CN106756016A - A kind of method for extraction and purification of thulium oxide - Google Patents
A kind of method for extraction and purification of thulium oxide Download PDFInfo
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- 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
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Abstract
The invention discloses a kind of method for extraction and purification of thulium oxide, by configuring liquid to be purified, middle agent configuration, splitter preparation, the transition of drip washing post, adsorption operations, eluent ion swap operation, by volume collection liquid being sampled analysis, precipitation is concentrated to merge the steps such as collection, liquid waste processing, the low-purity thulium oxide that existing roughing is collected is purified again so that thulium oxide purity reaches 99.995% 99.99999%.
Description
Technical field
The present invention relates to a kind of rare earth oxide separation and Extraction purification process, more particularly to purity in 99.9%-99.99%
Thulium oxide method for extraction and purification.
Background technology
Rare earth is by 15 lanthanide series (lanthanum La cerium Ce promethium Pm praseodymium Pr neodymium Nd samarium Sm europium Eu gadoliniums
Gd terbium Tb dysprosium Dy holmium Ho erbium Er thulium Tm lutetium Lu) and scandium Sc yttriums Y totally 17 kinds of elements composition, wherein promethium
Pm does not exist in nature, and scandium Sc seldom, only contains other 15 kinds of elements in rare earth mineral content in general Rare Earth Mine.By
It is closely similar in the property of various rare earth elements, therefore, separate relatively difficult.
The mineral species of rare earth are a lot, and that industrially applies at present mainly has bastnaesite, monazite, ion type
Rare Earth Mine, xenotime, industrial conventional processing method mainly have sulfuric acid decomposition method, caustic soda decomposition method, soda roasting method, soda acid
Combination method etc..
China is rare earth resources big country, and Rare Earth Mine is wide in variety, and reserves are big, and its middle wrapping head mixed type Rare Earth Mine is China first
Big Rare Earth Mine, accounts for more than the 80% of China's total rare earth (TRE) reserves, and it is also the first big light rare earth ore deposit, Baotou rare earth ore concentrate in the world
The mixed type Rare Earth Mine being made up of bastnaesite and monazite, at present, 90% Baotou rare earth ore concentrate is using at sulfuric acid process
Reason, will Baotou rare earth ore concentrate carry out concentrated sulfuric acid roasting-water logging removal of impurities, obtain pure mixing rare earth sulfate solution.
Two kinds of techniques are now used from mixing rare earth sulfate solution separation and Extraction rare earth：One kind is made the transition using carbon ammonium precipitation
Production carbonated rare earth, then by dissolving with hydrochloric acid, ammonia soap P507 extract and separates, the technique is in precipitation transition and extraction process
Substantial amounts of ammonia nitrogen waste water is produced, according to statistics, Baotou region year produces such waste water millions of tons, the ammonia-nitrogen content in waste water
5-10g/L, beyond secondary discharge standard (25mg/L) hundreds times of national regulation, causes water quality serious eutrophication, and this gives up
Water is difficult to reclaim because concentration is dilute, system is complicated, and solution needs carbon ammonium precipitation-dissolving with hydrochloric acid to make the transition in addition, chemical materials
Consumption.
Another technique is to add sulfuric acid acid adjustment degree to 0.2mol/L rare earth sulfate solution, directly uses P204
(D2EHPA, two (2-ethylhexyl phosphates) carry out Nd/Sm extraction packets, and raffinate is after neutralizing deacidification, then uses
P204 extracts-hydrochloric acid back extraction entirely, obtains high concentration LaCePrNd re chloride (Chinese patents
CN80105043.6), then using ammonia soap P507 extract and separate single rare earths, the technique abstraction and type-reverting process does not produce ammonia nitrogen
Extracting power is very strong in acid condition for waste water, alkali consumption reduction, but P204, and emulsification is also easy to produce when feed acidity is low, extracts
When need to add a certain amount of acid, packet raffinate needs to neutralize filtering, and middle heavy rare earth is stripped highly difficult, strip liquor spent acid
Height, acid consumption is big, and sulfuric acid rare earth concentration is low, and Nd/Sm extraction packet cell bodies are big.
At present, be also used for the separating-purifying of single rare earth using ion-exchange chromatography technology in market, but it is common from
Son exchanges that the production cycle is long, high cost, and purity also can only achieve 99.99% product, it is impossible to meet market needs.
The content of the invention
The present invention provides a kind of to low-purity thulium oxide method for extraction and purification, by original low-purity thulium oxide（99.9~
99.99%）Enter extraction, purifying and be finally reached the thulium oxide of high-purity（99.99999%）.
To achieve the above object, the present invention takes following technical scheme：
A kind of method for extraction and purification of thulium oxide, comprises the following steps：1st, liquid configuration to be purified：Configure thulium oxide mixing to be purified
Solution；2nd, middle agent configuration：Configuration delayer and eluent, delayer are Cu (NO3)2·3H2The configuration of O, water and nitric acid is formed,
Eluent is that the configuration of solid EDTA, water and ammoniacal liquor is formed；3rd, splitter prepares：Splitter as ion exchange carrier；4、
Drip washing post makes the transition：Splitter is made the transition with the delayer in step 2；5th, adsorption operations：The thulium oxide configured in step 1 is mixed
Close solution carries out adsorption operations with splitter；6th, drip washing operation：Drip washing behaviour is carried out to the splitter in step 5 by eluent
Make；7th, to pressing volume collection by the liquid batch collected after eluent drip washing in step 6, and sampling analysis purity is carried out, is collected
Middle precipitation merges collects；8th, liquid waste processing.
