JP2007269885A - Method for hydrogenation refining of fuel base - Google Patents

Method for hydrogenation refining of fuel base Download PDF

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JP2007269885A
JP2007269885A JP2006094669A JP2006094669A JP2007269885A JP 2007269885 A JP2007269885 A JP 2007269885A JP 2006094669 A JP2006094669 A JP 2006094669A JP 2006094669 A JP2006094669 A JP 2006094669A JP 2007269885 A JP2007269885 A JP 2007269885A
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hydrorefining
catalyst
fuel
base material
fuel base
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JP4834438B2 (en
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Hiroyuki Seki
浩幸 関
Hirobumi Konno
博文 紺野
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Eneos Corp
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Nippon Oil Corp
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Priority to PCT/JP2007/055703 priority patent/WO2007119455A1/en
Priority to CN 200780010849 priority patent/CN101410486A/en
Priority to AU2007239954A priority patent/AU2007239954B2/en
Priority to MYPI20083516 priority patent/MY146894A/en
Priority to RU2008143027/04A priority patent/RU2429278C2/en
Priority to CN201510279681.4A priority patent/CN104987881A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for hydrogenation refining of fuel base with which conversion of a normal paraffin to an isoparaffin is sufficiently carried out besides removal of oxygen-containing compound and hydrogenation of an olefin. <P>SOLUTION: The method for hydrogenation refining of fuel base comprises bringing a fuel base containing an oxygen-containing compound, an olefin and a normal paraffin into contact with a hydrogenation refining catalyst composed of a silica-zirconia-containing carrier and a metal of the group VIII of the periodic table supported on the carrier in the presence of hydrogen. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、水素の存在下、燃料基材と水素化精製触媒とを接触させる水素化精製方法に関する。   The present invention relates to a hydrorefining method in which a fuel substrate and a hydrorefining catalyst are brought into contact in the presence of hydrogen.

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、一酸化炭素及び水素を原料としたフィッシャー・トロプシュ（Fischer-Tropsh、以下、「ＦＴ」と略す。）合成法が検討されている。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-Tropsh (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.

しかし、ＦＴ合成法により得られる燃料基材は、含酸素化合物及びオレフィンを含むため、そのままガソリンや軽油等の燃料として使用するのに必ずしも適していない。そのため、燃料として有効に利用するために、その燃料基材中の含酸素化合物の除去、並びにオレフィンの水素化によるパラフィンへの変換が必要となる。   However, since the fuel base material obtained by the FT synthesis method contains an oxygen-containing compound and an olefin, it is not necessarily suitable for use as it is as a fuel such as gasoline or light oil. Therefore, in order to use it effectively as a fuel, it is necessary to remove oxygen-containing compounds from the fuel base material and to convert it into paraffin by hydrogenation of olefins.

また、ＦＴ合成法により得られる燃料基材は、パラフィンの中でもノルマルパラフィン含有量が高いため、当該燃料基材をそのまま燃料として使用することは不適である。より具体的には、当該燃料基材は、自動車用ガソリンとして用いるためにはオクタン価が不十分であり、また、軽油として用いるためには低温流動性が不十分である。そこで、ＦＴ合成法により得られる燃料基材のオクタン価の向上、低温流動性の改善などを目的として、当該燃料基材中のノルマルパラフィンをイソパラフィンへ変換する水素化精製技術が重要となる。   Moreover, since the fuel base material obtained by the FT synthesis method has a high normal paraffin content among paraffins, it is unsuitable to use the fuel base material as a fuel as it is. More specifically, the fuel base material has an insufficient octane number for use as gasoline for automobiles, and low temperature fluidity for use as light oil. Therefore, for the purpose of improving the octane number of the fuel base material obtained by the FT synthesis method and improving the low-temperature fluidity, hydrorefining technology for converting normal paraffin in the fuel base material into isoparaffin is important.

