WO2006028196A1 - Method for desulfurization of heavy oil - Google Patents

Method for desulfurization of heavy oil Download PDF

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Publication number
WO2006028196A1
WO2006028196A1 PCT/JP2005/016572 JP2005016572W WO2006028196A1 WO 2006028196 A1 WO2006028196 A1 WO 2006028196A1 JP 2005016572 W JP2005016572 W JP 2005016572W WO 2006028196 A1 WO2006028196 A1 WO 2006028196A1
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WO
WIPO (PCT)
Prior art keywords
heavy oil
desulfurization
oil
catalyst
mass
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PCT/JP2005/016572
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French (fr)
Japanese (ja)
Inventor
Nobuo Aoki
Toshio Waku
Wataru Sahara
Yuichi Tanaka
Kazuaki Hayasaka
Hirofumi Konno
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Nippon Oil Corporation
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Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to EP05778519A priority Critical patent/EP1798275A4/en
Priority to CA002578864A priority patent/CA2578864A1/en
Publication of WO2006028196A1 publication Critical patent/WO2006028196A1/en
Priority to US11/681,991 priority patent/US20070151902A1/en

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Classifications

    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G55/04—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 thermal 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils

Definitions

  • the present invention relates to a method for desulfurizing heavy oil continuously for a long period of time. More specifically, in the oil refining process, heavy oil such as atmospheric residual oil is desulfurized continuously for a long time without catalyst replacement.
  • Heavy oil such as atmospheric residue and vacuum residue produced in the oil refining process usually contains several percent by mass of sulfur and is difficult to produce as it is. Under the present circumstances, a desulfurization treatment is carried out using a catalyst to reduce the sulfur concentration. Since the product obtained from the desulfurization process of heavy oil is further subjected to secondary treatment to become various useful products such as gasoline, kerosene and light oil, the desulfurization process of heavy oil Plays an important role in today's oil refining (see Non-Patent Document 1, for example). If this desulfurization process is stopped, other processes will be affected, and the economics of the refinery will be greatly affected.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-180 0 109
  • Patent Document 2 Japanese Patent Laid-Open No. 1 1 1 1 5 1 4 4 1
  • Non-patent document 1 "Petroleum refining process", Japan Petroleum Institute, 1998, p. 88
  • An object of the present invention is to improve the economics of petroleum refining by dramatically increasing the catalyst life in desulfurization of heavy oil.
  • the present inventors have conducted an operation for decomposing heavy oil at a low decomposition rate in a heavy oil desulfurization step in a state where the concentration of heavy oil is diluted with a dilution medium. It has been found that the life of the desulfurization catalyst can be extended by including the operation, and the present invention has been completed.
  • the present invention is characterized by including an operation of decomposing heavy oil at a decomposition rate of 10% or less in a state where the concentration of heavy oil is diluted to 90% by mass or less with a dilution medium.
  • the present invention relates to a method for desulfurization of heavy oil.
  • the concentration of the heavy oil is 90 masses by the dilution medium. /.
  • the present invention relates to a desulfurization method for heavy oil, characterized in that the heavy oil is decomposed at a decomposition rate of 10% or less in the diluted state, the dilution medium is removed, and then desulfurized in a desulfurization step.
  • the heavy oil used in the present invention includes carbon and hydrogen having an initial boiling point of 300 ° C. or higher and a fraction having a boiling point of 360 ° C. or higher of 90% by mass or more as main constituent elements. Yes Heavy oil.
  • the type of heavy oil used in the present invention is not particularly limited, but examples of typical oils include atmospheric residual oil and reduced-pressure residual oil produced in an oil refining process.
  • the dilution medium used in the present invention is inactive against the heavy oil to be processed.
  • those which are compatible with the heavy oil to be treated at the decomposition temperature are preferable, and a dilution medium having a boiling point of 120 ° C. or lower is particularly preferable.
  • Examples of a preferable dilution medium include aromatic hydrocarbons such as benzene and toluene. With these dilution media, heavy oil can be diluted uniformly.
