JP2000256676A - Distillation method - Google Patents
Distillation methodInfo
- Publication number
- JP2000256676A JP2000256676A JP11064422A JP6442299A JP2000256676A JP 2000256676 A JP2000256676 A JP 2000256676A JP 11064422 A JP11064422 A JP 11064422A JP 6442299 A JP6442299 A JP 6442299A JP 2000256676 A JP2000256676 A JP 2000256676A
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- JP
- Japan
- Prior art keywords
- oil
- gas oil
- cracked gas
- weight
- cracked
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、重質油特に常圧残
油を水素化分解して分解軽油を製造する方法に関する。[0001] The present invention relates to a method for producing cracked gas oil by hydrocracking heavy oil, in particular, atmospheric residual oil.
【０００２】[0002]
【従来の技術】都市部での大気環境汚染が深刻化する
中、日本では１９９７年よりディーゼル軽油中の硫黄含
有量規制値は２０００ｐｐｍから５００ｐｐｍに引き下
げられた。しかし、欧米での軽油中の硫黄含有量規制は
２００５年より５０ｐｐｍまで低減され、日本でも現在
よりも厳しい規制が設けられる方向である。石油業界で
はこれらの規制に対して、できるだけ大がかりな設備改
造を行なうことなく、低硫黄軽油基材を製造する技術を
確立することを緊急かつ重大な問題として取り組んでい
る。2. Description of the Related Art As the air pollution in urban areas has become more serious, the regulation value of sulfur content in diesel gas oil has been reduced from 2000 ppm to 500 ppm in Japan since 1997. However, regulations on sulfur content in diesel oil in Europe and the United States have been reduced to 50 ppm since 2005, and regulations in Japan will be more stringent than at present. In response to these regulations, the petroleum industry has been tackling the urgent and serious problem of establishing a technology for producing low-sulfur gas oil base materials without making major equipment modifications.
【０００３】常圧残油を水素化分解、脱硫して得られる
分解油中の中でも高沸点留分中には難脱硫性のため脱硫
されずに残留した硫黄化合物が局在していると言われて
いる。分解軽油留分の硫黄分も主に高沸点留分中に含ま
れ、分解油を蒸留し分解軽油を得る際にその沸点を低く
することで分解軽油中の硫黄分を低下させることができ
る。ところが、沸点を低くすれば分解軽油中の硫黄濃度
は低くなるが、分解軽油の沸点が低くなるほどセタン指
数は減少する傾向にある。従って、適切な沸点範囲で蒸
留を行わなければ、硫黄濃度およびセタン指数の両方の
性能を満足するような分解軽油を得ることは難しかっ
た。せいぜい、同じ分解油に対する過去の経験や試行錯
誤によりこれを調整しているのが現状であった。[0003] Among the cracked oils obtained by hydrocracking and desulfurizing normal pressure residual oils, it is said that high boiling fractions contain sulfur compounds remaining without being desulfurized due to their difficulty in desulfurization. Have been done. The sulfur content of the cracked gas oil fraction is also mainly contained in the high boiling fraction, and the sulfur content of the cracked gas oil can be reduced by lowering the boiling point when the cracked oil is distilled to obtain the cracked gas oil. However, when the boiling point is lowered, the sulfur concentration in the cracked gas oil decreases, but as the boiling point of the cracked gas oil decreases, the cetane index tends to decrease. Therefore, it was difficult to obtain a cracked gas oil that satisfies both the sulfur concentration and the cetane index performance without distillation in an appropriate boiling point range. At best, this was adjusted based on past experience and trial and error with the same cracked oil.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の問題
点を踏まえ常圧残油から得られる水素化分解油から簡便
にバランスの取れた高品質の分解軽油を製造する方法を
提供することを目的としている。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a method for easily producing a well-balanced high-quality cracked gas oil from a hydrocracked oil obtained from an atmospheric residue. It is an object.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、常圧残油を少な
くとも水素化分解を含む水素化処理をして得られた分解
油から蒸留して分解軽油を製造する際、所望の分解軽油
の目標硫黄濃度および目標セタン指数に対しそれぞれ原
料油常圧残油、生成分解軽油の５重量％蒸留点、９５重
量％蒸留点等が特別の相関式を満足するときに上記課題
を解決できることを見いだし、本発明を完成したもので
ある。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that cracking obtained by subjecting a normal pressure residual oil to a hydrotreating process including at least hydrocracking. When producing cracked gas oil by distilling from oil, 5% by weight distillation point, 95% by weight distillation point, etc. of the desired crude oil residual pressure and the produced cracked gas oil with respect to the target sulfur concentration and target cetane index of the desired cracked gas oil, respectively It has been found that the above problem can be solved when satisfies a special correlation formula, and the present invention has been completed.
【０００６】すなわち、本発明の要旨は以下のとおりで
ある。 〔１〕 常圧残油を少なくとも水素化分解を含む水素化
処理をして得られた分解油から下式（１）および（２）
を満足するように蒸留して分解軽油を製造する方法。 Ｂ ≧ ２７８．５Ｙ／（０．１９４ＸＸ＋０．０７２ＹＹ−０．０１７Ａ＋ ４３．６）−６５．７ ・・・・（１） Ｃ ≦ ２６．５Ｘ／（−１２．０ＸＸ−８．０ＹＹ＋１．ｌＡ＋１２６４． ０）＋３３２．９ ・・・・（２） ここで Ａ（℃） ： 原料常圧残油の５重量％蒸留点 ＸＸ（重量％） ： 原料常圧残油中の３４３℃以上の
留分の分解率 ＹＹ（重量％） ： 原料常圧残油の脱硫率 Ｂ（℃） ： 分解軽油の５重量％蒸留点 Ｃ（℃） ： 分解軽油の９５重量％蒸留点 Ｘ（重量ｐｐｍ）： 分解軽油の目標硫黄濃度 Ｙ（無次元） ： 分解軽油の目標セタン指数 を表す。That is, the gist of the present invention is as follows. [1] The following formulas (1) and (2) are obtained from a cracked oil obtained by subjecting a normal pressure residual oil to a hydrotreating process including at least hydrocracking.