かかる水素化精製技術に用いる触媒としては、ヘキサンの水素化異性化に用いられる触媒（例えば、特許文献１を参照）が知られている。また、特許文献２には、水素化精製触媒として、特定の細孔容積を有するアモルファス状のシリカアルミナから得られる担体にパラジウムを担持した触媒が開示されている。
米国特許第４６３７９９２号明細書 欧州特許出願公開第５８７２４６号明細書 As a catalyst used for such a hydrorefining technique, a catalyst used for hydroisomerization of hexane (for example, see Patent Document 1) is known. Patent Document 2 discloses a catalyst in which palladium is supported on a carrier obtained from amorphous silica alumina having a specific pore volume as a hydrorefining catalyst.
US Pat. No. 4,637,992 European Patent Application No. 587246

従来、含酸素化合物、オレフィン及びノルマルパラフィンを含む燃料基材を原料として水素化精製を行う場合、含酸素化合物の除去並びにオレフィンの水素化は十分達成されている。しかしながら、含酸素化合物の除去及びオレフィンの水素化に加えて、ノルマルパラフィンのイソパラフィンへの変換をも十分に行える水素化精製方法は知られていない。   Conventionally, when hydrorefining is performed using a fuel base material containing an oxygen-containing compound, olefin, and normal paraffin as a raw material, removal of the oxygen-containing compound and hydrogenation of the olefin have been sufficiently achieved. However, there is no known hydrorefining method capable of sufficiently converting normal paraffin to isoparaffin in addition to removal of oxygen-containing compounds and olefin hydrogenation.

そこで、本発明は上記事情にかんがみてなされたものであり、含酸素化合物の除去及びオレフィンの水素化に加えて、ノルマルパラフィンのイソパラフィンへの変換をも十分に行える燃料基材の水素化精製方法の提供を目的とする。   Therefore, the present invention has been made in view of the above circumstances, and in addition to the removal of oxygen-containing compounds and the hydrogenation of olefins, a method for hydrorefining a fuel substrate that can sufficiently convert normal paraffins to isoparaffins. The purpose is to provide.

上記目的を達成するために、本発明は、水素の存在下、含酸素化合物、オレフィン及びノルマルパラフィンを含有する燃料基材を、シリカジルコニアを含有する担体と、その担体に担持された周期律表第ＶＩＩＩ族金属とを含む水素化精製触媒に接触させる燃料基材の水素化精製方法を提供する。   In order to achieve the above object, the present invention provides a fuel base material containing an oxygen-containing compound, an olefin, and normal paraffin in the presence of hydrogen, a carrier containing silica zirconia, and a periodic table carried on the carrier. Provided is a method for hydrorefining a fuel substrate that is contacted with a hydrotreating catalyst comprising a Group VIII metal.

かかる燃料基材の水素化精製方法によれば、含酸素化合物を十分に除去し、オレフィンを十分に水素化すると共に、ノルマルパラフィンをイソパラフィンへ十分変換することが可能となる。その結果、本発明の燃料基材の水素化精製方法は、イソパラフィンに富んだ燃料基材を収率よく製造することが可能となり、優れた経済性を有することとなる。   According to such a hydrorefining method for a fuel base, it is possible to sufficiently remove oxygen-containing compounds, sufficiently hydrogenate olefins, and sufficiently convert normal paraffin to isoparaffin. As a result, the fuel substrate hydrorefining method of the present invention can produce a fuel substrate rich in isoparaffin in a high yield, and has excellent economic efficiency.

本発明の水素化精製方法において、水素化精製触媒は、上述の金属として、パラジウム及び／又は白金を含むと好ましい。かかる水素化精製触媒を用いると、ノルマルパラフィンのイソパラフィンへの変換を更に効率よく行うことができ、触媒劣化をより抑制することが可能となる。   In the hydrorefining method of the present invention, the hydrorefining catalyst preferably contains palladium and / or platinum as the above-mentioned metal. When such a hydrorefining catalyst is used, conversion of normal paraffin to isoparaffin can be performed more efficiently, and catalyst deterioration can be further suppressed.

本発明の水素化精製方法において、水素化精製触媒は、リンを更に含むと好ましい。これにより、ノルマルパラフィンのイソパラフィンへの変換を一層効率的に行うことができる。   In the hydrorefining method of the present invention, it is preferable that the hydrorefining catalyst further contains phosphorus. Thereby, conversion of normal paraffin to isoparaffin can be performed more efficiently.

