JP4908037B2

JP4908037B2 - Method for treating synthetic oil, hydrocarbon oil for kerosene smoke point improver and hydrocarbon oil for diesel fuel base material

Info

Publication number: JP4908037B2
Application number: JP2006095201A
Authority: JP
Inventors: 祐一田中; 信也高橋; 善文千葉
Original assignee: JXTG Nippon Oil and Energy Corp
Current assignee: Eneos Corp
Priority date: 2006-03-30
Filing date: 2006-03-30
Publication date: 2012-04-04
Anticipated expiration: 2026-03-30
Also published as: CN101410491A; CN101410491B; JP2007269899A

Description

本発明は、合成油の処理方法、並びに、かかる処理方法により得られる灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油に関する。 The present invention relates to a method for treating synthetic oil, and a hydrocarbon oil for a kerosene smoke point improver and a hydrocarbon oil for a diesel fuel base material obtained by such a treatment method.

近年、環境負荷低減の観点から、硫黄分及び芳香族炭化水素の含有量が低く、環境にやさしいクリーンな液体燃料が求められている。そこで、石油業界においては、クリーン燃料の製造方法として、一酸化炭素と水素を原料としたフィッシャー・トロプシュ合成法（以下、「ＦＴ合成法」と略す。）が検討されている。ＦＴ合成法によれば、パラフィン含有量に富み、かつ硫黄分を含まない液体燃料基材を製造することができるため、その期待は非常に大きい。 In recent years, clean liquid fuels that are low in sulfur content and aromatic hydrocarbon content and that are friendly to the environment have been demanded from the viewpoint of reducing environmental impact. Therefore, in the petroleum industry, a Fischer-Tropsch synthesis method (hereinafter abbreviated as “FT synthesis method”) using carbon monoxide and hydrogen as raw materials is being studied as a method for producing clean fuel. According to the FT synthesis method, a liquid fuel base material having a high paraffin content and no sulfur content can be produced.

ところで、ＦＴ合成法によって得られる合成油（以下、「ＦＴ合成油」という場合もある。）は広い炭素数分布を有しており、このＦＴ合成油からは、例えば、沸点範囲１５０℃以下の炭化水素を多く含むＦＴナフサ留分、沸点１５０℃〜３６０℃の留分を多く含むＦＴ中間留分及びこの中間留分より重質なＦＴワックス分を得ることができる。これらの留分のうち、ＦＴナフサ留分は、直鎖型の炭化水素（ノルマルパラフィン分、直鎖アルコール分及びα−オレフィン分などを指す）の含有量が高く、オクタン価が極端に低いため、燃料基材としては付加価値が低い。これに対して、ＦＴ中間留分やＦＴワックス分は、水素化処理によってディーゼル燃料、灯油、水素製造用炭化水素油などの付加価値の高い燃料基材に適した成分へと転換できる。そのため、燃料製造プロセスの経済性を向上させる観点から、ＦＴ合成油のうち特に沸点１５０℃以上の留分を高付加価値成分へと効率よく転換できる技術が求められている。 By the way, a synthetic oil obtained by the FT synthesis method (hereinafter sometimes referred to as “FT synthetic oil”) has a wide carbon number distribution. From this FT synthetic oil, for example, a boiling point range of 150 ° C. or less. It is possible to obtain an FT naphtha fraction rich in hydrocarbons, an FT middle fraction rich in fractions having a boiling point of 150 ° C. to 360 ° C., and a FT wax fraction heavier than the middle fraction. Of these fractions, the FT naphtha fraction has a high content of linear hydrocarbons (referring to normal paraffin content, linear alcohol content, α-olefin content, etc.) and an extremely low octane number. Low added value as a fuel substrate. On the other hand, the FT middle distillate and the FT wax can be converted into components suitable for high-value-added fuel base materials such as diesel fuel, kerosene, and hydrogen-producing hydrocarbon oil by hydrotreatment. Therefore, from the viewpoint of improving the economic efficiency of the fuel production process, there is a demand for a technology that can efficiently convert a fraction having a boiling point of 150 ° C. or higher among FT synthetic oils into high value-added components.

ＦＴ合成油からディーゼル燃料基材を製造する方法はこれまでにも検討されており、例えば、重質なワックス分を水素化分解する技術（例えば、特許文献１を参照）や、ＦＴ中間留分を水素化精製する技術（例えば、特許文献２を参照）が知られている。 A method for producing a diesel fuel base material from FT synthetic oil has been studied so far. For example, a technique for hydrocracking a heavy wax component (see, for example, Patent Document 1), an FT middle distillate, or the like. A technique for hydrotreating (see, for example, Patent Document 2) is known.

また、ＦＴ合成油から灯油やジェット燃料を製造する方法としては、例えば、ＦＴ合成油を水素化分解および異性化して得られた生成油を分留する技術が提案されている（例えば、特許文献３を参照）。 In addition, as a method for producing kerosene or jet fuel from FT synthetic oil, for example, a technique for fractionating a product oil obtained by hydrocracking and isomerizing FT synthetic oil has been proposed (for example, Patent Documents). 3).

国際公開第００／０２０５３５号パンフレットInternational Publication No. 00/020535 Pamphlet フランス国特許公開第２８２６９７１号明細書French Patent Publication No. 2826971 特開２００４−３２３６２６号公報JP 2004-323626 A

しかしながら、近時、従来にも増して燃料製造コストへの要求が厳しくなっている状況下にあっては、上記従来技術であってもプロセスの経済性を十分に向上させるには以下の理由により必ずしも十分なものではない。 However, under the circumstances where the demand for fuel production cost has become stricter than ever in the past, even with the above-described conventional technology, the following reasons can be taken to sufficiently improve the economics of the process. Not always enough.

すなわち、上記特許文献１〜３に記載の技術は特定の燃料基材に有用な成分を得るためのものであり、ＦＴ合成油を商業的な規模で処理した場合には低付加価値若しくは余剰な成分が多く併産されてしまう。そのため、プロセスの経済性を更に高い水準へと高めるには更なる改善が必要である。 That is, the techniques described in Patent Documents 1 to 3 are for obtaining a useful component for a specific fuel base material. When the FT synthetic oil is processed on a commercial scale, low added value or surplus is obtained. Many ingredients are co-produced. Therefore, further improvements are needed to raise the economics of the process to a higher level.

本発明は、上記課題に鑑みてなされたものであり、ＦＴ合成油を高い転換率で高付加価値成分に転換でき、燃料製造プロセスにおける経済性が高水準で達成されることを可能とする合成油の処理方法、並びに、かかる処理方法によって得られ、高付加価値であるとともに経済性に優れた灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を提供することを目的とする。 The present invention has been made in view of the above problems, and is a synthesis that can convert FT synthetic oil into a high value-added component at a high conversion rate and achieve high economic efficiency in the fuel production process. It is an object of the present invention to provide a method for treating oil, and a hydrocarbon oil for kerosene smoke point improver and a hydrocarbon oil for diesel fuel base material, which are obtained by such a treatment method and have high added value and are excellent in economy. To do.

上記目的を達成する本発明の灯油煙点向上剤用炭化水素油の製造方法は、フィッシャー・トロプシュ合成法により得られる合成油を含む被処理物を分留することにより、沸点１５０〜３６０℃の留分の含有量が９０質量％以上である中間留分と、当該中間留分よりも重質なワックス分とを得る第１の分留工程と、第１の分留工程で得られる中間留分を、水素存在下、結晶性ゼオライト並びに耐熱性を有する無定形金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成される担体に、周期律表第ＶＩＩＩ族に属する金属を担持した水素化精製触媒と接触させ、水素化精製物における沸点１５０℃以下の留分の含有率の増加量が９質量％以下、イソパラフィンの含有率の増加量が３０質量％以上となるように、水素化分解及び水素化異性化を含む水素化精製に供する水素化精製工程と、水素化精製工程で得られる水素化精製物を分留することにより、沸点１５０〜２５０℃の留分の含有量が９０質量％以上である第１の留分と、当該第１の留分よりも重質な第２の留分とを得る第２の分留工程と、第１の分留工程で得られるワックス分を、水素存在下、結晶性ゼオライト並びに耐熱性を有する無定形金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成される担体に、周期律表第ＶＩＩＩ族に属する金属を担持した水素化分解触媒と接触させ、水素化分解生成物における沸点３６０℃以下の留分の含有量が４５〜８５質量％となるように、水素化異性化を含む水素化分解に供する水素化分解工程と、水素化分解工程で得られた水素化分解生成物を分留することにより、沸点１５０〜３６０℃の留分の含有量が９０質量％以上である第３の留分を得る第３の分留工程と、第２の留分と第３の留分とを混合する混合工程とを備え、第１の留分を灯油煙点向上剤用炭化水素油として取得することを特徴とする。また、本発明のディーゼル燃料基材用炭化水素油の製造方法は、フィッシャー・トロプシュ合成法により得られる合成油を含む被処理物を分留することにより、沸点１５０〜３６０℃の留分の含有量が９０質量％以上である中間留分と、当該中間留分よりも重質なワックス分とを得る第１の分留工程と、第１の分留工程で得られる中間留分を、水素存在下、結晶性ゼオライト並びに耐熱性を有する無定形金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成される担体に、周期律表第ＶＩＩＩ族に属する金属を担持した水素化精製触媒と接触させ、水素化精製物における沸点１５０℃以下の留分の含有率の増加量が９質量％以下、イソパラフィンの含有率の増加量が３０質量％以上となるように、水素化分解及び水素化異性化を含む水素化精製に供する水素化精製工程と、水素化精製工程で得られる水素化精製物を分留することにより、沸点１５０〜２５０℃の留分の含有量が９０質量％以上である第１の留分と、当該第１の留分よりも重質な第２の留分とを得る第２の分留工程と、第１の分留工程で得られるワックス分を、水素存在下、結晶性ゼオライト並びに耐熱性を有する無定形金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成される担体に、周期律表第ＶＩＩＩ族に属する金属を担持した水素化分解触媒と接触させ、水素化分解生成物における沸点３６０℃以下の留分の含有量が４５〜８５質量％となるように、水素化異性化を含む水素化分解に供する水素化分解工程と、水素化分解工程で得られる水素化分解生成物を分留することにより、沸点１５０〜３６０℃の留分の含有量が９０質量％以上である第３の留分を得る第３の分留工程と、第２の留分と第３の留分とを混合する混合工程と、を備え、第２の留分と第３の留分との混合物をディーゼル燃料基材用炭化水素油として取得することを特徴とする。 The method for producing a hydrocarbon oil for a kerosene smoke point improver of the present invention that achieves the above-mentioned object has a boiling point of 150 to 360 ° C. by fractionating an object to be treated containing synthetic oil obtained by a Fischer-Tropsch synthesis method. A first fractionation step for obtaining a middle fraction having a fraction content of 90% by mass or more, a wax fraction heavier than the middle fraction, and a middle fraction obtained in the first fractionation step In the presence of hydrogen , a carrier comprising one or more solid acids selected from crystalline zeolite and heat-resistant amorphous metal oxide is added to a metal belonging to Group VIII of the periodic table. Contact with the supported hydrorefining catalyst so that the increase in the content of the fraction having a boiling point of 150 ° C. or less in the hydrofinished product is 9% by mass or less and the increase in the content of isoparaffin is 30% by mass or more. , Hydrocracking and hydroisomerization A hydrorefining process for subjected to hydrotreating including, by fractionating the hydrotreated product obtained by the hydrorefining process, the content of fraction having a boiling point of 150 to 250 ° C. is 90 wt% or more In the presence of hydrogen, a second fractionation step for obtaining a first fraction and a second fraction heavier than the first fraction, and a wax fraction obtained in the first fractionation step are obtained. Hydrocracking catalyst in which a metal belonging to Group VIII of the Periodic Table is supported on a carrier comprising one or more kinds of solid acids selected from amorphous zeolite having heat resistance and crystalline zeolite is contacted with, as the content of the following fractions boiling point 360 ° C. in hydrocracking products is 45 to 85 wt%, and hydrocracking processes that Kyosu the hydrocracking hydroisomerisation, hydrogenation by fractionating the resulting hydrocracking product of decomposition step, A third fractionation step for obtaining a third fraction having a content of a fraction having a point of 150 to 360 ° C. of 90% by mass or more, and a mixing step for mixing the second fraction and the third fraction with the door, the first fraction and said Rukoto Tokusu preparative as kerosene smoke point improvers for hydrocarbon oils. Moreover, the manufacturing method of the hydrocarbon oil for diesel fuel base materials of this invention contains the fraction of boiling point 150-360 degreeC by fractionating the to-be-processed object containing the synthetic oil obtained by a Fischer-Tropsch synthesis method. A middle fraction having an amount of 90% by mass or more, a first fractionation step for obtaining a wax fraction heavier than the middle fraction, and a middle fraction obtained in the first fractionation step, Hydrogenation in which a metal belonging to Group VIII of the Periodic Table is supported on a support comprising one or more solid acids selected from crystalline zeolite and amorphous metal oxide having heat resistance in the presence Hydrocracking so that the increase in the content of fractions with boiling points of 150 ° C. or less in the hydrorefined product is 9% by mass or less and the increase in the content of isoparaffin is 30% by mass or more in contact with the purification catalyst. And including hydroisomerization A hydrorefining step to be subjected to hydrorefining and a hydrorefined product obtained in the hydrorefining step are subjected to fractional distillation, whereby the content of a fraction having a boiling point of 150 to 250 ° C. is 90% by mass or more. A wax fraction obtained in the second fractionation step for obtaining a fraction and a second fraction heavier than the first fraction, and the first fractionation step in the presence of hydrogen; A support comprising one or more solid acids selected from zeolite and heat-resistant amorphous metal oxide is brought into contact with a hydrocracking catalyst supporting a metal belonging to Group VIII of the periodic table. In the hydrocracking process and hydrocracking process, the hydrocracking product is subjected to hydrocracking including hydroisomerization so that the content of the fraction having a boiling point of 360 ° C. or less in the hydrocracking product is 45 to 85 mass%. By fractionating the resulting hydrocracked product, a boiling point of 15 A third fractionation step of obtaining a third fraction having a content of a fraction of ˜360 ° C. of 90% by mass or more, a mixing step of mixing the second fraction and the third fraction; And a mixture of the second fraction and the third fraction is obtained as a hydrocarbon oil for a diesel fuel base material.

