TW201936998A - Fluorinated liquid regeneration method and regeneration apparatus using such method - Google Patents
Fluorinated liquid regeneration method and regeneration apparatus using such method Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 349
- 238000011069 regeneration method Methods 0.000 title claims abstract description 99
- 230000008929 regeneration Effects 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000008346 aqueous phase Substances 0.000 claims abstract description 16
- 239000002798 polar solvent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000012459 cleaning agent Substances 0.000 claims description 55
- 238000004821 distillation Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- -1 cyclic amidine Chemical class 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- USSXDYGXZRVYHU-UHFFFAOYSA-N N-methyl-N-(2-methylprop-1-enyl)formamide Chemical compound CC(C)=CN(C=O)C USSXDYGXZRVYHU-UHFFFAOYSA-N 0.000 claims 1
- 239000003586 protic polar solvent Substances 0.000 claims 1
- 239000003599 detergent Substances 0.000 abstract description 50
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 238000005406 washing Methods 0.000 description 25
- 239000012153 distilled water Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical group O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02803—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
- C23G5/02861—Oxygen-containing compounds
- C23G5/02877—Ethers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0419—Solvent extraction of solutions which are liquid in combination with an electric or magnetic field or with vibrations
- B01D11/0423—Applying ultrasound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0446—Juxtaposition of mixers-settlers
- B01D11/0457—Juxtaposition of mixers-settlers comprising rotating mechanisms, e.g. mixers, mixing pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0446—Juxtaposition of mixers-settlers
- B01D11/0469—Juxtaposition of mixers-settlers with gas agitation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/48—Regeneration of cleaning solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Vapour Deposition (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Electroluminescent Light Sources (AREA)
- Extraction Or Liquid Replacement (AREA)
- Detergent Compositions (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
本揭露係關於氟化液體再生方法及使用該方法之再生設備。 This disclosure relates to a method for regenerating a fluorinated liquid and a regeneration apparatus using the same.
例如，製造有機EL顯示器(在下文中有時稱為「OLED」)的方法包括經由金屬遮罩在諸如玻璃的基材上氣相沉積RGB三色顏料以形成有機發光層的步驟。由於金屬遮罩係昂貴的部件，故透過用N-甲基-2-吡咯啶酮(在下文中有時稱為「NMP」)溶液洗滌，然後用氟化液體沖洗的步驟及乾燥步驟來再使用金屬遮罩。 For example, a method of manufacturing an organic EL display (hereinafter sometimes referred to as "OLED") includes a step of vapor-depositing an RGB tri-color pigment on a substrate such as glass via a metal mask to form an organic light emitting layer. Since the metal mask is an expensive part, it is reused by a step of washing with a solution of N-methyl-2-pyrrolidone (hereinafter sometimes referred to as "NMP"), and then rinsing with a fluorinated liquid and a drying step. Metal mask.
專利文獻1(JP 2006-313753 A)描述了一種洗滌方法，其中在製造低分子量有機EL元件之真空氣相沉積步驟中使用的金屬遮罩係藉由使用含有諸如N-甲基-2-吡咯啶酮的非質子極性溶劑之洗滌液組成物浸漬或噴水進行洗滌，然後用氫氟醚沖洗。 Patent Document 1 (JP 2006-313753 A) describes a washing method in which a metal mask used in a vacuum vapor deposition step of manufacturing a low molecular weight organic EL element is made by using The aprotic polar solvent washing liquid composition of pyridone is immersed or sprayed with water for washing, and then washed with hydrofluoroether.
專利文獻2(JP 07-076787 A)描述了一種金屬清潔劑再生設備，其包括：使用NMP作為金屬清潔劑之洗滌設備，以及經組態以從洗滌後獲得之NMP洗滌液移除污染物且將NMP洗滌液再循環至 洗滌設備之再生設備；其中設置於再生設備內部之過濾器介質係至少含有聚丙烯之粒狀過濾器介質，且在NMP中係漂浮的。 Patent Document 2 (JP 07-076787 A) describes a metal cleaning agent regeneration device including a washing device using NMP as a metal cleaning agent, and a configuration configured to remove contaminants from the NMP washing liquid obtained after washing, and Recycle NMP Wash Solution to Regeneration equipment of washing equipment; the filter medium set inside the regeneration equipment is a granular filter medium containing at least polypropylene, and is floating in NMP.
專利文獻3(JP 2008-163400 A)描述了一種洗滌系統，其包括：洗滌槽，該洗滌槽經組態以容納洗滌液，該洗滌液包括一或多種選自(1a)烴、(1b)乙二醇醚、及(1c)酯之類型作為主要組分，將待洗滌之物品浸入其中；沖洗液槽，該沖洗液槽經組態以容納沖洗液，該沖洗液包括一或多種選自(2a)氫氟烴及(2b)氫氟醚之類型作為主要組分，將待洗滌之物品浸入其中；蒸氣槽，該蒸氣槽經組態以容納沖洗液且產生沖洗液之蒸氣；及包括蒸餾器之再生單元。 Patent Document 3 (JP 2008-163400 A) describes a washing system including a washing tank configured to receive a washing liquid, the washing liquid including one or more selected from (1a) a hydrocarbon, (1b) Types of glycol ethers and (1c) esters are used as the main component to immerse the items to be washed therein; a washing liquid tank configured to hold a washing liquid, the washing liquid including one or more selected from (2a) types of hydrofluorocarbons and (2b) hydrofluoroethers as the main component, immersing the items to be washed therein; a steam tank configured to hold a washing liquid and generate steam of the washing liquid; and include Regeneration unit of still.
專利文獻1：JP 2006-313753 A Patent Document 1: JP 2006-313753 A
專利文獻2：JP 07-076787 A Patent Document 2: JP 07-076787 A
專利文獻3：JP 2008-163400 A Patent Document 3: JP 2008-163400 A
隨著洗滌及沖洗金屬遮罩的次數增加，沖洗槽中清潔劑的污染率增加。因此，沖洗槽最終被清潔劑污染，且因此需要定期更換沖洗液。然而，由於用作沖洗液之氟化液體亦係昂貴的溶劑，故氟化液體通常係藉由使用蒸餾構件從污染的沖洗液回收，然後再使用。然而，在目前最佳技術中，由於可藉由此類蒸餾構件回收之氟化液體的量非常低，故大部分氟化液體被丟棄。 As the number of times the metal mask is washed and rinsed increases, the contamination rate of the detergent in the rinse tank increases. Therefore, the washing tank is finally contaminated with the cleaning agent, and therefore the washing liquid needs to be changed regularly. However, since the fluorinated liquid used as a rinsing liquid is also an expensive solvent, the fluorinated liquid is usually recovered from the contaminated rinsing liquid by using a distillation member, and then reused. However, in the current best technology, most of the fluorinated liquid is discarded because the amount of fluorinated liquid that can be recovered by such a distillation component is very low.
本揭露提供對被清潔劑污染之氟化液體具有優異的再生效率的氟化液體再生方法，以及使用該方法之再生設備。 The present disclosure provides a fluorinated liquid regeneration method having excellent regeneration efficiency for a fluorinated liquid contaminated with a detergent, and a regeneration apparatus using the same.
根據本揭露之一實施例，提供一種氟化液體再生方法，其包括下列步驟：使被清潔劑污染之氟化液體與水接觸，以使位於上層之水相之清潔劑的濃度小於約80質量%；及將該水接觸後獲得之混合液體分離成位於該上層之水相及位於下層之氟化液體的兩種液體，然後移除該上層之液體並收集該下層之液體；其中該清潔劑係溶解於該氟化液體中之非質子極性溶劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。 According to an embodiment of the present disclosure, there is provided a method for regenerating a fluorinated liquid, which includes the following steps: contacting the fluorinated liquid contaminated by the cleaning agent with water, so that the concentration of the cleaning agent in the upper aqueous phase is less than about 80 mass %; And the mixed liquid obtained after contacting the water is separated into two liquids in the water phase in the upper layer and the fluorinated liquid in the lower layer, and then the liquid in the upper layer is removed and the liquid in the lower layer is collected; wherein the cleaning agent It is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof.
根據本揭露之另一實施例，提供一種使用藉由使用上述再生方法再生之氟化液體作為用於有機EL顯示器製造設備中之部件的沖洗液的方法。 According to another embodiment of the present disclosure, there is provided a method of using a fluorinated liquid regenerated by using the above-mentioned regeneration method as a rinsing liquid for a component in an organic EL display manufacturing apparatus.
根據本揭露之又一實施例，提供一種氟化液體再生設備，其包括：用於使被清潔劑污染之氟化液體與水接觸以使位於上層之水相之清潔劑的濃度小於約80質量%的構件；及用於將該水接觸後獲得之混合液體分離成位於該上層之水相及位於下層之氟化液體的兩種液體，然後移除該上層之液體並收集該下層之液體的構件；其中該清潔劑係溶解於該氟化液體中之非質子極性溶劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。 According to yet another embodiment of the present disclosure, a fluorinated liquid regeneration apparatus is provided, which includes: contacting a fluorinated liquid contaminated with a cleaning agent with water so that the concentration of the cleaning agent in an aqueous phase located on the upper layer is less than about 80 mass % Of the components; and the liquid used to separate the mixed liquid obtained after contacting the water into the liquid phase in the upper layer and the fluorinated liquid in the lower layer, and then remove the liquid in the upper layer and collect the liquid in the lower layer Component; wherein the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof.