本発明の水素化精製方法において、燃料基材はＦＴ反応により生成した成分を含有すると好ましい。かかる成分を含有する燃料基材を原料とすることで、本発明の水素化精製方法による、含酸素化合物の除去、オレフィンの水素化、並びにノルマルパラフィンのイソパラフィンへの変換という効果が、更に効率的かつ確実に奏される。   In the hydrorefining method of the present invention, the fuel base material preferably contains a component generated by the FT reaction. By using a fuel base material containing such components as raw materials, the effects of removal of oxygenated compounds, hydrogenation of olefins, and conversion of normal paraffins to isoparaffins by the hydrorefining method of the present invention are more efficient. And played reliably.

本発明によれば、含酸素化合物の除去及びオレフィンの水素化に加えて、ノルマルパラフィンのイソパラフィンへの変換まで十分に達成できる燃料基材の水素化精製方法の提供が可能となる。   ADVANTAGE OF THE INVENTION According to this invention, in addition to removal of an oxygen-containing compound and hydrogenation of an olefin, it becomes possible to provide a method for hydrorefining a fuel substrate that can sufficiently achieve conversion of normal paraffin to isoparaffin.

以下、本発明の好適な実施形態について詳細に説明する。   Hereinafter, preferred embodiments of the present invention will be described in detail.

本発明の燃料基材の水素化精製方法は、水素の存在下、含酸素化合物、オレフィン及びノルマルパラフィンを含有する燃料基材を、シリカジルコニアを含有する担体と、その担体に担持された周期律表第ＶＩＩＩ族金属とを含む水素化精製触媒に接触させるものである。   The method for hydrorefining a fuel substrate according to the present invention comprises a fuel substrate containing an oxygen-containing compound, an olefin and normal paraffin in the presence of hydrogen, a carrier containing silica zirconia, and a periodic rule carried on the carrier. It is made to contact the hydrorefining catalyst containing a Table VIII metal.

燃料基材は、含酸素化合物、オレフィン及びノルマルパラフィンを含有するものであれば特に限定されず、例えば、石油系又は合成系のガソリン基材、灯油基材、軽油基材、あるいはこれらの２種以上の混合物が挙げられる。したがって、燃料基材の沸点範囲も特に制限はなく、目的とする生成油に応じて調整されればよい。例えば、燃料油がガソリン基材の場合、沸点範囲は室温〜１４０℃が一般的であり、燃料油が軽油基材の場合、沸点範囲は１４０〜３６０℃が一般的である。   The fuel base material is not particularly limited as long as it contains an oxygen-containing compound, olefin, and normal paraffin. For example, petroleum-based or synthetic gasoline base, kerosene base, light oil base, or two of these The above mixture is mentioned. Therefore, the boiling range of the fuel base material is not particularly limited, and may be adjusted according to the target generated oil. For example, when the fuel oil is a gasoline base, the boiling range is generally from room temperature to 140 ° C., and when the fuel oil is a light oil base, the boiling range is generally from 140 to 360 ° C.

なお、例えば、ガソリン基材と軽油基材とを混合して、原料の燃料基材として用いてもよいが、ガソリン基材と軽油基材とは別々に水素化精製する方が好ましい。ガソリン基材と軽油基材とを混合した基材を水素化精製した場合、ガソリン基材の一部が、より軽質なガス留分に変換されて、生成物中のガソリン基材の収率が減少する傾向にある。   For example, a gasoline base material and a light oil base material may be mixed and used as a raw material fuel base material, but it is preferable that the gasoline base material and the light oil base material be separately hydrorefined. When hydrorefining a base material that is a mixture of a gasoline base material and a light oil base material, part of the gasoline base material is converted into a lighter gas fraction, resulting in a yield of the gasoline base material in the product. It tends to decrease.

含酸素化合物には、燃料基材がガソリン基材である場合、炭素数２〜８のアルコール類が、燃料基材が灯油基材である場合、炭素数８〜１３のアルコール類が、燃料基材が軽油基材である場合、炭素数１２〜１８のアルコール類が、主として含まれる。また、燃料基材には、上述のアルコール類の他、アルデヒド類及びケトン類を含んでもよい。   The oxygen-containing compounds include alcohols having 2 to 8 carbon atoms when the fuel base material is a gasoline base material, and alcohols having 8 to 13 carbon atoms when the fuel base material is a kerosene base material. When the material is a light oil base, alcohols having 12 to 18 carbon atoms are mainly included. In addition to the alcohols described above, the fuel base material may contain aldehydes and ketones.

