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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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 50
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000007127 saponification reaction Methods 0.000 title claims abstract description 43
- 239000012074 organic phase Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 19
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 title claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 35
- 239000012071 phase Substances 0.000 claims abstract description 34
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 yttrium-substituted acetic acid Chemical class 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003350 kerosene Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000000926 separation method Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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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
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Abstract
本发明公开取代乙酸和有机磷复合有机相的钇皂化方法，以氢氧根型强碱性苯乙烯阴离子交换树脂为助剂，来实现取代乙酸和酸性有机磷复合有机相的钇皂化。在皂化反应器中，依次加入取代乙酸和酸性有机磷复合萃取剂的煤油或磺化煤油溶液、氯化钇水溶液和氢氧根型强碱性苯乙烯阴离子交换树脂；室温下充分搅拌反应完毕后静置分层。上层为钇皂化取代乙酸和有机磷复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相；放出水相和强碱性苯乙烯阴离子交换树脂，放出水相和苯乙烯系阴离子交换树脂相，获得皂化率为60%～90%的钇皂化取代乙酸和有机磷复合有机相。本发明具有提高钇产品纯度、降低生产成本、节省能量等优点。The invention discloses a yttrium saponification method for substituting the composite organic phase of acetic acid and organophosphorus, using hydroxide type strongly basic styrene anion exchange resin as an auxiliary agent to realize the saponification of yttrium replacing the composite organic phase of acetic acid and acidic organophosphorus. In the saponification reactor, sequentially add kerosene or sulfonated kerosene solution, yttrium chloride aqueous solution, and hydroxide-type strongly basic styrene anion exchange resin to replace acetic acid and acidic organophosphorus composite extractant; Let stand to layer. The upper layer is a composite organic phase substituted by yttrium saponification of acetic acid and organic phosphorus, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase; the water phase and the strong basic styrene anion exchange resin are released, and the water phase and benzene are released. The ethylene-based anion exchange resin phase is used to obtain a saponified yttrium-substituted acetic acid and organic phosphorus composite organic phase with a saponification rate of 60% to 90%. The invention has the advantages of improving the purity of yttrium products, reducing production costs, saving energy and the like.
Description
技术领域technical field
本发明涉及取代乙酸和有机磷复合有机相的钇皂化方法，特别是涉及一种以氢氧根型强碱性苯乙烯阴离子交换树脂为助剂的取代乙酸和酸性有机磷复合有机相的钇皂化方法。本发明具体属于溶剂萃取技术领域。The invention relates to a yttrium saponification method for substituting acetic acid and organophosphorus composite organic phase, in particular to a yttrium saponification method for substituting acetic acid and acidic organophosphorus composite organic phase with hydroxide type strongly basic styrene anion exchange resin as auxiliary agent method. The invention specifically belongs to the technical field of solvent extraction.
背景技术Background technique
1999年，李德谦等人提出了以取代乙酸和有机磷试剂复合有机相为萃取剂来实现钇与镧系元素的分离，该工艺已经成为工业化制备高纯钇产品的最佳方法之一(李德谦等，液－液萃取分离高纯钇工艺，中国专利，申请号991182618，1999-09-11)。该发明专利所用的取代乙酸多为仲辛基苯氧基取代乙酸，所用的有机磷试剂为酸性磷类萃取剂，主要是P507、C272(即Cyanex272)、C302(即Cyanex302)等。In 1999, Li Deqian and others proposed to replace acetic acid and organophosphorus reagent composite organic phase as the extraction agent to realize the separation of yttrium and lanthanides. This process has become one of the best methods for industrially preparing high-purity yttrium products (Li Deqian et al. , Liquid-liquid extraction and separation of high-purity yttrium process, Chinese patent, application number 991182618, 1999-09-11). The substituted acetic acid used in this invention patent is mostly sec-octylphenoxy substituted acetic acid, and the organophosphorus reagent used is an acidic phosphorus extractant, mainly P507, C272 (ie Cyanex272), C302 (ie Cyanex302) and the like.