Further, the thulium oxide mixed solution to be purified in the step 1 is the oxidation that purity is 99.9%-99.99%
Thulium is added to by the dense HNO of 50L3Stirred in the solution configured with 150L pure water, and be heated to 60-70 DEG C, it is completely molten to thulium oxide
Solution, with pure water cooling solution and is diluted to 40 ~ 60g/L, and adjusts acidity PH=0.6 ~ 1.5 with ammoniacal liquor.
Further, the delayer in the step 2 is to weigh 60kgCu (NO3)2·3H2O is dissolved in water, and is transferred to 1m3
Groove in, add 600N nitric acid, water is diluted to 1m3, Cu in solution2+：0.25mol/L, H+：0.6mol/L.
Further, eluent, to claim EDTA to add a small amount of water to stir, adds ammoniacal liquor slowly molten in the step 2
Solution, pours into dosage bunker, adds water dilute to scale, and stirring adjusts PH to setting value, then supplies water to 1 cube, and solution E DTA0.03 ~
0.07mol/L,PH7~8。
Further, the splitter in the step 3 includes at least 4 radical ion exchange columns, and ion exchange column is that benzene second is dilute
The ion exchange column that the dilute benzene highly acid macropore cation resin of diethyl is made, setting is sequentially connected in series between exchange column by valve,
Wherein it respectively is the first adsorption column, the second drip washing post, the 3rd drip washing post and the 4th splitter, at least 1, the 3rd drip washing post.
Further, the 4 radical ion exchange column is 3 huge pillars and 1 pillar, 3 huge pillars be respectively the first adsorption column,
Second drip washing post and the 3rd drip washing post, column dimensions are：φ40cm×250cm；1 pillar is the 4th splitter, column dimensions
For：φ15×150cm；There is one layer of chuck to be heated for recirculated water outside all posts, have liner in post, as anti-corrosion, every post
Son can be independent charging, discharging.
Further, the step 4 drip washing post transition, starts to enter with 1 ~ 4cm/min of linear velocity to the second drip washing column top
The delayer of 490 ~ 530L is made the transition, and transition completion washes the second drip washing post with pure water, checks the second drip washing post water outlet saliva
Phase PH ~ 7, stop washing；The delayer that 3rd drip washing column top starts to enter 490 ~ 530L with 1 ~ 4cm/min of linear velocity is turned
Type, transition completion washes the 3rd drip washing post with pure water, checks the 3rd drip washing post water outlet saliva phase PH ~ 7, stops washing.
Further, the step 4 drip washing post transition, starts to enter with 1 ~ 4cm/min of linear velocity to the second drip washing column top
The delayer of 500L is made the transition, transition completion pure water the second drip washing post of washing, and the second drip washing post water outlet saliva phase PH of inspection ~
7, stop washing；The delayer that 3rd drip washing column top starts to enter 520L with 1 ~ 4cm/min of linear velocity is made the transition, has been made the transition
The 3rd drip washing post is washed into pure water, the 3rd drip washing post water outlet saliva phase PH ~ 7 are checked, stops washing.
Further, step 5 adsorption operations, thulium oxide mixed solution to be purified is entered by the first adsorption column top, is used
Measuring pump is fed with 1 ~ 2cm/min of linear velocity, and the first adsorption column efflux saturated oxalic acid inspection, detects rare earth ion,
Stop charging, and the first drip washing post is washed, to water outlet phase PH ~ 7.
Further, the step 6 drip washing operation, leacheate is heated to 45 DEG C ~ 65 DEG C, pillar circulating water heating to 45
DEG C ~ 65 DEG C, leacheate drip washing by the first adsorption column, linear velocity .1 ~ 4cm/min, the first adsorption column efflux saturation grass
Acid checks whether out rare earth ion, goes out the first absorption, the series connection of the second drip washing post after rare earth ion；Continue drip washing, flow velocity is constant；The
Two drip washing post efflux saturated oxalic acid inspections, go out the first adsorption column, the second drip washing post, the 3rd drip washing post string after rare earth ion
Connection, continues drip washing, and flow velocity is constant, after the 3rd drip washing post goes out rare earth ion, the first adsorption column, the second drip washing post, the 3rd drip washing post,
4th splitter is connected, and leacheate linear velocity is changed to 0.2 ~ 0.6cm/min, and the 4th splitter efflux saturated oxalic acid inspection is
It is no go out rare earth ion；After detecting rare earth ion, the efflux of the 4th splitter is collected in batches by certain volume, until efflux
All go out, pure water cleans up 4 pillars, and return to step 4 works on.
Compared with prior art, have the advantage that：The high capacity of technique, high-purity（99.99999%）, in high yield
（94~97%）, cycle is short, low cost is easy to operate, steady quality, with very big economic benefit and application value.
Specific embodiment
Technique of the invention is further illustrated below by way of specific embodiment.
Embodiment 1
First, liquid configuration to be purified
Dense HNO is added in a kettle.350L, pure water 150L, are heated to 60 DEG C, and purity is added while stirring in 99.9%-
99.99% thulium oxide heating is completely dissolved thulium oxide；And it is diluted to 40g/L, ammoniacal liquor regulation acidity PH=with cooling pure water
0.6。
Following rare earth element removes thulium（Tm）Outward, other rare earth elements are substituted with RE.
2nd, middle agent configuration
Delayer Cu (NO3)2·3H2O is prepared：Weigh 60kgCu (NO3)2·3H2O is dissolved in water, and is transferred to 1m3Groove in, plus
Enter 600N nitric acid, water is diluted to 1m3, Cu in solution2+：0.25mol/L, H+：0.6mol/L.