  • the concentration of heavy oil is 90% by mass or less, preferably 85% by mass or less, and particularly preferably 80% by mass or less by using these dilution media. If the concentration of heavy oil exceeds 90% by mass, a sufficient effect for extending the life of the catalyst cannot be obtained.
  • the lower limit is not particularly limited, but is 20 mass from the viewpoint of process efficiency. / 0 or more is preferable, and 30% by mass or more is more preferable.
  • the mixing temperature is preferably 60 ° C or higher.
  • the heavy oil is decomposed in such a state that the concentration of the heavy oil is diluted to 90% by mass or less with a dilution medium. It is essential that the decomposition process be performed at a low decomposition rate of 10% or less.
  • the cracking rate here means a fraction that is lighter than the raw material heavy oil produced by the cracking process (the fraction having a boiling point lower than the initial boiling point of the raw material heavy oil and does not include the dilution medium). This is the ratio (by mass) of the oil produced.
  • the decomposition rate is controlled to 10% or less, preferably 8% or less. When it is higher than 10%, the effect of extending the life of the desulfurization catalyst is insufficient.
  • the lower limit is not particularly limited, but is preferably 1% or more, more preferably 2% or more from the viewpoint of stable operation.
  • the heavy oil decomposition treatment in the present invention is usually carried out by thermal decomposition.
  • the temperature range used in the pyrolysis is preferably 400 to 60 ° C, more preferably 420 to 5400 ° C.
  • the range of LHSV is preferably 6 to 20 h 1 , more preferably 8 to 15 h 1 .
  • There is no particular limitation on the pressure and it can be carried out at normal to slightly pressurized pressure, but it is usually carried out at normal pressure.
  • the diluted medium is removed from the resulting product oil, and then the desulfurization process is performed in the desulfurization step.
  • the method for removing the dilution medium is not particularly limited, but the dilution medium is usually removed by atmospheric distillation.
  • the catalyst conditions for the desulfurization reaction there are no particular restrictions on the catalyst conditions for the desulfurization reaction, and any known catalyst conditions used for conventional heavy oil desulfurization reactions can be used.
  • the catalyst for example, a catalyst in which molybdenum or tungsten is supported on alumina.
  • Typical reaction conditions include a reaction temperature of 380 to 480 ° C, a reaction pressure of 5 to 20 MPa, and an LHSV of 0.1 to 2.0 h 1 .
  • the desulfurized product oil is further subjected to secondary treatment as before, and can be used as a base material for products such as gasoline, kerosene, light oil and heavy oil.
  • the desulfurization rate of the desulfurization catalyst is reduced, and the life of the catalyst can be extended.
  • vacuum residue (initial boiling point 580 ° C, sulfur content 4.3 mass%) is diluted with benzene to reduce the concentration of vacuum residue to 78 mass%.
  • LHSV 1 O h 1 was supplied.
  • the treated product oil contained 7.7 mass% of decomposition products with a boiling point of less than 580 ° C (decomposition rate 7.7%).
  • This product oil is supplied together with hydrogen to a reaction tower packed with a commercially available heavy oil desulfurization catalyst, and the sulfur content of the product oil after the reaction is reduced under LH S V0.2 h to reaction pressure 15 MPa. It was operated for 30 days while controlling the reaction temperature to be 4% by mass.
  • the reaction temperature gradually increases from 452.0 ° C at the start at a roughly constant rate, and opens at the end of the reaction. 1. 6 ° C higher than the beginning. During this period, the average deterioration rate of the catalyst was 0.053 ° CZ days.
  • Example 2 The same operation as in Example 1 was performed except that the dilution low-decomposition treatment in Example 1 was omitted.
  • the temperature rise for 30 days was 4.8 ° C, and the average catalyst degradation rate was 0.160 ° CZ days.
  • the treated product oil contained 9.7% by mass of decomposition products.
  • this treated oil was desulfurized in the same manner as in Example 1, the reaction temperature increased by 3.5 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.1 1 7 ° C / day.
  • the treated product oil contained 14.7% by mass of decomposition products.
  • the reaction temperature increased by 4.6 ° C in 30 days.
  • the average deterioration rate of the catalyst was 0.1 53 ° CZ days.
  • Example 2 The same operation as in Example 1 was performed except that toluene was used instead of benzene in Example 1.
  • the treated product oil contained 8.7% by weight of decomposition products.
  • this treated product oil was desulfurized as in Example 1, the reaction temperature increased by 1.9 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.063 ° 0 days.

