JP3227521B2 - Process for recovering organic sulfur compounds from liquid oil - Google Patents

Process for recovering organic sulfur compounds from liquid oil

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JP3227521B2
JP3227521B2 JP11235092A JP11235092A JP3227521B2 JP 3227521 B2 JP3227521 B2 JP 3227521B2 JP 11235092 A JP11235092 A JP 11235092A JP 11235092 A JP11235092 A JP 11235092A JP 3227521 B2 JP3227521 B2 JP 3227521B2
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oil
organic sulfur
sulfur compounds
layer
acid
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JPH05286869A (en )
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哲夫 相田
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哲夫 相田
舟越 泉
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G27/00Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G53/00Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes
    • C10G53/02Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】この発明は,石油,オイルサンド,オイルシェール及び石炭液化油から得られる液状油(以下,鉱物油という)中から,医薬,農薬,耐熱性樹脂等の製造分野で工業的に有用な有機硫黄化合物を回収する方法に関する。 BACKGROUND OF THE INVENTION The present invention, oil, oil sand, liquid oils obtained from oil shale and coal liquefied oil (hereinafter, mineral oil hereinafter) industry from within, medicines, agricultural chemicals, in the field of manufacturing such heat-resistant resin to a method of recovering useful organic sulfur compounds.

【0002】 [0002]

【従来の技術】石油,オイルサンド,オイルシェール及び石炭液化油から得られる液状油中に各種の有機硫黄化合物が含有されていることは古くから知られている。 BACKGROUND ART Petroleum, oil sands, the various organic sulfur compounds in the liquid oil resulting from oil shale and coal liquefied oil is contained has been known for a long time. 例えば,ディーゼルエンジンの燃料油中に含有される硫黄分は環境汚染の元凶の一つとして,近年,注目を集めており,有効な脱硫技術の開発が急がれている。 For example, the sulfur content in the fuel oil in a diesel engine as one of main cause of environmental pollution in recent years, has attracted attention, it has been urgent to develop effective desulfurization technology. このように,鉱物油中に含有される有機硫黄分に対しては,従来から,有害物としての認識が強く,その除去を主目的とした技術開発がなされてきた。 Thus, for the organic sulfur contained in the mineral oil, conventionally, strong recognition as harmful substances, technological development with the primary purpose of its removal have been made.

【0003】従来,廃ガス等の工業ガス中から有機硫黄化合物を回収する技術としては,特公昭53−2657 Conventionally, as a technique for recovering organic sulfur compounds from in industrial gases, such as waste gas, JP-B-53-2657
7号公報に開示されたものがあるが,該工業ガス中から有機硫黄化合物を回収方法は,有機硫黄化合物を含有する廃ガスを鉱油で加圧吸収した後,有機硫黄化合物を高濃度ガスとして回収するものである。 There is disclosed in 7 JP, organic sulfur compounds recovery methods from 該工 industry gas, waste gases containing organic sulfur compounds was pressurized absorbed in mineral oil, an organic sulfur compound as a dense phase gas it is intended to recover. 即ち,その回収方法は,有機硫黄化合物を含有する工業用ガスを鉱油をもって加圧下で洗浄し,有機硫黄化合物を吸収した鉱油を脱圧した後に,スチームにより有機硫黄化合物を放散し,吸収塔へ循環使用すると共に,放散した有機硫黄化合物,鉱油及び水蒸気から成る混合蒸気を凝縮して油層と水層とに分離し,先に脱圧の際に発生したガスと油層とを接触させて高濃度の有機硫黄化合物を含むガスを得るものである。 That is, the method of recovery, the industrial gases containing organic sulfur compounds with mineral oil was washed under pressure, a mineral oil that has absorbed organic sulfur compounds after depressurized, the organic sulfur compound is dissipated by the steam, to the absorber tower while recycling, organic sulfur compounds dissipated, by condensing the vapor mixture consisting of mineral oil and steam is separated into the oil layer and an aqueous layer, a high concentration by contacting the gas and the oil layer generated during the depressurization previously it is intended to obtain a gas containing organic sulfur compounds.

【0004】 [0004]

【発明が解決しようとする課題】しかしながら,鉱物油中に含有されている有機硫黄化合物は,物理的性質及び化学的性質が鉱物油自身に極めて良く似ているため,蒸留や溶剤抽出等の一般的な分離精製手段が有効でない。 [0007] However, the organic sulfur compounds contained in mineral oil, because the physical and chemical properties are very similar to the mineral oil itself, generally such distillation or solvent extraction It is not a valid separation purification means.
現在では,有機硫黄化合物の分離除去のために,高温, Currently, due to the separation and removal of organic sulfur compounds, high temperature,
高圧という激しい反応条件下で触媒を用いて水素ガスと反応させ,有機硫黄化合物を有毒な硫化水素にまで変換して分離するという技術が主流になっている。 The catalyst is reacted with hydrogen gas using a violent reaction conditions of high pressure, technology has become the mainstream of separating by converting the organic sulfur compounds to a toxic hydrogen sulfide. 有機硫黄化合物をできる限り,元の化学構造を維持したままで, As possible organic sulfur compound, while maintaining the original chemical structure,
鉱物油中から取り出し,該有機硫黄化合物の有効利用を行うためには,このような水素還元脱硫法は適用できないものである。 Removed from mineral oil, in order to perform an effective utilization of the organic sulfur compounds, such hydrogen reduction desulfurization is inapplicable.