本揭露之氟化液體再生方法及再生設備可改善被清潔劑污染之氟化液體的再生效率。 The disclosed fluorinated liquid regeneration method and regeneration equipment can improve the regeneration efficiency of the fluorinated liquid contaminated by cleaning agents.
此外，在本揭露之幾個實例中，藉由實現充分的分離，可以省去額外的蒸餾步驟及加熱步驟。在此等實例中，由於該過程係在室溫下完成，故能量效率更高，且不需要額外的操作。 In addition, in the examples of the present disclosure, by achieving sufficient separation, an additional distillation step and a heating step can be omitted. In these examples, since the process is completed at room temperature, it is more energy efficient and requires no additional operations.
以上描述不應被解讀為表示已經揭示了本揭露之所有實施例及與本揭露相關之所有優點。 The above description should not be interpreted as indicating that all embodiments of the present disclosure and all advantages related to the present disclosure have been disclosed.
圖1係顯示在使用NMP作為清潔劑及使用根據本揭露之實施例的氟化液體再生方法時，水中之清潔劑濃度與各種氟化液體中之各者的純度及產量之間的關係的曲線圖。 FIG. 1 is a graph showing the relationship between the concentration of the cleaning agent in water and the purity and yield of each of various fluorinated liquids when NMP is used as the cleaning agent and the fluorinated liquid regeneration method according to the embodiment of the present disclosure is used. Illustration.
圖2係繪示基於僅使用蒸餾之氟化液體再生方法及根據本揭露之實施例的氟化液體再生方法的再生後獲得之氟化液體的丟棄量的關係的圖。 FIG. 2 is a graph showing the relationship between the discarded amount of the fluorinated liquid obtained after regeneration based on the fluorinated liquid regeneration method using only distillation and the fluorinated liquid regeneration method according to the embodiment of the disclosure.
本揭露之第一實施例中之氟化液體再生方法包括下列步驟：使被清潔劑污染之氟化液體與水接觸，以使位於上層之水相之清潔劑的濃度小於約80質量%；及將水接觸後獲得之混合液體分離成位於上層之水相及位於下層之氟化液體的兩種液體，然後移除上層之液體並收集下層之液體；其中該清潔劑係溶解於該氟化液體中之非質子極性溶 劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。本揭露之再生方法可簡單地藉由使規定量的水與含有特定清潔劑及特定氟化液體之混合系統接觸而以高產量(產率)再生具有高純度之氟化液體。 The fluorinated liquid regeneration method in the first embodiment of the present disclosure includes the following steps: contacting the fluorinated liquid contaminated with the cleaning agent with water, so that the concentration of the cleaning agent in the upper water phase is less than about 80% by mass; and The mixed liquid obtained after water contact is separated into two liquids in an upper water phase and a fluorinated liquid in a lower layer, and then the upper liquid is removed and the lower liquid is collected; wherein the cleaning agent is dissolved in the fluorinated liquid Aprotic polarity Agent, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof. The regeneration method of the present disclosure can simply regenerate a fluorinated liquid with high purity by contacting a prescribed amount of water with a mixed system containing a specific detergent and a specific fluorinated liquid at a high yield (yield).
第一實施例中之氟化液體再生方法中的非質子極性溶劑可以係基於環狀醯胺之溶劑、基於胺之溶劑、基於乙二醇醚之溶劑、丙酮、二甲基亞碸、二甲基甲醯胺、或其混合溶劑。此類非質子極性溶劑的組合可進一步改善氟化液體再生效率。其中，當第一實施例中之氟化液體再生方法中的非質子極性溶劑係基於環狀醯胺之溶劑時，可進一步改善氟化液體再生效率。在本文中，再生效率係指由再生之氟化液體的純度、產量等判定的效率。當氟化液體可以高純度及高產量再生時，再生效率被認為係優異的。 The aprotic polar solvent in the fluorinated liquid regeneration method in the first embodiment may be a cyclic amidine-based solvent, an amine-based solvent, a glycol ether-based solvent, acetone, dimethylmethylene, and dimethyl Methylformamide, or a mixed solvent thereof. The combination of such aprotic polar solvents can further improve the efficiency of fluorinated liquid regeneration. Among them, when the aprotic polar solvent in the fluorinated liquid regeneration method in the first embodiment is a cyclic amidine-based solvent, the efficiency of fluorinated liquid regeneration can be further improved. In this context, regeneration efficiency refers to the efficiency judged by the purity, yield, etc. of the regenerated fluorinated liquid. When the fluorinated liquid can be regenerated with high purity and high yield, the regeneration efficiency is considered to be excellent.
在第一實施例中之氟化液體再生方法中，所收集的下層液體中氟化液體的純度可不小於約95%。 In the fluorinated liquid regeneration method in the first embodiment, the purity of the fluorinated liquid in the collected lower layer liquid may be not less than about 95%.
第一實施例中之氟化液體再生方法可進一步包括在收集下層之液體的步驟之後蒸餾下層之液體的步驟。進一步應用蒸餾步驟，且因此，可再生具有更高純度之氟化液體。 The fluorinated liquid regeneration method in the first embodiment may further include a step of distilling the liquid in the lower layer after the step of collecting the liquid in the lower layer. A distillation step is further applied, and therefore, a fluorinated liquid having a higher purity can be regenerated.
在第一實施例中之氟化液體再生方法中，當使用蒸餾步驟時，藉由蒸餾收集之液體中氟化液體的純度可不小於約99.0%。 In the fluorinated liquid regeneration method in the first embodiment, when a distillation step is used, the purity of the fluorinated liquid in the liquid collected by distillation may be not less than about 99.0%.
本揭露之第二實施例中之作為用於有機EL顯示器製造設備中之部件的沖洗液的使用方法可使用藉由使用第一實施例中之氟化液體再生方法再生的氟化液體。部件之實例可包括金屬遮罩及防沉積片材。在第一實施例中之氟化液體再生方法中，由於與僅使用蒸餾之習 知再生方法相比，待丟棄之氟化液體的量可大大減少，故使用藉由第一實施例之再生方法獲得的氟化液體的第二實施例中之方法可進一步降低有機EL顯示器之製造成本。 The method of using the rinsing liquid as a component in an organic EL display manufacturing apparatus in the second embodiment of the present disclosure may use a fluorinated liquid regenerated by using the fluorinated liquid regeneration method in the first embodiment. Examples of components may include metal masks and anti-deposition sheets. In the fluorinated liquid regeneration method in the first embodiment, since the Compared with the known regeneration method, the amount of fluorinated liquid to be discarded can be greatly reduced, so the method of the second embodiment using the fluorinated liquid obtained by the regeneration method of the first embodiment can further reduce the manufacturing of the organic EL display. cost.
本揭露之第三實施例中之氟化液體再生設備包括用於使被清潔劑污染之氟化液體與水接觸以使位於上層之水相之清潔劑的濃度小於約80質量%的構件；及用於將該水接觸後獲得之混合液體分離成位於該上層之水相及位於下層之氟化液體的兩種液體，然後移除該上層之液體並收集該下層之液體的構件；其中該清潔劑係溶解於該氟化液體中之非質子極性溶劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。本揭露之再生設備可在含有特定清潔劑及特定氟化液體之混合系統中以高產量(產率)再生具有高純度之氟化液體。 The fluorinated liquid regeneration apparatus in the third embodiment of the present disclosure includes a means for contacting the fluorinated liquid contaminated with the cleaning agent with water so that the concentration of the cleaning agent in the upper water phase is less than about 80% by mass; and A component for separating the mixed liquid obtained after contacting the water into two liquids in an upper water phase and a fluorinated liquid in a lower layer, and then removing the upper liquid and collecting the lower liquid; and the cleaning The agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. The regeneration equipment disclosed in this disclosure can regenerate a fluorinated liquid with high purity in a high-output (yield) in a mixed system containing a specific detergent and a specific fluorinated liquid.
第三實施例中之氟化液體再生設備可進一步包括在用於收集下層之液體的構件之後的用於蒸餾下層之液體的構件。進一步應用蒸餾步驟，且因此，可再生具有更高純度之氟化液體。 The fluorinated liquid regeneration apparatus in the third embodiment may further include a means for distilling the liquid in the lower layer after the means for collecting the liquid in the lower layer. A distillation step is further applied, and therefore, a fluorinated liquid having a higher purity can be regenerated.
出於舉例說明的目的，下面將進一步詳細描述本揭露之典型實施例，但本揭露不限於此等實施例。 For the purpose of illustration, the exemplary embodiments of the present disclosure will be described in further detail below, but the present disclosure is not limited to these embodiments.
