KR101986367B1 - Recovery method of the organic solution from the waste result solution of polyimide production process and its production system - Google Patents
Recovery method of the organic solution from the waste result solution of polyimide production process and its production system Download PDFInfo
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- KR101986367B1 KR101986367B1 KR1020170163739A KR20170163739A KR101986367B1 KR 101986367 B1 KR101986367 B1 KR 101986367B1 KR 1020170163739 A KR1020170163739 A KR 1020170163739A KR 20170163739 A KR20170163739 A KR 20170163739A KR 101986367 B1 KR101986367 B1 KR 101986367B1
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- organic solvent
- water
- acetic acid
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 229920001721 polyimide Polymers 0.000 title claims abstract description 33
- 239000004642 Polyimide Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 title description 7
- 238000011084 recovery Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000003960 organic solvent Substances 0.000 claims abstract description 45
- 239000010887 waste solvent Substances 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 19
- 238000000066 reactive distillation Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 238000004508 fractional distillation Methods 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 104
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 28
- -1 ester compound Chemical class 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 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
- 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
- 238000005191 phase separation 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
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- 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 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 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 compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 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 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
- 229920005575 poly(amic acid) Polymers 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
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 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
- 238000005194 fractionation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
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Classifications
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- 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
- C08G85/00—General processes for preparing compounds provided for in this subclass
-
- 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
Abstract
Description
본 발명은 반도체와 디스플레이용 폴리이미드 필름 제조시 발생하는 유기용매의 회수방법 그리고 이 회수 방법에 적합한 장치에 관한 것이다.TECHNICAL FIELD The present invention relates to a method for recovering an organic solvent that occurs when a semiconductor and a display polyimide film are produced, and a device suitable for the recovery method.
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. 그리고, 이러한 유리 대체 용도 등에 사용하는 재료로서, 고도의 내열성을 가지며, 또한 가벼우며 유연한 폴리이미드를 포함하는 필름이 개발되었다.In the fields of displays using organic electroluminescent devices and display devices such as liquid crystal displays, etc., it has been required to have light transmittance as well as glass, sufficiently high heat resistance, and appearance of a light and flexible material. As a material for use in such glass substitute applications, a film including a highly heat-resistant, lightweight and flexible polyimide has been developed.
열경화성 폴리이미드는 열안정성, 내화학성, 안정적인 기계적 특성 그리고 특이한 오렌지/황색을 갖는 것으로 알려져 있다.Thermosetting polyimides are known to have thermal stability, chemical resistance, stable mechanical properties and unusual orange / yellow color.
일반적으로 폴리이미드(PI) 필름은 폴리이미드 수지를 필름화 한 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 made of a polyimide resin. The polyimide resin is produced by preparing a polyamic acid derivative by combining an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate in solution, Refers to a high heat-resistant resin produced by imidization.
이러한 폴리이미드 제조시, 디안하이드라이드 성분과 디아민 성분을 유기용매중에 축중합 반응시켜 목적한 필름을 합성한다. 그리고 합성후 사용된 유기용매는 초산, 반응 촉매, 물 등을 포함하여 유기용매와 혼합되어있다.In producing such a polyimide, a dianhydride component and a diamine component are subjected to condensation polymerization in an organic solvent to synthesize a desired film. The organic solvent used after the synthesis is mixed with organic solvent including acetic acid, reaction catalyst, water and the like.
유기용매는 우선 폐기 처리함에 있어 특수화학물질로 별도의 폐기물 처리관련법에 의하여 엄격한 처리절차를 거쳐야 하므로 원가 상승과 환경오염의 문제의 근본원인이 되고 있다.Organic solvent is a special chemical substance in the first disposal process, and it is a root cause of cost increase and environmental pollution because it has to undergo strict treatment procedure according to separate waste treatment law.
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 order to extract and recycle only organic solvent, incineration treatment is carried out at a high cost in disposal, and relatively expensive organic solvents are also incinerated, resulting in waste of resources as well as 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 Laid-Open No. 10-2016-0102378, which is disclosed in the patent documents of the prior art documents, discloses a process for preparing a pressure-sensitive adhesive composition comprising the steps of: a) dispersing a dianhydride compound and a diamine compound in water; b) Filtration and drying of the reaction product obtained by reacting the dianhydride compound and the diamine compound at a temperature of from room temperature to room temperature to obtain a polyimide in a single reaction step, and c) separating the water vapor produced in step b) Withdrawing, cooling and condensing the water to recover the water. And recovering the water produced after the reaction.
