CN114007715A - Method for purifying fluorinated liquids and purification apparatus using the method - Google Patents
Method for purifying fluorinated liquids and purification apparatus using the method Download PDFInfo
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- CN114007715A CN114007715A CN202080044430.7A CN202080044430A CN114007715A CN 114007715 A CN114007715 A CN 114007715A CN 202080044430 A CN202080044430 A CN 202080044430A CN 114007715 A CN114007715 A CN 114007715A
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- 239000007788 liquid Substances 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000000746 purification Methods 0.000 title claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000012459 cleaning agent Substances 0.000 claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 50
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003950 cyclic amides Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 238000004821 distillation Methods 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 19
- 239000003599 detergent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000000052 comparative effect Effects 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000005675 difluoroethenyl group Chemical group [H]C(*)=C(F)F 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZHOFTZAKGRZBSL-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-methoxyoctane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZHOFTZAKGRZBSL-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011521 glass Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003953 γ-lactams Chemical class 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
-
- 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
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
- C11D7/30—Halogenated hydrocarbons
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5018—Halogenated solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- 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
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The present invention provides a method for purifying a fluorinated liquid according to one embodiment of the present disclosure, the method comprising performing an extraction step two or more times, the extraction step comprising a first step of contacting water with a fluorinated liquid having a cleaning agent mixed therein, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquids in the lower layer, wherein the total amount of water contacted with the liquid up to the final extraction step is about 30.0 mass% or less, the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
Description
Technical Field
The present disclosure relates to a method for purifying fluorinated liquids and a purification apparatus using the method.
Background
For example, a method for manufacturing an organic EL display includes a step of evaporating RGB trichromatic dyes on a substrate such as glass through a metal mask to form an organic light emitting layer. Since the metal mask is an expensive member, the metal mask will be reused after cleaning the metal mask with a cleaning agent such as N-methyl-2-pyrrolidone, and then performing a rinsing step and a drying step using a fluorinated liquid.
Patent document 1 (japanese unexamined patent application publication No.2006-313753) describes a cleaning method in which, when a low-molecular-weight organic EL element is manufactured, a metal mask used in a vacuum evaporation step is cleaned by immersion with a cleaning liquid composition containing an aprotic polar solvent such as N-methyl-2-pyrrolidone or with a jet flow, followed by rinsing with hydrofluoroether.
Patent document 2 (japanese unexamined patent application publication No. h07-076787) describes a purification apparatus of a metal cleaning agent, which includes a cleaning apparatus using NMP as a metal cleaning agent, and a purification apparatus that removes contaminants from an NMP cleaning liquid after cleaning and circulates the resultant liquid to the cleaning apparatus, wherein a filter material provided in the purification apparatus is a granular filter material containing at least polypropylene and having floatability for NMP.
Patent document 3 (japanese unexamined patent application publication No. 2008-: a cleaning tank in which a cleaning liquid containing one or more selected from (1a) a hydrocarbon, (1b) a glycol ether, and (1c) an ester is stored, and which is immersed in a material to be cleaned; a rinsing liquid tank in which a rinsing liquid containing one or more selected from (2a) hydrofluorocarbons and (2b) hydrofluoroethers as a main component is stored and which is immersed in a material to be cleaned; a steam tank storing a rinsing liquid and generating steam of the rinsing liquid; and a purification unit having a distiller.
List of cited documents
Patent document
[ patent document 1 ]: JP 2006-313753A
[ patent document 2 ]: JP H07-076787A
[ patent document 3 ]: JP 2008-163400A
Disclosure of Invention
Generally, increasing the number of cleaning and rinsing operations also increases the mixing rate of the cleaning agent into the rinse tank. Therefore, the rinsing tank is contaminated with the cleaning agent, and thus the rinsing liquid needs to be replaced periodically. However, since the fluorinated liquid used as the rinsing liquid is also an expensive solvent, a technique for efficiently collecting and reusing the fluorinated liquid from the contaminated rinsing liquid is required.
In recent years, regulations such as reduction of environmental load have been developed in various countries/regions, and for example, in various production lines, measures are required to cope with strict drainage regulations such as reduction of wastewater.
