CN114394938A - Method for effectively removing metal ions in ionic liquid water system - Google Patents
Method for effectively removing metal ions in ionic liquid water system Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 102
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000003795 desorption Methods 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract 3
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- -1 alkyl imidazole salt Chemical class 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 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 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 5
- HQWOEDCLDNFWEV-UHFFFAOYSA-M diethyl phosphate;1-ethyl-3-methylimidazol-3-ium Chemical compound CC[N+]=1C=CN(C)C=1.CCOP([O-])(=O)OCC HQWOEDCLDNFWEV-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- Molecular Biology (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
技术领域technical field
本发明涉及离子液体回收处理技术领域，尤其涉及一种离子液体水体系中杂质金属离子分离的方法。The invention relates to the technical field of ionic liquid recovery and treatment, in particular to a method for separating impurity metal ions in an ionic liquid water system.
背景技术Background technique
近年来，离子液体以其优良的物化性质，如极性强、不挥发、结构可设计等优点受到了广泛的关注，其作为绿色溶剂和催化剂等在工业中应用广泛，包括离子液体作为溶剂萃取分离碱/碱土金属、回收正丁醇、提纯牛磺酸等。此外，离子液体作为溶剂在纤维素的溶解过程中也有良好的应用，但是在离子液体溶解纤维素过程中，会伴随着微量纤维素降解的现象，而且由于纤维素中含有一些杂质离子，在离子液体溶解纺丝工艺的牵伸、水洗工序得到的离子液体水溶液中会不可避免地引入杂质离子(Na+、K+、Ca2+、Mg2+、Fe3+、Cu2+、Zn2+等)。由于杂质离子在凝固浴和水洗浴中的不断累积，并且部分进入到再生纤维中，严重影响了再生纤维的性能及离子液体的循环利用。因此，离子液体水溶液中杂质离子的去除和离子液体的回收利用是一个亟待解决的工程问题，对资源的综合利用具有十分重要的意义。In recent years, ionic liquids have received extensive attention due to their excellent physicochemical properties, such as strong polarity, non-volatility, and designable structure. They are widely used in industry as green solvents and catalysts, including ionic liquids as solvent extraction. Separation of alkali/alkaline earth metals, recovery of n-butanol, purification of taurine, etc. In addition, ionic liquids are also used as solvents in the dissolving process of cellulose, but in the process of dissolving cellulose by ionic liquids, there will be a small amount of cellulose degradation, and because cellulose contains some impurity ions, in the ionic liquid Impurity ions (Na + , K + , Ca 2+ , Mg 2+ , Fe 3+ , Cu 2+ , Zn 2+ ) are inevitably introduced into the ionic liquid aqueous solution obtained in the drawing and water washing process of the liquid dissolution spinning process. Wait). Due to the continuous accumulation of impurity ions in the coagulation bath and the water bath, and some of them enter into the regenerated fibers, the performance of the regenerated fibers and the recycling of the ionic liquid are seriously affected. Therefore, the removal of impurity ions in ionic liquid aqueous solutions and the recycling of ionic liquids is an urgent engineering problem to be solved, which is of great significance to the comprehensive utilization of resources.
目前公开的材料中已有离子液体的回收相关专利，以下列举几个已报道的专利进行详细说明：CN202011324962.4提供一种离子液体体系中杂质离子的脱除方法，以装填纤维素-壳聚糖微球的净化装置吸附离子液体水溶液中的重金属离子Fe3+和Cu2+，但未涉及到碱金属离子Na+、K+和碱土金属Ca2+、Mg2+的去除及后续离子液体的回收。CN101503866提供了一种以离子液体为溶剂的再生纤维素纤维制备中溶剂的回收方法，离子液体溶液经过滤、反渗透和减压蒸馏，得到水含量小于2％的离子液体。CN101664612公开了一种提纯分离离子液体和水的方法，以糖为添加剂实现离子液体和水的分相，后续通过梯度结晶分离离子液体和糖。There are patents related to the recovery of ionic liquids in the currently disclosed materials, and several reported patents are listed below for detailed description: CN202011324962.4 provides a method for removing impurity ions in an ionic liquid system to fill cellulose-chitosan The purification device of sugar microspheres adsorbs heavy metal ions Fe 3+ and Cu 2+ in ionic liquid aqueous solution, but does not involve the removal of alkali metal ions Na + , K + and alkaline earth metals Ca 2+ , Mg 2+ and subsequent ionic liquids recycling. CN101503866 provides a method for recovering a solvent in the preparation of regenerated cellulose fibers using an ionic liquid as a solvent. The ionic liquid solution is filtered, reverse osmosis and vacuum distillation to obtain an ionic liquid with a water content of less than 2%. CN101664612 discloses a method for purifying and separating ionic liquid and water, using sugar as an additive to realize phase separation of ionic liquid and water, and subsequently separating ionic liquid and sugar through gradient crystallization.
