarbonate solution and sodium carbonate liquor, and the precipitant is sodium bicarbonate solution；With
To concentration<Be passed through in the leaching at low-concentration mother solution of 1g/L in cleaner II and remove removing aluminum impurity, then will be except aluminum after
Mother solution (leaching mother solution gained rare earth supernatant after except aluminum) is passed through in ion exchange column and carries out the adsorption and enrichment of rare earth ion,
Desorbing is carried out with acid again, obtain liquid rare-earth products；Wherein, the cleaner II is lime cream.
Specifically, in first, the mid-term injection leaching ore deposit agent of leaching ore deposit；Cross peak value and decline when the content of rare earth in mother solution is leached
During to 60%, stop the agent of leaching ore deposit and inject, injection top water is changed to, adds contracting agent to inject in the lump in the water of top, when in leaching mother solution
Content of rare earth when dropping to 0.1 grams per liter, stop injection top water and simultaneously receive liquid, terminate leaching ore deposit.
After terminating leaching ore deposit, the middle and high concentration for concentration >=1g/L leaches mother solution sodium bicarbonate and sodium carbonate mixed liquor
After remove impurity, directly being precipitated with sodium bicarbonate solution, censorship after " solid-state " rare-earth products is obtained through clear water washing, filtration, calcination；Right
In concentration<After the leaching at low-concentration mother solution of 1g/L lime cream is except aluminum, supernatant is passed through to be handed over equipped with macroporous acrylic cation
The exchange column for changing resin carries out adsorption and enrichment, remove impurity, obtains censorship after " liquid " rare-earth products through resolving hydrochloric acid.
Rare earth sample ore leaches mother solution main chemical compositions such as table 2 through soaking the middle and high concentration mischmetal of gained after ore deposit agent is leached
Shown.
The middle and high concentration mischmetal of table 2 leaches the main chemical compositions table of mother solution
Rare earth sample ore leaches mother solution main chemical compositions such as 3 institute of table through soaking gained low concentration mischmetal after ore deposit agent is leached
Show.
3 low concentration mischmetal of table leaches mother solution main chemical compositions table
| Element | REO | Al | Fe | Ca | Mg | Si | pH |
| Content g/L | 0.98 | 0.33 | <0.01 | 0.05 | 1.83 | 0.03 | 3.7 |
It is as shown in table 4 that low concentration of rare earth leaches mother solution gained rare earth supernatant main chemical compositions after except aluminum.
Table 4 removes liquid main chemical compositions table after aluminum
| Element | RE | Al | Fe | Ca | Mg | Si |
| Except aluminum supernatant | 0.89 | 0.02 | <0.01 | 0.05 | 1.77 | 0.03 |
Embodiment 2
Measure middle and high concentration mischmetal and leach mother solution (as shown in table 2) 1L, sodium bicarbonate using 8% and 10%
Sodium carbonate 1:1 mixed liquor carries out remove impurity, filtration, and remove impurity experimental condition is 4.7, at the conditions of the experiments described above, dilute for control ph
Native loss rate is 1.21%, and gained rare earth oxide aluminium content is 1.0%；After filtration, supernatant is carried out using 8% sodium bicarbonate
Clear water washing, filtration, calcination, at the conditions of the experiments described above, rare-earth precipitation rate is 97.4%.
Embodiment 3
Measure middle and high concentration mischmetal and leach mother solution (as shown in table 2) 1L, sodium bicarbonate using 8% and 10%
Sodium carbonate 1:1 mixed liquor carries out remove impurity, filtration, and remove impurity experimental condition is 4.9, at the conditions of the experiments described above, dilute for control ph
Native loss rate is 1.81%, and gained rare earth oxide aluminium content is 0.42%；After filtration, supernatant is carried out using 8% sodium bicarbonate
Clear water washing, filtration, calcination, at the conditions of the experiments described above, rare-earth precipitation rate is 97.19%.