The present disclosure provides a method for purifying a fluorinated liquid, which contributes to reduction of environmental load and has excellent purification efficiency for a fluorinated liquid in which a cleaning agent is mixed, and a purification apparatus using the same.
Solution to the problem
According to an embodiment of the present disclosure, there is provided a method for purifying a fluorinated liquid, the method comprising performing an extraction step two or more times, the extraction step comprising a first step of contacting water with a fluorinated liquid having a cleaning agent mixed therein, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquids in the lower layer, wherein a total amount of the water contacted until the final extraction step is about 30.0% by mass or less, the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
According to another embodiment of the present disclosure, there is provided a method of using a fluorinated liquid purified by using the above-described method for purifying a fluorinated liquid as a rinsing liquid for a member used in an organic EL display manufacturing apparatus.
According to still another embodiment of the present disclosure, there is provided a fluorinated liquid purification apparatus including an extraction device for performing an extraction step two or more times, the extraction step including a first step of contacting water with a fluorinated liquid having a cleaning agent mixed therein, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquids in the lower layer, wherein a total amount of the water contacted until the final extraction step is about 30.0% by mass or less, the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
Advantageous effects of the invention
According to the present disclosure, it is possible to provide a method for purifying a fluorinated liquid, which contributes to reduction of environmental load and has excellent purification efficiency for a fluorinated liquid in which a cleaning agent is mixed, and a purification apparatus using the same.
The above description should not be taken as disclosing all aspects of the disclosure and all advantages of the disclosure.
Detailed Description
A more detailed description will be provided below in order to illustrate representative embodiments of the present disclosure, but the present disclosure is not limited to these embodiments.
In a method for purifying a fluorinated liquid according to an embodiment of the present disclosure, an extraction step is performed two or more times, the extraction step including a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquids in the lower layer, a total amount of the water contacted until the final extraction step is about 30.0 mass% or less, where the cleaning agent used is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. According to the purification method of the present disclosure, even when the total amount of water contacted until the final extraction step is as low as about 30.0 mass% or less, the purification efficiency of the fluorinated liquid is excellent and the amount of waste water is small, and thus can contribute to reduction or suppression of environmental load.
The cleaning agent that can be mixed in the method for purifying a fluorinated liquid of the present disclosure is a cleaning agent used during cleaning of various members, and examples thereof include a cleaning agent used during cleaning of a metal mask, an anti-deposition plate, and the like in an organic EL display manufacturing apparatus. The cleaning agent is not particularly limited as long as it is an aprotic polar solvent dissolved in the fluorinated liquid. Examples thereof include at least one selected from the group consisting of cyclic amide-based solvents, amine-based solvents, glycol ether-based solvents, acetone, dimethyl sulfoxide, and dimethylformamide. These detergents have excellent cleaning action and are more soluble in water than in fluorinated liquids and are therefore suitable detergents in the purification process of the present disclosure using water to remove detergents from fluorinated liquids. Among them, from the viewpoint of cleaning performance of various members such as a metal mask and an anti-deposition plate and solubility balance in a fluorinated liquid and water, a cyclic amide-based solvent is preferable, and an N-alkyl pyrrolidone solvent such as N-methyl-2-pyrrolidone (NMP) and N-butyl-2-pyrrolidone (NBP) or a solvent called a γ -lactam solvent is more preferable, and N-methyl-2-pyrrolidone (NMP) is particularly preferable. Such aprotic polar solvents may be used alone or in combination of two or more thereof. If the above cleaning agents are used, the fluorinated liquid can be efficiently purified by the purification method of the present disclosure. The cleaning agent may contain, in addition to the above-described cleaning agent, other cleaning agents within a range that does not inhibit the purification efficiency of the fluorinated liquid; however, it is preferable not to contain other cleaning agents from the viewpoint of purification efficiency and the like.
The boiling point of the detergent is not particularly limited, but is preferably about 55 ℃ or higher, about 100 ℃ or higher, about 120 ℃ or higher, about 150 ℃ or higher, about 180 ℃ or higher, about 200 ℃ or higher, or about 250 ℃ or higher, in consideration of, for example, the application of the distillation step described below. The upper boiling point limit of the detergent is not particularly limited, and may be set to, for example, about 300 ℃ or less, about 280 ℃ or less, or about 260 ℃ or less.
