KR102012041B1 - Recovery system of the organic solution from the waste result solution of polyimide production process - Google Patents
Recovery system of the organic solution from the waste result solution of polyimide production processInfo
- Publication number
- KR102012041B1 KR102012041B1 KR1020170163746A KR20170163746A KR102012041B1 KR 102012041 B1 KR102012041 B1 KR 102012041B1 KR 1020170163746 A KR1020170163746 A KR 1020170163746A KR 20170163746 A KR20170163746 A KR 20170163746A KR 102012041 B1 KR102012041 B1 KR 102012041B1
- Authority
- KR
- South Korea
- Prior art keywords
- reaction
- alcohol
- organic solvent
- solvent
- generated
- Prior art date
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 36
- 239000004642 Polyimide Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 239000002699 waste material Substances 0.000 title description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000003960 organic solvent Substances 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010887 waste solvent Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000004508 fractional distillation Methods 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 15
- 238000000066 reactive distillation Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- -1 dianhydride compound Chemical class 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/02—Filters adapted for location in special places, e.g. pipe-lines, pumps, stop-cocks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치에 관한 것이다.
본 발명은 반도체 또는 플렉시블 디스플레이용 폴리이미드 합성공정에서 발생하는 유기용매 및 알콜 과 물로 이루어진 수성성분 그리고 반응촉매와 불순물로 이루어진 고체입자 혼합물로 이루어진 반응폐용제를 회수하여 함유된 고체입자를 여과하는 반응폐용제 여과 장치(S1);
상기 반응폐용제 여과장치에서 여과된 반응폐용제에 기상상태의 알콜을 공급하기전 예열하는 예열장치(S2);
상기 예열장치에서 예열처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하며, 발생한 초산과 알콜의 에스테르 반응체는 연속적으로 회수하는 반응성 증류장치(S3);
상기 반응성 증류장치 처리후에도 잔류하는 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치(S4);
상기 흡착 장치 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 고순도의 유기용제를 분별증류하는 분별증류장치(S5);를 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치를 제공한다.
따라서, 본 발명에 의하여 소각 폐기에 의존하던 유기용매류의 연속적인 고순도 정제로, 연속적인 폴리이미드 화학반응시 발생하는 용매의 재활용으로 원가 절감은 물론 연속적인 재투입으로 폴리이미드 생산성의 획기적 증가를 가능하게 하는 효과를 제공하게 되는 것이다.The present invention relates to a continuous recovery apparatus of an organic solvent generated after the production of a polyimide film for semiconductors and flexible displays.
The present invention recovers a reaction waste solvent consisting of an organic solvent generated in the polyimide synthesis process for semiconductor or flexible display, an aqueous component consisting of alcohol and water, and a solid particle mixture composed of a reaction catalyst and impurities, and filtering the solid particles contained therein. Waste solvent filtration device (S1);
A preheater (S2) for preheating before supplying alcohol in a gaseous state to the reaction waste solvent filtered by the reaction waste solvent filtering device;
A reactive distillation apparatus (S3) which adds alcohol in a gaseous state to the reaction waste solvent preheated by the preheater to esterify acetic acid contained in the reaction waste solvent, and continuously recovers the ester reactant of the generated acetic acid and alcohol;
An adsorption device (S4) for removing unreacted acetic acid and impurities remaining after the reactive distillation apparatus by passing through the adsorption column;
After the adsorption device treatment, to remove the remaining impurities and at the same time to increase the purity fractional distillation apparatus (S5) for distilling high-purity organic solvent; comprising an organic solvent generated after the production of a polyimide film for semiconductor and flexible display Provides a continuous recovery device of.
Therefore, according to the present invention, continuous high-purity purification of organic solvents, which depended on incineration disposal, reduced the cost by recycling solvents generated during continuous polyimide chemical reactions, and dramatically increased polyimide productivity by continuous re-entry. It will provide the effect that makes it possible.
Description
본 발명은 반도체와 디스플레이용 폴리이미드 필름 제조시 발생하는 유기용매의 연속 회수장치에 관한 것이다.The present invention relates to a continuous recovery apparatus of an organic solvent generated during the production of a polyimide film for semiconductors and displays.
유기 전계발광 소자를 사용한 디스플레이나 액정 디스플레이 등의 디스플레이 기기의 분야 등에 있어서, 유리와 같이 광투과성이 높으며 또한 충분히 높은 내열성을 가짐과 함께, 가벼우며 유연한 재료의 출현이 요구되어 왔다.BACKGROUND ART In the field of display devices such as a display using an organic electroluminescent element, a liquid crystal display, and the like, there has been a demand for the emergence of a light and flexible material having high light transmittance and high heat resistance like glass.
그리고, 이러한 유리 대체 용도 등에 사용하는 재료로서, 고도의 내열성을 가지며, 또한 가벼우며 유연한 폴리이미드를 포함하는 필름이 개발되었다.And as a material used for such a glass replacement use etc., the film which has a high heat resistance and also contains a light and flexible polyimide was developed.
열경화성 폴리이미드는 열안정성, 내화학성, 안정적인 기계적 특성 그리고 특이한 오렌지/황색을 갖는 것으로 알려져 있다.Thermoset polyimides are known to have thermal stability, chemical resistance, stable mechanical properties and unusual orange / yellow color.
일반적으로 폴리이미드(PI) 필름은 폴리이미드 수지를 필름화한 것으로, 폴리이미드 수지는 방향족 디안하이드라이드와 방향족 디아민 또는 방향족 디이소시아네이트를 용액중합하여 폴리아믹산 유도체를 제조한 후, 고온에서 폐환탈수시켜 이미드화하여 제조되는 고내열 수지를 일컫는다. In general, a polyimide (PI) film is a film of a polyimide resin. The polyimide resin is a solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring dehydration at high temperature. The high heat resistant resin manufactured by imidation is called.