本揭露之實施例的氟化液體再生方法包括下列步驟：使被清潔劑污染之氟化液體與水接觸，以使位於上層之水相之清潔劑的濃度小於約80質量%(在下文中有時稱為「水接觸步驟」)；及將水接觸後獲得之混合液體分離成位於上層之水相及位於下層之氟化液體的兩 種液體，然後移除上層之液體並收集下層之液體(在下文中有時稱為「分離及收集步驟」)；其中該清潔劑係溶解於該氟化液體中之非質子極性溶劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。 The fluorinated liquid regeneration method according to the embodiment of the present disclosure includes the following steps: contacting the fluorinated liquid contaminated with the cleaning agent with water, so that the concentration of the cleaning agent in the upper water phase is less than about 80% by mass (sometimes hereinafter (Referred to as a "water contact step"); and separating the mixed liquid obtained after contacting the water into two phases of an aqueous phase in the upper layer and a fluorinated liquid in the lower layer A liquid, and then remove the upper liquid and collect the lower liquid (sometimes referred to as "separation and collection steps" hereinafter); wherein the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorine Chemical fluid system hydrofluoroether, hydrofluoroolefin, or a mixture thereof.
在本揭露之氟化液體再生方法中可為污染物之清潔劑係用於洗滌各種部件之清潔劑。清潔劑之實例包括用於洗滌有機EL顯示器製造設備中之各種部件，諸如金屬遮罩及防沉積片材的清潔劑。此種清潔劑可為任何清潔劑，只要清潔劑係溶解於氟化液體中之非質子極性溶劑。清潔劑之實例包括(但不限於)基於環狀醯胺之溶劑、基於胺之溶劑、基於乙二醇醚之溶劑、丙酮、二甲基亞碸、二甲基甲醯胺或其混合物。從洗滌金屬遮罩或防沉積片材之能力的角度來看，較佳使用基於環狀醯胺之溶劑，且在基於環狀醯胺之溶劑中，更佳的是稱為N-烷基吡咯啶酮溶劑或γ-內醯胺溶劑的溶劑，諸如N-甲基-2-吡咯啶酮(NMP)及N-丁基-2-吡咯啶酮(NBP)。作為非質子極性溶劑，可以單獨使用此等溶劑中之一者，或者可以組合使用此等溶劑中之二或更多者。只要使用上述清潔劑，氟化液體就可以藉由本揭露之再生方法有效地再生。清潔劑可包括除上述清潔劑之外的清潔劑，只要此種清潔劑不妨礙氟化液體之再生效率，但從再生效率等的角度來看，清潔劑較佳不包括其他清潔劑。 Detergents that can be contaminants in the fluorinated liquid regeneration method of the present disclosure are cleaners used to wash various components. Examples of the cleaning agent include cleaning agents for washing various parts in an organic EL display manufacturing apparatus, such as a metal mask and an anti-deposition sheet. Such a cleaning agent may be any cleaning agent as long as the cleaning agent is an aprotic polar solvent dissolved in a fluorinated liquid. Examples of cleaning agents include, but are not limited to, cyclic amidine-based solvents, amine-based solvents, glycol ether-based solvents, acetone, dimethylmethane, dimethylformamide, or mixtures thereof. From the viewpoint of the ability to wash a metal mask or an anti-deposition sheet, a cyclic amidine-based solvent is preferably used, and among the cyclic amidine-based solvents, it is more preferably called N-alkylpyrrole Solvents of pyrimidone solvents or γ-lactamamine solvents such as N-methyl-2-pyrrolidone (NMP) and N-butyl-2-pyrrolidone (NBP). As the aprotic polar solvent, one of these solvents may be used alone, or two or more of these solvents may be used in combination. As long as the cleaning agent is used, the fluorinated liquid can be efficiently regenerated by the regeneration method disclosed in this disclosure. The cleaning agent may include cleaning agents other than the above-mentioned cleaning agents, as long as the cleaning agent does not hinder the regeneration efficiency of the fluorinated liquid, but from the perspective of the regeneration efficiency and the like, the cleaning agent preferably does not include other cleaning agents.
從應用下述蒸餾步驟等的角度來看，清潔劑之沸點較佳不低於約55℃，不低於約100℃，不低於約150℃，不低於約200℃，或不低於約250℃。 From the viewpoint of applying the following distillation steps, etc., the boiling point of the cleaning agent is preferably not lower than about 55 ° C, not lower than about 100 ° C, not lower than about 150 ° C, not lower than about 200 ° C, or not lower than About 250 ° C.
可藉由本揭露之氟化液體再生方法再生的氟化液體的實例可包括氫氟醚(在下文中有時縮寫為「HFE」)、氫氟烯烴(在下文中有時縮寫為「HFO」)、或其混合物。氟化液體亦可包括除上述氟化液體之外的氟化液體(例如，氫氯氟烴及氫氟烴)，只要此種氟化液體不妨礙再生效率，但從再生效率等的角度來看，氟化液體較佳不包括其他氟化液體。 Examples of the fluorinated liquid that can be regenerated by the fluorinated liquid regeneration method of the present disclosure may include hydrofluoroether (hereinafter sometimes abbreviated as "HFE"), hydrofluoroolefin (hereinafter sometimes abbreviated as "HFO"), or Its mixture. The fluorinated liquid may also include fluorinated liquids (for example, hydrochlorofluorocarbons and hydrofluorocarbons) other than the above-mentioned fluorinated liquids, as long as such fluorinated liquids do not hinder the regeneration efficiency, but from the perspective of the regeneration efficiency, etc. The fluorinated liquid preferably does not include other fluorinated liquids.
從應用下述蒸餾步驟等的角度來看，氟化液體之沸點較佳不低於約30℃，不低於約55℃，不低於約60℃，或不低於約75℃，且不高於約150℃，不高於約100℃，或不高於約80℃。 From the viewpoint of applying the following distillation steps, etc., the boiling point of the fluorinated liquid is preferably not less than about 30 ° C, not less than about 55 ° C, not less than about 60 ° C, or not less than about 75 ° C, and not less than Above about 150 ° C, not higher than about 100 ° C, or not higher than about 80 ° C.
在上述氟化液體中，從再生效率等的角度來看，較佳使用氫氟醚。氫氟醚係在氫氟烴的碳原子之間含有醚鍵結氧原子之化合物。一個氫氟醚分子中存在的醚鍵結氧原子的數量可以係1個，或者可以係2個或更多個。從使得易於用作溶劑之沸點的角度來看以及從穩定性等角度來看，一個氫氟醚分子中存在的醚鍵結氧原子的數量較佳為1個或2個，且更佳為1個。氫氟醚之分子結構可以係鏈，且可以係直鏈 或支鏈，但從再生效率等角度來看，較佳係直鏈。氫氟醚之實例可包括(但不限於)隔離的氫氟醚，諸如C4F9OCH3、C4F9OCH2CH3、C5F11OCH3、C5F11OCH2CH3、C6F13OCH3、C6F13OCH2CH3、C7F15OCH3、C7F15OCH2CH3、C8F17OCH3、C8F17OCH2CH3、C9F19OCH3、C9F19OCH2CH3、C10F21OCH3、及C10F21OCH2CH3；及氫氟醚，諸如CF3CH2OCF2CF2H、CF3CHFOCH2CF3、CF3CH2OCF2CFHCF3、CHF2CF2CH2OCF2CF2H、C3F7OC3F6OCFHCF3、CF3CF(CF3)CF(OCH3)CF2CF3、CF3CF(CF3)CF(OC2H5)CF2CF3、CF2(OCH2CF3)CF2H、CF2(OCH2CF3)CFHCF3、CF2(OCH2CF2CF2H)CF2H、及CF2(OCH2CF2CF2H)CFHCF3。其中，由於使用隔離的氫氟醚可簡單地藉由使隔離的氫氟醚與水接觸而實現不小於約97%、不小於約98%、或不小於約99%之高純度，故隔離的氫氟醚係特別較佳之氟化液體。其中，特別較佳的隔離的氫氟醚係C4F9OCH3及C4F9OCH2CH3。在本文中，「隔離的(segregated)」係指醚鍵將氧原子夾在中間之結構，其中一個醚鍵完全氟化，且另一個由碳及氫構成。作為氫氟醚，可以單獨使用此等氫氟醚中之一者，或者可以組合使用此等氫氟醚中之二或更多者。 Among the above fluorinated liquids, hydrofluoroether is preferably used from the viewpoint of regeneration efficiency and the like. Hydrofluoroethers are compounds containing ether-bonded oxygen atoms between the carbon atoms of the hydrofluorocarbon. The number of ether-bonded oxygen atoms present in one hydrofluoroether molecule may be one, or may be two or more. From the viewpoint of making it easy to be used as a boiling point of a solvent and from the viewpoint of stability and the like, the number of ether-bonded oxygen atoms present in one hydrofluoroether molecule is preferably 1 or 2, and more preferably 1 Each. The molecular structure of hydrofluoroether can be chained, and can be linear or branched, but from the perspective of regeneration efficiency, it is preferably linear. Examples of hydrofluoroethers may include, but are not limited to, isolated hydrofluoroethers, such as C 4 F 9 OCH 3 , C 4 F 9 OCH 2 CH 3 , C 5 F 11 OCH 3 , C 5 F 11 OCH 2 CH 3 , C 6 F 13 OCH 3 , C 6 F 13 OCH 2 CH 3 , C 7 F 15 OCH 3 , C 7 F 15 OCH 2 CH 3 , C 8 F 17 OCH 3 , C 8 F 17 OCH 2 CH 3 , C 9 F 19 OCH 3 , C 9 F 19 OCH 2 CH 3 , C 10 F 21 OCH 3 , and C 10 F 21 OCH 2 CH 3 ; and hydrofluoroethers such as CF 3 CH 2 OCF 2 CF 2 H, CF 3 CHFOCH 2 CF 3 , CF 3 CH 2 OCF 2 CFHCF 3 , CHF 2 CF 2 CH 2 OCF 2 CF 2 H, C 3 F 7 OC 3 F 6 OCFHCF 3 , CF 3 CF (CF 3 ) CF (OCH 3 ) CF 2 CF 3 , CF 3 CF (CF 3 ) CF (OC 2 H 5 ) CF 2 CF 3 , CF 2 (OCH 2 CF 3 ) CF 2 H, CF 2 (OCH 2 CF 3 ) CFHCF 3 , CF 2 (OCH 2 CF 2 CF 2 H) CF 2 H and CF 2 (OCH 2 CF 2 CF 2 H) CFHCF 3 . Among them, since the use of isolated hydrofluoroether can simply achieve high purity of not less than about 97%, not less than about 98%, or not less than about 99% by contacting the isolated hydrofluoroether with water, the isolated Hydrofluoroether is a particularly preferred fluorinated liquid. Among them, particularly preferred isolated hydrofluoroethers are C 4 F 9 OCH 3 and C 4 F 9 OCH 2 CH 3 . In this context, "segregated" refers to a structure in which an oxygen bond sandwiches an oxygen atom, one of which is completely fluorinated, and the other is composed of carbon and hydrogen. As the hydrofluoroether, one of these hydrofluoroethers may be used alone, or two or more of these hydrofluoroethers may be used in combination.