【0005】従来,廃ガスから有機硫黄化合物の回収方法として,特公昭53−26577号があるが,これは,鉱物油中から有機硫黄化合物を回収するものではない。 Conventionally, as a method for recovering organic sulfur compounds from waste gases, there are JP-B-53-26577, which is not intended to recover the organic sulfur compounds from mineral oil.

【0006】 [0006]

【課題を解決するための手段】この発明の目的は,有機硫黄化合物をできる限り,鉱物油中に含まれる元の化学構造を維持した状態で,鉱物油中から取り出し,該有機硫黄化合物を有効利用するものであり,酸化剤を使用して酸化状態の有機硫黄化合物を蒸留等の分離手段によって簡単に且つ経済的に鉱物油から有機硫黄化合物を回収する方法を提供することである。 Means for Solving the Problems The object of the invention is, as much as possible organic sulfur compound, while maintaining the original chemical structure included in mineral oil was removed from the mineral oil, enable organosulfur compound is intended to be used, it is to provide a process for recovering organic sulfur compounds from easily and economically mineral oils by separating means such as distillation of the organic sulfur compounds in the oxidation state using an oxidizing agent.

【0007】この発明は,石油,オイルサンド,オイルシェール及び石炭から得られる有機硫黄化合物を含有する液状油を酸化剤で処理して前記有機硫黄化合物をスルホキシド化合物及び/又はスルホン化合物にし,これを蒸留,溶剤抽出及び/又は吸着の手段で分離して,酸化された前記有機硫黄化合物である前記スルホキシド化合物及び/又はスルホン化合物を前記液状油から分離回収することを特徴とする液状油中から有機硫黄化合物を回収する方法に関する。 [0007] The present invention, oil, oil sands, a liquid oil containing organic sulfur compounds obtained from oil shale and coal is treated with an oxidizing agent wherein the organic sulfur compound to a sulfoxide compound and / or a sulfone compound, it distillation, and separated by means of solvent extraction and / or adsorption, organic said sulfoxide compound is said organic sulfur compounds are oxidized and / or sulfone compound from a liquid oil, characterized in that the separated and recovered from said liquid oil It relates to a process for the recovery of sulfur compounds.

【0008】この有機硫黄化合物の回収方法は,上記のように構成したので,液状油即ち鉱物油を各種酸化剤で予め処理することにより,有機硫黄化合物をその分子骨格をほぼ維持したままの酸化物に変換し,それによって生じる分子の極性,沸点,融点等の物理的,化学的性質の変化を利用して鉱物油から工業上有用な有機硫黄化合物を効率良く,簡単に且つ低コストで分離回収するものである。 [0008] method for recovering organic sulfur compounds, since the structure described above, by pre-treating the liquid oil i.e. mineral oil with various oxidizing agent, the oxidation of the organic sulfur compound remains substantially retains its molecular skeleton converted to an object, the polarity of the molecules thereby producing, boiling, physical melting point such as, efficiently industrially useful organic sulfur compounds from available to mineral oils a change in chemical properties, easily and separated at a low cost it is intended to recover.

【0009】この有機硫黄化合物の回収方法は,先ず, [0009] method for recovering organic sulfur compounds, first,
鉱物油中に含有されている2価の原子価を持つ硫黄原子からなる有機硫黄化合物を,酸化力の異なる種々の酸化剤を用いて反応させることにより,スルホキシド化合物及び/又はスルホン化合物に変化させ,次に,この化学変換によって生じる反応生成物の化学的,物理的性質の変化を利用し,他の成分と分離する。 Organic sulfur compounds comprising a sulfur atom with two valences contained in the mineral oil, by reaction with a variety of oxidizing agents having different oxidizing power, is changed to a sulfoxide compound and / or a sulfone compound , then, using a chemical change in the physical properties of the reaction products resulting from the chemical transformation, to separate the other components. 例えば,沸点が著しく上昇する事実を利用すれば,蒸留操作によって,これらを容易に分離,精製できるし,化合物分子の極性の上昇に基づく各種溶媒に対する溶解性の変化を利用すると,それら酸化された有機硫黄化合物を選択的に抽出, For example, by utilizing the fact that the boiling point is increased remarkably, by distillation, to these can be easily separated, purified, utilizing a change in solubility in various solvents based on polarity rise in compound molecules were those oxidized selectively extracting organic sulfur compounds,
精製することが可能となる。 It is possible to purification.

【0010】更に,上記の化学的性質の変化は,シリカゲルやアルミナ等の吸着剤に対する被吸着力をも著しく向上させるため,吸着剤を使用する吸着,分離,精製が極めて効率良く,容易に行うことができるようになる。 Furthermore, changes in the chemical nature of the above, in order to remarkably improve also the suction force for the adsorbent such as silica gel or alumina, adsorption using an adsorbent, separation, purification may very efficiently, easily performed it becomes possible.
また,上記の分離,精製法を組み合わせて処理することにより,より好ましい結果を得ることができる。 Further, by treating in combination the above separation, the purification method, it is possible to obtain better results.

