JP5986203B2 - 流動接触分解プロセスにおける酸化的脱硫 - Google Patents
流動接触分解プロセスにおける酸化的脱硫 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- 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
- C10G2300/4056—Retrofitting operations
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Description
本願は、その内容がそのまま本明細書にて引用される、2011年7月29日出願の米国仮特許出願第61/513062号の利益を主張する。
本発明は、酸化的脱硫に、より具体的には液体炭化水素原料の統合される酸化的脱硫および流動接触分解に関する。
従来の石油精製の操作では、多様なプロセスが個々のユニットおよび/または工程にて起こっている。これは、一般に、天然に存する原油全体の混合成分が複雑であること、ならびに製油所で処理される原油原料が、しばしば、生産井の場所および年数、生産井での前処理活性、および原油を精油プラントに輸送するのに用いる手段を基礎として異なるという事実によるものである。
a.炭化水素原料、有効量の含酸素ガス、有効量の加熱されたクラッキング触媒を合わせ、酸化機能性を含有する有効量の不均一系触媒添加物を適宜合わせて、懸濁液を形成させる工程;
b.該懸濁液を流動接触分解反応装置の反応帯を通して維持し、
炭化水素原料中の有機硫黄化合物の少なくとも一部を酸化させて、酸化有機硫黄化合物を形成させ、
酸化有機硫黄化合物の炭素−硫黄結合を切断し、硫黄不含炭化水素化合物および酸化硫黄を形成させ、および
酸化および非酸化化合物(非酸化硫黄不含炭化水素化合物、非酸化有機硫黄化合物、および酸化有機硫黄化合物を含む)を、低沸点の炭化水素化合物に接触分解し、
ここで、接触分解が炭化水素原料中の化合物の熱分解よりも接触分解に有利に作用する条件下で起こる
工程;
c.分解した成分およびクラッキング触媒粒子を分離して回収する工程;
d.分離したクラッキング触媒粒子の少なくとも一部を再生する工程;および
e.再生クラッキング触媒粒子の少なくとも一部を、工程(a)の炭化水素原料および含酸素ガスと一緒に戻す工程
を含む。
Claims (11)
- 有機硫黄化合物を含有する炭化水素原料を接触分解し、かつ酸化脱硫し、それにより該炭化水素原料と比べて、沸点の低い炭化水素成分を含み、有機硫黄化合物の濃度が低い生成物ストリームを回収するプロセスであって:
a.炭化水素原料、ガス酸化剤、加熱されたクラッキング触媒を合わせて、懸濁液を形成させる工程;
b.該懸濁液を流動接触分解反応装置の反応帯を通して維持し、
炭化水素原料中の有機硫黄化合物の少なくとも一部を酸化させ、酸化有機硫黄化合物を形成させ、
酸化有機硫黄化合物の炭素−硫黄結合を切断し、硫黄不含炭化水素化合物および酸化硫黄を形成させ、および
非酸化硫黄不含炭化水素化合物、非酸化有機硫黄化合物、および酸化有機硫黄化合物を含む、酸化および非酸化化合物を接触分解して、低沸点の炭化水素化合物にし、
ここで、接触分解は炭化水素原料中の化合物の熱分解よりも接触分解に有利に作用する条件下で起こる
工程;
c.分解した成分およびクラッキング触媒粒子を分離して回収する工程;
d.分離したクラッキング触媒粒子の少なくとも一部を再生する工程;および
e.再生されたクラッキング触媒粒子の少なくとも一部を、工程(a)の炭化水素原料およびガス酸化剤と一緒に戻す工程
を含み、
クラッキング触媒の炭化水素原料に対する重量割合が1:1〜40:1の範囲にあり、
ガス酸化剤中の利用可能な酸素原子の原料中にある硫黄化合物に対するモル比が、1:5〜1:500モル:モルの範囲にある、
プロセス。 - 工程(a)が酸化機能性を有する不均一系触媒添加物をさらに添加することを含む、請求項1記載のプロセス。
- 酸化機能性を有する均一系触媒添加物を工程(a)の上流にて原料に添加することをさらに含む、請求項1または2記載のプロセス。
- 反応帯が400℃〜565℃の範囲にある温度で操作される、請求項1記載のプロセス。
- 反応帯が1秒〜60秒の範囲にある滞留時間で操作される、請求項4記載のプロセス。
- 反応帯が500℃〜650℃の範囲にある温度で操作される、請求項1記載のプロセス。
- 反応帯が0.1秒〜5秒の範囲にある滞留時間で操作される、請求項6記載のプロセス。
- 回収される分解成分が50重量%までの硫黄の減少を示す、請求項1記載のプロセス。
- クラッキング触媒の炭化水素原料に対する重量割合が1:1〜15:1の範囲にある、請求項1記載のプロセス。
- 不均一系触媒がクラッキング触媒の10重量%〜100重量%の範囲で存在する、請求項2記載のプロセス。
- 均一系触媒が炭化水素原料の30重量%までの範囲で存在する、請求項3記載のプロセス。
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US201161513062P | 2011-07-29 | 2011-07-29 | |
US61/513,062 | 2011-07-29 | ||
PCT/US2012/048572 WO2013019629A1 (en) | 2011-07-29 | 2012-07-27 | Oxidative desulfurization in fluid catalytic cracking process |
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JP5986203B2 true JP5986203B2 (ja) | 2016-09-06 |
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US (1) | US9062259B2 (ja) |
EP (1) | EP2737012B1 (ja) |
JP (1) | JP5986203B2 (ja) |
KR (1) | KR20140064801A (ja) |
CN (1) | CN103827264B (ja) |
ES (1) | ES2566129T3 (ja) |
WO (1) | WO2013019629A1 (ja) |
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US9061273B2 (en) | 2008-03-26 | 2015-06-23 | Auterra, Inc. | Sulfoxidation catalysts and methods and systems of using same |
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CN106147832B (zh) * | 2015-04-20 | 2017-11-14 | 中国石化工程建设有限公司 | 一种催化裂化选择性反应再生工艺 |
US10450516B2 (en) | 2016-03-08 | 2019-10-22 | Auterra, Inc. | Catalytic caustic desulfonylation |
US11174441B2 (en) | 2018-10-22 | 2021-11-16 | Saudi Arabian Oil Company | Demetallization by delayed coking and gas phase oxidative desulfurization of demetallized residual oil |
US10894923B2 (en) | 2018-10-22 | 2021-01-19 | Saudi Arabian Oil Company | Integrated process for solvent deasphalting and gas phase oxidative desulfurization of residual oil |
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ES2566129T3 (es) | 2016-04-11 |
CN103827264A (zh) | 2014-05-28 |
US9062259B2 (en) | 2015-06-23 |
JP2014522904A (ja) | 2014-09-08 |
US20130026071A1 (en) | 2013-01-31 |
EP2737012A1 (en) | 2014-06-04 |
CN103827264B (zh) | 2015-09-02 |
WO2013019629A1 (en) | 2013-02-07 |
KR20140064801A (ko) | 2014-05-28 |
EP2737012B1 (en) | 2016-01-13 |
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