氫氟烯烴係指烯烴中存在的一個或二或更多個氫原子被氟原子取代之化合物。氫氟烯烴中存在的氟原子的數量沒有特別限制， 但可不小於1個或不小於2個且不大於10個或不大於6個。氫氟烯烴可以係E型(反式)及Z型(順式)中之任一者。氫氟烯烴可以係氫氯氟烯烴(HCFO)。氫氯氟烯烴係指烯烴中存在的一個或二或更多個氫原子被氟原子取代且烯烴中存在的一個或二或更多個其他氫原子被氯原子取代之化合物。氫氯氟烯烴中存在的氯原子的數量沒有特別限制，但可不小於1個且不大於5個或不大於3個。沒有氯原子之氫氟烯烴的實例包括CF3-CH=CH2、CF3-CF=CH2、CHF2-CH=CHF、CHF2-CF=CH2、CH2F-CH=CF2、CH2F-CF=CHF、CH3-CF=CF2、CF3-CH=CH-CF3、CF3-CH=CF-CH3、CF3-CF=CH-CH3、CF3-CH=CH-CH2F、CHF2-CF=CF-CH3、CHF2-CF=CH-CH2F、CHF2-CH=CF-CH2F、CHF2-CH=CH-CHF2、CH2F-CF=CF-CH2F、CH2F-CH=CH-CF3、CH2F-CF=CH-CHF2、CF3-CH2-CF=CH2、CF3-CHF-CH=CH2、CF3-CH2-CH=CHF、CHF2-CF2-CH=CH2、CHF2-CHF-CF=CH2、CHF2-CHF-CH=CHF、CH2F-CF2-CF=CH2、CH2F-CF2-CH=CHF、CH2F-CHF-CF=CHF、CH2F-CHF-CF=CF2、CH2F-CH2-CF=CF2、CH3-CF2-CF=CHF、及CH3-CF2-CH=CF2。具有氯原子之氫氟烯烴(即，氫氯氟烯烴)的實例包括CF3-CH=CHCl、CHF2-CF=CHCl、CHF2-CH=CFCl、CHF2-CCl=CHF、CH2F-CCl=CF2、CHFCl-CF=CHF、CH2Cl-CF=CF2、及CF3-CCl=CH2。特別較佳的具有氯原子之氫氟烯烴係CF3-CH=CHCl。作為氫氟烯烴(此處亦包括氫氯氟烯烴)，可以單獨使用此等氫氟烯烴中之一者，或者可以組合使用此等氫氟烯烴中之二或更多者。 A hydrofluoroolefin refers to a compound in which one or two or more hydrogen atoms present in an olefin are replaced with fluorine atoms. The number of fluorine atoms present in the hydrofluoroolefin is not particularly limited, but may be not less than 1 or not less than 2 and not more than 10 or not more than 6. The hydrofluoroolefin may be either an E-type (trans) or a Z-type (cis). The hydrofluoroolefin may be a hydrochlorofluoroolefin (HCFO). A hydrochlorofluoroolefin refers to a compound in which one or two or more hydrogen atoms present in an olefin are replaced with fluorine atoms and one or two or more other hydrogen atoms present in the olefin are replaced with chlorine atoms. The number of chlorine atoms present in the hydrochlorofluoroolefin is not particularly limited, but may be not less than one and not more than five or not more than three. Examples of hydrofluoroolefins without a chlorine atom include CF 3 -CH = CH 2 , CF 3 -CF = CH 2 , CHF 2 -CH = CHF, CHF 2 -CF = CH 2 , CH 2 F-CH = CF 2 , CH 2 F-CF = CHF, CH 3 -CF = CF 2 , CF 3 -CH = CH-CF 3 , CF 3 -CH = CF-CH 3 , CF 3 -CF = CH-CH 3 , CF 3 -CH = CH-CH 2 F, CHF 2 -CF = CF-CH 3 , CHF 2 -CF = CH-CH 2 F, CHF 2 -CH = CF-CH 2 F, CHF 2 -CH = CH-CHF 2 , CH 2 F-CF = CF-CH 2 F, CH 2 F-CH = CH-CF 3 , CH 2 F-CF = CH-CHF 2 , CF 3 -CH 2 -CF = CH 2 , CF 3 -CHF-CH = CH 2 , CF 3 -CH 2 -CH = CHF, CHF 2 -CF 2 -CH = CH 2 , CHF 2 -CHF-CF = CH 2 , CHF 2 -CHF-CH = CHF, CH 2 F-CF 2 -CF = CH 2 , CH 2 F-CF 2 -CH = CHF, CH 2 F-CHF-CF = CHF, CH 2 F-CHF-CF = CF 2 , CH 2 F-CH 2 -CF = CF 2 , CH 3 -CF 2 -CF = CHF, and CH 3 -CF 2 -CH = CF 2 . Examples of hydrofluoroolefins having a chlorine atom (ie, hydrochlorofluoroolefins) include CF 3 -CH = CHCl, CHF 2 -CF = CHCl, CHF 2 -CH = CFCl, CHF2-CCl = CHF, CH 2 F-CCl = CF 2 , CHFCl-CF = CHF, CH 2 Cl-CF = CF 2 , and CF 3 -CCl = CH 2 . Particularly preferred is a hydrofluoroolefin-based CF 3 -CH = CHCl having a chlorine atom. As the hydrofluoroolefin (also including hydrochlorofluoroolefin), one of these hydrofluoroolefins may be used alone, or two or more of these hydrofluoroolefins may be used in combination.
本揭露之氟化液體再生方法中的水可以係任何水。可使用之水的實例包括(但不限於)自來水、蒸餾水、及離子交換水。 The water in the fluorinated liquid regeneration method of the present disclosure may be any water. Examples of water that can be used include, but are not limited to, tap water, distilled water, and ion-exchanged water.
本揭露之氟化液體再生方法包括使被清潔劑污染之氟化液體與水接觸，以使位於上層之水相之清潔劑的濃度小於約80質量%的步驟(水接觸步驟)。從再生效率的角度來看，在水接觸步驟中位於上層之水相之清潔劑的濃度可以在小於約75質量%的範圍或者小於約70質量%的範圍內。清潔劑之濃度的下限值沒有特別限制，但可(例如)在大於約10質量%的範圍、大於約15質量%的範圍、或大於約20質量%的範圍內。在本文中，位於上層之水相中之清潔劑的濃度可藉由(例如)從上層之混合液體萃取清潔劑組分並藉由氣相層析及微量水分測量設備進行分析來測量。 The fluorinated liquid regeneration method disclosed in this disclosure includes a step (water contact step) of contacting the fluorinated liquid contaminated with the cleaning agent with water so that the concentration of the cleaning agent in the aqueous phase in the upper layer is less than about 80% by mass. From the viewpoint of the regeneration efficiency, the concentration of the cleaning agent in the upper water phase in the water contacting step may be in a range of less than about 75% by mass or in a range of less than about 70% by mass. The lower limit value of the concentration of the detergent is not particularly limited, but may be, for example, in a range of greater than about 10% by mass, a range of greater than about 15% by mass, or a range of greater than about 20% by mass. Herein, the concentration of the detergent in the upper water phase can be measured by, for example, extracting the detergent components from the upper mixed liquid and analyzing by gas chromatography and trace moisture measurement equipment.