【0011】更に,この発明による液状油中から有機硫黄化合物を回収する方法は,鉱物油中の有機硫黄化合物自身が有する酸化反応に対する反応性の差異を利用し, Furthermore, a method for recovering organic sulfur compounds from liquid oil according to this invention utilizes the difference in reactivity to oxidation reaction with an organic sulfur compound itself in mineral oil,
酸化剤を適宜選択しながら反応を行い,ある特定の有機硫黄化合物群のみを選択的に取り出すことが可能になることである。 The reaction was carried out while selecting oxidizing agent suitably is that it is possible to extract only a specific organic sulfur compounds selectively. 即ち,2価の硫黄原子を含む有機硫黄化合物をスルホキシド化合物へのみ選択的に酸化することができる酸化剤を使用すると,取り出される有機硫黄化合物は,スルホキシドの形で得られるし,更にスルホン化合物にまで酸化する能力を有する酸化剤を用いれば,スルホンの形で得ることができる。 That is, when using an oxidizing agent to organic sulfur compounds can be viewed selectively oxidized to the sulfoxide compound containing a divalent sulfur atom, an organic sulfur compound removed is to be obtained in the form of a sulfoxide, a more sulfone compound by using an oxidizing agent having an ability to oxidize up, it can be obtained in the form of sulfones. また,有機硫黄化合物分子中の構造変化に基づく立体障害によって反応性が著しく変化する性質を利用すると,酸化剤の反応性の強さを使い分けることにより,これら立体障害を持つ特殊な有機硫黄化合物群を選択的に取り出すことも可能になる。 Further, utilizing the property of changing significantly reactive by steric hindrance based on structural changes of the organic sulfur compounds in the molecule, by selectively reactive strength of the oxidizing agent, particular organic sulfur compounds with these sterically hindered it also becomes possible to take out a selective.

【0012】また,この発明による液状油中から有機硫黄化合物を回収する方法において,有機硫黄化合物を含有する鉱物油としては,原油,オイルシェール,オイルサンド,コールタール,石炭の液化油及び,それらから直接得られる製油製品,即ち,ナフサ,ガソリン,灯油,軽油,重油,ピッチ又はそれらを化学分解して得られる間接的製油製品から選択されるものである。 Further, in the process for recovering organic sulfur compounds from liquid oil according to this invention, the mineral oil containing organic sulfur compounds, oil, oil shale, oil sands, coal tar, liquefied oil of coal and their refinery products obtained directly from, i.e., those selected naphtha, gasoline, kerosene, gas oil, heavy oil, pitch or them from indirect refinery products obtained by chemical decomposition.

【0013】また,この発明による液状油中から有機硫黄化合物を回収する方法において,酸化剤としては,酸素ガス,空気,四酸化窒素ガス,オゾンガス,塩素ガス,臭素,メタ過ヨウ素酸ナトリウム,重クロム酸カリウム,過マンガン酸カリウム,無水クロム酸,次亜塩素酸,過酸化水素,過酢酸,過酸化水素水と酢酸の混合物,過蟻酸,過酸化水素水と蟻酸の混合物,メタクロロ過安息香酸,過酸化水素水とメタクロロ安息香酸の混合物,過クロロ酢酸,過酸化水素水とクロロ酢酸の混合物,過ジクロロ酢酸,過酸化水素水とジクロロ酢酸の混合物,過トリクロロ酢酸,過酸化水素水とトリクロロ酢酸の混合物,過トリフロロ酢酸,過酸化水素水とトリフロロ酢酸の混合物,過メタンスルホン酸,過酸化水素水とメタンスルホン酸の混 Further, in the process for recovering organic sulfur compounds from liquid oil according to this invention, the oxidizing agent, oxygen gas, air, nitrogen tetroxide gas, ozone, chlorine gas, bromine, sodium metaperiodate, heavy potassium chromate, potassium permanganate, chromic acid anhydride, hypochlorous acid, hydrogen peroxide, peracetic acid, a mixture of hydrogen peroxide and acetic acid, peracetic formic, a mixture of hydrogen peroxide and formic acid, meta-chloroperbenzoic acid , a mixture of hydrogen peroxide and metachloroperbenzoic acid, peracetic chloroacetic acid, mixtures of hydrogen peroxide and chloroacetic acid, peracetic dichloroacetic acid, a mixture of hydrogen peroxide and dichloroacetic acid, peracetic trichloroacetic acid, and hydrogen peroxide trichloro acetic acid, peracetic trifluoroacetic acid, mixture of hydrogen peroxide and trifluoroacetic acid, peracetic methanesulfonic acid, mixing of hydrogen peroxide and methane sulphonic acid 物,過硫酸,過酸化水素水と硫酸の混合物から選択されるものを使用することができる。 Things, can be used those selected from persulfate, mixture of hydrogen peroxide and sulfuric acid.