Abstract

A method for the desulfurization of a heavy oil, which comprises diluting a heavy oil with a dilution medium to 90 mass % or less, and an operation of subjecting the resultant diluted heavy oil to a decomposition treatment with a decomposition rate of 10 % or less. The above method can be used for prolonging the life of a catalyst in a process for the desulfurization of a heavy oil.

Description

重質油の脱硫方法  Heavy oil desulfurization method
[技術分野] [Technical field]
本発明は長期間連続的に重質油を脱硫する方法に関する。 更に詳しくは、 石油 精製工程において、 触媒交換なしに長期間連続して常圧残油等の重質油を脱硫す 明  The present invention relates to a method for desulfurizing heavy oil continuously for a long period of time. More specifically, in the oil refining process, heavy oil such as atmospheric residual oil is desulfurized continuously for a long time without catalyst replacement.
る方法に関する。 田 Related to the method. Rice field
[背景技術] [Background]
石油精製工程で生成する常圧残油や減圧残油等の重質油には通常数質量％の硫 黄分が含有されており、 そのままでは製品化が困難なため、 通常、 高圧の水素存 在下において触媒を用いて硫黄濃度を低減させる脱硫処理が行われている。 この 重質油の脱硫工程から得られる生成物は、 そのかなりの部分が更に二次処理に付 されて、 ガソリン ·灯油 ·軽油等の各種の有用な製品となるため、 重質油の脱硫 工程は今日の石油精製において重要な役割を担っている （例えば、 非特許文献 1 参照） 。 この脱硫工程の運転が停止されると、 他の工程にも影響を及ぼし、 製油 所の経済性に大きな影響が出る。 このため、 触媒寿命、 即ち、 一度充填した触媒 を用いて運転できる期間をいかにして高めるかが石油精製業界の大きな課題とな つている。 従って、 石油精製の経済性を向上させるために、 重質油の脱硫装置を 長期間安定的に運転することが必要になっている。  Heavy oil such as atmospheric residue and vacuum residue produced in the oil refining process usually contains several percent by mass of sulfur and is difficult to produce as it is. Under the present circumstances, a desulfurization treatment is carried out using a catalyst to reduce the sulfur concentration. Since the product obtained from the desulfurization process of heavy oil is further subjected to secondary treatment to become various useful products such as gasoline, kerosene and light oil, the desulfurization process of heavy oil Plays an important role in today's oil refining (see Non-Patent Document 1, for example). If this desulfurization process is stopped, other processes will be affected, and the economics of the refinery will be greatly affected. For this reason, how to increase the life of the catalyst, that is, the period in which the catalyst can be operated using a once packed catalyst, has become a major issue in the oil refining industry. Therefore, in order to improve the economics of oil refining, it is necessary to operate heavy oil desulfurization equipment stably for a long period of time.
しかしながら、 触媒上のコーキングを主因とする劣化要因のために触媒寿命が 不十分となり、 触媒交換のために比較的短期間で運転を停止せざるを得ないのが 実情である。 石油業界では、 重質油の脱硫工程の長期運転を実現すべく、 これま で脱硫触媒の長寿命化のための研究に精力的に取り組んで来ており、 触媒自体の 改良、 即ち、 触媒担体や担持金属種の最適化による長寿命化の研究開発が盛んに 行われてきた （例えば、 特許文献 1および 2参照） 。 しかし、 いまだ満足できる 結果は得られておらず、 このため重質油用脱硫触媒の長寿命化は不可能とする見 方が業界では支配的であった。 However, the catalyst life is insufficient due to deterioration factors mainly due to coking on the catalyst, and the fact is that the operation must be stopped in a relatively short period of time for catalyst replacement. In the petroleum industry, in order to realize the long-term operation of the heavy oil desulfurization process, we have been energetically working on research to extend the life of desulfurization catalysts. In addition, research and development for extending the life by optimizing supported metal species has been actively conducted (for example, see Patent Documents 1 and 2). However, satisfactory results have not yet been obtained, and it is considered impossible to extend the life of heavy oil desulfurization catalysts. Was dominant in the industry.
( 1 ) 特許文献 1 ：特開平 1 0— 1 8 0 1 0 9号公報 (1) Patent Document 1: Japanese Patent Laid-Open No. 10-180 0 109
( 2 ) 特許文献 2 :特開平 1 1一 1 5 1 4 4 1号公報  (2) Patent Document 2: Japanese Patent Laid-Open No. 1 1 1 1 5 1 4 4 1
( 3 ) 非特許文献 1 ： 「石油精製プロセス」 ， (社)石油学会， 1998年， 88頁  (3) Non-patent document 1: "Petroleum refining process", Japan Petroleum Institute, 1998, p. 88