なお、上記増加量とは、接触後の中間留分における沸点１５０℃以下の留分の含有率（質量％）から接触前の中間留分における沸点１５０℃以下の留分の含有率（質量％）を引いた値を意味する。 In addition, the said increase amount is the content (mass%) of the fraction (mass%) of the boiling point of 150 degrees C or less in the middle distillate before contact from the content (mass%) of the fraction of boiling points 150 degrees C or less in the middle distill after contact. ) Means the value minus.

本発明の方法によれば、ＦＴ合成油から、灯油煙点向上効果に優れた上記第１の留分と、ディーゼル燃料基材として有用な上記第２の留分及び第３の留分の混合物との双方を高収率で得ることができる。 According to how the present invention, the FT synthetic oil, and the first fraction which is excellent in kerosene smoke point improvement, diesel useful the second fraction as a fuel base material and the third fraction Both with the mixture can be obtained in high yield.

ところで、ディーゼル自動車に供されるディーゼル燃料は、燃料ポンプの不調や油膜切れによる燃焼筒内での焼きつきを防止する観点から、常温及び高温においてある程度の動粘度を示すことが望ましい。例えば、日本工業規格ＪＩＳＫ２２８３の２号軽油動粘度規格においては、３０℃での動粘度が２．５ｍｍ^２／ｓ以上と定められている。そのため、ディーゼル燃料基材として用いられる炭化水素油は、低温流動性及び動粘度の双方が十分改善されたものである必要がある。 By the way, it is desirable that the diesel fuel supplied to the diesel vehicle exhibits a certain degree of kinematic viscosity at normal temperature and high temperature from the viewpoint of preventing burning in the combustion cylinder due to malfunction of the fuel pump or running out of the oil film. For example, in the Japanese Industrial Standard JIS K2283 No. 2 diesel oil kinematic viscosity standard, the kinematic viscosity at 30 ° C. is defined as 2.5 mm ² / s or more. Therefore, the hydrocarbon oil used as a diesel fuel base material needs to be sufficiently improved in both low temperature fluidity and kinematic viscosity.

一方、一部の原油（例えばドバイ原油、イスマス原油）から得られる直留灯油留分や、灯油より沸点範囲が相対的に重質な石油留分を水素化または接触分解処理したときに併産される分解灯油留分は、水素化処理しても煙点が低く、直接灯油として供することができない。そこで、特開２０００−２５６６８１号公報に記載の方法のように、煙点が高い灯油基材を灯油煙点向上剤として混合して灯油の増産を図ることが検討されている。しかし、上記従来の方法で用いられる灯油基材は灯油煙点向上が不十分であり、大量の配合が必要であった。 On the other hand, when a straight-run kerosene fraction obtained from some crude oils (for example, Dubai crude oil or Ismas crude oil) or a petroleum fraction having a heavier boiling range than kerosene is hydrotreated or catalytically cracked The cracked kerosene fraction thus produced has a low smoke point even when it is hydrotreated, and cannot be directly used as kerosene. Then, like the method of Unexamined-Japanese-Patent No. 2000-256681, it is examined to increase the production of kerosene by mixing the kerosene base material with a high smoke point as a kerosene smoke point improver. However, the kerosene base material used in the above-described conventional method has insufficient improvement of the kerosene smoke point, and a large amount of blending is required.

これらに対して、本発明の方法によれば、−７．５℃以下の流動点及び３０℃において２．５ｍｍ^２／ｓ以上の動粘度を示す炭化水素油、及び、煙点２２ｍｍ以下の劣質な灯油に配合したときの煙点向上効果が配合割合（配合後の灯油全量基準）１０質量％当たりの換算値で２．３ｍｍ以上である炭化水素油を、それぞれ上記第２の留分及び第３の留分の混合物、及び、上記第１の留分として高収率で得ることが可能である。従って、本発明によれば、燃料基材の製造における経済性を極めて高い水準で達成できる。 For these, according to the way of the present invention, -7.5 ° C. below the pour point and 30 ° C. hydrocarbon oil showing a kinematic viscosity of more than 2.5 mm ² / s at, and, following smoke point 22mm A hydrocarbon oil whose smoke point improving effect when blended with inferior kerosene is 2.3 mm or more in terms of a blending ratio (based on the total amount of kerosene after blending) of 10% by mass is the second fraction and A mixture of the third fraction and the first fraction can be obtained in high yield. Therefore, according to the present invention, economic efficiency in the production of the fuel base material can be achieved at a very high level.

なお、本発明において「灯油の煙点」とは、ＪＩＳＫ２５３７試験法に従って測定される値を意味する。 In the present invention, the “smoke point of kerosene” means a value measured according to the JIS K2537 test method.

本発明の灯油煙点向上剤用炭化水素油の製造方法及びディーゼル燃料基材用炭化水素油の製造方法においては、上記第３の分留工程で得られる、第３の留分よりも重質なワックス分の一部又は全部を水素化分解工程に供することが好ましい。かかるワックス分をリサイクルして水素化分解することにより、ディーゼル燃料基材として有用な成分、すなわち第２の留分と第３の留分との混合物の収率を更に向上させることができる。 In the method for producing a hydrocarbon oil for a kerosene smoke point improver and a method for producing a hydrocarbon oil for a diesel fuel base material of the present invention, it is heavier than the third fraction obtained in the third fractionation step. It is preferable that a part or all of the wax component is subjected to a hydrocracking step. By recycling and hydrocracking such a wax component, the yield of a component useful as a diesel fuel base, that is, a mixture of the second fraction and the third fraction can be further improved.

本発明の方法においては、水素化分解触媒に接触後のワックス分における沸点３６０℃以下の留分の含有量が４５〜８５質量％となるようにワックス分を水素化分解する。かかる含有量が４５質量％未満であると、ディーゼル燃料基材として有用な成分、すなわち第２の留分と第３の留分との混合物の収率が低下したり、かかる混合物の低温流動性が低下したりする傾向にある。一方、含有量が８５質量％を超えると、ディーゼル燃料基材として有用な成分、すなわち第２の留分と第３の留分との混合物の収率が低下する傾向にある。
In how the present invention, you hydrocracking a wax fraction as the content of the following fractions boiling point 360 ° C. in the wax fraction after contact with the hydrocracking catalyst is 45 to 85 mass%. When the content is less than 45% by mass, the yield of a component useful as a diesel fuel base material, that is, the mixture of the second fraction and the third fraction is reduced, or the low temperature fluidity of the mixture is reduced. Tend to decrease. On the other hand, when the content exceeds 85% by mass, the yield of a component useful as a diesel fuel base, that is, a mixture of the second fraction and the third fraction tends to be lowered.

本発明の合成油の処理方法においては、中間留分と接触させる水素化精製触媒が、結晶性ゼオライト０．１質量％〜８０．０質量％と耐熱性を有する無定形金属酸化物とを含む担体、および、当該担体上に担持された周期律表第ＶＩＩＩ族に属する金属からなる群より選択される１種類以上の金属を含むものであることが好ましい。 In the method for treating synthetic oil of the present invention, the hydrorefining catalyst brought into contact with the middle distillate contains 0.1% by mass to 80.0% by mass of crystalline zeolite and an amorphous metal oxide having heat resistance. It is preferable to include one or more metals selected from the group consisting of a carrier and a metal belonging to Group VIII of the Periodic Table carried on the carrier.

本発明の合成油の処理方法においては、ワックス分と接触させる水素化分解触媒が、結晶性ゼオライト０．１質量％〜８０．０質量％と耐熱性を有する無定形金属酸化物０．１質量％〜６０．０質量％とを含む担体、および、当該担体上に担持された周期律表第ＶＩＩＩ族に属する金属からなる群より選択される１種類以上の金属を含むものであることが好ましい。 In the method for treating synthetic oil of the present invention, the hydrocracking catalyst to be brought into contact with the wax content is 0.1% by mass to 80.0% by mass of crystalline zeolite and 0.1% by mass of amorphous metal oxide having heat resistance. It is preferable that it contains one or more kinds of metals selected from the group consisting of a carrier containing 1% to 60.0% by mass and a metal belonging to Group VIII of the periodic table carried on the carrier.

本発明の合成油の処理方法においては、中間留分と水素化精製触媒とを接触させるときの反応温度が２００〜３７０℃、水素分圧が１．０〜５．０ＭＰａおよび液空間速度が０．３〜３．５ｈ^−１であり、且つ、ワックス分と水素化分解触媒とを接触させるときの反応温度が２００〜３７０℃、水素分圧が１．０〜５．０ＭＰａおよび液空間速度が０．３〜３．５ｈ^−１であることが好ましい。 In the method for treating synthetic oil of the present invention, the reaction temperature when contacting the middle distillate and the hydrorefining catalyst is 200 to 370 ° C., the hydrogen partial pressure is 1.0 to 5.0 MPa, and the liquid space velocity is 0. 3 to 3.5 h ⁻¹ , and the reaction temperature when the wax component and the hydrocracking catalyst are contacted is 200 to 370 ° C., the hydrogen partial pressure is 1.0 to 5.0 MPa, and the liquid space velocity is It is preferable that it is 0.3-3.5h- ¹ .

本発明の合成油の処理方法においては、プロセスの経済性を十分確保する観点から、第１の留分、第２の留分及び第３の留分の合計質量を、ＦＴ合成油のうち実質的に沸点が１５０℃以上である留分の質量に対して６６質量％以上とすることが好ましい。 In the synthetic oil processing method of the present invention, from the viewpoint of sufficiently ensuring the economics of the process, the total mass of the first fraction, the second fraction and the third fraction is substantially equal to the FT synthetic oil. In particular, the boiling point is preferably 66% by mass or more based on the mass of the fraction having a temperature of 150 ° C. or more.