Examples of fluorinated liquids that can be purified by the methods for purifying fluorinated liquids of the present disclosure include hydrofluoroethers, hydrofluoroolefins, or mixtures thereof. In addition to the above-described fluorinated liquid, the fluorinated liquid may contain other fluorinated liquids (for example, hydrofluoroolefin, hydrofluorocarbon, etc.) within a range that does not inhibit the purification efficiency; however, it is preferable not to contain other fluorinated liquid from the viewpoint of purification efficiency and the like.
The solubility of water in the fluorinated liquid is not particularly limited. For example, the solubility of water at 25 ℃ is advantageously about 500ppm or less, about 300ppm or less, about 200ppm or less, or about 150ppm or less from the viewpoint of separation performance and purification efficiency between the aqueous phase and the phase containing the fluorinated liquid. The lower limit of the solubility is not particularly limited, and may be set to, for example, about 10ppm or more, about 30ppm or more, or about 50ppm or more. A cleaning agent such as NMP is more soluble in water than in fluorinated liquids. Thus, when the solubility of water in the fluorinated liquid is within this range, water is difficult to dissolve in the fluorinated liquid, and thus when in contact with water, the cleaning agent in the fluorinated liquid tends to become more easily incorporated into the water, and the percentage of cleaning agent remaining in the fluorinated liquid can be further reduced. Here, "solubility of water in the fluorinated liquid" means a mass ratio of water that can be maximally dissolved in the fluorinated liquid under an atmospheric environment of 25 ℃, and is a value according to JIS K0068: karl Fischer titration (coulometry) defined in 2001 uses a micro-wet measurement apparatus (manufactured by Mitsubishi Chemical Analytech co., Ltd.) to measure at least five times to obtain an average value.
The boiling point of the fluorinated liquid is not particularly limited, but is preferably about 30 ℃ or higher, about 55 ℃ or higher, about 60 ℃ or higher, or about 75 ℃ or higher, and preferably about 150 ℃ or lower, about 100 ℃ or lower, or about 80 ℃ or lower, in view of the application of, for example, the distillation step described below.
Among the above fluorinated liquids, hydrofluoroethers are preferably used from the viewpoint of the separation performance and purification efficiency of the aqueous phase and the phase containing the fluorinated liquid. Hydrofluoroethers are compounds containing oxygen atoms that can be ether-bonded between the carbon atoms of hydrofluorocarbons. The number of etherally bondable oxygen atoms contained in one molecule of the hydrofluoroether may be one or two or more. From the viewpoint of boiling point, stability, etc., which are easy to use as a solvent, -one or two are preferable, and one is more preferable. The molecular structure of the hydrofluoroether need only be a chain and may be linear or branched, but linear is preferred from the viewpoint of purification efficiency and the like.
Examples of hydrofluoroethers include: segregated hydrofluoroethers, such as C4F9OCH3、C4F9OCH2CH3、C5F11OCH3、C5F11OCH2CH3、C6F13OCH3、C6F13OCH2CH3、C7F15OCH3、C7F15OCH2CH3、C8F17OCH3、C8F17OCH2CH3、C9F19OCH3、C9F19OCH2CH3、C10F21OCH3And C10F21OCH2CH3(ii) a And such as CF3CH2OCF2CF2H、CF3CHFOCH2CF3、CF3CH2OCF2CFHCF3、CHF2CF2CH2OCF2CF2H、C3F7OC3F6OCFHCF3、CF3CF(CF3)CF(OCH3)CF2CF3、CF3CF(CF3)CF(OC2H5)CF2CF3、CF2(OCH2CF3)CF2H、CF2(OCH2CF3)CFHCF3、CF2(OCH2CF2CF2H)CF2H and CF2(OCH2CF2CF2H)CFHCF3The hydrofluoroether of (1). Such hydrofluoroethers may be used alone or in combination of two or more thereof.