[発明の開示] [Disclosure of the Invention]
本発明の目的は、 重質油の脱硫における触媒寿命を飛躍的に高めることによつ て、 石油精製の経済性を向上させることにある。  An object of the present invention is to improve the economics of petroleum refining by dramatically increasing the catalyst life in desulfurization of heavy oil.
本発明者らは前記課題につレ、て銳意検討した結果、重質油の脱硫工程において、 重質油の濃度を希釈媒体により希釈した状態で、 重質油を低分解率で分解する操 作を含むことにより脱硫触媒の長寿命化が達成されることを見出し、 本発明を完 成するに至ったものである。  As a result of a thorough examination of the above problems, the present inventors have conducted an operation for decomposing heavy oil at a low decomposition rate in a heavy oil desulfurization step in a state where the concentration of heavy oil is diluted with a dilution medium. It has been found that the life of the desulfurization catalyst can be extended by including the operation, and the present invention has been completed.
すなわち、 本発明は、 重質油の濃度を希釈媒体により 9 0質量％以下に希釈し た状態で、 重質油を分解率 1 0 %以下で分解処理する操作を含むことを特徴とす る重質油の脱硫方法に関する。  That is, the present invention is characterized by including an operation of decomposing heavy oil at a decomposition rate of 10% or less in a state where the concentration of heavy oil is diluted to 90% by mass or less with a dilution medium. The present invention relates to a method for desulfurization of heavy oil.
また本発明は、 重質油の濃度を希釈媒体により 9 0質量。/。以下に希釈した状態 で、 重質油を分解率 1 0 %以下で分解処理した後、 希釈媒体を除去し、 その後、 脱硫工程で脱硫処理することを特徴とする重質油の脱硫方法に関する。  In the present invention, the concentration of the heavy oil is 90 masses by the dilution medium. /. The present invention relates to a desulfurization method for heavy oil, characterized in that the heavy oil is decomposed at a decomposition rate of 10% or less in the diluted state, the dilution medium is removed, and then desulfurized in a desulfurization step.
以下、 本発明について詳述する。 Hereinafter, the present invention will be described in detail.
本発明において用いられる重質油とは、 初留点が 3 0 0 °C以上であって、 沸点 3 6 0 °C以上の留分を 9 0質量％以上含む炭素および水素を主要構成元素とする 重質油を指す。  The heavy oil used in the present invention includes carbon and hydrogen having an initial boiling point of 300 ° C. or higher and a fraction having a boiling point of 360 ° C. or higher of 90% by mass or more as main constituent elements. Yes Heavy oil.
本発明において用いられる重質油としては、 その種類に特に制限はないが、 典 型例として、 石油精製プロセスで生成する常圧残油や減圧残油等を挙げることが できる。  The type of heavy oil used in the present invention is not particularly limited, but examples of typical oils include atmospheric residual oil and reduced-pressure residual oil produced in an oil refining process.
本発明において用いられる希釈媒体としては、 処理される重質油に対して不活 性であること以外に特に制限はない。 また、 分解温度において、 処理される重質 油と相溶性のあるものが好ましく、 特に沸点が 1 2 0 °C以下の希釈媒体が好まし い。 The dilution medium used in the present invention is inactive against the heavy oil to be processed. There is no particular limitation other than being sex. In addition, those which are compatible with the heavy oil to be treated at the decomposition temperature are preferable, and a dilution medium having a boiling point of 120 ° C. or lower is particularly preferable.
好ましい希釈媒体の例としては、 ベンゼン、 トルエン等の芳香族炭化水素を挙 げることができる。 これら希釈媒体により、 重質油を均一に希釈することができ る。  Examples of a preferable dilution medium include aromatic hydrocarbons such as benzene and toluene. With these dilution media, heavy oil can be diluted uniformly.
本発明においては、 これら希釈媒体により、 重質油の濃度を 9 0質量％以下、 好ましくは 8 5質量％以下、 特に好ましくは 8 0質量％以下にする。 重質油の濃 度が 9 0質量％を超えると、 触媒の長寿命化に十分な効果が得られない。 下限に ついては特に制限はないが、 プロセスの効率の観点から 2 0質量。 /0以上が好まし く、 3 0質量％以上がより好ましい。 In the present invention, the concentration of heavy oil is 90% by mass or less, preferably 85% by mass or less, and particularly preferably 80% by mass or less by using these dilution media. If the concentration of heavy oil exceeds 90% by mass, a sufficient effect for extending the life of the catalyst cannot be obtained. The lower limit is not particularly limited, but is 20 mass from the viewpoint of process efficiency. / 0 or more is preferable, and 30% by mass or more is more preferable.