オレフィンには、燃料基材がガソリン基材である場合、炭素数４〜９の不飽和脂肪族炭化水素が、主として含まれる。また、燃料基材が灯油基材である場合、炭素数１０〜１４の不飽和脂肪族炭化水素が、主として含まれる。燃料基材が軽油基材である場合、炭素数１５〜２０の不飽和脂肪族炭化水素が、主として含まれる。   The olefin mainly contains an unsaturated aliphatic hydrocarbon having 4 to 9 carbon atoms when the fuel base is a gasoline base. Moreover, when a fuel base material is a kerosene base material, a C10-14 unsaturated aliphatic hydrocarbon is mainly contained. When a fuel base material is a light oil base material, a C15-C20 unsaturated aliphatic hydrocarbon is mainly contained.

ノルマルパラフィンには、燃料基材がガソリン基材である場合、炭素数４〜９の直鎖状飽和脂肪族炭化水素が、主として含まれる。また、燃料基材が灯油基材である場合、炭素数１０〜１４の直鎖状飽和脂肪族炭化水素が、主として含まれる。燃料基材が軽油基材である場合、炭素数１５〜２０の直鎖状飽和脂肪族炭化水素が、主として含まれる。   The normal paraffin mainly contains a linear saturated aliphatic hydrocarbon having 4 to 9 carbon atoms when the fuel base material is a gasoline base material. Moreover, when a fuel base material is a kerosene base material, a C10-C14 linear saturated aliphatic hydrocarbon is mainly contained. When a fuel base material is a light oil base material, a C15-20 linear saturated aliphatic hydrocarbon is mainly contained.

原料である燃料基材中の各成分の含有割合は特に限定されない。ただし、ノルマルパラフィンのイソパラフィンへの異性化を有効に進行させるためには、燃料基材の総量に対するノルマルパラフィンの含有割合が３０質量％以上であると好ましく、５０質量％以上であるとより好ましく、７０質量％以上であると特に好ましい。   The content ratio of each component in the fuel base material which is a raw material is not particularly limited. However, in order to effectively promote the isomerization of normal paraffin to isoparaffin, the content ratio of normal paraffin to the total amount of the fuel base is preferably 30% by mass or more, more preferably 50% by mass or more, It is especially preferable that it is 70 mass% or more.

また、本発明に係る燃料基材は、上述した本発明の効果を更に有効に奏するために、ＦＴ反応により生成した成分を含有することが好ましく、ＦＴ反応により生成した成分のみを含有することがより好ましい。   Further, the fuel base material according to the present invention preferably contains a component generated by the FT reaction, and only contains a component generated by the FT reaction, in order to achieve the above-described effects of the present invention more effectively. More preferred.

本発明の水素化精製方法に用いられる水素化精製触媒は、担体としてシリカジルコニアを含有し、その上に担持される金属として周期律表第ＶＩＩＩ属金属を含有するものであれば特に限定されない。   The hydrorefining catalyst used in the hydrorefining method of the present invention is not particularly limited as long as it contains silica zirconia as a support and a metal of group VIII of the periodic table as a metal supported thereon.

担体であるシリカジルコニアにおけるシリカ／ジルコニアのモル比は特に限定されないが、１０以下であると好ましい。このモル比が１０を超えると水素化精製触媒の活性が低下する傾向にある。   The molar ratio of silica / zirconia in silica zirconia as a carrier is not particularly limited, but is preferably 10 or less. When this molar ratio exceeds 10, the activity of the hydrorefining catalyst tends to decrease.

また、本発明で用いられる水素化精製触媒は、担体成型のためのバインダーを更に含有してもよい。バインダーは特に制限されないが、好ましいバインダーとしてはアルミナ又はシリカが挙げられる。担体の形状は特に制限されず、粒状、円柱状（ペレット）などの形状とすることができる。   The hydrorefining catalyst used in the present invention may further contain a binder for forming a carrier. The binder is not particularly limited, but preferred binders include alumina or silica. The shape of the carrier is not particularly limited, and may be a granular shape, a cylindrical shape (pellet), or the like.