반응용매로 유기용매 대신 물을 사용하여 고가의 유기용매의 폐기에 따른 문제점을 해소하는 새로운 제조방법을 제시하고 있어, 유기용매의 사용을 회피하는 방식을 제시할 뿐 범용으로 사용하는 유기용매에 의한 합성법에서는 적용이 어려운 현실이다.The present invention provides a new manufacturing method for solving the problem of disposal of expensive organic solvent by using water instead of organic solvent as a reaction solvent and suggesting a way to avoid the use of organic solvent. It is a difficult reality to apply in synthesis method.
본 발명은 상기 폴리이미드 합성후에 반응후 폐기 처리하는 용액중에서 고가의 유기용매를 회수하여 재활용하는 방법 그리고 이에 적합한 장치를 제공하려는데 그 목적이 있다.It is an object of the present invention to provide a method for recovering and recycling an expensive organic solvent in a solution for post-reaction discarding treatment after synthesis of the polyimide, and a suitable apparatus therefor.
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 유기용매를 분별 증류 가능하게 하였다.In order to solve the problem that it is difficult to separate them by a fractional distillation method due to the presence of an organic solvent, acetic acid, catalyst, water and the like in the residual waste liquid after the synthesis reaction of the polyimide by the condensation reaction of an acid and an alcohol, After conversion to the ester, the organic solvent was fractionally distilled at a high price by removing it.
따라서, 본 발명은 반도체 또는 플렉시블 디스플레이용 폴리이미드 합성공정에서 발생하는 유기성 및 수성 그리고 고체입자 혼합물로 이루어진 반응폐용제를 회수하여 함유된 고체입자를 여과하는 반응폐용제 여과 공정과, 여과처리한 반응폐용제에 알콜과 산을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류 공정 및 상기 반응성 증류 공정을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각응축기로 냉각하며, 냉각후 혼합액을 데칸터에서 층분리후 물을 제외한 에스테르 화합물과 알콜을 반응조로 공급하는 과정을 반복하는 냉각환류공정과, 목적한 수준으로 반응폐용제의 초산함량이 낮아지면 반응조에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 기타 부유물을 흡착 제거하는 중화 흡착공정과, 흡착칼럼을 통과시킨 유기용매, 알콜 과 물의 혼합물을 분별증류하여 목적한 유기용매를 고순도로 분리하는 분별증류공정을 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법을 그 특징으로 한다.Accordingly, the present invention relates to a process for producing a polyimide for semiconductor or flexible display, which comprises a reaction waste solvent filtration process for recovering a reaction waste solvent comprising organic and aqueous and a solid particle mixture, A reactive distillation step for esterifying the acetic acid contained in the reaction waste solvent by adding alcohol and acid to the waste solvent, and an azeotropic mixture of the ester compound, water, and alcohol generated through the above reactive distillation step are cooled with a cold condenser, A cooling reflux step of repeating a step of separating the water from the decanter and feeding the ester compound and the alcohol into the reaction tank except for the water, and the step of adding the alkali to neutralize the acid in the reaction tank when the acetic acid content of the reaction waste solvent becomes low to the desired level A neutralization adsorption step of adsorbing and removing unreacted materials and other suspended matters, And a fractional distillation step of fractionating an organic solvent, an alcohol and a water mixture passed through an adsorption column, and separating the objective organic solvent into a high purity, and a method for recovering an organic solvent after the production of a semiconductor and a polyimide film for a flexible display It is characterized by.
상기 반응성 증류 공정은, 여과처리한 반응폐용제에 알콜과 산을 가하여 CH3COOH + ROH <-> ROAc + H2O 식과 같이 반응하는 것을 다른 특징으로 한다. 상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기이다.The reactive distillation process is characterized in that an alcohol and an acid are added to the filtered reaction waste solvent and reacted in the same manner as in CH 3 COOH + ROH <-> ROAc + H 2 O. Wherein R is any one selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, and Ac is an acetyl group.
상기 냉각 환류 공정은, 반응성 증류 공정에 의하여 생성된 에스테르류를 포함한 알콜, 물을 데칸타에서 층분리하며, 상층의 알콜과 에스테르만을 반응조에 환류(Reflux)시키는 것을 또 다른 특징으로 한다.In the cooling and reflux process, the alcohol and water containing esters produced by the reactive distillation process are separated in a decanter, and only the alcohol and ester in the upper layer are refluxed into the reaction tank.
상기 중화 흡착공정은, 목표한 값 이하로 초산농도가 낮아지면, 가해진 산성촉매를 알카리, 보다 바람직하게는 가성소다로 중화반응시켜 제거하며, 미반응물인 초산과 불순물을 활성탄, 제올라이트, 실리카겔, 활성알루미나 혹은 이들의 혼합물로 이루어진 흡착제를 충진한 흡착칼럼을 통과시켜 제거하는 것을 또 다른 특징으로 한다.In the neutralization adsorption step, when the acetic acid concentration is lower than the target value, the added acid catalyst is neutralized with an alkali, more preferably, caustic soda to remove the acid, and the unreacted acetic acid and the impurities are reacted with activated carbon, zeolite, silica gel, Alumina, or a mixture thereof is passed through an adsorption column filled with an adsorbent.