在分离提取钇的工艺中，必须采用碱性试剂对取代乙酸和酸性有机磷复合有机相进行皂化才能保持较高的萃取效率。随着氨氮排放标准的要求提高，以氨水为皂化剂的氨皂化已经被淘汰了。目前使用的皂化剂是有氢氧化钠。以氢氧化钠为皂化剂的最大缺点是氢氧化钠中的部分钠离子会进入钇产品而形成皂化沾污，对制备高纯和超高纯钇产生非常不利的影响。因为钠严重影响高纯和超高纯钇材料的性能，所以在制备高纯和超高的后续工艺中通常还需要建立分离钇产品中钠皂化杂质分离工艺。实际上，当钇产品中钠的含量较低时分离也是十分困难的。为了防止钠离子污染高纯特别是超高纯钠产品，本发明建立一种取代乙酸和有机磷复合有机相的新钇皂化方法。In the process of separating and extracting yttrium, alkaline reagents must be used to saponify the composite organic phase of substituted acetic acid and acidic organophosphorus in order to maintain a high extraction efficiency. With the increase of ammonia nitrogen emission standards, ammonia saponification using ammonia water as saponification agent has been eliminated. The saponification agent currently used is sodium hydroxide. The biggest disadvantage of using sodium hydroxide as saponification agent is that some sodium ions in sodium hydroxide will enter the yttrium product and form saponification stains, which will have a very adverse effect on the preparation of high-purity and ultra-high-purity yttrium. Because sodium seriously affects the performance of high-purity and ultra-high-purity yttrium materials, it is usually necessary to establish a separation process for the separation of sodium saponification impurities in yttrium products in the subsequent process of preparing high-purity and ultra-high purity materials. In practice, separation is also very difficult when the sodium content in the yttrium product is low. In order to prevent sodium ions from polluting high-purity, especially ultra-high-purity sodium products, the invention establishes a new yttrium saponification method that replaces the composite organic phase of acetic acid and organic phosphorus.
在分离工艺中，评价离子交换树脂的重要技术指标是有效交换容量。有效交换容量有时简称交换容量。阴离子离子交换树脂的有效交换容量是指每kg干树脂有效交换一价阴离子的摩尔数；此时，有效交换容量的单位为mol/kg。也有人采用每升干树脂有效交换一价阴离子的摩尔数；此时，有效交换容量的单位则为mol/L。虽然采以质量计的单位mol/kg与以体积计的单位mol/L可以换算。但是，就有效交换容量的准确度而言，采用质量计单位mol/kg高于采用体积计单位mol/L。顺便说明一下，一定质量的干树脂的总交换量通过以下公式来计算：In the separation process, the important technical index to evaluate the ion exchange resin is the effective exchange capacity. Effective switching capacity is sometimes referred to simply as switching capacity. The effective exchange capacity of anion ion exchange resin refers to the number of moles of monovalent anions effectively exchanged per kg of dry resin; at this time, the unit of effective exchange capacity is mol/kg. Some people also use the number of moles of monovalent anions effectively exchanged per liter of dry resin; at this time, the unit of effective exchange capacity is mol/L. Although the unit mol/kg in terms of mass and the unit mol/L in volume can be converted. However, in terms of the accuracy of the effective exchange capacity, the mass unit mol/kg is higher than the volume unit mol/L. By the way, the total exchange capacity of a given mass of dry resin is calculated by the following formula:
n＝m×Q (1)n=m×Q (1)
式(1)中，m为干树脂的质量，其单位为kg；Q为树脂的有效交换容量，其单位为mol/kg；n为总交换量，其单位为mol。由式(1)可知，总交换量是指给定树脂质量m时的最大有效交换量。实际上，总交换量就是给定树脂质量m时的最大交换摩尔数，因此总交换量也称为总交换摩尔数。In formula (1), m is the mass of dry resin, and its unit is kg; Q is the effective exchange capacity of resin, and its unit is mol/kg; n is the total exchange capacity, and its unit is mol. It can be known from formula (1) that the total exchange capacity refers to the maximum effective exchange capacity at a given resin mass m. In fact, the total exchange capacity is the maximum exchange mole number for a given resin mass m, so the total exchange capacity is also called the total exchange mole number.
