CN106435172B - The technique that classification shunting processing is carried out to rare earth Situ Leaching mother liquor - Google Patents
The technique that classification shunting processing is carried out to rare earth Situ Leaching mother liquor Download PDFInfo
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- CN106435172B CN106435172B CN201610898627.2A CN201610898627A CN106435172B CN 106435172 B CN106435172 B CN 106435172B CN 201610898627 A CN201610898627 A CN 201610898627A CN 106435172 B CN106435172 B CN 106435172B
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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
Abstract
The invention discloses a kind of techniques carrying out classification shunting processing to rare earth Situ Leaching mother liquor, including：It is passed through cleaner I into the middle and high concentration of concentration >=1g/L leaching mother liquor to clean, be precipitated through precipitating reagent after removal of impurities, then solid-state rare-earth products are obtained through clear water washing, filtering, calcination；Wherein, the cleaner I is the mixed liquor of sodium bicarbonate solution and sodium carbonate liquor, and the precipitating reagent is sodium bicarbonate solution；With to concentration<It is passed through cleaner II neutralizations in the leaching at low-concentration mother liquor of 1g/L and removes removing aluminum impurity, the adsorption and enrichment of progress rare earth ion in ion exchange column then will be passed through except aluminium Mother liquor, then desorbed with acid, obtains liquid rare-earth products；Wherein, the cleaner II is milk of lime.Present invention process carries out classification shunting processing to the mother liquor of various concentration, obtains solid-state and two kinds of different shape rare-earth products of liquid respectively, so that ion type rareearth mine is exploited, the frontline technology high into high-efficiency and economic, a resource utilization.
Description
Technical field
The present invention relates to mining technology technical fields, and in particular to a kind of to carry out classification shunting to rare earth Situ Leaching mother liquor
The technique of processing.
Background technology
So far, there are mainly two types of the leaching of " ion type rareearth ore " and process of enriching, one kind is " pond leaching ", and one kind is " original
Soak mine in ground ".Destruction ecological environment brought by " pond leaching " with influence very big, China exploits implementation to " ion type rareearth ore "
Extraction technique policy has been eliminated, and what is now carried out is " in_situ leaching " technique.The flow diagram of both excavated technologies point
Not 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 progress for soaking mine, soaks mine initial stage
Liquid rare earth concentration is relatively low before soaking mine, and leaching mine mid-term rare earth concentration steps up, and (can reach several g/L or more) after reaching peak value, again
It gradually reduces, leaching mine later stage rare earth tail washings rare earth concentration reaches 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 liquor of " ionic " Rare-earth Mine, is collected to it by liquid collection system now.Though
Right this receipts liquid mode can effectively collect most rare earth mother solution, but the rare earth concentration collected is low, often averagely only has
0.5~1.5g/L or so.The rare earth mother solution of this concentration cannot be directly into slot point since rare earth concentration is low, impurity content is high
From.Existing production technology only uses carbon ammonium precipitation or oxalic acid precipitation, to obtain ammonium bicarbonate rare earth or rare earth oxalate.This technique
Though can preferably precipitating rare earth, also bring many 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 severely exceeds, and pollutes environment, constrains the use of technique, many mines is caused to suspend operations for consolidation for many years,
So far it does not reproduce.
(3) to the leaching mother liquor of collection, cannot accomplish reasonably, scientifically to handle, only a kind of processing mode carries out
Removal of impurities and precipitation, the solid rare earth oxide product of production list one, product structure is single, and selectivity is small.
(4) leaching mother liquid concentration is low, impurity content is high, cannot directly be detached into slot.
(5) product of existing technique productions, need to be cleaned to leaching mother liquor, precipitate, be dehydrated, press filtration, the processes such as calcination, obtain
Solid mixed rare-earth oxide；The mine rare-earth products again carry out solid rare earth oxide before the extraction and separation of separation factory
Acid is molten and cleans, and is made and meets into after the qualified feed liquid of slot, could enter separating and extracting processing.As it can be seen that the production technology and point
The complicated, long flow path from factory's subsequent process, overall cost is high, and also acid mist influences problem.
(6) rare-earth products of prior art processes production, non-rare earth impurity content are higher.
Invention content
In view of this, the object of the present invention is to provide a kind of works carrying out classification shunting processing to rare earth Situ Leaching mother liquor
Skill, to solve aforementioned at least one technical problem existing in the prior art.
