JP5695665B2 - 改良した水素除去を伴う多峰性ポリオレフィンポリマーの製造方法 - Google Patents
改良した水素除去を伴う多峰性ポリオレフィンポリマーの製造方法 Download PDFInfo
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- JP5695665B2 JP5695665B2 JP2012545147A JP2012545147A JP5695665B2 JP 5695665 B2 JP5695665 B2 JP 5695665B2 JP 2012545147 A JP2012545147 A JP 2012545147A JP 2012545147 A JP2012545147 A JP 2012545147A JP 5695665 B2 JP5695665 B2 JP 5695665B2
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- polymerization reactor
- polymerization
- heat exchanger
- flash drum
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- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
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- VRZUGJZANQBFRT-UHFFFAOYSA-N magnesium;butan-1-olate;octan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCCCCCC[O-] VRZUGJZANQBFRT-UHFFFAOYSA-N 0.000 description 1
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Description
a) 第1重合反応器から水素を含む懸濁媒体中の固体ポリオレフィン粒子懸濁液を引き抜くこと;
b) 第1重合反応器の圧力よりより低い圧力のフラッシュドラムに該懸濁液を供給すること;
c) 懸濁媒体の一部を気化させること;
d) フラッシュドラムから水素減少懸濁液を引き抜き、該引き抜き物を第2重合反応器に供給すること;
e) 該フラッシュドラムの気相から気体を引き抜き、該引き抜き物を熱交換器に供給すること;
f) フラッシュドラムから引き抜いた気体の一部を濃縮すること;および
g) 該熱交換器中の得られた液体を、懸濁液が存在する点において重合プロセスに戻すこと
の各工程を含む。
4、12 熱交換器
7 フラッシュドラム
9 第2重合反応器
チタン化合物として、三価もしくは四価チタンのハロゲン化物またはアルコキシドから一般的に製造されるものを使用し、チタンアルコキシハロゲン化合物または種々のチタン化合物の混合物も可能である。適切なチタン化合物の例は、TiBr3、TiBr4、TiCl3、TiCl4、Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(O-i-C3H7)Cl3、Ti(O-n-C4H9)Cl3、Ti(OC2H5)Br3、Ti(O-n-C4H9)Br3、Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(O-n-C4H9)2Cl2、Ti(OC2H5)2Br2、Ti(OCH3)3Cl、Ti(OC2H5)3Cl、Ti(O-n-C4H9)3Cl、Ti(OC2H5)3Br、Ti(OCH3)4、Ti(OC2H5)4またはTi(O-n-C4H9)4である。ハロゲンとして塩素を含むチタン化合物を使用するのが好ましい。チタンに加えてハロゲンのみを含むハロゲン化チタンも同様に好ましく、これらのうち、特に塩化チタン、特に四塩化チタンが好ましい。バナジウム化合物のうち、ハロゲン化バナジウム、バナジウムオキシハライド、バナジウムアルコキシドおよびバナジウムアセチルアセトネートからなるものを特に挙げることができる。酸化状態が3〜5のバナジウム化合物が好適である。
より高い水素濃度の第1重合反応器からより低い水素濃度の第2重合反応器に懸濁液を移送するために、懸濁液を第1重合反応器から引き抜き、いわゆるフラッシュドラムに供給する。
