CN102516177A - Preparation method for high-purity ionic liquid - Google Patents
Preparation method for high-purity ionic liquid Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 title abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 halide ions Chemical class 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 125000002091 cationic group Chemical group 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 8
- 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 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000005649 metathesis reaction Methods 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 150000008045 alkali metal halides Chemical class 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000001514 detection method Methods 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 4
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 3
- 150000001768 cations Chemical class 0.000 abstract 2
- 238000005349 anion exchange Methods 0.000 abstract 1
- 238000005341 cation exchange Methods 0.000 abstract 1
- 229910001408 cation oxide Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000008859 change Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A preparation method for a high-purity ionic liquid is disclosed, which orderly comprises five steps of metathetical reaction, ion exchange for removing halide ions, ion exchange for removing potassium ions, acid-alkali neutralization and solvent recovery. The method specifically comprises the following steps of: performing stirring reaction on the haloid of a target cation and potassium hydroxide for 2-24 hours in ethanol, and filtering to remove potassium halide, so as to obtain an alkaline liquid containing the target cation; adding water to dilute, and removing the residual halide ions and potassium ions through an anion exchange unit and a cation exchange unit orderly; and performing neutralization reaction for 2-6 hours with the conjugate acid of a target anion to obtain ionic liquid solution, filtering to remove solid insoluble substances, evaporating to recover a solvent, and drying to obtain the high-purity ionic liquid. Showed in the figure, the method disclosed by the invention is simple in technical process, good in the quality of product, low in cost, capable of unifying a plurality of ionic liquids in common technology, and with great industrialization prospect.
Description
Technical field
But the present invention relates to a kind of preparation method of high-purity ion liquid of industriallization amplification.
Technical background
Ionic liquid by organic cation and inorganic or organic anion constitutes, at room temperature or be the salt of liquid state near the room temperature under the temperature.Owing to form by ion fully, the advantage that ionic liquid has many conventional solvents not possess,, Heat stability is good low, non-volatile like fusing point, dissolving power is strong, character is adjustable etc.Therefore, ionic liquid can be used as green solvent and is applied to industrial production, also can and change structure through design and come accommodation property, to reach certain applications purposes such as catalysis, separation, material prepn.
At present, non-chlorine aluminic acid ionic liquid mainly adopts two-step approach synthetic.The first step is the alkylated reaction of tertiary amine and halohydrocarbon, and second step replaced the reaction of halide-ions for the target negatively charged ion.Existing research shows have several different methods can accomplish the replacement of target negatively charged ion to halide-ions, and more representative has following several kinds:
1) replacement(metathesis)reaction in the nonaqueous phase; This method utilizes object ion liquid and the halogen dissolubility difference in organic solvent to accomplish the replacement process; Method is simple but have the higher metal ion and halide-ions residual (University of Petroleum's journal, 2004,28 (4): 105～111).The research report is arranged, adopt in this method synthetic [emim] [BF4] [Na
+] content reaches 1380ppm, [Cl
-] then up to 62125ppm; [Na in the synthetic [bmim] [BF4]
+] content reaches 1150ppm, [Cl
-] also reach 15265ppm.In order to remove impurity, usually adopt a large amount of solvents that ionic liquid is washed or extracts, both increased ion liquid loss, also need mass energy consumption to be used for solvent recuperation.
2) silver salt method, this method adopt silver suboxide, silver acetate etc. to form insoluble silver halide precipitation (Journal of Chem.Soc.Chem.Comm, 1992 with halide-ions; P965); Though the ionic liquid yield and the purity of preparation are all very high,, be not suitable for extensive use because silver salt costs an arm and a leg.
3) electrolytic process, this method be through the aqueous solution of electrolysis target positively charged ion and halide-ions, produces halogen simple substance and the cationic oxyhydroxide of target, the latter again with the anionic conjugate acid neutralization reaction of target, obtain object ion liquid (US2003/0094380A1).Because the positively charged ion volume that ionic liquid is commonly used is bigger; Transport number is low in electric field; Cause utilization rate of electrical low; And have the problem that the target cationic hydroxide decomposes easily under the high temperature, so this method has only at present several kinds of simple quaternary ammonium hydroxides (like TMAH, tetraethyl ammonium hydroxide etc.) of being directed against that the industriallization report is arranged.It is complicated with operation in these processes, also to exist device, and halogen simple substance that produces in the electrolytic process or halogenated alkane (CN1978708A) are prone to produce environmental pollution problems, still have distance from heavy industrialization.
