KR100769774B1 - 연속 용액중합 방법 및 장치 - Google Patents
연속 용액중합 방법 및 장치 Download PDFInfo
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- KR100769774B1 KR100769774B1 KR1020037005815A KR20037005815A KR100769774B1 KR 100769774 B1 KR100769774 B1 KR 100769774B1 KR 1020037005815 A KR1020037005815 A KR 1020037005815A KR 20037005815 A KR20037005815 A KR 20037005815A KR 100769774 B1 KR100769774 B1 KR 100769774B1
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Abstract
Description
반응기내의 공급물 | 반응기 내측에서의 중합 | 감쇠밸브 상류의 중합체 용액 | 감쇠밸브 하류의 중합체 용액 | 중합체 희박상 | 중합체 풍부상 | 압출기로부터 탈휘발된 중합체의 양 | |
플라스토머 | 0 또는 -15℃; 총분압 120bar; 단량체 분압 50bar | 150 내지 200℃; 100 또는 120bar; 15 내지 22중량% 중합체 | 220℃; 40 또는 100bar; 15 내지 22중량% 중합체 | 220℃; 40 bar; 15 내지 22중량% 중합체 | 220℃; 40 bar; 0.1중량% 미만 중합체 | 220℃; 40 bar; 30 내지 40중량% 중합체 | 높음 |
탄성 중합체 | 0 또는 -15℃; 총분압 120bar; 단량체 분압 50bar | 100℃; 100 또는 120bar; 8 내지 12중량% 중합체 | 220℃; 100 bar; 8 내지 12중량% 중합체 | 220℃; 40 bar; 8 내지 12중량% 중합체 | 220℃; 40 bar; 0.1중량% 미만 중합체 | 220℃; 40 bar; 30중량% 중합체 | 중간 |
주로 프로필렌을 함유한 공중합체 | 0 또는 -15℃; 총분압 120bar; 단량체 분압 50bar | 50 또는 60℃; 120bar; 7 내지 8중량% 중합체 | 220℃; 100 bar; 7 내지 8중량% 중합체 | 220℃; 40 bar; 7 내지 8중량% 중합체 | 220℃; 40 bar; 0.1중량% 미만 중합체 | 220℃; 40 bar; 30 내지 35중량% 중합체 | 낮음 |
Claims (18)
- 단일 부위 촉매가 공급되어 중합체를 함유하는 중합성 반응 혼합물이 형성되는 연속식 교반 탱크 반응기 배열, 및그의 하류에 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리수단을 가지며, 상기 분리 수단이 중합성 혼합물을 희박 상(lean phase)과 농축 상으로 분리시키는 초기 액상 분리기를 적어도 포함하며(A) 고용량 저점도 펌프가 공급물의 압력을 75 bar 이상으로 상승시켜 펌프의 운동을 통해서 그리고 상기 반응기 배열과 압력 감소 수단 사이에 추가적인 펌핑수단이 없이도 혼합물을 반응기 배열로부터 가열단을 통하여 액상 분리기 상류의 압력 감소 수단까지 통과시키는 단계; 및(B) 촉매 킬러(catalyst killer)를 반응기 배열의 하류 및 액상 분리기의 상류에 첨가하여 가열된 중합성 혼합물이 분리되는 분리기내에서의 추가적인 중합을 억제하며, 이때 희박 상은 냉각기 및 선택적으로 건조기를 통과하여 펌프의 유입구측으로 되돌아 오며, 농축 상은 하류에서 용매가 추가로 제거됨으로써 고상 중합체를 수득하는 단계를 포함하는,가압하에서 탄화수소 용매중의 올레핀계 불포화 단량체 공급물을 연속으로 용액중합시키는 방법(process for continuous solution polymerization).
- 제 1 항에 있어서,액상 분리기로부터 수득된 농축 상을 수용하는 저압 분리기를, 농축 상으로부터 제거된 휘발 상을 추가의 압축수단없이 정제용 분별탑으로 이송시키기에 충분한 수준에서 2바 게이지(bar gauge) 이상의 압력으로 조작시키는, 연속으로 용액중합시키는 방법.
