CN1054645C - Technology for concentrating rare earth feed liquid by extraction method - Google Patents
Technology for concentrating rare earth feed liquid by extraction method Download PDFInfo
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- CN1054645C CN1054645C CN95117987A CN95117987A CN1054645C CN 1054645 C CN1054645 C CN 1054645C CN 95117987 A CN95117987 A CN 95117987A CN 95117987 A CN95117987 A CN 95117987A CN 1054645 C CN1054645 C CN 1054645C
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- rare earth
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Abstract
The present invention relates to a new method for continuously concentrating feed liquid by an extraction method. The inherent properties of an extraction system are utilized to realize the continuous concentration operations of rare earth feed liquid or organic phase feed liquid at a normal temperature and normal pressure by only adding 2 to 4 grades of extraction grooves on a basis of separating a main groove without additionally consuming acid and alkali. The method can improve the concentration of the feed liquid in multiples and can remove impurity ions in a concentration process, such as NH4 <+>, Na<+>, Ca<2+>, etc. so that the purity and the yield of products can be improved; meanwhile, due to the improvement of the concentration of the feed liquid, the processing load of subsequent working sections is greatly increased.
Description
The present invention relates to a kind of method with extraction process continuous concentration rare earth feed liquid.
When solvent extration is produced rare-earth products, when containing a plurality of component in the raw material, to isolate each rare earth element one by one, need to use a plurality of centrifugal stations, it is the outlet organic phase of the preceding paragraph raffinate water or load mishmetal that each section separates raw materials used, carrying out along with separation circuit, the organic phase exit concentration of later separation section raffinate water or load mishmetal constantly reduces, thereby cause the reduction of follow-up workshop section treatment capacity, the cell body volume increases relatively, two phase stratification is the variation with comparing imbalance also, and foreign ion constantly accumulates simultaneously, directly influences quality product and yield.For the water rare earth feed liquid, generally adopt heating means to concentrate at present, but there are two significant disadvantages in this method: the one, needing increases thickening equipment and consumes heat energy, and the 2nd, this concentrating makes that non-rare earth impurity is (as NH in the rare earth feed liquid
4 +, Na
+, Ca
2+Deng) concentration improve simultaneously.The technology that adopts extraction process to concentrate aqueous phase liquid is also arranged, but all be to adopt two-stage method (one-section abstraction rare earth, one section back extraction rare earth) just to be achieved, both increased more equipment, again industrial chemicals such as additive decrementation soda acid.Then still not having suitable method for the organic phase rare earth feed liquid is concentrated.
The invention provides a kind of method with extraction process continuous concentration rare earth feed liquid.Utilize the character of extraction system itself, at normal temperatures and pressures, the additive decrementation soda acid does not only need increase 2-4 level extraction tank on the basis of separating major trough, just can realize the continuous concentration operation of rare earth feed liquid or organic phase feed liquid.
The inventive method comprises:
(1) comprises that with acid organophosphorus compounds or carboxylic acid alkyl carboxylic acid or naphthenic acid are extraction agent; Kerosene or sulfonated kerosene are thinner; Alcohols or alcohol mixture are additive; Aqueous media is hydrochloric acid or nitric acid; Raw material is the rare earth of any composition, extracts.With wherein water or any composition rare earth feed liquid of organic phase is raw material, operates.The raffinate water is as the isolating feed liquid of next section, and its concentration method is that the extracting rare-earth function of the first step of common cell body (promptly entering the one-level of blank saponification organic phase) is carried out separately in different cell bodies respectively separately with the rare earth exchanged function.As illustrate shown in Figure 1, use 2-4 level (contrary) chute A altogether earlier, make blank saponification organic phase 1 and raffinate water 2 (first step outlet water) aqueous phase extracted rare earth in this section, supported rare earth ionic organic phase 3 enters separates required counter-current extraction groove B, and 4 of waters only contain the NH that saponification is introduced
4 +, Na
+, Ca
2+Deng non-rare earth impurity, it is discarded.Because the organic phase of supported rare earth enters behind the main separator tank substantially no longer extracting rare-earth, and only carry out two alternate rare earth ion exchanged, thereby not reducing the rare earth concentration of first step water in the main separator tank substantially, its (2 and 5) rare earth concentration can be brought up to and the essentially identical level of other grades of extraction section water rare earth concentration.Concentrate feed liquid from 3 or 5 grades of clarifying chambers by should the amount of drawing drawing.