Among them, the segregated hydrofluoroethers have low solubility in water, and in the case of contact with water, the proportion of dissolution in the aqueous phase can be reduced compared to other hydrofluoroethers or hydrofluoroolefins, thereby facilitating phase separation of the aqueous phase from the fluorinated liquid-containing phase. Thus, the separated aqueous phase is less likely to be contaminated by fluorinated liquid, and thus for example it may comply with relatively stringent drainage regulations. In segregated hydrofluoroethers, C4F9OCH3Or C4F9OCH2CH3Is more preferred. Here, "isolated" refers to a structure in which one side is fully fluorinated and the other side is composed of carbon and hydrogen with an ether bond interposed between the two sides.
Hydrofluoroolefins are intended to be compounds in which one or more hydrogen atoms in the olefin are replaced by fluorine atoms. The number of fluorine atoms contained in the hydrofluoroolefin is not particularly limited, and may be one or more or two or more, and ten or less or six or less. Hydrofluoroolefins may be of type E (trans) and Z (cis). The hydrofluoroolefin may be a hydrochlorofluoroolefin. Hydrochlorofluoroolefins are intended to be compounds in which one or two or more hydrogen atoms in the olefin are replaced by fluorine atoms and one or two or more other hydrogen atoms in the olefin are replaced by chlorine atoms. The number of chlorine atoms in the hydrochlorofluoroolefin is not particularly limited, and may be one or more, and five or less or three or less.
Examples of hydrofluoroolefins having no chlorine atoms include 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 and CH3-CF2-CH＝CF2. Examples of hydrofluoroolefins having chlorine atoms (i.e., hydrochlorofluoroolefins) include CF3-CH＝CHCl、CHF2-CF＝CHCl、CHF2-CH＝CFCl、CHF2-CCl＝CHF、CH2F-CCl＝CF2、CHFCl-CF＝CHF、CH2Cl-CF＝CF2And CF3-CCl＝CH2. A particularly preferred hydrofluoroolefin having a chlorine atom is CF3-CH ═ CHCl. Hydrofluoroolefins (also including hydrochlorofluoroolefins) may be used alone or in combinations of two or more thereof.
The water used in the method for purifying a fluorinated liquid of the present disclosure is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, or the like may be used.
In the method for purifying a fluorinated liquid of the present disclosure, an extraction step is performed two or more times, the extraction step including a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed, and a second step of separating a mixed solution after the water contact into two liquids, i.e., an aqueous phase located in an upper layer and a phase containing a fluorinated liquid located in a lower layer, and then collecting the liquid in the lower layer. The upper limit of the number of times of performing the extraction step is not particularly limited, but is advantageous from the viewpoint of simplifying the purification process, for example, 5 times or less, 4 times or less, or 3 times or less.
The method of contacting water with the fluorinated liquid having the cleaning agent mixed therein in the first step is not particularly limited, and the methods such as (1) to (7) below may be used alone or in combination of two or more of them, and may be performed by appropriately combining some of the methods of (1) to (7). For example, the physical stirring method using vibration, a stirrer, or the like, the stirring method using air, the stirring method using ultrasonic waves, or the like described in (3), (6), or (7) can be applied to the method (1) or (2).
(1) A method for dripping a fluorinated liquid mixed with a cleaning agent into a container containing water from above the container.
(2) A method for adding water from below a container to a container containing a fluorinated liquid mixed with a cleaning agent.
(3) A method for physically stirring a container of a mixed solution containing a cleaning agent, a fluorinated liquid and water by using a stirrer, a stirring blade or the like.
(4) A method in which an upper layer and a lower layer are connected to each other by a pipe or the like, and in the case where a mixed solution has been separated into two layers in a container containing a mixed solution of a detergent, a fluorinated liquid and water, the upper layer liquid is moved to the lower layer by gravity or a pump.
(5) A method in which an upper layer and a lower layer are connected to each other by a pipe or the like, and in a case where a mixed solution has been separated into two layers in a container containing a mixed solution of a cleaning agent, a fluorinated liquid and water, the lower layer liquid is moved to the upper layer by gravity or a pump.