To achieve the goals above, the present invention provides a kind of work carrying out classification shunting processing to rare earth Situ Leaching mother liquor
Skill comprising：
Cleaner I is passed through into the middle and high concentration of concentration >=1g/L leaching mother liquor to clean, it is heavy through precipitating reagent after removal of impurities
It forms sediment, then solid-state rare-earth products is obtained through clear water washing, filtering, calcination；Wherein, the cleaner I is sodium bicarbonate solution and carbon
The mixed liquor of acid sodium solution, the precipitating reagent are sodium bicarbonate solution；With
To concentration<It is passed through cleaner II neutralizations in the leaching at low-concentration mother liquor of 1g/L and removes removing aluminum impurity, after then removing aluminium
Mother liquor (leaching mother liquor through except gained rare earth supernatant after aluminium) is passed through the adsorption and enrichment that rare earth ion is carried out in ion exchange column,
It is desorbed again with acid, obtains liquid rare-earth products；Wherein, the cleaner II is milk of lime.
Wherein, described to leach the meaning that mother liquor is this field routine, i.e., the Rare Earth Mine obtained through leaching mine in situ leaches mother liquor.
Preferably, the leaching mother liquor is obtained by following methods：Injection leaching mine agent and contracting agent, original place inside to ore body
Leaching mine in situ makes " ion phase " and part " other phases " rare earth leach, and obtains leaching mother liquor；
Wherein, the leaching mine agent is made by the magnesite of iron content, manganese and calcium, and the preparation process of the leaching mine agent is：Ore
It is sized mixing after crushed with water, acid is then added and decomposes to the weakly acidic leaching mine agent to get liquid；
The contracting agent is calcium chloride solution.
Preferably, iron in the magnesite<10%, manganese<3%, calcium<10%, the percentage is mass percent.
Preferably, leaching mine process includes leaching mine agent injection stage and top water injection stage；In leaching mine agent injection stage injection
Mine agent is soaked, in top water injection stage injection top water；
It wherein in top water injection stage, is added to calcium chloride solution as contracting agent in the water of top, is injected together with top water.
Wherein, when leach the content of rare earth in mother liquor cross peak value and locate during the decline, stop leaching mine agent injection,
It is changed to injection top water (including contracting agent)；When leaching the content of rare earth in mother liquor and dropping to 0.1 grams per liter, stop injection top water
(including contracting agent) and liquid is received, terminates leaching mine.It is highly preferred that when the content of rare earth leached in mother liquor is crossed peak value and is dropped to
When (peak value) 80%~50%, stop leaching mine agent injection, is changed to injection top water.
Wherein, described be passed through when cleaner I is cleaned preferably controls pH≤5.2.
Wherein, the cleaner II is milk of lime, but be may be otherwise with cleaner I (i.e. sodium bicarbonate solution and carbonic acid
The mixed liquor of sodium solution) substitute milk of lime clean.
Wherein, the preferred acrylic acid type cation exchange resin of the ion exchange column.
Compared with prior art, the present invention has following advantages：
(1) middle and high concentration rare earth leaches mother liquor, and rare earth total output can account for 50% or more, but leach the volume amount of mother liquor
The 1/4~1/3 of recovered liquid total amount generally is not exceeded, depositing technology facility can be substantially reduced with technical process, shorten, and reduce phase
The disposable investment and production cost of pass.
(2) present invention process is larger to leachate liquid measure, accounts for about the low concentration of rare earth mother liquor for leaching mother liquor amount 2/3, takes
The processing of ion exchange adsorption enrichment method.The superiority of this method is exactly big using equipment treating capacity, works continuously.Such mother liquor
Liquid storage tank and tail washings liquid storage tank, can reduce with liquid pool, reduce disposable investment.Due to middle and high concentration mother liquor into
Enter the processing system of front, it is possible thereby to design smaller complete set of equipments to handle low concentration mother liquor.This equipment is disposably thrown
After money, it can reuse for a long time.
Description of the drawings
Fig. 1 is the flow diagram of Rare Earth Mine " pond leaching " technique.
Fig. 2 is the flow diagram of prior art Rare Earth Mine " in_situ leaching " technique.