(2) in above-mentioned extraction system, the outlet organic phase is made the feed liquid of next segregation section, or as the feed liquid of rare earth phase transition, its concentration method is: the back extraction rare earth function of the last step (promptly entering the one-level of washing acid) of common cell body is carried out separately in different cell bodies respectively with the rare earth exchanged function.When the outlet organic phase is made the feed liquid of next segregation section, as illustrate shown in Figure 2, increase the 2-4 stage countercurrent or be total to cross-flow back extraction rare earth groove A ', make wash acid 1 ' with the part 2 of the outlet organic phase of supported rare earth ' in this section, contact and clean organic phase in rare earth, contain the washing lotion 3 of rare earth ' enter and separate required counter-current extraction groove B ', blank organic phase 4 ' then continue to recycle.Owing to contain behind the main separator tank of the washing lotion 3 of rare earth ' enter basically no longer back extraction rare earth, and only carry out two alternate rare earth ion exchanged, thereby do not reduce the rare earth concentration of the middle last step organic phase of main separator tank B ' basically, wherein (2 ' and 5 ') rare earth concentration can be brought up to the essentially identical level of rare earth concentration with other grades of washing section organic phase.When exporting organic phase as rare earth phase transition feed liquid, as illustrate shown in Figure 3, to wash acid 1 and " add back extraction rare earth groove A " with the sour regurgitation form, in this section cell body with the outlet organic phase 2 " contact and clean organic phase in rare earth; blank organic phase 3 " continues to recycle, an anti-fluid part 4 that contains rare earth " advances to separate required counter-current separation rinse bath B ", owing to contain the washing lotion 4 of rare earth " enter behind the major trough basically no longer back extraction rare earth; and only carry out two alternate rare earth ion exchanged; thereby do not reduce main separator tank B substantially " in the rare earth concentration of last step organic phase, they are 2 years old, and " rare earth concentration can be brought up to and the essentially identical level of other grades of washing section organic phase rare earth concentration.Outlet organic phase 2 " raising of rare earth concentration will correspondingly improve anti-fluid 4 ", 5 " rare earth concentration, reduce the spent acid degree of anti-fluid 4 ", 5 ", handle again for the rare earth after the phase transition and provide convenience.
The inventive method in sum comprises:
(1). raw material: be the rare earth of any composition, medium is hydrochloride or nitrate, forms the water stock liquid,
(2). organic phase:, comprise that alkyl carboxylic acid or naphthenic acid are extraction agent with acid organophosphorus compounds or carboxylic-acid, kerosene or sulfonated kerosene are thinner; Alcohols or alcohol mixture are additive; With ammoniacal liquor or sodium hydroxide saponification,
(3). with the water stock liquid in the saponification organic phase extracting in (2) (1),
(4). raffinate water and blank saponification organic phase after the extraction in (3) are carried out 2-4 level rare earth extraction in tandem counter-current extraction groove, then, discard the raffinate water,
(5). the organic phase that is loaded with rare earth ion that obtains after the extraction in (4) is introduced in the counter-current extraction groove, only carried out the rare earth ion exchanged between organic phase and water in counter-current process, the feed liquid after the exchange is drawn from the 3rd or 5 grade of clarifying chamber by drawing the solute amount,
(6). make the organic phase feed liquid of the part of the organic phase that is loaded with rare earth ion after (5) intermediate ion exchanges as another separating technology section; The organic phase that another one contains rare earth contacts with sour regurgitation at 2-4 stage countercurrent reextraction groove, the rare earth in the reextraction organic phase, and in the water introducing counter-current extraction groove that contains rare earth that will obtain thus, carry out ion-exchange, the regeneration organic phase recycles,
(7). or make the organic phase that is loaded with rare earth ion after the ion-exchange in (5) in the back extraction groove with wash acid and contact, and the rare earth in the organic phase of stripping fully, and the part of the strip liquor that contains rare earth that will obtain introducing counter-current extraction groove, carry out ion-exchange, the regeneration organic phase recycles; Another part contains the aqueous phase liquid of the strip liquor of rare earth as another separating technology section.
