CN105779764B - The yttrium method for saponification of substituted acetic acid and the compound organic phase of organophosphor - Google Patents
The yttrium method for saponification of substituted acetic acid and the compound organic phase of organophosphor Download PDFInfo
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- CN105779764B CN105779764B CN201610305003.5A CN201610305003A CN105779764B CN 105779764 B CN105779764 B CN 105779764B CN 201610305003 A CN201610305003 A CN 201610305003A CN 105779764 B CN105779764 B CN 105779764B
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- acetic acid
- yttrium
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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
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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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
Abstract
The present invention discloses substituted acetic acid and the yttrium method for saponification of the compound organic phase of organophosphor, using hydroxyl type strong-basicity styrene anion exchange resin as auxiliary agent, to realize the yttrium saponification of substituted acetic acid and the compound organic phase of acidic organo phosphorus.In saponification device, kerosene or sulfonated kerosene solution, the yttrium chloride aqueous solution and hydroxyl type strong-basicity styrene anion exchange resin of substituted acetic acid and acidic organo phosphorus composite extractant are sequentially added；Stratification after completion of the reaction is sufficiently stirred at room temperature.Upper strata is yttrium saponification substituted acetic acid and the compound organic phase of organophosphor, and middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state；Aqueous phase and strong-basicity styrene anion exchange resin are released, releases aqueous phase and styrene series anion exchange resin phase, obtains yttrium saponification substituted acetic acid and the compound organic phase of organophosphor that saponification rate is 60%~90%.The present invention has the advantages that to improve yttrium product purity, reduces production cost, saves energy.
Description
Technical field
The present invention relates to substituted acetic acid and the yttrium method for saponification of the compound organic phase of organophosphor, more particularly to one kind with hydrogen-oxygen
Root type strong-basicity styrene anion exchange resin is the substituted acetic acid of auxiliary agent and the yttrium saponification of the compound organic phase of acidic organo phosphorus
Method.The present invention particularly belongs to solvent extraction technology field.
Background technology
1999, Li Deqian et al. was proposed using substituted acetic acid and the compound organic phase of organophosphorus reagent as extractant to realize
The separation of yttrium and lanthanide series, the technique have become one of best approach of preparation of industrialization high-purity yttrium product (Li Deqian etc.,
Art for prodn. of high purity yttrium, Chinese patent, application number 991182618,1999-09-11).Used in the patent of invention
Substituted acetic acid be mostly secondary octyl phenoxy group substituted acetic acid, organophosphorus reagent used is acidic phosphorus extractant, mainly
P507, C272 (i.e. Cyanex272), C302 (i.e. Cyanex302) etc..
In the technique of separation and Extraction yttrium, it is necessary to using alkaline reagent to substituted acetic acid and the compound organic phase of acidic organo phosphorus
Higher extraction efficiency could be kept by carrying out saponification.Improved with the requirement of ammonia nitrogen discharge standard, the ammonia using ammoniacal liquor as saponification agent
Saponification has been eliminated.The saponification agent used at present is that have sodium hydroxide.Disadvantage using sodium hydroxide as saponification agent is
Part sodium ion in sodium hydroxide can enter yttrium product and form saponification contamination, be produced very to preparing high-purity and ultra-pure yttrium
Detrimental effect.It is high-purity and superelevation follow-up preparing because sodium has a strong impact on the performance of high-purity and ultra-pure yttrium material
Generally also need to establish soda soap impurity separating technology in separating yttrium product in technique.In fact, when the content of sodium in yttrium product
Separated when relatively low and very difficult.In order to prevent the high-purity particularly ultra-pure sodium product of sodium ion pollution, the present invention establishes
A kind of new yttrium method for saponification of the compound organic phase of substituted acetic acid and organophosphor.
