CN102371078A - Recovery method for ionic liquid solvent generated from homogeneous acylation reaction of cellulose - Google Patents
Recovery method for ionic liquid solvent generated from homogeneous acylation reaction of cellulose Download PDFInfo
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- CN102371078A CN102371078A CN2010102497504A CN201010249750A CN102371078A CN 102371078 A CN102371078 A CN 102371078A CN 2010102497504 A CN2010102497504 A CN 2010102497504A CN 201010249750 A CN201010249750 A CN 201010249750A CN 102371078 A CN102371078 A CN 102371078A
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- imidazoles
- acylation reaction
- waste liquid
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920002678 cellulose Polymers 0.000 title claims abstract description 31
- 239000001913 cellulose Substances 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title claims abstract description 29
- 238000005917 acylation reaction Methods 0.000 title claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 title abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 121
- 150000002500 ions Chemical class 0.000 claims abstract description 76
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 238000000199 molecular distillation Methods 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 82
- 238000004821 distillation Methods 0.000 claims description 26
- 230000006837 decompression Effects 0.000 claims description 23
- -1 imidazoles halogen ion Chemical class 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 230000008521 reorganization Effects 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004061 bleaching Methods 0.000 claims description 4
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical class [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 claims description 2
- AJDNKVINGDHHEY-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)propanoic acid Chemical class OC(=O)C(C)C1=NC=CN1 AJDNKVINGDHHEY-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000005466 alkylenyl group Chemical group 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 229940070710 valerate Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 230000010933 acylation Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- 239000002826 coolant Substances 0.000 description 6
- 238000005374 membrane filtration Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002895 organic esters Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- ZJZHZLJGFSIHFD-UHFFFAOYSA-N C(CCC)(=O)O.C(C)N1CN(C=C1)C Chemical compound C(CCC)(=O)O.C(C)N1CN(C=C1)C ZJZHZLJGFSIHFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明涉及的纤维素均相酰化反应后离子液体溶剂的回收方法，是先将纤维素均相酰化后的离子液体废液脱色、过滤，然后对过滤后的离子液体废液减压蒸馏，再将减压蒸馏后的离子液体废液加入分子蒸馏装置中，选择适当的进料温度，进料速度、蒸发温度、蒸发压强、刮膜旋转速度、冷凝温度进行分子蒸馏，收集所得重组分即为回收后的离子液体；本发明的方法将减压蒸馏和分子蒸馏技术相结合可高效地脱除纤维素均相酰化后离子液体溶剂废液中有机残留物和水，使得到的离子液体纯度在99％以上。本发明具有能耗较低、工艺简单、效率较高优点，回收的离子液体可循环利用。The method for recovering the ionic liquid solvent after the cellulose homogeneous acylation reaction of the present invention is to decolorize and filter the ionic liquid waste liquid after the cellulose homogeneous acylation reaction, and then distill the filtered ionic liquid waste liquid under reduced pressure , then add the ionic liquid waste liquid after vacuum distillation to the molecular distillation device, select the appropriate feed temperature, feed speed, evaporation temperature, evaporation pressure, wiper rotation speed, condensation temperature for molecular distillation, and collect the heavy components It is the ionic liquid after recovery; the method of the present invention combines vacuum distillation and molecular distillation technology to efficiently remove organic residues and water in the ionic liquid solvent waste liquid after cellulose homogeneous acylation, so that the obtained ions The liquid purity is above 99%. The invention has the advantages of low energy consumption, simple process and high efficiency, and the recovered ionic liquid can be recycled.
Description
Technical field
The present invention relates to the ion liquid solvent recovery method, particularly relate to the recovery method of ion liquid solvent after a kind of cellulose homogeneous-phase acylation reaction.
Background technology
Cellulose is the abundantest a kind of renewable resource of occurring in nature, extensively is present in the string.Along with the continuous consumption of non-renewable resources such as oil, coal is deficient, through coming development environment green industrial products friendly, high added value more and more to cause people's attention to cellulose modified.Wherein the research of cellulose organic ester has been become the focus of people's research.As cellulosic a kind of modified product, cellulose organic ester has important effect in coating, coating and paint, field of medicaments, is widely used in fields such as national defence, chemical industry, biology, medicine, building, space flight.