To sum up analysis is visible, and existing method mainly exists foreign matter content high, the synthetic high shortcoming of cost, and the single-minded shortage general character of method, these all seriously limit ion liquid suitability for industrialized production, become problem demanding prompt solution.
Summary of the invention
The objective of the invention is in order to overcome the defective of high, the synthetic cost height of the product foreign matter content that exists in the existing method for synthesizing ionic liquid, the single-minded shortage general character of method; Provide a kind of technological process simple; Good product quality; Cost is low, can most ionic liquids be unified in the method under the general character technology, has the good industrial prospect.
The present invention adopts following technical scheme for realizing above-mentioned purpose:
A kind of preparation method of high-purity ion liquid, it comprises the steps:
Step 1, replacement(metathesis)reaction
With the cationic halogen of target and alkali metal hydroxide stirring reaction in ethanol, the ratio of halogen and the amount of substance of oxyhydroxide is 1: 1～1.1, and the reaction times is 2～24 hours, and temperature of reaction is controlled at 0～50 ℃.Reaction finishes after-filtration and removes alkali metal halide, obtains the cationic hydroxide solution of target.
Most ionic liquids can be dissolved in the organic solvent of low carbon number; The solubleness of basic metal halogen is then less; As: (under 25 ℃; Sodium-chlor and the Repone K solubleness in ethanol is respectively 0.07g/100g ethanol and 0.036g/100g ethanol, and the solubleness of Repone K in propyl alcohol is the 0.006g/100g propyl alcohol).Utilize this dissolubility difference, the alkali metal halide that metathesis is produced is constantly separated out, and removes most halogens.This method is simple to operate, and is with low cost, but still has a spot of halide-ions to remove.Halide-ions has very strong corrodibility and coordination property, causes the poisoning of transition-metal catalyst easily, and influences ion liquid electrochemical window, and the existence of halogen can have a strong impact on ion liquid industrial applications.Simultaneously, metals ion residual needs that also has part considered.
Step 2, IX remove halide-ions
The cationic hydroxide solution of target that step 1 is obtained is diluted with water to the aqueous solution that hydroxide radical concentration is 0.5～1mol/L; Through the ion exchange column of anionite-exchange resin is housed; Remove halide-ions; Service temperature is controlled at 10～40 ℃, and the operations flows speed control is built in 3～15BV/h (BV is the resin bed volume).
The cationic hydroxide solution of the target that step 1 obtains still contains a spot of halide-ions and alkalimetal ion, in order further to remove the impurity in the above-mentioned solution, needs to select more efficiently foreign ion separation method.Ion exchange method is widely used in trace impurity ionic removal in the water treatment, technology maturation, economical and effective.Its shortcoming is, the exchange capacity of resin is lower, when handling the bigger system of impurity concentration, needs frequent regeneration, produces a large amount of spent acid, salkali waste simultaneously.In the present invention; Owing at first adopted organic solvent medium that the overwhelming majority's halide-ions is removed from the target positively charged ion, remaining content of halide ions has only 1000～1500ppm, adopts ion exchange method this moment again; Then can avoid the problems referred to above, treatment capacity increases greatly.
Anionite-exchange resin is selected in the removal of halide-ions for use, and it has very big selectivity (K to halide-ions
Cl-/OH-=22, K
Br-/OH-=50, K
I-/OH-=175).
Step 3, IX remove metals ion
The solution that step 2 is obtained is removed alkalimetal ion through the ion exchange column of Zeo-karb is housed, and service temperature is controlled at 10～40 ℃, and the operations flows speed control is built in 3～15BV/h (BV is the resin bed volume).