使被清潔劑污染之氟化液體與水接觸之方法的實例包括(但不限於)下文描述之(1)至(7)的方法。可以單獨使用此等方法中之一者，或者可以組合使用此等方法中之二或更多者，且(1)至(7)之方法的一部分可以適當地組合進行。例如，(3)、(6)、或(7)中描述之使用搖動、攪拌棒等的物理攪拌方法、使用空氣的攪拌方法、或使用超音波等的攪拌方法可以應用於(1)或(2)的方法。 Examples of a method of contacting the fluorinated liquid contaminated with the cleaning agent with water include, but are not limited to, the methods (1) to (7) described below. One of these methods may be used alone, or two or more of these methods may be used in combination, and a part of the methods of (1) to (7) may be appropriately combined. For example, the physical stirring method using shaking, a stirring rod, or the like described in (3), (6), or (7), the stirring method using air, or the stirring method using ultrasonic waves can be applied to (1) or ( 2).
(1)將被清潔劑污染之氟化液體從容器上方滴落至含有水之容器中的方法。 (1) A method of dripping a fluorinated liquid contaminated with a cleaning agent from above a container into a container containing water.
(2)將水從容器下方添加至含有被清潔劑污染之氟化液體的容器中的方法。 (2) A method of adding water from below the container to a container containing a fluorinated liquid contaminated with a cleaning agent.
(3)藉由使用搖動或使用攪拌棒或攪拌葉片物理攪拌含有清潔劑、氟化液體、及水之混合液體之容器的方法。 (3) A method of physically stirring a container containing a mixed liquid of a detergent, a fluorinated liquid, and water by using shaking or using a stirring rod or a stirring blade.
(4)在含有清潔劑、氟化液體、及水之混合液體之容器中，在混合液體已經被分成兩層的狀態下，用管子等連接上層及下層，並藉由重力或泵等將上層液體轉移至下層的方法。 (4) In a container containing a mixture of detergent, fluorinated liquid, and water, in the state where the mixed liquid has been separated into two layers, connect the upper layer and the lower layer with a pipe or the like, and connect the upper layer by gravity or a pump, etc. Method for transferring liquid to the lower layer.
(5)在含有清潔劑、氟化液體、及水之混合液體之容器中，在混合液體已經被分成兩層的狀態下，用管子等連接上層及下層，並藉由重力或泵等將下層液體轉移至上層的方法。 (5) In a container containing a mixture of detergent, fluorinated liquid, and water, in a state where the mixed liquid has been separated into two layers, connect the upper layer and the lower layer with a pipe or the like, and connect the lower layer by gravity or a pump, etc. Method for transferring liquid to the upper layer.
(6)在含有清潔劑、氟化液體、及水之混合液體之容器中，在混合液體已經被分成兩層的狀態下，向容器中鼓泡通入氣體，諸如空氣以使混合液體混合的方法。 (6) In a container containing a mixed liquid of detergent, fluorinated liquid, and water, in a state where the mixed liquid has been separated into two layers, a gas such as air is bubbled into the container to mix the mixed liquid method.
(7)在含有清潔劑、氟化液體、及水之混合液體之容器中，在混合液體已經被分成兩層的狀態下，向容器中施加超音波以使混合液體混合的方法。 (7) In a container containing a mixed liquid of a detergent, a fluorinated liquid, and water, in a state where the mixed liquid has been separated into two layers, an ultrasonic wave is applied to the container to mix the mixed liquid.
使被清潔劑污染之氟化液體與水接觸所使用的溫度及時間可根據需要的性能而變化，諸如再生之氟化液體的純度，但溫度及時間的實例可包括(但不限於)在不低於約20℃、不低於約23℃、或不 低於約25℃、且不高於約40℃、不高於約35℃、或不高於約30℃之範圍內的溫度。 The temperature and time used to bring the fluorinated liquid contaminated with the cleaner into contact with water can vary depending on the required performance, such as the purity of the regenerated fluorinated liquid, but examples of temperature and time can include (but are not limited to) Below about 20 ° C, not below about 23 ° C, or not A temperature in a range of less than about 25 ° C, and not more than about 40 ° C, not more than about 35 ° C, or not more than about 30 ° C.
本揭露之氟化液體再生方法包括將水接觸後獲得之混合液體分離成位於上層之水相及位於下層之氟化液體的兩種液體，然後移除上層之液體並收集下層之液體的步驟。可透過上述水接觸步驟及隨後使含有清潔劑及氟化液體之混合液體靜置的步驟分離成上層及下層之兩種液體。 The disclosed fluorinated liquid regeneration method includes the steps of separating the mixed liquid obtained after contacting water into two liquids in an upper water phase and a fluorinated liquid in a lower layer, and then removing the upper liquid and collecting the lower liquid. It can be separated into two liquids in the upper layer and the lower layer through the above-mentioned water contacting step and the subsequent step of allowing the mixed liquid containing the cleaning agent and the fluorinated liquid to stand still.
下層液體可藉由(例如)以下方式來收集：經由管等從含有混合液體之容器下方直接收集，或者從容器上方收集上層液體，然後收集下層液體，或者將管等從容器上方延伸至容器底部附近並藉由抽吸來收集下層液體。 The lower liquid can be collected by, for example, directly from below the container containing the mixed liquid via a tube or the like, or collecting the upper liquid from above the container, and then collecting the lower liquid, or extending the tube, etc. from above the container to the bottom of the container The lower layer was collected nearby and by suction.
在該階段收集之下層液體的純度可取決於清潔劑及氟化液體等的組合而變化，但通常，在水接觸步驟之前不大於約90%的氟化液體的純度可達到不小於約95%、不小於約96%、或不小於約97%。 The purity of the lower layer liquid collected at this stage may vary depending on the combination of cleaning agent, fluorinated liquid, etc., but generally, the purity of the fluorinated liquid that is not greater than about 90% before the water contact step may reach not less than about 95% , Not less than about 96%, or not less than about 97%.
在本揭露之氟化液體再生方法中，可選地，可以單獨應用一個步驟，諸如蒸餾步驟(例如，沸騰蒸餾步驟、減壓蒸餾步驟等)、冷卻及分離步驟等，或者可以適當地組合應用此等步驟中之二或更多者。 In the fluorinated liquid regeneration method of the present disclosure, optionally, a step such as a distillation step (for example, a boiling distillation step, a reduced-pressure distillation step, etc.), a cooling and separation step, or the like may be applied alone, or may be appropriately combined and applied Two or more of these steps.
在可選的步驟中，當再生更高純度之氟化液體係所欲的時，較佳收集下層液體，隨後對下層液體應用蒸餾步驟。蒸餾步驟中之蒸餾溫度的實例可包括(但不限於)不低於約70℃、不低於約72℃、或不低於約75℃、且不高於約100℃、不高於約95℃、或不高於約90℃。藉由蒸餾收集之液體中氟化液體的純度可取決於清潔劑及氟化液體的組合而變化，但通常，可實現不低於約99.0%、不低於約99.2%、或不低於約99.4%的純度。 In an optional step, when it is desired to regenerate a higher purity fluorinated liquid system, it is preferable to collect the lower layer liquid, and then apply a distillation step to the lower layer liquid. Examples of the distillation temperature in the distillation step may include, but are not limited to, not less than about 70 ° C, not less than about 72 ° C, or not less than about 75 ° C, and not more than about 100 ° C, not more than about 95 ° C, or no higher than about 90 ° C. The purity of the fluorinated liquid in the liquid collected by distillation may vary depending on the combination of the detergent and the fluorinated liquid, but generally, no less than about 99.0%, no less than about 99.2%, or no less than about 99.4% purity.
本揭露之實施例的氟化液體再生設備包括用於使被清潔劑污染之氟化液體與水接觸，以使位於上層之水相之清潔劑的濃度小於80質量%的構件(在下文中有時稱為「水接觸構件」)；及用於將水接觸後獲得之混合液體分離成位於上層之水相及位於下層之氟化液體的兩種液體，然後移除上層之液體並收集下層之液體的構件(在下文中有時稱為「分離及收集構件」)；其中該清潔劑係溶解於該氟化液體中之非質子極性溶劑，且該氟化液體係氫氟醚、氫氟烯烴、或其混合物。上述再生設備中使用之清潔劑、氟化液體、及水與上述再生方法中使用之彼等相同。 The fluorinated liquid regeneration apparatus of the embodiment of the present disclosure includes a means for contacting the fluorinated liquid contaminated with the cleaning agent with water so that the concentration of the cleaning agent in the aqueous phase in the upper layer is less than 80% by mass (sometimes hereinafter (Referred to as "water contact member"); and for separating the mixed liquid obtained after contacting water into two liquids in an upper water phase and a fluorinated liquid in a lower layer, and then removing the upper liquid and collecting the lower liquid (Hereinafter sometimes referred to as "separation and collection member"); wherein the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or Its mixture. The cleaning agents, fluorinated liquids, and water used in the above-mentioned regeneration equipment are the same as those used in the above-mentioned regeneration method.