【0014】この発明による液状油中から有機硫黄化合物を回収する方法は,鉱物油を有機過酸系酸化剤又は無機系酸化剤と,0〜100℃の温度範囲で撹拌しながら反応させ,反応後,酸化反応生成物を含む油分をとり, [0014] process for recovering organic sulfur compounds from liquid oil according to the invention, a mineral oil organic peracid based oxidizing agent or an inorganic oxidizing agent, and reacted with stirring at a temperature range of 0 to 100 ° C., the reaction after taking the oil comprising an oxidation reaction product,
これに水を加えて洗浄後,乾燥し,生成した有機硫黄酸化物を鉱物油から回収することができる。 After washing this was added water, dried, and the resulting organic sulfur oxides can be recovered from the mineral oil.

【0015】或いは,この発明による液状油中から有機硫黄化合物を回収する方法は,鉱物油を酸化剤で処理された後,アセトニトリル,プロピオニトリル,ブチロニトリル,ニトロメタン,ニトロエタン,ニトロプロパン,ニトロベンゼン,ジメチルスルホキシド,N,N' [0015] Alternatively, a method for recovering organic sulfur compounds from liquid oil according to this invention, after being processed mineral oil with an oxidizing agent, acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethyl sulfoxide, N, N '
−ジメチルホルムアミド,N,N'−ジメチルアセトアミド,N−メチルピロリジノン,トリメチル燐酸エステル,トリエチル燐酸エステル,ヘキサメチル燐酸アミド,ホスホランのいずれか,又は,これらの溶媒に対して0〜50%の濃度範囲で水を含有させた混合物から選択されるものを抽出溶媒とした抽出操作により,生成した有機硫黄酸化物を鉱物油から回収することができる。 - dimethylformamide, N, N'-dimethylacetamide, N- methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethylphosphoric acid amide, or a phosphorane, or, with 0-50% of the concentration range for these solvents the extraction operation of those selected from a mixture which contains water and an extraction solvent, the resulting organic sulfur oxides can be recovered from the mineral oil.

【0016】又は,この発明による液状油中から有機硫黄化合物を回収する方法は,鉱物油を酸化剤で処理した後,活性白土,シリカゲル,アルミナのいずれか又は, [0016] Alternatively, a method for recovering organic sulfur compounds from liquid oil according to the present invention, after processing the mineral oil with an oxidizing agent, activated clay, silica gel, or alumina, or,
これらの混合物から選択される吸着剤を充填した吸着塔を通過させることにより生成した有機硫黄酸化物をいったん吸着させた後,メタノール,エタノール,プロパノール,ブタノール,アセトン,アセトニトリル,ニトロメタン,又はこれらの混合物から選択される溶剤で脱着,分離して有機硫黄酸化物を鉱物油から回収することができる。 After temporarily adsorbing the organic sulfur oxides produced by passing the adsorption column filled with the adsorbent mixtures thereof, methanol, ethanol, propanol, butanol, acetone, acetonitrile, nitromethane, or mixtures thereof desorbed solvent selected from the organic sulfur oxides can be recovered from the mineral oil to separate.

【0017】更に,この液状油中から有機硫黄化合物を回収する方法は,精密蒸留塔を用いて出来るだけ狭い沸点範囲で蒸留した鉱物油留分を酸化剤と反応させた後, Furthermore, after the process for recovering organic sulfur compounds from liquid oil is a mineral oil fraction was distilled in a narrow boiling range as possible using a precision distillation column is reacted with an oxidizing agent,
酸化反応生成物を含む油分を取り,水で洗浄し,乾燥した後,酸化剤と処理する前の鉱物油と同じ沸点範囲で再び蒸留して得られる蒸留残渣中に,生成した有機硫黄酸化物を濃縮し,分離する。 Take the oil comprising an oxidation reaction product is washed with water, dried, distilled residue obtained by distilled again in the same boiling range as the previous mineral oil to be processed with an oxidizing agent, organic sulfur oxides generated It was concentrated, to separate.

【0018】 [0018]

【発明の実施の形態】以下,この発明による液状油中から有機硫黄化合物を回収する方法の実施例を説明する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of a process for recovering organic sulfur compounds from liquid oil according to the present invention.

【0019】(実施例1) ホモジナイザー撹拌機,還流冷却器,ガス導入管付き2 [0019] (Example 1) homogenizer stirrer, reflux condenser, gas inlet tube with 2
00ml硬質ガラス製丸底フラスコに,軽油(沸点範囲220〜300℃,可燃性硫黄分0.53重量%)10 In 00ml hard glass round-bottomed flask, gas oil (boiling range 220 to 300 ° C., combustible sulfur 0.53 wt%) 10
0mlを0℃に冷却しておき,オゾン(約1.0%)を含有する空気を通しながら1時間撹拌を行う。 The 0ml allowed to cool to 0 ° C., for one hour stirring while passing air containing ozone (about 1.0%). それからオゾンを止めて,空気のみ更に1時間通した後,フラスコ全体の温度を徐々に,20℃まで上げながら,さらに1時間撹拌を続ける。 Then stop the ozone was passed through a further 1 hour only air gradually the temperature of the entire flask, while raising 20 ° C., it is continued for a further 1 hour. 得られた反応液に2規定の亜硫酸ナトリウム水溶液50ml加えて洗浄し,更に水で洗浄した後,軽油層とタール層を分離し,軽油層を精密蒸留装置で蒸留して沸点220〜330℃の留分92mlと蒸留残渣8mlを得る。 The resulting reaction solution was washed by adding 2N aqueous sodium sulfite solution 50 ml, further washed with water, light oil layer and the tar layer separated, boiling point 220 to 330 ° C. was distilled light oil layer by precision distillation apparatus obtaining a fraction 92ml distilled residue 8 ml. 蒸留分中の硫黄分は0.32% The sulfur content in the distillation fraction is 0.32%
で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体であり,蒸留残渣及びタール分中の全硫黄分はそれぞれ,1.7%及び7.8%で,主成分は,それらの酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 In the main component is a benzothiophene and dibenzothiophene derivatives, respectively the total sulfur content of the distillation residue and in tar, with 1.7% and 7.8%, the main component is, their oxidation products, i.e., , sulfoxide, was a mixture of sulfone.