이러한 폴리이미드 제조시, 디안하이드라이드 성분과 디아민 성분을 유기욤매중에 축중합 반응시켜 목적한 필름을 합성한다. 그리고 합성후 사용된 유기용매는 초산, 반응 촉매, 물 등을 포함하여 유기용매와 혼합되어있다. 유기용매는 우선 폐기 처리함에 있어 특수화학물질로 별도의 폐기물 처리관련법에 의하여 엄격한 처리절차를 거쳐야 하므로 원가 상승과 환경오염의 문제의 근본원인이 되고 있다. 유기용매만을 추출하여 재활용하기 위해서는, 폐기처리함에 있어 고가의 비용을 들여 소각처리하는 것이 현재의 실정이며, 비교적 고가의 유기용매들도 함께 소각되어 자원의 낭비는 물론 환경적으로 좋지 않은 결과를 낳고 있다.In preparing such a polyimide, the dianhydride component and the diamine component are subjected to a polycondensation reaction in an organic solvent to synthesize a desired film. The organic solvent used after synthesis is mixed with an organic solvent including acetic acid, reaction catalyst, water and the like. Organic solvents are special chemicals in the treatment of wastes and must go through rigorous treatment procedures under separate waste disposal laws, which is the root cause of the problem of cost increase and environmental pollution. In order to extract and recycle only organic solvents, it is currently incinerated at a high cost in disposal, and relatively expensive organic solvents are also incinerated, resulting in waste of resources and environmentally unfavorable results. have.
선행기술문헌의 특허문헌으로 개시된 한국공개특허 10-2016-0102378호는 " a) 다이안하이드라이드 화합물과 다이아민 화합물을 물에 분산시키는 단계; b) 상기 분산액을 압력용기에 넣고, 5℃ 내지 400℃ 온도 및 가압 조건에서 다이안하이드라이드 화합물과 다이아민 화합물을 반응시켜 얻은 반응 생성물을 여과하고 건조시켜 단일 반응 스텝으로 폴리이미드를 수득하는 단계; 및 c) 단계 b)에서 생성된 수증기를 압력용기로부터 배출시켜 냉각 및 응축하여 물을 회수하는 단계를 포함하는 폴리이미드의 제조에 있어 물을 회수하는 방법." 에 의하여 반응후 생성된 물을 회수하는 방법을 제시하고 있다. Korean Patent Publication No. 10-2016-0102378 disclosed as a patent document of the prior art document "a) dispersing a dianhydride compound and a diamine compound in water; b) putting the dispersion in a pressure vessel, 5 ℃ to 400 Filtering and drying the reaction product obtained by reacting the dianhydride compound with the diamine compound at a temperature and a pressurized condition to obtain a polyimide in a single reaction step; and c) the water vapor generated in step b) from the pressure vessel. A method for recovering water in the manufacture of a polyimide comprising the steps of: draining, cooling and condensing to recover water. It proposes a method for recovering the water produced after the reaction by.
반응용매로 유기용매 대신 물을 사용하여 고가의 유기용매의 폐기에 따른 문제점을 해소하는 새로운 제조방법을 제시하고 있다. Using a water instead of an organic solvent as a reaction solvent has been proposed a new manufacturing method to solve the problems caused by the disposal of expensive organic solvents.
본 발명은 상기 폴리이미드 합성후에 반응후 폐기 처리하는 용액 중에서 고가의 유기용매를 연속으로 회수하여 재활용하는 장치를 제공하려는데 그 목적이 있는 것이다.It is an object of the present invention to provide an apparatus for continuously recovering and recycling an expensive organic solvent in a solution which is disposed of after the reaction after the polyimide synthesis.
본 발명은 풀리이미드 합성반응후에 잔류 폐액이 유기용매, 초산, 촉매 그리고 물 등이 혼재함으로, 이들을 분별증류법으로 분리하기에 어렵다는 문제점을 해소하고자, 산과 알콜을 산성촉매에 의하여 축합반응시켜 휘발성이 높은 에스테르로 변환후 제거함에 따라 고가의 유기욤매를 분별증류가능하게 하였다.The present invention is to solve the problem that it is difficult to separate them by fractional distillation, because the residual waste is mixed with the organic solvent, acetic acid, catalyst and water after the synthesis of the polyimide, the condensation reaction of acid and alcohol by acidic catalyst, Expensive organic solvents were fractionated and distilled off after conversion to esters.
따라서, 본 발명은, 반도체 또는 플렉시블 디스플레이용 폴리이미드 합성공정에서 발생하는 유기성 및 수성 그리고 고체입자 혼합물로 이루어진 반응폐용제를 회수하여 함유된 고체입자를 여과하는 반응폐용제 여과 장치와, 반응폐용제를 공급하기전 예열하는 예열장치와, 여과처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류장치와, 중화공정후에도 잔류하는 소량의 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치 및 흡착컬럼을 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 분별증류하여 고순도의 유기용매를 회수하는 분별증류장치를 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치에 그 특징이 있다.Accordingly, the present invention is a reaction waste solvent filtration device for recovering the reaction waste solvent consisting of a mixture of organic, aqueous and solid particles generated in the polyimide synthesis process for semiconductors or flexible displays and filtering the contained solid particles, the reaction waste solvent A preheating device to preheat before supplying, a reactive distillation device to esterify the acetic acid contained in the reaction waste solvent by adding a gaseous alcohol to the filtered reaction waste solvent, and a small amount of unreacted acetic acid remaining after the neutralization process. A semiconductor and flexible display comprising an adsorption device for removing impurities through an adsorption column and a fractionation distillation device for recovering organic solvents of high purity by fractional distillation to remove residual impurities and to increase purity after processing the adsorption column. Continuous recovery apparatus of organic solvent generated after the production of polyimide film for There is a characteristic.