- 제 1 항 또는 제 2 항에 있어서,용매가 저비점 알칸계 용매이며, 중합성 혼합물내의 중합체가 존재하는 전체 단량체중에 50 몰% 이상의 에틸렌 또는 프로필렌 유도된 단위를 함유하는, 연속으로 용액중합시키는 방법.
- 제 1 항 또는 제 2 항에 있어서,반응기 배열로부터 수득된 중합성 혼합물을 열교환기를 이용하여 연속적으로 분리기내에서 분리하기 위한 온도로 가열하고, 분리기로부터 수득된 희박 상을 이용하여 상기 열교환기들중 상류 열교환기에 열을 공급하는, 연속으로 용액중합시키는 방법.
- 제 1 항 또는 제 2 항에 있어서,희박 상을 액체 형태로 중합도중에 첨가되거나 발생된 수소를 제거하기 위한 수단에 통과시키고, 이 수단이 역류 배열로 희박 상을 스트리핑 증기(stripping vapor)와 접촉시켜 희박 상 재순환물로부터 제거하기 위해 증기상내의 수소를 농축시키는 수단을 포함하는, 연속으로 용액중합시키는 방법.
- 단일 부위 촉매가 공급되어 중합체를 함유하는 중합성 반응 혼합물을 형성할 수 있는 연속식 교반 탱크 반응기 배열, 및상기 반응기 배열의 하류에 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리수단을 포함하며, 상기 수단이 중합성 혼합물을 농축 상과 희박 상으로 분리시키는 초기 액상 분리기를 적어도 포함하는 플랜트로서,(A) 공급물의 압력을 75bar 이상으로 상승시키기 위한 고용량 저점도 펌프가 배치되고 가열 배열을 구비함으로써 상기 반응기와 압력 감소 수단 사이에 추가의 펌핑수단을 전혀 구비하지 않고서도 혼합물을 상기 반응기 배열로부터 가열 배열을 통하여 액상분리기(14) 상류의 압력 감소수단으로 통과시키며;(B) 반응기 배열의 하류 및 액상분리기의 상류에 촉매 킬러를 도입하여 가열된 중합성 혼합물을 분리시키는 분리기내에서의 추가의 중합을 억제하기 위한 수단이 구비되어 있고, 희박 상을 냉각시키기 위한 수단이 구비되어 있으며, 촉매 킬링 잔사를 제거하기 위해, 선택적인 건조된 재순환 스트림을 펌프의 유입구측으로 되돌려 보낼 수 있는 건조기가 배열되어 있는,가압하에서 탄화수소 용매중의 올레핀계 불포화 단량체 공급물을 연속으로 용액중합시키는 공정을 수행하기 위한 플랜트.
- 단일 부위 촉매가 공급되어 중합체를 함유하는 중합성 반응 혼합물을 형성하기 위한 연속식 교반 탱크 반응기 배열, 및그의 하류에 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리수단을 가지며, 상기 수단이 중합성 혼합물을 희박 상과 농축 상으로 분리시키기 위한 초기 액상 분리기를 적어도 포함하며,(A) 펌프가 중합 반응기내에서 75 bar 이상의 압력을 유지하고, 중합 반응기 배열내의 온도가 분리수단내에서 보다 낮거나 동일하게 유지되며, 가열 배열을 분리수단의 상류에 구비하여 반응 혼합물을 선택적으로 가열시켜 분리수단내의 온도를 상승시킴으로써, 분리수단의 압력 강하시 초기 중합온도와 무관하게 혼합물이 더 낮은 임계용액 상 경계를 통과하며;(B) 촉매 킬러를 반응기 배열의 하류 및 액상분리기의 상류에 첨가하여 가열된 중합성 혼합물을 분리시키는 분리기내에서의 추가적인 중합을 억제하며, 이때 희박 상은 냉각기 및 선택적으로 건조기를 통과하여 펌프의 유입구측으로 되돌아오며, 농축 상을 하류에서 용매를 추가로 제거함으로써 고상 중합체를 수득하는 것을 포함하는,가압하에서의 탄화수소 용매중의 올레핀계 불포화 단량체 공급물을 연속으로 용액중합시키는 방법.