【0020】(実施例2) ホモジナイザー撹拌機,還流冷却器付き200ml硬質ガラス製丸底フラスコに軽油(沸点範囲220〜300 [0020] (Example 2) homogenizer stirrer, gas oil with a reflux condenser 200ml hard glass round-bottom flask (boiling range 220 to 300
℃,可燃性硫黄分0.53重量%)100mlを取り, ° C., takes a combustible sulfur 0.53 wt%) 100 ml,
これに過酸化水素水(30%)10ml,蟻酸10ml This hydrogen peroxide solution (30%) 10ml, 10ml formic acid
を加え,20℃で1時間撹拌した後,反応温度を50℃ Was added and after stirring for 1 hour at 20 ° C., the reaction temperature 50 ° C.
に上げ,さらに,1時間撹拌を続ける。 To increase, further, it continued for 1 hour stirring. 反応後,0℃まで冷却して静置し,タール分と軽油層を分離し,2規定の亜硫酸ナトリウム水溶液で洗浄し,更に水で洗浄した後,軽油層を精密蒸留装置で蒸留して沸点220〜33 After the reaction was allowed to stand and cooled to 0 ° C., the tar and light oil layer was separated, washed with 2N aqueous sodium sulfite, it was washed further with water, distilling the light oil layer by precision distillation apparatus boiling 220-33
0℃の留分86ml及び,蒸留残渣12mlを得る。 0 ℃ fraction 86ml and obtain a distillation residue 12 ml. 蒸留分中の硫黄分は0.04%で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体であり,蒸留残渣及びタール分中の全硫黄分はそれぞれ,2.1%及び8.4%で,主成分は,それらの酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 The sulfur content in the distillation fraction at 0.04%, the main component is a benzothiophene and dibenzothiophene derivatives, the total sulfur content of the distillation residue and in tars are respectively 2.1% and 8.4%, main components, their oxidation products, i.e., sulfoxides, was a mixture of sulfone.

【0021】(実施例3) ホモジナイザー撹拌機,還流冷却器付き200ml硬質ガラス製丸底フラスコに軽油(沸点範囲220〜300 [0021] (Example 3) homogenizer stirrer, gas oil with a reflux condenser 200ml hard glass round-bottom flask (boiling range 220 to 300
℃,可燃性硫黄分0.53重量%)100mlを取り, ° C., takes a combustible sulfur 0.53 wt%) 100 ml,
これに過酸化水素水(30%)10ml,ジクロロ酢酸10mlを加え,40℃で1時間撹拌した後,反応温度を70℃に上げ,更に,1時間撹拌を続ける。 To this aqueous hydrogen peroxide (30%) 10ml, dichloroacetic acid 10ml were added and stirred for 1 hour at 40 ° C., raising the reaction temperature to 70 ° C., further continued for 1 hour. 反応後, After the reaction,
0℃まで冷却し,タール分と軽油層を分離する。 To 0 ℃ cooled, to separate the tar and light oil layer. 2規定の亜硫酸ナトリウム水溶液で洗浄し,更に水で洗浄した後,再び軽油層を分離し,これにニトロメタン10ml Washed with 2N aqueous sodium sulfite, was washed further with water, separating the light oil layer again, this nitromethane 10ml
を加え,室温で1時間激しく撹拌してから静置,軽油層とニトロメタン層を分離する。 Was added to separate stand, light oil layer and nitromethane layer was stirred vigorously for 1 hour at room temperature. 軽油層中の硫黄分は, The sulfur content of diesel fuel layer,
0.03%で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体であり,ニトロメタン溶液及びタール分中の全硫黄分はそれぞれ,0.21%及び6.5% 0.03% main component, a benzothiophene and dibenzothiophene derivatives, respectively the total sulfur content of nitromethane solution and in tars are 0.21% and 6.5%
で,主成分は,それらの酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 In the main component is, their oxidation products, i.e., sulfoxides, was a mixture of sulfone.