Embodiment 4
Measure middle and high concentration mischmetal and leach mother solution (as shown in table 2) 4L, sodium bicarbonate using 8% and 10%
Sodium carbonate 1:1 mixed liquor carries out remove impurity, filtration, and remove impurity experimental condition is 4.85, at the conditions of the experiments described above, dilute for control ph
Native loss rate is 1.93%, and gained rare earth oxide aluminium content is 0.35%；After filtration, supernatant is carried out using 8% sodium bicarbonate
Clear water washing, filtration, calcination, at the conditions of the experiments described above, rare-earth precipitation rate is 97.07%.
Embodiment 5
Measure low concentration mischmetal and mother solution (as shown in table 3) 4L is leached, add in beaker, open stirring, continuous Deca
Lime cream, monitors pH value with pH meter, adjusts pH value to 5.0, after continuing stirring 30min and makes pH value keep constant, filters after terminal,
Cake Wash, drying.At the conditions of the experiments described above, except Fe in liquid (leaching mother solution through removing gained rare earth supernatant after aluminum) after aluminum
<0.01g/L, Al be 0.07g/L, Ca be 0.05g/L, Mg be 1.80g/L, Si be 0.03g/L, rare earth concentration be 0.962g/L,
Rare-earth yield is 99.39%.
Embodiment 6
Measure low concentration mischmetal and mother solution (as shown in table 3) 4L is leached, add in beaker, open stirring, continuous Deca
Lime cream, monitors pH value with pH meter, adjusts pH value to 5.15, after continuing stirring 30min and makes pH value keep constant, mistake after terminal
Filter, Cake Wash, drying.At the conditions of the experiments described above, except liquid (leaching mother solution through removing gained rare earth supernatant after aluminum) after aluminum
Middle Fe<0.01g/L, Al be 0.02g/L, Ca be 0.05g/L, Mg be 1.75g/L, Si be 0.03g/L, rare earth concentration is
0.941g/L, rare-earth yield is 98.90%.
Embodiment 7
Measure low concentration mischmetal and mother solution (as shown in table 3) 4L is leached, add in beaker, open stirring, continuous Deca
Lime cream, monitors pH value with pH meter, adjusts pH value to 5.3, after continuing stirring 30min and makes pH value keep constant, filters after terminal,
Cake Wash, drying.At the conditions of the experiments described above, except Fe in liquid (leaching mother solution through removing gained rare earth supernatant after aluminum) after aluminum
<0.01g/L, Al be 0.01g/L, Ca be 0.05g/L, Mg be 1.70g/L, Si be 0.03g/L, rare earth concentration be 0.895g/L,
Rare-earth yield is 96.59%.
Embodiment 8
The single-stage that H type macroporous acrylic cation exchanger resin (filling post with 134 grams of dry weight resins) wherein will be housed is inhaled
(post footpath compares 8 to attached column:1) pretreatment is carried out, (feed liquid shown in table 4) is fed in the way of the flow velocity of 600ml/h, bottom in and top out,
Outlet liquid is absorption extraction raffinate.Starting stage, absorption extraction raffinate no rare earth, as absorption proceeds, the rare earth of adsorption column absorption
More and more, from light to dark, after 32h, outlet absorption extraction raffinate oxalic acid water detects rare earth to color of resin, continues feed liquor, per 1h
Sample EDTA solution detection rare earth concentration is taken, it is equal with feed liquor rare earth concentration to go out liquid rare earth after 23h, resin saturation, with clear
Water washing resin, until outlet no rare earth, stops water inlet, surveys rare earth absorption extraction raffinate.Carried out using 4.5N hydrochloric acid after adsorption saturation
Desorbing, resolution speed is controlled to 100ml/h, will absorption extraction raffinate and stripping liquid analysis detection.At the conditions of the experiments described above, list is measured
The total adsorbance of post resin is 21.35g rare earth, and saturated adsorption capacity is 157.41mg/g；Rare earth resolution factor is 99%, and desorbed solution is most
High concentration is RE=75g/L, Ca=0.8g/L, Mg=0.12g/L, Al=0.65g/L.