上述の担体には、周期律表第ＶＩＩＩ族金属が担持される。第ＶＩＩＩ族金属としては、具体的には、鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金などが挙げられる。これらの金属の中でも、担体に担持される金属として、ニッケル、ロジウム、パラジウム、イリジウム及び白金からなる群より選ばれる１種以上の金属を用いることが好ましい。また、担体に担持される金属として、パラジウム及び／又は白金を用いることが更に好ましく、パラジウム及び白金の混合物を用いることが特に好ましい。これにより、原料の燃料基材に硫黄分が含まれている場合、触媒劣化をより有効に抑制することが可能となる。   The above-mentioned carrier carries a Group VIII metal of the periodic table. Specific examples of the Group VIII metal include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Among these metals, it is preferable to use at least one metal selected from the group consisting of nickel, rhodium, palladium, iridium and platinum as the metal supported on the carrier. Further, it is more preferable to use palladium and / or platinum as the metal supported on the carrier, and it is particularly preferable to use a mixture of palladium and platinum. Thereby, when the sulfur content is contained in the raw fuel substrate, it is possible to more effectively suppress catalyst deterioration.

これらの金属を担体に担持させる方法は特に制限されず、例えば、上記金属を含む水溶液を担体に含浸させ、乾燥、焼成を行う方法であってもよい。水素化精製触媒における上記金属の担持量は特に制限されないが、通常、担体１００質量部に対して０．１〜２．０質量部である。   The method for supporting these metals on the carrier is not particularly limited, and for example, a method in which the carrier is impregnated with an aqueous solution containing the metal, followed by drying and baking may be used. The amount of the metal supported in the hydrotreating catalyst is not particularly limited, but is usually 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the support.

また、本発明に係る水素化精製触媒は、リンを更に含むと好ましく、リンは含浸法などにより担体に添加することが好ましい。これにより、ノルマルパラフィンからイソパラフィンへの異性化を一層促進することができる。リンの含有割合は、担体１００質量部に対して０．０２〜１０．０質量部であると好ましい。リンの含有割合が０．０２質量部を下回ると、リンの添加効果が十分に発揮され難くなり、１０．０質量部を超えると、生成物の軽質化に伴い、所望とする燃料基材の収率が低下する傾向にある。   The hydrorefining catalyst according to the present invention preferably further contains phosphorus, and phosphorus is preferably added to the support by an impregnation method or the like. Thereby, the isomerization from normal paraffin to isoparaffin can be further promoted. The phosphorus content is preferably 0.02 to 10.0 parts by mass with respect to 100 parts by mass of the carrier. When the phosphorus content is less than 0.02 parts by mass, the effect of adding phosphorus is hardly exhibited, and when the content exceeds 10.0 parts by mass, the lightening of the product leads to the desired fuel substrate. The yield tends to decrease.

本発明の燃料基材の水素化精製方法に使用される水素化精製装置は、水素存在下で燃料基材と水素化精製触媒とを接触させて、水素化精製可能なものであれば特に限定されない。よって、例えば、従来の固定床反応装置を使用することができる。   The hydrorefining apparatus used in the method for hydrorefining a fuel base of the present invention is particularly limited as long as it can be hydrorefined by contacting the fuel base with a hydrorefining catalyst in the presence of hydrogen. Not. Thus, for example, a conventional fixed bed reactor can be used.

また、水素化精製の際の反応温度は、１８０〜３２０℃であると好ましい。反応温度が１８０℃未満であると、ノルマルパラフィンからイソパラフィンへの異性化が十分に進行しない傾向にある。また、反応温度が３２０℃を上回ると、生成物の軽質化を抑制するのが困難となり、所望とする燃料基材の収率が低下する傾向にある。   Moreover, the reaction temperature in hydrorefining is preferably 180 to 320 ° C. If the reaction temperature is less than 180 ° C., isomerization from normal paraffin to isoparaffin tends not to proceed sufficiently. On the other hand, when the reaction temperature exceeds 320 ° C., it becomes difficult to suppress the lightening of the product, and the yield of the desired fuel base material tends to decrease.

