JP4434750B2 - 重質軽油から高品質留出油を生産するための新しい水素化分解法 - Google Patents
重質軽油から高品質留出油を生産するための新しい水素化分解法 Download PDFInfo
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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Description
・全体として、最小の反応器容積及び触媒容積を使用した高変換
・より良好な生成物品質
・より少ない水素消費
流れ1で供給される予熱された油は、予熱された循環及び補給水素ガス(反応器供給ガス)である、流れ40の水素ガスと混合される。供給原料は、供給ポンプによって反応器の圧力にまで加圧されたプロセス熱交換機内で予熱されている。供給原料及び反応器供給ガスの混合物、ここでは流れ2、は、第1段の下降流固定層主反応器(3)に入る前に、熱交換(熱交換機41内で)及び最終炉(42)により、さらに予熱される。主反応器又は第1段反応器は、水素精製又は水素分解の触媒層でありうる、水素化処理触媒の多数の層を含む。循環ガス圧縮機からの冷えた水素は、層間冷却材(4、5、6)として使用される。
本発明の第1の実施形態では、広範囲のさまざまな炭化水素供給原料を用いる。通常の原料油は、392°F(200℃)を超える沸点を有する、重質又は合成油流分或いは工程流れを含む。そのような原料油は、減圧軽油、重質常圧軽油(heavy atmospheric gas oil)、減圧残油、ディレードコーカー軽油(delayed coker gas oil)、ビスブレーカー軽油脱金属油(visbreaker gas oil demetallized oil)、常圧残油、脱歴油、フィッシャー−トロプシュ流れ、及びFCC流れを含む。
どちらの実施形態におけるいずれの水素化処理域も、唯一つの触媒、又はいくつかの組合せ触媒を含む。好ましい実施形態では、第1領域では水素化分解が進行し続け、第2領域では水素化精製が進行し続ける。
水素化分解反応域の反応条件は、約250℃〜約500℃(482°F〜932°F)の反応温度、約3.5MPa〜約24.2MPa(500〜3500psi)の圧力、及び約0.1〜20hr−1の供給原料速度(油の容積/触媒の容積・時間)を有する。水素の循環速度は、一般に、約350標準リットルH2/kg油〜1780標準リットルH2/kg油(2310〜11750標準立方フィート/バレル)の範囲である。好ましい反応温度は、約340℃〜約455℃(644°F〜851°F)の範囲である。好ましい全反応圧力は、約7.0MPa〜約20.7MPa(1000〜3000psi)の範囲である。好ましい触媒系では、好ましい工程条件は、約13.8Mpa〜約20.7MPa(2000〜3000psi)の圧力、約379〜909標準リットルH2/kg油(2500〜6000標準立方フィート/バレル)の油に対するガスの比率、約0.5〜1.5hr−1のLHSV、及び360℃〜427℃(680°F〜800°F)の範囲の温度を含む水素化分解条件下で、石油原料油を水素と接触させることを含むことを発見した。
第2精油装置供給原料の流れは、一般に第1精油装置供給原料の流れより低い沸点範囲を有する。実際、第2精油装置供給原料流れのかなりの部分が、中間留分範囲内に標準沸点を有する結果、沸点を下げるための分解が必要でないことが、本方法の特徴である。従って、適切な第2精油装置の流れの少なくとも約75容積%が、約1000°F未満の標準沸点を有している。その成分の少なくとも約75容積%が250°F〜700°Fの範囲内に標準沸点を有する精油装置流れは、好ましい第2精油装置供給原料流れの例である。
水素化精製装置は、第2精油装置の流れから来る窒素の少なくとも一部及び芳香族化合物の少なくとも一部を除去するのに十分な条件に維持されている。反応域内の発熱による加熱から温度勾配が生じ、1つ又は複数の反応域へ相対的に冷却された流れを加えることによりこれを和らげる場合を除いて、水素化精製装置は、水素化分解装置より低い温度で動作する。反応域を通る反応液体の流れの供給速度は、0.1〜20hr−1液空間速度の範囲である。水素化精製装置を通る供給原料の速度は、水素化分解装置を通る供給原料速度と比較して、第2精油装置供給原料流れ中の液体供給量の分だけ上昇し、やはり、0.1〜20hr−1液空間速度の範囲にある。第1反応域のために選択されたこれらの工程条件は、水素化精製法のために通常選択される条件より、厳しいと考えてよい。
本発明の実施形態は、約250〜700°F(121〜371℃)の範囲で沸騰する中間留分の製造に特に有用である。中間留分は、約250〜700°Fのおよその沸騰範囲を有するものと定義される。中間留分成分の少なくとも75容積%、好ましくは85容積%が、250°Fを超える標準沸点を有する。中間留分成分の少なくとも約75容積%、好ましくは85容積%が700°F未満の標準沸点を有する。「中間留分」という用語は、ディーゼル燃料、ジェット燃料及び灯油沸騰範囲留分を含む。灯油又はジェット燃料の沸点範囲は、280〜525°F(38〜274℃)の範囲を云う。
Claims (6)
- 炭化水素原料油を水素化処理する方法であって、単一反応ループ内の多段反応域を使用し、
(a)炭化水素原料油を、水素化処理触媒を含む1つ又は複数の層を有する第1水素化処理域へ送り、前記水素化処理域を水素化処理条件に維持しておき、原料油を触媒及び水素に接触させるステップと、
(b)ステップ(a)の流出液を直接高温高圧分離機へ送り、前記流出液を高温で水素に富むストリッピングガスに接触させて、水素、炭化水素原料油の沸騰範囲を超えない温度で沸騰する炭化水素化合物、硫化水素、アンモニアを含む蒸気の流れ、並びに前記炭化水素原料油とほぼ同じ範囲で沸騰する炭化水素化合物及びディーゼル燃料の沸騰範囲で沸騰する炭化水素化合物の一部を含むボトムの流れを生成するステップと、
(c)ステップ(b)からの前記蒸気の流れを、冷却し部分的に凝縮させた後、水素化精製触媒を少なくとも1層含む高温水素ストリッパに送り、そこで水素と対向流で接触させ、その間、ステップ(b)の液体の流れを第2反応器へ送るステップと、
(d)ステップ(c)の高温水素ストリッパからのオーバーヘッド蒸気の流れを、冷却し水と接触させた後、第1低温高圧分離機へ送り、そこで水素、硫化水素及び軽質炭化水素ガスを上部で除去し、ナフサ及び中間留分を含む液体の流れを分別に送り、それによりアンモニアの大部分及び硫化水素のいくらかを(サワー水流れが低温高圧分離機を離れるときに、そのサワー水流れ中の水硫化アンモニウムとして)除去するステップと、