To produce cracked gas oil by distillation to satisfy the above. B ≧ 278.5Y / (0.194XX + 0.072YY−0.017A + 43.6) −65.7 (1) C ≦ 26.5X / (-12.0XX−8.0YY + 1.lA + 1264.0) ) +332.9 (2) where A (° C.): 5% by weight distillation point of raw material residual pressure XX (% by weight): Decomposition of 343 ° C. or higher fraction in raw material residual pressure residual oil YY (% by weight): Desulfurization rate of raw pressure residual oil B (° C.): Distillation point of 5% by weight of cracked gas oil C (° C.): Distillation point of 95% by weight of cracked gas oil X (weight ppm): of cracked gas oil Target sulfur concentration Y (dimensionless): Indicates the target cetane index of cracked gas oil.
【０００７】ただし、 ＸＸ≧３５ ２４０≧Ｂ≧１６０ ３７０≧Ｃ≧２８０ Ｃ−Ｂ≧６０ を満足する範囲である。 〔２〕 水素化分解を含む水素化処理が水素化脱金属、
水素化分解および水素化脱硫の各水素化処理を含むもの
である〔１〕記載の分解軽油を製造する方法。However, XX ≧ 35 240 ≧ B ≧ 160 370 ≧ C ≧ 280 CB ≧ 60. [2] Hydrotreating including hydrocracking involves hydrodemetallation,
[1] The method for producing cracked gas oil according to [1], which includes hydrotreating of hydrocracking and hydrodesulfurization.
【０００８】[0008]
【発明の実施の形態】以下に、本発明の実施の形態を説
明する。本発明は、重質油特に常圧残油を少なくとも水
素化分解を含む水素化処理をして得られた分解油を特定
の条件下で蒸留して分解軽油を製造する方法に関するも
のである。そこで、まず水素化処理方法に付き説明す
る。水素化処理は水素化分解を含むものであればよい
が、さらに水素化脱硫処理を含むものまたは水素化脱金
属および水素化脱硫の各水素化処理を含むものが好適で
ある。特に、水素化脱金属、水素化分解および水素化脱
硫の順でまたは水素化脱金属、水素化脱硫および水素化
分解の順で実施する方法が好ましい。さらに、触媒の種
類によってはこれらの処理は同時になされる場合もあ
る。例えば、脱硫と脱金属や分解と脱硫は同じ触媒の存
在下で反応が進行する場合が多い。Embodiments of the present invention will be described below. The present invention relates to a method for producing a cracked gas oil by distilling a cracked oil obtained by subjecting a heavy oil, particularly an atmospheric residue to a hydrotreating process including at least hydrocracking under specific conditions. Therefore, the hydrotreating method will be described first. The hydrogenation treatment may be any treatment that includes hydrocracking, and it is preferable that the treatment further includes hydrodesulfurization treatment or that includes each hydrotreatment of hydrodemetallation and hydrodesulfurization. In particular, a method in which hydrodemetallation, hydrocracking, and hydrodesulfurization are performed in this order, or hydrodemetallation, hydrodesulfurization, and hydrocracking are performed in this order is preferable. Furthermore, depending on the type of catalyst, these treatments may be performed simultaneously. For example, desulfurization and demetallation or decomposition and desulfurization often proceed in the presence of the same catalyst.
【０００９】原料として使用される重質油は常圧残油、
減圧残油、減圧軽油、重質軽油および原油、あるいはこ
れらの混合物などがある。その中でも常圧残油が特に好
適な原料油として挙げられる。以下に代表的な例として
重質油として常圧残油を用い、水素化脱金属、水素化脱
硫、水素化分解、蒸留の順で分解軽油を製造する本発明
の製造方法を各工程毎に説明する。なお、以下の説明は
他の重質油を原料油とし、上記したような他の水素化処
理による分解油を同様に蒸留して分解軽油を製造する場
合にも適用できる。The heavy oil used as a raw material is a normal pressure residual oil,
Vacuum resid, vacuum gas oil, heavy gas oil and crude oil, or a mixture thereof. Among them, atmospheric residual oil is mentioned as a particularly suitable raw material oil. A typical example is the use of atmospheric residual oil as a heavy oil, and the production method of the present invention for producing cracked gas oil in the order of hydrodemetallation, hydrodesulfurization, hydrocracking, and distillation is performed for each step. explain. The following description can also be applied to a case in which another heavy oil is used as a feedstock oil and the cracked oil obtained by the above-described other hydrogenation treatment is similarly distilled to produce a cracked light oil.