상기 분별 증류 공정은, 흡착칼럼을 통과시켜 미반응 초산과 불순물을 제거한 유기용제, 알콜, 물의 혼합물을 분별증류에 의해 정제하는 것을 또 다른 특징으로 한다.The above-mentioned fractionation process is characterized in that a mixture of an organic solvent, alcohol and water in which unreacted acetic acid and impurities are removed by passing through an adsorption column is purified by fractional distillation.
그리고 본 발명은, 가열장치에 의하여 반응에 적합한 온도를 유지하며, 내부에는 반응액의 교반을 위한 교반장치를 설치하여, CH3COOH + ROH <->ROAc + H2O 식(상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기임)의 반응이 이루어지는 반응조와, 반응된 에스테르화합물과 알콜등의 스트리핑(striping)을 유도하기 위한 다단의 트레이 혹은 팩킹구조로 이루어진 반응탑과, 상기 반응탑을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각하는 냉각하여 데칸터에 공급하기 위한 냉각응축기 및 상기 냉각응축기에 의하여 냉각 응축된 것을 상분리유도하며, 상분리된 것중 하부의 물과 알콜을 제거하는 동시에 상부의 에스테르화합물과 알콜을 상부환류하는 환류데칸타와, 반응중 계속 초산의 농도를 스캔하며, 초산의 농도가 목표값 이하로 측정되면, 반응조에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 기타 불순물을 흡착제거하여 목적한 유기용매를 수거하는 흡착장치로 이루어지는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수장치를 다른 특징으로 한다.And the present invention, and kept at the temperature suitable for reaction by a heating apparatus, the inside is installed with a stirrer for stirring the reaction liquid, CH 3 COOH + ROH <- > ROAc + H 2 O Equation (in which R is (Wherein A is an acetyl group), and a reaction tank in which a reaction of the ester compound with an alcohol or the like is induced in a multi-stage A cooling condenser for cooling the azeotropic mixture of the ester compound, water and alcohol produced through the reaction tower and supplying the cooled azeotrope to the decanter, and a cooling and condensing device for cooling and condensing the azeotrope, A reflux decanter for removing water and alcohol from the lower part of the phase-separated product and for refluxing the upper ester compound and the alcohol, and And an adsorption device for collecting the desired organic solvent by adsorbing the unreacted material and other impurities by neutralizing the alkali by neutralizing the acid in the reaction tank when the concentration of the acetic acid is measured below the target value, Another feature of the present invention is an apparatus for recovering an organic solvent after manufacturing a semiconductor and a polyimide film for a flexible display.
상기 환류데칸타는, 하부의 물과 알콜은 반응계의 외부로 배출하며,In the reflux decanter, the lower water and the alcohol are discharged to the outside of the reaction system,
상부의 에스테르화합물과 알콜을 반응탑의 상부로 환류하는 것을 또 다른 특징으로 한다.And further refluxing the upper ester compound and the alcohol to the upper part of the reaction tower.
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 relates to a continuous high purity purification of an organic solvent that relies on incineration disposal, which enables recycling of a solvent generated during a continuous polyimide chemical reaction to reduce the cost and enable a dramatic increase in polyimide productivity by continuous re- It is effective.
도 1 은 본 발명의 전체적인 공정을 나타내는 공정도,
도 2 는 본 발명의 공정에 적합한 장치의 구성도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process drawing showing the overall process of the present invention,
2 is a block diagram of an apparatus suitable for the process of the present invention.
본 발명의 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조 후 발생하는 유기용매의 회수방법에 대하여 첨부된 바람직한 실시 도면에 의거하여 보다 상세히 설명하면 다음과 같다.A method of recovering organic solvent generated after manufacturing a semiconductor and a polyimide film for a flexible display according to the present invention will be described in more detail with reference to 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.The reaction in the present invention is a synthesis reaction of amine-based monomers for the synthesis of polyimide polymers, and a detailed description of these synthesis reaction steps will be omitted. In the present invention, the reaction waste solution or the reaction waste solvent after the synthesis reaction is a waste solution obtained by mixing residual organic solvent, catalyst, water, etc. after the synthesis reaction.