상기 예열장치는, 회수한 반응폐용제와 반응을 위한 알콜을 40 ~ 70 ℃ 의 온도로 예열하여 공급하는 것을 다른 특징으로 한다.The preheating device is characterized in that the preheated supply of the recovered reaction waste solvent and the alcohol for the reaction at a temperature of 40 ~ 70 ℃.
상기 반응성 증류장치는, 미세 부유물이나 고상입자들이 제거된 반응폐용제에 알코올과 에스테르화 촉매를 반응탑(R)에 가하여 초산과 알콜간의 에스테르화를 유도하기 위하여, 반응탑의 중앙부에는 에스테르화촉매층(3c)이 설치되며, 에스테르화촉매층의 상부에는 반응폐용제의 공급부(3d)를 구성하고, 하부는 에스테르화 반응을 위한 알콜공급부(3e)로 이루어지도록 구성하여 알콜과 반응폐용제의 초산이 CH3COOH + ROH <-> CH3COOR(ROAc) + H2O (상기 식에서 R = 알킬기로서, 바람직하게는 메틸, 에틸, n-프로필, 이소프로필 중의 어느 하나이며, Ac 는 아세틸기임) 식과 같이 에스테르화촉매층에서 반응하도록 이루어지는 것을 또 다른 특징으로 한다.The reactive distillation apparatus, in order to induce esterification between acetic acid and alcohol by adding an alcohol and an esterification catalyst to the reaction tower (R) to the reaction waste solvent from which fine suspended solids or solid particles are removed, an esterification catalyst layer at the center of the reaction column (3c) is installed, the upper portion of the esterification catalyst layer constitutes the supply portion of the reaction waste solvent (3d), the lower portion is composed of an alcohol supply portion (3e) for the esterification reaction to the acetic acid of alcohol and the reaction waste solvent CH 3 COOH + ROH <-> CH 3 COOR (ROAc) + H 2 O (wherein R is an alkyl group, preferably one of methyl, ethyl, n-propyl, isopropyl, and Ac is an acetyl group) Another feature is that it is made to react in the esterification catalyst layer as described above.
상기 에스테르화촉매층에 공급하는 알콜을 기상상태로 공급하는 것을 또 다른 특징으로 한다.It is another feature that the alcohol supplied to the esterification catalyst layer is supplied in a gaseous state.
상기 반응성 증류장치에 의하여 생성된 에스테르류를 포함한 알콜, 물을 데칸타 층분리하며, 상층(ROAc, ROH)을 환류(Reflux)하는 환류장치를 포함하는 것을 또 다른 특징으로 한다.Alcohol, including the esters produced by the reactive distillation device, and decanta layer separation of water, it characterized in that it comprises a reflux device for refluxing the upper layer (ROAc, ROH).
상기 흡착 장치는, 활성탄, 제올라이트, 실리카겔, 활성알루미나 중의 어느 하나 혹은 이들의 혼합물로 구성한 다층 구조의 흡착칼럼으로 연속적으로 흡착과 재생하는 것을 또 다른 특징으로 한다.The adsorption device is further characterized by continuously adsorbing and regenerating a multi-layered adsorption column composed of any one or a mixture of activated carbon, zeolite, silica gel and activated alumina.
상기 분별 증류 장치는, 1차 분별증류탑에서 유기용매를 알콜, 물과 분별증류한 후, 2차 분별증류탑으로 이송하여 유기용매와 고비점의 불순물을 분별증류하여 고순도의 유기용매를 회수하는 것을 또 다른 특징으로 한다.The fractional distillation apparatus, after distilling the organic solvent and fractional distillation of the organic solvent with alcohol, water in the first fractional distillation column, and transfer to the second fractional distillation column to separate the organic solvent and impurities of high boiling point to recover the high purity organic solvent It is another feature.
본 발명은 소각 폐기에 의존하던 유기용매류의 연속적인 고순도 정제로, 연속적인 폴리이미드 화학반응시 발생하는 용매의 재활용으로 원가 절감은 물론 연속적인 재투입으로 폴리이미드 생산성의 획기적 증가를 가능하게 하는 효과가 있다.The present invention is a continuous high-purity purification of organic solvents that depended on incineration disposal, which enables a dramatic increase in polyimide productivity as well as cost reduction through continuous recycling of solvents generated during continuous polyimide chemical reactions. It works.
그리고 유기용매의 재순환이 연속적으로 이루어지면서 반응중 약간의 부족한 용매만의 보충과 순도 확인에 의하여 연속적인 합성반응이 유지되어 품질의 균일화를 가능하게 하는 효과가 있다.And while recycling of the organic solvent is made continuously, a continuous synthesis reaction is maintained by replenishing only a small amount of solvent during the reaction and confirming purity, thereby enabling uniformity of quality.
도 1은 본 발명의 전체적인 공정을 나타내는 공정도,
도 2는 본 발명의 공정에 적합한 장치의 구성도이다.1 is a process chart showing the overall process of the present invention,
2 is a block diagram of a device suitable for the process of the present invention.
본 발명에 따른 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치를 첨부된 바람직한 실시도면에 의거하여 보다 상세히 설명하면 다음과 같다.The continuous recovery apparatus of the organic solvent generated after manufacturing the polyimide film for semiconductor and flexible display according to the present invention will be described in more detail based on the accompanying drawings.