综上所述，在现有的离子液体回收处理工艺中，通常未综合考虑离子液体中Na+、K+、Ca2+、Mg2+、Fe3+、Cu2+、Zn2+等金属离子的去除和离子液体的后续回收，因此开发一种具有高效率、低能耗、易操作的离子液体水体系中离子液体回收的工艺方法，实现离子液体的回收利用，具有重要的经济价值和研究意义。To sum up, in the existing ionic liquid recovery and treatment process, metals such as Na + , K + , Ca 2+ , Mg 2+ , Fe 3+ , Cu 2+ , Zn 2+ in the ionic liquid are usually not considered comprehensively The removal of ions and the subsequent recovery of ionic liquids, therefore, to develop a process method for the recovery of ionic liquids in ionic liquid water systems with high efficiency, low energy consumption, and easy operation, to realize the recycling of ionic liquids, which has important economic value and research. significance.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明的目的在于提供一种离子液体水体系中金属离子有效去除的方法，该方法既能有效去除离子液体水体系中的Na+、K+、Ca2+、Mg2+、Fe3+、Cu2+、Zn2+等杂质金属离子，又避免了体系中离子液体的损失，适用于不同离子液体水体系，具有较强的普适性和工业应用前景。In view of the deficiencies of the prior art, the object of the present invention is to provide a method for effectively removing metal ions in an ionic liquid water system, which can effectively remove Na + , K + , Ca 2+ , Mg in the ionic liquid water system 2+ , Fe 3+ , Cu 2+ , Zn 2+ and other impurity metal ions, and avoid the loss of ionic liquid in the system, suitable for different ionic liquid water systems, with strong universality and industrial application prospects.
为达到此发明目的，本发明采用以下技术方案：将含金属离子杂质的离子液体水溶液引入填有离子吸附剂的吸附塔进行金属离子的去除，流出液经高温减压蒸馏实现离子液体的脱水至水分合格，吸附饱和后的吸附塔通入解吸液稀盐酸进行再生和循环利用。In order to achieve this purpose of the invention, the present invention adopts the following technical scheme: the ionic liquid aqueous solution containing metal ion impurities is introduced into an adsorption tower filled with ion adsorbents to remove metal ions, and the effluent is subjected to high-temperature vacuum distillation to achieve dehydration of the ionic liquid to If the moisture content is qualified, the adsorption tower after adsorption saturation is passed into the desorption liquid dilute hydrochloric acid for regeneration and recycling.
优选地，离子液体为烷基咪唑盐、烷基吡啶盐、烷基季胺盐以及烷基季磷盐中的一种或多种，其中烷基的碳数为1～10。Preferably, the ionic liquid is one or more of alkyl imidazolium salts, alkyl pyridinium salts, alkyl quaternary ammonium salts and alkyl quaternary phosphorus salts, wherein the carbon number of the alkyl group is 1-10.
优选地，所述离子液体水体系中离子液体的质量浓度为1～10％。Preferably, the mass concentration of the ionic liquid in the ionic liquid water system is 1-10%.
优选地，所述杂质金属离子种类为Na+、K+、Ca2+、Mg2+、Fe3+、Cu2+、Zn2+种的一种或多种，质量浓度为10～200mg/L。Preferably, the impurity metal ion species is one or more of Na + , K + , Ca 2+ , Mg 2+ , Fe 3+ , Cu 2+ , and Zn 2+ , and the mass concentration is 10-200 mg/ L.
优选地，金属离子吸附剂为人造沸石、4A分子筛、5A分子筛和钠X分子筛中的一种或多种。Preferably, the metal ion adsorbent is one or more of artificial zeolite, 4A molecular sieve, 5A molecular sieve and sodium X molecular sieve.
优选地，所述高温减压蒸馏的温度为90～120℃，压力为10～1000Pa。Preferably, the temperature of the high-temperature vacuum distillation is 90-120° C., and the pressure is 10-1000 Pa.
优选地，稀盐酸的浓度为0.1～0.5mol/L。Preferably, the concentration of dilute hydrochloric acid is 0.1-0.5 mol/L.