Embodiment 9
Prepare 8 plural serial stages pretreated resin column (with embodiment 8), with the flow velocity of 1000ml/h, bottom in and top out
The mode of (1 bottom feed of testing column, 8 top of testing column is flowed out) feeds (feed liquid shown in table 4), and each adsorption column of real-time detection goes out
The liquid rare earth concentration of mouth, after the outlet of testing column 1 has rare earth, detects first outlet rare earth concentration per 1h, and after 41h, rare earth is dense
Degree is equal to 0.94g/L, 1 saturation of testing column, and the detection outlet of testing column 3 has rare earth, and testing column 4 exports no rare earth.Feed always straight
There is rare earth to the detection outlet of testing column 8, continue charging, and outlet rare earth feed liquid is collected, until 8 outlet rare earth concentration of testing column etc.
In 0.94g/L, stop charging.Washed with clear water, be washed till testing column 8 and no rare earth is exported, using 4.5N resolving hydrochloric acid, segmentation is intercepted
Desorbed solution, until testing column 8 exports no rare earth and stops into hydrochloric acid.At the conditions of the experiments described above, total co-feeding 260L, testing column 8
Outlet liquid (penetrating liquid) 37L, 0.65g/L containing rare earth, 8 post series connection adsorption column is 220.35g to the total adsorbance of rare earth；Desorbed solution
Highest rare earth concentration is 183g/L, and it is 99.14% that desorbed solution total amount of rare earth is 218.45g, rare earth resolution factor, dense from highest rare earth
Degree desorbed solution analyzes non-rare earth impurity concentration：Al=0.82g/L, Mg=0.62g/L, Ca=1.1g/L, Fe=0.03g/L.
Embodiment 10
Prepare 8 plural serial stages pretreated resin column (with embodiment 9), with the flow velocity of 600ml/h, bottom in and top out
The mode of (1 bottom feed of testing column, 8 top of testing column is flowed out) feeds (feed liquid shown in table 4), and each adsorption column of real-time detection goes out
Oral fluid body rare earth concentration, after the outlet of testing column 1 has rare earth, detects first outlet rare earth concentration, rare earth concentration after 65h per 1h
Equal to 0.94g/L, first saturation, the detection outlet of testing column 3 has rare earth, and testing column 4 exports no rare earth.Charging always is until inspection
Surveying the outlet of testing column 8 has rare earth, continues charging, and collects outlet rare earth feed liquid, until 8 rare earth concentration of testing column is equal to 0.94g/
L, stops charging.Washed with clear water, until testing column 8 exports no rare earth, using 5.5N resolving hydrochloric acid, segmentation intercepts desorbed solution,
Until testing column 8 exports no rare earth and stops into hydrochloric acid.At the conditions of the experiments described above, total co-feeding 260.5L, testing column 8 goes out oral fluid
Body (penetrating liquid) 37L, 0.58g/L containing rare earth, 8 post series connection adsorption column is 220.83g to the total adsorbance of rare earth；Desorbed solution highest is dilute
Native concentration 215g/L, it is 99.40% that desorbed solution total amount of rare earth is 219.51g, rare earth resolution factor, from highest rare earth concentration desorbed solution
Analyzing non-rare earth impurity concentration is：Al=0.31g/L, Mg=0.52g/L, Ca=1.03g/L, Fe=0.02g/L.
Above-described embodiment, some measured datas in conjunction with the present invention in implementation process, as a result show, compare existing skill
Art, the present invention has following advantages：
The leaching rare earth mother solution mean concentration of prior art processes is generally 0.5～1.5g/L, and the rare earth of high concentration
Mother solution (>More than 40% 1g/L) is accounted for.And the leaching mother liquid concentration of present invention acquisition is higher than prior art processes by about 22～46%, in advance
Meter productive concept is averagely up to 0.6～2.3g/L.The present invention recommends " cut ridge, to cut to leach that mother solution " classification shunting " processes
High point " is set to " 1.0g/L ", in this, as work examination and the reference index of production, rare earth mother solution is carried out shunting process of classifying.Should
Controlling indicator, can verify in commerical test from now on and production practices further and suitably be revised as needed.