本発明の合成油の処理方法において上記第３の分留工程で得られる、第３の留分よりも重質なワックス分の一部又は全部を水素化分解工程に供する場合、プロセスの経済性を更に向上させる観点から、第１の留分、第２の留分及び第３の留分の合計質量を、ＦＴ合成油のうち実質的に沸点が１５０℃以上である留分の質量に対して７７質量％以上とすることが好ましい。 In the method for treating synthetic oil according to the present invention, when part or all of the wax heavier than the third fraction obtained in the third fractionation step is subjected to the hydrocracking step, the economics of the process From the viewpoint of further improving the ratio, the total mass of the first fraction, the second fraction, and the third fraction is based on the mass of the FT synthetic oil whose boiling point is substantially 150 ° C. or higher. 77 mass% or more is preferable.

また、本発明は、上記本発明の合成油の処理方法により得られる第２の留分と第３の留分との混合物を含み、流動点が−７．５℃以下であり、且つ、３０℃での動粘度が２．５ｍｍ^２／ｓ以上であることを特徴とするディーゼル燃料基材用炭化水素油を提供する。 The present invention also includes a mixture of the second fraction and the third fraction obtained by the synthetic oil processing method of the present invention, and has a pour point of −7.5 ° C. or lower, and 30 Provided is a hydrocarbon oil for a diesel fuel base material, which has a kinematic viscosity at 2.5 ° C. of 2.5 mm ² / s or more.

また、本発明は、上記本発明の合成油の処理方法により得られる第１の留分を含み、煙点が４４ｍｍ以上であることを特徴とする灯油煙点向上剤用炭化水素油を提供する。 The present invention also provides a hydrocarbon oil for a kerosene smoke point improver comprising the first fraction obtained by the synthetic oil processing method of the present invention and having a smoke point of 44 mm or more. .

本発明のディーゼル燃料基材用炭化水素油及び灯油煙点向上剤用炭化水素油はそれぞれ、本発明の合成油の処理方法により高性能であるとともに高収率で取得可能であることから、コストパフォーマンスに非常に優れたものである。従って、本発明のディーゼル燃料基材用炭化水素油によれば、環境低負荷型のディーゼル燃料の低コスト化を実現できる。また、本発明の灯油煙点向上剤用炭化水素油によれば、より低コストで灯油の増産を図ることが可能となる。 Since the hydrocarbon oil for diesel fuel base material and the hydrocarbon oil for kerosene smoke point improver of the present invention have high performance and can be obtained in high yield by the synthetic oil processing method of the present invention, respectively, the cost can be reduced. Very good performance. Therefore, according to the hydrocarbon oil for diesel fuel base material of the present invention, it is possible to realize cost reduction of environmentally low load type diesel fuel. Moreover, according to the hydrocarbon oil for a kerosene smoke point improver of the present invention, it becomes possible to increase the production of kerosene at a lower cost.

本発明よれば、ＦＴ合成油を高い転換率で高付加価値成分に転換でき、燃料製造プロセスにおける経済性が高水準で達成されることを可能とする合成油の処理方法、並びに、かかる処理方法によって得られ、高付加価値であるとともに経済性に優れた灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the synthetic | combination oil processing method which can convert FT synthetic oil into a high added value component with high conversion rate, and can achieve economical efficiency in a fuel manufacturing process at high level, and this processing method It is possible to provide a hydrocarbon oil for a kerosene smoke point improver and a hydrocarbon oil for a diesel fuel base material, which are obtained by the above, and have high added value and are excellent in economy.

以下、添付図面を参照しながら、本発明の好適な実施形態について詳細に説明する。なお、図面の説明において、同一または相当要素には同一の符号を付し、重複する説明は省略する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

図１は、本発明の合成油の処理方法を実施する炭化水素油製造装置の一例を示すフロー図である。図１に示される炭化水素油製造装置１００は、ＦＴ合成油を含む原料が導入されるＦＴ合成油導入流路Ｌ１と、ＦＴ合成油導入流路１から導入された合成油を軽質留分と中間留分と重質ワックス分とに分留する第１の蒸留塔１０と、蒸留塔１０から中間留分流路Ｌ２を通じて供給される中間留分を水素化精製する水素化精製装置２０と、蒸留塔１０からワックス分流路Ｌ３を通じて供給される重質ワックス分を水素化分解する水素化分解装置３０と、水素化精製装置２０を経た中間留分（水素化精製物）を軽質中間留分（第１の留分）と当該軽質中間留分よりも重質な重質中間留分（第２の留分）とに分留する第２の蒸留塔４０と、水素化分解装置３０を経た重質ワックス分（水素化分解生成物）を中間留分（第３の留分）と当該中間留分よりも重質なワックス分（未分解ワックス分）とに分留する第３の蒸留塔５０と、第２の蒸留塔４０から軽質中間留分（第１の留分）を系外へと取り出すための流路Ｌ６と、第２の蒸留塔４０から流路Ｌ７を通じて供給される重質中間留分（第２の留分）及び第３の蒸留塔５０から流路Ｌ１０を通じて供給される中間留分（第３の留分）を混合して系外へと取り出すための流路Ｌ１３とを備えて構成されている。なお、水素化精製装置２０と第２の蒸留塔４０とは流路Ｌ５で接続されており、この流路の途中には水素化精製物からガス成分を除去する気液分離槽（図示せず）が設けられている。また、水素化分解装置３０と第３の蒸留塔５０とは流路Ｌ９で接続されており、この流路の途中には水素化分解生成物からガス成分を除去する気液分離槽（図示せず）が設けられている。更に、第３の蒸留塔５０には、中間留分（第３の留分）よりも軽質な留分を取り出すための流路Ｌ１２、及び、中間留分（第３の留分）よりも重質なワックス分を必要に応じて水素化分解装置３０に供給して水素化分解するための循環流路Ｌ１１が接続されている。 FIG. 1 is a flow diagram showing an example of a hydrocarbon oil production apparatus that implements the synthetic oil treatment method of the present invention. A hydrocarbon oil production apparatus 100 shown in FIG. 1 includes an FT synthetic oil introduction channel L1 into which a raw material containing FT synthetic oil is introduced, and a synthetic oil introduced from the FT synthetic oil introduction channel 1 as a light fraction. A first distillation column 10 that fractionates into a middle distillate and a heavy wax fraction, a hydrorefining device 20 that hydrotreats the middle distillate supplied from the distillation column 10 through the middle distillate flow path L2, and a distillation A hydrocracking apparatus 30 for hydrocracking a heavy wax component supplied from the tower 10 through a wax splitting flow path L3, and a middle distillate (hydrocracked product) passed through the hydrorefining apparatus 20 as a light middle distillate (first 1) and a second distillation column 40 that fractionates into a heavy middle distillate (second distillate) heavier than the light middle distillate, and a heavy through the hydrocracking apparatus 30. Use wax fraction (hydrocracking product) as middle fraction (third fraction) and middle fraction In order to take out a light middle distillate (first distillate) from the third distillation column 50 and the second distilling column 40, which fractionate into a heavy wax component (undecomposed wax component). , The heavy middle distillate (second fraction) supplied from the second distillation column 40 through the flow channel L7, and the middle distillate supplied from the third distillation column 50 through the flow channel L10. A flow path L13 for mixing (third fraction) and taking it out of the system is provided. The hydrorefining apparatus 20 and the second distillation column 40 are connected by a flow path L5, and a gas-liquid separation tank (not shown) for removing gas components from the hydrofinished product is provided in the middle of the flow path. ) Is provided. The hydrocracking apparatus 30 and the third distillation column 50 are connected by a flow path L9, and a gas-liquid separation tank (not shown) for removing gas components from the hydrocracking product is provided in the middle of the flow path. Z). Further, the third distillation column 50 has a flow path L12 for taking out a lighter fraction than the middle distillate (third distillate) and a heavier than the middle distillate (third distillate). A circulation flow path L11 for supplying a high-quality wax component to the hydrocracking apparatus 30 as necessary and hydrocracking is connected.

以下、図１の炭化水素油製造装置１００を参照しながら本発明の合成油の処理方法について詳細に説明する。 Hereinafter, the synthetic oil treatment method of the present invention will be described in detail with reference to the hydrocarbon oil production apparatus 100 of FIG.

（ＦＴ合成油を含む原料の分留）
まず、本発明の合成油の処理方法に供される原料（被処理物）に含まれるＦＴ合成油としては、ＦＴ合成法により生成されるものであれば特に限定されないが、沸点１５０℃以上の炭化水素をＦＴ合成油全量基準で８０質量％以上含み、且つ、沸点３６０℃以上の炭化水素をＦＴ合成油全量基準で３５質量％以上含むものが好ましい。なお、ＦＴ合成油全量とは、ＦＴ合成法により生成される炭素数５以上の炭化水素の合計を意味する。 (Fractionation of raw materials containing FT synthetic oil)
First, the FT synthetic oil contained in the raw material (the material to be treated) used in the synthetic oil treatment method of the present invention is not particularly limited as long as it is produced by the FT synthesis method, but has a boiling point of 150 ° C. or higher. It is preferable to contain 80% by mass or more of hydrocarbons based on the total amount of FT synthetic oil and 35% by mass or more of hydrocarbons having a boiling point of 360 ° C. or higher based on the total amount of FT synthetic oil. The total amount of FT synthetic oil means the total of hydrocarbons having 5 or more carbon atoms produced by the FT synthesis method.

第１の蒸留塔１０では、２つのカットポイントを設定してＦＴ合成油を含む原料を分留することにより、第１のカットポイント以下の留分を軽質留分、第１のカットポイントから第２のカットポイントまでの留分を中間留分、第２のカットポイント以上の留分を塔底油（重質なワックス分）として得ることができる。本実施形態においては、第１のカットポイント及び第２のカットポイントを適宜設定することにより、沸点１５０〜３６０℃の留分の含有量が９０質量％以上である中間留分と、かかる中間留分よりも重質なワックス分とを得る。 In the first distillation column 10, by setting two cut points and fractionating the raw material containing FT synthetic oil, the fractions below the first cut point are separated from the light cut and the first cut point. The fraction up to the second cut point can be obtained as the middle fraction, and the fraction above the second cut point can be obtained as the bottom oil (heavy wax content). In the present embodiment, by appropriately setting the first cut point and the second cut point, an intermediate fraction having a boiling point of 150 to 360 ° C. with a content of 90% by mass or more, and such an intermediate distillate To obtain a heavier wax than a minute.

中間留分における沸点１５０〜３６０℃の留分の含有量は、例えば、中間留分流路Ｌ２でサンプリングしたものをガスクロマトグラフィー等、公知の方法により分析し、求めることができる。 The content of a fraction having a boiling point of 150 to 360 ° C. in the middle distillate can be obtained by analyzing a sample sampled in the middle distillate flow path L2 by a known method such as gas chromatography.

上記第１のカットポイント及び上記第２のカットポイントはそれぞれ、１３５〜１７０℃の範囲内及び３３０〜３７０℃の範囲内に設定することが好ましく、１４５〜１５５℃の範囲内及び３５５〜３６５℃の範囲内に設定することがより好ましい。 The first cut point and the second cut point are preferably set within the range of 135 to 170 ° C and within the range of 330 to 370 ° C, respectively, within the range of 145 to 155 ° C and 355 to 365 ° C. It is more preferable to set within the range.

なお、第１の蒸留塔１０におけるカットポイントの数は、２つに限定されるものではなく、上述の中間留分及びワックス分が得られるのであれば３つ以上設定することもできる。 Note that the number of cut points in the first distillation column 10 is not limited to two, and can be set to three or more as long as the above middle distillate and wax can be obtained.

