JP2017115143A - 単一の主要反応器と小さいサイズの保護反応器とを用いるオレフィン供給原料の選択的水素化方法 - Google Patents
単一の主要反応器と小さいサイズの保護反応器とを用いるオレフィン供給原料の選択的水素化方法 Download PDFInfo
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- JP2017115143A JP2017115143A JP2016246069A JP2016246069A JP2017115143A JP 2017115143 A JP2017115143 A JP 2017115143A JP 2016246069 A JP2016246069 A JP 2016246069A JP 2016246069 A JP2016246069 A JP 2016246069A JP 2017115143 A JP2017115143 A JP 2017115143A
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Abstract
【解決手段】少なくとも2個の触媒床A1およびA2を含む単一の固定床主要反応器と、より小さいサイズの固定床保護反応器Bとを用い、これら2基の水素化反応器は、直列に接続されて配置され、一連の工程に従ってサイクル方式で用いられ、連続的操作を確実なものとしつつ、保護反応器Bを用いて、少なくとも部分的に失活した主要反応器の触媒床A1,A2(単数または複数)を迂回するために用いられ得る方法。迂回された主要反応器の触媒床A1,A2は、同時進行で含まれる触媒の再生及び/又は新触媒との交換を行う、方法。
【選択図】図2
Description
‐工程a)、この工程中、供給原料は、主要反応器の触媒床の全てを連続して通過し、
‐主要反応器の第1触媒床が失活し始めると、工程b)、この工程中、供給原料は、保護反応器に導入され、次いで、主要反応器の部分的に失活した第1触媒床を迂回することにより、前記主要反応器の、供給原料の移動方向に関してすぐ下流に位置する次の失活していない触媒床へと導かれ、
‐工程c)、この工程中、供給原料は、主要反応器の触媒床の全てを、専ら(uniquely)かつ連続的に、通過し、
‐工程c’)、 この工程中、工程c)と同時進行で、保護反応器の触媒床(単数または複数)の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられ、
‐工程d)、この工程中、供給原料は、保護反応器のみを通過し、
‐工程d’)、 この工程中、工程d)と同時進行で、主要反応器の少なくとも2個の触媒床の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられる。
・工程a)は、tAmaxの10〜70%、
・工程b)は、tBmaxの40〜100%、
・工程c)は、tCmaxの90〜100%、
・工程d)は、tDmaxの70〜100%。
‐工程a)、この工程中、供給原料は、主要反応器の触媒床の全てを連続して通過し、
‐主要反応器の第1触媒床が失活し始めると、工程b)、この工程中、供給原料は、保護反応器に導入され、次いで、主要反応器の部分的に失活した第1触媒床を迂回することにより、前記主要反応器の、供給原料の移動方向に関してすぐ下流に位置する次の失活していない触媒床へと導かれ、
‐工程c)、この工程中、供給原料は、主要反応器の触媒床の全てを、専らかつ連続的に、通過し、
‐工程c’)、工程c)と同時に、この工程中、保護反応器の触媒床(単数または複数)の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられ、
‐工程d)、この工程中、供給原料は、保護反応器のみを通過し、
‐工程d’)、工程d)と同時進行で、この工程中、主要反応器の少なくとも2個の触媒床の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられる。
・工程d)の間中、保護反応器Bの温度を上昇させること、および/または
・工程d)の間中、水素を含む相の流れを増大させること、および/または
・供給原料の流量を低減させること、および/または
・再循環量を増大させること。
本発明による方法の利点から利益を得るためには、少なくとも1個の触媒床を含む保護反応器Bが、主要反応器よりサイズが小さいことが重要である。
失活時間
本発明に関連して、主要反応器または保護反応器の触媒床(単数または複数)、特に、供給原料の移動方向において一番目の触媒床に含まれる触媒(単数または複数)は、徐々に失活してくる。触媒(単数または複数)が、失活あるいは、部分的に失活すると、1つの工程から別の工程への切り替えが開始される。
・工程a)は、tAmaxの10〜70%、好ましくは20〜60%であり、
・工程b)は、tBmaxの40〜100%、好ましくは70〜100%であり、
・工程c)は、tCmaxの90〜100%、好ましくは100%であり、
・工程d)は、tDmaxの70〜100%、好ましくは85〜100%である。
水素化条件
本発明による方法に関連して、多価不飽和供給原料は、水素化を可能とする条件、特に温度、圧力、および毎時空間速度(HSV)の下、水素化触媒の存在下に、水素を含む気相と接触させられる。