【００１０】（１）水素化脱金属工程 本発明において対象とする原料油は原油の常圧蒸留から
得られる常圧残油であることが好ましい。この常圧残油
と水素ガスを混合した混合物は、初めに反応工程の第１
段である水素化脱金属工程に送られる。水素化脱金属工
程は、１塔及至複数塔の反応塔からなる。そして、固定
床の場合、各反応塔は通常は複数の触媒床に分割され各
触媒床には反応物を冷却するための流体（通常は水素ガ
ス）が導入される。この水素化脱金属処理に使用される
触媒は、水素化脱金属処理に通常使用されているもので
よい。即ち、アルミナ、シリカ、シリカーアルミナ又は
セピオライト等の多孔性無機酸化物を担体として、周期
律表第５、６、８、９及び１０族の金属あるいは金属化
合物（以下、単に金属ということがある。）の内、１種
または複数を酸化物の状態で担持させたものを使用でき
る。そして、この水素化脱金属処理の条件としては、反
応温度３００〜４５０℃、水素分圧３０〜２００ｋｇ／
ｃｍ2 Ｇ、水素／油比３００〜２，０００Ｎｍ3 ／ｋ
ｌ、ＬＨＳＶ（液時空間速度）０．１〜１０ｈｒ-1、好
ましくは反応温度３６０〜４２０℃、水素分圧１００〜
１８０ｋｇ／ｃｍ2 Ｇ、水素／油比５００〜１，０００
Ｎｍ3 ／ｋｌ、ＬＨＳＶ０．３〜５．０ｈｒ-1である。(1) Hydrodemetallization Step The feedstock used in the present invention is preferably an atmospheric residual oil obtained from atmospheric distillation of crude oil. The mixture obtained by mixing the atmospheric residual oil and hydrogen gas is first used in the first reaction step.
It is sent to a stage, a hydrodemetallization step. The hydrodemetallization step comprises one or more reaction towers. In the case of a fixed bed, each reaction tower is usually divided into a plurality of catalyst beds, and a fluid (usually hydrogen gas) for cooling a reactant is introduced into each catalyst bed. The catalyst used for this hydrodemetallization treatment may be the one usually used for hydrodemetallization treatment. That is, a porous inorganic oxide such as alumina, silica, silica-alumina or sepiolite is used as a carrier, and a metal or a metal compound of Group 5, 6, 8, 9 and 10 of the periodic table (hereinafter sometimes simply referred to as metal). ), One or more of which are supported in an oxide state can be used. The conditions of the hydrodemetallization treatment are as follows: a reaction temperature of 300 to 450 ° C., a hydrogen partial pressure of 30 to 200 kg /
cm 2 G, hydrogen / oil ratio 300-2,000 Nm 3 / k
1, LHSV (liquid hourly space velocity) 0.1 to 10 hr -1 , preferably 360 to 420 ° C., hydrogen partial pressure 100 to 100
180 kg / cm 2 G, hydrogen / oil ratio 500-1,000
Nm 3 / kl, LHSV 0.3 to 5.0 hr −1 .
【００１１】（２）水素化分解工程 水素化脱金属工程で処理された処理油は次いで水素化分
解工程へ送られる。水素化分解工程は、１塔及至複数塔
の反応塔からなる。そして、固定床の場合、通常は各反
応塔は複数の触媒床に分割され各触媒床には反応物を冷
却するための流体（通常は水素ガス）が導入される。水
素化分解工程に使用される触媒としては、特開昭６０−
４９１３１、特開昭６１−２４４３３、特開平３−２１
４８４等に開示されている技術によって造られるものを
使用することができる。すなわち、鉄含有ゼオライト２
０〜８０重量％と無機酸化物８０〜２０重量％からなる
担体に、周期律表第６、８、９及び１０族の金属を１種
又は複数を酸化物の状態で担持させたものである。ま
た、特開平２−２８９４１９に開示されている技術によ
って造られた鉄含有ゼオライト１０〜９０重量％と無機
酸化物９０〜１０重量％からなる担体に、周期律表第
６、８、９及び１０族の金属の内、１種又は複数を酸化
物の状態で担持させたものを使用することもできる。こ
の後者の水蒸気処理した鉄含有スチーミングゼオライト
を鉄塩水溶液で処理して得られる鉄含有アルミノシリケ
ートを使用すると、軽油留分の改質効果が高く効果的で
ある。水素化分解処理の条件としては、反応温度３００
〜４５０℃、水素分圧３０〜２００ｋｇ／ｃｍ2 Ｇ、水
素／油比３００〜２，０００Ｎｍ3 ／ｋｌ、ＬＨＳＶ
（液時空間速度）０．１〜２．０ｈｒ-1、好ましくは反
応温度３８０〜４２０℃、水素分圧１００〜１８０ｋｇ
／ｃｍ2 Ｇ、水素／油比５００〜１，０００Ｎｍ3 ／ｋ
ｌ、ＬＨＳＶ０．２〜１．０ｈｒ-1である。(2) Hydrocracking Step The treated oil treated in the hydrodemetallizing step is then sent to the hydrocracking step. The hydrocracking step comprises one or more reaction towers. And in the case of a fixed bed, each reaction tower is usually divided into a plurality of catalyst beds, and a fluid (usually hydrogen gas) for cooling a reactant is introduced into each catalyst bed. The catalyst used in the hydrocracking step is disclosed in
49131, JP-A-61-24433, JP-A-3-21
484 and the like can be used. That is, iron-containing zeolite 2
A carrier comprising 0 to 80% by weight and 80 to 20% by weight of an inorganic oxide is obtained by supporting one or more metals belonging to Groups 6, 8, 9 and 10 of the periodic table in an oxide state. . Further, a carrier comprising 10 to 90% by weight of an iron-containing zeolite and 90 to 10% by weight of an inorganic oxide prepared by the technique disclosed in Japanese Patent Application Laid-Open No. 2-289419 is provided on the periodic table Nos. 6, 8, 9 and 10. It is also possible to use one in which one or more of the metals of the group are supported in the form of an oxide. When the iron-containing aluminosilicate obtained by treating the latter steam-treated iron-containing steaming zeolite with an aqueous iron salt solution is used, the effect of reforming the gas oil fraction is high and effective. The conditions for the hydrocracking treatment are as follows:
４５０450 ° C., hydrogen partial pressure 30〜200 kg / cm 2 G, hydrogen / oil ratio 300〜2,000 Nm 3 / kl, LHSV
(Liquid hourly space velocity) 0.1-2.0 hr -1 , preferably 380-420 ° C., hydrogen partial pressure 100-180 kg
/ Cm 2 G, hydrogen / oil ratio 500-1,000 Nm 3 / k
1, LHSV 0.2 to 1.0 hr -1 .