" 1.0g/L " becomes to leaching what rare earth mother solution " classification shunting " was processed as most important production flow-dividing control point
" separation ".That is,：>=1.0g/L is carried out remove impurity, precipitation enrichment, obtains as " cutting high " mother solution (middle and high concentration rare earth mother solution)
Arrive " solid-state " mischmetal product；The conduct of ＜ 1.0g/L " takes low " mother solution (low concentration of rare earth mother solution), carries out ion-exchange absorption
Attached enrichment, obtains " liquid " mischmetal product.Supernatants after precipitation, ionic adsorption extraction raffinate return leaching ore deposit after proportioning process.
Often spent acid is higher for ion exchange desorbing gained rare-earth enrichment liquid, is neutralized with the rareearth enriching material of precipitation, can prepare highly concentrated
Degree rare earth feed liquid is for separating factory's use.
Present invention process carries out rationally, scientifically process, carrying out the mother solution of variable concentrations and " classifying to leaching rare earth mother solution
Shunting " is processed, and obtains the rare-earth products of " solid-state " and " liquid " two kinds of different shapes respectively, exploits ion type rareearth mine,
The high frontline technology of high-efficiency and economic, a resource utilization is entered, is characterized in particular in：
(1) invention proposition and the technological thought that sets up and process route, can be carried out reasonably, scientifically to leaching mother solution
Processing, that is, " classification shunting " is carried out to the mother solution of variable concentrations processes.Liquid measure is relatively small, but concentration belongs to middle and high level
Mother solution, enters " solid-state " rare-earth products production system, obtains " solid-state " rare-earth products；Liquid measure is relatively large, but concentration is relatively low
Mother solution, enters " liquid " rare-earth products production system, obtains " liquid " rare-earth products.
(2) present invention process is than existing technique, and on product structure, how a kind of " liquid " product, increased enterprise to producing
The selectivity of product, product structure has more motility and practicality.
(3) implement " classification shunting " to process to mother solution, investment is reduced, improves the comprehensive benefit of enterprise.
(4) " liquid " rare-earth products of present invention process production, concentration height, impurity is low, and concentration ratio is big；Product quality is better than
The main non-rare earth impurity content such as prior art processes product, especially Fe, Al, Si is very low, is conducive to separating；Meet and separate factory pair
Enter the requirement of " the qualified rare earth feed liquid " of groove, the product is available for separation factory and directly enters groove separation.
(5) " liquid " the production system in present invention process, simplifies mine and the production process for separating factory, flow process
Short.It also solves the problem of " acid mist " impact environment for separating in prepared by factory's rare earth feed liquid.
Particular embodiments described above, has been carried out to the purpose of the present invention, technical scheme and beneficial effect further in detail
Describe in detail bright, it should be understood that the foregoing is only the specific embodiment of the present invention, be not limited to the present invention, all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement that is done etc., should be included in the protection of the present invention
Within the scope of.
Claims (8)
1. a kind of rare earth Situ Leaching mother solution is carried out classifying shunts the technique for processing, it is characterised in that include：
Cleaner I being passed through in the middle and high concentration leaching mother solution of concentration >=1g/L carries out remove impurity, precipitates through precipitant after remove impurity,
Through clear water washing, filtration, calcination, solid-state rare-earth products are obtained again；Wherein, the cleaner I is sodium bicarbonate solution and sodium carbonate
The mixed liquor of solution, the precipitant is sodium bicarbonate solution；With
To concentration<It is passed through in the leaching at low-concentration mother solution of 1g/L in cleaner II and removing aluminum impurity is removed, then will be except aluminum Mother liquor
Being passed through in ion exchange column carries out the adsorption and enrichment of rare earth ion, then carries out desorbing with acid, obtains liquid rare-earth products；Wherein,
The cleaner II is lime cream.