EDTA leacheates 0.03mol/L is prepared：Claim 8.76kgEDTA acid plus a small amount of water to stir, add ammoniacal liquor slowly
Dissolving, pours into dosage bunker, adds water dilute to 0.03mol/L, and stirring adjusts PH to setting value, then supplies water to 1 cube, solution pH value
7。
The leacheate that following EDTA is prepared, i.e. ammonium salt are referred to as：（NH4）3HL。
3rd, splitter prepares
4 radical ion exchange columns are made, ion exchange column is made up of the dilute benzene highly acid macropore cation resin of the dilute diethyl of benzene second, has
Active group energy（G-SO3H）, using active group can with the ion in solution occur exchange reaction, first post as adsorption column,
Second and the 3rd is drip washing post, and the 4th is splitter, and 4 pillars are sequentially connected in series using multiple access valves and used, 4
Ion exchange column is 3 huge pillars and 1 pillar, and 3 huge pillars are respectively the first adsorption column, the second drip washing post and the 3rd drip washing post,
Column dimensions are：φ 40cm × 250cm, 1 pillar is the 4th splitter, and column dimensions are：15 × 150cm of φ, there is one outside post
Layer chuck is heated for recirculated water, there is liner in post, as anti-corrosion, charging, discharging, benzene second that every pillar can be independent
The pore size of the ion exchange column that dilute dilute benzene highly acid macropore cation resin of diethyl is made is in 100-200 mesh.
4th, drip washing post transition
Enter delayer liquid with measuring pump, linear velocity 1cm/min, the second drip washing post enters 500L delayer liquid, and the 3rd drip washing post enters
520L delayer liquid；Transition is over and the second drip washing post, the 3rd drip washing post are washed respectively with pure water, finally detects the second drip washing post
Go out saliva phase PH ~ 7, stop washing；3rd drip washing column outlet water phase PH ~ 7 stop washing.
The reaction equation for wherein relating generally to is as follows：
2（G-SO3）NH4+Cu(NO3)2→(G-SO3)2Cu+2NH4NO3
G-SO3NH4+HNO3→G-SO3H+NH4NO3
5th, adsorption operations
First adsorption column enters liquid to be purified, is fed with linear velocity 0.5cm/min with measuring pump, rare earth ion and adsorption column occur from
Son is exchanged, and is all Tricationic due to rare earth ion, and the hydration radius of ion is smaller, bigger, the La of selectivity3+>Ce3+>Pr3+>
Nd3+>Sm3+>Eu3+>Gd3+>Tb3+>Y3+>Dy3+>Ho3+>Er3+>Tm3+>Yb3+>Lu3+.So the affinity on adsorption column is not
Together so that variant rare earth ion is adsorbed in adsorption column higher slice, and up, the small absorption of affinity exists the big absorption of affinity
Lower section, after rare earth ion adsorption saturation on adsorption column, can contain rare earth ion in efflux.Detected with saturated oxalic acid inspection
Rare earth ion, stops charging, and the first adsorption column is washed to PH ~ 7.
The reaction equation for wherein relating generally to is as follows：
3（G-SO3）NH4 +Tm(NO3)3→(G-SO3)3Tm + 3NH4NO3
3（G-SO3）NH4 +RE(NO3)3→(G-SO3)3RE + 3NH4NO3
6th, drip washing operation
Leacheate is heated to 45 DEG C, and pillar circulating water heating is to 45 DEG C；Leacheate drip washing, linear velocity by the first drip washing post
1cm/min, the first drip washing column outlet water saturated oxalic acid checks whether out rare earth ion, goes out the first absorption after rare earth ion
Post, the series connection of the second drip washing post；Continue to use EDTA leacheate drip washing, flow velocity is constant；Second drip washing post efflux is examined with saturated oxalic acid
Look into, go out the first adsorption column, the second drip washing post, the series connection of the 3rd drip washing post after rare earth ion, EDTA leacheates continue drip washing, and flow velocity is not
Become, after the 3rd drip washing post goes out rare earth ion, the first adsorption column, the second drip washing post, the 3rd drip washing post, the series connection of the 4th splitter are drenched
Washing lotion linear velocity is changed to 0.2cm/min, and the 4th splitter efflux saturated oxalic acid checks whether out rare earth ion, detects dilute
After native ion, rare earth ion liquid is collected in batches by certain volume, until rare earth ion liquid has all gone out, pure water cleans up 4
Pillar, return to step 4 works on.
The reaction equation for wherein relating generally to is as follows：
Drip washing reaction on first adsorption column：Eluent（NH4）3HL（The ammonium salt of EDTA）
(G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
Above-mentioned two reaction leacheate parses rare earth.
The suction-operated of resin and the desorption of compounding ingredient can occur ERnWith RE(n+1)Exchange
ERnL- +(G-SO3)3RE(n+1)→RE(n+1)L-+ (G-SO3)3REn
It is big that the meeting for making the molecular weight for having parsed small displaces molecular weight, also adsorbs on resin.（The big rare earth of molecular weight
Element is big with the ammonium salt complexation constant of EDTA, can walk before efflux）The use of EDTA is coordinated to allow Tm and the element that is connected to divide
Greatly improved from coefficient（Er-Tm separations 1.005 bring up to 3.3, Tm-Yb separations 1.004 and bring up to 2.1）
Reaction on second and third drip washing post, the use of delayer helps to increase that absorption-desorption number of times, does not allow RE quickly by dividing
From post
3(G-SO3)2Cu+4H++2NH4TmL→2(G-SO3)3Tm+(NH4)2CuL +2H2CuL
3(G-SO3)2Cu + 4H++2HTmL→2(G-SO3)3Tm+ 3H2CuL
When first adsorption column efflux is on second and third drip washing post, exchanged with Cu on post, rare earth ion is adsorbed to again
On post, the rare earth being adsorbed to again on post is leached liquid wash-out again,
G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
REnL- +(G-SO3)3RE(n+1) →RE(n+1)L-+ (G-SO3)3REn
Separated by repeatedly exchanging, complexation constant identical rare earth is concentrated in together, finally mixed and disorderly rare earth according to certain
Order is arranged（Same rare earth element is in same bands of a spectrum, 15 kinds of 15 sections of elements point）.