In separating technology, the important technology index for evaluating ion exchange resin is effective exchange capacity.Effectively exchange and hold
Measure abbreviation exchange capacity sometimes.Effective exchange capacity of anionic ion-exchange resins refers to that every kg dried resins effectively exchange monovalence
The molal quantity of anion；Now, the unit of effective exchange capacity is mol/kg.Also someone effectively exchanges one using every liter of dried resin
The molal quantity of valency anion；Now, the unit of effective exchange capacity is then mol/L.Although adopt unit mol/kg in mass
It can be converted with unit mol/L by volume.But for the degree of accuracy of effective exchange capacity, using quality meter unit
Mol/kg, which is higher than, uses stereometer unit mol/L.By the way, total exchange capacity of the dried resin of certain mass passes through following
Formula calculates：
N=m × Q (1)
In formula (1), m is the quality of dried resin, and its unit is kg；Q is effective exchange capacity of resin, and its unit is mol/
kg；N is total exchange capacity, and its unit is mol.From formula (1), maximum when total exchange capacity refers to give resin quality m is effectively
Exchange capacity.In fact, maximum exchange molal quantity when total exchange capacity is exactly given resin quality m, therefore total exchange capacity is also referred to as
It is total to exchange molal quantity.
The content of the invention
The purpose of the present invention is part sodium when using sodium hydroxide saponification for substituted acetic acid and the compound organic phase of organophosphor
Ion can stain the shortcomings that yttrium product, establish a kind of substituted acetic acid of no saponification contamination and the yttrium saponification of the compound organic phase of organophosphor
Method.
The yttrium saponification of the present invention, is expressed as with chemical equation：
In reaction equation (2) and (3), HA represents substituted acetic acid extractant；HB represents substitution acidic organo phosphorus extractant；
R4NOH represents hydroxyl type strong-basicity styrene anion exchange resin, R4NCl represents chlorine root type strong-basicity styrene anion
Exchanger resin, subscript " o " represent organic phase, and subscript " a " represents aqueous phase, and subscript " s " represents the resin phase of solid-state.The present invention passes through
The yttrium saponification of substituted acetic acid and the compound organic phase of organophosphor is realized in reaction equation (2) and (3).From reaction equation (2) and (3), sheet
Invention is occurred by the hydroxyl in the chlorion in the aqueous solution and hydroxyl type strong-basicity styrene anion exchange resin
Exchange interaction promotes the saponification of ruthenium ion and substituted acetic acid and acid phosphorus extractant.
The yttrium method for saponification of the compound organic phase of substituted acetic acid and organophosphor of the present invention comes real especially by following process program
It is existing.
It is 0.20 to control the ratio between the molal quantity of yttrium chloride and the molal quantity of combination of acidic extractant:1~0.30:1st, hydroxyl
Type strong-basicity styrene anion exchange resin is 7 with respect to the ratio between molal quantity of total exchange molal quantity and yttrium chloride of chlorion:1
~9:1；Sequentially added in saponification device containing 0.6M~1.0M substituted acetic acids, the extraction of 0.02M~0.08M acidic organo phosphorus
Agent and percentage by volume are the unsupported compound organic phase of 10%~20% sec-octyl alcohol, pH be 1~3 and yttrium concentration be 0.6M~
The 1.2M yttrium chloride aqueous solution, effective exchange capacity with respect to chlorion is 3mol/kg~5mol/kg and average grain diameter is
0.4mm~0.6mm hydroxyl type strong-basicity styrene anion exchange resin.40min~60min is sufficiently stirred at room temperature
Afterwards, stratification.Upper strata is yttrium saponification substituted acetic acid and the compound organic phase of organophosphor, and middle level is aqueous phase, and lower floor is strong for solid-state
Basicity styrene anion exchange resin phase.Aqueous phase and strong-basicity styrene anion exchange resin phase are released, obtains yttrium saponification
Substituted acetic acid and the compound organic phase of organophosphor, its saponification rate are 60%~90%.