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 a polyimide used for a semiconductor and a flexible display includes a unit structure derived from a diamine-based monomer and a unit structure derived from a dianhydride-based monomer, and pyromellitic acid dianhydride (PMDA) or biphenyltetracarboxylic acid dianhydride (BPDA). The aromatic diamine components include oxydianiline (ODA), p-phenylenediamine (p-PDA), m-phenylenediamine -PDA), methylene dianiline (MDA), bisaminophenylhexafluoropropane (HFDA), etc. are mainly used. A description of these synthetic reaction monomers and various synthetic reaction raw materials free of them and a description of the synthetic reaction thereof will be 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. 이외에도 테트라하이드로퓨란(THF), 클로로포름과 같은 저비점 용액 또는 γ-부티로락톤과 같은 저흡수성 용매를 사용할 수 있다.The organic solvent (first solvent) for 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. Examples of the organic solvent (first solvent) include m-cresol, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, At least one polar solvent is used. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform or a low-absorbency solvent such as? -Butyrolactone may be used.
본 발명에서 디아민계 디안하이드라이드계 모노머의 반응을 통한 폴리이미드 수지제조법을 특별히 제한하는 것은 아니며, 이들 반응에 있어 사용되는 다양한 용매류의 사용과 이들로 부터 고순도의 유기용매의 재활용을 위한 회수가 가능하다는 가능성을 예시하며, 이들 예시에 의하여 본 발명의 실시범위나 권리범위를 제한하는 것은 아니다.In the present invention, the production method of the polyimide resin through the reaction of the diamine-based dianhydride monomer is not particularly limited, and the use of various solvents used in these reactions and the recovery thereof for recycling the high purity organic solvent And the scope of the present invention is not limited by these examples.
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 a sufficient reaction of the monomers, and usually 9 to 15 times the weight of the monomer is used.
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.After the reaction, acetic acid is generated by the reaction between the dehydration catalyst and water, and an azeotrope mixture is formed with various catalysts and acetic acid, water, DMF, methylpyridine and the like, and by simple fractional distillation, It is impossible to separate them.
본 발명은 반응 후 잔류하는 초산을 알콜과 에스테르 축합하여 초산에스테르로 변환시킴으로써 유기용매와 분별이 가능하게 되어 분별증류시켜 폐유기용매를 고순도로 정제하여 재활용이 가능하게 하였다.In the present invention, the acetic acid remaining after the reaction is condensed with an alcohol to convert it into an acetic acid ester, so that it can be separated from the organic solvent and fractional distillation is carried out to purify the waste organic solvent with high purity.
본 발명의 구체적인 회수 방법은, In the specific recovery method of the present invention,
반도체 또는 플렉시블 디스플레이용 폴리이미드 합성공정에서 발생하는 유기성 및 수성 그리고 고체입자 혼합물로 이루어진 반응폐용제를 회수하여 함유된 고체입자를 여과하는 반응폐용제 여과 공정(S1)과,A reactive waste solvent filtration step (S1) for recovering a reaction waste solvent comprising organic and aqueous and solid particle mixture generated in a polyimide synthesis process for a semiconductor or a flexible display to filter solid particles contained therein,
여과처리한 반응폐용제에 알콜과 산을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류 공정(S2)과,A reactive distillation step (S2) of esterifying the acetic acid contained in the reaction waste solvent by adding alcohol and acid to the filtered reaction waste solvent;
상기 반응성 증류 공정을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각응축기로 냉각하며, 냉각후 혼합액을 데칸터에서 층분리후 물을 제외한 에스테르 화합물과 알콜을 반응조로 공급하는 과정을 반복하는 냉각환류공정(S3)과,The ester compound produced through the above reactive distillation process, the azeotropic mixture of water and alcohol is cooled with a cold condenser, and after cooling, the mixture liquid is separated from the decanter, and then the ester compound and water except for water are fed to the reaction vessel A cooling and reflux step (S3)
목적한 수준으로 반응폐용제의 초산함량이 낮아지면 반응조에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 부유물을 흡착 제거하는 중화 흡착공정(S4)과,A neutralization step (S4) of neutralizing the neutralized acid by neutralizing the acid in the reaction tank when the acetic acid content of the reaction waste solvent is lowered to a desired level, and adsorbing and removing unreacted materials and suspended matters;
흡착칼럼을 통과시킨 유기용매, 알콜 그리고 물의 혼합물을 분별증류하여 목적한 유기용매를 고순도로 분리하는 분별증류공정(S5)을 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법으로 이루어진다.(S5) for fractionating a mixture of an organic solvent, an alcohol and water having passed through an adsorption column and separating a desired organic solvent into a high purity (S5). The organic solvent after the production of a semiconductor and a polyimide film for a flexible display Recovery method.
상기 각 공정에 대한 대표적인 실시예를 첨부된 도 1의 공정도와 도 2의 공정에 적합한 장치를 예시하여 설명한다.Exemplary embodiments of each of the above processes will be described with reference to the accompanying flow chart of FIG. 1 and an apparatus suitable for the process of FIG.