发明内容Contents of the invention
本发明的目的是针对取代乙酸和有机磷复合有机相采用氢氧化钠皂化时部分钠离子会沾污钇产品的缺点，建立一种无皂化沾污的取代乙酸和有机磷复合有机相的钇皂化方法。The purpose of the present invention is aimed at the shortcoming that some sodium ions will contaminate the yttrium product when sodium hydroxide is used to saponify the composite organic phase of acetic acid and organic phosphorus, and to establish a saponification of yttrium saponification of acetic acid and organic phosphorus composite organic phase without saponification contamination. method.
本发明的钇皂化原理，以化学反应方程式表示为：The yttrium saponification principle of the present invention is expressed as:
反应式(2)和(3)中，HA表示取代乙酸萃取剂；HB表示取代酸性有机磷萃取剂；R4NOH表示氢氧根型强碱性苯乙烯阴离子交换树脂，R4NCl表示氯根型强碱性苯乙烯阴离子交换树脂，下标“o”表示有机相，下标“a”表示水相，下标“s”表示固态的树脂相。本发明通过反应式(2)和(3)实现取代乙酸和有机磷复合有机相的钇皂化。由反应式(2)和(3)可知，本发明是通过水溶液中的氯离子与氢氧根型强碱性苯乙烯阴离子交换树脂中的氢氧根发生交换作用来促进钇离子与取代乙酸和酸性磷萃取剂的皂化反应。In the reaction formulas (2) and (3), HA represents a substituted acetic acid extractant; HB represents a substituted acidic organophosphorus extractant; R 4 NOH represents a hydroxide-type strongly basic styrene anion exchange resin, and R 4 NCl represents a chloride radical Type strong basic styrene anion exchange resin, the subscript "o" indicates the organic phase, the subscript "a" indicates the water phase, and the subscript "s" indicates the solid resin phase. The present invention realizes the yttrium saponification of the substituted acetic acid and organophosphorus composite organic phase through the reaction formulas (2) and (3). By reaction formula (2) and (3) as can be known, the present invention promotes yttrium ion and replacement acetic acid and the hydroxide radical in the hydroxide radical type strongly basic styrene anion exchange resin by the chloride ion in the aqueous solution and the exchange action Saponification of acidic phosphorus extractants.
本发明取代乙酸和有机磷复合有机相的钇皂化方法具体通过以下工艺方案来实现。The yttrium saponification method of the present invention that replaces the composite organic phase of acetic acid and organic phosphorus is specifically realized through the following process scheme.
控制氯化钇的摩尔数与复合酸性萃取剂的摩尔数之比为0.20:1～0.30:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数与氯化钇的摩尔数之比为7:1～9:1；在皂化反应器中依次加入含有0.6M～1.0M取代乙酸、0.02M～0.08M酸性有机磷萃取剂及体积百分数为10％～20％仲辛醇的未负载复合有机相，pH为1～3及钇浓度为0.6M～1.2M的氯化钇水溶液，相对氯离子的有效交换容量为3mol/kg～5mol/kg及平均粒径为0.4mm～0.6mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌40min～60min后，静置分层。上层为钇皂化取代乙酸和有机磷复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和有机磷复合有机相，其皂化率为60％～90％。Control the ratio of the number of moles of yttrium chloride to the number of moles of the compound acidic extractant to be 0.20:1 to 0.30:1, and the total exchange moles of hydroxide-type strongly basic styrene anion exchange resin relative to chloride ions and the ratio of the number of moles of yttrium chloride The molar ratio of 7:1 to 9:1; sequentially add 0.6M to 1.0M substituted acetic acid, 0.02M to 0.08M acidic organophosphorus extractant and 10% to 20% by volume in the saponification reactor An unloaded composite organic phase of octanol, an aqueous solution of yttrium chloride with a pH of 1 to 3 and a yttrium concentration of 0.6M to 1.2M, an effective exchange capacity for chloride ions of 3mol/kg to 5mol/kg and an average particle size of 0.4 mm～0.6mm hydroxide type strongly basic styrene anion exchange resin. After fully stirring at room temperature for 40 to 60 minutes, let stand to separate layers. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and organic phosphorus, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. The water phase and the strongly basic styrene anion exchange resin phase are released to obtain a compound organic phase substituted by yttrium saponification for acetic acid and organic phosphorus, and the saponification rate is 60%-90%.
