KR20190064300A - 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 process Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 31
- 239000004642 Polyimide Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000011084 recovery Methods 0.000 title claims description 11
- 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 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000003960 organic solvent Substances 0.000 claims abstract description 50
- 239000010887 waste solvent Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000004508 fractional distillation Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000066 reactive distillation Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005194 fractionation Methods 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000725 suspension Substances 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000000217 alkyl group Chemical group 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
- 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
- 239000003463 adsorbent Substances 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000001419 dependent effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 6
- -1 dianhydride compound Chemical class 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 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 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
- 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
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 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
- 238000010438 heat treatment Methods 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
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 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
- 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
- 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction 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
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 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
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 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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- 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
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- 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
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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
- B01D3/009—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
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- 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
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- 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
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Abstract
Description
본 발명은 반도체와 디스플레이용 폴리이미드 필름 제조시 발생하는 유기용매의 연속 회수장치에 관한 것이다.BACKGROUND OF THE
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.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.
그리고, 이러한 유리 대체 용도 등에 사용하는 재료로서, 고도의 내열성을 가지며, 또한 가벼우며 유연한 폴리이미드를 포함하는 필름이 개발되었다.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 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 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 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 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. 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. 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 있다. A new manufacturing method is proposed in which water is used instead of an organic solvent as a reaction solvent to solve the problem of discarding expensive organic solvents.
본 발명은 상기 폴리이미드 합성후에 반응후 폐기 처리하는 용액 중에서 고가의 유기용매를 연속으로 회수하여 재활용하는 장치를 제공하려는데 그 목적이 있는 것이다.An object of the present invention is to provide an apparatus for continuously recovering and recycling an expensive organic solvent in a solution for post-reaction discarding treatment after the polyimide is synthesized.
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.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 and removal, the expensive organic solvent was fractionally distilled.
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 유기용제를 회수하는 분별증류장치를 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치에 그 특징이 있다.Accordingly, the present invention provides a reactive waste solvent filtration apparatus for recovering a reactive waste solvent comprising an organic, aqueous and solid particle mixture generated in a polyimide synthesis process for a semiconductor or a flexible display to filter solid particles contained therein, A reactive distillation apparatus for esterifying the acetic acid contained in the reaction waste solvent by adding alcohol in a gaseous state to the filtered reaction waste solvent and a small amount of unreacted acetic acid remaining after the neutralization step An adsorption device for removing impurities by passing through an adsorption column, and a fractionation device for recovering high purity organic solvent by fractional distillation so as to remove impurities remaining after treatment of the adsorption column, The present invention relates to a continuous recovery apparatus for an organic solvent, Feature.
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 recovered waste solvent and alcohol for reaction are preheated at a temperature of 40 to 70 ° C and supplied.
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.In the reactive distillation apparatus, in order to induce esterification between acetic acid and alcohol by adding alcohol and an esterification catalyst to a reaction column (R) in a reaction waste solvent from which fine suspensions or solid particles have been removed, an esterification catalyst layer (3c) is provided at the upper part of the esterification catalyst layer, and the upper part of the esterification catalyst layer is constituted of the supply part (3d) of the reaction waste solvent and the lower part is composed of the alcohol supply part (3e) for the esterification reaction. CH 3 COOH + ROH <->
상기 에스테르화촉매층에 공급하는 알콜을 기상상태로 공급하는 것을 또 다른 특징으로 한다.And the alcohol to be 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.And a reflux device for separating alcohol and water containing esters produced by the reactive distillation device into decanter layers and 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 apparatus is characterized in that adsorption and regeneration are successively carried out in an adsorption column of a multi-layer structure composed of any one of activated carbon, zeolite, silica gel and activated alumina or a mixture thereof.
상기 분별 증류 장치는, 1차 분별증류탑에서 유기용매를 알콜, 물과 분별증류한 후, 2차 분별증류탑으로 이송하여 유기용매와 고비점의 불순물을 분별증류하여 고순도의 유기용제를 회수하는 것을 또 다른 특징으로 한다.The above-mentioned fractionation distillation apparatus is characterized in that the organic solvent is fractionally distilled from alcohol and water in the first fractionation tower, and then transferred to the second fractionation tower to recover the highly pure organic solvent by fractional distillation of the organic solvent and the high- Other features.