1. One. 반응폐용제Reactive waste solvent 여과공정(S1) Filtration step (S1)
플렉시블 디스플레이용 폴리이미드 필름을 제조하는 과정에서 생성되는 폐유기용제, 초산, 물과 기타 불순물로 이루어진다. 상기 반응폐용제중 유기용제의 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 공정이다. Is composed of a waste oil agent, acetic acid, water, and other impurities produced in the process of producing a polyimide film for a flexible display. The content 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 content of the catalyst is 2 to 10%, and the content of moisture is 1 to 60%. In addition to these liquid solvents, various fine suspended particles are contained in the recovery process, and these solid particles are removed.
2. 반응성 증류 공정(S2)2. Reactive distillation process (S2)
미세 부유물이나 고상입자들이 제거된 반응페용제에 알콜과 에스테르화 촉매를 가하여 초산과 알콜간의 에스테르화를 유도한다.The esterification reaction between acetic acid and alcohol is induced by adding an alcohol and an esterification catalyst to a reaction solvent in which fine suspensions or solid particles have been removed.
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 에스테르체는 연속적으로 회수한다.The reactive waste solvent remaining after the synthesis reaction is composed of 2 to 30% of acetic acid, 30 to 90% of organic solvent, 1 to 60% of water and 2 to 10% of catalyst based on the total weight, Is from 2 to 30% at most, and the esterification with alcohol continuously proceeds as in the following formula, and the resulting ester is continuously recovered.
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 아세틸기 임.)(Wherein R is any one selected from the group consisting of methyl, ethyl, n-propyl and 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, esters formed by the reaction of acetic acid and alcohol are converted into acetic acid ester by reactive distillation and removed by azeotropic mixture of water and alcohol.
3. 냉각 환류 공정(S3)3. Cooling Reflow Process (S3)
반응성 증류 공정에 의하여 반응된 에스테르화합물에는 물, 알코올, 초산에스테르가 복잡한 공비(azeotrope)로 증발하여 냉각조(6)를 통과하면서 응축된다Water, alcohol, and acetic acid ester are evaporated into a complex azeotrope in the ester compound reacted by the reactive distillation process, and condensed while passing through the cooling bath (6)
냉각조를 통과한 응축액은 두 층으로 갈라지면서 데칸타(7)에 모이게 된다. 모여진 혼합물에서, 에스테르와 알콜로 이루어진 상층은 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. 에스테르화반응으로 초산은 초산알킬에스테르체로 변하면서 알콜은 물과 함께 연속적으로 분리제거된다.The condensate, which has passed through the cooling bath, is separated into two layers and collected in decanter (7). In the pooled mixture, the upper layer of ester and alcohol is refluxed to bring back the contained alcohol back into the reaction and the lower layer separates the mixture of water and alcohol. The esterification reaction was promoted by maintaining the alcohol at a high concentration due to the reflux of the alcohol in the reversible esterification reaction. In the esterification reaction, the acetic acid is converted into the acetic acid alkyl ester form, and the alcohol is continuously separated and removed together with water.
4. 중화 흡착 공정(S4)4. Neutralization process (S4)
상기 분별 농축 공정이 진행되면서 계속 초산농도를 스캔하여 목표한 값이하로 초산농도가 낮아지면, 가해진 산성촉매를 알카리, 보다 바람직하게는 가성소다로 중화반응시켜 제거하며, 미반응물인 초산과 불순물을 흡착칼럼을 통과시켜 제거한다. 흡착칼럼은 활성탄, 제올라이트, 실리카겔, 활성알루미나 등의 흡착제를 충진한 구조이다. When the concentration of acetic acid is lowered below the target value by continuously scanning the acetic acid concentration as the fractional concentration process proceeds, the added acidic catalyst is neutralized with alkali, more preferably, caustic soda to remove the unreacted acetic acid and impurities It is removed by passing through an adsorption column. The adsorption column is a structure packed with an adsorbent such as activated carbon, zeolite, silica gel, or activated alumina.
5.분별 증류 공정(S5)5. Fractional Distillation Process (S5)
상기 중화 흡착 공정을 통하여 흡착 처리후, 유기용매, 알콜 그리고 물의 혼합물을 분별증류하여 목적한 유기용매를 고순도로 분리하는 공정이다.After the adsorption treatment through the neutralization adsorption process, the mixture of the organic solvent, alcohol and water is fractionally distilled to separate the desired organic solvent with high purity.
본 발명의 상기한 공정에 적합한 장치를 도 2의 공정 구성도를 참조하여 설명하면 다음과 같다.An apparatus suitable for the above-described process of the present invention will be described with reference to the process configuration diagram of FIG.