所述的复合酸性萃取剂的摩尔数是指复合有机相中取代乙酸的摩尔数与酸性有机磷萃取剂的摩尔数之和；The molar number of described composite acidic extractant refers to the sum of the molar number of substituted acetic acid and the molar number of acidic organophosphorus extractant in the composite organic phase;
所述的复合有机相是取代乙酸、酸性有机磷萃取剂、仲辛醇的煤油或磺化煤油溶液；The composite organic phase is substituted acetic acid, acidic organic phosphorus extractant, kerosene or sulfonated kerosene solution of secondary octanol;
所述的取代乙酸为仲辛基苯氧基取代乙酸或仲壬基苯氧基取代乙酸或仲庚基苯氧基取代乙酸；The substituted acetic acid is sec-octylphenoxy substituted acetic acid or sec-nonylphenoxy substituted acetic acid or sec-heptylphenoxy substituted acetic acid;
所述的酸性有机磷萃取剂为P507或P229或C272。The acidic organic phosphorus extractant is P507 or P229 or C272.
所述的摩尔数之比计算公式：氯化钇的摩尔数与复合酸性萃取剂的摩尔数之比＝氯化钇的摩尔数/(取代乙酸的摩尔数+酸性有机磷萃取剂的摩尔数)。The ratio calculation formula of described moles: the ratio of the moles of yttrium chloride to the moles of compound acidic extractant=the moles of yttrium chloride/(the moles of substituted acetic acid+acid organic phosphorus extractant) .
本发明的优点是：可以消除氢氧化钠皂化时钠离子对钇产品的玷污，提高钇产品的纯度；同时可以免去在后续工艺中分离钇产品中钠杂质的工序，降低生产成本；室温下皂化，节省能量。本发明特别适宜于制备高纯和超高纯钇产品分离工艺中萃取有机相的皂化。The present invention has the advantages of: it can eliminate the contamination of yttrium products by sodium ions during saponification of sodium hydroxide, and improve the purity of yttrium products; simultaneously, it can eliminate the process of separating sodium impurities in yttrium products in subsequent processes, reducing production costs; Saponification saves energy. The invention is particularly suitable for the saponification of the extracted organic phase in the separation process for preparing high-purity and ultra-high-purity yttrium products.
具体实施方式detailed description
下面结合具体实施例对本发明所述的取代乙酸和有机磷复合有机相的钇皂化方法作进一步描述。The yttrium saponification method of the substituted acetic acid and organic phosphorus composite organic phase described in the present invention will be further described below in conjunction with specific examples.
实施例1Example 1
控制氯化钇的摩尔数/(仲辛基苯氧基取代乙酸的摩尔数+P507的摩尔数)等于0.25:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数(即总交换量)与氯化钇的摩尔数之比为8:1；在皂化反应器中依次加入含有0.8M仲辛基苯氧基取代乙酸、0.05M P507及体积百分数为15％仲辛醇的磺化煤油溶液，pH为2及钇浓度为0.9M的氯化钇水溶液，相对氯离子的有效交换容量为4mol/kg～5mol/kg、平均粒径为0.5mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌50min后，静置分层。上层为钇皂化取代乙酸和P507复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和P507复合有机相，其皂化率为75％。Control the number of moles of yttrium chloride/(the number of moles of 2-octylphenoxy substituted acetic acid+the number of moles of P507) to be equal to 0.25:1, the total exchange mole of hydroxide type strongly basic styrene anion exchange resin relative to chloride ion The ratio of the number (that is, the total exchange capacity) to the mole number of yttrium chloride is 8:1; in the saponification reactor, sequentially add 0.8M sec-octylphenoxy substituted acetic acid, 0.05M P507 and 15% sec. Octanol sulfonated kerosene solution, yttrium chloride aqueous solution with a pH of 2 and a yttrium concentration of 0.9M, a hydroxide type with an effective exchange capacity of 4mol/kg to 5mol/kg for chloride ions and an average particle size of 0.5mm Strongly basic styrene anion exchange resin. After fully stirring at room temperature for 50 min, the mixture was allowed to stand still to separate layers. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and P507, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. Release the water phase and the strongly basic styrene anion exchange resin phase to obtain the composite organic phase of yttrium saponified substituted acetic acid and P507, with a saponification rate of 75%.