Zeo-karb is selected in the removal of alkalimetal ion for use, because the proton hydrogen on ion liquid target positively charged ion and the foreign metal pair ion resin has the competition permutoid reaction, this just needs to adopt the Zeo-karb of high-crosslinking-degree.This be because, the increase of degree of crosslinking can increase the duct ratio in resin inner aperture footpath, basic metal exchanges in the duct of small-bore, outside the target positively charged ion that volume is bigger then is blocked in.Simultaneously, because the existence of the cationic competition exchange of target can cause the target positively charged ion of a part to be attracted to (about 5～10%) on the resin,, can before use resin be immersed in the cationic halide salt solution of target and carry out pre-treatment for reducing the loss.
Through the cationic hydroxide solution of target that above-mentioned ion exchange method was handled, impurity ion content wherein reduces greatly, can directly be used for neutralization reaction.
Step 4, acid-base neutralisation
Cationic hydroxide solution of purified target and the anionic conjugate acid of target that step 3 is obtained reacted 2～6 hours down at 10～40 ℃, and wherein alkali is m with the ratio of the amount of acid, and m is the positive integer that is not more than proton hydrogen number in a part acid.
At present, the ion liquid anion species of having reported is various, and the great majority in them exist corresponding water miscible conjugate acid.Therefore, can react, generate corresponding object ion liquid with the cationic alkaline solution acid-base neutralisation of target.This just is unified in existing most of ion liquid compound methods under the method for one general character, can use a cover industrial flow to realize the production of different kinds of ions class of liquids.
Step 5, solvent recuperation
The object ion liquor of step 4 is left standstill, filter, the second alcohol and water is reclaimed in evaporation successively, and vacuum-drying obtains highly purified object ion liquid to constant weight.
The acid-base neutralisation reaction very easily takes place; Transformation efficiency can reach 100%, so the solution that step 4 obtains contains the object ion product liquid, the second alcohol and water; As long as can obtain highly purified object ion liquid through simple evaporation except that desolvating, avoid the use of a large amount of organic solvents.
The preparation method of above-mentioned high-purity ion liquid, the cationic halogen of the described target of step 1 is N, N; N, N-tetraalkyl quaternary ammonium halogen or N, N-dialkylimidazolium halogen or N-alkyl pyridine halogen or N; N, N, N-tetraalkyl season phosphine halogen; Wherein, alkyl can be the straight or branched alkyl of 1～8 carbon atom.Wherein, alkyl can be the straight or branched alkyl of 1～8 carbon atom or the alkyl that includes functional groups such as hydroxyl, amino, allyl group or benzyl, and the carbon atom number on each alkyl is identical or inequality.
The preparation method of above-mentioned high-purity ion liquid, the consumption of the alcohol solvent that step 1 is used is crucial process parameter, the ratio of its consumption and reaction raw materials total mass is 2.5～6.
The preparation method of above-mentioned high-purity ion liquid; Step 2 and 3 described ion exchange column aspect ratio >=5; Its material is glass or plastics; Wherein anionite-exchange resin is strong base styrene series anion exchange resin or macropore strong base styrene series anion exchange resin (chlorine type); Like model is 201 * 7 or the resin of D201 type, and Zeo-karb is that degree of crosslinking is not less than 12 strong acid type styrene type cation exchange resin, is 001 * 12 or 001 * 14 or 001 * 16 resin like model.
The preparation method of above-mentioned high-purity ion liquid; The described anionite-exchange resin of step 3 is before using first or adsorb and need manipulation of regeneration after saturated; Treatment process is: earlier the deionized water with 1～3 BV washs resin, and is first then with 4～10% lower concentration NaOH drip washing, again concentration is increased to 10～30% drip washing; Again concentration is reduced to 4～10% drip washing at last, the total consumption of NaOH solution is 3～10BV.NaOH drip washing is washed till neutrality with the deionized water of 1～3BV later, and the manipulation of regeneration flow velocity is 0.5～5BV/h.
The preparation method of above-mentioned high-purity ion liquid; The described Zeo-karb of step 3 uses and need carry out manipulation of regeneration later; Treatment process is: the deionized water with 1～3 BV washs resin earlier, uses 3～10% HCl solution drip washing then, and solution usage is 1～5BV; Deionized water with 1～3BV is washed till neutrality at last, and the manipulation of regeneration flow velocity is 0.5～5BV/h.