Reaction on 4th splitter
HREnL+3G-SO3NH4→(G-SO3)3REn+（NH4）3HL
REnL- +(G-SO3)3RE(n+1)→RE(n+1)L-+ (G-SO3)3REn
15 kinds of rare earths are pacified sequencing by the 4th splitter efflux, and be separated from each other outflow, and final rare earth element is REL-Form
Out.
7th, each flowed out to the 4th splitter in step 6 is sampled purity assay by volume collection liquid, concentrates precipitation
Merge and collect
And the rare earth collection liquid to each batch is sampled constituent analysis, the collection liquid to same purity carries out concentrating precipitation to collect,
Pillar pure water is washed till that PH ~ 7 are stand-by, due to liquid to be purified in main composition be thulium, other rare earth element occupancy volumes are few, and thulium exists
It is to be flowed out with efflux with the 3rd order in 15 elements, so basic in collection liquid it was determined that being in intermediate collection
Most of efflux in thulium content highest, and outflow when be essentially single-element outflow, by existing process precipitate, mistake
Filter, extraction, the purity of the thulium oxide of collection reach the 99.995% of requirement.
8th, liquid waste processing
Waste liquid includes EDTA- rare earth elements waste liquid, Cu- rare earth element-EDTA waste liquids and Cu-EDTA waste liquids；The EDTA- rare earths
Element waste liquid takes efflux purity detecting containing rare earth ion of the sample to fraction collection, remerges precipitation, adds in a kettle.
Enter EDTA- rare earth element waste liquids, be heated to 80 DEG C, plus saturated oxalic acid precipitation, filter precipitating rare earth, and grass is washed with 2% nitric acid
Acid-rare earth, pure water oxalic acid-rare earth, drains, and fills 800 DEG C of calcinations of crucible, and mother liquor regulation acidity PH=1 stirrings tie EDTA
Crystalline substance, is stood, filters, washs, reclaims, and EDTA can be reused；Cu- rare earth elements-EDTA the solution reduces Cu with Zn powder,
Ibid method is settled out rare earth, and mother liquor regulation acidity PH=1 stirrings crystallize EDTA, stand, filter, wash, reclaim, and EDTA can
Reuse；The Cu-EDTA waste liquids electrolysis removes Cu, and electrolysis unit is to apply calcium with titanium to do anode, and copper coin does negative electrode, to EDTA-Cu
Solution is electrolysed, electrolyzing copper, and efflux crystallizes EDTA without copper color, efflux regulation acidity PH=1 stirrings, stand, filter,
Washing, recovery, EDTA can be reused.
Embodiment 2
Each item data in embodiment 2 is that the optimal data for extracting, purifying thulium oxide comprises the following steps：
First, liquid configuration to be purified
Dense HNO is added in a kettle.350L, pure water 150L, are heated to 60 DEG C, and purity is added while stirring in 99.9%-
99.99% thulium oxide, heating is completely dissolved thulium oxide；And it is diluted to 50g/L, ammoniacal liquor regulation acidity PH=1 with cooling pure water.
Following rare earth element removes thulium（Tm）Outward, other rare earth elements are substituted with RE.
2nd, middle agent configuration
Delayer Cu (NO3)2·3H2O is prepared：Weigh 60kgCu (NO3)2·3H2O is dissolved in water, and is transferred to 1m3Groove in, plus
Enter 600N nitric acid, water is diluted to 1m3, Cu in solution2+：0.25mol/L, H+：0.6mol/L.
EDTA leacheates 0.05mol/L is prepared：Claim 14.6kgEDTA acid plus a small amount of water to stir, add ammoniacal liquor slowly
Dissolving, pours into dosage bunker, adds water dilute to 0.05mol/L, and stirring adjusts PH to setting value, then supplies water to 1 cube, solution pH value
7.5。
The leacheate that following EDTA is prepared, i.e. ammonium salt are referred to as：（NH4）3HL。
3rd, splitter prepares
4 radical ion exchange columns are made, ion exchange column is made up of the dilute benzene highly acid macropore cation resin of the dilute diethyl of benzene second, has
Active group energy（G-SO3H）, using active group can with the ion in solution occur exchange reaction, first post as adsorption column,
Second and the 3rd is drip washing post, and the 4th is splitter, and 4 pillars are sequentially connected in series using multiple access valves and used, 4
Ion exchange column is 3 huge pillars and 1 pillar, and 3 huge pillars are respectively the first adsorption column, the second drip washing post and the 3rd drip washing post,
Column dimensions are：φ 40cm × 250cm, 1 pillar is the 4th splitter, and column dimensions are：15 × 150cm of φ, there is one outside post
Layer chuck is heated for recirculated water, there is liner in post, as anti-corrosion, charging, discharging, benzene second that every pillar can be independent
The pore size of the ion exchange column that dilute dilute benzene highly acid macropore cation resin of diethyl is made is in 100-200 mesh.
4th, drip washing post transition
Enter delayer liquid with measuring pump, linear velocity 2cm/min, the second drip washing post enters 500L delayer liquid, and the 3rd drip washing post enters
520L delayer liquid；Transition is over and the second drip washing post, the 3rd drip washing post are washed respectively with pure water, finally detects the second drip washing post
Go out saliva phase PH ~ 7, stop washing；3rd drip washing column outlet water phase PH ~ 7 stop washing.