一种离子液体水体系中金属离子有效去除的方法，该方法操作简单，避免了体系中离子液体的损失，是一种环境友好的离子液体纯化回收的方法。A method for effectively removing metal ions in an ionic liquid water system, the method is simple to operate, avoids the loss of the ionic liquid in the system, and is an environment-friendly method for purifying and recovering the ionic liquid.
技术优势：本发明提供一种离子液体水体系中金属离子有效去除的方法，该方法既能有效去除离子液体体系中的Na+、K+、Ca2+、Mg2+、Fe3+、Cu2+、Zn2+等杂质金属离子，又避免了体系中离子液体的损失，适用于不同离子液体水体系，具有较强的普适性和工业应用前景。Technical advantages: the present invention provides a method for effectively removing metal ions in an ionic liquid water system, which can effectively remove Na + , K + , Ca 2+ , Mg 2+ , Fe 3+ , Cu in the ionic liquid system 2+ , Zn 2+ and other impurity metal ions, and avoid the loss of ionic liquid in the system, it is suitable for different ionic liquid water systems, and has strong universality and industrial application prospects.
附图说明Description of drawings
图1为本发明所述一种离子液体水体系中金属离子有效去除的方法的工艺流程图。1 is a process flow diagram of a method for effectively removing metal ions in an ionic liquid water system according to the present invention.
图中代号含义如下：The meanings of the symbols in the figure are as follows:
V1～V3：原料液罐、再生液罐、再生液回收罐V1～V3: raw material liquid tank, regeneration liquid tank, regeneration liquid recovery tank
T1～T2：吸附塔和减压蒸馏塔T1～T2: adsorption tower and vacuum distillation tower
具体实施方式Detailed ways
本发明所使用的吸附剂为市售的分子筛，其吸附金属离子杂质的机理为分子筛具有与杂质金属水合离子半径相似的孔道结构，可与分子筛内部的游离阳离子进行离子交换。而离子液体的阳离子以团簇的形式存在，空间半径较大，难以进入分子筛内部，因此限制了分子筛对离子液体的吸附，避免了离子液体在吸附过程中的损失。The adsorbent used in the present invention is a commercially available molecular sieve, and the mechanism for adsorbing metal ion impurities is that the molecular sieve has a pore structure similar to that of the impurity metal hydrated ion radius, and can perform ion exchange with free cations inside the molecular sieve. The cations of ionic liquids exist in the form of clusters, and the space radius is large, which makes it difficult to enter the interior of the molecular sieve, thus limiting the adsorption of the ionic liquid by the molecular sieve and avoiding the loss of the ionic liquid in the adsorption process.
根据本发明的一些实施方式，采用装填分子筛的吸附塔进行金属离子的去除，所述离子液体水溶液进入吸附塔的流速为每小时5～50BV(床体积)，优选离子液体水溶液进入吸附塔的流速为每小时10～30BV(床体积)。According to some embodiments of the present invention, an adsorption tower packed with molecular sieves is used to remove metal ions, and the flow rate of the ionic liquid aqueous solution entering the adsorption tower is 5-50 BV per hour (bed volume), preferably the flow rate of the ionic liquid aqueous solution entering the adsorption tower. 10-30 BV per hour (bed volume).
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例所描述的具体的物料配比、工艺条件及其结果仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the specific material ratios, process conditions and results described in the examples are only to help understand the present invention, and should not be regarded as a specific limitation of the present invention.
实施例1Example 1
本实施例提供一种离子液体水体系中金属离子有效去除的方法，待回收离子液体水溶液中离子液体为1-乙基-3甲基咪唑氯盐，质量分数为2％，杂质离子为Ca2+、Mg2+、Fe3+和Cu2+，浓度均为100mg/L。具体步骤如下：将离子液体水溶液以15BV/h的流速引入装填有4A分子筛的吸附塔中，对流出液进行ICP和紫外分光光度计分析，确定金属离子的去除效率和离子液体的损失情况。流出液在100℃、200Pa条件下减压蒸馏3h，最终得到水质量含量为1.2％的1-乙基-3甲基咪唑氯盐，离子液体回收率为98.5％。吸附饱和后，以0.2mol/L的盐酸溶液进行再生，对再生液进行ICP分析，确定脱附效率，其结果如表1所示。This embodiment provides a method for effectively removing metal ions in an ionic liquid water system. The ionic liquid in the ionic liquid aqueous solution to be recovered is 1-ethyl-3 methylimidazolium chloride, the mass fraction is 2%, and the impurity ion is Ca 2 + , Mg 2+ , Fe 3+ and Cu 2+ , all at a concentration of 100 mg/L. The specific steps are as follows: the ionic liquid aqueous solution is introduced into an adsorption tower filled with 4A molecular sieve at a flow rate of 15 BV/h, and the effluent is analyzed by ICP and UV spectrophotometer to determine the removal efficiency of metal ions and the loss of ionic liquid. The effluent was distilled under reduced pressure at 100°C and 200Pa for 3h, and finally 1-ethyl-3-methylimidazolium chloride with a water content of 1.2% was obtained, and the recovery rate of ionic liquid was 98.5%. After the adsorption was saturated, regeneration was performed with a 0.2 mol/L hydrochloric acid solution, and ICP analysis was performed on the regeneration solution to determine the desorption efficiency. The results are shown in Table 1.