The preparation method of above-mentioned high-purity ion liquid; Step 3 is described to be that the Zeo-karb of Hydrogen all need carry out surface conversion treatment before using first or after the regeneration; Its treatment process is at first washing resin with the deionized water of 1～3BV; Then with 1～3BV 5～10% contain the drip washing of the cationic halogen aqueous solution of target, be washed till effluent with the deionized water of 1～3BV at last and detect with AgNO3 and do not have deposition, the flow velocity of surface conversion treatment is 3～15BV/h.
The preparation method of above-mentioned high-purity ion liquid, the anionic conjugate acid of the described target of step 4 is mineral acid or organic acid.Wherein, mineral acid is common mineral acid, like nitric acid, sulfuric acid, phosphoric acid, Tetrafluoroboric acid or phosphofluoric acid; Organic acid is common organic acid, like carboxylic acid, sulfonic acid, ketone acid, alcohol acid or amino acid.
The preparation method of above-mentioned high-purity ion liquid, the described etoh solvent of step 5 is in a rectifying tower, to reclaim, flash distillation recycle-water in an evaporating pot more afterwards, the second alcohol and water of all recovery can recycle.
The present invention overcomes the defective of high, synthetic cost height of the product foreign matter content that exists in the existing method for synthesizing ionic liquid and the single-minded shortage general character of method; Provide a kind of technological process simple; Good product quality; Cost is low, can most ionic liquids be unified in the method under the general character technology, has the good industrial prospect.
Description of drawings
Fig. 1 is a high-purity ion liquid preparing method's of the present invention process flow diagram, and wherein: A is the replacement(metathesis)reaction reaction kettle, and B is a whizzer; C is a thinning tank, and D is an anion-exchange resin column, and E is a cation exchange resin column; F is the neutralization reaction still, and G is a rectifying tower, and H is a flash tank; 1 is the ethanolic soln of target positively charged ion halogen, and 2 is potassium hydroxide-ethanol solution, and 3 is the potassium halide solid, and 4 is water, and 5 is the target negatively charged ion conjugate acid aqueous solution, and 6 is ethanol, and 7 is water, and 8 is the object ion product liquid.
Embodiment
Characteristics of the present invention will give unrestriced explanation through following examples.
The preparation of embodiment 1,1-methyl-3-NSC 158165 acetato-liquid
Step 1, the synthetic 1-methyl of replacement(metathesis)reaction-3-NSC 158165 alkali
214.2g chloridization 1-methyl-3-butyl imidazole salt (0.9mol) is dissolved in the 300g absolute ethyl alcohol, is placed in the 1L reactor drum, 50.4g Pottasium Hydroxide (0.9mol) is dissolved in the 250g absolute ethyl alcohol; Slowly add in the reactor drum; Reacted 12 hours under the room temperature down well-beaten, reaction finishes to remove by filter the Repone K deposition; Obtain mass content and be about 1-methyl-3-NSC 158165 alkaline solution of 28%, productive rate (in 1-methyl-3-NSC 158165 alkali) about 95%.
Step 2, IX remove cl ions
In the glass column that is of a size of Φ 16 * 500mm, load 201 * 7 strong basic type anion-exchange resins (chlorine type), loading height is 450mm.With the 100mL deionized water resin is washed earlier, use the NaOH drip washing of 100mL 4% then, then, use the NaOH drip washing of 100mL 4% again, be washed till neutrality with the 200mL deionized water at last, accomplish the ion exchange resin conversion pre-treatment with the NaOH drip washing of 150mL 16%.
In 1-methyl-3-NSC 158165 alkaline solution that step 1 obtains, add a certain amount of water, make that concentration hydroxy is 0.5mol/L.Record that the mass ratio of cl ions and quaternary ammonium hydroxide is 1500ppm in the solution this moment, the mass ratio of potassium ion and quaternary ammonium hydroxide is 1020ppm.This aqueous solution is flowed through in the above-mentioned ion exchange column with the flow velocity of 900ml/h (10BV/h), when effluent becomes alkalescence, begin to collect, after solution all flows through, use pure water drip washing resin again, until being washed till neutrality, and collect leacheate.
