CN107488786A - A kind of method that saponification is carried out to P204 - Google Patents
A kind of method that saponification is carried out to P204 Download PDFInfo
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- CN107488786A CN107488786A CN201710682365.0A CN201710682365A CN107488786A CN 107488786 A CN107488786 A CN 107488786A CN 201710682365 A CN201710682365 A CN 201710682365A CN 107488786 A CN107488786 A CN 107488786A
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- saponification
- lime
- edta
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- ethylene diamine
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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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of method to P204 saponification, the method of the present invention is using disodium ethylene diamine tetraacetate as auxiliary agent, saponification is directly carried out to P204 using EDTA Ca at normal temperatures, used in saponification extraction raffinate lime with Posterior circle to saponifying process, and EDTA reaction requirement is supplemented according to filter residue entrainment loss in lime N-process；The present invention can obtain higher, stable saponification rate, and one-level saponification rate is up to more than 70%；Thoroughly solve the problems such as long-term existing ammonia and nitrogen pollution in saponification process, reduce the demand to high energy consumption product (liquid caustic soda, ammonia), be advantageous to environmental protection and sustainable development.
Description
Technical field
The invention belongs to non-ferrous metal, rare-earth wet method smelt in saponifiable extraction technology field, and in particular to be
A kind of method that saponification is carried out to P204.
Background technology
The Rare Earth Separation in China is mainly extracted with extractants such as P204 at present.Before the use, extractant first has to use
Liquid caustic soda (sodium hydroxide solution) or ammoniacal liquor carry out saponification to extractant, and extractant with re chloride extract instead after saponification
Should, generate the extractant and ammonia (sodium) salting liquid of supported rare earth, the extractant of supported rare earth carries out dilute in multitple extraction equipment
Soil is exchanged after purification, and aqueous phase rare earth feed liquid is obtained after acid is stripped.The saponification of extractant is the core process of saponifiable extraction technology.
The saponification process of extractant mainly has at present：Ammonia saponification process, lime (calcium hydroxide) saponification process etc..
Ammoniacal liquor is that current rare earth extraction separates most commonly used saponification agent in industry, the waste water (saponification of separation process production
Abandon water) in ammonia can cause environmental pollution.In addition, liquefied ammonia need to be transported and stored at elevated pressures, there is certain danger.
Can solve the problems, such as ammonia and nitrogen pollution as saponification agent using liquid caustic soda or soda ash solution, but production cost can be improved.In addition, in industry
On, liquefied ammonia and sodium hydroxide belong to the higher product of energy consumption, and largely using such raw material, the energy for increasing relevant industries is disappeared
Consumption, the sound development of influence area economy.
Often contain more impurity in natural lime raw material, saponification is such as carried out using milk of lime, because can not effectively remove
Impurity, the insoluble impurities element in lime will produce harmful effect to extraction process so that and saponification organic phase split-phase is difficult, and
Cause impurity content exceeding index, influence product quality.In addition, the basicity metering of milk of lime has certain difficulty, it is unfavorable in production
Control to organic phase saponification degree.Because solubility of the calcium hydroxide in water is smaller, the basicity for clarifying limewash is only
0.02mol/L or so, directly with the larger aqueous phase volume of clarification limewash saponification needs, the requirement to saponification equipment is too high.It is logical
Often the saponification number of organic phase is 0.5mol/L in production, i.e., 1 part of volume organic phase of saponification needs to clarify 25 parts of volumes of limewash
Amount.Aqueous phase volume is excessive after the completion of saponification, can cause larger with the organic phase loss for abandoning water discharge.Therefore, using clarification lime
Water carries out saponification and also lacks operability in actual production.
The content of the invention
The present invention uses the auxiliary agent-disodium ethylene diamine tetraacetate that can be recycled, and improves the solubility of lime calcium in water,
Saponification is carried out to organic phase using the EDTA-Ca compound saponification liquors after dissolving, to reach in the extraction separation process being carried out continuously
Middle saving cost of material, reduce the purpose of contaminated wastewater.
Disodium ethylene diamine tetraacetate is soluble in water, and during lime slaking, its solution can react with lime, make
The calcium obtained in lime is largely soluble in water in the form of calcium ion.Lysate obtains EDTA-Ca solution after clarifying or filtering naturally,
Solution is limpid transparent, and the insoluble impurities overwhelming majority in lime is stayed in slag.Compound more than saponification clear liquid PH12, with current work
The volume organic phase of saponification 1 only needs about 2 volume auxiliary agents in industry production, the process conditions such as the mixing of saponification process, settling time with
Existing industrial process conditions are close, are adapted to use in the industrial production.