实施例2Example 2
控制氯化钇的摩尔数/(仲庚基苯氧基取代乙酸的摩尔数+C272的摩尔数)等于0.20:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数(即总交换量)与氯化钇的摩尔数之比为7:1；在皂化反应器中依次加入含有0.6M仲庚基苯氧基取代乙酸、0.02M C272及体积百分数为10％仲辛醇的煤油溶液，pH为3及钇浓度为0.6M的氯化钇水溶液，相对氯离子的有效交换容量为3mol/kg、平均粒径为0.4mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌40min后，静置分层。上层为钇皂化取代乙酸和C272复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和C272复合有机相，其皂化率为60％。Control the number of moles of yttrium chloride/(the number of moles of sec-heptylphenoxy substituted acetic acid+the number of moles of C272) is equal to 0.20:1, the total exchange mole of hydroxide type strongly basic styrene anion exchange resin relative to chloride ion The ratio of the number (that is, the total exchange amount) to the mole number of yttrium chloride is 7:1; in the saponification reactor, sequentially add 0.6M sec-heptylphenoxy substituted acetic acid, 0.02M C272 and 10% sec. Octanol kerosene solution, yttrium chloride aqueous solution with pH 3 and yttrium concentration 0.6M, hydroxide-type strongly basic styrene anion with an effective exchange capacity of 3 mol/kg for chloride ions and an average particle size of 0.4 mm Exchange resin. After fully stirring at room temperature for 40 min, the layers were separated. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and C272, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. Release the water phase and the strongly basic styrene anion exchange resin phase to obtain the yttrium saponified acetic acid and C272 composite organic phase with a saponification rate of 60%.
实施例3Example 3
控制氯化钇的摩尔数/(仲壬基苯氧基取代乙酸的摩尔数+P229的摩尔数)等于0.30:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数(即总交换量)与氯化钇的摩尔数之比为9:1；在皂化反应器中依次加入含有1.0M仲壬基苯氧基取代乙酸、0.08M P229及体积百分数为20％仲辛醇的磺化煤油溶液，pH为1及钇浓度为1.2M的氯化钇水溶液，相对氯离子的有效交换容量为5mol/kg、平均粒径为0.6mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌60min后，静置分层。上层为钇皂化取代乙酸和P229复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和P229复合有机相，其皂化率为90％。Control the number of moles of yttrium chloride/(the number of moles of secondary nonylphenoxy substituted acetic acid+the number of moles of P229) to be equal to 0.30:1, the total exchange mole of hydroxide radical type strongly basic styrene anion exchange resin relative to chloride ion The ratio of the number (that is, the total exchange capacity) to the mole number of yttrium chloride is 9:1; in the saponification reactor, sequentially add 1.0M sec-nonylphenoxy substituted acetic acid, 0.08M P229 and 20% sec. Octanol sulfonated kerosene solution, yttrium chloride aqueous solution with a pH of 1 and a yttrium concentration of 1.2M, a hydroxide-type strongly basic benzene with an effective exchange capacity of 5 mol/kg for chloride ions and an average particle size of 0.6 mm Ethylene anion exchange resin. After fully stirring at room temperature for 60 min, the mixture was allowed to stand still to separate layers. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and P229, the middle layer is an aqueous phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. Release the water phase and the strongly basic styrene anion exchange resin phase to obtain the yttrium saponified acetic acid and P229 composite organic phase with a saponification rate of 90%.