본 발명에서 반응은 폴리이미드 고분자 합성을 위한 아민계 모노머들의 합성반응이며, 이들 합성 반응 공정에 대한 자세한 설명은 생략토록 한다. 본 발명에서 합성반응후에 반응폐액 혹은 반응폐용제 등으로 설명하는 것은 모두 합성반응후에 잔류하는 유기용매, 촉매, 물 등이 혼합한 폐액으로, 이하 모두 반응폐용제로 통일하여 사용한다.In the present invention, the reaction is a synthesis reaction of amine monomers for polyimide polymer synthesis, and detailed description of these synthesis reaction processes will be omitted. In the present invention, what is described as a reaction waste solution or a reaction waste solvent after the synthesis reaction is a waste solution in which an organic solvent, a catalyst, water, and the like remaining after the synthesis reaction are mixed, and all are used as a reaction waste solvent.
본 발명에서 반도체와 플렉시블 디스플레이용으로 사용하는 폴리이미드의 합성반응에는 디아민계 모노머로부터 유래된 단위구조와 디안하이드라이드계 모노머로 유래된 단위구조를 포함하며 방향족 디안하이드라이드 성분으로서 피로멜리트산이무수물(PMDA) 또는 비페닐테트라카르복실산이무수물(BPDA)등을 주로 사용하고 있고, 방향족 디아민 성분으로서는 옥시디아닐린(ODA), p-페닐렌 디아민(p-PDA), m-페닐렌 디아민(m-PDA), 메틸렌디아닐린(MDA), 비스아미노페닐헥사플루오로프로판(HFDA) 등을 주로 사용하는 다양한 예시가 가능하다. 이들 합성반응용 모노머와 그에 유리된 다양한 합성반응원재료에 대한 설명과 그 합성반응에 대한 설명은 생략토록 한다.In the present invention, the synthesis reaction of the polyimide used for the semiconductor and the flexible display includes a unit structure derived from a diamine monomer and a unit structure derived from a dianhydride monomer, and pyromellitic dianhydride as an aromatic dianhydride component. (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is mainly used, and the aromatic diamine component is oxydianiline (ODA), p-phenylene diamine (p-PDA), m-phenylene diamine (m -PDA), methylenedianiline (MDA), bisaminophenylhexafluoropropane (HFDA) and the like are mainly various examples. The description of these synthetic reaction monomers and the various synthetic reaction raw materials, and the description of the synthetic reaction raw materials are omitted.
합성반응에 있어 모노머들의 용액 중합반응을 위한 유기용매(제1 용매)는 폴리아믹산을 용해하는 용매라면 특별히 한정되지 않는다. 상기 유기용매(제1 용매)로는 m-크레졸, N-메틸-2-피롤리돈(NMP), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 디메틸설폭사이드(DMSO), 디에틸아세테이트 중에서 선택된 하나 이상의 극성용매를 사용한다.The organic solvent (first solvent) for the solution polymerization of the monomers in the synthesis reaction is not particularly limited as long as it is a solvent that dissolves the polyamic acid. The organic solvent (the first solvent) is m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl acetate One or more polar solvents selected from among are used.
이외에도 테트라하이드로퓨란(THF), 클로로포름과 같은 저비점 용액 또는 γ-부티로락톤과 같은 저흡수성 용매를 사용할 수 있다. 본 발명에서 디아민계 디안하이드라이드계 모노머의 반응을 통한 폴리이미드 수지제조법을 특별히 제한하는 것은 아니며, 이들 반응에 있어 사용되는 용매의 예시도 다양한 예시로 이러한 다양한 용매류의 사용과 이들로 부터 고순도의 유기용매의 재활용을 위한 회수가 가능하다는 가능성을 예시하며, 특별한 제한을 두어 본 발명의 권리범위를 제한하는 것은 아니다.In addition, low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as γ-butyrolactone may be used. In the present invention, the polyimide resin production method through the reaction of the diamine-based dianhydride-based monomers is not particularly limited. Examples of the solvent used in these reactions are also various examples. Illustrates the possibility of recovery for the recycling of organic solvents, and does not limit the scope of the present invention with a particular limitation.
상기 유기용매는 상기 모노머들의 충분한 반응을 가능하게 하기 위하여 충분한 양이 사용되며, 통상적으로 상기 모노머의 중량을 기준으로 9 내지 15배를 사용한다.The organic solvent is used in an amount sufficient to enable sufficient reaction of the monomers, and typically 9 to 15 times based on the weight of the monomer.
또한, 반응후에는 탈수촉매와 물과의 반응으로 인한 초산을 생성하며, 다양한 촉매류와 초산은 물, DMF, Methylpyridine 등과 공비혼합물(Azeotropic mixture)을 형성하여 상기 혼합물에서 단순 분별증류에 의하여는 유기용매 만을 분리하여 수거하는 것이 불가능하다.In addition, after the reaction, acetic acid is produced by the reaction between the dehydration catalyst and water, and various catalysts and acetic acid form an azeotropic mixture with water, DMF, Methylpyridine, and the like. It is not possible to separate bays separately.
본 발명은 반응 후 잔류하는 초산을 알콜과 에스테르 축합하여 초산에스테르로 변환시킴으로써 유기용매와 분별이 가능하게 되어 분별증류시켜 폐유기용매를 고순도로 정제하여 재활용이 가능하게 하였다.According to the present invention, acetic acid remaining after the reaction is condensed with alcohol to be converted into acetic acid ester, thereby allowing the organic solvent to be fractionated and fractionated by distillation to recycle the organic solvent with high purity.