实施例2Example 2
本实施例提供一种离子液体水体系中金属离子有效去除的方法，待回收离子液体水溶液中离子液体为1-乙基-3甲基咪唑磷酸二乙酯盐，质量分数为5％，杂质离子为K+、Ca2 +、Mg2+、Fe3+和Zn2+，浓度均为50mg/L。具体步骤如下：将离子液体水溶液以10BV/h的流速引入装填有4A分子筛的吸附塔中，对流出液进行ICP和紫外分光光度计分析，确定金属离子的去除效率和离子液体的损失情况。流出液在120℃、300Pa条件下减压蒸馏3h，最终得到水质量含量为1.5％的1-乙基-3甲基咪唑磷酸二乙酯盐，离子液体回收率为99.2％。吸附饱和后，以0.2mol/L的盐酸溶液进行再生，对再生液进行ICP分析，确定脱附效率，其结果如表1所示。This embodiment provides a method for effectively removing metal ions in an ionic liquid water system. The ionic liquid in the ionic liquid aqueous solution to be recovered is 1-ethyl-3-methylimidazolium diethyl phosphate salt, the mass fraction is 5%, the impurity ions are It is K + , Ca 2 + , Mg 2+ , Fe 3+ and Zn 2+ , and the concentrations are all 50 mg/L. The specific steps are as follows: the ionic liquid aqueous solution is introduced into an adsorption tower filled with 4A molecular sieve at a flow rate of 10 BV/h, and the effluent is analyzed by ICP and UV spectrophotometer to determine the removal efficiency of metal ions and the loss of ionic liquid. The effluent was distilled under reduced pressure at 120° C. and 300 Pa for 3 hours to obtain 1-ethyl-3-methylimidazolium diethyl phosphate with a water content of 1.5%, and the recovery rate of ionic liquid was 99.2%. After the adsorption was saturated, regeneration was performed with a 0.2 mol/L hydrochloric acid solution, and ICP analysis was performed on the regeneration solution to determine the desorption efficiency. The results are shown in Table 1.
实施例3Example 3
本实施例提供一种离子液体水体系中金属离子有效去除的方法，待回收离子液体水溶液中离子液体为1-烯丙基-3甲基吡啶磷酸二乙酯盐，质量分数为3％，杂质离子为Na+、Fe3+、Cu2+和Zn2+，浓度均为150mg/L。具体步骤如下：将离子液体水溶液以10BV/h的流速引入装填有4A、5A分子筛混合物的吸附塔中，对流出液进行ICP和紫外分光光度计分析，确定金属离子的去除效率和离子液体的损失情况。流出液在110℃、500Pa条件下减压蒸馏4h，最终得到水质量含量为1.1％的1-烯丙基-3甲基吡啶磷酸二乙酯盐，离子液体回收率为97.8％。吸附饱和后，以0.5mol/L的盐酸溶液进行再生，对再生液进行ICP分析，确定脱附效率，其结果如表1所示。This embodiment provides a method for effectively removing metal ions in an ionic liquid water system. The ionic liquid in the ionic liquid aqueous solution to be recovered is 1-allyl-3 methylpyridine diethyl phosphate salt, the mass fraction is 3%, and impurities The ions were Na + , Fe 3+ , Cu 2+ and Zn 2+ , and the concentrations were all 150 mg/L. The specific steps are as follows: the ionic liquid aqueous solution is introduced into an adsorption tower filled with a mixture of 4A and 5A molecular sieves at a flow rate of 10BV/h, and the effluent is analyzed by ICP and UV spectrophotometer to determine the removal efficiency of metal ions and the loss of ionic liquid Happening. The effluent was distilled under reduced pressure at 110° C. and 500 Pa for 4 hours to obtain diethyl 1-allyl-3-picoline phosphate salt with a water content of 1.1%, and the recovery rate of ionic liquid was 97.8%. After the adsorption was saturated, the regeneration was performed with a 0.5 mol/L hydrochloric acid solution, and the regenerated liquid was analyzed by ICP to determine the desorption efficiency. The results are shown in Table 1.