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.
그리고 유기용매의 재순환이 연속적으로 이루어지면서 반응중 약간의 부족한 용매만의 보충과 순도 확인에 의하여 연속적인 합성반응이 유지되어 품질의 균일화를 가능하게 하는 효과가 있다.In addition, since the recycle of the organic solvent is continuously performed, the continuous synthesis reaction can be maintained by supplementing only the insufficient solvent and confirming the purity during the reaction, thereby achieving the uniformity of the quality.
도 1은 본 발명의 전체적인 공정을 나타내는 공정도,
도 2는 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 발명에 따른 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치를 첨부된 바람직한 실시도면에 의거하여 보다 상세히 설명하면 다음과 같다.A continuous recovery apparatus for recovering organic solvents generated after manufacturing a semiconductor and a polyimide film for a flexible display according to the present invention will now 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.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.
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, a low boiling point solution such as tetrahydrofuran (THF), chloroform or a low-absorbency solvent such as? -Butyrolactone may be used. In the present invention, the production method of the polyimide resin through the reaction of the diamine-based dianhydride-based monomer is not particularly limited. Examples of the solvents used in these reactions include various kinds of solvents, The possibility of recovery for the recycling of the organic solvent is exemplified, and the present invention is not limited by the specific 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 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 장치는, The specific recovering apparatus 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 장치(S1)와,A reaction waste solvent filtering device (S1) for recovering a reaction waste solvent composed of an organic, aqueous and solid particle mixture generated in a polyimide synthesis process for a semiconductor or a flexible display and filtering the contained solid particles,
반응폐용제를 공급하기전 예열하는 예열장치(S2)와,A preheating device S2 for preheating before supplying the reaction waste solvent,
여과처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류장치(S3)와,A reactive distillation apparatus (S3) for esterifying the acetic acid contained in the reaction waste solvent by adding alcohol in a gaseous state to the filtered reaction waste solvent,
중화공정후에도 잔류하는 소량의 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치(S4)와An adsorption device S4 for removing a small amount of unreacted acetic acid and impurities remaining after the neutralization step through an adsorption column;
흡착컬럼을 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 분별증류하여 고순도의 유기용제를 회수하는 분별증류장치(S5)로 이루어진다.And a fractionation device (S5) for treating the adsorption column to remove residual impurities and fractional distillation so as to increase the purity, thereby recovering a high purity organic solvent.
상기 각 장치에 대한 보다 구체적인 설명을 도 1의 공정도와 도 2의 장치도에 의하여 설명한다.A more detailed description of each of the above-described apparatuses will be described with reference to the flow chart of FIG. 1 and the apparatus diagram of FIG.
1. One. 반응폐용제Reactive waste solvent 여과 장치(S1) The filtration device (S1)
플렉시블 디스플레이용 폴리이미드 필름을 제조하는 과정에서 생성되는 폐유기용제, 초산, 물과 기타 불순물로 이루어진다. 상기 반응폐용제중 유기용제의 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. 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 weight of the organic solvent in the reaction waste solvent is 30 to 90% by weight, the acetic acid content is 2 to 30%, the catalyst content is 2 to 10%, and the water content is 1 to 60%. In addition to these liquid solvents, various fine suspensions are included in the recovery process, and the filtration device 1a removes these solid particles.
2. 예열 장치(S2)2. Preheating device (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.The recovered waste solvent and the alcohol for the reaction are preheated to a temperature of 40 to 70 ° C to supply the reaction heat for the esterification reaction. This 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 ° C, the reaction rate is slow and the productivity is lowered. If the temperature is higher than 70 ° C, the azeotropic distillation of acetic acid in addition to the organic solvent having low boiling point causes no desired reaction with the ester catalyst. Reference numeral 2a denotes a preheater.