作為本揭露之氟化液體再生設備中的水接觸構件，可使用任何類型的構件，只要此類構件可在上述氟化液體再生方法中施加水 接觸步驟。例如，可根據設備的使用應用或使用環境等，適當地選擇經組態以容納清潔劑、氟化液體、及水的容器(有時稱為「槽」)的材料、體積、形狀、數量、設置位置等。 As the water contact member in the fluorinated liquid regeneration apparatus of the present disclosure, any type of member may be used as long as such a member can apply water in the above-mentioned fluorinated liquid regeneration method Contact steps. For example, the material, volume, shape, quantity, etc. of a container (sometimes referred to as a "tank") configured to contain detergents, fluorinated liquids, and water can be appropriately selected according to the application or environment in which the device is used, Set location, etc.
作為本揭露之氟化液體再生設備中的分離及收集構件，可使用任何類型的構件，只要此類構件可在上述氟化液體再生方法中施加分離及收集步驟。例如，可根據設備的使用應用或使用環境等，適當地選擇經組態以容納分離的液體的容器(有時稱為「槽」)的材料、體積、形狀、數量、設置位置等。 As the separation and collection member in the fluorinated liquid regeneration apparatus of the present disclosure, any type of member may be used as long as such a member can be subjected to the separation and collection steps in the above-mentioned fluorinated liquid regeneration method. For example, the material, volume, shape, quantity, installation position, etc. of a container (sometimes referred to as a "tank") configured to contain a separated liquid may be appropriately selected according to the use application of the device, the use environment, and the like.
在本揭露之氟化液體再生設備中，可使用任何類型的構件，只要此類構件可在上述氟化液體再生方法中施加可選的步驟，諸如蒸餾步驟(例如沸騰蒸餾步驟、減壓蒸餾步驟等)以及冷卻及分離步驟。例如，可根據設備的使用應用或使用環境等，適當地選擇經組態以儲存蒸餾步驟等中使用之下層液體等的容器的材料、體積、形狀、數量、設置位置等。各種構件中之一者，諸如蒸餾構件以及冷卻及分離構件可以單獨應用於氟化液體再生設備，或者各種構件中之二或更多者可以組合應用於氟化液體再生設備。 In the fluorinated liquid regeneration apparatus of the present disclosure, any type of components may be used as long as such components can apply optional steps such as a distillation step (e.g., a boiling distillation step, a reduced pressure distillation step) in the above-mentioned fluorinated liquid regeneration method. Etc.) and cooling and separation steps. For example, the material, volume, shape, number, setting position, etc. of the container configured to store the lower layer liquid used in the distillation step or the like can be appropriately selected according to the use application of the device, the use environment, and the like. One of various components, such as a distillation component and a cooling and separation component, may be applied to the fluorinated liquid regeneration equipment alone, or two or more of the various components may be applied to the fluorinated liquid regeneration equipment in combination.
在可選的構件中，當再生更高純度之氟化液體係所欲的時，較佳收集下層液體，隨後添加用於對下層液體進行蒸餾之蒸餾構 件。作為蒸餾構件，可以使用包括蒸餾釜及冷卻器之習知設備，該蒸餾釜經組態以儲存及加熱收集之下層液體，且該冷卻器與蒸餾釜連通連接並經組態以冷凝下層液體之蒸氣。 In optional components, when regenerating a higher purity fluorinated liquid system is desired, it is preferable to collect the lower layer liquid, and then add a distillation structure for distilling the lower layer liquid. Pieces. As the distillation component, conventional equipment including a still kettle and a cooler configured to store and heat the lower liquid can be used, and the cooler is connected to the still and configured to condense the lower liquid Steam.
本揭露之氟化液體再生方法及再生設備可以線上(online)或線外(offline)用於例如有機EL顯示器製造步驟中。當線上使用本揭露之氟化液體再生方法及再生設備時，氟化液體再生方法及再生設備可以適當地經組態以使得再生之氟化液體能夠再次輸入洗滌步驟。當線外使用氟化液體再生方法及再生設備時，再生之氟化液體可以在有機EL顯示器製造步驟之洗滌步驟中再使用，同時再生之氟化液體亦可在不同於此種應用的應用中再使用，例如，可以再用作印刷電路板之沖洗液。 The fluorinated liquid regeneration method and the regeneration apparatus disclosed in the present disclosure may be used online or offline in, for example, an organic EL display manufacturing step. When the disclosed fluorinated liquid regeneration method and regeneration equipment are used online, the fluorinated liquid regeneration method and regeneration equipment can be appropriately configured so that the regenerated fluorinated liquid can be input into the washing step again. When the fluorinated liquid regeneration method and regeneration equipment are used off-line, the regenerated fluorinated liquid can be reused in the washing step of the manufacturing step of the organic EL display, and the regenerated fluorinated liquid can also be used in applications different from this application Reuse, for example, can be reused as a rinse solution for printed circuit boards.
藉由本揭露之氟化液體再生方法及再生設備再生及獲得之氟化液體可具有例如但不限於以下用途：用於有機EL顯示器製造設備，及用作暴露於洗滌及沖洗操作之各種部件，諸如金屬遮罩及防沉積片材中的各者的沖洗液，以及用作各種電子部件、精密部件、金屬部件、印刷電路板等中的各者的沖洗液。此處，防沉積片材係指例如設置於用於製造有機EL顯示器之真空氣相沉積設備之真空室的內側上的部件，且係能夠被移除及洗滌以防止作為蒸發源之RGB三色顏料污染真空室的部件。用作沖洗液的用途不限於直接用作用於浸漬待洗滌物品以沖洗掉附著的清潔劑等的液體，亦包括間接用於蒸發沖洗液並將蒸發的氣體附著至待洗滌物品之表面以沖洗掉清潔劑等。 The fluorinated liquid regenerated and obtained by the fluorinated liquid regeneration method and the regeneration device disclosed in this disclosure may have, for example, but not limited to the following uses: for organic EL display manufacturing equipment, and various parts exposed to washing and rinsing operations, such as Washing liquid for each of metal masks and anti-deposition sheets, and washing liquid for each of various electronic parts, precision parts, metal parts, printed circuit boards, and the like. Here, the anti-deposition sheet refers to, for example, a member provided on the inside of a vacuum chamber of a vacuum vapor deposition apparatus for manufacturing an organic EL display, and is an RGB tri-color that can be removed and washed to prevent evaporation. Pigments contaminate parts of the vacuum chamber. The use as a rinsing liquid is not limited to being directly used as a liquid for immersing the item to be washed to rinse off the attached detergent, etc., but also indirectly used to evaporate the rinsing liquid and attach the evaporated gas to the surface of the item to be washed to rinse off. Cleaners, etc.
本揭露之具體實施例在下面描述的實例中舉例說明，但本揭露不限於此等實施例。 Specific embodiments of this disclosure are illustrated in the examples described below, but this disclosure is not limited to these embodiments.
本實例中使用的產品等顯示於表1中。 The products and the like used in this example are shown in Table 1.
收集的液體如下所述進行評估。 The collected liquid was evaluated as described below.
藉由使用購自Agilent Technologies,Inc.之7890A型號，藉由氣相層析來評估再生之氟化液體的純度。氣相層析的測量條件如下。 The purity of the regenerated fluorinated liquid was evaluated by gas chromatography by using a 7890A model purchased from Agilent Technologies, Inc. The measurement conditions of gas chromatography are as follows.
管柱類型：HP-1301 Column Type: HP-1301
管柱長度：60m String length: 60m
管柱溫度：260℃ Column temperature: 260 ℃
載氣類型：氦氣 Carrier gas type: Helium
載氣流速：205mL/分鐘 Carrier gas flow rate: 205mL / min
進樣量：1μL Injection volume: 1 μL
在水接觸步驟之後收集之下層液體中的水分含量係藉由使用購自Mitsubishi Chemical Corporation之微量水分測量設備來測量。 The moisture content in the lower layer liquid collected after the water contacting step was measured by using a trace moisture measuring device purchased from Mitsubishi Chemical Corporation.
將100g NOVEC(商品名)7100(氟化液體)及10g NMP(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入40g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的NOVEC(商品名)7100的純度。結果顯示於表2中。注意，非質子極性溶劑清潔劑比氟化液體更容易轉移至蒸餾水側，但由於清潔劑的量相對於蒸餾水及清潔劑總量的比例(在下文中有時稱為「水中之清潔劑濃度」)係20質量%，故位於上層之水相之清潔劑的濃度不超過20質量%。 100 g of NOVEC (trade name) 7100 (fluorinated liquid) and 10 g of NMP (detergent) were added to the sample bottles and shaken for 30 minutes. To this mixed liquid was added 40 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of NOVEC (trade name) 7100 as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that aprotic polar solvent cleaners are easier to transfer to the distilled water side than fluorinated liquids, but due to the ratio of the amount of detergent to the total amount of distilled water and detergent (hereinafter sometimes referred to as "cleaner concentration in water") Since it is 20% by mass, the concentration of the cleaning agent in the aqueous phase in the upper layer does not exceed 20% by mass.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例1相同的方式測量純度。 The purity was measured in the same manner as in Example 1 except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100.
