JP2005516078A - 段間分留を伴う分解ナフサ流の多段水素化脱硫 - Google Patents
段間分留を伴う分解ナフサ流の多段水素化脱硫 Download PDFInfo
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- C10G2300/301—Boiling range
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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Abstract
Description
a)水素及び触媒として有効量の水素化脱硫触媒の存在下でかつ約232℃(450°F)〜約427℃(800°F)の温度、約60〜800psigの圧力及び1バレルあたり約1000〜6000標準立方フィートの水素処理ガス速度を含めた水素化脱硫反応条件で、第1の硫黄除去段で原材料流を水素化脱硫させて、有機結合した硫黄の少なくとも約50重量%を硫化水素に転換させ、有機結合硫黄を約100〜約1000wppm含有する第1の生成物流を生成する工程と;
b)軽質留分が約100wppm未満の有機結合硫黄及び硫化水素を含有し、重質留分が生成物流由来の残りの有機結合硫黄を含有するような温度に分留カットポイントがある、前記第1の生成物流を軽質留分と重質留分に分留させる工程と;
c)その硫化水素の少なくとも一部分の前記軽質留分をストリッピングする工程と;
d)プロセスから離れた所へ、例えばさらなる処理又は製油所ガソリンプールまでストリッピング済みの軽質留分を導く工程と;
e)残留有機結合硫黄のレベルが低減され、かくして第2の生成物流が生成される第2の硫黄除去段まで重質留分を導く工程と、
を含んでなるプロセスが提供されている。
その特性が下表1に示されているcatナフサ供給原料を、2段で選択的に水素化脱硫した。第1の硫黄除去段では、約280m2/gの表面積及び約95Åの中孔径を有するアルミナ担体上の約4.3重量%のMoO3及び1.2重量%のCoOからなる触媒を使用した。第2の硫黄除去段では、約260m2/gの表面積及び約80Åの中孔径を有するアルミナ担体上の約15.0重量%のMoO3及び4.0重量%のCoOからなる触媒を使用した。第1段及び第2段の両方で使用されたプロセス条件が下表2に示されている。
第1段生成物が、C5−195°F留分と195〜430°F留分に分留されたという点を除いて、実施例1の手順に従った。第1段生成物及び留分は、下表4で特徴づけされている。
Claims (15)
- 50°F(10℃)〜450°F(232℃)の範囲内で沸とうし、有機結合した硫黄及びオレフィンを実質的量だけ含有しているオレフィンナフサ原材料流を、水素化脱硫し、実質的量のオレフィンを保留するための水素化脱硫方法であって、
a)水素及び水素化脱硫触媒の存在下で、かつ232℃(450°F)〜427℃(800°F)の温度、60〜800psigの圧力及び1バレルあたり1000〜6000標準立方フィートの水素処理ガス速度を含めた水素化脱硫反応条件で、第1の硫黄除去段で前記原材料流を水素化脱硫して、有機結合した硫黄の少なくとも50重量%を硫化水素に転換させ、有機結合硫黄を100〜1000wppm含有する第1の生成物流を生成する工程と;
b)軽質留分が100wppm未満の有機結合硫黄及び幾分かの硫化水素を含有し、重質留分が残りの有機結合硫黄を含有するような温度に分留カットポイントがある、前記生成物流を軽質留分と重質留分に分留させる工程と;
c)その硫化水素の少なくとも一部分の前記軽質留分をストリッピングする工程と;
d)プロセスから離れた所へ前記ストリッピング済みの軽質留分を導く工程と;
e)前記残留有機結合硫黄の少なくとも一部分が除去される第2の硫黄除去段まで前記重質留分を導く工程と、
を含んでなることを特徴とする水素化脱硫方法。 - 前記軽質留分の有機結合硫黄レベルが50wppm以下である温度にカットポイントがあることを特徴とする請求項1に記載の水素化脱硫方法。
- 前記ナフサ原材料流は、1000〜6000wppmの硫黄と60重量%までの濃度のオレフィンを含有していることを特徴とする請求項1に記載の水素化脱硫方法。
- 前記水素化処理触媒は、無機金属担体上の少なくとも1つの第VIII族金属及び少なくとも1つの第VI族金属で構成されており、これらの族は、元素周期表から選択されることを特徴とする請求項1に記載の水素化脱硫方法。
- 前記無機酸化物担体は、ゼオライト、アルミナ、シリカ、チタニア、酸化カルシウム、酸化ストロンチウム、酸化バリウム、炭素、ジルコニア、珪藻土、酸化セリウム、酸化ランタン、酸化ネオジム(neodynium oxide)、酸化イットリウム、酸化プラセオジム(praesodynium oxide)、クロミア、酸化トリウム、ウラニア、ニオブ(niobia)、タンタル(tantala)、酸化スズ、及び酸化亜鉛からなる群から選択されることを特徴とする請求項4に記載の水素化脱硫方法。
- 第VIII族金属がNi又はCoから選択され、第VI族金属がMoであることを特徴とする請求項5に記載の水素化脱硫方法。
- 触媒の総重量を基準にして、水素化処理触媒中の第VIII族金属の量が1〜5重量%であり、第VI族金属の量が1〜15重量%であることを特徴とする請求項6に記載の水素化脱硫方法。
- 前記水素化脱硫触媒は、Mo触媒成分、Co触媒成分及び担体成分で構成されており、前記Mo成分がMoO3として計算されて1〜10重量%の量で存在し、前記Co成分がCoOとして計算されて0.1〜5重量%の量で存在し、Co/Mo原子比が0.1〜1であることを特徴とする請求項1に記載の水素化脱硫方法。
- 50°F〜430°Fの範囲内で沸とうし、1500〜5000wppmの有機結合した硫黄及び少なくとも5重量%のオレフィンを含有しているオレフィンナフサ原材料流を、水素化脱硫し、実質的量のオレフィンを保留するための水素化脱硫方法であって、
a)少なくとも1つの第VIII族金属及び少なくとも1つの第VI族金属からなる水素化脱硫触媒の存在下で、かつ450°F〜800°Fの温度、60〜150psigの圧力及び1バレルあたり2000〜4000標準立方フィートの水素処理ガス速度を含めた水素化脱硫反応条件で、第1の硫黄除去段で前記原材料流を水素化脱硫させる工程であって、ここで、有機結合した硫黄の少なくとも50重量%は硫化水素に転換され、さらに有機結合硫黄を100〜1000wppm含有する第1の生成物流を生成する工程と;
b)軽質留分が100wppm未満の有機結合硫黄及び硫化水素を含有し、重質留分が第1の生成物流由来の残りの有機結合硫黄を含有するような温度に分留カットポイントがある、前記第1の生成物流を前記軽質留分と重質留分に分留させる工程と;