본 발명은 가열장치(2)에 의하여 반응에 적합한 온도를 유지하며, 내부에는 반응액의 교반을 위한 교반장치(3)가 설치된 반응조(1)와,The present invention relates to a reaction tank (1) which maintains a temperature suitable for a reaction by a heating device (2) and in which an agitation device (3) for stirring a reaction liquid is provided,
상기 반응조(1)에 반응폐용제에 알콜과 산을 가하여 반응폐용제에 함유된 초산을 에스테르화하면, 반응된 에스테르화합물과 알콜등의 스트리핑(striping)을 유도하기 위한 다단의 트레이 혹은 팩킹구조로 이루어진 반응탑(5)과,When acetic acid contained in the reaction waste solvent is esterified by adding alcohol and acid to the reaction waste solvent in the
상기 반응성 증류 공정을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각하는 냉각하여 데칸터에 공급하기 위한 냉각응축기(6)와,A cooling condenser (6) for cooling the azeotropic mixture of the ester compound produced through the reactive distillation process with water and the alcohol to supply the cooled azeotrope to the decanter,
상기 냉각응축기(6)에 의하여 냉각 응축된 것을 상분리유도하며, 상분리된 것중 하부의 물과 알콜을 제거하는 동시에 상부의 에스테르화합물과 알콜을 반응탑의 상부환류하는 환류데칸타(7)와,A reflux decanter (7) for inducing phase separation of the cooled and condensed by the cooling condenser (6), removing water and alcohol in the lower part of the phase separated and refluxing the upper ester compound and alcohol to the upper part of the reaction tower,
반응중 계속 초산의 농도를 스캔하며, 초산의 농도가 목표값 이하로 측정되면, 반응조(1)에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 기타 불순물을 흡착 제거하여 목적한 유기용매를 수거하는 흡착장치(8)로 이루어진다.When the concentration of acetic acid is measured to be lower than the target value, alkali is neutralized by neutralizing acid in the reaction tank (1), and unreacted materials and other impurities are removed by adsorption to remove the desired organic solvent And an adsorption device (8) for collecting the adsorbent.
상기 반응조(1)는, 가열장치(2)에 의하여 반응에 적합한 온도를 유지하며, 내부에는 반응액의 교반을 위한 교반장치(3)를 설치하여,The
하기 식 The following formula
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 and isopropyl, and Ac is an acetyl group)
의 반응이 이루어진다..
도 2에서 온도계(4)는 외부에서 육안 관측 가능하며, 원격감지 장치에 의하여 원격제어도 가능하다.In FIG. 2, the thermometer 4 can be visually observed from the outside and remotely controlled by a remote sensing device.
이하 본 발명의 실제 반응폐용제 1000g 을 수거하여 회수하는 실험을 진행하였다. [실시예 1]은 본 발명의 대표적인 실시를 예시하는 것으로서, 실시예에서 제시하는 반응조건들로 본 발명의 기술적 범위가 제한을 받는 것은 아니며, 다양한 반응조건의 변화로 실시 가능하며, 제시한 실시예는 다양한 실시 가능성들의 한가지 예시이다. Experiments were conducted to collect 1000 g of the actual reaction waste solvent of the present invention and collect it. [Example 1] exemplifies a representative embodiment of the present invention. The technical scope of the present invention is not limited to the reaction conditions set forth in the examples, but can be carried out by changing various reaction conditions. An example is one example of various implementations.