【００１２】（３）水素化脱硫工程 水素化脱金属処理され、次いで水素化分解処理された水
素化分解処理工程からの生成油は、更に水素化脱硫工程
に送られる。水素化脱硫工程は、１塔及至複数塔の反応
塔からなる。そして、固定床の場合、通常は各反応塔は
複数の触媒床に分割され各触媒床には反応物を冷却する
ための流体が導入される。水素化脱硫工程に使用される
触媒は、重質油水素化脱硫処理に通常使用されているも
のでよい。即ち、アルミナ、シリカ、ゼオライトあるい
はこれらの混合物の担体等に周期律表第５、６、８，９
及び１０族の金属の内、１種又は複数を酸化物の状態で
担持させたものを使用することができる。そして、この
水素化脱硫処理の条件としては、反応温度３００〜４５
０℃、水素分圧３０〜２００ｋｇ／ｃｍ2 Ｇ、水素／油
比３００〜２，０００Ｎｍ3 ／ｋｌ、ＬＨＳＶ（液時空
間速度）０．１〜２．０ｈ-1、好ましくは反応温度３６
０〜４２０℃、水素分圧１００〜１８０ｋｇ／ｃｍ
2 Ｇ、水素／油比５００〜１，０００Ｎｍ3 ／ｋｌ、Ｌ
ＨＳＶ０．１〜０．５ｈｒ-1である。(3) Hydrodesulfurization Step The product oil from the hydrocracking step which has been subjected to hydrodemetallization treatment and then hydrocracked is further sent to the hydrodesulfurization step. The hydrodesulfurization step comprises one or more reaction towers. In the case of a fixed bed, each reaction tower is usually divided into a plurality of catalyst beds, and a fluid for cooling the reactants is introduced into each catalyst bed. The catalyst used in the hydrodesulfurization step may be the one usually used in heavy oil hydrodesulfurization treatment. That is, a carrier of alumina, silica, zeolite, or a mixture thereof, or the like may be used in the Periodic Table No. 5, 6, 8, 9
Among them, a metal in which one or more of the metals belonging to Group 10 are supported in an oxide state can be used. The conditions for this hydrodesulfurization treatment are as follows:
0 ° C., hydrogen partial pressure 30 to 200 kg / cm 2 G, hydrogen / oil ratio 300 to 2,000 Nm 3 / kl, LHSV (liquid hourly space velocity) 0.1 to 2.0 h −1 , preferably reaction temperature 36
0-420 ° C, partial pressure of hydrogen 100-180kg / cm
2 G, hydrogen / oil ratio 500-1,000 Nm 3 / kl, L
HSV is 0.1 to 0.5 hr -1 .
【００１３】（４）分離工程 このように、水素化脱金属、水素化分解および水素化脱
硫を終えて反応工程を出た生成油は、複数の分離槽で処
理することによって気体部分と液体部分に分離される。
その内、気体部分は、硫化水素、アンモニアなどを除去
してから水素純度アップなどの処理を受け、新しい供給
水素ガスに混合して反応工程へ再循環することができ
る。 一方、分離工程で分離された液体部分は分解油で
あり、次の蒸留工程へと導入される。(4) Separation Step As described above, the product oil that has gone through the reaction step after the completion of the hydrodemetallation, hydrocracking, and hydrodesulfurization is treated in a plurality of separation tanks to form a gas part and a liquid part. Is separated into
Among them, the gas portion can be subjected to a treatment such as an increase in hydrogen purity after removing hydrogen sulfide, ammonia and the like, mixed with a new supply hydrogen gas and recycled to the reaction process. On the other hand, the liquid part separated in the separation step is cracked oil and is introduced into the next distillation step.
【００１４】（５）蒸留工程 分離工程で分離された分解油は蒸留工程に導入され各留
分に分離される。この蒸留は常圧蒸留で行っても減圧蒸
留で行っても良い。本発明者等は、分解軽油の性状、特
に分解軽油の硫黄濃度またはセタン指数を所望の性状と
する方法として得られた分解軽油の蒸留性状、その中で
も分解軽油の硫黄濃度の場合は９５％蒸留点を、セタン
指数の場合は５％蒸留点を管理指標として蒸留を行うこ
とが有効であることを見い出した。さらに、原料重質油
の５％蒸留点、原料重質油の分解率、原料重質油の脱硫
率を組み合わせて分解油の蒸留の管理指標とすることが
効果的であることを見い出した。具体的には、本発明で
は、蒸留して得られる分解軽油の５重量％蒸留点をＢ
℃、９５重量％蒸留点をＣ℃としたとき、下式（１）お
よび（２）を満足するように蒸留して分解軽油を製造す
ることが必要である。 Ｂ ≧ ２７８．５Ｙ／（０．１９４ＸＸ＋０．０７２ＹＹ−０．０１７Ａ＋ ４３．６）−６５．７ ・・・・（１） Ｃ ≦ ２６．５Ｘ／（−１２．０ＸＸ−８．０ＹＹ＋１．ｌＡ＋１２６４． ０）＋３３２．９ ・・・・（２） ここで Ａ（℃） ： 原料常圧残油の５重量％蒸留点 ＸＸ（重量％） ： 原料常圧残油中の３４３℃以上の
留分の分解率 ＹＹ（重量％） ： 原料常圧残油の脱硫率 Ｂ（℃） ： 分解軽油の５重量％蒸留点 Ｃ（℃） ： 分解軽油の９５重量％蒸留点 Ｘ（重量ｐｐｍ）： 分解軽油の目標硫黄濃度 Ｙ（無次元） ： 分解軽油の目標セタン指数 を表す。(5) Distillation Step The cracked oil separated in the separation step is introduced into the distillation step and separated into each fraction. This distillation may be performed by atmospheric distillation or vacuum distillation. The present inventors have studied the properties of cracked gas oil, in particular, the distillation properties of cracked gas oil obtained as a method for making the sulfur concentration or cetane index of cracked gas oil the desired property. In the case of the cetane index, it has been found that it is effective to carry out distillation using a 5% distillation point as a control index. Furthermore, it has been found that it is effective to combine the 5% distillation point of the raw heavy oil, the cracking rate of the raw heavy oil, and the desulfurization rate of the raw heavy oil as a management index for the distillation of the cracked oil. Specifically, in the present invention, the distillation point of 5% by weight of the cracked gas oil obtained by distillation is defined as B