c)その硫化水素の少なくとも一部分の軽質留分をストリッピングする工程と;
d)前記ストリッピング済み軽質留分を収集する工程と;
e)少なくとも1つの第VIII族金属及び少なくとも1つの第VI族金属からなる水素化脱硫触媒の存在下で、水素化脱硫条件で第2の硫黄除去段内で前記重質留分を水素化脱硫して、前記重質留分の有機結合硫黄の少なくとも一部分を除去し、第2の生成物流を生成する工程と;
f)前記ストリッピング済み軽質留分を前記第2の生成物流と組合わせる工程と、
を含んでなることを特徴とする水素化脱硫方法。 - 前記無機酸化物担体は、ゼオライト、アルミナ、シリカ、チタニア、酸化カルシウム、酸化ストロンチウム、酸化バリウム、炭素、ジルコニア、珪藻土、酸化セリウム、酸化ランタン、酸化ネオジム、酸化イットリウム、酸化プラセオジム、クロミア、酸化トリウム、ウラニア、ニオブ、タンタル、酸化スズ、及び酸化亜鉛からなる群から選択されていることを特徴とする請求項9に記載の水素化脱硫方法。
- 第VIII族金属がNi又はCoから選択され、第VI族金属がMoであることを特徴とする請求項9に記載の水素化脱硫方法。
- 触媒の総重量を基準にして、前記水素化処理触媒内の第VIII族金属の量が1〜5重量%であり、第VI族金属の量が1〜15重量%であることを特徴とする請求項10に記載の水素化脱硫方法。
- 前記水素化脱硫触媒は、Mo触媒成分、Co触媒成分及び担体成分で構成されており、前記Mo成分がMoO3として計算されて1〜10重量%の量で存在し、前記Co成分がCoOとして計算されて0.1〜5重量%の量で存在し、Co/Mo原子比が0.1〜1であることを特徴とする請求項9に記載の水素化脱硫方法。
- 前記ストリッピング済み軽質留分中の有機結合硫黄の含有量は、前記第2の生成物流中の有機結合硫黄の含有量よりも多いことを特徴とする請求項9に記載の水素化脱硫方法。
- 前記ストリッピング済み軽質留分中の有機結合硫黄の含有量は、前記ストリッピング済み軽質留分及び前記第2の生成物流の両方からなる組合せ流の中の有機結合硫黄の含有量よりも多いことを特徴とする請求項9に記載の水素化脱硫方法。
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US33457201P | 2001-11-30 | 2001-11-30 | |
US10/274,021 US6913688B2 (en) | 2001-11-30 | 2002-10-18 | Multi-stage hydrodesulfurization of cracked naphtha streams with interstage fractionation |
PCT/US2002/035954 WO2003048273A1 (en) | 2001-11-30 | 2002-11-08 | Multi-stage hydrodesulfurization of cracked naphtha streams with interstage fractionation |
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JP2009517499A (ja) * | 2005-11-23 | 2009-04-30 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 高温メルカプタン分解を伴う選択的ナフサ水素化脱硫 |
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US7153415B2 (en) * | 2002-02-13 | 2006-12-26 | Catalytic Distillation Technologies | Process for the treatment of light naphtha hydrocarbon streams |
AU2003267854A1 (en) * | 2003-10-10 | 2005-04-27 | Instituto Mexicano Del Petroleo | Catalytic composition for the hydroprocessing of light and intermediate petroleum fractions |
WO2005044959A1 (ja) | 2003-11-07 | 2005-05-19 | Japan Energy Corporation | 無鉛ガソリン組成物及びその製造方法 |
US7419586B2 (en) * | 2004-12-27 | 2008-09-02 | Exxonmobil Research And Engineering Company | Two-stage hydrodesulfurization of cracked naphtha streams with light naphtha bypass or removal |
US7837861B2 (en) | 2006-10-18 | 2010-11-23 | Exxonmobil Research & Engineering Co. | Process for benzene reduction and sulfur removal from FCC naphthas |
US7749375B2 (en) | 2007-09-07 | 2010-07-06 | Uop Llc | Hydrodesulfurization process |
US7875167B2 (en) * | 2007-12-31 | 2011-01-25 | Exxonmobil Research And Engineering Company | Low pressure selective desulfurization of naphthas |
US8894844B2 (en) | 2011-03-21 | 2014-11-25 | Exxonmobil Research And Engineering Company | Hydroprocessing methods utilizing carbon oxide-tolerant catalysts |
US9783747B2 (en) | 2013-06-27 | 2017-10-10 | Uop Llc | Process for desulfurization of naphtha using ionic liquids |