The reaction equation for wherein relating generally to is as follows：
2（G-SO3）NH4+Cu(NO3)2→(G-SO3)2Cu+2NH4NO3
G-SO3NH4+HNO3→G-SO3H+NH4NO3
5th, adsorption operations
First adsorption column enters liquid to be purified, is fed with linear velocity 1.5cm/min with measuring pump, rare earth ion and adsorption column occur from
Son is exchanged, and is all Tricationic due to rare earth ion, and the hydration radius of ion is smaller, bigger, the La of selectivity3+>Ce3+>Pr3+>
Nd3+>Sm3+>Eu3+>Gd3+>Tb3+>Y3+>Dy3+>Ho3+>Er3+>Tm3+>Yb3+>Lu3+.So the affinity on adsorption column is not
Together so that variant rare earth ion is adsorbed in adsorption column higher slice, and up, the small absorption of affinity exists the big absorption of affinity
Lower section, after rare earth ion adsorption saturation on adsorption column, can contain rare earth ion in efflux.Detected with saturated oxalic acid inspection
Rare earth ion, stops charging, and the first adsorption column is washed to PH ~ 7.
The reaction equation for wherein relating generally to is as follows：
3（G-SO3）NH4 +Tm(NO3)3→(G-SO3)3Tm + 3NH4NO3
3（G-SO3）NH4 +RE(NO3)3→(G-SO3)3RE + 3NH4NO3
6th, drip washing operation
Leacheate is heated to 50 DEG C, and pillar circulating water heating is to 50 DEG C；Leacheate drip washing, linear velocity by the first drip washing post
2cm/min, the first drip washing column outlet water saturated oxalic acid checks whether out rare earth ion, goes out the first absorption after rare earth ion
Post, the series connection of the second drip washing post；Continue to use EDTA leacheate drip washing, flow velocity is constant；Second drip washing post efflux is examined with saturated oxalic acid
Look into, go out the first adsorption column, the second drip washing post, the series connection of the 3rd drip washing post after rare earth ion, EDTA leacheates continue drip washing, and flow velocity is not
Become, after the 3rd drip washing post goes out rare earth ion, the first adsorption column, the second drip washing post, the 3rd drip washing post, the series connection of the 4th splitter are drenched
Washing lotion linear velocity is changed to 0.4cm/min, and the 4th splitter efflux saturated oxalic acid checks whether out rare earth ion, detects dilute
After native ion, rare earth ion liquid is collected in batches by certain volume, until rare earth ion liquid has all gone out, pure water cleans up 4
Pillar, return to step 4 works on.
The reaction equation for wherein relating generally to is as follows：
Drip washing reaction on first adsorption column：Eluent（NH4）3HL（The ammonium salt of EDTA）
(G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
Above-mentioned two reaction leacheate parses rare earth.
The suction-operated of resin and the desorption of cooperation EDTA can occur ERnWith RE(n+1)Exchange
ERnL- +(G-SO3)3RE(n+1)→RE(n+1)L-+ (G-SO3)3REn
It is big that the meeting for making the molecular weight for having parsed small displaces molecular weight, also adsorbs on resin.（The big rare earth of molecular weight
Element is big with the ammonium salt complexation constant of EDTA, can walk before efflux）The use of EDTA is coordinated to allow Tm and the element that is connected to divide
Greatly improved from coefficient（Er-Tm separations 1.005 bring up to 3.3, Tm-Yb separations 1.004 and bring up to 2.1）
Reaction on second and third drip washing post, the use of delayer helps to increase that absorption-desorption number of times, does not allow RE quickly by dividing
From post
3(G-SO3)2Cu+4H++2NH4TmL→2(G-SO3)3Tm+(NH4)2CuL +2H2CuL
3(G-SO3)2Cu + 4H++2HTmL→2(G-SO3)3Tm+ 3H2CuL
When first adsorption column efflux is on second and third drip washing post, exchanged with Cu on post, rare earth ion is adsorbed to again
On post, the rare earth being adsorbed to again on post is leached liquid wash-out again,
G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
REnL- +(G-SO3)3RE(n+1) →RE(n+1)L-+ (G-SO3)3REn
Separated by repeatedly exchanging, complexation constant identical rare earth is concentrated in together, finally mixed and disorderly rare earth according to certain
Order is arranged（Same rare earth element is in same bands of a spectrum, 15 kinds of 15 sections of elements point）.
Reaction on 4th splitter
HREnL+3G-SO3NH4→(G-SO3)3REn+（NH4）3HL
REnL- +(G-SO3)3RE(n+1) →RE(n+1)L-+ (G-SO3)3REn
15 kinds of rare earths are pacified sequencing by the 4th splitter efflux, and be separated from each other outflow, and final rare earth element is REL-Form
Out.
7th, in step 6 each be sampled purity assay by volume collection liquid, concentrate precipitation to merge and collect
And the rare earth collection liquid to each batch is sampled constituent analysis, the collection liquid to same purity carries out concentrating precipitation to collect,
Pillar pure water is washed till that PH ~ 7 are stand-by, due to liquid to be purified in main composition be thulium, other rare earth element occupancy volumes are few, and thulium exists
It is to be flowed out with efflux with the 3rd order in 15 elements, so in collection liquid middle position subbase sheet it was determined that in centre
The content highest of thulium in most of efflux of collection, and single-element outflow is essentially during outflow, precipitated by existing process,
Filtering, extraction, the purity of the thulium oxide of collection reach the 99.99999% of requirement.
8th, liquid waste processing
Waste liquid includes EDTA- rare earth elements waste liquid, Cu- rare earth element-EDTA waste liquids and Cu-EDTA waste liquids；The EDTA- rare earths
Element waste liquid takes efflux purity detecting containing rare earth ion of the sample to fraction collection, remerges precipitation, adds in a kettle.