（中間留分の水素化精製）
水素化精製装置２０では、第１の蒸留塔１０で得られた中間留分が水素化精製される。水素化精製装置２０としては、公知の固定床反応塔を用いることができる。本実施形態では、反応塔において、所定の水素化精製触媒を固定床の流通式反応器に充填し、この反応器に水素及び第１の蒸留塔１０で得られた中間留分を流通させることにより水素化精製を実施することが好ましい。ここでいう水素化精製には、水素化分解及び水素化異性化の双方が包含される。なお、分解とは分子量の低下を伴う化学反応を意味し、異性化とは分子量及び分子を構成する炭素数を維持したまま、炭素骨格の異なる他の化合物への転換を意味する。 (Hydrofining of middle distillate)
In the hydrorefining apparatus 20, the middle distillate obtained in the first distillation column 10 is hydrorefined. As the hydrorefining apparatus 20, a known fixed bed reaction tower can be used. In the present embodiment, in a reaction tower, a predetermined hydrorefining catalyst is filled into a fixed bed flow reactor, and hydrogen and the middle distillate obtained in the first distillation tower 10 are passed through the reactor. It is preferable to carry out hydrorefining. The hydrorefining here includes both hydrocracking and hydroisomerization. Decomposition means a chemical reaction accompanied by a decrease in molecular weight, and isomerization means conversion to another compound having a different carbon skeleton while maintaining the molecular weight and the number of carbon atoms constituting the molecule.

水素化精製触媒としては、例えば、固体酸を含んで構成される担体に、活性金属として周期律表第ＶＩＩＩ族に属する金属を担持したものが挙げられる。 Examples of the hydrorefining catalyst include a catalyst in which a solid acid-containing carrier is loaded with a metal belonging to Group VIII of the periodic table as an active metal.

好適な担体としては、超安定化Ｙ型（ＵＳＹ）ゼオライト、ＨＹゼオライト、モルデナイト及びβゼオライトなどの結晶性ゼオライト、並びに、シリカアルミナ、シリカジルコニア及びアルミナボリアなどの耐熱性を有する無定形金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成されるものが挙げられる。更に、担体は、ＵＳＹゼオライトと、シリカアルミナ、アルミナボリア及びシリカジルコニアの中から選ばれる１種類以上の固体酸とを含んで構成されるものであることがより好ましく、ＵＳＹゼオライトとシリカアルミナとを含んで構成されるものであることが更に好ましい。 Suitable supports include crystalline zeolites such as ultra-stabilized Y-type (USY) zeolite, HY zeolite, mordenite and β zeolite, and amorphous metal oxides having heat resistance such as silica alumina, silica zirconia and alumina boria. What is comprised including 1 or more types of solid acids chosen from these is mentioned. Further, the carrier is more preferably composed of USY zeolite and one or more solid acids selected from silica alumina, alumina boria and silica zirconia. More preferably, it is configured to include.

ＵＳＹゼオライトは、Ｙ型のゼオライトを水熱処理及び／又は酸処理により超安定化したものであり、Ｙ型ゼオライトが本来有する２０Å以下のミクロ細孔と呼ばれる微細細孔構造に加え、２０〜１００Åの範囲に新たな細孔が形成されている。水素化精製触媒の担体としてＵＳＹゼオライトを使用する場合、その平均粒子径に特に制限は無いが、好ましくは１．０μｍ以下、より好ましくは０．５μｍ以下である。また、ＵＳＹゼオライトにおいて、シリカ／アルミナのモル比率（アルミナに対するシリカのモル比率；以下、「シリカ／アルミナ比」という。）は１０〜２００であると好ましく、１５〜１００であるとより好ましく、２０〜６０であるとさらにより好ましい。 USY zeolite is obtained by ultra-stabilizing Y-type zeolite by hydrothermal treatment and / or acid treatment, and in addition to the fine pore structure of 20 pores or less originally possessed by Y-type zeolite, New pores are formed in the area. When USY zeolite is used as the carrier for the hydrotreating catalyst, the average particle size is not particularly limited, but is preferably 1.0 μm or less, more preferably 0.5 μm or less. In the USY zeolite, the silica / alumina molar ratio (molar ratio of silica to alumina; hereinafter referred to as “silica / alumina ratio”) is preferably 10 to 200, more preferably 15 to 100, and 20 It is still more preferable that it is -60.

また、担体は、結晶性ゼオライト０．１質量％〜８０質量％と、耐熱性を有する無定形金属酸化物０．１質量％〜６０質量％とを含んで構成されるものであることが好ましい。 Moreover, it is preferable that a support | carrier is comprised including 0.1 mass%-80 mass% of crystalline zeolite, and the amorphous metal oxide which has heat resistance 0.1 mass%-60 mass%. .

触媒担体は、上記固体酸とバインダーとを含む混合物を成形した後、焼成することにより製造することができる。固体酸の配合割合は、担体全量を基準として１〜７０質量％であることが好ましく、２〜６０質量％であることがより好ましい。また、担体がＵＳＹゼオライトを含んで構成される場合、ＵＳＹゼオライトの配合量は、担体全量を基準として０．１〜１０質量％であることが好ましく、０．５〜５質量％であることがより好ましい。更に、担体がＵＳＹゼオライト及びアルミナボリアを含んで構成される場合、ＵＳＹゼオライトとアルミナボリアとの配合比（ＵＳＹゼオライト／アルミナボリア）は、質量比で０．０３〜１であることが好ましい。また、担体がＵＳＹゼオライト及びシリカアルミナを含んで構成される場合、ＵＳＹゼオライトとシリカアルミナとの配合比（ＵＳＹゼオライト／シリカアルミナ）は、質量比で０．０３〜１であることが好ましい。 The catalyst carrier can be produced by molding a mixture containing the solid acid and the binder and then firing the mixture. The blending ratio of the solid acid is preferably 1 to 70% by mass and more preferably 2 to 60% by mass based on the total amount of the carrier. Moreover, when a support | carrier is comprised including USY zeolite, it is preferable that the compounding quantity of USY zeolite is 0.1-10 mass% on the basis of the support whole quantity, and it is 0.5-5 mass%. More preferred. Furthermore, when the carrier is configured to contain USY zeolite and alumina boria, the blending ratio of USY zeolite to alumina boria (USY zeolite / alumina boria) is preferably 0.03 to 1 in terms of mass ratio. Moreover, when a support | carrier is comprised including USY zeolite and a silica alumina, it is preferable that the compounding ratio (USY zeolite / silica alumina) of USY zeolite and a silica alumina is 0.03-1.

バインダーとしては、特に制限はないが、アルミナ、シリカ、シリカアルミナ、チタニア、マグネシアが好ましく、アルミナがより好ましい。バインダーの配合量は、担体全量を基準として２０〜９８質量％であることが好ましく、３０〜９６質量％であることがより好ましい。 The binder is not particularly limited, but alumina, silica, silica alumina, titania and magnesia are preferable, and alumina is more preferable. The blending amount of the binder is preferably 20 to 98% by mass, more preferably 30 to 96% by mass based on the total amount of the carrier.

混合物の焼成温度は、４００〜５５０℃の範囲内であることが好ましく、４７０〜５３０℃の範囲内であることがより好ましく、４９０〜５３０℃の範囲内であることが更に好ましい。 The firing temperature of the mixture is preferably in the range of 400 to 550 ° C, more preferably in the range of 470 to 530 ° C, and still more preferably in the range of 490 to 530 ° C.

第ＶＩＩＩ族の金属としては、具体的にはコバルト、ニッケル、ロジウム、パラジウム、イリジウム、白金などが挙げられる。これらのうち、ニッケル、パラジウム及び白金の中から選ばれる金属を、１種を単独で又は２種以上を組み合わせて用いることが好ましい。 Specific examples of the Group VIII metal include cobalt, nickel, rhodium, palladium, iridium, and platinum. Among these, it is preferable to use a metal selected from nickel, palladium, and platinum alone or in combination of two or more.

これらの金属は、含浸やイオン交換等の常法によって上述の担体に担持させることができる。担持する金属量は特に制限はないが、金属の合計量が担体に対して０．１〜３．０質量％であることが好ましい。 These metals can be supported on the above-mentioned carrier by a conventional method such as impregnation or ion exchange. The amount of metal to be supported is not particularly limited, but the total amount of metal is preferably 0.1 to 3.0% by mass with respect to the support.

中間留分の水素化精製は、次のような反応条件下で行うことができる。水素分圧としては、０．５〜１２ＭＰａが挙げられるが、１．０〜５．０ＭＰａが好ましい。中間留分の液空間速度（ＬＨＳＶ）としては、０．１〜１０．０ｈ^−１が挙げられるが、０．３〜３．５ｈ^−１が好ましい。水素／油比としては、特に制限はないが、５０〜１０００ＮＬ／Ｌが挙げられ、７０〜８００ＮＬ／Ｌが好ましい。 The hydrorefining of the middle distillate can be performed under the following reaction conditions. Examples of the hydrogen partial pressure include 0.5 to 12 MPa, but 1.0 to 5.0 MPa is preferable. The liquid hourly space velocity of the middle fraction (LHSV), including but 0.1~10.0h ^{^-1,} 0.3~3.5h ^-1 are preferred. Although there is no restriction | limiting in particular as hydrogen / oil ratio, 50-1000NL / L is mentioned, 70-800NL / L is preferable.

なお、本明細書において、「ＬＨＳＶ（liquid hourly space velocity；液空間速度）」とは、触媒が充填されている触媒層の容量当たりの、標準状態（２５℃、１０１３２５Ｐａ）における原料油の体積流量のことをいい、単位「ｈ^−１」は時間（ｈｏｕｒ）の逆数を示す。また、水素／油比における水素容量の単位である「ＮＬ」は、正規状態（０℃、１０１３２５Ｐａ）における水素容量（Ｌ）を示す。 In this specification, “LHSV (liquid hourly space velocity)” means the volume flow rate of the raw material oil in the standard state (25 ° C., 101325 Pa) per volume of the catalyst layer filled with the catalyst. The unit “h ⁻¹ ” indicates the reciprocal of time (hour). Further, “NL”, which is a unit of hydrogen capacity in the hydrogen / oil ratio, indicates a hydrogen capacity (L) in a normal state (0 ° C., 101325 Pa).

また、水素化精製における反応温度としては、１８０〜４００℃が挙げられるが、２００〜３７０℃が好ましく、２５０〜３５０℃がより好ましく、２８０〜３５０℃がさらにより好ましい。水素化分解における反応温度が３７０℃を越えると、ナフサ留分へ分解する副反応が増えて第１の留分及び第２の留分の収率が極度に減少するだけでなく、生成物が着色し、燃料基材としての使用が制限されるため好ましくない。また、反応温度が２００℃を下回ると、アルコール分が除去しきれずに残存するため好ましくない。 Moreover, 180-400 degreeC is mentioned as reaction temperature in hydrorefining, However, 200-370 degreeC is preferable, 250-350 degreeC is more preferable, 280-350 degreeC is still more preferable. When the reaction temperature in hydrocracking exceeds 370 ° C., side reactions that decompose into naphtha fractions increase and the yields of the first fraction and the second fraction are extremely reduced. It is unfavorable because it is colored and its use as a fuel substrate is limited. On the other hand, when the reaction temperature is lower than 200 ° C., the alcohol component cannot be completely removed and is not preferable.

また、本実施形態においては、触媒と接触後の中間留分における沸点１５０℃以下の炭化水素の含有率（質量％）の増加量が９質量％以下となるように中間留分を水素化精製することが必要である。なお、上記沸点１５０℃以下の炭化水素の含有率（質量％）の増加量とは、接触後の中間留分における沸点１５０℃以下の留分の含有率（質量％）から接触前の中間留分における沸点１５０℃以下の留分の含有率（質量％）を引いた値を意味する。また、触媒と接触後の中間留分におけるイソパラフィンの含有率（質量％）の増加量が３０質量％以上となるように中間留分を水素化精製することが好ましい。なお、上記イソパラフィンの含有率（質量％）の増加量とは、接触後の中間留分におけるイソパラフィンの含有率（質量％）から接触前の中間留分におけるイソパラフィンの含有率（質量％）を引いた値を意味する。 In this embodiment, the middle distillate is hydrorefined so that the increase in the content (mass%) of hydrocarbons having a boiling point of 150 ° C. or lower in the middle distillate after contact with the catalyst is 9% by mass or less. It is necessary to. The increase in the content (mass%) of hydrocarbons with a boiling point of 150 ° C. or lower is the middle distillate before contact from the content (mass%) of the fraction with a boiling point of 150 ° C. or lower in the middle distillate after contact. It means a value obtained by subtracting the content (mass%) of a fraction having a boiling point of 150 ° C. or less. In addition, it is preferable to hydrorefin the middle distillate so that the increase in isoparaffin content (% by mass) in the middle distillate after contact with the catalyst is 30% by mass or more. The amount of increase in the isoparaffin content (mass%) is obtained by subtracting the isoparaffin content (mass%) in the middle distillate before contact from the isoparaffin content (mass%) in the middle distillate after contact. Value.