希釈の方法については、特に制限はないが、通常、混合槽を設けて混合するか、 ラインミキシングを用いて行う。' その際、 重質油を十分低粘度化した状態で混合 させるために、 混合温度は 6 0 °C以上とするのが好ましい。  There are no particular restrictions on the method of dilution, but it is usually done by mixing in a mixing tank or using line mixing. 'At that time, in order to mix the heavy oil in a sufficiently low viscosity state, the mixing temperature is preferably 60 ° C or higher.
次に、 このように希釈媒体により重質油の濃度を 9 0質量％以下に希釈した状 態で、 重質油の分解処理を行う。 分解処理は分解率 1 0 %以下という低分解率で 行うことが必須である。 ここでいう分解率とは、 分解処理により生成する原料重 質油よりも軽質な留分 （原料重質油の初留点よりも低沸点の留分をいい、 希釈媒 体は含まない。 ） の生成油中の割合 （質量基準） をいう。  Next, the heavy oil is decomposed in such a state that the concentration of the heavy oil is diluted to 90% by mass or less with a dilution medium. It is essential that the decomposition process be performed at a low decomposition rate of 10% or less. The cracking rate here means a fraction that is lighter than the raw material heavy oil produced by the cracking process (the fraction having a boiling point lower than the initial boiling point of the raw material heavy oil and does not include the dilution medium). This is the ratio (by mass) of the oil produced.
本発明においては分解率を 1 0 %以下、好ましくは 8 %以下に制御する。 1 0 % よりも高い場合には脱硫触媒の長寿命化効果が不十分である。 下限については特 に制限はないが、 安定運転の観点から 1 %以上が好ましく、 2 %以上がより好ま しい。  In the present invention, the decomposition rate is controlled to 10% or less, preferably 8% or less. When it is higher than 10%, the effect of extending the life of the desulfurization catalyst is insufficient. The lower limit is not particularly limited, but is preferably 1% or more, more preferably 2% or more from the viewpoint of stable operation.
本発明における重質油の分解処理は、 通常、 熱分解によって行う。 熱分解で使 用する温度範囲として 4 0 0〜6 0 0 °Cが好ましく、 より好ましくは 4 2 0〜 5 4 0 °Cである。また、その際の L H S Vの範囲としては 6〜2 0 h 1が好ましく、 より好ましくは 8〜1 5 h 1である。 圧力については特に限定はなく、 常圧〜若 干加圧で行うことができるが、 通常は常圧で行う。 The heavy oil decomposition treatment in the present invention is usually carried out by thermal decomposition. The temperature range used in the pyrolysis is preferably 400 to 60 ° C, more preferably 420 to 5400 ° C. In this case, the range of LHSV is preferably 6 to 20 h 1 , more preferably 8 to 15 h 1 . There is no particular limitation on the pressure, and it can be carried out at normal to slightly pressurized pressure, but it is usually carried out at normal pressure.
前記の如く、 重質油を希釈して低分解率で処理した後、 得られる生成油から希 釈媒体を除去し、 その後、 脱硫工程で脱硫処理が行われる。 希釈媒体の除去方法については特に制限はないが、 通常、 常圧蒸留を用いて希 釈媒体の除去を行う。 As described above, after the heavy oil is diluted and processed at a low decomposition rate, the diluted medium is removed from the resulting product oil, and then the desulfurization process is performed in the desulfurization step. The method for removing the dilution medium is not particularly limited, but the dilution medium is usually removed by atmospheric distillation.
脱硫反応の触媒おょぴ条件については特に制限はなく、 従来の重質油の脱硫反 応に採用されている公知の触媒おょぴ条件が使用できる。 触媒については、 例え ば、 アルミナにモリブデンやタングステンを担持したものが挙げられる。 また典 型的な反応条件としては、 反応温度は 380〜480°C、 反応圧力は 5〜20M P a、 LHSVは 0. 1〜2. 0 h 1の範囲を挙げることができる。 There are no particular restrictions on the catalyst conditions for the desulfurization reaction, and any known catalyst conditions used for conventional heavy oil desulfurization reactions can be used. As for the catalyst, for example, a catalyst in which molybdenum or tungsten is supported on alumina. Typical reaction conditions include a reaction temperature of 380 to 480 ° C, a reaction pressure of 5 to 20 MPa, and an LHSV of 0.1 to 2.0 h 1 .
脱硫処理された生成油は、 従来同様、 更に二次処理に付されて、 ガソリン '灯 油 -軽油 ·重油等の製品の基材等として用いることができる。  The desulfurized product oil is further subjected to secondary treatment as before, and can be used as a base material for products such as gasoline, kerosene, light oil and heavy oil.
[産業上の利用可能性] [Industrial applicability]