除了使用1233Z代替NOVEC(商品名)7100之外，以與實例1相同的方式測量純度。 The purity was measured in the same manner as in Example 1 except that 1233Z was used instead of NOVEC (trade name) 7100.
除了使用Asahiklin(商品名)AE-3000代替NOVEC(商品名)7100之外，以與實例1相同的方式測量純度。 The purity was measured in the same manner as in Example 1 except that Asahiklin (trade name) AE-3000 was used instead of NOVEC (trade name) 7100.
將100g NOVEC(商品名)7100(氟化液體)及5g NBP(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入10g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的NOVEC(商品名)7100的純度。結果顯示於表2中。注意，由於在本實例之模式中水中之清潔劑的濃度係33.3質量%，故位於上層之水相之清潔劑的濃度不超過33.3質量%。 100 g of NOVEC (trade name) 7100 (fluorinated liquid) and 5 g of NBP (detergent) were added to the sample bottles and shaken for 30 minutes. To this mixed liquid was added 10 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of NOVEC (trade name) 7100 as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that since the concentration of the cleaning agent in water in the mode of this example is 33.3% by mass, the concentration of the cleaning agent in the aqueous phase in the upper layer does not exceed 33.3% by mass.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例5相同的方式測量純度。 The purity was measured in the same manner as in Example 5 except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100.
除了使用1233Z代替NOVEC(商品名)7100之外，以與實例5相同的方式測量純度。 The purity was measured in the same manner as in Example 5 except that 1233Z was used instead of NOVEC (trade name) 7100.
除了使用Asahiklin(商品名)AE-3000代替NOVEC(商品名)7100之外，以與實例5相同的方式測量純度。 The purity was measured in the same manner as in Example 5 except that Asahiklin (trade name) AE-3000 was used instead of NOVEC (trade name) 7100.
將100g NOVEC(商品名)7100(氟化液體)及10g TETRAGLYME(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入80g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的NOVEC(商品名)7100的純度。結果顯示於表2中。注意，由於在本實例之模式中水中之清潔劑的濃度係11.1質量%，故位於上層之水相之清潔劑的濃度不超過11.1質量%。 100 g of NOVEC (trade name) 7100 (fluorinated liquid) and 10 g of TETRAGLYME (detergent) were added to the sample bottles and shaken for 30 minutes. To this mixed liquid was added 80 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of NOVEC (trade name) 7100 as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that since the concentration of the detergent in the water in the mode of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase in the upper layer does not exceed 11.1% by mass.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例9相同的方式測量純度。 The purity was measured in the same manner as in Example 9 except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100.
除了使用Asahiklin(商品名)AE-3000代替NOVEC(商品名)7100之外，以與實例9相同的方式測量純度。 The purity was measured in the same manner as in Example 9 except that Asahiklin (trade name) AE-3000 was used instead of NOVEC (trade name) 7100.
將100g NOVEC(商品名)7100(氟化液體)及10g AC(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入80g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的NOVEC(商品名)7100的純度。結果顯示於表2中。注意，由於在本實例之模式中水中之清潔劑的濃度係11.1質量%，故位於上層之水相之清潔劑的濃度不超過11.1質量%。 100 g of NOVEC (trade name) 7100 (fluorinated liquid) and 10 g of AC (detergent) were added to the sample bottles and shaken for 30 minutes. To this mixed liquid was added 80 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of NOVEC (trade name) 7100 as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that since the concentration of the detergent in the water in the mode of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase in the upper layer does not exceed 11.1% by mass.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例12相同的方式測量純度。 The purity was measured in the same manner as in Example 12, except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100.
將100g 1233Z(氟化液體)及10g DMSO(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入10g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的1233Z的純度。結果顯示於表2中。注意，由於在本實例之模式中水中之清潔劑的濃度係50質量%，故位於上層之水相之清潔劑的濃度不超過50質量%。 Add 100g of 1233Z (fluorinated liquid) and 10g of DMSO (detergent) to the sample bottle and shake for 30 minutes. To this mixed liquid was added 10 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of 1233Z as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that, since the concentration of the detergent in water in the mode of this example is 50% by mass, the concentration of the detergent in the aqueous phase in the upper layer does not exceed 50% by mass.
除了使用Asahiklin(商品名)AE-3000代替1233Z之外，以與實例14相同的方式測量純度。 The purity was measured in the same manner as in Example 14 except that Asahiklin (trade name) AE-3000 was used instead of 1233Z.
將100g NOVEC(商品名)7100(氟化液體)及10g DMF(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入10g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的NOVEC(商品名)7100的純度。結果顯示於表2中。注意，由於在該實例之模式中水中之清潔劑的濃度係50質量%，故位於上層之水相之清潔劑的濃度不超過50質量%。 100 g of NOVEC (trade name) 7100 (fluorinated liquid) and 10 g of DMF (detergent) were added to the sample bottles and shaken for 30 minutes. To this mixed liquid was added 10 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of NOVEC (trade name) 7100 as a fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that since the concentration of the detergent in the water in the mode of this example is 50% by mass, the concentration of the detergent in the aqueous phase in the upper layer does not exceed 50% by mass.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例16相同的方式測量純度。 The purity was measured in the same manner as in Example 16 except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100.
除了使用1233Z代替NOVEC(商品名)7100之外，以與實例16相同的方式測量純度。 The purity was measured in the same manner as in Example 16 except that 1233Z was used instead of NOVEC (trade name) 7100.
將100g Asahklin(商品名)AE-3000(氟化液體)及10g DMF(清潔劑)分別加入樣本瓶中，並搖動30分鐘。向此混合液體中加入80g蒸餾水，並再搖動30分鐘。然後，將獲得之混合液體轉移至分液漏斗，並靜置直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，並測量作為下層液體中之氟化液體的Asahklin(商品名)AE-3000的純度。結果顯示於表2中。注意，由於在本實例之模式中水中之清潔劑的濃度係11.1質量%，故位於上層之水相之清潔劑的濃度不超過11.1質量%。 100 g of Asahklin (trade name) AE-3000 (fluorinated liquid) and 10 g of DMF (detergent) were added to each sample bottle and shaken for 30 minutes. To this mixed liquid was added 80 g of distilled water, and it was shaken for another 30 minutes. Then, the obtained mixed liquid was transferred to a separating funnel, and left to stand until the mixed liquid was separated into two layers of an upper layer and a lower layer. The lower layer liquid of the two-layered liquid was collected, and the purity of Asahklin (trade name) AE-3000 as the fluorinated liquid in the lower layer liquid was measured. The results are shown in Table 2. Note that since the concentration of the detergent in the water in the mode of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase in the upper layer does not exceed 11.1% by mass.
從表2中之結果可以清楚地看出，能夠確認，當使用本揭露之氟化液體再生方法時，可簡單地藉由使氟化液體與水接觸以不低於約95%之純度使氟化液體再生。 From the results in Table 2, it is clear that it can be confirmed that when the fluorinated liquid regeneration method of the present disclosure is used, the fluorine can be simply made by contacting the fluorinated liquid with water with a purity of not less than about 95%. Chemical liquid regeneration.
測量純度(%)，並以與實例1相同的方式進一步測量所收集之下層液體中之各者的產量(g)，不同之處在於水接觸步驟用各種添加量的蒸餾水進行，如下：2.5g(水中之清潔劑的濃度：80.0質量%)、5g(水中之清潔劑的濃度：66.7質量%)、10g(水中之清潔劑的濃度：50.0質量%)、20g(水中之清潔劑的濃度：33.3質量%)、40g(水中之清潔劑的濃度：20.0質量%)、60g(水中之清潔劑的濃度：14.3質量%)、及80g(水中之清潔劑的濃度：11.1質量%)。圖1中顯示基於藉由將測量之純度與測量之產量相乘獲得的值(在下文中有時稱為「再生值」)及基於水中之清潔劑的濃度(質量%)的曲線圖。此處，就圖1而言，較高的再生值意味著較好的氟化液體再生狀態。 The purity (%) was measured, and the yield (g) of each of the collected lower liquids was further measured in the same manner as in Example 1, except that the water contacting step was performed with various added amounts of distilled water, as follows: 2.5 g (Concentration of detergent in water: 80.0% by mass), 5g (Concentration of detergent in water: 66.7% by mass), 10g (Concentration of detergent in water: 50.0% by mass), 20g (Concentration of detergent in water: 33.3% by mass), 40g (concentration of detergent in water: 20.0% by mass), 60g (concentration of detergent in water: 14.3% by mass), and 80g (concentration of detergent in water: 11.1% by mass). FIG. 1 shows a graph based on a value obtained by multiplying the measured purity by the measured yield (hereinafter sometimes referred to as a “regeneration value”) and a concentration (mass%) of a detergent in water. Here, in terms of FIG. 1, a higher regeneration value means a better regeneration state of the fluorinated liquid.