(6) A method in which a gas such as air is blown into a container and bubbled to mix a mixed solution, and in the case where the mixed solution has been separated into two layers in a container containing a mixed solution of a cleaning agent, a fluorinated liquid and water, the liquid of the lower layer is moved to the upper layer by gravity or a pump.
(7) A method in which ultrasonic waves are applied to a container to mix a mixed solution, and in a case where the mixed solution has been separated into two layers in the container containing the mixed solution of a cleaning agent, a fluorinated liquid, and water, a lower layer liquid is moved to an upper layer by gravity or a pump.
In each extraction step, the amount of water contacted in the first step may be the same or different from each other. For example, in the case where the extraction step is performed three times, a total of 3.0g of water may be added to and contacted with 1.0g of the fluorinated liquid having the cleaning agent mixed therein, or 1.5g of water may be added for the first time, 1.0g of water may be added for the second time, and 0.5g of water may be added for the third time.
According to the method for purifying a fluorinated liquid of the present disclosure, even if the amount of water contacted in the first step performed for the first time is small and the total amount of water contacted until the final extraction step is about 30.0 mass% or less, excellent purification efficiency can be achieved by performing the extraction step two or more times. The amount of water contacted in the first step performed for the first time may be about 20.0% by mass or less, about 19.0% by mass or less, or about 18.0% by mass or less, and may be about 3.0% by mass or more, about 4.0% by mass or more, or about 5.0% by mass or more. Here, the "amount of water contacted in the first step performed for the first time" means a value calculated as a percentage of the mass of the added water with respect to the mass of the cleaning agent contained in the fluorinated liquid and the mass of the added water in the first step performed for the first time. Furthermore, the mass of the cleaning agent contained in the fluorinated liquid at the first time of the first step can be determined by quantitative analysis methods using a calibration curve indicating the correlation of the concentration of the cleaning agent in the fluorinated liquid previously generated by a gas chromatograph analyzer.
The temperature and timing at which water is contacted with the fluorinated liquid having the cleaning agent mixed therein are not particularly limited as it may vary depending on the desired properties, scale size, contacting method, etc. of the purified fluorinated liquid. For example, the temperature may be about 20 ℃ or more, about 23 ℃ or more, or about 25 ℃ or more, and about 40 ℃ or less, about 35 ℃ or less, or about 30 ℃ or less, and the contact time may be set to about 30 seconds or more, about 1 minute or more, or about 5 minutes or more, and may be about 1 day or less, about 10 hours or less, about 1 hour or less, or about 30 minutes or less.
The second step in the extraction step comprises a step of separating the mixed solution after the water contact into two liquids, i.e., an aqueous phase located in the upper layer and a phase containing the fluorinated liquid located in the lower layer, and then collecting the liquid in the lower layer. The separation of the two liquids of the upper layer and the lower layer can be achieved, for example, by a step of standing a mixed solution containing a cleaning agent and a fluorinated liquid.
The lower layer of liquid may be collected directly from below the container containing the upper and lower layers of liquid via a tube or the like, or the upper layer of liquid may be collected from above the container and the lower layer of liquid may then be collected, or the tube or the like may be stretched and pulled from above the container to near the bottom of the container.
The total amount of water contacted until the final extraction step is about 30.0 mass% or less, and when considering, for example, a reduction in the amount of wastewater and a balance of purification efficiency, the total amount is desirably about 29.0 mass% or less, about 28.0 mass% or less, or about 27.0 mass% or less, about 25.0 mass% or less, about 23.0 mass% or less, or about 20.0 mass% or less, and is desirably about 5.0 mass% or more, about 7.0 mass% or more, or about 9.0 mass% or more. Here, "the total amount of water contacted up to the final extraction step" means a value calculated as a percentage of the total amount of water added with respect to the mass of the cleaning agent contained in the fluorinated liquid at the first time of the first step and the total amount of water added.
The purity of the fluorinated liquid purified by the methods for purifying fluorinated liquids of the present disclosure can be achieved to be about 95.0% or higher, about 96.0% or higher, about 97.0% or higher, or about 98.0% or higher. The upper purity limit of the fluorinated liquid is not particularly limited, and may be set to, for example, less than about 100%, about 99.9% or less, or about 99.8% or less.