Fig. 3 is that typical rare earth leaches curve.
Fig. 4 is the process flow diagram that classification shunting processing is carried out to rare earth Situ Leaching mother liquor of the present invention.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
In this field, the preservation character of " ionic " Rare Earth Mine rare earth is made 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 same crystalline state of diving).By this " four
The rare-earth mineral of eight state of phase " is constituted in ion adsorption type rare earth ore, so-called " full phase " rare-earth mineral.About " 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 refers to removing " ion phase " rare-earth mineral in ion type rareearth ore
Except, the rare-earth mineral of remaining " phase ".
Present inventor is directed to outstanding problem existing in the prior art, classifies in a creative way to leaching mother liquor
Shunting is handled, to obtain the product of different shape by different treatment process.
Shown in please referring to Fig.3, for the technique stream for carrying out classification shunting processing to rare earth Situ Leaching mother liquor of the present invention
Journey schematic diagram.The present invention to rare earth Situ Leaching mother liquor carry out classification shunting processing technique include：
Cleaner I is passed through into the middle and high concentration of concentration >=1g/L leaching mother liquor to clean, it is heavy through precipitating reagent after removal of impurities
It forms sediment, then solid-state rare-earth products is obtained through clear water washing, filtering, calcination；Wherein, the cleaner I is sodium bicarbonate solution and carbon
The mixed liquor of acid sodium solution, the precipitating reagent are sodium bicarbonate solution；With
To concentration<It is passed through cleaner II neutralizations in the leaching at low-concentration mother liquor of 1g/L and removes removing aluminum impurity, after then removing aluminium
Mother liquor (leaching mother liquor through except gained rare earth supernatant after aluminium) is passed through the adsorption and enrichment that rare earth ion is carried out in ion exchange column,
It is desorbed again with acid, obtains liquid rare-earth products；Wherein, the cleaner II is milk of lime.
Further include following preparation in general before formally starting to soak mine exploitation work：
1, geologic prospect is supplemented；
2, engineering design and construction；
3, 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 supply and distribution system；
(6) other assistant systems；
(7) ionic adsorption removal of impurities, enrichment system and storage tank (vehicle).
It is several specific embodiments using present invention process below, this hair is understood by specific embodiment in detail
Bright realization and its technique effect.Wherein, REO refers to rare earth oxide (rare earth oxide), and RE refers to rare earth (rare
earth)。
The leaching mine agent used in following embodiments is made by the magnesite of iron content, manganese and calcium, the preparation of the leaching mine agent
Cheng Wei：Ore is sized mixing with water after crushed, and acid is then added and decomposes to weakly acidic to get the leaching mine agent, obtained leaching mine
Agent contains the composite cations such as magnesium, iron, manganese and calcium.Wherein, iron in the magnesite<10%, manganese<3%, calcium<10%, described hundred
Divide than being mass percent.
The contracting agent used in following embodiments is 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 period is carried out：
1, geologic prospect is supplemented；
2, engineering design and construction；
3, 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 supply and distribution system；
(6) other assistant systems；
(7) ionic adsorption removal of impurities, enrichment system and storage tank (vehicle).
Then, start to soak mine enrichment work：
Step 1：Injection leaching mine agent and contracting agent inside to ore body, In-situ leaching mine keep " ion phase " and part " other
Phase " rare earth leaches, and obtains leaching mother liquor；
Step 2：Cleaner I is passed through into the middle and high concentration of concentration >=1g/L leaching mother liquor to clean, clean time control
PH≤5.2 processed, are precipitated after removal of impurities through precipitating reagent, then obtain solid-state rare-earth products through clear water washing, filtering, calcination；Wherein, described
Cleaner I is the mixed liquor of sodium bicarbonate solution and sodium carbonate liquor, and the precipitating reagent is sodium bicarbonate solution；With
To concentration<It is passed through cleaner II neutralizations in the leaching at low-concentration mother liquor of 1g/L and removes removing aluminum impurity, after then removing aluminium
Mother liquor (leaching mother liquor through except gained rare earth supernatant after aluminium) is passed through the adsorption and enrichment that rare earth ion is carried out in ion exchange column,
It is desorbed again with acid, obtains liquid rare-earth products；Wherein, the cleaner II is milk of lime.