When the distillation point at 95 ° C. and 95% by weight is C ° C., it is necessary to produce cracked gas oil by distillation so as to satisfy the following formulas (1) and (2). B ≧ 278.5Y / (0.194XX + 0.072YY−0.017A + 43.6) −65.7 (1) C ≦ 26.5X / (-12.0XX−8.0YY + 1.lA + 1264.0) ) +332.9 (2) where A (° C.): 5% by weight distillation point of raw material residual pressure XX (% by weight): Decomposition of 343 ° C. or higher fraction in raw material residual pressure residual oil YY (% by weight): Desulfurization rate of raw pressure residual oil B (° C.): Distillation point of 5% by weight of cracked gas oil C (° C.): Distillation point of 95% by weight of cracked gas oil X (weight ppm): of cracked gas oil Target sulfur concentration Y (dimensionless): Indicates the target cetane index of cracked gas oil.
【００１５】ただし、 ＸＸ≧３５ ２４０≧Ｂ≧１６０ ３７０≧Ｃ≧２８０ Ｃ−Ｂ≧６０ を満足する範囲である。However, XX ≧ 35 240 ≧ B ≧ 160 370 ≧ C ≧ 280 CB ≧ 60.
【００１６】なお、本発明における常圧残油、分解軽油
の蒸留における各留出温度（５重量％蒸留点等）はＡＳ
ＴＭ Ｄ２８８７による蒸留試験で規定されるものであ
り。セタン指数はＡＳＴＭ Ｄ４３３７で規定されるも
のである。また、原料重質油中の３４３℃以上の留分の
分解率ＸＸ（重量％）は ＸＸ ＝ １００×｛１００−（分解軽油中の３４３℃
以上の留分の得率ｗｔ％）｝／（原料油中の３４３℃以
上の留分の得率ｗｔ％） により定義されるものである。In the present invention, each distillation temperature (distillation point of 5% by weight, etc.) in the distillation of atmospheric residual oil and cracked gas oil is AS
Specified in a distillation test according to TM D2887. The cetane index is specified by ASTM D4337. The cracking rate XX (% by weight) of the fraction of 343 ° C. or higher in the raw material heavy oil is XX = 100 × ｛100− (343 ° C. in the cracked gas oil).
The yield of the above fraction wt%) / (the yield of the fraction of 343 ° C. or higher in the feed oil, wt%).
【００１７】分解軽油の５重量％蒸留点が式（１）を満
足しない場合には、分解軽油のセタン指数が目標値Ｙを
下回る。また、９５重量％蒸留点が式（２）を満足しな
い場合には分解軽油の硫黄濃度が目標値Ｘを上回る。そ
の為、ＢおよびＣを上記（１）式および（２）式を満足
するように蒸留塔の温度等の条件を調整して分解軽油を
蒸留すればよい。なお、Ｂを上記（１）式の右辺より極
端に大きくする場合、およびＣを上記（２）式の右辺よ
り極端に小さくする場合は本発明の各要件を満足してい
ても分解軽油の得率が低下するので好ましくない。な
お、通常の蒸留性状やセタン指数を持つ分解軽油を製造
するという観点からはＸＸ≧３５、２４０≧Ｂ≧１６
０、３７０≧Ｃ≧２８０およびＣ−Ｂ≧６０の各条件を
満足する必要がある。When the 5% by weight distillation point of the cracked gas oil does not satisfy the formula (1), the cetane index of the cracked gas oil falls below the target value Y. When the 95% by weight distillation point does not satisfy the formula (2), the sulfur concentration of the cracked gas oil exceeds the target value X. Therefore, the cracked gas oil may be distilled by adjusting the conditions such as the temperature of the distillation column so that B and C satisfy the above equations (1) and (2). When B is made extremely larger than the right side of the above formula (1), and when C is made extremely smaller than the right side of the above formula (2), it is possible to obtain cracked gas oil even if each requirement of the present invention is satisfied. It is not preferable because the rate decreases. XX ≧ 35, 240 ≧ B ≧ 16 from the viewpoint of producing cracked gas oil having ordinary distillation properties and cetane index.
0, 370 ≧ C ≧ 280 and CB ≧ 60 must be satisfied.
【００１８】[0018]
【実施例】次に、本発明を実施例により具体的に説明す
るが、これらの実施例になんら制限されるものではな
い。原料油として、アラビアンヘビー原油を常圧蒸留し
て得た二種の常圧残油Ａ、Ｂを用いた。 表１にその性
状を示す。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. As the raw material oil, two types of normal pressure residual oils A and B obtained by normal pressure distillation of Arabian heavy crude oil were used. Table 1 shows the properties.