본 발명의 구체적인 회수 장치는, Specific recovery device of the present invention,
반도체 또는 플렉시블 디스플레이용 폴리이미드 합성공정에서 발생하는 유기용매 및 알콜 과 물로 이루어진 수성성분 그리고 반응촉매와 불순물로 이루어진 반응폐용제를 회수하여 함유된 고체입자를 여과하는 반응폐용제 여과 장치(S1)와,Reaction waste solvent filtration device (S1) for filtering the solid particles contained by recovering the organic solvent, the aqueous component consisting of alcohol and water, and the reaction catalyst and impurities generated in the polyimide synthesis process for semiconductor or flexible display ,
상기 반응폐용제 여과장치에서 여과된 반응폐용제를 공급하기전 예열하는 예열장치(S2)와,A preheater (S2) for preheating before supplying the reaction waste solvent filtered by the reaction waste solvent filtering device;
상기 예열장치에서 예열처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하며, 발생한 초산과 알콜의 에스테르 반응체는 연속적으로 회수하는 반응성 증류장치(S3)와,A reactive distillation apparatus (S3) for adding esters of acetic acid contained in the reaction waste solvent by adding alcohol in a gaseous state to the reaction waste solvent preheated by the preheater, and recovering the ester reactant of the generated acetic acid and alcohol continuously;
상기 반응성 증류장치 처리후에도 잔류하는 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치(S4)와Adsorption apparatus (S4) for removing the unreacted acetic acid and impurities remaining after the reactive distillation apparatus through the adsorption column and
상기 흡착 장치 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 고순도의 유기용매를 분별증류하는 분별증류장치(S5)로 이루어진다.After treatment with the adsorption device, a fractionation distillation apparatus (S5) for separating and distilling the organic solvent of high purity so as to remove the remaining impurities and increase the purity.
상기 각 장치에 대한 보다 구체적인 설명을 도 1의 공정도와 도 2의 장치도에 의하여 설명한다.A more detailed description of each apparatus will be described with reference to the process diagram of FIG. 1 and the apparatus diagram of FIG. 2.
1. One. 반응폐용제Reaction Waste Solvent 여과 장치(S1) Filtration device (S1)
플렉시블 디스플레이용 폴리이미드 필름을 제조하는 과정에서 생성되는 폐유기용매, 초산, 물과 기타 불순물로 이루어진다. 상기 반응폐용제중 유기용매의 중량 함량은 30~90중량%, 초산의 함량은 2~30%, 촉매 함량은 2~10%, 수분 함량은 1~60% 로 이루어진다. 이러한 액상 용제 외에도 회수중에 유입되는 다양한 미세 부유물들이 포함되어 있으며, 이들 고상 입자를 제거하는 필터장치(1a)로 이루어진다. It consists of waste organic solvent, acetic acid, water and other impurities produced in the process of manufacturing the polyimide film for flexible display. The weight of the organic solvent in the reaction waste solvent is 30 to 90% by weight, the content of acetic acid is 2 to 30%, the catalyst content is 2 to 10%, the moisture content is 1 to 60%. In addition to these liquid solvents, various fine suspended matters introduced during recovery are included, and the filter device 1a removes these solid particles.
2. 예열 장치(S2)2. Preheater (S2)
상기 회수한 반응폐용제와 반응을 위한 알콜을 에스테르화 반응을 위한 반응열을 공급하기 위하여 40 ~ 70 ℃ 의 온도로 예열하는 장치이다. 에스테르화 반응에 있어 알콜의 수산기와 산의 카르복실기 간의 축합반응을 최적화하기 위한 것이다.It is a device for preheating the recovered reaction solvent and the alcohol for the reaction at a temperature of 40 ~ 70 ℃ to supply the reaction heat for the esterification reaction. It is to optimize the condensation reaction between the hydroxyl group of the alcohol and the carboxyl group of the acid in the esterification reaction.
온도가 40 ℃보다 낮으면 반응 속도가 늦어 생산성이 떨어지며, 70 ℃보다 높으면 비점이 낮은 유기용매외 초산의 공비 증류현상으로 에스테르 촉매와의 목적한 반응이 이루어지지 않는다. 부호 2a는 예열기를 나타낸다.If the temperature is lower than 40 ℃, the reaction rate is slow, the productivity is lowered, If the temperature is higher than 70 ℃, the azeotropic distillation of acetic acid other than the low boiling point solvent does not achieve the desired reaction with the ester catalyst. 2a represents a preheater.
3. 반응성 증류장치(S3)3. Reactive distillation unit (S3)
미세 부유물이나 고상입자들이 제거된 반응폐용제에 에스테르화 촉매로 이루어진 반응탑(R)에 알콜을 공급하여 초산과 알콜간의 에스테르화를 유도한다.Alcohol is supplied to the reaction tower (R) consisting of an esterification catalyst to the reaction waste solvent from which fine suspended solids or solid particles are removed to induce esterification between acetic acid and alcohol.
반응탑(R)의 중앙부에는 반응촉매층(3c)이 설치되며, 반응촉매층의 상부에는 반응폐용제의 공급부(3d)를 구성하고, 하부는 에스테르화 반응을 위한 알콜공급부(3e)로 이루어진다.The reaction catalyst layer 3c is installed at the center of the reaction tower R, the upper portion of the reaction catalyst layer constitutes the supply portion 3d of the reaction waste solvent, and the lower portion is composed of the alcohol supply portion 3e for the esterification reaction.
합성 반응후에 잔류하는 반응폐용제에는 전체 중량을 기준으로 초산 2 ~ 30%, 유기용매 30 ~ 90 %, 물 1 ~60 % 그리고 촉매 2 ~10 %로 이루어지며, 초산의 함량이 상기하듯이 적게는 2% 에서 많게는 30% 이르며, 하기 식과 같이 알콜과의 에스테르화를 연속적으로 진행하며, 발생하는 에스테르 반응체는 연속적으로 회수한다.The reaction waste solvent remaining after the synthesis reaction is composed of 2-30% acetic acid, 30-90% organic solvent, 1-60% water and 2-10% catalyst based on the total weight. Is from 2% to as much as 30%, and the esterification with alcohol is continuously carried out as in the following formula, and the resulting ester reactant is recovered continuously.