Enter EDTA- rare earth element waste liquids, be heated to 80 DEG C, plus saturated oxalic acid precipitation, filter precipitating rare earth, and grass is washed with 2% nitric acid
Acid-rare earth, pure water oxalic acid-rare earth, drains, and fills 800 DEG C of calcinations of crucible, and mother liquor regulation acidity PH=1 stirrings tie EDTA
Crystalline substance, is stood, filters, washs, reclaims, and EDTA can be reused；Cu- rare earth elements-EDTA the solution reduces Cu with Zn powder,
Ibid method is settled out rare earth, and mother liquor regulation acidity PH=1 stirrings crystallize EDTA, stand, filter, wash, reclaim, and EDTA can
Reuse；The Cu-EDTA waste liquids electrolysis removes Cu, and electrolysis unit is to apply calcium with titanium to do anode, and copper coin does negative electrode, to EDTA-Cu
Solution is electrolysed, electrolyzing copper, and efflux crystallizes EDTA without copper color, efflux regulation acidity PH=1 stirrings, stand, filter,
Washing, recovery, EDTA can be reused.
Embodiment 3
First, liquid configuration to be purified
Dense HNO is added in a kettle.350L, pure water 150L, are heated to 60 DEG C, and purity is added while stirring in 99.9%-
99.99% thulium oxide, heating is completely dissolved thulium oxide；And it is diluted to 60g/L, ammoniacal liquor regulation acidity PH=1.5 with cooling pure water.
Following rare earth element removes thulium（Tm）Outward, other rare earth elements are substituted with RE.
2nd, middle agent configuration
Delayer Cu (NO3)2·3H2O is prepared：Weigh 6 0kgCu (NO3)2·3H2O is dissolved in water, and is transferred to 1m3Groove in, plus
Enter 600N nitric acid, water is diluted to 1m3, Cu in solution2+：0.25mol/L, H+：0.6mol/L.
EDTA leacheates 0.07mol/L is prepared：Claim 17.52kgEDTA acid plus a small amount of water to stir, add ammoniacal liquor slowly
Dissolving, pours into dosage bunker, adds water dilute to 0.07mol/L, and stirring adjusts PH to setting value, then supplies water to 1 cube, solution pH value
8。
The leacheate that following EDTA is prepared, i.e. ammonium salt are referred to as：（NH4）3HL。
3rd, splitter prepares
4 radical ion exchange columns are made, ion exchange column is made up of the dilute benzene highly acid macropore cation resin of the dilute diethyl of benzene second, has
Active group energy（G-SO3H）, using active group can with the ion in solution occur exchange reaction, first post as adsorption column,
Second and the 3rd is drip washing post, and the 4th is splitter, and 4 pillars are sequentially connected in series using multiple access valves and used, 4
Ion exchange column is 3 huge pillars and 1 pillar, and 3 huge pillars are respectively the first adsorption column, the second drip washing post and the 3rd drip washing post,
Column dimensions are：φ 40cm × 250cm, 1 pillar is the 4th splitter, and column dimensions are：15 × 150cm of φ, there is one outside post
Layer chuck is heated for recirculated water, there is liner in post, as anti-corrosion, charging, discharging, benzene second that every pillar can be independent
The pore size of the ion exchange column that dilute dilute benzene highly acid macropore cation resin of diethyl is made is in 100-200 mesh.
4th, drip washing post transition
Enter delayer liquid with measuring pump, 1 ~ 4cm/min of linear velocity, the second drip washing post enters 500L delayer liquid, and the 3rd drip washing post enters
520L delayer liquid；Transition is over and the second drip washing post, the 3rd drip washing post are washed respectively with pure water, finally detects the second drip washing post
Go out saliva phase PH ~ 7, stop washing；3rd drip washing column outlet water phase PH ~ 7 stop washing.
The reaction equation for wherein relating generally to is as follows：
2（G-SO3）NH4+Cu(NO3)2→(G-SO3)2Cu+2NH4NO3
G-SO3NH4+HNO3→G-SO3H+NH4NO3
5th, adsorption operations
First adsorption column enters liquid to be purified, is fed with 1 ~ 4cm/min of linear velocity with measuring pump, rare earth ion and adsorption column occur from
Son is exchanged, and is all Tricationic due to rare earth ion, and the hydration radius of ion is smaller, bigger, the La of selectivity3+>Ce3+>Pr3+>
Nd3+>Sm3+>Eu3+>Gd3+>Tb3+>Y3+>Dy3+>Ho3+>Er3+>Tm3+>Yb3+>Lu3+.So the affinity on adsorption column is not
Together so that variant rare earth ion is adsorbed in adsorption column higher slice, and up, the small absorption of affinity exists the big absorption of affinity
Lower section, after rare earth ion exchanged after adsorption saturation on adsorption column, can contain rare earth ion in efflux.Checked with saturated oxalic acid
Rare earth ion is detected, stops charging, the first adsorption column is washed to PH ~ 7.
The reaction equation for wherein relating generally to is as follows：
3（G-SO3）NH4 +Tm(NO3)3→(G-SO3)3Tm + 3NH4NO3
3（G-SO3）NH4 +RE(NO3)3→(G-SO3)3RE + 3NH4NO3
6th, drip washing operation
Leacheate is heated to 65 DEG C, and pillar circulating water heating is to 65 DEG C；Leacheate drip washing, linear velocity by the first drip washing post
4cm/min, the first drip washing column outlet water saturated oxalic acid checks whether out rare earth ion, goes out the first absorption after rare earth ion
Post, the series connection of the second drip washing post；Continue to use EDTA leacheate drip washing, flow velocity is constant；Second drip washing post efflux is examined with saturated oxalic acid
Look into, go out the first adsorption column, the second drip washing post, the series connection of the 3rd drip washing post after rare earth ion, EDTA leacheates continue drip washing, and flow velocity is not
Become, after the 3rd drip washing post goes out rare earth ion, the first adsorption column, the second drip washing post, the 3rd drip washing post, the series connection of the 4th splitter are drenched
Washing lotion linear velocity is changed to 1cm/min, and the 4th splitter efflux saturated oxalic acid checks whether out rare earth ion, detects rare earth
After ion, rare earth ion liquid is collected in batches by certain volume, until rare earth ion liquid has all gone out, pure water cleans up 4 posts
Son, return to step 4 works on.