The molal quantity of described combination of acidic extractant refers to there there is the molal quantity of substituted acetic acid with acidity in compound organic phase
The molal quantity sum of machine phosphorus extractant；
Described compound organic phase is that substituted acetic acid, acidic organo phosphorus extractant, the kerosene of sec-octyl alcohol or sulfonated kerosene are molten
Liquid；
Described substituted acetic acid is secondary octyl phenoxy group substituted acetic acid or secondary Nonylphenoxy substituted acetic acid or secondary heptyl benzene
Epoxide substituted acetic acid；
Described acidic organo phosphorus extractant is P507 or P229 or C272.
The ratio between described molal quantity calculation formula：The ratio between the molal quantity of yttrium chloride and the molal quantity of combination of acidic extractant=
The molal quantity of yttrium chloride/(molal quantity of the molal quantity of substituted acetic acid+acidic organo phosphorus extractant).
It is an advantage of the invention that：Sodium ion is stained to yttrium product when can eliminate sodium hydroxide saponification, improves yttrium product
Purity；The process of the sodium impurity in separating yttrium product in subsequent technique can be removed from simultaneously, reduce production cost；Soap at room temperature
Change, save energy.Present invention is particularly suited to prepare the saponification of extraction organic phase in high-purity and ultra-pure yttrium product separating technology.
Embodiment
With reference to specific embodiment to substituted acetic acid of the present invention and the yttrium saponification side of the compound organic phase of organophosphor
Method is further described.
Embodiment 1
Molal quantity/(molal quantity+P507 of the secondary octyl phenoxy group substituted acetic acid molal quantity) of control yttrium chloride is equal to
0.25:1st, total exchange molal quantity (i.e. total exchange capacity) of the hydroxyl type strong-basicity styrene anion exchange resin with respect to chlorion
It is 8 with the ratio between the molal quantity of yttrium chloride:1；Sequentially added in saponification device containing 0.8M secondary octyl phenoxy groups substituted acetic acid,
0.05M P507 and the sulfonated kerosene solution that percentage by volume is 15% sec-octyl alcohol, the yttrium chloride that pH is 2 and yttrium concentration is 0.9M
The aqueous solution, the hydroxyl type that effective exchange capacity with respect to chlorion is 4mol/kg~5mol/kg, average grain diameter is 0.5mm are strong
Basicity styrene anion exchange resin.After being sufficiently stirred 50min at room temperature, stratification.Upper strata is yttrium saponification substituted acetic acid
With the compound organic phases of P507, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase
With strong-basicity styrene anion exchange resin phase, obtain yttrium saponification substituted acetic acid and the compound organic phases of P507, its saponification rate are
75%.
Embodiment 2
Molal quantity/(molal quantity+C272 of the Zhong Gengji phenoxy group substituted acetic acids molal quantity) of control yttrium chloride is equal to
0.20:1st, total exchange molal quantity (i.e. total exchange capacity) of the hydroxyl type strong-basicity styrene anion exchange resin with respect to chlorion
It is 7 with the ratio between the molal quantity of yttrium chloride:1；Sequentially added in saponification device containing the secondary heptyl phenoxy group substituted acetic acids of 0.6M,
0.02M C272 and the kerosin that percentage by volume is 10% sec-octyl alcohol, the yttrium chloride that pH is 3 and yttrium concentration is 0.6M are water-soluble
Liquid, the hydroxyl type strong-basicity styrene that effective exchange capacity with respect to chlorion is 3mol/kg, average grain diameter is 0.4mm are cloudy
Ion exchange resin.After being sufficiently stirred 40min at room temperature, stratification.Upper strata is that yttrium saponification substituted acetic acid and C272 are compounded with
Machine phase, middle level are aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong basicity benzene second
Alkene anion exchange resin phase, obtains yttrium saponification substituted acetic acid and the compound organic phases of C272, and its saponification rate is 60%.