Specifically, in first, the mid-term injection leaching mine agent of leaching mine；It crosses peak value when leaching the content of rare earth in mother liquor and declines
When to 60%, stop leaching mine agent injection, is changed to injection top water, addition contracting agent injects together in push up water, when leaching in mother liquor
Content of rare earth when dropping to 0.1 grams per liter, stop injection top water and simultaneously receive liquid, terminate leaching mine.
After terminating leaching mine, mother liquor sodium bicarbonate and sodium carbonate mixed liquor are leached for the middle and high concentration of concentration >=1g/L
It after removal of impurities, is directly precipitated with sodium bicarbonate solution, the inspection after clear water washing, filtering, calcination obtain " solid-state " rare-earth products；It is right
In concentration<After the leaching at low-concentration mother liquor of 1g/L removes aluminium with milk of lime, supernatant is passed through to be handed over equipped with macroporous acrylic cation
The exchange column for changing resin carries out adsorption and enrichment, removal of impurities, the inspection after resolving hydrochloric acid obtains " liquid " rare-earth products.
Rare earth sample ore middle and high concentration mischmetal of gained after leaching mine agent is leached leaches mother liquor main chemical compositions such as table 2
It is shown.
2 middle and high concentration mischmetal of table leaches the main chemical compositions table of mother liquor
Rare earth sample ore gained low concentration mischmetal after leaching mine agent is leached leaches mother liquor main chemical compositions such as 3 institute of table
Show.
3 low concentration mischmetal of table leaches mother liquor 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 liquor gained rare earth supernatant main chemical compositions after removing aluminium.
Table 4 removes liquid main chemical compositions table after aluminium
| Element | RE | Al | Fe | Ca | Mg | Si |
| Except aluminium supernatant | 0.89 | 0.02 | <0.01 | 0.05 | 1.77 | 0.03 |
Embodiment 2
It measures middle and high concentration mischmetal and leaches mother liquor (as shown in table 2) 1L, using 8% sodium bicarbonate and 10%
Sodium carbonate 1:1 mixed liquor is cleaned, is filtered, and pH value is 4.7 to removal of impurities experimental condition in order to control, at the conditions of the experiments described above, dilute
Native loss late is 1.21%, and gained rare earth oxide aluminium content is 1.0%；Supernatant is carried out using 8% sodium bicarbonate after filtering
Clear water washing, filtering, calcination, at the conditions of the experiments described above, rare-earth precipitation rate are 97.4%.
Embodiment 3
It measures middle and high concentration mischmetal and leaches mother liquor (as shown in table 2) 1L, using 8% sodium bicarbonate and 10%
Sodium carbonate 1:1 mixed liquor is cleaned, is filtered, and pH value is 4.9 to removal of impurities experimental condition in order to control, at the conditions of the experiments described above, dilute
Native loss late is 1.81%, and gained rare earth oxide aluminium content is 0.42%；Supernatant is carried out using 8% sodium bicarbonate after filtering
Clear water washing, filtering, calcination, at the conditions of the experiments described above, rare-earth precipitation rate are 97.19%.
Embodiment 4
It measures middle and high concentration mischmetal and leaches mother liquor (as shown in table 2) 4L, using 8% sodium bicarbonate and 10%
Sodium carbonate 1:1 mixed liquor is cleaned, is filtered, and pH value is 4.85 to removal of impurities experimental condition in order to control, at the conditions of the experiments described above, dilute
Native loss late is 1.93%, and gained rare earth oxide aluminium content is 0.35%；Supernatant is carried out using 8% sodium bicarbonate after filtering
Clear water washing, filtering, calcination, at the conditions of the experiments described above, rare-earth precipitation rate are 97.07%.
Embodiment 5
It measures low concentration mischmetal and leaches mother liquor (as shown in table 3) 4L, be added in beaker, open stirring, be constantly added dropwise
Milk of lime monitors pH value with pH meter, adjusts pH value to 5.0, continues to stir after 30min and pH value is made to remain unchanged, filtered after terminal,
Washing of Filter Cake, drying.At the conditions of the experiments described above, except Fe in liquid (leaching mother liquor through except gained rare earth supernatant after aluminium) after aluminium
<0.01g/L, Al 0.07g/L, Ca 0.05g/L, Mg 1.80g/L, Si 0.03g/L, rare earth concentration 0.962g/L,
Rare-earth yield is 99.39%.
