JP2023508753A - 懸濁媒質のワークアップを含むエチレン重合体の製造のための懸濁プロセス - Google Patents
懸濁媒質のワークアップを含むエチレン重合体の製造のための懸濁プロセス Download PDFInfo
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- 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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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
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- B08B17/00—Methods preventing fouling
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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
【選択図】なし
Description
重合触媒の存在下で、40~150℃の温度及び0.1~20MPaの圧力でエチレンを重合するか、又はエチレンと1つ以上のC3-C12-1-アルケンとを共重合し、炭化水素希釈液を含む懸濁媒質中でエチレン重合体粒子の懸濁液を形成するステップと、
エチレン重合体粒子の懸濁液を固液分離器内に移送するステップであって、懸濁液は、エチレン重合体粒子及び母液に分離されるステップと、
母液の一部を、母液のワックス枯渇部分を生産するための蒸発ユニットを含むワークアップセクション内に移送するステップであって、ワークアップセクション内に移送される母液の一部にプロトン剤(protic agent)を添加するステップと、
母液のワックス枯渇部分の少なくとも一部を、重合反応器又は一連の重合反応器に再循環させるステップと、を含む、プロセスを提供する。
比較例A
ライン(38)を介してプロトン剤を添加しなかったことを除いては、図1に示すように、3つの重合反応器を含む商業的に作動する反応器システムでポリエチレンを連続的に製造した。5年を超える期間にわたって、エチレンと任意選択的に共単量体としての1-ブテンとの重合を65℃~85℃の範囲の反応器温度及び0.2MPa~1.3MPaの反応器圧力でチーグラー型触媒の存在下で行ない、異なるグレードの様々なポリエチレンを製造した。グレードによって、生産速度は、30~41t/hの範囲で異なる。遠心分離機(13)から排出され、ライン(20)を介して母液収集容器(21)に移送される母液の量は、常に95~185t/hの範囲であった。ワークアップされる母液は、ライン(23)から分岐し、ライン(30)及び(37)を通過して予熱器(34)に入った。ワークアップされた母液の量は、30~55t/hの範囲であった。液液分離容器(66)から排出され、ライン(70)を介して母液タンク(31)に移送されるヘキサン相の量は、3~7t/hの範囲であった。
比較例Aの重合を繰り返したが、ライン(37)を永久的に閉鎖し、ワークアップされる母液の全量をライン(30)を介して母液タンク(31)内に移送した。図1に示すように、ライン(38)を介してプロトン剤として水を、ライン(30)を通過して母液タンク(31)に入る母液1トン当たり250gの水の量で添加した。
比較例Aの重合を繰り返したが、図2に示すように、ライン(40)を介してプロトン剤として水を、ライン(37)を通過した母液1トン当たり250gの水の量で添加した。
実施例2の重合を繰り返したが、図2に示すように、ライン(40)を介してプロトン剤としてLINEVOL 911、n‐ノナノール、n‐デカノール及びn‐ウンデカノール(Shell Chemicalsから市販されている)の混合物を、ライン(37)を通過した母液1トン当たり750gのLINEVOL 911の量で添加した。
Claims (13)
- 重合反応器又は一連の重合反応器において懸濁重合におけるエチレン重合体を製造するプロセスであって、
重合触媒の存在下で、40~150℃の温度及び0.1~20MPaの圧力でエチレンを重合するか、又はエチレンと1つ以上のC3-C12-1-アルケンとを共重合し、炭化水素希釈液を含む懸濁媒質中でエチレン重合体粒子の懸濁液を形成するステップと、
前記エチレン重合体粒子の懸濁液を固液分離器内に移送するステップであって、前記懸濁液は、エチレン重合体粒子及び母液に分離されるステップと、
前記母液の一部を、前記母液のワックス枯渇部分を生産するための蒸発ユニットを含むワークアップセクション内に移送するステップであって、前記ワークアップセクション内に移送される前記母液の一部にプロトン剤(protic agent)を添加するステップと、
前記母液のワックス枯渇部分の少なくとも一部を、前記重合反応器又は前記一連の重合反応器に再循環させるステップと、を含む、プロセス。 - 前記プロトン剤は、水、アルコール、酸又はそれらの混合物である、請求項1に記載のプロセス。
- 前記プロトン剤は、水であり、前記水は、スチームとして、又は有機若しくは無機化合物の水溶液として、液体形態で添加される、請求項2に記載のプロセス。
- 前記ワークアップセクション内に移送される母液と、添加されるプロトン剤との混合物は、前記ワークアップセクションに入る前に混合デバイスを通過する、請求項1~3のいずれか一項に記載のプロセス。
- 前記混合デバイスは、インラインミキサー、ジェットミキサー、混合ノズル、ハイドロサイクロン、混合要素が備えられた容器、ロータ/ステータミキサー又はホモジナイザー又は乳化器である、請求項4に記載のプロセス。
- 予熱器として作動する熱交換器は、前記蒸発ユニットの上流に設置され、前記ワークアップセクション内に移送される母液と、添加されたプロトン剤との混合物は、前記蒸発ユニットに入る前に、この熱交換器を通過する、請求項1~5のいずれか一項に記載のプロセス。
- 前記蒸発ユニットは、熱交換器及び分離容器を含む循環蒸発ユニットであり、前記循環蒸発ユニットは、蒸発する液相を前記熱交換器内に供給し、前記熱交換器で前記液相を部分的に気化させ、生成された液体及び蒸気混合物を前記分離容器に戻すことによって作動する、請求項1~6のいずれか一項に記載のプロセス。
- 前記蒸発ユニットで生産された前記母液のワックス枯渇部分は、前記重合反応器又は前記一連の重合反応器に再循環する前に蒸留プロセスにさらにかけられる、請求項1~7のいずれか一項に記載のプロセス。
- 低沸点成分が枯渇した前記母液のワックス含有部分は、前記蒸発ユニットから排出され、直接スチーム蒸留によって作動するワックス除去ユニットに移送される、請求項1~8のいずれか一項に記載のプロセス。
- 前記ワックス除去ユニットは、凝縮した後、液液分離器内で、水相及び炭化水素相に分離されるガス状炭化水素/スチーム混合物を生産し、前記炭化水素相は、前記蒸発ユニットに再循環する、請求項9に記載のプロセス。
- 前記製造されたエチレン重合体は、マルチモーダルエチレン共重合体である、請求項1~10のいずれか一項に記載のプロセス。
- 前記エチレン重合体の製造は、一連の重合反応器で行われ、エチレン単独重合体は、前記重合反応器のいずれか1つで製造される、請求項11に記載のプロセス。
- 前記エチレン単独重合体は、前記一連の重合反応器のうちの第1の重合反応器で製造され、エチレンの共重合体は、後続の重合反応器で製造される、請求項12に記載のプロセス。
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