【0022】(実施例4) ホモジナイザー撹拌機,還流冷却器付き200ml硬質ガラス製丸底フラスコに重油(可燃性硫黄分1.87重量%)100mlを取り,これに過酸化水素水(30 [0022] (Example 4) homogenizer stirrer, heavy oil with a reflux condenser 200ml hard glass round-bottom flask (combustible sulfur 1.87 wt%) takes a 100 ml, this aqueous hydrogen peroxide (30
%)10ml,蟻酸10mlを加え,30℃で1時間撹拌した後,反応温度を50℃に上げ,更に,1時間撹拌を続ける。 %) 10ml, formic acid 10ml were added and stirred for 1 hour at 30 ° C., raising the reaction temperature to 50 ° C., further continued for 1 hour. 反応後,2層に分離した上層を分液ロートで分離し,2規定の亜硫酸ナトリウム水溶液で洗浄し,更に水で洗浄した後,再び重油層を分離し,これに10% After the reaction, the upper layer was separated into two layers were separated in a separating funnel, washed with 2N aqueous sodium sulfite, was washed further with water, separating the oil layer again, this 10%
の水を含有するN,N'−ジメチルホルムアミド溶液5 N containing water, N'- dimethylformamide 5
0mlを加え,室温で1時間激しく撹拌してから静置し,重油層と10%の水を含有するN,N'−ジメチルホルムアミド層とを分離する。 0ml was added, and allowed to stand was stirred vigorously for 1 hour at room temperature, N containing oil layer, 10% water, separating the N'- dimethylformamide layer. 重油層中の硫黄分は, The sulfur content of heavy fuel oil layer,
0.21%で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体であり,N,N'−ジメチルホルムアミド溶液及びタール分中の全硫黄分はそれぞれ,1. 0.21% main component, a benzothiophene and dibenzothiophene derivatives, N, N'-dimethylformamide and the total sulfur content of the tar component in each, 1.
60%で,主成分は,それらの酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 60%, the main component is, their oxidation products, i.e., sulfoxides, was a mixture of sulfone.

【0023】(実施例5) ホモジナイザー撹拌機,還流冷却器,ガス導入管付き2 [0023] (Example 5) homogenizer stirrer, reflux condenser, gas inlet tube with 2
00ml硬質ガラス製丸底フラスコに重油(可燃性硫黄分1.87重量%)100ml,蒸留水20mlを取り,0℃で,塩素ガスをバブリングさせながら1時間撹拌し反応させる。 00ml hard glass round bottom flask oil (combustible sulfur 1.87 wt%) 100 ml, take the distilled water 20 ml, at 0 ° C., it is stirred for 1 hour while bubbling chlorine gas reaction. 反応後,重油層を分液ロートで分離し,2規定の亜硫酸ナトリウム水溶液で洗浄し,更に水で洗浄した後,重油層を分離し,これに10%の水を含有するトリメチル燐酸エステル溶液5mlを加え,室温で2時間激しく撹拌してから静置,鉱油の層と10%の水を含有するトリメチル燐酸エステル層とに分離する。 After the reaction, separating the oil layer in a separatory funnel, washed with 2N aqueous sodium sulfite, was washed further with water, heavy oil layer was separated, trimethyl phosphate solution 5ml containing the same 10% water was added, separated from the stirred vigorously for 2 hours at room temperature standing, in a trimethyl phosphate layer containing a layer of 10% water mineral oil.
重油層中の硫黄分は,それぞれ0.35%で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体であり,トリメチル燐酸エステル溶液中の全硫黄分はそれぞれ,1.53%で,主成分は,それらの酸化生成物, Sulfur heavy oil layer is 0.35%, respectively, the main component is a benzothiophene and dibenzothiophene derivatives, respectively the total sulfur content of the trimethyl phosphate solution, 1.53% main component, their oxidation products,
即ち,スルホキシド,スルホンの混合物であった。 Namely, sulfoxide, was a mixture of sulfone.

【0024】(実施例6) ホモジナイザー撹拌機,還流冷却器付き200ml硬質ガラス製丸底フラスコにコールタール(可燃性硫黄分0.67重量%)50gと減粘剤としてのベンゼン10 [0024] (Example 6) homogenizer stirrer, benzene 10 as with a reflux condenser 200ml hard glass round bottom flask coal tar (combustible sulfur 0.67 wt%) 50 g and a viscosity-reducing agent
mlを取り,これに過酸化水素水(30%)5ml,蟻酸10mlを加え,40℃で3時間撹拌しながら反応を行う。 Take ml, which aqueous hydrogen peroxide (30%) 5 ml, formic acid 10ml was added, the reaction is carried out with stirring for 3 hours at 40 ° C.. 反応後,コールタール層を分離し,2規定の亜硫酸ナトリウム水溶液で洗浄した後,コールタール層を分離し,これに10%の水を含有するN−メチルピロジノン溶液100mlを加え,室温で1時間激しく撹拌してから静置し,コールタール層とN−メチルピロジノン層とに分離する。 After the reaction, separating the coal tar layer was washed with 2N aqueous sodium sulfite, separating the tar layer, this containing 10% water N- Mechirupirojinon solution 100ml were added, at room temperature for 1 and allowed to stand after stirring time vigorously, separated into a coal tar layer and the N- Mechirupirojinon layer. N−メチルピロジノン溶液中の硫黄分は0.25%で,主成分は,ベンゾチオフェン及びジベンゾチオフェン誘導体の酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 Sulfur N- Mechirupirojinon solution at 0.25%, the main component, the oxidation products of benzothiophene and dibenzothiophene derivatives, i.e., sulfoxides, was a mixture of sulfone.