实施例4Example 4
本实施例提供一种离子液体水体系中金属离子有效去除的方法，待回收离子液体水溶液中离子液体为1-乙基-3甲基咪唑磷酸二乙酯盐，质量分数为10％，杂质离子为K+、Ca2 +和Mg2+，浓度均为100mg/L。具体步骤如下：将离子液体水溶液以20BV/h的流速引入装填有4A分子筛和5A分子筛混合物的吸附塔中，对流出液进行ICP和紫外分光光度计分析，确定金属离子的去除效率和离子液体的损失情况。流出液在120℃、200Pa条件下减压蒸馏4h，最终得到水质量含量为0.8％的1-乙基-3甲基咪唑磷酸二乙酯盐，离子液体回收率为99.4％。吸附饱和后，以0.3mol/L的盐酸溶液进行再生，对再生液进行ICP分析，确定脱附效率。This embodiment provides a method for effectively removing metal ions in an ionic liquid water system. The ionic liquid in the ionic liquid aqueous solution to be recovered is 1-ethyl-3-methylimidazolium diethyl phosphate salt, the mass fraction is 10%, and the impurity ions are For K + , Ca 2 + and Mg 2+ , the concentrations are all 100 mg/L. The specific steps are as follows: the ionic liquid aqueous solution is introduced into an adsorption tower filled with a mixture of 4A molecular sieve and 5A molecular sieve at a flow rate of 20 BV/h, and the effluent is analyzed by ICP and UV spectrophotometer to determine the removal efficiency of metal ions and the ionic liquid. loss situation. The effluent was distilled under reduced pressure at 120° C. and 200 Pa for 4 hours to obtain 1-ethyl-3-methylimidazolium diethyl phosphate with a water content of 0.8%, and the recovery rate of ionic liquid was 99.4%. After the adsorption is saturated, it is regenerated with a 0.3 mol/L hydrochloric acid solution, and the regenerated liquid is analyzed by ICP to determine the desorption efficiency.
实施例5Example 5
本实施例提供一种离子液体水体系中金属离子有效去除的方法，待回收离子液体水溶液中离子液体为1-丁基-3甲基咪唑氯盐，质量分数为10％，杂质离子为Ca2+和Mg2+，浓度均为100mg/L。具体步骤如下：将离子液体水溶液以10BV/h的流速引入装填有钠X分子筛的吸附塔中，对流出液进行ICP和紫外分光光度计分析，确定金属离子的去除效率和离子液体的损失情况。流出液在120℃、300Pa条件下减压蒸馏5h，最终得到水质量含量为1.0％的1-丁基-3甲基咪唑氯盐，离子液体回收率为99.4％。吸附饱和后，以0.2mol/L的盐酸溶液进行再生，对再生液进行ICP分析，确定脱附效率，其结果如下表所示。This embodiment provides a method for effectively removing metal ions in an ionic liquid water system. The ionic liquid in the ionic liquid aqueous solution to be recovered is 1-butyl-3 methylimidazolium chloride, the mass fraction is 10%, and the impurity ion is Ca 2 + and Mg 2+ , the concentrations are both 100 mg/L. The specific steps are as follows: the ionic liquid aqueous solution is introduced into an adsorption tower filled with sodium X molecular sieve at a flow rate of 10 BV/h, and the effluent is analyzed by ICP and UV spectrophotometer to determine the removal efficiency of metal ions and the loss of ionic liquid. The effluent was distilled under reduced pressure at 120°C and 300Pa for 5 hours, and finally 1-butyl-3-methylimidazolium chloride with a water content of 1.0% was obtained, and the recovery rate of ionic liquid was 99.4%. After the adsorption is saturated, regenerate with 0.2 mol/L hydrochloric acid solution, and perform ICP analysis on the regenerated liquid to determine the desorption efficiency. The results are shown in the following table.
以上显示和描述了本发明的实施实例，或者附图的技术方案，均体现了本发明的一种离子液体水溶液体系中离子液体回收的工艺。应当理解的是，对于本领域技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。The embodiments of the present invention shown and described above, or the technical solutions of the accompanying drawings, all embody the process of ionic liquid recovery in an ionic liquid aqueous solution system of the present invention. It should be understood that for those skilled in the art, improvements or changes can be made according to the above description, and all such improvements and changes should fall within the protection scope of the appended claims of the present invention.
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