Embodiment 6
It measures low concentration mischmetal and leaches mother liquor (as shown in table 3) 4L, be added in beaker, open stirring, be constantly added dropwise
Milk of lime monitors pH value with pH meter, adjusts pH value to 5.15, continues to stir after 30min and pH value is made to remain unchanged, mistake after terminal
Filter, Washing of Filter Cake, drying.At the conditions of the experiments described above, except liquid (leaching mother liquor through except gained rare earth supernatant after aluminium) after aluminium
Middle Fe<0.01g/L, Al 0.02g/L, Ca 0.05g/L, Mg 1.75g/L, Si 0.03g/L, rare earth concentration are
0.941g/L, rare-earth yield 98.90%.
Embodiment 7
It measures low concentration mischmetal and leaches mother liquor (as shown in table 3) 4L, be added in beaker, open stirring, be constantly added dropwise
Milk of lime monitors pH value with pH meter, adjusts pH value to 5.3, continues to stir after 30min and pH value is made to remain unchanged, filtered after terminal,
Washing of Filter Cake, drying.At the conditions of the experiments described above, except Fe in liquid (leaching mother liquor through except gained rare earth supernatant after aluminium) after aluminium
<0.01g/L, Al 0.01g/L, Ca 0.05g/L, Mg 1.70g/L, Si 0.03g/L, rare earth concentration 0.895g/L,
Rare-earth yield is 96.59%.
Embodiment 8
The single-stage that H-type macroporous acrylic cation exchanger resin (filling column with 134 grams of dry weight resins) will be wherein housed is inhaled
(column diameter is than 8 for attached column:1) it is pre-processed, (feed liquid shown in table 4) is fed in a manner of the flow velocity of 600ml/h, bottom in and top out,
It is absorption extraction raffinate to export liquid.Starting stage, absorption extraction raffinate is without rare earth, as absorption continues, the rare earth of adsorption column absorption
More and more, from light to dark, after 32h, outlet absorption extraction raffinate detects rare earth to color of resin with oxalic acid water, continues feed liquor, per 1h
Sample EDTA solution detection rare earth concentration is taken, goes out that liquid rare earth is equal with feed liquor rare earth concentration, and resin is saturated after 23h, with clear
Water washing resin surveys rare earth and adsorbs extraction raffinate until outlet stops water inlet without rare earth.It is carried out using 4.5N hydrochloric acid after adsorption saturation
Desorption, resolution speed control are 100ml/h, and absorption extraction raffinate and stripping liquid analysis are detected.At the conditions of the experiments described above, list is measured
The total adsorbance of column resin is 21.35g rare earths, saturated adsorption capacity 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 pretreated resin columns of plural serial stage (with embodiment 8), with the flow velocity of 1000ml/h, bottom in and top out
The mode of (1 bottom of testing column is fed, 8 top outflow of testing column) feeds (feed liquid shown in table 4), detects each adsorption column in real time and goes out
The liquid rare earth concentration of mouth detects first outlet rare earth concentration per 1h, rare earth is dense after 41h after there is rare earth in the outlet of testing column 1
Degree is equal to 0.94g/L, and testing column 1 is saturated, and the outlet of detection testing column 3 has rare earth, testing column 4 to export without rare earth.Charging is straight always
There is rare earth to the outlet of detection testing column 8, continues to feed, and collect outlet rare earth feed liquid, until 8 outlet rare earth concentration of testing column etc.
In 0.94g/L, stop charging.It is washed with clear water, is washed till the outlet of testing column 8 without rare earth, using 4.5N resolving hydrochloric acids, segmentation interception
Desorbed solution, until the outlet of testing column 8 stops without rare earth into hydrochloric acid.At the conditions of the experiments described above, total co-feeding 260L, testing column 8
It is 220.35g to the total adsorbance of rare earth to export liquid (penetrating liquid) column of 37L, 0.65g/L containing rare earth, 8 series connection adsorption column；Desorbed solution
Highest rare earth concentration is 183g/L, and desorbed solution total amount of rare earth is 218.45g, and rare earth resolution factor is 99.14%, dense from highest rare earth
It is a concentration of to spend desorbed solution analysis non-rare earth impurity：Al=0.82g/L, Mg=0.62g/L, Ca=1.1g/L, Fe=0.03g/L.