触媒と接触前の中間留分及び接触後の中間留分における、沸点１５０℃以下の炭化水素の含有率（質量％）は、例えば、上記反応塔の入口及び出口でサンプリングしたものをガスクロマトグラフィー等、公知の方法により分析し、求めることができる。また、触媒と接触前の中間留分及び接触後の中間留分における、イソパラフィンの含有率（質量％）は、例えば、上記反応塔の入口及び出口でサンプリングしたものをガスクロマトグラフィー等、公知の方法により分析し、求めることができる。 The content (mass%) of hydrocarbons having a boiling point of 150 ° C. or lower in the middle distillate before contact with the catalyst and the middle distillate after contact is, for example, gas chromatography obtained by sampling at the inlet and outlet of the reaction tower. Etc., and can be determined by a known method. Further, the content (mass%) of isoparaffin in the middle distillate before contact with the catalyst and the middle distillate after contact is known, for example, by gas chromatography using samples sampled at the inlet and outlet of the reaction tower. It can be analyzed and determined by the method.

なお、本実施形態の合成油の処理方法においては、上述の方法により、触媒と接触前の中間留分及び接触後の中間留分における各炭素数の炭化水素の含有率を確認しながら、触媒と接触後の中間留分における沸点１５０℃以下の炭化水素の含有率（質量％）の増加量が９質量％以下となる反応条件を予め決定し、この条件で水素化精製を行ってもよい。好ましくは、中間留分における沸点１５０℃以下の炭化水素の含有率（質量％）の増加量が９質量％以下となり、且つ、イソパラフィンの含有率（質量％）の増加量が３０質量％以上となる反応条件を予め決定し、この条件で水素化精製を行ってもよい。 In the synthetic oil treatment method of the present embodiment, the above-described method is used to confirm the content of hydrocarbons of each carbon number in the middle distillate before contact with the catalyst and the middle distillate after contact with the catalyst. The reaction conditions in which the increase in the content (mass%) of hydrocarbons having a boiling point of 150 ° C. or less in the middle distillate after contacting with the catalyst is determined to be 9 mass% or less, and hydrorefining may be performed under these conditions. . Preferably, the increase in the content (mass%) of hydrocarbons having a boiling point of 150 ° C. or less in the middle distillate is 9 mass% or less, and the increase in the content (mass%) of isoparaffin is 30 mass% or more. The reaction conditions may be determined in advance, and the hydrorefining may be performed under these conditions.

（重質なワックス分の水素化分解）
水素化分解装置３０では、第１の蒸留塔１０で得られた重質なワックス分が水素化分解される。水素化分解装置３０としては、公知の固定床反応塔を用いることができる。本実施形態においては、本実施形態では、反応塔において、所定の水素化分解触媒を固定床の流通式反応器に充填し、この反応器に水素及び第１の蒸留塔１０で得られたワックス分を流通させることにより水素化分解を実施することが好ましい。なお、ワックス分の水素化分解は、分子量の低下を伴う化学反応が主に進行するものであるが、かかる水素化分解には水素化異性化も包含される。 (Hydrolysis of heavy wax)
In the hydrocracking apparatus 30, the heavy wax content obtained in the first distillation column 10 is hydrocracked. As the hydrocracking apparatus 30, a known fixed bed reaction tower can be used. In the present embodiment, in this embodiment, a predetermined hydrocracking catalyst is charged in a fixed bed flow reactor in the reaction tower, and hydrogen and the wax obtained in the first distillation tower 10 are filled in the reactor. It is preferable to carry out the hydrocracking by circulating the fraction. The hydrocracking of the wax mainly involves a chemical reaction accompanied by a decrease in molecular weight. Such hydrocracking includes hydroisomerization.

水素化分解触媒としては、例えば、固体酸を含んで構成される担体に、活性金属として周期律表第ＶＩＩＩ族に属する金属を担持したものが挙げられる。 Examples of the hydrocracking catalyst include a catalyst in which a solid acid-containing carrier is loaded with a metal belonging to Group VIII of the periodic table as an active metal.

重質なワックス分の水素化分解は、次のような反応条件下で行うことができる。水素分圧としては、０．５〜１２ＭＰａが挙げられるが、１．０〜５．０ＭＰａが好ましい。中間留分の液空間速度（ＬＨＳＶ）としては、０．１〜１０．０ｈ^−１が挙げられるが、０．３〜３．５ｈ^−１が好ましい。水素／油比としては、特に制限はないが、５０〜１０００ＮＬ／Ｌが挙げられ、７０〜８００ＮＬ／Ｌが好ましい。 The hydrocracking of heavy wax can be performed under the following reaction conditions. Examples of the hydrogen partial pressure include 0.5 to 12 MPa, but 1.0 to 5.0 MPa is preferable. The liquid hourly space velocity of the middle fraction (LHSV), including but 0.1~10.0h ^{^-1,} 0.3~3.5h ^-1 are preferred. Although there is no restriction | limiting in particular as hydrogen / oil ratio, 50-1000NL / L is mentioned, 70-800NL / L is preferable.

また、本実施形態においては、触媒と接触後のワックス分における沸点３６０℃以下の留分の含有量が４５〜８５質量％となるようにワックス分を水素化分解することが好ましい。この場合、下記式（１）で定義される分解率が４５〜８５質量％となるようにワックス分を水素化分解することができる。なお、式（１）で示される分解率は、例えば、ワックス分の水素化分解生成物（生成油及び生成ガス）のガスクロマトグラフィー測定の結果から算出することができる。

In this embodiment, it is preferable to hydrocrack the wax so that the content of the fraction having a boiling point of 360 ° C. or less in the wax after contact with the catalyst is 45 to 85% by mass. In this case, the wax can be hydrocracked so that the decomposition rate defined by the following formula (1) is 45 to 85% by mass. In addition, the decomposition rate shown by Formula (1) is computable from the result of the gas chromatography measurement of the hydrocracking product (product oil and product gas) of a wax part, for example.

触媒と接触前のワックス分及び接触後のワックス分における、沸点３６０℃以下の留分の含有量は、例えば、上記反応塔の入口及び出口でサンプリングしたものをガスクロマトグラフィー等、公知の方法により分析し、求めることができる。 The content of the fraction having a boiling point of 360 ° C. or lower in the wax content before contact with the catalyst and the wax content after contact is measured by a known method such as gas chromatography using samples sampled at the inlet and outlet of the reaction tower. Can be analyzed and determined.

なお、本実施形態の合成油の処理方法においては、上述の方法により、接触後のワックス分における沸点３６０℃以下の留分の含有量が４５〜８５質量％となる反応条件を予め決定し、この条件で水素化分解を行ってもよい。 In the synthetic oil treatment method of the present embodiment, the above-described method is used to determine in advance reaction conditions in which the content of the fraction having a boiling point of 360 ° C. or less in the wax content after contact is 45 to 85% by mass, Hydrogenolysis may be performed under these conditions.

（水素化精製物の分留）
水素化精製装置２０から流出する水素化精製後の中間留分（以下、「水素化精製物」という場合もある）は、気液分離槽を経てから第２の蒸留塔４０に移送され、所定の留分へと分留される。 (Fractionation of hydrofinished product)
The middle distillate after hydrorefining flowing out from the hydrotreating apparatus 20 (hereinafter sometimes referred to as “hydropurified product”) is transferred to the second distillation column 40 after passing through the gas-liquid separation tank, Is fractionated into

気液分離槽では、上記の水素化精製物が、例えば、未反応水素ガスや炭素数４以下の炭化水素からなる軽質炭化水素ガスと、炭素数５以上の炭化水素からなる液状の炭化水素組成油とに分離される。この場合、液状の炭化水素組成油が、水素化精製物として第２の蒸留塔４０に移送される。気液分離槽としては、公知のものを使用できる。 In the gas-liquid separation tank, the hydrorefined product is composed of, for example, a light hydrocarbon gas composed of unreacted hydrogen gas or a hydrocarbon having 4 or less carbon atoms, and a liquid hydrocarbon composition composed of a hydrocarbon having 5 or more carbon atoms. Separated into oil. In this case, the liquid hydrocarbon composition oil is transferred to the second distillation column 40 as a hydrorefined product. A well-known thing can be used as a gas-liquid separation tank.

第２の蒸留塔４０では、２つのカットポイントを設定して水素化精製物を分留することにより、第１のカットポイント以下の留分をナフサ留分、第１のカットポイントから第２のカットポイントまでの留分を軽質中間留分（第１の留分）、第２のカットポイント以上の留分を重質中間留分（第２の留分）として得ることができる。本実施形態においては、軽質中間留分（第１の留分）は、沸点１５０〜２５０℃の留分の含有量が９０質量％以上となるように分留されたものであり、かかる軽質中間留分（第１の留分）が発明に係る灯油煙点向上剤用炭化水素油として流路Ｌ６から取り出される。また、流路Ｌ７から取り出される重質中間留分（第２の留分）は後述する第３の留分と混合される。そして、この混合物が本発明に係るディーゼル燃料基材用炭化水素油として流路Ｌ１３から取り出される。 In the second distillation column 40, by setting two cut points and fractionating the hydrofinished product, the fraction below the first cut point is divided into the naphtha fraction, the first cut point to the second cut point. The fraction up to the cut point can be obtained as a light middle fraction (first fraction), and the fraction above the second cut point can be obtained as a heavy middle fraction (second fraction). In the present embodiment, the light middle distillate (first distillate) is fractionated so that the content of the fraction having a boiling point of 150 to 250 ° C. is 90% by mass or more. A fraction (first fraction) is taken out from the flow path L6 as a hydrocarbon oil for a kerosene smoke point improver according to the invention. Further, the heavy middle distillate (second distillate) taken out from the flow path L7 is mixed with a third distillate to be described later. And this mixture is taken out from the flow path L13 as the hydrocarbon oil for diesel fuel base materials which concerns on this invention.

上記第１のカットポイント及び上記第２のカットポイントはそれぞれ、１３５〜１７０℃の範囲内及び２１０〜２６５℃の範囲内に設定することが好ましく、１４５〜１５５℃の範囲内及び２３０〜２６０℃の範囲内に設定することがより好ましい。 The first cut point and the second cut point are preferably set in the range of 135 to 170 ° C and in the range of 210 to 265 ° C, respectively, in the range of 145 to 155 ° C and 230 to 260 ° C. It is more preferable to set within the range.

なお、第２の蒸留塔４０におけるカットポイントの数は、２つに限定されるものではなく、上述の本発明に係る留分が得られるのであれば３つ以上設定することもできる。 Note that the number of cut points in the second distillation column 40 is not limited to two, and can be set to three or more as long as the above-described fraction according to the present invention is obtained.

（水素化分解生成物の分留）
水素化分解装置３０から流出する水素化分解後のワックス分（以下、「水素化分解生成物」という場合もある）は、気液分離槽を経てから第３の蒸留塔５０に移送され、所定の留分へと分留される。 (Fractionation of hydrocracking products)
The hydrocracked wax component flowing out from the hydrocracking apparatus 30 (hereinafter sometimes referred to as “hydrocracking product”) is transferred to the third distillation column 50 after passing through the gas-liquid separation tank, Is fractionated into

気液分離槽では、上記の水素化分解生成物が、例えば、未反応水素ガスや炭素数４以下の炭化水素からなる軽質炭化水素ガスと、炭素数５以上の炭化水素からなる液状の炭化水素組成油とに分離される。この場合、液状の炭化水素組成油が、水素化分解生成物として第３の蒸留塔５０に移送される。気液分離槽としては、公知のものを使用できる。 In the gas-liquid separation tank, the hydrocracking product is, for example, a light hydrocarbon gas composed of unreacted hydrogen gas or a hydrocarbon having 4 or less carbon atoms, and a liquid hydrocarbon composed of a hydrocarbon having 5 or more carbon atoms. Separated into composition oils. In this case, the liquid hydrocarbon composition oil is transferred to the third distillation column 50 as a hydrocracking product. A well-known thing can be used as a gas-liquid separation tank.