Ion liquid solvent is that the ion liquid solvent of a kind of novel green solvent, especially some ad hoc structures of rising in recent years has good solvability to cellulose.Because it has ultralow vapour pressure, high thermal stability and chemical stability; Therefore; The cellulose homogeneous-phase derivatization that with the ion liquid solvent is medium has caused the extensive concern on chemical boundary, wherein in ion liquid solvent, cellulose is carried out the homogeneous phase acidylate and prepares cellulose organic ester a lot of reports has been arranged.
Though ion liquid solvent as a kind of good green solvent in cellulose modified engineering; Have good environment, society, economic benefit, but when it is released in the water environment, because its bigger toxicity and difficult biodegradability; Will cause very big pollution to environment; It is expensive than conventional solvent to add ion liquid solvent, thereby still is that economic aspect is considered from environmental no matter, and the recovery of ion liquid solvent all has great importance with purifying research.
Oneself has many reports about the technology that from waste liquid or waste water, reclaims ion liquid solvent; For example: Chinese patent CN1804161A has announced a kind of recovery method of cellulose spinning waste water intermediate ion liquid flux; This method makes as cellulose solvent and is effectively reclaimed through the ion liquid solvent that wet spinning gets into coagulating bath the operation of spinning coagulation bath waste water through deposition-filtration-decompression distillation-air-distillation; But because the content of the ion liquid solvent in the filature wastewater is lower, therefore directly the distillation energy consumption is higher, is unfavorable for energy-saving and emission-reduction.Disclose a kind of elder generation among the Chinese patent CN1944357A with extractant enrichment hydrophilic ionic-liquid solvent, water washes out ion liquid solvent again, gets into the technology of evaporation process at last; Disclose the specific inorganic salts of adding in the aqueous solution of ion liquid solvent among the China CN1973943A, thereby formed double-aqueous phase system, carried out next step separation again.Though these two kinds of methods have concentration effect preferably, complex process, and since introduce inorganic salts simultaneously can the contaminated ion liquid flux, await further research; Chinese patent CN101219840A adopts the integrated processes of preliminary treatment, ultrafiltration, nanofiltration or counter-infiltration, decompression distillation from filature wastewater, to reclaim ion liquid solvent.Because membrane material is relatively more expensive, the recycle of film is difficulty relatively, and cost is bigger, and the ionic liquid concentration that reclaims is not high.What Chinese patent CN101003510A invented only is to utilize molecular clock to synthetic thick ion liquid purification, does not relate to the recovery of participating in reaction back ion liquid solvent waste liquid.
Molecular clock is under vacuum condition, utilizes different molecular mean free path difference to cause its surface evaporation speed different and reach the method for separation; Because molecular clock is to carry out under far below the temperature of boiling point in high vacuum; Distillation time is short; Separate the gentleest distillating method of purpose product so this process has become, be particularly suitable for separating the material of low volatility, HMW, higher boiling, high viscosity, thermal sensitivity and biologically active; Oneself is in the application of succeeding of industries such as petrochemical industry, food, plastics, medicine.
Summary of the invention
The object of the invention is to provide the recovery method of ion liquid solvent after a kind of cellulose homogeneous-phase acylation reaction; Promptly adopt decompression distillation and the molecular clock method that combines to reclaim the ion liquid solvent in the ion liquid solvent waste liquid; Can overcome prior art and have defective, it is little to have energy consumption, and efficient is high; Technology is simple, good benefits in environment and economic benefit.