Step 3, IX remove potassium ion
In the glass column that is of a size of Φ 16 * 500mm, load 001 * 12 strong acid type anionite-exchange resin (Hydrogen), loading height is 450mm.At first the deionized water with 100mL washs resin, uses 150mL5%HCl drip washing then, is washed till neutrality with the 200mL deionized water at last, accomplishes the resin pre-treatment.Follow aqueous solution drip washing, be washed till effluent with the 200mL deionized water again and detect the nothing deposition, accomplish the resin surface conversion with AgNO3 with the chloridization 1-methyl-3-butyl imidazole salt of 150mL 5%.
The solution of step 2 is then flow through above-mentioned ion exchange column with the flow velocity of 900ml/h (10BV/h), when effluent becomes alkalescence, begin to collect, after solution all flows through, use pure water drip washing resin again, until being washed till neutrality, and collect leacheate.
Step 4, the synthetic 1-methyl of acid-base neutralisation-3-NSC 158165 ionic liquid
The purified 1-methyl that obtains in the step 3-3-NSC 158165 alkali aqueous solution is placed in the 1L reactor drum, at room temperature slowly added the acetate of 54g (0.9mol) while stirring, reacted 2 hours, obtain 1-methyl-3-NSC 158165 acetato-liquor.
Step 5, solvent recuperation
The product of step 4 is fed rectifying tower recovery alcohol solvent, and the rectifying tower packed height is 5.5m, and theoretical plate number is 30, and feed entrance point is 2m (apart from a cat head), and tower top pressure is normal pressure (0.1MPa), and temperature is 85 ℃, and column bottom temperature is 105 ℃, and reflux ratio is 2.The ethanol cycle of cat head extraction 99% concentration is used.The extraction ionic liquid aqueous solution is sent in the flash tank at the bottom of the tower, and the flash tank bottom temp is 140 ℃, and head temperature is 100 ℃; Pressure 0.1MPa; The top obtains pure water with recycle, and the bottom is purified 1-methyl-3-NSC 158165 acetato-liquid, and the product ultimate yield is 90%; Chloride ion content is 10ppm, and potassium content is 8ppm.
Embodiment 2～3
Change step 1 Pottasium Hydroxide consumption, other conditions are identical with embodiment 1, and the result sees table 1
Embodiment 4～5
Change concentration hydroxy in the step 2, other conditions are identical with embodiment 1, and the result sees table 1
Embodiment 6～7
Solution stream is crossed the operation flow velocity of resin bed in change step 2 and the step 3, and other conditions are identical with embodiment 1, and the result sees table 1
Embodiment 8～10
Change the type of the anion and cation exchange resin in step 2 and the step 3, other conditions are identical with embodiment 1, and the result sees table 2
Embodiment 11～17
Raw material target positively charged ion halogen in the change step 1 and the anionic conjugate acid of target in the step 4, other conditions are identical with embodiment 1, and the result sees table 3
Table 1: the ionic liquid of preparations such as different ratios of raw materials, hydroxide radical concentration, operation flow velocity
Table 2: the ionic liquid of different anion and cation exchange resin preparations
Table 3: the ionic liquid of different material preparation
Claims (9)
1. the preparation method of a high-purity ion liquid is characterized in that it comprises the steps:
Step 1, replacement(metathesis)reaction
With the cationic halogen of target and alkali metal hydroxide stirring reaction in ethanol, the ratio of halogen and the amount of substance of oxyhydroxide is 1: 1～1.1, and the reaction times is 2～24 hours, and temperature of reaction is controlled at 0～50 ℃.Reaction finishes after-filtration and removes alkali metal halide, obtains the cationic hydroxide solution of target;
Step 2, IX remove halide-ions
The cationic hydroxide solution of target that step 1 is obtained is diluted with water to the aqueous solution that hydroxide radical concentration is 0.5～1mol/L; Through the ion exchange column of anionite-exchange resin is housed; Remove halide-ions, service temperature is controlled at 10～40 ℃, and the operations flows speed control is built in 3～15BV/h;
Step 3, IX remove metals ion
The solution that step 2 is obtained is removed alkalimetal ion through the ion exchange column of Zeo-karb is housed, and service temperature is controlled at 10～40 ℃, and the operations flows speed control is built in 3～15BV/h;
Step 4, acid-base neutralisation
Cationic hydroxide solution of purified target and the anionic conjugate acid of target that step 3 is obtained reacted 2～6 hours down at 10～40 ℃, and wherein alkali is m with the ratio of the amount of acid, and m is the positive integer that is not more than proton hydrogen number in a part acid;
Step 5, solvent recuperation
The object ion liquor of step 4 is left standstill, filter, the second alcohol and water is reclaimed in evaporation successively, and vacuum-drying obtains highly purified object ion liquid to constant weight.