3. 반응성 증류장치(S3)3. Reactive distillation unit (S3)
미세 부유물이나 고상입자들이 제거된 반응폐용제에 알코올과 에스테르화 촉매를 반응탑(R)에 가하여 초산과 알콜간의 에스테르화를 유도한다.Alcohol and an esterification catalyst are added to a reaction column (R) in a reactive waste solvent from which fine suspensions or solid particles have been removed to induce esterification between acetic acid and alcohol.
반응탑(R)의 중앙부에는 에스테르화촉매층(3c)이 설치되며, 에스테르화촉매층의 상부에는 반응폐용제의 공급부(3d)를 구성하고, 하부는 에스테르화 반응을 위한 알콜공급부(3e)로 이루어진다.An
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 as much as 30%, and the esterification with alcohol continuously proceeds as in the following formula, and the resulting ester is continuously recovered.
CH3COOH + ROH <-> CH3COOR(ROAc) + H2OCH 3 COOH + ROH <-> CH 3 COOR (ROAc) + H 2 O
(상기 식에서 R = 알킬기로서, 바람직하게는 메틸, 에틸, n-프로필, 이소프로필 중의 어느 하나이며, Ac 는 아세틸기임)(Wherein R is an alkyl group, preferably any one 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.
본 발명의 또 다른 특징은 반응탑(R)의 상측과 하측에 다공성의 트레이 혹은 팩킹구조를 갖으며, 중간부에는 에스테르화촉매층(3c)을 구성하였다. 반응탑의 상부에서는 반응폐용제를, 탑하부에서는 알콜을 공급한다.Another feature of the present invention is that a porous tray or packing structure is provided on the upper and lower sides of the reaction tower R, and an
공급되는 알콜은 기화 가능하도록 예열처리하여 공급됨에 따라 기상(氣相) 상태로 하부에 설치한 다공성의 트레이 혹은 팩킹을 통하여 공급되어 중간의 에스테르화촉매층(3c)으로 이송토록 하였다.The supplied alcohol is preheated so as to be vaporized and fed through a porous tray or packing provided in the lower part in a gas phase to be fed to the intermediate
상부에서 주입하는 폐액중 초산과 하층에 투입한 후 증발되어 올라오는 알콜(ROH)과 에스테르화촉매층에서 반응하여 에스테르(ROAc)가 생성되며, 이 에스테르는 반응탑의 상부로 이송하여 데칸타(3b)에서 응축한다.(ROH) reacts with the alcohol (ROH) which is evaporated after being injected into acetic acid and the lower layer of the waste liquid to be injected from the upper part and reacts in the esterification catalyst layer to produce an ester (ROAc). This ester is transferred to the upper part of the reaction tower, Lt; / RTI >
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 present invention is that it further includes the
모여진 혼합물은 상층(ROAc, ROH)은 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 with the upper layer (ROAc, ROH) to return the contained alcohol to the reaction, and the mixture of water and alcohol in the lower layer is separated. 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.
4. 흡착 장치(S4)4. Adsorption 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 or activated alumina, and two or more columns are used in parallel to enable adsorption and regeneration continuously.
5. 분별 증류 장치(S5)5. Fractionation device (S5)
흡착컬럼(4a)을 통과함에 따라 미량의 미반응 초산과 기타 불순물이 대부분 제거 되어진다.As it passes through the adsorption column 4a, a trace amount of unreacted acetic acid and other impurities are mostly removed.
목적으로 하는 유기용매의 순도를 높이기 위하여 반응 참여 후에 잔류한 촉매, 미반응 알콜 그리고 일부 함께 이송된 물을 분별증류한다.The remaining catalyst, unreacted alcohol, and partially entrained water are separated by fractionation to increase the purity of the desired organic solvent.
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 first fractional distillation, the organic solvent is fractionally distilled from the first fractionation tower (5a). Since the organic solvent purified in the first fractionation tower contains a part of the high boiling point fraction, the second fractionation tower (5b ) To purify impurities at high boiling points with higher purity.
1,2차의 분별증류에 의하여 유기용매의 순도는 99% 이상이 회수가 가능해진다.The purity of the organic solvent can be recovered by 99% or more by the fractional distillation of the first and second phases.