Embodiment 10
Prepare 8 pretreated resin columns of plural serial stage (with embodiment 9), with the flow velocity of 600ml/h, bottom in and top out
The mode of (1 bottom of testing column is fed, 8 top outflow of testing column) feeds (feed liquid shown in table 4), detects each adsorption column in real time and goes out
Oral fluid body rare earth concentration detects first outlet rare earth concentration per 1h, rare earth concentration after 65h after there is rare earth in the outlet of testing column 1
Equal to 0.94g/L, first saturation, the outlet of detection testing column 3 has rare earth, testing column 4 to export without rare earth.Charging always is until inspection
Surveying the outlet of testing column 8 has rare earth, continues to feed, and collect outlet rare earth feed liquid, until 8 rare earth concentration of testing column is equal to 0.94g/
L stops charging.It is washed with clear water, until the outlet of testing column 8, without rare earth, using 5.5N resolving hydrochloric acids, segmentation intercepts desorbed solution,
Until the outlet of testing column 8 stops without rare earth into hydrochloric acid.At the conditions of the experiments described above, total co-feeding 260.5L, testing column 8 go out oral fluid
Body (penetrating liquid) column of 37L, 0.58g/L containing rare earth, 8 series connection adsorption column is 220.83g to the total adsorbance of rare earth；Desorbed solution highest is dilute
Native concentration 215g/L, desorbed solution total amount of rare earth are 219.51g, and rare earth resolution factor is 99.40%, from highest rare earth concentration desorbed solution
It is a concentration of to analyze non-rare earth impurity：Al=0.31g/L, Mg=0.52g/L, Ca=1.03g/L, Fe=0.02g/L.
Above-described embodiment, in conjunction with some measured datas of the present invention in implementation process, the results show that comparing existing skill
Art, the present invention have 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 liquor (>1g/L) account for 40% or more.And the leaching mother liquid concentration that the present invention obtains is higher than prior art processes by about 22~46%, in advance
It is average up to 0.6~2.3g/L to count productive concept.The present invention recommend to leach mother liquor " classification shunt " processing " cut ridge is cut
High point " is set as " 1.0g/L ", tries, with the reference index produced, rare earth mother solution to be carried out classification shunting processing in this, as work.It should
Controlling indicator can be made further to verify and suitably revised as needed in commerical test and production practices from now on.
" 1.0g/L " is used as most important production flow-dividing control point, becomes to leaching rare earth mother solution " classification shunting " processing
" separation ".That is,：>=1.0g/L is cleaned as " cutting height " mother liquor (middle and high concentration rare earth mother solution), is precipitated enrichment, obtained
To " solid-state " mischmetal product；The conduct of ＜ 1.0g/L " takes low " mother liquor (low concentration of rare earth mother liquor), carries out ion-exchange absorption
Attached enrichment obtains " liquid " mischmetal product.Supernatants after precipitation, ionic adsorption extraction raffinate return to leaching mine after proportioning is handled.
Often spent acid is higher for ion exchange desorption gained rare-earth enrichment liquid, is neutralized, can be prepared highly concentrated with the rareearth enriching material of precipitation
Rare earth feed liquid is spent to use for separation factory.
Present invention process to leaching rare earth mother solution rationally, scientifically handle, and " classification is carried out to the mother liquor of various concentration
Shunting " processing, obtains the rare-earth products of " solid-state " and " liquid " two kinds of different shapes, ion type rareearth mine is made to exploit respectively,
The frontline technology high into high-efficiency and economic, a resource utilization, is characterized in particular in：
(1) technological thought and process route that the invention is proposed and established can carry out reasonably, scientifically to leaching mother liquor
Processing, that is, " classification shunts " processing is carried out to the mother liquor of various concentration.Liquid measure is relatively small, but concentration belongs to middle and high level
Mother liquor obtains " solid-state " rare-earth products into " solid-state " rare-earth products production system；Liquid measure is relatively large, but concentration is lower
Mother liquor obtains " liquid " rare-earth products into " liquid " rare-earth products production system.
(2) present invention process is than existing technique, and on product structure, a kind of more " liquid " products increase enterprise to production
The selectivity of product, product structure is more flexible and practicability.