Embodiment 3
Molal quantity/(molal quantity+P229 of the secondary Nonylphenoxy substituted acetic acid molal quantity) of control yttrium chloride is equal to
0.30:1st, total exchange molal quantity (i.e. total exchange capacity) of the hydroxyl type strong-basicity styrene anion exchange resin with respect to chlorion
It is 9 with the ratio between the molal quantity of yttrium chloride:1；Sequentially added in saponification device containing the secondary Nonylphenoxy substituted acetic acids of 1.0M,
0.08M P229 and the sulfonated kerosene solution that percentage by volume is 20% sec-octyl alcohol, the yttrium chloride that pH is 1 and yttrium concentration is 1.2M
The aqueous solution, the hydroxyl type strong basicity benzene second that effective exchange capacity with respect to chlorion is 5mol/kg, average grain diameter is 0.6mm
Alkene anion exchange resin.After being sufficiently stirred 60min at room temperature, stratification.Upper strata is that yttrium saponification substituted acetic acid and P229 are answered
Organic phase is closed, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong basicity
Styrenic anion exchanger resin phase, obtains yttrium saponification substituted acetic acid and the compound organic phases of P229, and its saponification rate is 90%.
Embodiment 4
Molal quantity/(molal quantity+P507 of the secondary octyl phenoxy group substituted acetic acid molal quantity) of control yttrium chloride is equal to
0.20:1st, total exchange molal quantity (i.e. total exchange capacity) of the hydroxyl type strong-basicity styrene anion exchange resin with respect to chlorion
It is 7 with the ratio between the molal quantity of yttrium chloride:1；Sequentially added in saponification device containing 0.9M secondary octyl phenoxy groups substituted acetic acid,
0.04M P507 and the kerosin that percentage by volume is 12% sec-octyl alcohol, the yttrium chloride that pH is 1 and yttrium concentration is 0.8M are water-soluble
Liquid, the hydroxyl type strong-basicity styrene that effective exchange capacity with respect to chlorion is 3mol/kg, average grain diameter is 0.4mm are cloudy
Ion exchange resin.After being sufficiently stirred 45min at room temperature, stratification.Upper strata is that yttrium saponification substituted acetic acid and P507 are compounded with
Machine phase, middle level are aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong basicity benzene second
Alkene anion exchange resin phase, obtains yttrium saponification substituted acetic acid and the compound organic phases of P507, and its saponification rate is 60%.
Embodiment 5
Molal quantity/(molal quantity+P507 of the secondary octyl phenoxy group substituted acetic acid molal quantity) of control yttrium chloride is equal to
0.30:1st, total exchange molal quantity (i.e. total exchange capacity) of the hydroxyl type strong-basicity styrene anion exchange resin with respect to chlorion
It is 9 with the ratio between the molal quantity of yttrium chloride:1；Sequentially added in saponification device containing 1.0M secondary octyl phenoxy groups substituted acetic acid,
0.08M P507 and the sulfonated kerosene solution that percentage by volume is 20% sec-octyl alcohol, the yttrium chloride that pH is 3 and yttrium concentration is 1.0M
The aqueous solution, the hydroxyl type strong basicity benzene second that effective exchange capacity with respect to chlorion is 5mol/kg, average grain diameter is 0.6mm
Alkene anion exchange resin.After being sufficiently stirred 55min at room temperature, stratification.Upper strata is that yttrium saponification substituted acetic acid and P507 are answered
Organic phase is closed, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange resin phase of solid-state.Release aqueous phase and strong basicity
Styrenic anion exchanger resin phase, obtains yttrium saponification substituted acetic acid and the compound organic phases of P507, and its saponification rate is 90%.