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. Hereinafter, the experiment of collecting and recovering 100 kg of the actual reaction waste solvent of the present invention was conducted. The present embodiments are to be considered as illustrative of the present invention and are not to be construed as limiting the scope of the present invention to the reaction conditions set forth in the examples, One example of feasibility.
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 figure, reference numeral 5c denotes a receiver tank, which is refluxed to the primary fractionation tower as described above, and an objective organic solvent having a purity of 99% or more is recovered in the
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 tower exemplified in the present invention is exemplified as the first or the second order, it is possible to provide a tertiary or more tertiary or more according to the environment of the installation and the characteristics of the organic solvent used in the reaction waste solvent. All of the various embodiments of the present invention, 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 ratio를 조절하여（2:1~5:1） 상부온도를 58℃이하로 유지시켰다.100 kg of a reaction waste solvent generated in the production of a film for a flexible display was collected. The reaction waste solvent was analyzed to contain 68.5% DMF, 12.5% acetic acid, 2.7% 3-methylpyridine, and 14.1% water. 100Kg of the waste solvent mixture was passed through a microfilter and then preheated to the upper portion of the fractionation tower filled with Amberlyst-15 in the middle portion. The mixture was heated to 60-64 ° C and sprayed at 4L per minute. Methanol was injected at 0.8L per minute (Twice the equivalent of acetic acid) was also fed through the preheater to the bottom of the column by heating at 60 to 64 ° C. The resulting methyl acetate / methanol / water mixture was condensed in the upper decanter through the upper condenser, (Upper layer: methyl acetate / methanol; lower layer: methanol / water). The lower layer was continuously removed and the upper layer was refluxed. At this time, the reflux ratio was adjusted (2: 1 ~ 5: 1) to keep the upper temperature below 58 ℃.
하부 리보일러에 남은 혼합물은 연속적으로 활성탄이 충진된 흡착탑을 통과시켜 잔존 초산과 불순물을 제거하고 １차 증류탑으로 보내졌다．The mixture remaining in the bottom reboiler was continuously passed through an adsorption tower filled with activated carbon to remove residual acetic acid and impurities and sent to the first distillation tower.
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 얻었다수율 89.2%)The primary distillation tower was maintained at a temperature not higher than 105 ° C. and the final product was obtained by condensing the DMF in the second distillation column with the upper condenser by heating the reboiler with a preheater at 140 to 145 ° C. At this time, Maintained at 153-5 ° C. The collected DMF had a purity of> 99.8% and a total amount of 61.6 kg was obtained. The yield was 89.2%
S1: 여과장치 S2: 예열장치
S3: 반응성 증류장치 S4: 흡착장치
S5: 분별증류장치 1a: 필터장치
2a: 예열기 R: 반응탑
3b: 데칸타 3c: 에스테르화촉매층
3d: 공급부 3e:알콜공급부
3f: 환류장치 4a: 흡착칼럼
5a,5b: 분별증류탑 5c,5d: 리시버탱크S1: Filtration unit S2: Preheating unit
S3: Reactive distillation device S4: Adsorption device
S5: fractionation distillation apparatus 1a: filter apparatus
2a: preheater R: reaction tower
3b:
3d:
3f: reflux device 4a: adsorption column
5a, 5b:
Claims (7)
반응폐용제를 공급하기전 예열하는 예열장치(S2);
여과처리한 반응폐용제에 기상 상태의 알콜을 가하여 반응폐용제에 함유된 초산을 에스테르화하는 반응성 증류장치(S3);
중화공정후에도 잔류하는 소량의 미반응초산과 불순물을 흡착칼럼을 통과시켜 제거하는 흡착 장치(S4);
흡착컬럼을 처리후, 잔류한 불순물을 제거하는 동시에 순도를 높이도록 분별증류하여 고순도의 유기용제를 회수하는 분별증류장치(S5);를 포함하여 이루어진 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
A reaction waste solvent filtration device (S1) for recovering a reaction waste solvent comprising organic, aqueous and solid particle mixture generated in a polyimide synthesis process for a semiconductor or a flexible display to filter solid particles contained therein;
A preheating device (S2) for preheating before supplying the reaction waste solvent;
A reactive distillation apparatus (S3) for esterifying the acetic acid contained in the reaction waste solvent by adding alcohol in a gaseous state to the filtered reaction waste solvent;
An adsorption device S4 for passing and removing a small amount of unreacted acetic acid and impurities remaining after neutralization through an adsorption column;
And a fractionation device (S5) for treating the adsorption column to remove residual impurities and fractional distillation so as to increase the purity, thereby recovering a high purity organic solvent. Continuous recovery of organic solvent.