フラッシュドラム中のポリマー懸濁液は、フラッシュドラムに供給される懸濁液に関して水素の減少があるが、フラッシュドラムから引き抜かれ、第2重合反応器に供給される。これは、好ましくは、移送ポンプにより行われる。好ましくは、第2重合反応器中の圧力は0.1〜5MPaであり、特に0.2〜1.2MPaであり、温度は50〜130℃、特に、60〜90℃である。
第1反応器から第2反応器に懸濁液を移送するために実行可能のスキームを示す。第1重合反応器(1)の懸濁液中のオレフィン類を重合するための反応混合物の成分を、1本以上の供給ライン(2)により、該反応器に供給する。懸濁液は、ポンプ(5)により少なくとも1基の熱交換器(4)を含む冷却サイクル(3)中で循環する。第1重合反応器の懸濁液が熱交換器(4)を通過前冷却サイクルから引き抜き、移送ライン(6)よりフラッシュドラム(7)に供給する。水素を減少させた懸濁液をフラッシュドラム(7)から引き抜き、ポンプ(10)により移送ライン(8)を経て第2重合反応器(9)へ供給する。フラッシュドラム(7)から気体を引き抜き、移送ライン(11)を経て熱交換器(12)へ供給する。熱交換器(12)に供給される気体の一部を濃縮し、ポンプ15により、移送ライン(13)を経て重合反応器(1)に液体として戻す。濃縮されていない、熱交換器(12)に供給される気体の残りの一部を、移送ライン(14)を経て重合プラントのワークアップ領域(図示せず)に供給する。
a) 懸濁状態でオレフィンを重合するように設計された第1重合反応器;
b) 第1重合反応器の下流フラッシュドラム;
c) フラッシュドラム下流の懸濁液中でオレフィンを重合するように設計された第2重合反応器;
d) フラッシュドラムから熱交換器へ気体を移送するための導管によりフラッシュドラムに結合された、気体を濃縮するように設計された該熱交換器;および
e) 懸濁液が存在する装置の位置に熱交換器中で得られる液体を戻すために熱交換器に結合された導管
を含む。
本発明装置の別の好適態様では、第1重合反応器は熱交換器を含む冷却サイクルを備え、第1重合反応器からフラッシュドラムへ懸濁液を移送するための導管は、冷却サイクルに結合され、好ましくは、循環懸濁液は熱交換器をまだ通過していない点で結合される。
Claims (8)
- 連結した第1重合反応器および第2重合反応器中で重合触媒の存在下で40〜150℃の温度および0.1〜20MPaの圧力で行う多峰性ポリオレフィンポリマーの製造方法であって、ここで、前記両反応器の上流または下流反応器にさらに別の重合反応器を結合でき、第1重合反応器中で、水素の存在下で第1ポリオレフィンポリマーを懸濁液中で製造し、第2重合反応器中で、第1重合反応器中よりもより低い濃度の水素の存在下で第2ポリオレフィンポリマーを製造し、当該方法は、
a) 第1重合反応器から水素を含む懸濁媒体中の固体ポリオレフィン粒子懸濁液を引き抜くこと;
b) 第1重合反応器の圧力よりもより低い圧力のフラッシュドラムに該懸濁液を供給すること;
c) 懸濁媒体の一部を気化させること;
d) フラッシュドラムから水素減少懸濁液を引き抜き、該引き抜き物を第2重合反応器に供給すること;
e) 該フラッシュドラムの気相から気体を引き抜き、該引き抜き物を熱交換器に供給すること;
f) フラッシュドラムから引き抜いた気体の一部を濃縮すること;および
g) 該熱交換器中で得られた液体を、重合プラントのワークアップ領域を通過することなく、懸濁液が存在する点において重合プロセスに戻すこと
の各工程を含む、上記多峰性ポリオレフィンポリマーの製造方法 - 前記熱交換器中で得られた液体を、第1反応器および第2反応器間に配置したフラッシュドラムに戻す、請求項1に記載の方法。
- 前記熱交換器中で得られた液体を、フラッシュドラムの上流に配置した重合反応器に戻す、請求項1に記載の方法。
- 前記熱交換器中で得られた液体を、第1重合反応器に戻す、請求項3に記載の方法。
- 前記第1重合反応器が、熱交換器を含む冷却サイクルを備え、前記懸濁液を冷却サイクルから引き抜く、請求項1〜4のいずれかに記載の方法。
- 前記懸濁液を、熱交換器に通過させる前に冷却サイクルから引き抜く、請求項5に記載の方法。
- 前記熱交換器が、一連の2基以上の熱交換器であり、フラッシュドラムから引き抜く気体の一部を、第1熱交換器において濃縮しないで、別の熱交換器に供給し、そこで、気体の別の一部を濃縮する、請求項1〜6のいずれかに記載の方法。
- 前記重合プロセスの終点における懸濁液のワークアップにおいて懸濁媒体および固体ポリオレフィン粒子を分離することにより得られる、懸濁媒体を第2重合反応器に供給する、請求項3〜7のいずれかに記載の方法。
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