Realize that the technical scheme that the object of the invention is taken is as follows：Using disodium ethylene diamine tetraacetate as auxiliary agent, using EDTA-
Ca directly carries out saponification to organic phase at normal temperatures, is used in saponification extraction raffinate lime with Posterior circle to saponifying process, and
According to the reaction requirement of filter residue entrainment loss supplement disodium ethylene diamine tetraacetate in lime N-process.
The allotment percent by volume of P204 organic phases is that P204 accounts for 25~30%, and surplus is kerosene；The ethylenediamine tetraacetic of use
The na concn of acetic acid two is 0.3~0.5mol/L；Causticization liquid PH >=9 after being neutralized to saponification extraction raffinate.
During saponification, the volume ratio O/A=1 of organic phase and aqueous phase:2~4；Neutralization circulation to saponification extraction raffinate
Number uses for Infinite Cyclic.
PH changes are little when the design of the present invention make use of extractant P204 (HR) and EDTA-Ca reactions, saponification knot
Beam, used with Posterior circle in saponification extraction raffinate lime.
Extractant organic phase HR reacts with saponification agent：
EDTA-Ca+2HR=CaR2+EDTA (1)
In lime and saponification extraction raffinate causticization regenerative response：
EDTA+Ca(OH)2=EDTA-Ca+H2O (2)
The method have the benefit that：Production cost is saved, for the purpose of reducing environmental pollution, use is cheap,
The lime that raw material is easy to get supplements the source of calcium, reduce consume while, produce, be advantageous to without nitrogen-containing wastewater, waste gas
Environmental protection；Saponification rate is high and stably, and one-level saponification rate is up to more than 70%, by increasing saponification series, comparing or improve and help
Agent concentration, higher saponification rate can be obtained；Technique is simply, stably, workable.
The advantages of this technology, embodies as follows：
1st, solubility of the EDTA-Ca in water is big, and the calcium ion for having abundance provides.
As long as the 2, the input of saponification first disodium ethylene diamine tetraacetate, lime, disodium ethylene diamine tetraacetate can be recycled,
EDTA-Ca is regenerated with lime causticization saponification extraction raffinate, only needs to supplement slag entrainment loss in a small amount of causticization process in process of production
Part, main consumption is lime in saponification process, and production cost is low.
3rd, causticizing reaction is not limited by temperature, milk of lime, pulverized limestone can be used to make saponification agent, reduces lime slaking mistake
Journey, the problem of avoiding volumetric expansion.
4th, causticization basicity need not be strictly controlled, causticization PH >=9, operation is simple.
5th, using the auxiliary agent disodium ethylene diamine tetraacetate that can be recycled, effective dissolving of lime is greatly improved
Degree；Saponification is carried out using clear liquid, the reaction time shortens within 1 minute and split-phase is fine, and existing industrial equipment need not
Especially transformation can use this technology, and saponification process can meet the needs of actual production；The saponification agent and soap that this method is selected
It is reasonable to change auxiliary agent, the problems such as thoroughly determining ammonia and nitrogen pollution, a large amount of discharge of wastewater can be solved, production cost is greatly reduced.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
Following experiment master data embodies the specific embodiment of the present invention.
Test master data
1. the relation of saponification assistant concentration and saponification rate
Experimental condition：
Organic phase composition：30%P204+70% kerosene
Causticization liquid is prepared：LEDTA adds lime to adjust solution PH 9.0
Compare：O/A=1:2
Saponification series：1 grade
Incorporation time：1min
The split-phase time：2min
| EDTA(mol/L) | Organic phase calcium (g/L) | Saponification rate (%) |
| 0.1 | 6.3 | 45 |
| 0.2 | 6.7 | 48 |
| 0.25 | 7.4 | 52 |
| 0.3 | 8.4 | 60 |
Result of the test shows：Saponification rate has direct relation with EDTA concentration, and the concentration for improving EDTA is advantageous to improve saponification
Rate.