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 according to claim 1,
The pre-
Wherein the recovered waste solvent and the alcohol for reaction are preheated at a temperature of 40 to 70 ° C. and supplied to the continuous recovery device for organic solvent after the production of the semiconductor and the polyimide film for flexible display.
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 하기 식과 같이 에스테르화촉매층에서 반응하도록 이루어지는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
CH3COOH + ROH <-> CH3COOR(ROAc) + H2O
(상기 식에서 R = 알킬기로서, 바람직하게는 메틸, 에틸, n-프로필, 이소프로필 중의 어느 하나이며, Ac 는 아세틸기임)
The method according to claim 1,
In the reactive distillation apparatus,
In order to induce esterification between acetic acid and alcohol by adding alcohol and an esterification catalyst to a reaction column (R) in a reaction waste solvent from which fine suspensions or solid particles have been removed,
An esterification catalyst layer 3c is provided at the center of the reaction tower, a supply portion 3d for the reaction waste solvent is formed at the upper part of the esterification catalyst layer, and an alcohol supply portion 3e for esterification is provided at the lower portion Characterized in that acetic acid of an alcohol and a reactive waste solvent reacts in an esterification catalyst layer as shown in the following formula.
CH 3 COOH + ROH <-> CH 3 COOR (ROAc) + H 2 O
(Wherein R is an alkyl group, preferably any one of methyl, ethyl, n-propyl and isopropyl, and Ac is an acetyl group)
에스테르화촉매층에 공급하는 알콜을 기상상태로 공급하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method of claim 3,
Characterized in that the alcohol to be fed to the esterification catalyst layer is supplied in a gaseous state, and a continuous recovery apparatus for recovering an organic solvent after the production of a semiconductor and a polyimide film for a flexible display.
반응성 증류장치에 의하여 생성된 에스테르류를 포함한 알콜, 물을 데칸타 층분리하며,
상층(ROAc, ROH)을 환류(Reflux)하는 환류장치를 포함하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수방법.
The method of claim 3,
Separating the alcohol and water containing esters produced by the reactive distillation apparatus into a decanter layer,
And a reflux device for refluxing the upper layer (ROAc, ROH). The continuous recovery method of organic solvent after the production of a semiconductor and a polyimide film for a flexible display.
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 according to claim 1,
In the adsorption apparatus,
Characterized in that the adsorbent is continuously adsorbed and regenerated in a multi-layered adsorption column composed of any one of activated carbon, activated carbon, zeolite, silica gel and activated alumina or a mixture thereof, and a continuous recovery of the organic solvent after the production of the semiconductor and the polyimide film for flexible display Device.
분별 증류 장치는,
1차 분별증류탑에서 유기용매를 알콜, 물과 분별증류한 후, 2차 분별증류탑으로 이송하여 유기용매와 고비점의 불순물을 분별증류하여 고순도의 유기용제를 회수하는 것을 특징으로 하는 반도체와 플렉시블 디스플레이용 폴리이미드 필름 제조후 발생하는 유기용매의 연속 회수장치.
The method according to claim 1,
The fractionation distillation apparatus,
Separating the organic solvent from alcohol and water in the first fractionation tower and transferring it to the second fractionation tower to recover the organic solvent having a high purity by fractional distillation of the organic solvent and the high boiling point impurities. A continuous recovery device for organic solvents after the production of a polyimide film for use as a solvent.
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| KR20230022033A (en) | 2021-08-06 | 2023-02-14 | 주식회사 지티씨엔에스 | Recovery method of dimethylformamide from the waste solution of polyimide production process |
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