(e)ステップ(c)の高温水素ストリッパからの液体の流れを、第2反応器の水素化処理触媒層へ送り、そこで前記液体を水素の存在下で、水素化処理条件の下に触媒と接触させるステップと、
(f)ステップ(d)の低温高圧分離機からのオーバーヘッドをアミン吸収装置へ送り、そこで水素を圧縮し、ループ内の水素化処理容器へ再循環させる前に、硫化水素を除去するステップと、
(g)ステップ(b)の分離機のボトムを第2反応器へ送り、そこで水素の存在下で水素化分解触媒の少なくとも1つの層と接触させて、蒸気の流れ及び液体流出液を生成するステップと、
(h)ステップ(g)の蒸気の流れを、冷却した後、第2低温高圧分離機へ送り、そこで主として水素及び軽質炭化水素ガスを含む蒸気の流れを除去するステップと、
(i)ステップ(g)の液体流出液を、冷却した後、ステップ(h)の低温高圧分離機へ送り、前記液体流出液から、水素及び炭化水素ガスを分離するステップと、
(j)ステップ(h)及び(i)からの蒸気の流れを、さらに冷却し、凝縮液を分離した後、補給水素圧縮機へ送るステップと、
(k)補給水素圧縮機からの圧縮水素を主反応器ループへ送るステップと、
(l)ステップ(h)及び(i)からの液体流出液を分別システムへ送るステップと
を含む方法。 - 請求項1のステップ(g)で、請求項1のステップ(b)のボトムの流れに対して対向流となる方向に、水素が流れる請求項1に記載の方法。
- 炭化水素原料油が、減圧軽油、重質常圧軽油、ディレードコーカー軽油、ビスブレーカー軽油、脱金属油、FCCライトサイクルオイル、減圧残油脱歴油、及びフィッシャー−トロプシュ流れから成る群から選択される、請求項1に記載の方法。
- ステップ(e)で行われるセタン価の改善が、20〜45の範囲である、請求項1に記載の方法。
- ステップ(e)で行われる灯油煙点の改善が、7〜27の範囲である、請求項1に記載の方法。
- 第1水素化処理域及び第2反応器の水素化処理触媒が、分解成分及び水素化成分を含む、請求項1に記載の方法。
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US10/104,185 US6797154B2 (en) | 2001-12-17 | 2002-03-21 | Hydrocracking process for the production of high quality distillates from heavy gas oils |
PCT/US2003/008809 WO2003080769A1 (en) | 2002-03-21 | 2003-03-21 | New hydrocracking process for the production of high quality distillates from heavy gas oils |
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AR (1) | AR039040A1 (ja) |
AU (1) | AU2008237602B2 (ja) |
CA (2) | CA2668788A1 (ja) |
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Cited By (3)
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JP2008121019A (ja) * | 2002-03-21 | 2008-05-29 | Chevron Usa Inc | 重質軽油から高品質留出油を生産するための新しい水素化分解法 |
US8999256B2 (en) | 2013-06-20 | 2015-04-07 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
US9752085B2 (en) | 2013-06-20 | 2017-09-05 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
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JP2008121019A (ja) * | 2002-03-21 | 2008-05-29 | Chevron Usa Inc | 重質軽油から高品質留出油を生産するための新しい水素化分解法 |
US8999256B2 (en) | 2013-06-20 | 2015-04-07 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
US9752085B2 (en) | 2013-06-20 | 2017-09-05 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
Also Published As
Publication number | Publication date |
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EG23710A (en) | 2007-06-06 |
JP4672000B2 (ja) | 2011-04-20 |
ZA200406724B (en) | 2006-06-28 |
CA2479287C (en) | 2010-06-22 |
JP2008121019A (ja) | 2008-05-29 |
AR039040A1 (es) | 2005-02-02 |
US20030111386A1 (en) | 2003-06-19 |
AU2008237602A1 (en) | 2008-11-27 |
CA2668788A1 (en) | 2003-10-02 |
PL372338A1 (en) | 2005-07-11 |
EP1487941A4 (en) | 2010-11-24 |
IN2004CH02351A (en) | 2007-07-20 |
CA2479287A1 (en) | 2003-10-02 |
EP1487941A1 (en) | 2004-12-22 |
AU2008237602B2 (en) | 2010-11-25 |
US6797154B2 (en) | 2004-09-28 |
JP2005520918A (ja) | 2005-07-14 |
WO2003080769A1 (en) | 2003-10-02 |
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