The reaction equation for wherein relating generally to is as follows：
Drip washing reaction on first adsorption column：Eluent（NH4）3HL（The ammonium salt of EDTA）
(G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
Above-mentioned two reaction leacheate parses rare earth.
The suction-operated of resin and the desorption of cooperation EDTA can occur ERnWith RE(n+1)Exchange
ERnL- +(G-SO3)3RE(n+1)→RE(n+1)L-+ (G-SO3)3REn
It is big that the meeting for making the molecular weight for having parsed small displaces molecular weight, also adsorbs on resin.（The big rare earth of molecular weight
Element is big with the ammonium salt complexation constant of EDTA, can walk before efflux）The use of EDTA is coordinated to allow Tm and the element that is connected to divide
Greatly improved from coefficient（Er-Tm separations 1.005 bring up to 3.3, Tm-Yb separations 1.004 and bring up to 2.1）
Reaction on second and third drip washing post, the use of delayer helps to increase that absorption-desorption number of times, does not allow RE quickly by dividing
From post
3(G-SO3)2Cu+4H++2NH4TmL→2(G-SO3)3Tm+(NH4)2CuL +2H2CuL
3(G-SO3)2Cu + 4H++2HTmL→2(G-SO3)3Tm+ 3H2CuL
When first adsorption column efflux is on second and third drip washing post, exchanged with Cu on post, rare earth ion is adsorbed to again
On post, the rare earth being adsorbed to again on post is leached liquid wash-out again,
G-SO3)3Tm+（NH4）3HL→3NH4G-SO3 +HTmL
(G-SO3)3Tm+（NH4）3HL→2NH4G-SO3 +NH4TmL +H(G-SO3)
REnL- +(G-SO3)3RE(n+1) →RE(n+1)L-+ (G-SO3)3REn
Separated by repeatedly exchanging, complexation constant identical rare earth is concentrated in together, finally mixed and disorderly rare earth according to certain
Order is arranged（Same rare earth element is in same bands of a spectrum, 15 kinds of 15 sections of elements point）.
Reaction on 4th splitter
HREnL+3G-SO3NH4→(G-SO3)3REn+（NH4）3HL
REnL- +(G-SO3)3RE(n+1) →RE(n+1)L-+ (G-SO3)3REn
15 kinds of rare earths are pacified sequencing by the 4th splitter efflux, and be separated from each other outflow, and final rare earth element is REL-Form
Out.
7th, in step 6 each be sampled purity assay by volume collection liquid, concentrate precipitation to merge and collect
And the rare earth collection liquid to each batch is sampled constituent analysis, the collection liquid to same purity carries out concentrating precipitation to collect,
Pillar pure water is washed till that PH ~ 7 are stand-by, due to liquid to be purified in main composition be thulium, other rare earth element occupancy volumes are few, and thulium exists
It is to be flowed out with efflux with the 3rd order in 15 elements, so basic in collection liquid it was determined that being in intermediate collection
Most of efflux in thulium content highest, and outflow when be essentially single-element outflow, by existing process precipitate, mistake
Filter, extraction, the purity of the thulium oxide of collection reach the 99.995% of requirement.
8th, liquid waste processing
Waste liquid includes EDTA- rare earth elements waste liquid, Cu- rare earth element-EDTA waste liquids and Cu-EDTA waste liquids；The EDTA- rare earths
Element waste liquid takes efflux purity detecting containing rare earth ion of the sample to fraction collection, remerges precipitation, adds in a kettle.
Enter EDTA- rare earth element waste liquids, be heated to 80 DEG C, plus saturated oxalic acid precipitation, filter precipitating rare earth, and grass is washed with 2% nitric acid
Acid-rare earth, pure water oxalic acid-rare earth, drains, and fills 800 DEG C of calcinations of crucible, and mother liquor regulation acidity PH=1 stirrings tie EDTA
Crystalline substance, is stood, filters, washs, reclaims, and EDTA can be reused；Cu- rare earth elements-EDTA the solution reduces Cu with Zn powder,
Ibid method is settled out rare earth, and mother liquor regulation acidity PH=1 stirrings crystallize EDTA, stand, filter, wash, reclaim, and EDTA can
Reuse；The Cu-EDTA waste liquids electrolysis removes Cu, and electrolysis unit is to apply calcium with titanium to do anode, and copper coin does negative electrode, to EDTA-Cu
Solution is electrolysed, electrolyzing copper, and efflux crystallizes EDTA without copper color, efflux regulation acidity PH=1 stirrings, stand, filter,
Washing, recovery, EDTA can be reused.
Claims (10)
1. a kind of method for extraction and purification of thulium oxide, it is characterised in that：Comprise the following steps：1st, liquid configuration to be purified：Configuration is treated
Purification thulium oxide mixed solution；2nd, middle agent configuration：Configuration delayer and eluent, delayer are Cu (NO3)2·3H2O, water and
Nitric acid configuration is formed, and eluent is that the configuration of solid EDTA, water and ammoniacal liquor is formed；3rd, splitter prepares：Splitter is used as ion
The carrier of exchange；4th, drip washing post transition：Splitter is made the transition with the delayer in step 2；5th, adsorption operations：In step 1
The thulium oxide mixed solution of configuration carries out adsorption operations with splitter；6th, drip washing operation：By eluent to the separation in step 5
Post carries out drip washing operation；7th, to pressing volume collection by the liquid batch collected after eluent drip washing in step 6, and it is sampled
Purity assay, concentrates precipitation to merge and collects；8th, liquid waste processing.
2. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Oxidation to be purified in the step 1
Thulium mixed solution is to choose purity to be added to by the dense HNO of 50L in the thulium oxide of 99.9%-99.99%3It is molten with what 150L pure water was configured
Stirred in liquid, and be heated to 60-70 DEG C, be completely dissolved to thulium oxide, with pure water cooling solution and be diluted to 40 ~ 80g/L, be used in combination
Ammoniacal liquor regulation acidity PH0.6 ~ 1.5.
3. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Delayer in the step 2 is title
Take a certain amount of Cu (NO3)2·3H2O is dissolved in water, and is transferred to 1m3Groove in, add 600N nitric acid, water is diluted to 1m3, in solution
Cu2+：0.25mol/L, H+：0.6mol/L.
4. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Eluent is solid to claim in the step 2
Body EDTA adds a small amount of water to stir, and adds ammoniacal liquor slowly to dissolve, and pours into dosage bunker, adds water dilute to scale, and PH is adjusted in stirring
To setting value, then water to 1 cube is supplied, solution E DTA0.03 ~ 0.07 mol/L, PH7 ~ 8.
5. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Splitter in the step 3 includes
At least 4 radical ion exchange columns, ion exchange column is that the ion that the dilute benzene highly acid macropore cation resin of the dilute diethyl of benzene second is made is handed over
Post is changed, setting is sequentially connected in series by valve between exchange column, wherein respectively being the first adsorption column, the second drip washing post, the 3rd
Drip washing post and the 4th splitter, at least 1, the 3rd drip washing post.
6. the method for extraction and purification of thulium oxide as claimed in claim 5, it is characterised in that：The 4 radical ion exchange column is 3 big
Post and 1 pillar, 3 huge pillars are respectively the first adsorption column, the second drip washing post and the 3rd drip washing post, and column dimensions are：φ40cm
×250cm；1 pillar is the 4th splitter, and column dimensions are：φ15×150cm；There is one layer of chuck outside all posts for following
Ring water is heated, and has liner in post, as anti-corrosion, charging, discharging that every pillar can be independent.
7. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Step 4 drip washing post transition, to the
The delayer that two drip washing column tops start to enter 490 ~ 530L with 1 ~ 4cm/min of linear velocity is made the transition, and make the transition completion pure water water
The second drip washing post is washed, the second drip washing post water outlet saliva phase PH ~ 7 are checked, stops washing；3rd drip washing column top is started with linear speed
The delayer that 1 ~ 4cm/min of degree enters 490 ~ 530L is made the transition, and transition completion washes the 3rd drip washing post with pure water, checks that the 3rd drenches
Post water outlet saliva phase PH ~ 7 are washed, stops washing.
8. the method for extraction and purification of thulium oxide as claimed in claim 7, it is characterised in that：Step 4 drip washing post transition, to the
The delayer that two drip washing column tops start to enter 500L with 1 ~ 4cm/min of linear velocity is made the transition, and transition completion washes the with pure water
Two drip washing posts, check the second drip washing post water outlet saliva phase PH ~ 7, stop washing；3rd drip washing column top is started with linear velocity 1 ~
The delayer that 4cm/min enters 520L is made the transition, and transition completion washes the 3rd drip washing post with pure water, checks the 3rd drip washing post water outlet
Saliva phase PH ~ 7, stop washing.
9. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：Step 5 adsorption operations, by first
Thulium oxide mixed solution to be purified is entered at adsorption column top, is fed with 1 ~ 2cm/min of linear velocity with measuring pump, and the first adsorption column stream
Go out liquid saturated oxalic acid inspection, detect rare earth ion, stop charging, and the first drip washing post is washed, to water outlet phase PH ~ 7.
10. the method for extraction and purification of thulium oxide as claimed in claim 1, it is characterised in that：The step 6 drip washing operation, drip washing
Liquid is heated to 45 DEG C ~ 65 DEG C, pillar circulating water heating to 45 DEG C ~ 65 DEG C, leacheate drip washing by the first adsorption column, linear speed
1 ~ 2cm/min of degree, the first adsorption column efflux saturated oxalic acid checks whether out rare earth ion, goes out the first suction after rare earth ion
Attached, the second drip washing post series connection；Continue drip washing, flow velocity is constant；Second drip washing post efflux saturated oxalic acid inspection, goes out rare earth ion
The first adsorption column, the second drip washing post, the series connection of the 3rd drip washing post, continue drip washing afterwards, and flow velocity is constant, and the 3rd drip washing post goes out rare earth ion
Afterwards, the first adsorption column, the second drip washing post, the 3rd drip washing post, the series connection of the 4th splitter, leacheate linear velocity are changed to 0.2 ~ 0.6cm/
Min, the 4th splitter efflux saturated oxalic acid checks whether out rare earth ion；After detecting rare earth ion, by certain volume
Collect the efflux of the 4th splitter in batches, until efflux has all gone out, pure water cleans up 4 pillars, return to step 4 after
Continuous work.
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| CN109553122A (en) * | 2018-12-17 | 2019-04-02 | 中铝广西国盛稀土开发有限公司 | A kind of method that strong acid cation resin prepares high-purity rare-earth |
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| CN1109912A (en) * | 1994-09-10 | 1995-10-11 | 包头钢铁稀土公司稀土研究院 | Preparation method for preparing single medium-heavy rare earth oxide with content of more than or equal to 5N by cation exchange fiber chromatography |
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| CN109553122A (en) * | 2018-12-17 | 2019-04-02 | 中铝广西国盛稀土开发有限公司 | A kind of method that strong acid cation resin prepares high-purity rare-earth |
| CN109553122B (en) * | 2018-12-17 | 2021-06-08 | 中铝广西国盛稀土开发有限公司 | Method for preparing high-purity rare earth by using strong acid cation resin |
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