以上のように、 重質油を希釈媒体で希釈した状態で、 低分解率で分解処理した 後、 脱硫処理することにより、 脱硫触媒の劣化速度が低減され、 触媒の長寿命化 が可能となる。  As described above, after degrading heavy oil with a dilution medium at a low decomposition rate and then desulfurizing, the desulfurization rate of the desulfurization catalyst is reduced, and the life of the catalyst can be extended. .
[発明を実施するための最良の形態] [Best Mode for Carrying Out the Invention]
以下に実施例及ぴ比較例を挙げ、 本発明を具体的に説明するが、 本発明はこれ らに限定されるものではない。  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
(実施例 1 ) (Example 1)
入り口温度が 480°Cに制御された処理塔に、 減圧残油 （初留点 580°C、 硫 黄含量 4.3質量％)をベンゼンで希釈して減圧残油の濃度を 78質量％に下げ、 LHSV 1 O h 1で供給した。 ベンゼンを留去すると、 処理生成油中には沸点 5 80°C未満の分解生成物が 7. 7質量％含まれていた （分解率 7. 7%) 。 この 生成油を、 水素と共に、 市販の重質油脱硫触媒を充填した反応塔に供給し、 LH S V0. 2 h~ 反応圧力 1 5 MP aの下で、 反応後の生成油の硫黄含量が 0. 4質量％になるように反応温度を制御しながら 30日間運転した。 反応温度は開 始時の 452. 0°Cからゆるやかにほぼ一定の速度で上昇し、 反応終了時には開 始時より 1. 6°C高くなつた。 この間の触媒の平均劣化速度は 0. 053°CZ日 であった。 In a treatment tower whose inlet temperature is controlled at 480 ° C, vacuum residue (initial boiling point 580 ° C, sulfur content 4.3 mass%) is diluted with benzene to reduce the concentration of vacuum residue to 78 mass%. LHSV 1 O h 1 was supplied. When benzene was distilled off, the treated product oil contained 7.7 mass% of decomposition products with a boiling point of less than 580 ° C (decomposition rate 7.7%). This product oil is supplied together with hydrogen to a reaction tower packed with a commercially available heavy oil desulfurization catalyst, and the sulfur content of the product oil after the reaction is reduced under LH S V0.2 h to reaction pressure 15 MPa. It was operated for 30 days while controlling the reaction temperature to be 4% by mass. The reaction temperature gradually increases from 452.0 ° C at the start at a roughly constant rate, and opens at the end of the reaction. 1. 6 ° C higher than the beginning. During this period, the average deterioration rate of the catalyst was 0.053 ° CZ days.
(比較例 1 ) (Comparative Example 1)
実施例 1の希釈低分解処理を省いたこと以外は、 実施例 1と同様の操作を行つ た。 30日間の温度上昇は 4. 8 °C、 触媒の平均劣化速度は 0. 160 °CZ日で あった。  The same operation as in Example 1 was performed except that the dilution low-decomposition treatment in Example 1 was omitted. The temperature rise for 30 days was 4.8 ° C, and the average catalyst degradation rate was 0.160 ° CZ days.
(比較例 2 ) (Comparative Example 2)
実施例 1のベンゼンを用いない、 即ち希釈なしで低分解処理すると、 処理生成 油に 9. 7質量％の分解生成物が含まれていた。 この処理生成油を実施例 1と同 様に脱硫すると、 30日間で反応温度が 3. 5°C上昇した。 この間の触媒の平均 劣化速度は 0. 1 1 7°C/日であった  When the benzene of Example 1 was not used, that is, when the low decomposition treatment was performed without dilution, the treated product oil contained 9.7% by mass of decomposition products. When this treated oil was desulfurized in the same manner as in Example 1, the reaction temperature increased by 3.5 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.1 1 7 ° C / day.
(比較例 3 ) (Comparative Example 3)
実施例 1の予備処理の LHS Vを 5 h 1とすると、 処理生成油に 14. 7質 量％の分解生成物が含まれていた。 この処理生成油を実施例 1と同様に脱硫する と、 30日間で反応温度が 4. 6°C上昇した。この間の触媒の平均劣化速度は 0. 1 53°CZ日であった Assuming that the LHS V of the pretreatment in Example 1 was 5 h 1 , the treated product oil contained 14.7% by mass of decomposition products. When this treated oil was desulfurized in the same manner as in Example 1, the reaction temperature increased by 4.6 ° C in 30 days. During this time, the average deterioration rate of the catalyst was 0.1 53 ° CZ days.
(実施例 2 ) (Example 2)
実施例 1においてベンゼンに代えてトルエンを使用したこと以外は実施例 1と 同様の操作を行った。処理生成油には 8.7質量％の分解生成物が含まれていた。 この処理生成油を実施例 1と同様に脱硫すると、 30日間で反応温度が 1. 9°C 上昇した。 この間の触媒の平均劣化速度は 0. 063°0 日であった  The same operation as in Example 1 was performed except that toluene was used instead of benzene in Example 1. The treated product oil contained 8.7% by weight of decomposition products. When this treated product oil was desulfurized as in Example 1, the reaction temperature increased by 1.9 ° C in 30 days. During this period, the average deterioration rate of the catalyst was 0.063 ° 0 days.