DMF 70.5%, 초산 14.5%, 3-Methylpyridine 3.2%, 수분10.2%, 기타 불순물 1.6%의 조성을 갖는 플렉시블 디스프레이용 필름제조시 발생하는 반응폐용제 1,000g을 마이크로필터로 여과하여 교반기, 분별증류탑, 상부데칸터를 갖춘 반응기에 투입하고 메타놀 154.9g(4.8mol, 이론치의 200%), 98% 황산 20.0g을 투입하여 가열한다. 생성되는 초산메틸(Methyl Acetate)은 메타놀(공비온도 53.8℃), 물(공비온도 56.1℃)과 각각 공비를 형성하여 즉시 증발되어 증류탑을 통하여 농축되어 열교환기를 통하여 액화된 후 데칸터에서 상하층(상층: 초산메틸+메타놀; 하층 물+메타놀)으로 층을 형성하게 된다. 상층의 초산메틸과 메타놀 혼합물은 탑상부로 되돌려(Reflux) 초산메틸의 함량을 높이고 메타놀을 순환시킴으로써 반응을 촉진시키고 하층의 메타놀, 수분혼합물은 계속적으로 분리 제거함으로써 에스테르화 반응이 촉진된다. 반응기안의 초산함량이 미미해지면 반응으로 인한 더 이상의 수분이 나오지 않아 층이 분리되지 않게 되어 과량의 메타놀을 분별증류한 후 20%가성소다로 pH 6-7로 중화하고 활성탄이 충전된 칼럼을 통과시켜 미량의 아세트산과 불순물을 제거했다. 처리된 용액(2-Methylpyridine, DMF와 수분 함유)을 분별 증류하여 637.5ｇ(수율 >90%)의 순도99.5%의 DMF를 얻을 수 있었다. 1,000 g of a reaction waste solvent generated in the production of a flexible display film having a composition of 70.5% DMF, 14.5% acetic acid, 3.2% 3-methylpyridine, 10.2% moisture and 1.6% other impurities was filtered through a microfilter, (4.8 mol, 200% of theoretical value) and 20.0 g of 98% sulfuric acid were charged into a reactor equipped with a decanter and heated. The resulting methyl acetate was evaporated immediately after forming an azeotropic mixture with methanol (azeotropic temperature 53.8 ° C) and water (azeotropic temperature 56.1 ° C), concentrated through a distillation column, liquefied through a heat exchanger, Upper layer: methyl acetate + methanol; lower layer + methanol). The mixture of methyl acetate and methanol in the upper layer is returned to the upper part of the column (Reflux). The methyl acetate content is increased and the methanol is circulated to promote the reaction and the lower methanol and water mixture are continuously separated and removed to promote the esterification reaction. When the acetic acid content in the reactor becomes insignificant, no further water is produced due to the reaction and the layer is not separated. The excess methanol is fractionated, neutralized with 20% caustic soda to pH 6-7 and passed through a column filled with activated carbon Trace amounts of acetic acid and impurities were removed. The treated solution (containing 2-Methylpyridine, DMF and water) was fractionally distilled to obtain 637.5 g (yield> 90%) of DMF having a purity of 99.5%.
1: 반응조 2: 가열장치
3: 교반장치 4: 온도계
5: 반응탑 6: 냉각응축기
7: 환류데칸타 8: 흡착장치
S1: 반응폐용제 여과공정 S2: 반응성증류공정
S3: 냉각환류공정 S4: 중화흡착공정
S5: 분별증류공정1: Reactor 2: Heating device
3: stirrer 4: thermometer
5: Reaction tower 6: Refrigerated condenser
7: reflux decanter 8: adsorption device
S1: Reaction waste solvent Filtration S2: Reactive distillation process
S3: cooling and refluxing step S4: neutralization adsorption step
S5: fractional distillation process
Claims (7)
여과처리한 반응폐용제에 알콜과 산을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류 공정(S2);
상기 반응성 증류 공정을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각응축기로 냉각하며, 냉각후 혼합액을 데칸터에서 층분리후 물을 제외한 에스테르 화합물과 알콜을 반응조로 공급하는 과정을 반복하는 냉각환류공정(S3);
목적한 수준으로 반응폐용제의 초산함량이 낮아지면 반응조에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 부유물을 흡착 제거하는 중화 흡착공정(S4);
흡착칼럼을 통과시킨 유기용매, 알콜 과 물의 혼합물을 분별증류하여 목적한 유기용매를 고순도로 분리하는 분별증류공정(S5);을 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법.
A reactive waste solvent filtration step (S1) for recovering a reaction waste solvent comprising an organic, aqueous and solid particle mixture generated in a polyimide synthetic process for a semiconductor or a flexible display to filter solid particles contained therein;
A reactive distillation step (S2) of esterifying the acetic acid contained in the reaction waste solvent by adding alcohol and acid to the filtered waste solvent;
The ester compound produced through the above reactive distillation process, the azeotropic mixture of water and alcohol is cooled with a cold condenser, and after cooling, the mixture liquid is separated from the decanter, and then the ester compound and water except for water are fed to the reaction vessel A cooling reflux process (S3);
A neutralization process (S4) for neutralizing the acid by neutralizing the acid in the reaction tank when the acetic acid content of the reaction waste solvent is lowered to a desired level, and adsorbing and removing unreacted materials and suspended matters;
(S5) for fractionating a mixture of an organic solvent, an alcohol and water, which have passed through an adsorption column, in a high purity by separating a target organic solvent (S5). Lt; / RTI >
반응성 증류 공정(S2)은,
여과처리한 반응폐용제에 알콜과 산을 가하여 하기 식과 같이 반응하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법.
CH3COOH + ROH <-> ROAc + H2O
상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기임.
The method according to claim 1,
The reactive distillation step (S2)
A method for recovering an organic solvent after a polyimide film for a semiconductor and a flexible display is produced by adding alcohol and an acid to a filtered reaction waste solvent and reacting according to 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 and isopropyl, and Ac is an acetyl group.