US9399741B2 (en) | 2013-10-09 | 2016-07-26 | Uop Llc | Methods and apparatuses for desulfurizing hydrocarbon streams |
US10144883B2 (en) | 2013-11-14 | 2018-12-04 | Uop Llc | Apparatuses and methods for desulfurization of naphtha |
US9850435B2 (en) | 2014-08-26 | 2017-12-26 | Exxonmobil Research And Engineering Company | Hydroprocessing with drum blanketing gas compositional control |
FR3049955B1 (fr) | 2016-04-08 | 2018-04-06 | IFP Energies Nouvelles | Procede de traitement d'une essence |
FR3057578B1 (fr) | 2016-10-19 | 2018-11-16 | IFP Energies Nouvelles | Procede d'hydrodesulfuration d'une essence olefinique. |
WO2018156294A1 (en) | 2017-02-21 | 2018-08-30 | Exxonmobil Research And Engineering Company | Desulfurization of a naphtha boiling range feed |
EP3802743A1 (en) * | 2018-05-30 | 2021-04-14 | Haldor Topsøe A/S | Process for desulfurization of hydrocarbons |
MX2020012726A (es) * | 2018-05-30 | 2021-02-22 | Haldor Topsoe As | Proceso para desulfuracion de hidrocarburos. |
US11492560B2 (en) * | 2018-10-22 | 2022-11-08 | Total Marketing Services | Deep desulphurization of low sulphur content feedstock |
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AU513580B2 (en) | 1976-03-04 | 1980-12-11 | Amoco Corporation | The selective desulfurization of cracked naphthas |
US6126814A (en) | 1996-02-02 | 2000-10-03 | Exxon Research And Engineering Co | Selective hydrodesulfurization process (HEN-9601) |
US6231753B1 (en) | 1996-02-02 | 2001-05-15 | Exxon Research And Engineering Company | Two stage deep naphtha desulfurization with reduced mercaptan formation |
US6013598A (en) | 1996-02-02 | 2000-01-11 | Exxon Research And Engineering Co. | Selective hydrodesulfurization catalyst |
US5985136A (en) | 1998-06-18 | 1999-11-16 | Exxon Research And Engineering Co. | Two stage hydrodesulfurization process |
US6083378A (en) | 1998-09-10 | 2000-07-04 | Catalytic Distillation Technologies | Process for the simultaneous treatment and fractionation of light naphtha hydrocarbon streams |
US6303020B1 (en) | 2000-01-07 | 2001-10-16 | Catalytic Distillation Technologies | Process for the desulfurization of petroleum feeds |
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2002
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Cited By (1)
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JP2009517499A (ja) * | 2005-11-23 | 2009-04-30 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 高温メルカプタン分解を伴う選択的ナフサ水素化脱硫 |
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AU2002352577B2 (en) | 2009-09-17 |
US20030106839A1 (en) | 2003-06-12 |
US6913688B2 (en) | 2005-07-05 |
JP4423037B2 (ja) | 2010-03-03 |
EP1461401A1 (en) | 2004-09-29 |
EP1461401A4 (en) | 2008-12-24 |
ES2557984T3 (es) | 2016-02-01 |
WO2003048273A1 (en) | 2003-06-12 |
AU2002352577A1 (en) | 2003-06-17 |
NO20042963L (no) | 2004-06-29 |
CA2467879C (en) | 2012-10-30 |
CA2467879A1 (en) | 2003-06-12 |
EP1461401B1 (en) | 2015-10-21 |
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