CH3COOH + ROH <-> ROAc + H2OCH 3 COOH + ROH <-> ROAc + H 2 O
(상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기임)(Wherein R is any one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and Ac is an acetyl group)
상기하듯이 초산과 알콜의 반응으로 발생한 에스테르를 반응성 증류 (Reactive Distillation) 방법을 사용하여 함유된 초산을 초산에스테르로 변화시키며 물과 알콜의 공비혼합물로 제거한다.As described above, the ester generated by the reaction of acetic acid with alcohol is converted to acetic acid ester by using reactive distillation, and then removed with an azeotrope of water and alcohol.
본 발명의 또 다른 특징은 반응탑(R)의 상측과 하측에 다공성의 트레이 혹은 팩킹구조를 갖으며, 중간부에는 반응촉매층(3c)을 구성하였다. 반응탑의 상부에서는 반응폐용제를, 탑하부에서는 알콜을 공급한다.Another feature of the present invention has a porous tray or packing structure on the upper side and the lower side of the reaction tower R, and the reaction catalyst layer 3c is formed in the middle portion. The reaction waste solvent is supplied at the top of the reaction tower, and alcohol is supplied at the bottom of the tower.
공급되는 알콜은 기화 가능하도록 예열처리하여 공급됨에 따라 기상(氣相) 상태로 하부에 설치한 다공성의 트레이 혹은 팩킹을 통하여 공급되어 중간의 반응촉매층(3c)으로 이송토록 하였다.The alcohol supplied was preheated so as to be vaporized, and then supplied through a porous tray or packing installed at the bottom in a gaseous state to be transferred to the intermediate reaction catalyst layer 3c.
상부에서 주입하는 폐액중 초산과 하층에 투입한 후 증발되어 올라오는 알콜(ROH)과 반응촉매층에서 반응하여 에스테르(ROAc)가 생성되며, 이 에스테르반응체는 반응탑의 상부로 이송하여 데칸타(3b)에서 응축한다.In the waste liquid injected from the top, acetic acid and the lower layer are added to the lower layer, and the alcohol (ROH), which is evaporated, reacts with the reaction catalyst layer to produce ester (ROAc). Condensation in 3b).
본 발명의 또 다른 특징은 환류장치(3f)를 더 포함하는 것이다. 구체적으로는 에스테르화합물만이 데칸타(3b)로 이송되는 것이 아니라 물, 알코올, 초산에스테르가 복잡한 공비(azeotrope)로 증발하기 때문에 응축된 액은 두 층으로 갈라지면서 데칸타에 모이게 된다.Another feature of the invention is that it further includes a reflux device 3f. Specifically, not only the ester compound is transferred to decanta (3b), but water, alcohol, and acetate esters are evaporated in a complex azeotrope, so that the condensed liquid is divided into two layers and collected in decanta.
모여진 혼합물은 상층에서 에스테르와 알콜은 환류(Reflux)시켜 함유된 알코올을 되돌려 반응에 다시 참여하게 하고 하층의 물과 알콜의 혼합물은 분리한다. 가역반응인 에스테르화 반응에서 알콜의 환류로 인하여 알콜을 높은 농도로 유지함에 따라 에스테르화 반응이 촉진되도록 하였다.The collected mixture is refluxed of ester and alcohol in the upper layer to return the contained alcohol to participate in the reaction again, and the mixture of water and alcohol in the lower layer is separated. In the reversible esterification reaction, the esterification reaction was promoted by maintaining the alcohol at a high concentration due to the reflux of the alcohol.
4. 흡착 장치(S4)4. Suction device (S4)
함유된 소량의 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거한다.A small amount of unreacted acetic acid and impurities contained are removed by passing through an adsorption column.
흡착칼럼(4a)은 활성탄, 제올라이트, 실리카겔, 활성알루미나 등의 흡착제를 충진한 칼럼으로, 2기 이상의 칼럼을 병행하여 사용함으로 연속적으로 흡착과 재생을 가능하게 하는 구조이다.The adsorption column 4a is a column packed with an adsorbent such as activated carbon, zeolite, silica gel, and activated alumina. The adsorption column 4a is used to continuously adsorb and regenerate by using two or more columns in parallel.
5. 분별 증류 장치(S5)5. Fractional distillation apparatus (S5)
흡착칼럼(4a)을 통과함에 따라 미량의 미반응 초산과 기타 불순물이 대부분 제거 되어진다.As it passes through the adsorption column 4a, most of the unreacted acetic acid and other impurities are removed.
목적으로 하는 유기용매의 순도를 높이기 위하여 반응 참여 후에 잔류한 촉매, 미반응 알콜 그리고 일부 함께 이송된 물을 분별증류한다.To increase the purity of the desired organic solvent, fractional distillation of the catalyst, unreacted alcohol and some of the water transported together after the reaction has been carried out.
본 발명은 1차 분별증류시, 1차 분별증류탑(5a)에서 유기용매를 분별증류하되, 1차 분별증류탑에서 정제된 유기용매에는 고비점 분순물이 일부 포함되어 있으므로, 2차 분별증류탑(5b)으로 이송되어져 고비점의 불순물을 더 고순도로 정제한다.In the present invention, during the first fractional distillation, the organic solvent is fractionally distilled in the first fractional distillation tower (5a), but the organic solvent purified in the first fractional distillation tower includes a part of the high boiling point fraction, the second fractional distillation tower (5b). It is then transferred to) to purify high-boiling impurities with higher purity.