实施例4Example 4
控制氯化钇的摩尔数/(仲辛基苯氧基取代乙酸的摩尔数+P507的摩尔数)等于0.20:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数(即总交换量)与氯化钇的摩尔数之比为7:1；在皂化反应器中依次加入含有0.9M仲辛基苯氧基取代乙酸、0.04M P507及体积百分数为12％仲辛醇的煤油溶液，pH为1及钇浓度为0.8M的氯化钇水溶液，相对氯离子的有效交换容量为3mol/kg、平均粒径为0.4mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌45min后，静置分层。上层为钇皂化取代乙酸和P507复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和P507复合有机相，其皂化率为60％。Control the mole number of yttrium chloride/(the mole number of 2-octylphenoxy substituted acetic acid+the mole number of P507) to be equal to 0.20:1, the total exchange mole of hydroxide type strongly basic styrene anion exchange resin relative to chloride ion The ratio of the number (that is, the total exchange capacity) to the mole number of yttrium chloride is 7:1; in the saponification reactor, sequentially add 0.9M sec-octylphenoxy substituted acetic acid, 0.04M P507 and 12% sec. Octanol kerosene solution, yttrium chloride aqueous solution with a pH of 1 and a yttrium concentration of 0.8M, a hydroxide-type strongly basic styrene anion with an effective exchange capacity of 3 mol/kg for chloride ions and an average particle size of 0.4 mm Exchange resin. After fully stirring at room temperature for 45 min, the layers were separated. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and P507, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. Release the water phase and the strongly basic styrene anion exchange resin phase to obtain the yttrium saponified substituted acetic acid and P507 composite organic phase with a saponification rate of 60%.
实施例5Example 5
控制氯化钇的摩尔数/(仲辛基苯氧基取代乙酸的摩尔数+P507的摩尔数)等于0.30:1、氢氧根型强碱性苯乙烯阴离子交换树脂相对氯离子的总交换摩尔数(即总交换量)与氯化钇的摩尔数之比为9:1；在皂化反应器中依次加入含有1.0M仲辛基苯氧基取代乙酸、0.08M P507及体积百分数为20％仲辛醇的磺化煤油溶液，pH为3及钇浓度为1.0M的氯化钇水溶液，相对氯离子的有效交换容量为5mol/kg、平均粒径为0.6mm的氢氧根型强碱性苯乙烯阴离子交换树脂。室温下充分搅拌55min后，静置分层。上层为钇皂化取代乙酸和P507复合有机相，中层为水相，下层为固态的强碱性苯乙烯阴离子交换树脂相。放出水相和强碱性苯乙烯阴离子交换树脂相，获得钇皂化取代乙酸和P507复合有机相，其皂化率为90％。Control the number of moles of yttrium chloride/(the number of moles of 2-octylphenoxy substituted acetic acid+the number of moles of P507) to be equal to 0.30:1, the total exchange mole of hydroxide type strongly basic styrene anion exchange resin relative to chloride ion The ratio of the number (that is, the total exchange capacity) to the number of moles of yttrium chloride is 9:1; in the saponification reactor, sequentially add 1.0M sec-octylphenoxy substituted acetic acid, 0.08M P507 and 20% sec. Sulfonated kerosene solution of octanol, yttrium chloride aqueous solution with pH 3 and yttrium concentration of 1.0M, hydroxide type strongly basic benzene with an effective exchange capacity of 5 mol/kg for chloride ions and an average particle size of 0.6 mm Ethylene anion exchange resin. After fully stirring at room temperature for 55 min, the mixture was allowed to stand still to separate layers. The upper layer is a composite organic phase of yttrium saponified substituted acetic acid and P507, the middle layer is a water phase, and the lower layer is a solid strong basic styrene anion exchange resin phase. Release the water phase and the strongly basic styrene anion exchange resin phase to obtain the composite organic phase of yttrium saponification replacing acetic acid and P507, and the saponification rate is 90%.
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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 |
-
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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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