- 제 7 항에 있어서,액상 분리기 및 이로부터 수득된 농축 상을 수용하는 저압 분리기를, 농축상으로부터 제거된 휘발 상을 정제용 분별탑으로 이송시키기에 충분한 수준에서 2 bar gauge 이상의 압력으로 작동시키는, 연속으로 용액중합시키는 방법.
- 제 7 항 또는 제 8 항에 있어서,용매가 저비점 알칸계 용매이며, 중합성 혼합물내의 중합체가 존재하는 전체 단량체중에 50 몰% 이상의 에틸렌 또는 프로필렌 유도된 단위를 함유하는, 연속으로 용액중합시키는 방법.
- 제 7 항 또는 제 8 항에 있어서,반응기 배열로부터 수득된 중합성 혼합물을 열교환기를 이용하여 연속적으로 분리기내에서 분리 온도로 가열하고, 분리기로부터 수득된 희박 상을 이용하여 상기 열교환기들중 상류 열교환기에 열을 공급하는, 연속으로 용액중합시키는 방법.
- 제 7 항 또는 제 8 항에 있어서,희박 상을 액체 형태로 중합도중에 첨가되거나 발생된 수소를 제거용 수단으로 통과시키고, 이 수단이 역류 배열로 희박 상을 스트리핑 증기와 접촉시켜 희박 상 재순환류로부터 제거하기 위해 증기상내의 수소를 농축시키는 수단을 포함하는 연속으로 용액중합시키는 방법.
- (a) 압력 공급원,(b) 상기 압력 공급원의 하류에 위치한 중합 반응기,(c) 상기 중합 반응기의 하류에 위치하며, 반응 혼합물의 압력을 선택된 온도 압력-온도 곡선에서 20bar/sec 이상의 속도로 압력-온도 곡선의 스피노달 경계(spinodal boundary) 이하의 압력으로 감소시킬 수 있는 압력강하 장치, 및(d) 상기 압력강하 장치의 하류에 위치한 분리기를 포함하며,상기 압력 공급원은 상기 공정 플랜트가 작동하는 도중에 상기 반응 혼합물에 압력을 제공하여 상기 반응기와 분리기 사이에 추가의 압력 공급원 없이도 상기 반응기내에서는 단일상 액상 반응 혼합물을 생성시키고 상기 분리기내에서는 2상 액-액 반응 혼합물을 생성시키기에 충분한 것인,용액 중합반응 혼합물의 연속 순환에 적합한 공정 플랜트.
- 제 12 항에 있어서,반응 혼합물의 치환체 및 공정조건만을 변화시킴으로써 플라스토머, 탄성중합체, 또는 주로 프로필렌을 함유하는 공중합체를 생성시킬 수 있는 공정 플랜트.
- 단일 부위 촉매가 공급되어 중합체를 함유하는 중합성 반응 혼합물을 형성하는 연속식 교반 탱크 반응기 배열, 및그의 하류에 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리수단을 가지며, 상기 수단이 중합성 혼합물을 재순환을 통하여 반응기 배열로 되돌려 보내기 위한 희박 상과 농축 상으로 분리시키기 위한 초기 액상 분리기를 적어도 포함하며희박상이 액체 형태로 중합도중에 첨가되거나 발생된 수소 제거용 수단에 통과되고, 상기 수소 제거 수단이 역류 배열로 희박 상을 스트리핑 증기와 접촉시켜 희박 상 재순환물로부터 제거하기 위해 증기상내의 수소를 농축시키는 수단을 포함하는,가압하에서 탄화수소 용매중의 올레핀계 단량체 공급물을 연속으로 용액중합시키는 방법.
- 제 14 항에 있어서,스트리핑 증기가 후속 중합에 사용하기 위한 에틸렌을 포함하는, 연속으로 용액중합시키는 방법.
- 제 14 항 또는 제 15 항에 있어서,한쌍의 반응기를 직렬로 배열하고, 수소를 하류 반응기에 첨가하여 저분자량 분획을 생성시키는, 연속으로 용액중합시키는 방법.