The method for purifying a fluorinated liquid of the present disclosure can be optionally applied by using one or two or more of a heating step, a distillation step (such as a boiling distillation step, a vacuum distillation step, or the like), a cooling separation step, or the like in combination.
If it is desired to increase the purity of the fluorinated liquid, the purification process of the present disclosure may further include a distillation step to distill the lower layer of liquid collected by the final extraction step. In the related art, a distillation apparatus is generally used for purifying a fluorinated liquid, but in the case of purifying a fluorinated liquid by only a distillation apparatus, most of the fluorinated liquid must be basically discarded because the amount of the recoverable fluorinated liquid is extremely low. On the other hand, in the case where the distillation step is combined with the method for purifying a fluorinated liquid of the present disclosure, the recovery amount of the fluorinated liquid can be greatly increased as compared with the purification method using only a distillation apparatus.
The distillation temperature in the distillation step is not limited to the following temperature, and for example, it may be about 70 ℃ or higher, about 72 ℃ or higher, or about 75 ℃ or higher, and may be about 100 ℃ or lower, about 95 ℃ or lower, or about 90 ℃ or lower.
In some embodiments, the purification methods of the present disclosure may not employ an additional distillation step or heating step. Purification processes that do not include such steps can accomplish the purification at room temperature, thereby increasing energy efficiency and eliminating the need for additional operations. Therefore, it is advantageous not to employ a distillation step or a heating step from the viewpoint of reducing the environmental load.
A fluorinated liquid purification apparatus according to one embodiment of the present disclosure includes an extraction device for performing two or more times of the extraction steps performed, and the extraction steps include a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed, and a second step of separating into two phases, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquid in the lower layer, wherein a total amount of the water contacted until the final extraction step is about 30.0 mass% or less, the cleaning agent used here is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. Examples of the cleaning agent, the fluorinated liquid and the water which can be used in such a purification apparatus may be the same as those used in the above-described purification method. Further, such a purification apparatus can similarly exhibit the effects described in the above-described purification method.
The extraction device in the fluorinated liquid purification apparatus of the present disclosure is not particularly limited as long as the extraction device can perform the extraction step including the first step and the second step in the above-described method for purifying a fluorinated liquid. For example, the material, capacity, shape, number, position, and the like of the container (referred to as "tank" or the like in some cases) for storing the mixed solution containing the cleaning agent, the fluorinated liquid, and water used in the extraction device may be appropriately selected depending on the use application or use environment of the apparatus.
The fluorinated liquid purification apparatus of the present disclosure may optionally employ a device that can perform any step such as a heating step, a distillation step (such as a boiling distillation step, a vacuum distillation step, etc.), a cooling separation step, and the like in the above-described method for purifying a fluorinated liquid. For example, the material, capacity, shape, number, position, and the like of the container for storing the lower layer liquid used in the distillation step may be appropriately selected depending on the use application or use environment of the apparatus. Various devices such as a heating device, a distillation device, a cooling separation device, and the like may be applied to the fluorinated liquid purification apparatus alone or in combination of two or more thereof.
If it is desired to increase the purity of the fluorinated liquid, the purification apparatus of the present disclosure may further comprise a distillation device for distilling the lower layer liquid collected via the extraction device. The distillation apparatus may use known equipment including, for example, a still pot for storing and heating the collected lower layer liquid, and a cooler in communication with the still pot to condense and liquefy the vapor of the lower layer liquid.
In some embodiments, the purification apparatus of the present disclosure may not employ additional distillation or heating devices. Purification equipment that does not include such devices can accomplish purification at ambient temperatures, thereby increasing energy efficiency and eliminating the need for additional operations. Therefore, it is advantageous from the viewpoint of reducing the environmental load not to employ a distillation apparatus or a heating apparatus.
The disclosed methods and purification apparatus for purifying fluorinated liquids may be used on-line or off-line in various production lines as appropriate. In case of an on-line situation, when using the method and the purification apparatus for purifying a fluorinated liquid of the present disclosure, these may be suitably configured such that the purified fluorinated liquid may be reused, for example in a cleaning step or in a rinsing step. If these are used off-line, the fluorinated liquid that has been used in the production line of the organic EL display, such as a cleaning step or a rinsing step, is purified in another production line and can be reused in the production line of the organic EL display; on the other hand, the purified fluorinated liquid can be reused for another purpose than use, such as a cleaning liquid or a rinsing liquid for printed wiring boards.