The advantage of the inventive method is: produce continuous, low consumption, reliable and stable, can improve the rare earth concentration in water or the organic phase significantly, reduce foreign matter content, increase the subsequent process treatment capacity.Brief Description Of Drawings: Fig. 1 be the raffinate water as the isolating feed liquid of next section, with its spissated synoptic diagram, wherein:
A is for being total to counter-current extraction rare earth groove, and B is counter-current extraction groove (a body groove extraction section)
1 is blank saponification organic phase, and 2 is extracting phase,
3 is the supported rare earth organic phase, and 4 for abandoning water,
5 is as next section operation feed liquid.Fig. 2 makes the feed liquid of next segregation section for the outlet organic phase, with its spissated synoptic diagram:
A ' is the anti-rare earth groove of contrary (also) stream, and B ' is counter-current extraction groove (a body groove washing section),
1 ' be washing lotion, 2 ' be the part of supported rare earth organic phase,
3 ' be the washing lotion that contains rare earth, 4 ' be blank organic phase,
5 ' as next section operation feed liquid.Fig. 3 is for exporting organic phase as rare earth phase transition feed liquid, with its spissated synoptic diagram, wherein:
A " being the anti-rare earth groove of contrary (also) stream, B " is counter-current extraction groove (a body groove washing section),
1 " being washing lotion 2 " is the outlet organic phase,
3 " blank organic phase, 4 " be the part of anti-fluid,
5 " be the aftertreatment rare earth feed liquid.
In order to be illustrated more clearly in the present invention, enumerate following examples, but it is not limited to them to scope of the present invention.Embodiment 1.
With the rare earth feed liquid is raw material, and P507 is an extraction agent, and kerosene is thinner, and water is a hydrochloric acid medium, separates LaCePr/Nd.Feed liquid is formed: the molar fraction f of Nd in the rare earth
Nd=0.38, feed concentration C
f=1.60mol/L, inlet amount Mf=9.58mol/min; Organic phase concentration is 1.50mol/L, ammonia saponification, saponification value 0.51N; Wash acid and be 4.5N hydrochloric acid.Normalized parameter, i.e. the unit inlet amount loading capacity and the washing capacity that are: S=1.70, W=1.3186.Volume flow ratio is:
Organic phase (Vs): feed liquid (Vf): wash acid (Vw)=95.80: 5.99: 8.42 (l/min) if do not adopt the present invention, the rare earth concentration C of raffinate water
RE(1)=0.3-0.4mol/L; If adopt the present invention, make saponification organic phase and rare earth raffinate respectively with after 95.80: 10.86 (l/min) adverse current level Four, organic phase supported rare earth 0.17mol/L enters the first step of major trough extraction section, discards only residual NH
4 +, Na
+, Ca
2+Water Deng foreign ion.First step water rare earth concentration can be brought up to more than the 1.5mol/L by 0.3-0.4mol/L like this, and does not contain NH
4 +Deng foreign ion, also directly condensing crystal becomes rare earth chloride.Embodiment 2.
With the rich europium mishmetal of middle yttrium is raw material, and naphthenic acid is an extraction agent, and water is the hydrochloride medium, separates LaY and other rare earth elements.The molar fraction of LaY is 0.585 in the rare earth feed liquid, feed liquid rare earth concentration C
f=1.0mol/L, inlet amount M
f=6.30mol/min; The organic extractant phase agent concentration is 0.90mol/L, ammonia saponification, saponification value 0.63mol/L; Wash acid and be 3.0mol/L hydrochloric acid.Throughput ratio is:
Vs: Vf: Vw=75.0: 6.30: 13.3 (l/min) be not if adopt the present invention, raffinate water rare earth concentration C
RE(1)=0.16mol/L; If adopt the present invention, make blank saponification organic phase and raffinate respectively with after 75.0: 15.75 (l/min) adverse current Pyatyis, organic phase supported rare earth 0.21mol/l enters the major trough extraction section first step, this grade water rare earth concentration can be brought up to 1.0mol/L by 0.16mol/L, and does not contain NH
4 +Deng foreign ion, thereby can improve the treatment capacity of next segregation section.Embodiment 3.
With the mishmetal carried behind the LaY is raw material, and P507 is the collection agent, and water is a hydrochloric acid medium, carries out the Nd/Sm grouping, and the outlet organic phase is as the isolating raw material of Gd/Tb/Dy.Feed liquid is formed: the molar fraction f of Dy in the rare earth
Dy=0.44, feed concentration C
f=1.0mol/L, inlet amount Mf=0.86mol/min; Organic phase concentration is 1.50mol/L, ammonia saponification, saponification value 0.54mol/L; Wash acid and be 3.0mol/L hydrochloric acid.Throughput ratio is:
Vs: Vf: Vw=3.10: 0.86: 0.18 (l/min) if do not adopt the present invention, outlet organic phase rare earth concentration is 0.122mol/L; If adopt the present invention, with the section port organic phase with wash acid respectively with after six grades of 1.00: 0.18 (l/min) adverse currents, make washing lotion contain the last step that rare earth 1.0mol/L enters the major trough washing section, the rare earth concentration of this grade organic phase can be brought up to 0.18mol/L by 0.122mol/L, reaches the purpose that increases next separating treatment amount.Embodiment 4.