【００１９】〔実施例１〕１００ｃｃの固定床流通反応
器の上流側から順に水素化脱金属触媒２１容量％、水素
化分解触媒２６容量％、水素化腕硫触媒４３容量％をこ
の順序で充填し、アラビアンヘビー常圧残油Ａを原料と
して水素化処理を行い分解油を得た。各水素化処理触媒
としては、表２に示す触媒を使用した。水素化処理全体
としての処理条件は水素分圧１４０ｋｇ／ｃｍ2 Ｇ、水
素／油比９００Ｎｍ3 ／ｋｌ、ＬＨＳＶ０．１５ｈｒ-1
とした。反応温度は水素化脱金属触媒層４０５℃、水素
化分解触媒層４００℃および水素化脱硫触媒層３９５℃
とした。この時、脱硫率は９３重量％、３４３℃以上の
留分の分解率は４１重量％であった。Example 1 From the upstream side of a 100 cc fixed bed flow reactor, 21% by volume of a hydrodemetallation catalyst, 26% by volume of a hydrocracking catalyst, and 43% by volume of a hydrosulfurization catalyst were charged in this order. Then, a hydrogenated treatment was carried out using Arabian Heavy Atmospheric Residue A as a raw material to obtain a cracked oil. As each hydrotreating catalyst, a catalyst shown in Table 2 was used. The processing conditions for the entire hydrotreating were a hydrogen partial pressure of 140 kg / cm 2 G, a hydrogen / oil ratio of 900 Nm 3 / kl, and an LHSV of 0.15 hr -1.
And The reaction temperature was 405 ° C. for the hydrodemetallation catalyst layer, 400 ° C. for the hydrocracking catalyst layer, and 395 ° C. for the hydrodesulfurization catalyst layer.
And At this time, the desulfurization rate was 93% by weight, and the decomposition rate of the fraction at 343 ° C. or higher was 41% by weight.
【００２０】上記で得られた分解油を蒸留して分解軽油
を得るため、分解軽油の目標硫黄濃度を４００重量ｐｐ
ｍ、目標セタン指数を５０とした。この場合、前記
（１）式および（２）式より製造する分解軽油の５重量
％蒸留点≧１９７℃、９５重量％蒸留点≦３６２℃とす
ることが必要であると算出される。そこで留出分解軽油
の５重量％蒸留点２００℃、９５重量％蒸留点３６０℃
となるように上記で得た分解油の蒸留をした。結果等を
表３、表４に示す。In order to obtain the cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil is set to 400 wt.
m and the target cetane index were set to 50. In this case, it is calculated that the 5% by weight distillation point ≧ 197 ° C. and the 95% by weight distillation point ≦ 362 ° C. of the cracked gas oil produced from the formulas (1) and (2) are required. Therefore, 5% by weight of the distillation cracked gas oil has a distillation point of 200 ° C. and 95% by weight has a distillation point of 360 ° C.
The cracked oil obtained above was distilled so that Tables 3 and 4 show the results and the like.
【００２１】〔実施例２〕反応温度以外は実施例１と同
様にして水素化処理を行い分解油を得た。反応温度は水
素化脱金属触媒層４０５℃、水素化分解触媒層４０５℃
および水素化脱硫触媒層３９５℃とした。この時、脱硫
率は９４重量％、３４３℃以上の留分の分解率は４９重
量％であった。Example 2 Hydrolysis was performed in the same manner as in Example 1 except for the reaction temperature to obtain a cracked oil. The reaction temperature is 405 ° C. for the hydrodemetalization catalyst layer and 405 ° C. for the hydrocracking catalyst layer.
And the temperature of the hydrodesulfurization catalyst layer was 395 ° C. At this time, the desulfurization rate was 94% by weight, and the decomposition rate of the fraction at 343 ° C. or higher was 49% by weight.
【００２２】上記で得られた分解油を蒸留して分解軽油
を得るため、分解軽油の目標硫黄濃度を３００重量ｐｐ
ｍ、目標セタン指数を５０とした。この場合、前記
（１）式および（２）式より製造する分解軽油の５重量
％蒸留点≧１８９℃、９５重量％蒸留点≦３６４℃とす
ることが必要であると算出される。そこで留出分解軽油
の５重量％蒸留点２００℃、９５重量％蒸留点３６０℃
となるように上記で得た分解油の蒸留をした。結果等を
表３、表４に示す。In order to obtain the cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil is set to 300 wt.
m and the target cetane index were set to 50. In this case, it is calculated that the distillation point of the cracked gas oil produced from the above formulas (1) and (2) needs to be 5% by weight ≧ 189 ° C. and 95% by weight ≦ 364 ° C. Therefore, 5% by weight of the distillation cracked gas oil has a distillation point of 200 ° C. and 95% by weight has a distillation point of 360 ° C.
The cracked oil obtained above was distilled so that Tables 3 and 4 show the results and the like.
【００２３】〔実施例３〕実施例１と同様にして水素化
処理を行い分解油を得た。上記で得られた分解油を蒸留
して分解軽油を得るため、分解軽油の目標硫黄濃度を２
００重量ｐｐｍ、目標セタン指数を５０とした。この場
合、前記（１）式および（２）式より製造する分解軽油
の５重量％蒸留点≧１９７℃、９５重量％蒸留点≦３４
７℃とすることが必要であると算出される。そこで留出
分解軽油の５重量％蒸留点２００℃、９５重量％蒸留点
３４５℃となるように上記で得た分解油の蒸留をした。
結果等を表３、表４に示す。Example 3 Hydrocracking was performed in the same manner as in Example 1 to obtain a cracked oil. In order to obtain the cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil is set to 2
00 ppm by weight and a target cetane index of 50. In this case, the 5% by weight distillation point of the cracked gas oil produced from the above formulas (1) and (2) ≧ 197 ° C., the 95% by weight distillation point ≦ 34.