Technical scheme of the present invention is following:
The recovery method of ion liquid solvent after the cellulose homogeneous-phase acylation reaction provided by the invention; It is to utilize ion liquid solvent after the technology for recovery cellulose homogeneous-phase acylation reaction that decompression distillation and molecular clock combine; At first be with ion liquid solvent waste liquid after the cellulose homogeneous-phase acylation reaction through decolouring with filter, and then distill successively and molecular clock; Its concrete steps are following:
(1) the ion liquid solvent waste liquid after the cellulose homogeneous-phase acylation reaction is used activated carbon decolorizing;
Said active carbon is the micropore active carbon of pore radius 100～150nm, and bleaching temperature is 30～80 ℃, and bleaching time is 30min～120min, and said amount of activated is 1%～5% of a said ion liquid solvent waste liquid weight;
(2) will use filtering with microporous membrane through the ion liquid solvent waste liquid after the decolouring;
(3) the ion liquid solvent waste liquid after will filtering is poured Rotary Evaporators into and is carried out decompression distillation;
60～110 ℃ of vacuum distillation temperatures, 3～15 hours decompression distillation time, decompression distillation pressure 2～30kpa;
(4) the ion liquid solvent waste liquid after the decompression distillation is poured into carried out molecular clock in the scraped film type molecular distillation apparatus; The step of said molecular clock is following:
(a) ion liquid solvent waste liquid after decompression distillation is added in the feeder, and preheating to make its temperature be 50～80 ℃;
(b) pressure of adjustment scraped film type molecular distillation apparatus is 1Pa～100Pa, and the evaporating surface temperature of scraped film type molecular distillation apparatus is 80～110 ℃;
(c) open the charging valve, and open the knifing rotor of scraped film type molecular clock appearance simultaneously, the beginning dropping liquid also carries out molecular clock, collects the ion liquid solvent that the gained reorganization is divided into recovery;
The charging rate of said dropping liquid is 1～10ml/min;
Said knifing rotary speed of rotator is 275～440r/min;
The cryosurface temperature of said scraped film type molecular distillation apparatus is-15～15 ℃;
Ion liquid solvent in the said ion liquid solvent waste liquid is the C of imidazoles halogen ion liquid solvent or imidazoles
1～C
6The carboxylate ion liquid solvent.
The C of described imidazoles halogen or imidazoles
1～C
6The cation of carboxylate has formula:
R wherein
1Be C
1～C
20Alkyl or alkenyl.
Described imidazoles halogen ion liquid solvent is imidazoles villiaumite, imidazoles villaumite, imidazoles bromine salt or iodonium imidazolide salts.
The C of described imidazoles
1～C
6Carboxylate is imidazoles acetate, imidazolylpropionic acid salt, imidazoles butyrate, imidazoles valerate or imidazoles caproate.
The employed miillpore filter of said step (2) is polytetrafluoroethylene (PTFE) filter microporous barrier or aperture 0.22～1 μ m micropore ceramics film of aperture 0.22～1 μ m.
The recovery method of ion liquid solvent has following beneficial effect fruit after the cellulose homogeneous-phase acylation reaction of the present invention:
(1) energy consumption is low, cost is low: ion liquid solvent after the plain homogeneous phase acylation reaction of the method recycled fiber that the present invention utilizes decompression distillation to combine with molecular clock, reduce with directly utilizing vacuum distillation method and hyperfiltration, nano filtering process phase specific energy consumption and cost all to have largely;
(2) efficient is high, technology is simple: the present invention utilizes ion liquid solvent after the plain homogeneous phase acylation reaction of method recycled fiber that decompression distillation combines with molecular clock, and its efficient is higher than utilizes the molecular clock recovery method merely; Compare with utilizing the double-aqueous phase system separation method, its technology is more simple;
(3) rate of recovery is high, purity is high: because ion liquid solvent is not volatile; Ion liquid solvent after the plain homogeneous phase acylation reaction of the method recycled fiber that the present invention utilizes decompression distillation to combine with molecular clock; It is compared methods such as extraction and compares; Its rate of recovery is up to more than 95%, and the purity that reclaims ion liquid solvent is up to more than 99%.