(3) " classification shunts " processing is implemented to mother liquor, reduces investment, improves the comprehensive benefit of enterprise.
(4) " liquid " rare-earth products of present invention process production, concentration is high, and 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 detach；Meet separation factory pair
Into the requirement of " the qualified rare earth feed liquid " of slot, which directly detaches into slot for separation factory.
(5) " liquid " production system in present invention process, simplifies mine and detaches the production process of factory, flow
It is short.The problem of " acid mist " that it also solves in prepared by separation factory rare earth feed liquid influences environment.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention
Within the scope of.
Claims (7)
1. a kind of technique carrying out classification shunting processing to rare earth Situ Leaching mother liquor, which is characterized in that including：
It is passed through cleaner I into the middle and high concentration of concentration >=1g/L leaching mother liquor to clean, be precipitated through precipitating reagent after removal of impurities,
Again solid-state rare-earth products are obtained through clear water washing, filtering, calcination；Wherein, the cleaner I is sodium bicarbonate solution and sodium carbonate
The mixed liquor of solution, the precipitating reagent are sodium bicarbonate solution；With
To concentration<It is passed through cleaner II neutralizations in the leaching at low-concentration mother liquor of 1g/L and removes removing aluminum impurity, then will remove aluminium Mother liquor
It is passed through the adsorption and enrichment for carrying out rare earth ion in ion exchange column, then is desorbed with acid, liquid rare-earth products are obtained；Wherein,
The cleaner II is milk of lime；
The leaching mother liquor is obtained by following methods：Injection leaching mine agent and contracting agent inside to ore body, In-situ leaching mine make
" ion phase " and part " other phases " rare earth leach, and obtain leaching mother liquor；
Wherein, the leaching mine agent is made by the magnesite of iron content, manganese and calcium, and the preparation process of the leaching mine agent is：Ore is through powder
It is sized mixing with water after broken, acid is then added and decomposes to the weakly acidic leaching mine agent to get liquid；
The contracting agent is calcium chloride solution.
2. technique according to claim 1, which is characterized in that iron in the magnesite<10%, manganese<3%, calcium<10%,
The percentage is mass percent.
3. technique according to claim 1, which is characterized in that leaching mine process includes leaching mine agent injection stage and top water injection
Stage；In leaching mine agent injection stage injection leaching mine agent, in top water injection stage injection top water；
It wherein in top water injection stage, is added to calcium chloride solution as contracting agent in the water of top, is injected together with top water.
4. technique according to claim 3, which is characterized in that cross peak value when leaching the content of rare earth in mother liquor and be in
During decline, stop leaching mine agent injection, is changed to injection top water；When the content of rare earth leached in mother liquor drops to 0.1 grams per liter
When, stop injection top water and receive liquid, terminates leaching mine.
5. technique according to claim 4, which is characterized in that cross peak value when leaching the content of rare earth in mother liquor and decline
When to 80%~50%, stop leaching mine agent injection, is changed to injection top water.
6. technique according to claim 1, which is characterized in that wherein, described be passed through when cleaner I is cleaned controls pH
≤5.2。
7. technique according to claim 1, which is characterized in that the ion exchange column is acrylic acid series cation exchange tree
Fat.
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| CN110607440B (en) * | 2019-10-14 | 2021-07-20 | 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 |
| CN114522969B (en) * | 2022-02-11 | 2023-09-19 | 江西理工大学 | Ion type rare earth tailing leaching method |
| 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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| CN102190325B (en) * | 2010-03-17 | 2014-07-16 | 有研稀土新材料股份有限公司 | Method for recovering rare earth from ionic type rare earth crude ore |
| CN105132720B (en) * | 2015-10-08 | 2017-03-22 | 江西理工大学 | Method for recovering rare earth in ion adsorption type rare earth ore leaching solution through fractional precipitation |
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Address after: 341100 No. 148, Zhanqian Avenue, Meilin Town, Gan County, Ganzhou City, Jiangxi Province Patentee after: GANZHOU HONGMAO RARE EARTH ENGINEERING Co.,Ltd. Address before: 341100 Yingtan City, Jiangxi Province 148 Zhanqian Avenue, Meilin Town, Gan County, Ganzhou City, Jiangxi Province Patentee before: GANZHOU HONGMAO RARE EARTH ENGINEERING Co.,Ltd. |