It is calculated that 7 ° C. is necessary. Then, the cracked oil obtained above was distilled so that the distillation cracked gas oil had a 5% by weight distillation point of 200 ° C. and a 95% by weight distillation point of 345 ° C.
Tables 3 and 4 show the results and the like.
【００２４】〔実施例４〕水素化処理原料油をアラビア
ンヘビー常圧残油Ｂとし、反応温度以外は実施例１と同
様にして水素化処理を行い分解油を得た。反応温度は水
素化脱金属触媒層３９５℃、水素化分解触媒層４００℃
および水素化脱硫触媒層３９５℃とした。この時、脱硫
率は８８重量％、３４３℃以上の留分の分解率は３５重
量％であった。Example 4 A hydrotreated feedstock was used as Arabian Heavy Atmospheric Residue B, and hydrogenated in the same manner as in Example 1 except for the reaction temperature to obtain a cracked oil. The reaction temperature is 395 ° C. for the hydrodemetalization catalyst layer and 400 ° C. for the hydrocracking catalyst layer.
And the temperature of the hydrodesulfurization catalyst layer was 395 ° C. At this time, the desulfurization rate was 88% by weight, and the decomposition rate of the fraction at 343 ° C. or higher was 35% by weight.
【００２５】上記で得られた分解油を蒸留して分解軽油
を得るため、分解軽油の目標硫黄濃度を５００重量ｐｐ
ｍ、目標セタン指数を５０とした。この場合、前記
（１）式および（２）式より製造する分解軽油の５重量
％蒸留点≧２１３℃、９５重量％蒸留点≦３５６℃とす
ることが必要であると算出される。そこで留出分解軽油
の５重量％蒸留点２２０℃、９５重量％蒸留点３５０℃
となるように上記で得た分解油の蒸留をした。結果等を
表３、表４に示す。In order to obtain a cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil is set to 500 wt.
m and the target cetane index were set to 50. In this case, it is calculated that it is necessary to set the 5% by weight distillation point ≧ 213 ° C. and the 95% by weight distillation point ≦ 356 ° C. of the cracked gas oil produced from the formulas (1) and (2). Therefore, 5% by weight of the distillation cracked gas oil has a distillation point of 220 ° C. and 95% by weight has a distillation point of 350 ° C.
The cracked oil obtained above was distilled so that Tables 3 and 4 show the results and the like.
【００２６】〔比較例１〕実施例１と同様にして水素化
処理を行い分解油を得た。上記で得られた分解油を蒸留
して分解軽油を得るため、分解軽油の目標硫黄濃度を４
００重量ｐｐｍ、目標セタン指数を５０とした。この場
合、前記（１）式および（２）式より製造する分解軽油
の５重量％蒸留点≧１９７℃、９５重量％蒸留点≦３６
２℃とすることが必要であると算出される。しかし、留
出分解軽油の５重量％蒸留点２００℃、９５重量％蒸留
点３８０℃となるように上記で得た分解油の蒸留をし
た。結果等を表３、表４に示す。Comparative Example 1 Hydrogenation treatment was performed in the same manner as in Example 1 to obtain a cracked oil. In order to obtain the cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil was set to 4
00 ppm by weight and a target cetane index of 50. In this case, the 5% by weight distillation point ≧ 197 ° C. and the 95% by weight distillation point ≦ 36 of the cracked gas oil produced from the above formulas (1) and (2).
It is calculated that 2 ° C. is necessary. However, the cracked oil obtained above was distilled so that the distillation cracked gas oil had a 5% by weight distillation point of 200 ° C and a 95% by weight distillation point of 380 ° C. Tables 3 and 4 show the results and the like.
【００２７】〔比較例２〕水素化処理原料油をアラビア
ンヘビー常圧残油Ｂとした以外は実施例１と同様にして
水素化処理を行い分解油を得た。この時、脱硫率は９３
重量％、３４３℃以上の留分の分解率は４１重量％であ
った。上記で得られた分解油を蒸留して分解軽油を得る
ため、分解軽油の目標硫黄濃度を４００重量ｐｐｍ、目
標セタン指数を５０とした。この場合、前記（１）式お
よび（２）式より製造する分解軽油の５重量％蒸留点≧
１９７℃、９５重量％蒸留点≦３６２℃とすることが必
要であると算出される。しかし、留出分解軽油の５重量
％蒸留点１７０℃、９５重量％蒸留点３６０℃となるよ
うに上記で得た分解油の蒸留をした。結果等を表３、表
４に示す。Comparative Example 2 Hydrocracking was carried out in the same manner as in Example 1 except that the raw material oil for hydrotreating was Arabian heavy atmospheric residual oil B to obtain a cracked oil. At this time, the desulfurization rate was 93
% By weight, the decomposition rate of the fraction at 343 ° C. or higher was 41% by weight. In order to obtain a cracked gas oil by distilling the cracked oil obtained above, the target sulfur concentration of the cracked gas oil was 400 ppm by weight, and the target cetane index was 50. In this case, the distillation point of 5% by weight of the cracked gas oil produced from the above formulas (1) and (2) ≧
It is calculated that it is necessary to set 197 ° C. and 95% by weight distillation point ≦ 362 ° C. However, the cracked oil obtained above was distilled such that the distillation cracked gas oil had a 5% by weight distillation point of 170 ° C and a 95% by weight distillation point of 360 ° C. Tables 3 and 4 show the results and the like.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【表４】 [Table 4]
【００３２】表４からわかるように、実施例１〜４の場
合、分解軽油の実際の５％蒸留点または９５％蒸留点は
本発明に示す数式の条件を満たしており、その結果、分
解軽油の硫黄濃度の実績値は目標値以下、分解軽油のセ
タン指数の実績値は目標値以上となる。これに対し、比
較例１の場合、分解軽油の実際の９５重量％蒸留点が本
発明に示す数式の条件からはずれており、その結果、分
解軽油の硫黄濃度の実績値が目標値を上回っている。ま
た、比較例２の場合、分解軽油の実際の５重量％蒸留点
が本発明に示す数式の条件からはずれており、その結
果、分解軽油のセタン指数の実績値が目標値を下回って
いる。As can be seen from Table 4, in Examples 1 to 4, the actual 5% or 95% distillation point of the cracked gas oil satisfies the condition of the formula shown in the present invention. The actual value of the sulfur concentration is below the target value, and the actual value of the cetane index of the cracked gas oil is above the target value. On the other hand, in the case of Comparative Example 1, the actual 95% by weight distillation point of the cracked gas oil deviated from the condition of the formula shown in the present invention, and as a result, the actual value of the sulfur concentration of the cracked gas oil exceeded the target value. I have. In the case of Comparative Example 2, the actual 5% by weight distillation point of the cracked gas oil deviated from the condition of the formula shown in the present invention. As a result, the actual value of the cetane index of the cracked gas oil was lower than the target value.