The fluorinated liquid purified using the method for purifying a fluorinated liquid and the purification apparatus of the present disclosure is not limited to the following uses, and is used for an organic EL display manufacturing apparatus, for example, and can be used as a cleaning liquid or a rinsing liquid for various electronic parts, precision parts, metal parts, printed wiring boards, and the like, in addition to a rinsing liquid for various members exposed to cleaning and rinsing operations, such as metal masks and anti-deposition plates. Here, the "anti-deposition plate" refers to a member provided within a vacuum chamber of a vacuum evaporation apparatus for manufacturing an organic EL display, and is a member that can be removed and cleaned to prevent the vacuum chamber from being contaminated by three colors of red (R), green (G), and blue (B) as evaporation sources. The use of the rinsing liquid is not limited to direct use as a liquid, and for example, includes a use in which a deposited cleaning agent or the like is rinsed off by immersing a material to be rinsed and cleaned in the rinsing liquid, and a use in which the rinsing liquid is evaporated to attach vaporized gas to a surface to be rinsed and cleaned to rinse off the cleaning agent or the like.
Examples
Specific embodiments of the present invention will be illustrated in the following examples, but the present invention is not limited to these embodiments.
The products and the like used in the examples are shown in table 1 below.
[ Table 1]
The purity of the fluorinated liquid was evaluated by gas chromatography using 7890A manufactured by Agilent Technologies. The measurement conditions of the gas chromatography were as follows:
column type: HP-1301
Column length: 60m
Column temperature: 260 deg.C
Carrier gas type: helium gas
Carrier gas flow: 205 mL/min
Sample introduction volume: 1 μ L
Example 1
100g NOVEC (TM)7100 (fluorinated liquid) and 10g NMP (detergent) were added to a plastic bottle. 0.2g of distilled water was added to the mixed solution, and shaken in a mechanical shaker for 15 minutes. The resulting mixed solution was then separated into two layers, an upper layer (aqueous phase) and a lower layer (phase containing a fluorinated liquid), and the upper layer (aqueous phase) was removed from the plastic bottle by collecting the upper layer floating on the surface with a dropper (first extraction step). Samples for purity measurements were collected from the lower layer liquid using a micro-syringe and the purity of novec (tm)7100 in the lower layer liquid was measured. A series of operations from the addition of distilled water to the purity measurement was performed four times in total, and the results thereof are shown in table 2. Here, after performing the second time on the lower layer liquid obtained by removing the upper layer (aqueous phase), 0.2g of distilled water was added. Further, "amount of water after water contact (% by mass)" in table 2 is a value calculated as a percentage of the total added amount of water with respect to the total added amount of water and the initial blending amount (10g) of the detergent (NMP).
<Examples 2 to 5 and comparative examples 1 and 2 ″
The purity of the fluorinated liquid was measured in the same manner as in example 1 except that the amount of distilled water added was changed to the amount shown in table 2. Note that since the amount of water after water contact exceeds 30.0 mass%, the extraction step after the fourth time is not performed in embodiment 4 and the third or subsequent extraction step is not performed in embodiment 5. Further, in comparative example 1, in the second extraction step, the amount of water after water contact was already 30.0 mass% larger than in the first extraction step of comparative example 2, and therefore the subsequent extraction step was not performed.
It will be apparent to those skilled in the art that various modifications can be made to the embodiments and examples described above without departing from the underlying principles of the invention. In addition, it will be apparent to those skilled in the art that various improvements and modifications can be made to the present invention without departing from the spirit and scope of the invention.
Claims (11)
1. A method for purifying a fluorinated liquid comprising:
performing an extraction step two or more times, the extraction step including a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquid in the lower layer,
wherein the total amount of water contacted up to the final extraction step is about 30.0 mass% or less,
wherein the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and
wherein the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
2. The purification method according to claim 1, wherein the amount of water contacted in the first step performed for the first time is 3.0 to 20.0 mass%.