1,2차의 분별증류에 의하여 유기용매의 순도는 99% 이상이 회수가 가능해진다.By the first and second fractional distillation, 99% or more of the organic solvent can be recovered.
이하 본 발명의 실제 반응폐용제 100㎏ 을 수거하여 회수하는 실험을 진행하였다. 본 실시예는 본 발명의 대표적인 실시를 예시하는 것으로 실시예에서 제시하는 반응조건들로 본발명의 기술적 범위가 제한을 받는 것은 아니며, 다양한 반응조건의 변화로 실시가능하며, 제시한 실시예는 다양한 실시 가능성 들의 한가지 예시이다. The experiment was then conducted to collect and recover 100 kg of the actual reaction waste solvent of the present invention. This embodiment is to illustrate a representative implementation of the present invention by the reaction conditions presented in the examples are not limited to the technical scope of the present invention, it can be carried out with a variety of reaction conditions changes, the presented embodiments are various One example of implementation possibilities.
도면 중 5c 는 리시버탱크이며, 상기하듯이 1차 분별증류탑에 환류하며, 2차 분별증류탑에도 동일한 구조에 의한 리시버탱크(5d)에서는 목적으로 하는 순도 99% 이상의 유기용매를 회수한다.In the drawing, 5c is a receiver tank, and refluxed to the first fractionation tower as described above, and recovers the organic solvent having a purity of 99% or more in the receiver tank 5d having the same structure as the secondary fractionation tower.
본 발명에서 예시하는 분별증류탑은 1, 2 차로 예시하였지만, 설치환경과 반응폐용제에 사용된 유기용매의 특성에 따라 3차 이상도 설치가능하며, 모두 본발명의 다양한 실시예의 한가지로 기술적 범위에 속한다.Although the fractionation distillation tower illustrated in the present invention is illustrated as the first and second, it can be installed more than three times depending on the installation environment and the characteristics of the organic solvent used in the reaction waste solvent, all of the various embodiments of the present invention in the technical scope Belongs.
플렉시블디스프레이용 필름제조시 발생하는 반응폐용제 100 ㎏을 수거하였다. 반응폐용제는 DMF 68.5%, 초산 12.5%, 3-Methylpyridine 2.7%, 수분14.1%를 함유한 것으로 분석되었다. 폐용제혼합물 100Kg을 마이크로필터를 통과시킨 후 중간부위에 Amberlyst-15를 충진한 분별증류탑 상단에 프리히터를 거쳐 60~64℃로 가열하여 분당 4L로 스프레이시키고 메타놀을 탑 하부노즐에서 분당 0.8L로(초산의 당량의 ２배)역시 프리히터를 거쳐 60~64℃로 가열하여 연속적으로 탑하부에 주입시켰다．생성된 초산메틸／메타놀／물 혼합물이 상부콘덴서를 통하여 상부데칸터에 응축되어 상하층（상층：초산메틸／메타놀 ； 하층 : 메타놀/물）으로 분리되며 하층은 연속적으로 제거하며 상층은 Reflux시켰다. 이때 reflux ratio（2:1~5:1)를 조절하여 상부온도를 58℃이하로 유지시켰다.100 kg of the reaction waste solvent generated during the manufacture of the film for flexible display were collected. The reaction waste solvent contained 68.5% of DMF, 12.5% of acetic acid, 2.7% of 3-Methylpyridine, and 14.1% of water. After passing 100Kg of the waste solvent mixture through the micro filter, the preheater is heated to 60 ~ 64 ℃ by the preheater at the top of the fractionation tower, filled with Amberlyst-15 in the middle part, and sprayed to 4L per minute and 0.8L per minute at the bottom nozzle. (2 times the equivalent of acetic acid) The pre-heater was also heated to 60-64 ° C and injected continuously to the bottom of the tower. The resulting methyl acetate / methanol / water mixture was condensed on the upper decanter through the upper capacitor. (Upper layer: methyl acetate / metholol; lower layer: methanol / water), the lower layer was continuously removed, and the upper layer was refluxed. At this time, the reflux ratio (2: 1 to 5: 1) was adjusted to maintain the upper temperature below 58 ° C.
하부 리보일러에 남은 혼합물은 연속적으로 활성탄이 충진된 흡착탑을 통과시켜 잔존 초산과 불순물을 제거하고 １차 증류탑으로 보내졌다．The mixture left in the lower reboiler was continuously passed through an adsorption tower filled with activated carbon to remove residual acetic acid and impurities and to be sent to the first distillation column.