냉각 환류 공정(S3)은,
반응성 증류 공정에 의하여 생성된 에스테르류를 포함한 알콜, 물을 데칸타에서 층분리하며,
상층의 에스테르와 알콜만을 반응조에 환류(Reflux)시키는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법.
The method according to claim 1,
The cooling and reflux process (S3)
Alcohol and water containing esters produced by the reactive distillation process are separated in decanter,
Characterized in that only the ester and alcohol in the upper layer are refluxed in the reaction tank, and a method for recovering the organic solvent after the production of the semiconductor and the polyimide film for flexible display.
중화 흡착공정(S3)은
목표한 값 이하로 초산농도가 낮아지면, 가해진 산성촉매를 알카리로 중화반응시켜 제거하며, 미반응물인 초산과 불순물을 활성탄, 제올라이트, 실리카겔, 활성알루미나 혹은 이들의 혼합물로 이루어진 흡착제를 충진한 흡착칼럼을 통과시켜 제거하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법.
The method according to claim 1,
The neutralization adsorption step (S3)
When the acetic acid concentration is lower than the target value, the added acid catalyst is neutralized with an alkali to remove the acetic acid, and the unreacted acetic acid and the impurities are adsorbed in an adsorption column filled with an adsorbent made of activated carbon, zeolite, silica gel, activated alumina, And removing the organic solvent after the polyimide film for semiconductor and flexible display is manufactured.
분별 증류 공정(S4)은,
흡착칼럼을 통과시켜 미반응 초산과 불순물을 제거한 유기용제, 알콜, 물의 혼합물을 분별증류에 의해 정제하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수방법.
The method according to claim 1,
The fractional distillation step (S4)
Wherein the mixture of organic solvent, alcohol and water is passed through an adsorption column to remove unreacted acetic acid and impurities, and the mixture is purified by fractional distillation to recover a polyimide film for a semiconductor and a flexible display.
하기 식
CH3COOH + ROH <-> ROAc + H2O
(상기 식에서 R 은 메틸, 에틸, n-프로필, 이소프로필로 이루어진 군에서 선택되는 어느 하나이며, Ac 는 아세틸기임)
의 반응이 이루어지는 반응조(1);
반응된 에스테르화합물과 알콜등의 스트리핑(striping)을 유도하기 위한 다단의 트레이 혹은 팩킹구조로 이루어진 반응탑(5);
상기 반응탑(5)을 통하여 생성된 에스테르화합물과 물 그리고 알콜의 공비물을 냉각하는 냉각하여 데칸터에 공급하기 위한 냉각응축기(6);
상기 냉각응축기(6)에 의하여 냉각 응축된 것을 상분리유도하며, 상분리된 것중 하부의 물과 알콜을 제거하는 동시에 상부의 에스테르화합물과 알콜을 상부환류하는 환류데칸타(7);
반응중 계속 초산의 농도를 스캔하며, 초산의 농도가 목표값 이하로 측정되면, 반응조에 산을 중화하는 알카리를 첨가하여 중화하며, 미반응물과 기타 불순물을 흡착제거하여 목적한 유기용매를 수거하는 흡착장치(8);로 이루어지는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수장치.
A temperature suitable for the reaction is maintained by the heating device 2, and an agitating device 3 for stirring the reaction liquid is provided inside,
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 and isopropyl, and Ac is an acetyl group)
A reaction tank 1 in which a reaction is performed;
A reaction tower 5 having a multi-stage tray or packing structure for inducing stripping of the reacted ester compound with alcohol or the like;
A cooling condenser (6) for cooling the azeotropic mixture of the ester compound produced through the reaction tower (5) with water and alcohol, and supplying the cooled azeotrope to the decanter;
A reflux decanter (7) for inducing phase separation of the cooled and condensed by the cooling condenser (6), for removing water and alcohol in the lower part of the phase separation, and for refluxing the upper ester compound and alcohol;
When the concentration of acetic acid is measured to be lower than the target value, the alkali is neutralized by neutralizing the acid in the reaction tank, and the unreacted materials and other impurities are adsorbed to the adsorbent to collect the desired organic solvent And an apparatus (8) for recovering an organic solvent generated after manufacturing a semiconductor and a polyimide film for a flexible display.
환류데칸타(7)는,
하부의 물과 알콜은 반응계의 외부로 배출하며,
상부의 에스테르화합물과 알콜을 반응탑의 상부로 환류하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 회수장치.
The method according to claim 6,
The reflux decanter (7)
The lower water and alcohol are discharged to the outside of the reaction system,
Characterized in that the upper ester compound and the alcohol are refluxed to the upper part of the reaction tower. The apparatus for recovering an organic solvent after the production of a semiconductor and a polyimide film for a flexible display.
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