【0025】(実施例7) ホモジナイザー撹拌機,還流冷却器付き200ml硬質ガラス製丸底フラスコに軽油(沸点範囲220〜300 [0025] (Example 7) homogenizer stirrer, gas oil with a reflux condenser 200ml hard glass round-bottom flask (boiling range 220 to 300
℃,可燃性硫黄分0.53重量%)100mlを取り, ° C., takes a combustible sulfur 0.53 wt%) 100 ml,
アセトニトリル10ml,水10ml,過ヨウ素酸ナトリウム5gを加え,20℃で1時間激しく撹拌した後, Acetonitrile 10 ml, water 10 ml, sodium periodate 5g was added and after stirring vigorously for 1 hour at 20 ° C.,
反応温度を50℃に上げ,さらに,1時間撹拌を行う。 The reaction temperature was raised to 50 ° C., further, it performs stirring for 1 hour.
反応後,軽油層を分離し,水で洗浄した後,アルミナ1 After the reaction, the gas oil layer was separated, washed with water, alumina 1
0g,シリカゲル10gを混合した吸着剤を充填したカラムを通過させる。 0 g, is passed through a column packed with an adsorbent mixed with silica gel 10g. 得られた軽油中の硫黄分は,0.0 The resulting sulfur content in diesel fuel, 0.0
5%であった。 It was 5%. 一方,吸着カラムに,アセトン50ml On the other hand, the adsorption column, acetone 50ml
を通して得られた溶液中の硫黄分は,0.44%であった。 Sulfur content of the resulting solution through was 0.44%. なお,軽油中の主成分はベンゾチオフェン及びジベンゾチオフェン誘導体であり,アセトン溶液中の硫黄分の主成分は,それらの酸化生成物,即ち,スルホキシド,スルホンの混合物であった。 Incidentally, the main component in the gas oil are benzothiophenes and dibenzothiophene derivatives, sulfur main component in acetone solution, their oxidation products, i.e., sulfoxides, was a mixture of sulfone.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl. 7識別記号 FI C10G 21/00 C10G 21/00 25/00 25/00 27/00 27/00 (58)調査した分野(Int.Cl. 7 ,DB名) C07B 63/02 C07C 303/42 C07C 315/06 C07C 319/26 C10G 7/00 C10G 21/00 C10G 25/00 C10G 27/00 ────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. 7 identification mark FI C10G 21/00 C10G 21/00 25/00 25/00 27/00 27/00 (58) investigated the field (Int.Cl. 7 , DB name) C07B 63/02 C07C 303/42 C07C 315/06 C07C 319/26 C10G 7/00 C10G 21/00 C10G 25/00 C10G 27/00

Claims (1)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】 石油,オイルサンド,オイルシェール及び石炭から得られる有機硫黄化合物を含有する液状油を酸化剤で処理して前記有機硫黄化合物をスルホキシド化 1. A petroleum, oil sands, sulfoxidation a liquid oil containing organic sulfur compounds obtained from oil shale and coal is treated with an oxidizing agent wherein the organic sulfur compound
    合物及び/又はスルホン化合物にし ,これを蒸留,溶剤抽出及び/又は吸着の手段で分離して,酸化された前記有機硫黄化合物である前記スルホキシド化合物及び/又 The compounds and / or sulfone compound, distillation which separates by means other solvent extraction and / or adsorption, the sulfoxide compound is said organic sulfur compounds are oxidized and / or
    はスルホン化合物を前記液状油から分離回収することを特徴とする液状油中から有機硫黄化合物を回収する方法。 Process for recovering organic sulfur compounds from liquid oil, which comprises separating and recovering a sulfone compound from the liquid oil.
JP11235092A 1992-04-06 1992-04-06 Process for recovering organic sulfur compounds from liquid oil Expired - Fee Related JP3227521B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013035200A1 (en) * 2011-09-09 2013-03-14 Aida Tetsuo Method for producing ultra-low sulfur fuel oil