2. technique according to claim 1, it is characterised in that the leaching mother solution is obtained by following methods：To ore body
Internal injection leaching ore deposit agent and contracting agent, In-situ leaching ore deposit leaches " ion phase " and part " other phases " rare earth, is soaked
Go out mother solution；
Wherein, the leaching ore deposit agent is obtained by the magnesite of iron content, manganese and calcium, and the preparation process of the leaching ore deposit agent is：Ore is through powder
Sized mixing with water after broken, be subsequently adding acid and decompose in faintly acid, obtain final product the leaching ore deposit agent of liquid；
The contracting agent is calcium chloride solution.
3. technique according to claim 2, it is characterised in that ferrum in the magnesite<10%th, manganese<3%th, calcium<10%,
The percentage ratio is mass percent.
4. technique according to claim 2, it is characterised in that leaching ore deposit process includes to soak ore deposit agent injection stage and top water injection
Stage；In leaching ore deposit agent injection stage injection leaching ore deposit agent, in top water injection stage injection top water；
Wherein in top water injection stage, calcium chloride solution is added in the water of top as contracting agent, is injected with top water in the lump.
5. technique according to claim 4, it is characterised in that cross peak value and be in when the content of rare earth in mother solution is leached
During decline, stop the agent injection of leaching ore deposit, be changed to injection top water；0.1 grams per liter is dropped to when the content of rare earth in mother solution is leached
When, stop injection top water and liquid is received, terminate leaching ore deposit.
6. technique according to claim 5, it is characterised in that cross peak value and decline when the content of rare earth in mother solution is leached
During to 80%～50%, stop the agent injection of leaching ore deposit, be changed to injection top water.
7. technique according to claim 1, it is characterised in that wherein, the cleaner I that is passed through carries out controlling pH during remove impurity
≤5.2.
8. technique according to claim 1, it is characterised in that the ion exchange column be
Fat.
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| CN110382109A (en) * | 2017-03-07 | 2019-10-25 | 瑞乌诺有限公司 | For processing the system and method for including the mineral of lanthanide series and producing rare earth oxide |
| CN110607440A (en) * | 2019-10-14 | 2019-12-24 | 中铝广西有色稀土开发有限公司 | In-situ leaching method for ionic rare earth ore |
| CN111118312A (en) * | 2019-12-21 | 2020-05-08 | 钢研集团稀土科技有限公司 | Method for removing chlorine radicals and aluminum ions in alkali-precipitated high-aluminum rare earth solution |
| CN111285391A (en) * | 2020-03-13 | 2020-06-16 | 北京耀智环保科技有限公司 | Preparation method and device of high-purity rare earth carbonate and ion exchange resin |
| CN114522969A (en) * | 2022-02-11 | 2022-05-24 | 江西理工大学 | Method for leaching ionic rare earth tailings |
| CN117821783A (en) * | 2024-03-05 | 2024-04-05 | 矿冶科技集团有限公司 | Green exploitation method of ionic rare earth ore |
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| CN111118312A (en) * | 2019-12-21 | 2020-05-08 | 钢研集团稀土科技有限公司 | Method for removing chlorine radicals and aluminum ions in alkali-precipitated high-aluminum rare earth solution |
| CN111285391A (en) * | 2020-03-13 | 2020-06-16 | 北京耀智环保科技有限公司 | Preparation method and device of high-purity rare earth carbonate and ion exchange resin |
| CN114522969A (en) * | 2022-02-11 | 2022-05-24 | 江西理工大学 | Method for leaching ionic rare earth tailings |
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| CN117821783A (en) * | 2024-03-05 | 2024-04-05 | 矿冶科技集团有限公司 | Green exploitation method of ionic rare earth ore |
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