第３の蒸留塔５０では、２つのカットポイントを設定して水素化精製物を分留することにより、第１のカットポイント以下の留分を分解ナフサ留分、第１のカットポイントから第２のカットポイントまでの留分を分解中間留分（第３の留分）、第２のカットポイント以上の留分を塔底油（未分解ワックス分）として得ることができる。本実施形態においては、分解中間留分（第３の留分）は、沸点１５０〜３６０℃の留分の含有量が９０質量％以上となるように分留されたものであり、流路Ｌ１０から取り出される分解中間留分（第３の留分）は先に述べた重質中間留分（第２の留分）と混合される。そして、この混合物が本発明に係るディーゼル燃料基材用炭化水素油として流路Ｌ１３から取り出される。 In the third distillation column 50, by setting two cut points and fractionating the hydrorefined product, the fractions below the first cut point are separated from the cracked naphtha fraction, from the first cut point to the second. The fraction up to the first cut point can be obtained as cracking middle fraction (third fraction), and the fraction above the second cut point can be obtained as tower bottom oil (undecomposed wax fraction). In the present embodiment, the cracking middle fraction (third fraction) is fractionated so that the content of the fraction having a boiling point of 150 to 360 ° C. is 90% by mass or more, and the flow path L10. The cracking middle distillate (third fraction) taken out from is mixed with the heavy middle distillate (second fraction) described above. And this mixture is taken out from the flow path L13 as the hydrocarbon oil for diesel fuel base materials which concerns on this invention.

上記第１のカットポイント及び上記第２のカットポイントはそれぞれ、１３５〜１７０℃の範囲内及び３４５〜３７５℃の範囲内に設定することが好ましく、１４５〜１５５℃の範囲内及び３５５〜３６５℃の範囲内に設定することがより好ましい。 The first cut point and the second cut point are preferably set within the range of 135 to 170 ° C and the range of 345 to 375 ° C, respectively, within the range of 145 to 155 ° C and 355 to 365 ° C. It is more preferable to set within the range.

なお、第３の蒸留塔５０におけるカットポイントの数は、２つに限定されるものではなく、上述の本発明に係る分解中間留分（第３の留分）が得られるのであれば３つ以上設定することもできる。 Note that the number of cut points in the third distillation column 50 is not limited to two, but three if the cracking middle distillate (third distillate) according to the present invention is obtained. The above can also be set.

また、上記で得られる分解中間留分（第３の留分）よりも重質な未分解ワックス分の一部または全部は、必要に応じて循環流路Ｌ１１を通じて水素化分解装置３０に供給され水素化分解される。 In addition, a part or all of the undecomposed wax that is heavier than the cracked middle distillate (third fraction) obtained above is supplied to the hydrocracking apparatus 30 through the circulation flow path L11 as necessary. Hydrocracked.

（製品としての供給）
上記第２の蒸留塔４０で得られた軽質中間留分（第１の留分）は、例えば、そのまま製品タンクに貯留され、灯油煙点向上剤用炭化水素油として供される。 (Supply as a product)
The light middle distillate (first distillate) obtained in the second distillation tower 40 is, for example, stored in a product tank as it is and used as a hydrocarbon oil for a kerosene smoke point improver.

また、図１に示す炭化水素油製造装置１００においては、上記第２の蒸留塔４０で得られた重質中間留分（第２の留分）、及び、上記第３の蒸留塔５０で得られた分解中間留分（第３の留分）が流路Ｌ１３で混合されるが、それぞれ異なる製品タンクに貯留された後に適宜混合されるか、又は一つの製品タンク内で混合された後、ディーゼル燃料基材用炭化水素油として供されてもよい。 In the hydrocarbon oil production apparatus 100 shown in FIG. 1, the heavy middle distillate (second fraction) obtained in the second distillation column 40 and the third distillation column 50 are obtained. The obtained cracking middle distillate (third distillate) is mixed in the flow path L13, but is mixed appropriately after being stored in different product tanks, or after being mixed in one product tank, You may use as hydrocarbon oil for diesel fuel base materials.

また、重質中間留分（第２の留分）及び分解中間留分（第３の留分）を混合してディーゼル燃料基材を製造する際、必要に応じて燃料基材の流動点を更に低下させるために、３０℃における動粘度が２．５ｍｍ^２／ｓ以上に維持される条件で軽質中間留分（第１の留分）を適量混合してもかまわない。 Moreover, when producing a diesel fuel base material by mixing a heavy middle distillate (second fraction) and a cracking middle distillate (third fraction), the pour point of the fuel base is set as necessary. In order to further reduce, the light middle distillate (first fraction) may be mixed in an appropriate amount under the condition that the kinematic viscosity at 30 ° C. is maintained at 2.5 mm ² / s or more.

上述した本発明の合成油の処理方法によれば、流動点が−７．５℃以下であり、且つ、３０℃での動粘度が２．５ｍｍ^２／ｓ以上であるディーゼル燃料基材用炭化水素油と、煙点が４４ｍｍ以上である灯油煙点向上剤用炭化水素油との双方を高収率で得ることができる。得られたディーゼル燃料基材用炭化水素油は、例えば、環境低負荷型ディーゼル燃料の基材として好適に利用される。また、得られた灯油煙点向上剤用炭化水素油は、煙点２２ｍｍ以下の劣質な灯油に配合したときの煙点向上効果が配合割合（配合後の灯油全量基準）１０質量％当たりの換算値で２．３ｍｍ以上を達成することができることから、より低コストで灯油の増産を図ることが可能となる。 According to the method for treating a synthetic oil of the present invention described above, carbonization for diesel fuel base material having a pour point of −7.5 ° C. or lower and a kinematic viscosity at 30 ° C. of 2.5 mm ² / s or higher. Both hydrogen oil and hydrocarbon oil for kerosene smoke point improver having a smoke point of 44 mm or more can be obtained in high yield. The obtained hydrocarbon fuel for diesel fuel base material is suitably used, for example, as a base material for environmentally low load diesel fuel. In addition, the obtained hydrocarbon oil for kerosene smoke point improver has a smoke point improving effect when blended with inferior kerosene having a smoke point of 22 mm or less in terms of blending ratio (based on the total amount of kerosene after blending) per 10% by mass. Since the value of 2.3 mm or more can be achieved, it becomes possible to increase the production of kerosene at a lower cost.

以下、実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

＜触媒の調整＞
（触媒１）
平均粒子径１．１μｍのＵＳＹゼオライト（シリカ／アルミナのモル比：３７）、シリカアルミナ（シリカ／アルミナのモル比：１４）及びアルミナバインダーを重量比３：５７：４０で混合混練し、これを直径約１．６ｍｍ、長さ約４ｍｍの円柱状に成型した後、５００℃で１時間焼成し担体を得た。この担体に、塩化白金酸水溶液を含浸し、白金を担持した。これを１２０℃で３時間乾燥し、次いで５００℃で１時間焼成することで触媒Ａを得た。なお、白金の担持量は、担体に対して０．８質量％であった。 <Catalyst adjustment>
(Catalyst 1)
USY zeolite having an average particle diameter of 1.1 μm (silica / alumina molar ratio: 37), silica alumina (silica / alumina molar ratio: 14) and alumina binder were mixed and kneaded at a weight ratio of 3:57:40. After forming into a cylindrical shape having a diameter of about 1.6 mm and a length of about 4 mm, the carrier was obtained by firing at 500 ° C. for 1 hour. This carrier was impregnated with an aqueous chloroplatinic acid solution to carry platinum. This was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 1 hour to obtain Catalyst A. The supported amount of platinum was 0.8% by mass with respect to the carrier.

＜ＦＴ合成油の処理＞
（実施例１）
（ＦＴ合成油の分留）
ＦＴ合成法により得られた生成油（ＦＴ合成油）（沸点１５０℃以上の炭化水素の含有量：８２質量％、沸点３６０℃以上の炭化水素の含有量：４１質量％、いずれの含有量もＦＴ合成油全量（炭素数５以上の炭化水素の合計）基準）を蒸留塔で、沸点１５０℃以下の軽質留分と、沸点１５０〜３６０℃のＦＴ中間留分（沸点１５０〜３６０℃の炭化水素の含有量１００質量％、沸点３００〜３６０℃の炭化水素の含有量２５質量％、沸点１５０℃以下の炭化水素含有量０質量％）と、塔底残渣重質ＦＴワックス分（沸点３６０℃以上の留分に相当）とに分離した。 <Treatment of FT synthetic oil>
Example 1
(Fractionation of FT synthetic oil)
Product oil (FT synthetic oil) obtained by the FT synthesis method (content of hydrocarbons having a boiling point of 150 ° C. or higher: 82 mass%, content of hydrocarbons having a boiling point of 360 ° C. or higher: 41 mass%, both contents The total amount of FT synthetic oil (total of hydrocarbons having 5 or more carbon atoms) is distilled in a distillation column, a light fraction having a boiling point of 150 ° C. or less, and an FT middle fraction having a boiling point of 150 to 360 ° C. (carbonization having a boiling point of 150 to 360 ° C.). 100% by mass of hydrogen, 25% by mass of hydrocarbons having a boiling point of 300 to 360 ° C., 0% by mass of hydrocarbons having a boiling point of 150 ° C. or less, and a heavy bottom FT wax content (boiling point 360 ° C.) Equivalent to the above fraction).

（ＦＴ中間留分の水素化精製）
触媒Ａ（１００ｍｌ）を固定床の流通式反応器に充填し、上記で得られたＦＴ中間留分を反応塔の塔頂より２００ｍｌ／ｈの速度で供給して、水素気流下、下記の反応条件で水素化精製した。 (Hydrogenation of FT middle distillate)
Catalyst A (100 ml) was charged into a fixed bed flow reactor, and the FT middle distillate obtained above was supplied at a rate of 200 ml / h from the top of the reaction tower, and the following reaction was conducted under a hydrogen stream. Hydrorefining under conditions.

すなわち、中間留分に対して水素／油比３４０ＮＬ／Ｌで水素を塔頂より供給し、反応塔圧力が入口圧３．０ＭＰａで一定となるように背圧弁を調節し、この条件にて水素化精製後の中間留分（水素化精製物）中の沸点１５０℃以下の炭化水素の含有率が７質量％となるように反応温度（触媒床重量平均温度）を調節した。このときの反応温度は３１１℃であった。なお、上記含有率は、水素化精製後の中間留分（水素化精製物）のガスクロマトグラフィー測定により確認した。 That is, hydrogen was supplied from the top of the middle distillate at a hydrogen / oil ratio of 340 NL / L, and the back pressure valve was adjusted so that the reaction tower pressure was constant at an inlet pressure of 3.0 MPa. The reaction temperature (catalyst bed weight average temperature) was adjusted so that the content of hydrocarbons having a boiling point of 150 ° C. or lower in the middle distillate (hydropurified product) after hydrorefining was 7% by mass. The reaction temperature at this time was 311 degreeC. In addition, the said content rate was confirmed by the gas chromatography measurement of the middle distillate (hydrogenation refinement | purification thing) after hydrorefining.

（ＦＴワックス分の水素化分解）
一方、別の反応塔において、触媒Ａ（１００ｍｌ）を固定床の流通式反応器に充填し、上記で得られた塔底残渣重質ＦＴワックス分を反応塔の塔頂より２００ｍｌ／ｈの速度で供給して、水素気流下、下記の反応条件で水素化分解した。 (Hydrolysis of FT wax)
On the other hand, in another reaction tower, catalyst A (100 ml) was charged into a fixed bed flow reactor, and the heavy residue FT wax content obtained above was fed at a rate of 200 ml / h from the top of the reaction tower. And hydrocracked under the following reaction conditions under a hydrogen stream.