- 중합체를 함유하는 중합성 반응 혼합물을 형성시키는, 공급물 및 단일 부위 촉매성분을 위한 유입구를 가진 연속식 교반 탱크 반응기 배열, 및그의 하류에 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리수단을 포함하고, 이 분리수단이 중합성 혼합물을 재순환을 통하여 반응기 배열로 되돌려 보내기 위한 희박 상과 농축상으로 분리시키기 위한 초기 액상 분리기를 적어도 포함하는 것으로 중합도중에 첨가되거나 발생된 수소를 제거하기 위해 희박 상을 액체 형태로 스트리핑 배열로 통과시키기 위한 도관을 구비하며, 상기 스트리핑 배열이 역류 배열내에서 스트리핑 증기와 희박 상을 접촉시켜 희박 상 재순환류로부터 제거하기 위해 증기상내의 수소를 농축시키는 수단을 포함하는,가압하에서 탄화수소 용매중의 올레핀계 불포화 단량체 공급물을 연속으로 용액중합시키기 위한 플랜트.
- 삭제
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- 2001-10-17 ES ES01988739T patent/ES2271099T3/es not_active Expired - Lifetime
- 2001-10-17 AU AU2002222904A patent/AU2002222904A1/en not_active Abandoned
- 2001-10-17 EP EP01988739A patent/EP1339756B1/en not_active Expired - Lifetime
- 2001-10-17 KR KR1020037005815A patent/KR100769774B1/ko active IP Right Grant
- 2001-10-17 WO PCT/US2001/032299 patent/WO2002034795A1/en active IP Right Grant
- 2001-10-17 DE DE60122572T patent/DE60122572T2/de not_active Expired - Lifetime
- 2001-10-17 US US10/415,157 patent/US6881800B2/en not_active Expired - Lifetime
- 2001-10-17 AT AT01988739T patent/ATE337341T1/de not_active IP Right Cessation
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Cited By (7)
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KR101414298B1 (ko) * | 2010-01-14 | 2014-07-02 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 연속 용액 중합을 위한 방법 및 장치 |
KR101529977B1 (ko) * | 2015-01-16 | 2015-06-18 | 시엔시피이엘 주식회사 | 메탈로센 촉매 기반 폴리올레핀 계열의 용액중합 공정의 용매 분리 장치 및 그 방법 |
KR20180084869A (ko) * | 2015-12-21 | 2018-07-25 | 보레알리스 아게 | 폴리올레핀을 인출(withdrawing)하기 위한 공정 |
KR102023294B1 (ko) | 2015-12-21 | 2019-09-19 | 보레알리스 아게 | 폴리올레핀을 인출(withdrawing)하기 위한 공정 |
WO2017217709A1 (ko) * | 2016-06-16 | 2017-12-21 | 주식회사 엘지화학 | 용매 분리 장치 및 폐열 활용 방법 |
US10689499B2 (en) | 2016-06-16 | 2020-06-23 | Lg Chem, Ltd. | Solvent separation apparatus and waste heat utilization method |
US11859049B2 (en) | 2019-08-21 | 2024-01-02 | Lg Chem, Ltd. | Preparation method of polyalkylene carbonate |
Also Published As
Publication number | Publication date |
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AU2002222904A1 (en) | 2002-05-06 |
DE60122572T2 (de) | 2007-10-04 |
US7163989B2 (en) | 2007-01-16 |
WO2002034795A1 (en) | 2002-05-02 |
KR20030051748A (ko) | 2003-06-25 |
EP1339756A4 (en) | 2004-07-14 |
EP1339756B1 (en) | 2006-08-23 |
US6881800B2 (en) | 2005-04-19 |
US20040024146A1 (en) | 2004-02-05 |
DE60122572D1 (de) | 2006-10-05 |
ATE337341T1 (de) | 2006-09-15 |
ES2271099T3 (es) | 2007-04-16 |
US20050192416A1 (en) | 2005-09-01 |
EP1339756A1 (en) | 2003-09-03 |
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