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6160193A (en) * 1997-11-20 2000-12-12 Gore; Walter Method of desulfurization of hydrocarbons
US6171478B1 (en) 1998-07-15 2001-01-09 Uop Llc Process for the desulfurization of a hydrocarbonaceous oil
US6277271B1 (en) 1998-07-15 2001-08-21 Uop Llc Process for the desulfurization of a hydrocarbonaceoous oil
US5958224A (en) * 1998-08-14 1999-09-28 Exxon Research And Engineering Co Process for deep desulfurization using combined hydrotreating-oxidation
EP1261681A1 (en) * 1999-12-13 2002-12-04 DS2 Tech, Inc. Process for desulfurization of petroleum distillates
FR2802939B1 (en) * 1999-12-28 2005-01-21 Elf Antar France Process for desulfurization of derivatives of thiophene in fuels
US6402940B1 (en) * 2000-09-01 2002-06-11 Unipure Corporation Process for removing low amounts of organic sulfur from hydrocarbon fuels
US6872231B2 (en) 2001-02-08 2005-03-29 Bp Corporation North America Inc. Transportation fuels
US6673230B2 (en) 2001-02-08 2004-01-06 Bp Corporation North America Inc. Process for oxygenation of components for refinery blending of transportation fuels
US20020148754A1 (en) * 2001-02-08 2002-10-17 Gong William H. Integrated preparation of blending components for refinery transportation fuels
US6881325B2 (en) 2001-02-08 2005-04-19 Bp Corporation North America Inc. Preparation of components for transportation fuels
JP2005023090A (en) * 2001-03-30 2005-01-27 Ooteikusu Kk Method and apparatus for separation of sulfur compound contained in petroleum
JP2002322482A (en) * 2001-04-24 2002-11-08 Idemitsu Kosan Co Ltd Method for desulfurization of liquid oil containing organic sulfur compound
JP2002322483A (en) * 2001-04-24 2002-11-08 Idemitsu Kosan Co Ltd Method for desulfurization of liquid oil containing organic sulfur compound
US6544409B2 (en) 2001-05-16 2003-04-08 Petroleo Brasileiro S.A. - Petrobras Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams
JP2002363574A (en) * 2001-06-06 2002-12-18 Idemitsu Kosan Co Ltd Method for desulfurizing hydrocarbon oil and method for producing hydrogen for fuel cell
FR2829771A1 (en) * 2001-09-17 2003-03-21 Solvay Process for the desulfuration and/or denitrogenation of a hydrocarbon mixture, useful in the purification of fuels, involves oxidation and solvent extraction of the oxidized compounds
FR2839307B1 (en) * 2002-05-03 2004-07-09 Solvay A process for desulfurizing a hydrocarbon mixture
JP2004055483A (en) * 2002-07-24 2004-02-19 Idemitsu Kosan Co Ltd Method for manufacturing hydrogen for fuel cell
US7074375B2 (en) * 2002-12-03 2006-07-11 Engelhard Corporation Method of desulfurizing a hydrocarbon gas by selective partial oxidation and adsorption
US7175755B2 (en) 2003-05-06 2007-02-13 Petroleo Brasileiro S.A.-Petrobras Process for the extractive oxidation of contaminants from raw hydrocarbon streams
US7128829B1 (en) 2003-05-29 2006-10-31 Uop Llc Removal of impurities from liquid hydrocarbon streams
WO2005012458A1 (en) * 2003-08-01 2005-02-10 Bp Corporation North America Inc. Preparation of components for refinery blending of transportation fuels
US8016999B2 (en) 2004-05-31 2011-09-13 Agency For Science, Technology And Research Process for removing sulfur from fuels
CN1331987C (en) * 2004-07-09 2007-08-15 石油大学(北京) Oxidation and desulfurization method of petroleum oil product
JP4520808B2 (en) * 2004-10-01 2010-08-11 電源開発株式会社 Method for producing an organic sulfur oxides
US7276152B2 (en) 2004-11-23 2007-10-02 Cpc Corporation, Taiwan Oxidative desulfurization and denitrogenation of petroleum oils
US8715489B2 (en) * 2005-09-08 2014-05-06 Saudi Arabian Oil Company Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
DK1957118T3 (en) * 2005-10-28 2013-09-08 Indian Oil Corp Ltd A process for bio-oxidative desulfurization of liquid hydrocarbon fuels and products thereof
US20070140949A1 (en) * 2005-12-16 2007-06-21 Palmer Thomas R Extraction of peroxide treated petroleum streams
WO2007103440A3 (en) 2006-03-03 2007-12-13 Farhan M Al-Shahrani Catalytic process for deep oxidative desulfurization of liquid transportation fuels
WO2007106943A1 (en) 2006-03-22 2007-09-27 Ultraclean Fuel Pty Ltd Process for removing sulphur from liquid hydrocarbons
EP2436664A4 (en) * 2009-05-12 2012-10-31 Wako Pure Chem Ind Ltd Method for purifying organic solvent
US20120018350A1 (en) * 2010-07-20 2012-01-26 Hsin Tung Lin Mixing-assisted oxidative desulfurization of diesel fuel using quaternary ammonium salt and portable unit thereof
US9290712B2 (en) 2010-09-03 2016-03-22 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada Production of high-cetane diesel product
JP6215826B2 (en) * 2011-07-31 2017-10-18 サウジ アラビアン オイル カンパニー Integrated process for producing asphalt and desulfurized oil
EP2760975B1 (en) * 2011-09-27 2017-05-03 Saudi Arabian Oil Company Selective liquid-liquid extraction of oxidative desulfurization reaction products
CN102703111B (en) * 2012-07-03 2014-06-18 山东大学 Ultrasonic-assisted ozone oxidation desulfurization method
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
CN103708995B (en) * 2013-12-26 2016-04-20 郑州协和商贸有限公司 Fusel oil is one kind of coal methanol desulfurization method of deodorizing

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2749284A (en) * 1950-11-15 1956-06-05 British Petroleum Co Treatment of sulphur-containing mineral oils with kerosene peroxides
FR1472280A (en) * 1965-02-23 1967-03-10 Exxon Research Engineering Co A method for desulfurizing a hydrocarbon mixture
US3551328A (en) * 1968-11-26 1970-12-29 Texaco Inc Desulfurization of a heavy hydrocarbon fraction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013035200A1 (en) * 2011-09-09 2013-03-14 Aida Tetsuo Method for producing ultra-low sulfur fuel oil

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