除了使用NOVEC(商品名)7200代替NOVEC(商品名)7100之外，以與實例20相同的方式測量純度及產量。基於此等結果之曲線圖顯示於圖1中。 The purity and yield were measured in the same manner as in Example 20 except that NOVEC (trade name) 7200 was used instead of NOVEC (trade name) 7100. A graph based on these results is shown in FIG. 1.
除了使用VERTREL(商品名)XF代替NOVEC(商品名)7100之外，以與實例20相同的方式測量純度及產量。基於此等結果之曲線圖顯示於圖1中。 The purity and yield were measured in the same manner as in Example 20 except that VERTREL (trade name) XF was used instead of NOVEC (trade name) 7100. A graph based on these results is shown in FIG. 1.
除了使用Asahiklin(商品名)AK-225代替NOVEC(商品名)7100之外，以與實例20相同的方式測量純度及產量。基於此等結果之曲線圖顯示於圖1中。 The purity and yield were measured in the same manner as in Example 20 except that Asahiklin (trade name) AK-225 was used instead of NOVEC (trade name) 7100. A graph based on these results is shown in FIG. 1.
從圖1中之結果可以清楚地看出，能夠確認，對應於本揭露之再生方法之實例20及21的模式中之任一者均比使用氫氟烴及氫氯氟烴之比較例1及2的模式實現了更高的再生值，因此，透過水接觸步驟之再生對除氫氟烴及氫氯氟烴之外的氟化液體具有顯著的作用。具體而言，能夠確認，在實例20及21的模式中之任一者中，當水中之清潔劑的濃度係約30.0質量%至約60.0質量%時，再生值係優異的。這對應於進行水接觸以使位於上層之水相之清潔劑的濃度通常大於約30.0質量%且小於約60.0質量%的情況。 It is clear from the results in FIG. 1 that it can be confirmed that any of the modes corresponding to Examples 20 and 21 of the regeneration method of the present disclosure is better than Comparative Examples 1 and 2 using hydrofluorocarbons and hydrochlorofluorocarbons. The mode 2 achieves a higher regeneration value. Therefore, regeneration through the water contact step has a significant effect on fluorinated liquids other than hydrofluorocarbons and hydrochlorofluorocarbons. Specifically, it was confirmed that, in any of the modes of Examples 20 and 21, when the concentration of the detergent in the water was about 30.0% by mass to about 60.0% by mass, the regeneration value was excellent. This corresponds to a case where the water contact is performed so that the concentration of the detergent in the upper water phase is usually greater than about 30.0 mass% and less than about 60.0 mass%.
將100g Asahklin(商品名)AE-3000(HFE-347pc-f)及10g NMP分別加入樣本瓶中，並搖動30分鐘。向該混合液體中加入40g蒸餾水，並再搖動30分鐘，以產生含有比率為100：40：10之Asahklin(商品名)AE-3000(HFE-347pc-f)、水、及NMP的混合液體。然後，將混合液體轉移至分液漏斗，靜置，直至混合液體分成上層及下層的兩層。收集分成兩層之液體的下層液體，然後將其轉移至在實驗等 級上使用之普通蒸餾器的蒸餾燒瓶中，並在約80℃下開始蒸餾。假設安裝在Liebig冷凝器入口附近的溫度計的溫度下降的時間點係結束時間，則下層液體被分離成再生之氟化液體及待丟棄之殘留物。圖2的右側繪示一系列流程及結果。注意，小於100g之再生之氟化液體的量及殘留物中存在之氟化液體的量的總和被認為係實驗誤差。 100 g of Asahklin (trade name) AE-3000 (HFE-347pc-f) and 10 g of NMP were respectively added to the sample bottle and shaken for 30 minutes. 40 g of distilled water was added to the mixed liquid, and shaken for another 30 minutes to produce a mixed liquid containing Asahklin (trade name) AE-3000 (HFE-347pc-f), water, and NMP in a ratio of 100: 40: 10. Then, the mixed liquid is transferred to a separating funnel, and left to stand until the mixed liquid is separated into two layers of an upper layer and a lower layer. Collect the lower layer of the liquid that is separated into two layers, and then transfer it to the experiment, etc. In the distillation flask of the ordinary still used on the stage, distillation was started at about 80 ° C. Assuming that the temperature drop of the thermometer installed near the entrance of the Liebig condenser is the end time, the lower liquid is separated into a regenerated fluorinated liquid and a residue to be discarded. The right side of Figure 2 shows a series of processes and results. Note that the sum of the amount of regenerated fluorinated liquid less than 100 g and the amount of fluorinated liquid present in the residue is considered to be an experimental error.
將80g Asahklin(商品名)AE-3000(HFE-347pc-f)及20g NMP分別加入樣本瓶中，並搖動30分鐘。此混合液體藉由使用與實例22相同之蒸餾設備及蒸餾條件進行蒸餾，並分離成再生之氟化液體及待丟棄之殘留物。圖2的左側繪示一系列流程及結果。 80 g of Asahklin (trade name) AE-3000 (HFE-347pc-f) and 20 g of NMP were added to the sample bottles, respectively, and shaken for 30 minutes. This mixed liquid was distilled by using the same distillation equipment and distillation conditions as in Example 22, and separated into a regenerated fluorinated liquid and a residue to be discarded. The left side of Figure 2 shows a series of processes and results.
藉由使用校準曲線等推斷出，當含有氟化液體及清潔劑之混合液體在約80℃下蒸餾時，殘留物含有比率為約30%及約70%的清潔劑及氟化液體。在對應於僅使用蒸餾之習知氟化液體再生方法之比較例3中，如圖2之左側所繪示，當混合液體在約80℃下蒸餾時，僅33.3g氟化液體(HFE-347pc-f)能夠再生，且剩餘的46.7g氟化液體不能與清潔劑(NMP)分離，且因此必須丟棄。即，必須丟棄之氟化液體的量係再生之前獲得之混合液體中存在的氟化液體的58.4%。另一方面，在對應於使用蒸餾步驟之本揭露之氟化液體再生方法的實例22中，在透過水接觸步驟以及分離及收集步驟收集之下層液體中，大部分清潔劑 已經被移除，因此，當下層液體在約80℃下蒸餾時，如圖2之右側所繪示，92.6g氟化液體能夠再生，且待丟棄之氟化液體的量能夠保持在非常少量的5.8g。即，必須丟棄之氟化液體的量(該量除了殘留物中之5.8g氟化液體之外亦包括1.6g的誤差)僅為再生之前獲得之混合液體中存在的氟化液體的7.4%。因此，能夠確認，與僅使用蒸餾之習知再生方法相比，使用蒸餾步驟之本揭露之氟化液體再生方法將待丟棄之氟化液體的量減少了87.3%。 It is inferred from the use of a calibration curve and the like that when a mixed liquid containing a fluorinated liquid and a cleaning agent is distilled at about 80 ° C, the residue contains a cleaning agent and a fluorinated liquid at a ratio of about 30% and about 70%. In Comparative Example 3 corresponding to the conventional fluorinated liquid regeneration method using only distillation, as shown on the left side of FIG. 2, when the mixed liquid was distilled at about 80 ° C., only 33.3 g of the fluorinated liquid (HFE-347pc -f) Can be regenerated, and the remaining 46.7 g of fluorinated liquid cannot be separated from the detergent (NMP) and must therefore be discarded. That is, the amount of fluorinated liquid that must be discarded is 58.4% of the fluorinated liquid present in the mixed liquid obtained before regeneration. On the other hand, in Example 22, which corresponds to the fluorinated liquid regeneration method of the present disclosure using a distillation step, most of the cleaner is collected in the lower layer liquid through the water contact step and the separation and collection step. It has been removed, so when the lower liquid is distilled at about 80 ° C, as shown on the right side of Figure 2, 92.6g of fluorinated liquid can be regenerated, and the amount of fluorinated liquid to be discarded can be kept in a very small amount. 5.8g. That is, the amount of fluorinated liquid that must be discarded (this amount includes an error of 1.6 g in addition to 5.8 g of fluorinated liquid in the residue) is only 7.4% of the fluorinated liquid present in the mixed liquid obtained before regeneration. Therefore, it can be confirmed that the fluorinated liquid regeneration method using the present disclosure of the distillation step reduces the amount of fluorinated liquid to be discarded by 87.3% compared with the conventional regeneration method using only distillation.
對於所屬技術領域中具有通常知識者而言顯而易見，在不偏離本發明之基本原理的情況下，可對上述實施例及實例進行各種修改。此外，對於所屬技術領域中具有通常知識者而言顯而易見，在不偏離本發明之精神及範圍的情況下，可對本發明進行各種改進及修改。 It is obvious to those having ordinary knowledge in the technical field that various modifications can be made to the above embodiments and examples without departing from the basic principles of the present invention. In addition, it is obvious to those having ordinary knowledge in the technical field that various improvements and modifications can be made to the present invention without departing from the spirit and scope of the present invention.
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