2. saponification incorporation time is tested saponification rate
Experimental condition：
Organic phase composition：30%P204+70% kerosene
Causticization liquid is prepared：0.3mol/L LEDTA add lime to adjust solution PH 9.0
Compare：O/A=1:2
Saponification series：1 grade
The split-phase time：2min
| Saponification mixes (min) | Organic phase C a (g/L) | Saponification rate (%) |
| 1 | 8.3 | 59 |
| 2 | 8.5 | 60 |
| 3 | 8.4 | 60 |
| 4 | 8.5 | 60 |
As can be seen from the above data, saponification incorporation time and the relation of saponification rate are little, organic phase saponification rate and with
The increase of incorporation time and increase.Illustrate organic phase saponification, reaction balance is basically reached after 1min is mixed, extends mixing
Time has been chosen to be 1min without too big influence, the incorporation time of all saponification organic phases on organic phase saponification rate.
3. causticization liquid PH is tested saponification rate
Experimental condition：
Organic phase composition：30%P204+70% kerosene
Causticization liquid is prepared：LEDTA adds lime to adjust solution
Compare：O/A=1:2
Saponification series：1 grade
Incorporation time：1min
The split-phase time：2min
| Causticization liquid PH | Organic phase C a (g/L) | Saponification rate (%) |
| PH9.0 | 8.4 | 60 |
| PH10.0 | 8.9 | 63 |
| PH12.0 | 9.5 | 67 |
Result of the test shows：Saponification rate has direct relation with causticization liquid PH, improves causticization liquid PH and is advantageous to carry saponification rate.
4.EDTA auxiliary agent cyclic tests
With EDTA-Ca solution saponification P204 organic phases, saponification extraction raffinate is regenerated with lime causticization, saponification organic phase and chlorauride
Belong to feed liquid extraction, be the saponification again of unloaded organic phase after back extraction, so circulation is tested, and is investigated auxiliary agent EDTA and is recycled
During the stability of saponification rate and EDTA loss amount.
Experimental condition：
Organic phase composition：30%P204+70% kerosene
Compare：O/A=1:2
Causticization liquid is prepared：LEDTA adds lime to adjust causticization liquid PH12
Saponification series：1 grade
Incorporation time：1min
The split-phase time：2min
| Cycle-index | Organic phase C a (g/L) | Saponification rate (%) |
| 1 time | 9.5 | 67 |
| 2 times | 9.6 | 68 |
| 3 times | 9.5 | 67 |
| 15 times | 9.2 | 65 |
| 35 times | 8.8 | 62 |
Result of the test shows：By 35 cyclic tests of liquid of above 0.3mol/LEDTA causticizations, saponification rate is basicly stable, has
Calcium ion slightly reduces in machine phase, is supplemented in process of production according to the change of EDTA concentration, ensures the steady of saponification rate
It is fixed.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent circle.
Claims (3)
- A kind of 1. method that saponification is carried out to P204, it is characterised in that：Using disodium ethylene diamine tetraacetate as auxiliary agent, using EDTA- Ca directly carries out saponification to P204 organic phases at normal temperatures, makes in saponification extraction raffinate lime with Posterior circle to saponifying process With, and according to filter residue entrainment loss supplement disodium ethylene diamine tetraacetate reaction requirement in lime N-process.
- A kind of 2. method that saponification is carried out to P204 as claimed in claim 1, it is characterised in that：The allotment body of P204 organic phases Product percentage is that P204 accounts for 25~30%, and surplus is kerosene；The disodium ethylene diamine tetraacetate concentration used is 0.3~0.5mol/ L；PH >=9 after being neutralized to saponification extraction raffinate.
- A kind of 3. method that saponification is carried out to P204 as claimed in claim 2, it is characterised in that：During saponification, The volume ratio O/A=1 of organic phase and aqueous phase:2；Neutralization cycle-index to saponification extraction raffinate uses for Infinite Cyclic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710682365.0A CN107488786A (en) | 2017-08-10 | 2017-08-10 | A kind of method that saponification is carried out to P204 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710682365.0A CN107488786A (en) | 2017-08-10 | 2017-08-10 | A kind of method that saponification is carried out to P204 |
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| Publication Number | Publication Date |
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| CN107488786A true CN107488786A (en) | 2017-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710682365.0A Pending CN107488786A (en) | 2017-08-10 | 2017-08-10 | A kind of method that saponification is carried out to P204 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168799A (en) * | 2006-10-27 | 2008-04-30 | 胡建康 | Extraction separation method for circularly preparing saponification organic phase rear earth from chloride solvent |
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
-
2017
- 2017-08-10 CN CN201710682365.0A patent/CN107488786A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168799A (en) * | 2006-10-27 | 2008-04-30 | 胡建康 | Extraction separation method for circularly preparing saponification organic phase rear earth from chloride solvent |
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
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Application publication date: 20171219 |
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