供給原料
前記炭化水素供給原料は、少なくとも3個の炭素原子を含む少なくとも1個の多価不飽和分子を含む。より具体的には、前記処理される供給原料中に存在する前記多価不飽和炭化水素は、特に、少なくとも1種のアセチレン基(すなわち、少なくとも1つの三重結合)、および/または少なくとも1種のジエン基(すなわち、少なくとも2つの二重結合)、および/または少なくとも1種のアルケニル−芳香族基(すなわち、少なくとも1種のオレフィンリガンドを含む少なくとも1種の芳香環)を含む化合物である。特に、多価不飽和炭化水素の前記供給原料は、分子当たりアセチレン基およびジエン基の両方を含む少なくとも1種の化合物を含んでよい。
気相
本発明による方法に関連して、炭化水素供給原料は、水素を含む気相と接触させられる。
水素化触媒
以下の化学元素の群は、CAS分類(CRC Handbook of Chemistry and Physics, published by CRC press, editor-in-chief D.R. Lide, 81stedition, 2000-2001)に準拠している。例として、CAS分類に準拠した第VIII族は、新IUPAC分類の第8、9、および10欄の金属に対応する。
触媒は、特に、アルミナ(Al2O3)、シリカ(SiO2)、酸化チタン(TiO2)、セリア(CeO2)、およびジルコニア(ZrO2)から選択される少なくとも1つの単純な酸化物によって形成される多孔質担体を含む。好ましくは、前記担体は、アルミナ、シリカ、およびシリカ−アルミナから選択される。特に好ましくは、多孔質担体は、アルミナである。
再生/再活性化
1つの反応器内の触媒が失活してくると、それは再生され、および/または再活性化される(rejuvenated)。
再循環
本発明の好ましい実施形態によると、主要反応器または保護反応器から得られる気体/液体流出物の一部は、水素化されるべき供給原料との混合物として、戻されてもよい(すなわち、再循環させられてもよい)。
熱交換器(チラー)
好ましい実施形態によると、本発明による方法は、特に、各反応器の間に1基以上の熱交換器(単数または複数)(チラー)を用いてよく、これにより、特に、保護反応器と主要反応器の間で、すぐ上流に位置する反応器からの流出物が冷却される。流出物の温度は低下されて、これにより保護反応器Bで蒸発したオレフィンが液化される。この中間の熱交換器は、したがって発熱性を制御するために用いられ得る。
他の実施形態
本発明の方法の他の実施形態もまた、より困難な供給原料の処理のために、または図2に示すように、様々な工程の間中、触媒床を解放(relieve)するために想定されてよい。
MAV(MAVは、無水マレイン酸値(Maleic Anhydride Value)を表し、ジオレフィン含有量を測定する)が210であり、臭素価(臭素価はオレフィン含有量を測定する)が81であり、3%のスチレン(および8%のC9+スチレン化合物)を含有する、熱分解ガソリン「PyGas」の供給原料を、以下の操作条件下、図1に示す水素化方法を用いて処理した:
‐供給原料の流量:17t/h
‐水素を含む気相の組成:H2が95%、CH4が5%
‐全水素流量:0.4t/h(H2+CH4)
‐HSV(15℃での新鮮な供給原料の体積流量の、触媒の体積に対する比として定義される):1.5h−1
‐触媒の体積:直径1000mmの反応器中、17m3(第1主要反応器、活性触媒)
‐触媒の量:直径1000mmの反応器中、17m3(第2主要反応器、不活性触媒)
‐再循環流量:30t/h
‐反応器入口での絶対圧:3MPa(30バール)
‐反応器入口での温度:60℃
この実施例の目的は、反応器出口におけるスチレン含有率(ならびに、結果的に、水素化がより容易であるジオレフィンの大部分)を0.5重量%に低下させることであった。
主要反応器を用いて、12ヶ月の期間にわたり、触媒体積の全てを用いることが出来たことを意味する。
実施例1(比較例)で処理したものと同じオレフィン供給原料を、本発明による水素化方法を用いて処理した。本方法では、図2で示すように、直列および並列で接続された2基の(クエンチボックスを有するかまたは有しない)反応器を用いた。実施例1の2基の反応器内で用いた触媒と比較して、15体積%低減させた触媒の質量(34m3に代わって28m3)を、主要反応器中に70%の程度まで(第1床において30%、第2床において40%)、保護反応器中に30%の程度まで分布させた。実施例1(比較例)の方法と実施例2(本発明に合致する)の方法とを、等しい流量(30t/h)ならびに供給原料およびガスの品質(0.4t/h、H295%、CH45%)で比較した。操作条件は、以下の通りであった:
‐主要反応器のHSV(15℃での新鮮な供給原料の体積流量の、主要反応器の触媒の体積に対する比として定義される):1.5h−1
‐触媒の体積:直径1000mmの反応器中20m3(主要反応器、活性触媒)
‐触媒の体積:直径1000mmの反応器中8m3(保護反応器、活性触媒)
‐反応器の直径:1000mm
‐再循環流量:30t/h
‐反応器中の絶対圧:3MPa(30バール)
‐第1反応器における入口温度:60℃