The specific embodiment
Be used to further specify the present invention through specific embodiment (but not limiting said embodiment) below:
Embodiment 1
Take by weighing the ion liquid solvent 1-butyl-3-methyl imidazolium tetrafluoroborate waste liquid 500g of preparation behind the cellulose acetate, add the 5g active carbon, stir 30min at 30 ℃; Use the polytetrafluoroethylene (PTFE) membrane filtration of aperture 0.22 μ m then; Join in the Rotary Evaporators, under 60 ℃, 2kpa condition, decompression distillation 3 hours joins gains in the feeder of scraped film type molecular clock appearance then again; Open the feeder heater, set 50 ℃ of heating-up temperatures, open the evaporating temperature device of scraped film type molecular clock appearance, setting the evaporating surface temperature is 80 ℃; The ON cycle coolant pump, setting condensation temperature is-15 ℃, and keeps the open vacuum pump 20 minutes; Make pressure reach 1Pa, start blade applicator, making the rotating speed of knifing rotor is 275r/min, opens sampling valve; Charging rate is controlled at 10ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Water |
| Content | 99.04％ | 0.96％ | 0 |
Embodiment 2
Take by weighing the ion liquid solvent 1-pi-allyl-3-methylimidazole chlorate waste liquid 500g of preparation behind the cellulose acetate, add the 10g active carbon, stir 60min, use the polytetrafluoroethylene (PTFE) membrane filtration of 0.45 μ m then at 50 ℃; Join in the Rotary Evaporators, decompression distillation is 6 hours under 90 ℃, 10kpa, then gains is joined in the feeder of scraped film type molecular distillation apparatus again; Open the feeder heater, 70 ℃ of design temperatures are opened scraped film type molecular clock appearance evaporating temperature device; Design temperature is 100 ℃, the ON cycle coolant pump, and setting condensation temperature is-10 ℃; And kept 20 minutes, the open vacuum pump makes pressure reach 50Pa; Start blade applicator, making the rotating speed of knifing rotor is 385r/min, opens sampling valve; Charging rate is controlled at 5ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Water |
| Content | 99.24％ | 0.76％ | 0 |
Embodiment 3
Take by weighing the ion liquid solvent 1-butyl-3-methylimidazole iodized salt waste liquid 500g of preparation behind the cellulose acetate, add the 25g active carbon, stir 120min at 80 ℃; Use the polytetrafluoroethylene (PTFE) membrane filtration of 1 μ m then, join in the Rotary Evaporators again, decompression distillation is 15 hours under 110 ℃, 30kpa; Then gains are joined in the feeder of molecular distillation apparatus, open the feeder heater, 80 ℃ of design temperatures; Opening molecular clock appearance evaporating temperature device design temperature is 110 ℃, the ON cycle coolant pump, and setting condensation temperature is 15 ℃; And kept 20 minutes, the open vacuum pump makes pressure reach 100Pa; Start blade applicator, making the rotating speed of knifing rotor is 385r/min, opens sampling valve; Charging rate is controlled at 1ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Water |
| Content | 99.56％ | 0.44％ | 0 |
Embodiment 4
Take by weighing the ion liquid solvent 1-pi-allyl-3-methylimidazole acetate waste liquid 500g of preparation behind the cellulose acetate butyrate, add the 5g active carbon, stir 40min, use the micropore ceramics membrane filtration of 0.22 μ m then at 30 ℃; Join in the Rotary Evaporators, decompression distillation is 5 hours under 60 ℃, 5kpa, then gains is joined in the feeder of molecular distillation apparatus again; Open the feeder heater, 50 ℃ of design temperatures are opened molecular clock appearance evaporating temperature device; Design temperature is 90 ℃, the ON cycle coolant pump, and setting condensation temperature is-15 ℃; And kept 20 minutes, the open vacuum pump makes pressure reach 20Pa; Start blade applicator, making the rotating speed of knifing rotor is 440r/min, opens sampling valve; Charging rate is controlled at 8ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Butyric acid | Water |
| Content | 99.15％ | 0.35％ | 0.50％ | 0 |
Embodiment 5