With middle heavy rare earths mixed liquor is raw material, and P507 is an extraction agent, and water is the hydrochloride medium, carries out the Sm=Dy/HoY-Lu grouping, and the mole number mark of (HoY-Lu) is 0.715 in the feed liquid, feed concentration C
f=0.139mol/L, inlet amount Mf=1.748mol/min; Organic phase concentration is 1.50mol/L, ammonia saponification, saponification value 0.54mol/L; Wash acid and be 4.5N hydrochloric acid.Throughput ratio is:
Vs: Vf: Vw-10.69: 12.58: 1.59 (l/min) if do not adopt the technology of the present invention, outlet organic phase rare earth concentration is 0.055mol/L, the anti-liquid of stripping section (initial acidity 5.5mol/L) outlet: C
RE=0.67mol/L, Ch=3.5mol/L, concentrate through heating, in and acid adjustment just can serve as the feed liquid of segregation section.If adopt the technology of the present invention, the anti-fluid of part is replaced washing acid, enter the last step that separates the major trough washing with identical washing flux, the rare earth concentration of this grade organic phase can be brought up to 0.12-0.15mol/L by 0.055mol/L, the anti-fluid outlet of stripping section at this moment: C
RECan be increased to 1.16-1.33mol/L by 0.67omol/L, CH is reduced to 2.0-1.5mol/L by 3.5mol/L, only can serve as the feed liquid of segregation section through acid adjustment.
Claims (1)
1. the concentration method of a rare earth feed liquid is characterized in that, described method comprises:
(1). raw material: be the rare earth of any composition, medium is hydrochloride or nitrate, forms the water stock liquid,
(2). organic phase:, comprise that alkyl carboxylic acid or naphthenic acid are extraction agent with acid organophosphorus compounds or carboxylic-acid, kerosene or sulfonated kerosene are thinner; Alcohols or alcohol mixture are additive; With ammoniacal liquor or sodium hydroxide saponification,
(3). with the water stock liquid in the saponification organic phase extracting in (2) (1),
(4). raffinate water and blank saponification organic phase after the extraction in (3) are carried out 2-4 level rare earth extraction in tandem counter-current extraction groove, then, discard the raffinate water,
(5). the organic phase that is loaded with rare earth ion that obtains after the extraction in (4) is introduced in the counter-current extraction groove, only carried out the rare earth ion exchanged between organic phase and water in counter-current process, the feed liquid after the exchange is drawn from the 3rd or 5 grade of clarifying chamber by drawing the solute amount,
(6). make the organic phase feed liquid of the part of the organic phase that is loaded with rare earth ion after (5) intermediate ion exchanges as another separating technology section; The organic phase that another one contains rare earth contacts with sour regurgitation at 2-4 stage countercurrent reextraction groove, the rare earth in the reextraction organic phase, and in the water introducing counter-current extraction groove that contains rare earth that will obtain thus, carry out ion-exchange, the regeneration organic phase recycles,
(7). or make the organic phase that is loaded with rare earth ion after the ion-exchange in (5) in the back extraction groove with wash acid and contact, and the rare earth in the organic phase of stripping fully, and the part of the strip liquor that contains rare earth that will obtain introducing counter-current extraction groove, carry out ion-exchange, the regeneration organic phase recycles; Another part contains the aqueous phase liquid of the strip liquor of rare earth as another separating technology section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117987A CN1054645C (en) | 1995-11-08 | 1995-11-08 | Technology for concentrating rare earth feed liquid by extraction method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117987A CN1054645C (en) | 1995-11-08 | 1995-11-08 | Technology for concentrating rare earth feed liquid by extraction method |
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| Publication Number | Publication Date |
|---|---|
| CN1129256A CN1129256A (en) | 1996-08-21 |
| CN1054645C true CN1054645C (en) | 2000-07-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117987A Expired - Lifetime CN1054645C (en) | 1995-11-08 | 1995-11-08 | Technology for concentrating rare earth feed liquid by extraction method |
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| CN1880489B (en) * | 2006-02-27 | 2010-05-12 | 有研稀土新材料股份有限公司 | Non-saponifiable extraction full-separating process for high concentration rare earth solution |
| CN106244807B (en) * | 2016-07-29 | 2018-08-28 | 乐山东承新材料有限公司 | A method of the recovery purifying rare earth from ion adsorption type rare earth ore waste water |
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1995
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