2. the preparation method of high-purity ion liquid according to claim 1 is characterized in that: the cationic halogen of the described target of step 1 is N, N; N, N-tetraalkyl quaternary ammonium halogen or N, N-dialkylimidazolium halogen or N-alkyl pyridine halogen or N; N, N, N-tetraalkyl season phosphine halogen; Wherein, alkyl can be the straight or branched alkyl of 1～8 carbon atom or the alkyl that includes functional groups such as hydroxyl, amino, allyl group or benzyl, and the carbon atom number on each alkyl is identical or inequality.
3. the preparation method of high-purity ion liquid according to claim 1 is characterized in that: the consumption of the alcohol solvent that step 1 is used is crucial process parameter, and the ratio of its consumption and reaction raw materials total mass is controlled at 2.5～6.
4. the preparation method of high-purity ion liquid according to claim 1; It is characterized in that: step 2 and 3 described ion exchange column aspect ratio >=5; Its material is glass or plastics; Wherein anionite-exchange resin is strong base styrene series anion exchange resin or macropore strong base styrene series anion exchange resin, and Zeo-karb is that degree of crosslinking is not less than 12 strong acid type styrene type cation exchange resin.
5. the preparation method of high-purity ion liquid according to claim 1; It is characterized in that: the described anionite-exchange resin of step 2 is before using first or adsorb and need manipulation of regeneration after saturated; Treatment process is: earlier the deionized water with 1～3 BV washs resin, and is first then with 4～10% lower concentration NaOH drip washing, again concentration is increased to 10～30% drip washing; Again concentration is reduced to 4～10% drip washing at last, the total consumption of NaOH solution is 3～10BV.NaOH drip washing is washed till neutrality with the deionized water of 1～3BV later, and the manipulation of regeneration flow velocity is 0.5～5BV/h.
6. the preparation method of high-purity ion liquid according to claim 1; It is characterized in that: the described Zeo-karb of step 3 uses and need carry out manipulation of regeneration later; Treatment process is: the deionized water with 1～3 BV washs resin earlier, uses 3～10% HCl solution drip washing then, and solution usage is 1～5BV; Deionized water with 1～3BV is washed till neutrality at last, and the manipulation of regeneration flow velocity is 0.5～5BV/h.
7. the preparation method of high-purity ion liquid according to claim 1; It is characterized in that: step 3 is described to be that the Zeo-karb of Hydrogen all need carry out surface conversion treatment before using first or after the regeneration; Its treatment process is at first washing resin with the deionized water of 1～3BV; Contain the drip washing of the cationic halogen aqueous solution of target with 1～3BV 5～10% then; Deionized water with 1～3BV is washed till effluent with AgNO3 detection nothing deposition at last, and the flow velocity of surface conversion treatment is 3～15BV/h.
8. the preparation method of high-purity ion liquid according to claim 1 is characterized in that: the anionic conjugate acid of the described target of step 4 is mineral acid or organic acid, and wherein, mineral acid is nitric acid, sulfuric acid, phosphoric acid, Tetrafluoroboric acid or phosphofluoric acid; Organic acid is carboxylic acid, sulfonic acid, ketone acid, alcohol acid or amino acid.
9. the preparation method of high-purity ion liquid according to claim 1 is characterized in that: the described etoh solvent of step 5 is in a rectifying tower, to reclaim, flash distillation recycle-water in an evaporating pot more afterwards, and the second alcohol and water of all recovery can recycle.
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