Take by weighing the ion liquid solvent 1-ethyl-3-methylimidazole butyrate waste liquid 500g of preparation behind the cellulose acetate butyrate, add the 15g active carbon, stir 100min at 70 ℃; Use the micropore ceramics membrane filtration of 0.45 μ m then, join in the Rotary Evaporators again, decompression distillation is 10 hours under 90 ℃, 10kpa; Then gains are joined in the feeder of molecular distillation apparatus, open the feeder heater, 70 ℃ of design temperatures; Opening molecular clock appearance evaporating temperature device design temperature is 95 ℃, the ON cycle coolant pump, and setting condensation temperature is 0 ℃; And kept 20 minutes, the open vacuum pump makes pressure reach 60Pa; Start blade applicator, making the rotating speed of knifing rotor is 330r/min, opens sampling valve; Charging rate is controlled at 3ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Butyric acid | Water |
| Content | 99.35％ | 0.30％ | 0.35％ | 0 |
Embodiment 6
Take by weighing the ion liquid solvent 1-pi-allyl-3-methylimidazole caproate waste liquid 500g of preparation behind the cellulose acetate butyrate, add the 25g active carbon, stir 120min at 80 ℃; Use the micropore ceramics membrane filtration of 1 μ m then, join in the Rotary Evaporators, decompression distillation is 15 hours under 110 ℃, 5kpa; Then gains are joined in the feeder of molecular distillation apparatus, open the feeder heater, 80 ℃ of design temperatures; Opening molecular clock appearance evaporating temperature device design temperature is 110 ℃, the ON cycle coolant pump, and setting condensation temperature is 15 ℃; And kept 20 minutes, the open vacuum pump makes pressure reach 100Pa; Start blade applicator, making the rotating speed of knifing rotor is 440r/min, opens sampling valve; Charging rate is controlled at 1ml/min, and beginning dropping liquid molecular clock gets distillate, collects the ion liquid solvent that the gained reorganization is divided into recovery; It is following that the ion liquid solvent of collecting is detected data:
| Classification | Ionic liquid | Acetate | Butyric acid | Water |
| Content | 99.50％ | 0.20％ | 0.30％ | 0 |
Claims (5)
1. the recovery method of ion liquid solvent after the cellulose homogeneous-phase acylation reaction; It is to utilize ion liquid solvent after the technology for recovery cellulose homogeneous-phase acylation reaction that decompression distillation and molecular clock combine; At first be with ion liquid solvent waste liquid after the cellulose homogeneous-phase acylation reaction through decolouring with filter, and then distill successively and molecular clock; Its concrete steps are following:
(1) the ion liquid solvent waste liquid after the cellulose homogeneous-phase acylation reaction is used activated carbon decolorizing;
Said active carbon is the micropore active carbon of pore radius 100～150nm, and bleaching temperature is 30～80 ℃, and bleaching time is 30min～120min, and said amount of activated is 1%～5% of a said ion liquid solvent waste liquid weight;
(2) will use filtering with microporous membrane through the ion liquid solvent waste liquid after the decolouring;
(3) the ion liquid solvent waste liquid after will filtering is poured Rotary Evaporators into and is carried out decompression distillation;
60～110 ℃ of vacuum distillation temperatures, 3～15 hours decompression distillation time, decompression distillation pressure 2～30kpa;
(4) the ion liquid solvent waste liquid after the decompression distillation is poured into carried out molecular clock in the scraped film type molecular distillation apparatus; The step of said molecular clock is following:
(a) ion liquid solvent waste liquid after decompression distillation is added in the feeder, and preheating to make its temperature be 50～80 ℃;
(b) pressure of adjustment scraped film type molecular distillation apparatus is 1Pa～100Pa, and the evaporating surface temperature of scraped film type molecular distillation apparatus is 80～110 ℃;
(c) open the charging valve, and open the knifing rotor of scraped film type molecular clock appearance simultaneously, the beginning dropping liquid also carries out molecular clock, collects the ion liquid solvent that the gained reorganization is divided into recovery;
The charging rate of said dropping liquid is 1～10ml/min;
Said knifing rotary speed of rotator is 275～440r/min;
The cryosurface temperature of said scraped film type molecular distillation apparatus is-15～15 ℃;
Ion liquid solvent in the said ion liquid solvent waste liquid is the C of imidazoles halogen ion liquid solvent or imidazoles
1～C
6The carboxylate ion liquid solvent.
2. by the recovery method of ion liquid solvent after the described cellulose homogeneous-phase acylation reaction of claim 1, it is characterized in that the C of described imidazoles halogen or imidazoles
1～C
6The cation of carboxylate has formula:
R wherein
1Be C
1～C
20Alkyl or alkenyl.