すなわち、ワックス分に対して水素／油比６８０ＮＬ／Ｌで水素を塔頂より供給し、反応塔圧力が入口圧４．０ＭＰａで一定となるように背圧弁を調節し、この条件にて水素化分解後のワックス分（水素化分解生成物）中の沸点３６０℃以下の留分の含有量が約７０質量％（上記式（１）で定義される分解率が約７０質量％）となるように反応温度（触媒床重量平均温度）を調節した。このときの反応温度は３２６℃であった。なお、上記含有量（分解率）は、水素化分解後のワックス分（水素化分解生成物）をガスクロマトグラフィー測定し、その蒸留性状を分析することにより確認した。 That is, hydrogen was supplied from the top of the column at a hydrogen / oil ratio of 680 NL / L with respect to the wax content, and the back pressure valve was adjusted so that the reaction column pressure was constant at an inlet pressure of 4.0 MPa, and hydrogenation was performed under these conditions. The content of the fraction having a boiling point of 360 ° C. or less in the wax component (hydrocracking product) after decomposition is about 70% by mass (the decomposition rate defined by the above formula (1) is about 70% by mass). The reaction temperature (catalyst bed weight average temperature) was adjusted. The reaction temperature at this time was 326 degreeC. The content (decomposition rate) was confirmed by measuring the wax content (hydrocracking product) after hydrocracking by gas chromatography and analyzing its distillation properties.

（水素化精製物の分留）
上記で得られたＦＴ中間留分の水素化精製物を蒸留塔で分留し、沸点１５０〜２５０℃の留分を軽質中間留分として得、沸点２５０℃以上の留分を重質中間留分として得た。 (Fractionation of hydrofinished product)
The hydrotreated product of the FT middle distillate obtained above is fractionated in a distillation column to obtain a fraction having a boiling point of 150 to 250 ° C. as a light middle distillate, and a fraction having a boiling point of 250 ° C. or more is obtained as a heavy middle distillate. Obtained as minutes.

（水素化分解生成物の分留）
上記で得られたＦＴワックス分の水素化分解生成物を蒸留塔で分留し、沸点１５０〜３６０℃の留分を分解中間留分として得た。 (Fractionation of hydrocracking products)
The hydrocracked product of the FT wax obtained above was fractionated with a distillation column, and a fraction having a boiling point of 150 to 360 ° C. was obtained as a cracking middle fraction.

（灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油の調製）
上記で得られた軽質中間留分全量を実施例１の灯油煙点向上剤用炭化水素油として得た。また、上記で得られた重質中間留分と分解中間留分とをそれぞれの得率どおりの割合で混合し、この混合物を実施例１のディーゼル燃料基材用炭化水素油として得た。 (Preparation of hydrocarbon oil for kerosene smoke point improver and diesel fuel base material)
The total amount of the light middle distillate obtained above was obtained as the hydrocarbon oil for kerosene smoke point improver of Example 1. Moreover, the heavy middle distillate obtained above and the cracking middle distillate were mixed in proportions according to their respective yields, and this mixture was obtained as the hydrocarbon oil for diesel fuel base material of Example 1.

ＦＴ合成油の分留で得られたＦＴ中間留分及びＦＴワックス分の得率、ＦＴ中間留分の水素化精製により得られた軽質中間留分及び重質中間留分の得率、ＦＴワックス分の水素化分解により得られた分解中間留分の得率、並びに、灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油の得率を表１に示す。また、水素化精製におけるイソパラフィンの含有率（質量％）の増加量（質量％）（［水素化精製後のＦＴ中間留分におけるイソパラフィンの含有率（質量％）］−［水素化精製前のＦＴ中間留分におけるイソパラフィンの含有率（質量％）］）表１に示す。 FT middle fraction and FT wax content obtained by fractionation of FT synthetic oil, light middle and heavy middle fraction yield obtained by hydrorefining of FT middle distillate, FT wax Table 1 shows the yield of cracked middle distillate obtained by hydrocracking of water, and the yield of hydrocarbon oil for kerosene smoke point improver and hydrocarbon oil for diesel fuel base material. Further, an increase amount (mass%) of isoparaffin content (mass%) in hydrorefining ([isoparaffin content (mass%) in FT middle distillate after hydrorefining]]-[FT before hydrorefining The content of isoparaffin in the middle distillate (mass%)]) is shown in Table 1.

（実施例２）
ＦＴワックス分の水素化分解において、処理後のワックス分（水素化分解生成物）中の沸点３６０℃以下の留分の含有量が約４６質量％（上記式（１）で定義される分解率が約４６質量％）となるように反応温度（触媒床重量平均温度）を調節したこと以外は実施例１と同様にして、実施例２の灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を得た。なお、反応温度は３１５℃であった。 (Example 2)
In the hydrocracking of the FT wax, the content of the fraction having a boiling point of 360 ° C. or less in the treated wax (hydrocracking product) is about 46% by mass (decomposition rate defined by the above formula (1)) Hydrocarbon oil for kerosene smoke point improver and diesel fuel base of Example 2 except that the reaction temperature (catalyst bed weight average temperature) was adjusted to be about 46% by mass). A hydrocarbon oil for wood was obtained. The reaction temperature was 315 ° C.

ＦＴ合成油の分留で得られたＦＴ中間留分及びＦＴワックス分の得率、ＦＴ中間留分の水素化精製により得られた軽質中間留分及び重質中間留分の得率、ＦＴワックス分の水素化分解により得られた分解中間留分の得率、灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油の得率、並びに、水素化精製におけるイソパラフィンの含有率（質量％）の増加量（質量％）を表１に示す。 FT middle fraction and FT wax content obtained by fractionation of FT synthetic oil, light middle and heavy middle fraction yield obtained by hydrorefining of FT middle distillate, FT wax Yield of cracking middle distillate obtained by hydrocracking of water, yield of hydrocarbon oil for kerosene smoke point improver and hydrocarbon oil for diesel fuel base, and content of isoparaffin in hydrorefining ( Table 1 shows an increase (mass%) of (mass%).

（実施例３）
ＦＴワックス分の水素化分解において、処理後のワックス分（水素化分解生成物）中の沸点３６０℃以下の留分の含有量が約８４質量％（上記式（１）で定義される分解率が約８４質量％）となるように反応温度（触媒床重量平均温度）を調節したこと以外は実施例１と同様にして、実施例３の灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を得た。なお、反応温度は３３１℃であった。 Example 3
In the hydrocracking of FT wax, the content of the fraction having a boiling point of 360 ° C. or less in the treated wax (hydrocracking product) is about 84% by mass (decomposition rate defined by the above formula (1)) Hydrocarbon oil for kerosene smoke point improver and diesel fuel base of Example 3 except that the reaction temperature (catalyst bed weight average temperature) was adjusted so as to be about 84% by mass). A hydrocarbon oil for wood was obtained. The reaction temperature was 331 ° C.

（実施例４）
ＦＴワックス分の水素化分解において、未分解ワックス分の循環処理を想定し、下記の条件で水素化分解を行ったこと以外は実施例１と同様にして、実施例４の灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を得た。 Example 4
In the hydrocracking of FT wax, the kerosene smoke point improver of Example 4 was used in the same manner as in Example 1 except that the hydrocracking was performed under the following conditions, assuming cyclic treatment of the undecomposed wax. The hydrocarbon oil for diesel fuel and the hydrocarbon oil for diesel fuel base material were obtained.

すなわち、水素化分解に供されるＦＴワックス分として、ＦＴワックス分とＦＴワックス分の水素化分解で得られた沸点３６０℃以上のワックス分（未分解ワックス分）とを質量比１００：（１００−８４）で混合したものを用意した。この混合物を、反応塔の塔頂より１１６ｍｌ／ｈの速度で供給して、水素気流下、混合物に対して水素／油比６８０ＮＬ／Ｌで水素を塔頂より供給し、反応塔圧力が入口圧４．０ＭＰａで一定となるように背圧弁を調節し、この条件にて水素化分解後の混合物（水素化分解生成物）中の沸点３６０℃以下の留分の含有量が約８４質量％（上記式（１）で定義される分解率が約８４質量％）となるように反応温度（触媒床重量平均温度）を調節した。このときの反応温度は３３４℃であった。 That is, as the FT wax component to be subjected to hydrocracking, the mass ratio of the FT wax component and the wax component having a boiling point of 360 ° C. or higher (undecomposed wax component) obtained by hydrogenolysis of the FT wax component is 100: -84) was prepared. This mixture was supplied from the top of the reaction tower at a rate of 116 ml / h, and hydrogen was supplied from the top of the tower at a hydrogen / oil ratio of 680 NL / L to the mixture under a hydrogen stream. The back pressure valve was adjusted so as to be constant at 4.0 MPa, and the content of the fraction having a boiling point of 360 ° C. or less in the mixture after hydrocracking (hydrocracking product) under this condition was about 84% by mass ( The reaction temperature (catalyst bed weight average temperature) was adjusted so that the decomposition rate defined by the above formula (1) was about 84% by mass. The reaction temperature at this time was 334 degreeC.

（実施例５）
ＦＴワックス分の水素化分解において、未分解ワックス分の循環処理を想定し、下記の条件で水素化分解を行ったこと以外は実施例１と同様にして、実施例５の灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を得た。 (Example 5)
In the hydrocracking of the FT wax, the kerosene smoke point improver of Example 5 was used in the same manner as in Example 1 except that the hydrocracking was performed under the following conditions, assuming cyclic treatment of the undecomposed wax. The hydrocarbon oil for diesel fuel and the hydrocarbon oil for diesel fuel base material were obtained.

すなわち、水素化分解に供されるＦＴワックス分として、ＦＴワックス分とＦＴワックス分の水素化分解で得られた沸点３６０℃以上のワックス分（未分解ワックス分）とを質量比１００：（１００−４６）で混合したものを用意した。この混合物を、反応塔の塔頂より１５４ｍｌ／ｈの速度で供給して、水素気流下、混合物に対して水素／油比６８０ＮＬ／Ｌで水素を塔頂より供給し、反応塔圧力が入口圧４．０ＭＰａで一定となるように背圧弁を調節し、この条件にて水素化分解後の混合物（水素化分解生成物）中の沸点３６０℃以下の留分の含有量が約４６質量％（上記式（１）で定義される分解率が約４６質量％）となるように反応温度（触媒床重量平均温度）を調節した。このときの反応温度は３１９℃であった。 That is, as the FT wax component to be subjected to hydrocracking, the mass ratio of the FT wax component and the wax component having a boiling point of 360 ° C. or higher (undecomposed wax component) obtained by hydrogenolysis of the FT wax component is 100: What was mixed in -46) was prepared. This mixture was supplied from the top of the reaction tower at a rate of 154 ml / h, and hydrogen was supplied from the top of the tower at a hydrogen / oil ratio of 680 NL / L to the mixture under a hydrogen stream. The back pressure valve was adjusted to be constant at 4.0 MPa, and the content of the fraction having a boiling point of 360 ° C. or less in the mixture after hydrocracking (hydrocracking product) under this condition was about 46% by mass ( The reaction temperature (catalyst bed weight average temperature) was adjusted so that the decomposition rate defined by the above formula (1) was about 46 mass%. The reaction temperature at this time was 319 degreeC.

（比較例１）
ＦＴ中間留分の水素化精製において、水素化精製後の中間留分（水素化精製物）中の沸点１５０℃以下の炭化水素の含有率が１５質量％となるように反応温度（触媒床重量平均温度）を調節したこと以外は実施例１と同様にして、比較例１の灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油を得た。なお、反応温度は３２１℃であった。 (Comparative Example 1)
In hydrorefining of the FT middle distillate, the reaction temperature (catalyst bed weight) was adjusted so that the content of hydrocarbons having a boiling point of 150 ° C. or lower in the middle distillate (hydropurified product) after hydrorefining was 15 mass%. A hydrocarbon oil for a kerosene smoke point improver and a hydrocarbon oil for a diesel fuel base material of Comparative Example 1 were obtained in the same manner as in Example 1 except that the average temperature was adjusted. The reaction temperature was 321 ° C.