１차증류탑은 상부가 105℃를 넘지 않게 유지했으며 리보일러에서 프리히터를 거쳐 140~145℃로 가열하여 ２차증류탑에서 DMF를 상부콘덴서로 응축시켜 최종제품을 얻을 수 있었다．이때 탑상부의 온도는 153~5℃를 유지하였다．수거한 DMF는 >99.8%의 순도를 갖고 총량 61.6Kg을 얻었다. 수율 (89.2%)The primary distillation tower was kept above 105 ° C and heated to 140-145 ° C through the preheater in the reboiler to condense the DMF into the upper condenser in the secondary distillation tower to obtain the final product. Was maintained at 153 ~ 5 ℃. The collected DMF had a purity of> 99.8% and obtained a total amount of 61.6Kg. Yield (89.2%)
S1: 여과장치 S2: 예열장치
S3: 반응성 증류장치 S4: 흡착장치
S5: 분별증류장치 1a: 필터장치
2a: 예열기 R: 반응탑
3b: 데칸타 3c: 반응촉매층
3d: 공급부 3e:알콜공급부
3f: 환류장치 4a: 흡착칼럼
5a,5b: 분별증류탑 5c,5d: 리시버탱크S1: Filter S2: Preheater
S3: reactive distillation unit S4: adsorption unit
S5: fractional distillation unit 1a: filter unit
2a: preheater R: reaction column
3b: decanta 3c: reaction catalyst layer
3d: supply part 3e: alcohol supply part
3f: reflux device 4a: adsorption column
5a, 5b: fractionation tower 5c, 5d: receiver tank
Claims (7)
상기 반응폐용제 여과장치에서 여과된 반응폐용제에 기상상태의 알콜을 공급하기전 예열하는 예열장치(S2);
상기 예열장치에서 예열처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하며, 발생한 초산과 알콜의 에스테르 반응체는 연속적으로 회수하는 반응성 증류장치(S3);
상기 반응성 증류장치 처리후에도 잔류하는 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치(S4);
상기 흡착 장치 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 고순도의 유기용매를 분별증류하는 분별증류장치(S5);를 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
Reaction waste solvent filtration to recover the solid particles contained in the organic solvent generated in the polyimide synthesis process for semiconductor or flexible display, an aqueous component composed of alcohol and water, and a solid particle mixture composed of reaction catalyst and impurities. Apparatus S1;
A preheater (S2) for preheating before supplying alcohol in a gaseous state to the reaction waste solvent filtered by the reaction waste solvent filtering device;
A reactive distillation apparatus (S3) which adds alcohol in a gaseous state to the reaction waste solvent preheated by the preheater to esterify acetic acid contained in the reaction waste solvent, and continuously recovers the ester reactant of the generated acetic acid and alcohol;
An adsorption device (S4) for removing unreacted acetic acid and impurities remaining after the reactive distillation apparatus by passing through the adsorption column;
After the adsorption device treatment, to remove the remaining impurities and at the same time to increase the purity fractional distillation apparatus (S5) for distilling a high-purity organic solvent; comprising an organic solvent generated after the production of a polyimide film for semiconductor and flexible display Continuous recovery device.
예열장치는,
회수한 반응폐용제와 반응을 위한 알콜을 40 ~ 70 ℃ 의 온도로 예열하여 공급하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 1,
Preheater,
A continuous recovery apparatus for an organic solvent generated after the production of a polyimide film for semiconductors and flexible displays, wherein the recovered reaction waste solvent and alcohol for reaction are preheated and supplied at a temperature of 40 to 70 ° C.
반응성 증류장치는,
미세 부유물이나 고상입자들이 제거된 반응폐용제에 반응촉매로 이루어진 반응탑(R)에 알콜을 공급하여 초산과 알콜간의 에스테르화를 유도하기 위하여,
반응탑의 중앙부에는 반응촉매층(3c)이 설치되며, 반응촉매층의 상부에는 반응폐용제의 공급부(3d)를 구성하고, 하부는 에스테르화 반응을 위한 알콜공급부(3e)로 이루어지도록 구성하여 알콜과 반응폐용제의 초산이 하기 식과 같이 반응촉매층에서 반응하도록 이루어지는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
CH3COOH + ROH <-> ROAc + H2O
(상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기임)
The method of claim 1,
Reactive distillation apparatus,
In order to induce esterification between acetic acid and alcohol by supplying alcohol to the reaction tower (R) consisting of a reaction catalyst to a reaction waste solvent from which fine suspended solids or solid particles are removed,
The reaction catalyst layer (3c) is installed in the center of the reaction tower, the upper portion of the reaction catalyst layer constitutes the supply portion of the reaction waste solvent (3d), the lower portion is composed of an alcohol supply portion (3e) for the esterification reaction alcohol and A continuous recovery apparatus for an organic solvent generated after the production of a polyimide film for a semiconductor and a flexible display, characterized in that the acetic acid of the reaction waste solvent reacts in the reaction catalyst layer as in the following formula.
CH 3 COOH + ROH <-> ROAc + H 2 O
(Wherein R is any one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and Ac is an acetyl group)
반응촉매층에 공급하는 알콜을 기상상태로 공급하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 3, wherein
A continuous recovery apparatus for an organic solvent generated after the production of a polyimide film for a semiconductor and a flexible display, wherein the alcohol supplied to the reaction catalyst layer is supplied in a gaseous state.
반응성 증류장치에 의하여 생성된 에스테르 반응체를 포함한 알콜, 물을 데칸타 층분리하며,
상층의 에스테르와 알콜만을 환류(Reflux)하는 환류장치를 포함하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 3, wherein
Decanter layer separation of alcohol and water, including the ester reactant produced by the reactive distillation unit,
A continuous recovery apparatus for an organic solvent generated after the production of a polyimide film for a semiconductor and a flexible display, comprising a reflux device for refluxing only the ester and the alcohol of the upper layer.
흡착 장치는,
활성탄, 제올라이트, 실리카겔, 활성알루미나 중의 어느 하나 혹은 이들의 혼합물로 구성한 다층 구조의 흡착칼럼으로 연속적으로 흡착과 재생하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 1,
Adsorption device,
Continuous recovery of organic solvents generated after the production of polyimide films for semiconductors and flexible displays, characterized by continuous adsorption and regeneration in a multi-layered adsorption column composed of any one or a mixture of activated carbon, zeolite, silica gel and activated alumina. Device.
분별 증류 장치는,
1차 분별증류탑에서 유기용매를 알콜, 물과 분별증류한 후, 2차 분별증류탑으로 이송하여 유기용매와 고비점의 불순물을 분별증류하여 고순도의 유기용매를 회수하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 1,
Fractional distillation apparatus,
After separating and distilling the organic solvent with alcohol and water in the first separation distillation column, the organic solvent and the flexible display are recovered by separating the organic solvent and high boiling point impurities and recovering the high purity organic solvent. Continuous recovery apparatus of the organic solvent which arises after manufacture of the polyimide film for solvents.
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