3. The purification method according to claim 1 or 2, wherein the extraction step is performed 5 times or less.
4. The purification process according to any one of claims 1 to 3, wherein the aprotic polar solvent is at least one selected from the group consisting of cyclic amide-based solvents, amine-based solvents, glycol ether-based solvents, acetone, dimethyl sulfoxide, and dimethylformamide.
5. The purification process according to any one of claims 1 to 4, wherein the solubility of water in the fluorinated liquid is 500ppm or less.
6. The purification process according to any one of claims 1 to 5, further comprising a step of distilling the lower layer liquid collected by the final extraction step.
7. The purification process according to any one of claims 1 to 6, wherein the purity of the fluorinated liquid purified by the purification process is 95.0% or higher.
8. A method of using a fluorinated liquid purified by the purification method according to any one of claims 1 to 7 as a rinsing liquid for a member used in an organic EL display manufacturing apparatus.
9. The method of claim 8, wherein the component is a metal mask or an anti-deposition plate.
10. A fluorinated liquid purification apparatus comprising:
an extraction device that performs an extraction step two or more times, the extraction step including a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed, and a second step of separating a mixed solution after the water contact into two liquids, an aqueous phase located in an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquid in the lower layer,
wherein the total amount of water contacted up to the final extraction step is about 30.0 mass% or less,
wherein the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and
wherein the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
11. The purification apparatus of claim 10, further comprising means for distilling liquid in the lower layer collected by the extraction means.
Applications Claiming Priority (3)
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| JP2019115422A JP2021000603A (en) | 2019-06-21 | 2019-06-21 | Method for purifying fluorinated liquid and purification apparatus using same |
| JP2019-115422 | 2019-06-21 | ||
| PCT/IB2020/055649 WO2020254983A1 (en) | 2019-06-21 | 2020-06-17 | Method for purifying fluorinated liquid and purification apparatus using same |
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| CN114007715A true CN114007715A (en) | 2022-02-01 |
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| JP (1) | JP2021000603A (en) |
| KR (1) | KR20220024464A (en) |
| CN (1) | CN114007715A (en) |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10290963A (en) * | 1997-04-18 | 1998-11-04 | Otsuka Giken Kogyo Kk | Washing device |
| CN101622201A (en) * | 2007-02-23 | 2010-01-06 | 3M创新有限公司 | The purification process that contains the solution of fluorine-based solvent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0776787A (en) | 1993-09-07 | 1995-03-20 | Tonen Corp | Regenerating device for metal detergent |
| JP4129308B2 (en) * | 1997-10-15 | 2008-08-06 | 大塚技研工業株式会社 | Separation method of water and solvent |
| JP3877758B2 (en) * | 2006-05-26 | 2007-02-07 | 関東化学株式会社 | Cleaning liquid composition and cleaning method for mask used in vacuum deposition process of low molecular organic EL device production |
| JP2008163400A (en) | 2006-12-28 | 2008-07-17 | Asahi Glass Co Ltd | Cleaning system and cleaning method |
-
2019
- 2019-06-21 JP JP2019115422A patent/JP2021000603A/en active Pending
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2020
- 2020-06-17 WO PCT/IB2020/055649 patent/WO2020254983A1/en active Application Filing
- 2020-06-17 KR KR1020227000796A patent/KR20220024464A/en unknown
- 2020-06-17 CN CN202080044430.7A patent/CN114007715A/en not_active Withdrawn
- 2020-06-20 TW TW109120966A patent/TW202104140A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10290963A (en) * | 1997-04-18 | 1998-11-04 | Otsuka Giken Kogyo Kk | Washing device |
| CN101622201A (en) * | 2007-02-23 | 2010-01-06 | 3M创新有限公司 | The purification process that contains the solution of fluorine-based solvent |
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| KR20220024464A (en) | 2022-03-03 |
| TW202104140A (en) | 2021-02-01 |
| JP2021000603A (en) | 2021-01-07 |
| WO2020254983A1 (en) | 2020-12-24 |
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Application publication date: 20220201 |