（比較例２）
ＦＴ中間留分の水素化精製及びＦＴワックス分の水素化分解まで実施例１と同様に行った。次に、ＦＴ中間留分の水素化精製物とＦＴワックス分の水素化分解生成物とを混合し、この混合物を蒸留塔で分留し、沸点１５０〜２５０℃の混合軽質中間留分と、沸点２５０〜３６０℃の混合重質中間留分とを得た。なお、ＦＴ合成油の沸点１５０℃以上の留分に対する混合軽質中間留分の得率は３５質量％であり、ＦＴ合成油の沸点１５０℃以上の留分に対する混合重質中間留分の得率は３７質量％であった。 (Comparative Example 2)
The same procedure as in Example 1 was performed until hydrorefining of the FT middle distillate and hydrocracking of the FT wax. Next, the hydrotreated product of the FT middle distillate and the hydrocracked product of the FT wax are mixed, the mixture is fractionated in a distillation column, and a mixed light middle distillate having a boiling point of 150 to 250 ° C., A mixed heavy middle distillate having a boiling point of 250 to 360 ° C. was obtained. In addition, the yield of the mixed light middle distillate with respect to the fraction with a boiling point of 150 ° C. or higher of the FT synthetic oil is 35% by mass, and the yield of the mixed heavy middle distillate with respect to the fraction with a boiling point of 150 ° C. or higher of the FT synthetic oil. Was 37 mass%.

上記で得られた混合軽質中間留分全量を比較例２の灯油煙点向上剤用炭化水素油として得た。また、上記で得られた混合重質中間留分全量を比較例２のディーゼル燃料基材用炭化水素油として得た。 The total amount of the mixed light middle distillate obtained above was obtained as a hydrocarbon oil for kerosene smoke point improver of Comparative Example 2. Moreover, the mixed heavy middle distillate whole quantity obtained above was obtained as the hydrocarbon oil for diesel fuel base materials of the comparative example 2.

ＦＴ合成油の分留で得られたＦＴ中間留分及びＦＴワックス分の得率、並びに、灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油の得率を表１に示す。 Table 1 shows the yield of FT middle distillate and FT wax obtained by fractionation of FT synthetic oil, and the yield of hydrocarbon oil for kerosene smoke point improver and hydrocarbon oil for diesel fuel base material. .

（灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油の評価）
実施例１〜５、比較例１〜２で得られた灯油煙点向上剤用炭化水素油及びディーゼル燃料基材用炭化水素油について、下記の評価を行った。得られた結果を表２に示す。 (Evaluation of hydrocarbon oil for kerosene smoke point improver and hydrocarbon oil for diesel fuel base)
The following evaluation was performed about the hydrocarbon oil for kerosene smoke point improvers obtained in Examples 1-5 and Comparative Examples 1-2, and the hydrocarbon oil for diesel fuel base materials. The obtained results are shown in Table 2.

＜灯油煙点向上剤用炭化水素油の煙点の測定＞
得られた灯油煙点向上剤用炭化水素油について、ＪＩＳＫ２５３７試験法に従って煙点（ｍｍ）を測定した。 <Measurement of smoke point of hydrocarbon oil for kerosene smoke point improver>
About the obtained hydrocarbon oil for kerosene smoke point improvers, smoke point (mm) was measured according to the JIS K2537 test method.

＜灯油煙点向上剤用炭化水素油の煙点向上効果の評価＞
石油常圧残渣油の直接脱硫装置で得られた沸点範囲１５０℃〜２６０℃、煙点２０．５ｍｍの分解灯油留分に対して、得られた灯油煙点向上剤用炭化水素油を１５質量％及び３０質量％の割合でそれぞれ配合した。なお、灯油煙点向上剤用炭化水素油の配合割合（質量％）は、灯油煙点向上剤用炭化水素油及び分解灯油留分の合計質量基準である。次に、これらの煙点（ｍｍ）をＪＩＳＫ２５３７試験法に従って測定した。直接脱硫分解灯油に灯油煙点向上剤用炭化水素油を１５質量％配合したときの煙点増加量（ｍｍ）及び直接脱硫分解灯油に灯油煙点向上剤用炭化水素油を３０質量％配合したときの煙点増加量（ｍｍ）から、灯油煙点向上剤用炭化水素油の配合割合１０質量％あたりに換算した煙点増加量（ｍｍ／１０質量％）を算出し、これを煙点向上効果の指標とした。 <Evaluation of smoke point improvement effect of hydrocarbon oil for kerosene smoke point improver>
15 mass of the obtained hydrocarbon oil for kerosene smoke point improver is obtained with respect to the cracked kerosene fraction having a boiling point range of 150 ° C. to 260 ° C. and a smoke point of 20.5 mm obtained by a direct desulfurization apparatus for petroleum atmospheric residual oil. % And 30% by mass, respectively. The blending ratio (% by mass) of the kerosene smoke point improver hydrocarbon oil is based on the total mass of the kerosene smoke point improver hydrocarbon oil and the cracked kerosene fraction. Next, these smoke points (mm) were measured according to the JIS K2537 test method. The amount of smoke point increase (mm) when blended with 15% by weight of hydrocarbon oil for kerosene smoke point improver in direct desulfurization cracked kerosene and 30% by weight of hydrocarbon oil for kerosene smoke point improver in direct desulfurized cracked kerosene. From the amount of smoke point increase (mm), the smoke point increase amount (mm / 10 mass%) calculated per 10% by mass of the hydrocarbon oil for kerosene smoke point improver was calculated, and this was improved. It was used as an effect index.

＜ディーゼル燃料基材用炭化水素油の動粘度及び流動点＞
得られたディーゼル燃料基材用炭化水素油について、ＪＩＳＫ２２８３試験法に従って３０℃における動粘度（ｍｍ^２／ｓ）を測定し、ＪＩＳＫ２２６９試験法に従って流動点（℃）を測定した。 <Kinematic viscosity and pour point of hydrocarbon oil for diesel fuel base>
About the obtained hydrocarbon oil for diesel fuel base materials, kinematic viscosity (mm < ² > / s) in 30 degreeC was measured according to the JISK2283 test method, and the pour point (degreeC) was measured according to the JISK2269 test method.

表１及び表２に示されるように、実施例１〜５の合成油の処理方法によれば、ＦＴ合成油から、灯油煙点向上効果に優れた灯油煙点向上剤用炭化水素油と、流動点及び３０℃における動粘度が十分改善されたディーゼル燃料基材用炭化水素油との双方を高収率で得られることが分かった。
As shown in Table 1 and Table 2, according to the synthetic oil processing methods of Examples 1 to 5, from the FT synthetic oil, the kerosene smoke point improving hydrocarbon oil excellent in the kerosene smoke point improving effect, It was found that both the pour point and the hydrocarbon oil for diesel fuel base material with sufficiently improved kinematic viscosity at 30 ° C. can be obtained in high yield.

本発明の合成油の処理方法が実施される炭化水素油製造装置の一例を示すフロー図である。It is a flowchart which shows an example of the hydrocarbon oil manufacturing apparatus with which the processing method of the synthetic oil of this invention is implemented.

Explanation of symbols

Ｌ１…ＦＴ合成油導入流路、Ｌ２…中間留分流路，Ｌ３…ワックス分流路，Ｌ４〜Ｌ１０…流路、Ｌ１１…循環流路、Ｌ１２，Ｌ１３…流路、１０…第１の蒸留塔、２０…水素化精製装置、３０…水素化分解装置、４０…第２の蒸留塔、５０…第３の蒸留塔、１００…炭化水素油製造装置。 L1 ... FT synthetic oil introduction flow path, L2 ... middle distillate flow path, L3 ... wax distribution flow path, L4 to L10 ... flow path, L11 ... circulation flow path, L12, L13 ... flow path, 10 ... first distillation column, DESCRIPTION OF SYMBOLS 20 ... Hydrorefining apparatus, 30 ... Hydrocracking apparatus, 40 ... 2nd distillation tower, 50 ... 3rd distillation tower, 100 ... Hydrocarbon oil manufacturing apparatus.

Claims

By fractionating a material to be treated containing synthetic oil obtained by the Fischer-Tropsch synthesis method, an intermediate fraction having a boiling point of 150 to 360 ° C. having a fraction content of 90% by mass or more, and the intermediate fraction A first fractionation step to obtain a heavy wax content;
The middle fraction obtained in the first fractionation step is configured to contain one or more solid acids selected from crystalline zeolite and amorphous metal oxide having heat resistance in the presence of hydrogen. The support is brought into contact with a hydrorefining catalyst supporting a metal belonging to Group VIII of the periodic table, and the increase in the content of fractions having a boiling point of 150 ° C. or lower in the hydrorefined product is 9% by mass or less , and the content of isoparaffin as increase in the rate is 30 wt% or more, and the hydrorefining process for subjected to hydrotreating including hydrocracking and hydroisomerization,
By fractionating the hydrorefined product obtained in the hydrorefining step , the first fraction having a boiling point of 150 to 250 ° C. and having a content of 90% by mass or more, and the first fraction A second fractionation step to obtain a heavier second fraction,
A carrier comprising the wax obtained in the first fractionation step containing one or more solid acids selected from crystalline zeolite and amorphous metal oxide having heat resistance in the presence of hydrogen. In contact with a hydrocracking catalyst carrying a metal belonging to Group VIII of the periodic table , and the hydrogen cracking product has a fraction with a boiling point of 360 ° C. or less of 45 to 85% by mass. and hydrogenolysis step of subjected to hydrogenolysis including isomerization,
The third fractionation which obtains the 3rd fraction whose content of the fraction of boiling point 150-360 ° C is 90 mass% or more by fractionating the hydrocracking product obtained at the above-mentioned hydrocracking process Process,
A mixing step of mixing the second fraction and the third fraction,
It said first fraction a method for manufacturing a kerosene smoke point improvers for hydrocarbon oils and obtaining as kerosene smoke point improvers for hydrocarbon oils.

By fractionating a material to be treated containing synthetic oil obtained by the Fischer-Tropsch synthesis method, an intermediate fraction having a boiling point of 150 to 360 ° C. having a fraction content of 90% by mass or more, and the intermediate fraction A first fractionation step to obtain a heavy wax content;
The middle fraction obtained in the first fractionation step is configured to contain one or more solid acids selected from crystalline zeolite and amorphous metal oxide having heat resistance in the presence of hydrogen. The support is brought into contact with a hydrorefining catalyst supporting a metal belonging to Group VIII of the periodic table, and the increase in the content of fractions having a boiling point of 150 ° C. or lower in the hydrorefined product is 9% by mass or less, and the content of isoparaffin Hydrotreating step for hydrotreating including hydrocracking and hydroisomerization so that the rate increase is 30% by mass or more;
By fractionating the hydrorefined product obtained in the hydrorefining step, the first fraction having a boiling point of 150 to 250 ° C. and having a content of 90% by mass or more, and the first fraction A second fractionation step to obtain a heavier second fraction,
A carrier comprising the wax obtained in the first fractionation step containing one or more solid acids selected from crystalline zeolite and amorphous metal oxide having heat resistance in the presence of hydrogen. In contact with a hydrocracking catalyst carrying a metal belonging to Group VIII of the periodic table, and the hydrogen cracking product has a fraction with a boiling point of 360 ° C. or less of 45 to 85% by mass. Hydrocracking process for hydrocracking including hydroisomerization,
A third fraction obtained by fractionating the hydrocracked product obtained in the hydrocracking step to obtain a third fraction having a fraction having a boiling point of 150 to 360 ° C. of 90% by mass or more. Distillation process;
A mixing step of mixing the second fraction and the third fraction,
A method for producing a hydrocarbon oil for a diesel fuel base material, comprising obtaining a mixture of the second fraction and the third fraction as a hydrocarbon oil for a diesel fuel base material .

The kerosene according to claim 1, wherein a part or all of the wax that is heavier than the third fraction obtained in the third fractionation step is subjected to the hydrocracking step. Manufacturing method of hydrocarbon oil for smoke point improver .

3. The diesel according to claim 2, wherein a part or all of the wax that is heavier than the third fraction obtained in the third fractionation step is subjected to the hydrocracking step. A method for producing a hydrocarbon oil for a fuel substrate .