【００３３】[0033]
【発明の効果】以上説明したように、本発明により常圧
残油を水素化分解を含む水素化処理をして得られる分解
油を所定の蒸留温条件蒸留することにより、目標とする
硫黄濃度およびセタン指数の分解軽油が得られる。ま
た、上記の蒸留を既設の石油精製プラントにて行なう事
により、新たな精製設備を建設する、あるいは大きな設
備の改造を行なうことなく、今後の品質規制に対応しう
る低硫黄軽油の基材を試行錯誤を行うこと無く効率的に
製造できる。As described above, the cracked oil obtained by subjecting the normal pressure resid to a hydrotreating process including hydrocracking according to the present invention is distilled at a predetermined distillation temperature to obtain a target sulfur concentration. And a cracked gas oil having a cetane index. In addition, by performing the above distillation at an existing petroleum refining plant, a low-sulfur gas oil base material that can respond to future quality regulations can be obtained without constructing new refining equipment or remodeling large equipment. It can be manufactured efficiently without trial and error.
Claims (2)
水素化処理をして得られた分解油から下式（１）および
（２）を満足するように蒸留して分解軽油を製造する方
法。 Ｂ ≧ ２７８．５Ｙ／（０．１９４ＸＸ＋０．０７２ＹＹ−０．０１７Ａ＋ ４３．６）−６５．７ ・・・・（１） Ｃ ≦ ２６．５Ｘ／（−１２．０ＸＸ−８．０ＹＹ＋１．ｌＡ＋１２６４． ０）＋３３２．９ ・・・・（２） ここで Ａ（℃） ： 原料常圧残油の５重量％蒸留点 ＸＸ（重量％） ： 原料常圧残油中の３４３℃以上の
留分の分解率 ＹＹ（重量％） ： 原料常圧残油の脱硫率 Ｂ（℃） ： 分解軽油の５重量％蒸留点 Ｃ（℃） ： 分解軽油の９５重量％蒸留点 Ｘ（重量ｐｐｍ）： 分解軽油の目標硫黄濃度 Ｙ（無次元） ： 分解軽油の目標セタン指数 を表す。 ただし、 ＸＸ≧３５ ２４０≧Ｂ≧１６０ ３７０≧Ｃ≧２８０ Ｃ−Ｂ≧６０ を満足する範囲である。1. A cracked gas oil is produced by distilling a normal pressure residual oil from a cracked oil obtained by hydrotreating including at least hydrocracking so as to satisfy the following formulas (1) and (2). Method. B ≧ 278.5Y / (0.194XX + 0.072YY−0.017A + 43.6) −65.7 (1) C ≦ 26.5X / (-12.0XX−8.0YY + 1.lA + 1264.0) ) +332.9 (2) where A (° C.): 5% by weight distillation point of raw material residual pressure XX (% by weight): Decomposition of 343 ° C. or higher fraction in raw material residual pressure residual oil YY (% by weight): Desulfurization rate of raw pressure residual oil B (° C.): Distillation point of 5% by weight of cracked gas oil C (° C.): Distillation point of 95% by weight of cracked gas oil X (weight ppm): of cracked gas oil Target sulfur concentration Y (dimensionless): Indicates the target cetane index of cracked gas oil. However, XX ≧ 35 240 ≧ B ≧ 160 370 ≧ C ≧ 280 C−B ≧ 60.
金属、水素化分解および水素化脱硫の各水素化処理を含
むものである請求項１記載の分解軽油を製造する方法。2. The method for producing a cracked gas oil according to claim 1, wherein the hydrotreating including hydrocracking includes hydrotreating of hydrodemetallation, hydrocracking, and hydrodesulfurization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11064422A JP2000256676A (en) | 1999-03-11 | 1999-03-11 | Distillation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11064422A JP2000256676A (en) | 1999-03-11 | 1999-03-11 | Distillation method |
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| Publication Number | Publication Date |
|---|---|
| JP2000256676A true JP2000256676A (en) | 2000-09-19 |
Family
ID=13257836
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11064422A Pending JP2000256676A (en) | 1999-03-11 | 1999-03-11 | Distillation method |
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| Country | Link |
|---|---|
| JP (1) | JP2000256676A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007533442A (en) * | 2004-04-22 | 2007-11-22 | アルベマーレ ネザーランズ ビー．ブイ． | Hydrotreating catalyst containing group V metal |
-
1999
- 1999-03-11 JP JP11064422A patent/JP2000256676A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007533442A (en) * | 2004-04-22 | 2007-11-22 | アルベマーレ ネザーランズ ビー．ブイ． | Hydrotreating catalyst containing group V metal |
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