Claims (1)
1. the yttrium method for saponification of substituted acetic acid and the compound organic phase of organophosphor, it is characterised in that：Control yttrium chloride molal quantity with
The ratio between molal quantity of combination of acidic extractant is 0.20:1~0.30:1st, hydroxyl type strong-basicity styrene anion exchange resin
The ratio between molal quantity of total exchange molal quantity and yttrium chloride with respect to chlorion is 7:1~9:1；Sequentially added in saponification device
Containing 0.6 M~the M acidic organo phosphorus extractant of 1.0 M substituted acetic acids, 0.02 M~0.08 and percentage by volume be 10%~20%
The unsupported compound organic phase of sec-octyl alcohol, the yttrium chloride aqueous solution that pH is 1~3 and yttrium concentration is the M of 0.6 M~1.2, with respect to chlorine
The hydroxyl type that effective exchange capacity of ion is the mol/kg of 3 mol/kg~5 and average grain diameter is the mm of 0.4 mm~0.6
Strong-basicity styrene anion exchange resin；After being sufficiently stirred the min of 40 min~60 at room temperature, stratification；Upper strata is yttrium soap
Change substituted acetic acid and the compound organic phase of organophosphor, middle level is aqueous phase, and lower floor is the strong-basicity styrene anion exchange tree of solid-state
Lipid phase；Aqueous phase and strong-basicity styrene anion exchange resin phase are released, yttrium saponification substituted acetic acid is obtained and organophosphor is compounded with
Machine phase, its saponification rate are 60%~90%；
The molal quantity of described combination of acidic extractant refers to the molal quantity and acidic organo phosphorus of substituted acetic acid in compound organic phase
The molal quantity sum of extractant；
Described compound organic phase is substituted acetic acid, acidic organo phosphorus extractant, the kerosene of sec-octyl alcohol or sulfonated kerosene solution；
Described substituted acetic acid is secondary octyl phenoxy group substituted acetic acid or secondary Nonylphenoxy substituted acetic acid or Zhong Gengji phenoxy groups
Substituted acetic acid；
Described acidic organo phosphorus extractant is P507 or P229 or C272.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288069A (en) * | 1999-09-11 | 2001-03-21 | 中国科学院长春应用化学研究所 | Art for prodn. of high purity yttrium by liquid-liquid extraction separation |
| CN1563442A (en) * | 2004-03-19 | 2005-01-12 | 中国科学院长春应用化学研究所 | Technique for separating high purity yttrium oxide through solvent extraction |
| CN103789547A (en) * | 2014-01-15 | 2014-05-14 | 中国科学院长春应用化学研究所 | Ionic liquid extraction resin as well as preparation and application method thereof |
| CN104593592A (en) * | 2015-01-26 | 2015-05-06 | 江西理工大学 | Method for enriching rare earth from rare earth leaching mother liquor |
| CN104694750A (en) * | 2015-03-31 | 2015-06-10 | 德庆兴邦稀土新材料有限公司 | Environment-friendly yttrium oxide saponification-free extraction method |
-
2016
- 2016-05-10 CN CN201610305003.5A patent/CN105779764B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288069A (en) * | 1999-09-11 | 2001-03-21 | 中国科学院长春应用化学研究所 | Art for prodn. of high purity yttrium by liquid-liquid extraction separation |
| CN1563442A (en) * | 2004-03-19 | 2005-01-12 | 中国科学院长春应用化学研究所 | Technique for separating high purity yttrium oxide through solvent extraction |
| CN103789547A (en) * | 2014-01-15 | 2014-05-14 | 中国科学院长春应用化学研究所 | Ionic liquid extraction resin as well as preparation and application method thereof |
| CN104593592A (en) * | 2015-01-26 | 2015-05-06 | 江西理工大学 | Method for enriching rare earth from rare earth leaching mother liquor |
| CN104694750A (en) * | 2015-03-31 | 2015-06-10 | 德庆兴邦稀土新材料有限公司 | Environment-friendly yttrium oxide saponification-free extraction method |
Non-Patent Citations (1)
| Title |
|---|
| "稀土皂化P507-煤油有机相的制备及相关反应";宋丽莎等;《稀土》;20140831;第35卷(第4期);全文 * |
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