本実施例の目的は、参照用の方法より長い期間にわたり、プロセス出口においてスチレン転化率を0.5重量%に維持することである。このことを、触媒床の再構成、および触媒床の最適な順序付け(optimized sequencing)によって実現する一方、触媒の全体積(主要反応器および保護反応器の体積の合計として計算される)を低減させた。以下の表に、触媒全てを使ったサイクルの工程を記録する。
Claims (15)
- 少なくとも3個の炭素原子を含む多価不飽和分子を含む炭化水素供給原料の選択的水素化方法であって、前記供給原料と、水素を含む気相とが、水素化条件下で、少なくとも2個の触媒床を含む単一の固定床主要反応器内、および少なくとも1個の触媒床を含むより小さいサイズの固定床保護反応器内において、水素化触媒上を通過させられ、これらの反応器は、直列に配置され、以下に規定される工程a)、b)、c)、c’)、d)、およびd’)を連続的に繰り返すことによりサイクル方式で用いられる:
‐工程a)、この工程中、供給原料は、主要反応器の触媒床の全てを連続的に通過し、
‐主要反応器の第1触媒床が失活し始めると、工程b)、この工程中、供給原料は、保護反応器に導入され、次いで、主要反応器の部分的に失活した第1触媒床を迂回することにより、前記主要反応器の、供給原料の移動方向に関してすぐ下流に位置する次の失活していない触媒床へと導かれ、
‐工程c)、この工程中、供給原料は、主要反応器の触媒床の全てを、専らかつ連続的に、通過し、
‐工程c’)、工程c)と同時進行で、この工程中、保護反応器の触媒床(単数または複数)の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられ、
‐工程d)、この工程中、供給原料は、保護反応器のみを通過し、
‐工程d’)、工程d)と同時進行で、この工程中、主要反応器の少なくとも2個の触媒床の失活した触媒は、再生され、および/または新鮮な触媒と取り替えられる。 - 保護反応器の触媒床(単数または複数)に含まれる触媒の全体積は、主要反応器の触媒床に含まれる触媒の全体積の最大60%である、請求項1に記載の方法。
- 炭化水素供給原料は、水蒸気分解からのC3留分、水蒸気分解からのC4留分、水蒸気分解からのC5留分、および熱分解ガソリン、ならびにそれらの混合物によって構成される群より選択される、請求項1または2に記載の方法。
- 工程a’)が、工程a)と同時に行われ、この工程中、保護反応器の触媒床(単数または複数)の工程d)の間中に失活した触媒が、再生されるかまたは新鮮な触媒と取り替えられる、請求項1〜3のいずれか1つに記載の方法。
- 工程a)、b)、c)、およびd)の各操作期間(操作期間は、各工程の最長操作期間tmaxに対して規定され、最長操作期間は、所与の供給原料について、温度または選択性が最大許容値に達する時間である)は、以下の通りである、請求項1〜4のいずれか1つに記載の方法:
・工程a)は、tAmaxの10〜70%、
・工程b)は、tBmaxの40〜100%、
・工程c)は、tCmaxの90〜100%、
・工程d)は、tDmaxの70〜100%。 - ・C3供給原料の最大許容値は、有効な規格に従った選択度であり、
・C4供給原料の最大許容値は、160℃の最高温度であり、
・C5供給原料の最大許容値は、160℃の最高温度であり、
・熱分解ガソリンの供給原料の最大許容値は、200℃の最高温度である、
請求項5に記載の方法。 - 各反応器は、温度0〜200℃、圧力1〜6.5MPaの範囲、全体的な毎時空間速度(15℃における新鮮な供給原料の体積流量の、用いられる一連の反応器中に存在する触媒の全体積に対する比として定義される)1〜100h−1の範囲で操作される、請求項1〜6のいずれか1つに記載の方法。
- 主要反応器または保護反応器から得られる流出物の一部が、水素化されるべき供給原料との混合物として、再循環させられる、請求項1〜7のいずれか1つに記載の方法。
- 工程a)、b)、c)、およびd)の間中、水素化のための操作条件は、同一である、請求項1〜8のいずれか1つに記載の方法。
- 工程a)の始まりに用いられる温度、流れ、流量(単数または複数)のそれぞれに対して、工程d)の間中、保護反応器の温度は上げられ、および/または水素を含む相の流れは増大させられ、および/または保護反応器への再循環流量は増大させられ、および/または保護反応器に導入される供給原料の流量は低減させられる、請求項1〜8のいずれか1つに記載の方法。
- 工程a)の始まりに対して、工程d)の始まりにおける、保護反応器の温度上昇は、反応器の頭部で、0.5〜40℃の範囲である、請求項10に記載の方法。
- 工程a)の始まりにおける再循環流量に対する、工程d)の始まりにおける保護反応器の再循環流量の増加は、0.5〜100%の範囲である、請求項10または11に記載の方法。
- クエンチが、主要反応器または保護反応器中の2個の触媒床の間で導入され、前記クエンチは、液体クエンチおよび/または気体クエンチであってよい、請求項1〜12のいずれか1つに記載の方法。
- 1基以上の熱交換器(単数または複数)が、保護反応器と主要反応器の間に用いられる、請求項1〜13のいずれか1つに記載の方法。
- 用いられる水素化触媒は、主要反応器および/または保護反応器の触媒床(単数または複数)において、同一であるかまたは異なっている、請求項1〜14のいずれか1つに記載の方法。
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