Claims

請 求 の 範 囲 The scope of the claims
1 . 重質油の濃度を希釈媒体により 9 0質量％以下に希釈した状態で、 重質油を分解率 1 0 %以下で分解処理する操作を含むことを特徴とする重質油の 脱硫方法。 1. A method for desulfurization of heavy oil, comprising an operation of decomposing heavy oil at a decomposition rate of 10% or less in a state where the concentration of heavy oil is diluted to 90% by mass or less with a diluent medium .
2 . 重質油の濃度を希釈媒体により 9 0質量％以下に希釈した状態で、 重質油を分解率 1 0 %以下で分解処理した後、 希釈媒体を除去し、 その後、 脱硫 工程で脱硫処理することを特徴とする重質油の脱硫方法。 2. In the state where the concentration of heavy oil is diluted to 90% by mass or less with a dilution medium, the heavy oil is decomposed at a decomposition rate of 10% or less, then the dilution medium is removed, and then desulfurized in the desulfurization process. A desulfurization method for heavy oil, characterized by comprising:
3 . 希釈媒体がベンゼンおよび/またはトルエンであることを特徴とす る第 1項又は第 2項に記載の重質油の脱硫方法。 3. The heavy oil desulfurization method according to item 1 or 2, wherein the diluent medium is benzene and / or toluene.
PCT/JP2005/016572 2004-09-06 2005-09-02 Method for desulfurization of heavy oil WO2006028196A1 (en)

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