3. by the recovery method of ion liquid solvent after the described cellulose homogeneous-phase acylation reaction of claim 1, it is characterized in that described imidazoles halogen ion liquid solvent is imidazoles villiaumite, imidazoles villaumite, imidazoles bromine salt or iodonium imidazolide salts.
4. by the recovery method of ion liquid solvent after the described cellulose homogeneous-phase acylation reaction of claim 1, it is characterized in that the C of described imidazoles
1～C
6Carboxylate is imidazoles acetate, imidazolylpropionic acid salt, imidazoles butyrate, imidazoles valerate or imidazoles caproate.
5. by the recovery method of ion liquid solvent after the described cellulose homogeneous-phase acylation reaction of claim 1; It is characterized in that the employed miillpore filter of said step (2) is polytetrafluoroethylene (PTFE) filter microporous barrier or aperture 0.22～1 μ m micropore ceramics film of aperture 0.22～1 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010249750 CN102371078B (en) | 2010-08-10 | 2010-08-10 | Recovery method for ionic liquid solvent generated from homogeneous acylation reaction of cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010249750 CN102371078B (en) | 2010-08-10 | 2010-08-10 | Recovery method for ionic liquid solvent generated from homogeneous acylation reaction of cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102371078A true CN102371078A (en) | 2012-03-14 |
| CN102371078B CN102371078B (en) | 2013-10-16 |
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| CN106590809A (en) * | 2016-12-06 | 2017-04-26 | 西安科技大学 | Recycling method of coal mine ionic liquid inhibitor |
| CN108821259A (en) * | 2018-07-18 | 2018-11-16 | 贵州大学 | It is the method and application of precursor preparation nitrogen-doped porous carbon material using chitosan proton type poly ion liquid |
| CN109970263A (en) * | 2018-03-02 | 2019-07-05 | 柏天劳有限公司 | a purification device |
| CN112010900A (en) * | 2020-08-12 | 2020-12-01 | 湖北省兴发磷化工研究院有限公司 | Preparation method of high-purity reactive flame retardant THPO |
| CN112221180A (en) * | 2020-10-20 | 2021-01-15 | 江苏索普化工股份有限公司 | Secondary molecular distillation vacuum system dehydration and organic matter treatment process for ionic liquid solution |
| CN114044755A (en) * | 2021-10-25 | 2022-02-15 | 惠州市绿色能源与新材料研究院 | Efficient ionic liquid decoloring and purifying method |
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| CN106590809A (en) * | 2016-12-06 | 2017-04-26 | 西安科技大学 | Recycling method of coal mine ionic liquid inhibitor |
| CN106590809B (en) * | 2016-12-06 | 2019-09-27 | 西安科技大学 | A kind of recovery method of coal mine ionic liquid inhibitor |
| CN109970263A (en) * | 2018-03-02 | 2019-07-05 | 柏天劳有限公司 | a purification device |
| CN108821259A (en) * | 2018-07-18 | 2018-11-16 | 贵州大学 | It is the method and application of precursor preparation nitrogen-doped porous carbon material using chitosan proton type poly ion liquid |
| CN112010900A (en) * | 2020-08-12 | 2020-12-01 | 湖北省兴发磷化工研究院有限公司 | Preparation method of high-purity reactive flame retardant THPO |
| CN112010900B (en) * | 2020-08-12 | 2023-11-24 | 湖北省兴发磷化工研究院有限公司 | Preparation method of high-purity reactive flame retardant THPO |
| CN112221180A (en) * | 2020-10-20 | 2021-01-15 | 江苏索普化工股份有限公司 | Secondary molecular distillation vacuum system dehydration and organic matter treatment process for ionic liquid solution |
| CN114044755A (en) * | 2021-10-25 | 2022-02-15 | 惠州市绿色能源与新材料研究院 | Efficient ionic liquid decoloring and purifying method |
| CN114044755B (en) * | 2021-10-25 | 2023-09-22 | 惠州市绿色能源与新材料研究院 | Decolorization and purification method for ionic liquid |
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