また、反応圧力は特に制限されないが、水素分圧で１〜１２ＭＰａであると好ましく、２〜６ＭＰａであるとより好ましい。水素分圧が１ＭＰａを下回ると触媒の劣化が進行しやすくなる傾向にあり、１２ＭＰａを超えると、所望の燃料基材を得るための反応温度が高くなる傾向にある。液空間速度（ＬＨＳＶ）は、特に制限されないが、通常０．１〜５．０ｈ−１であれば、燃料基材の水素化精製を行うことができる。また、原料である燃料基材量に対する触媒層に供給する全水素量の比、すなわち水素／油比は特に制限されないが、通常１００〜８５０ＮＬ／Ｌの範囲である。 The reaction pressure is not particularly limited, but is preferably 1 to 12 MPa as hydrogen partial pressure, and more preferably 2 to 6 MPa. When the hydrogen partial pressure is less than 1 MPa, the catalyst tends to deteriorate, and when it exceeds 12 MPa, the reaction temperature for obtaining a desired fuel substrate tends to be high. The liquid hourly space velocity (LHSV) is not particularly limited. However, if it is usually 0.1 to 5.0 h −1 , hydrorefining of the fuel substrate can be performed. Further, the ratio of the total amount of hydrogen supplied to the catalyst layer relative to the amount of fuel base material which is a raw material, that is, the hydrogen / oil ratio is not particularly limited, but is usually in the range of 100 to 850 NL / L.

上記本発明の燃料基材の水素化精製方法においては、上述の水素化精製触媒と、含酸素化合物、オレフィン及びノルマルパラフィンを含有する燃料基材とを水素の存在下、所定の反応条件で接触させることにより、燃料基材に含まれるアルコール類などの含酸素化合物の除去、オレフィンの水素化、並びに含酸素化合物に由来するノルマルパラフィン及び燃料基材に本来的に含まれるノルマルパラフィンのイソパラフィンへの変換（異性化）を有効に行うことができる。   In the method for hydrorefining a fuel substrate of the present invention, the above-described hydrorefining catalyst is contacted with a fuel substrate containing an oxygen-containing compound, an olefin, and normal paraffin in the presence of hydrogen under predetermined reaction conditions. The removal of oxygenated compounds such as alcohols contained in the fuel substrate, the hydrogenation of olefins, and the normal paraffin derived from the oxygenated compound and the normal paraffin originally contained in the fuel substrate into isoparaffins Conversion (isomerization) can be carried out effectively.

より具体的には、燃料基材に含まれるアルコール類などの含酸素化合物は、炭化水素に変換されることにより除去される。また、燃料基材に本来的に含まれるオレフィン、及び燃料基材中のアルケノール類等から変換されたオレフィンは、水素化によりパラフィンに変換される。更に、アルコール類等から変換されたパラフィンのうちノルマルアルコール類などに由来するノルマルパラフィンは、燃料基材に本来的に含まれるノルマルパラフィンと共にイソパラフィンへと変換される。そして、本発明では、上記の水素化精製プロセスにおいて燃料基材の軽質化を抑制することもできるため、燃料基材の収率を維持しつつ、燃料基材に含まれる含酸素化合物の除去、オレフィンの水素化、並びにノルマルパラフィンのイソパラフィンへの変換を同時に十分達成することが可能となる。   More specifically, oxygen-containing compounds such as alcohols contained in the fuel base material are removed by being converted into hydrocarbons. In addition, olefins originally contained in the fuel base material and olefins converted from alkenols in the fuel base material are converted to paraffin by hydrogenation. Further, normal paraffins derived from normal alcohols among paraffins converted from alcohols and the like are converted into isoparaffins together with normal paraffins originally contained in the fuel substrate. And in the present invention, since it is possible to suppress the lightening of the fuel base material in the hydrorefining process, the removal of oxygenated compounds contained in the fuel base material while maintaining the yield of the fuel base material, It is possible to sufficiently achieve hydrogenation of olefins and conversion of normal paraffins to isoparaffins simultaneously.

以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。   The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

以下、実施例によって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.

［触媒の調製］
（触媒１）
シリカジルコニア（シリカ／ジルコニアのモル比：０．７）及びアルミナバインダーを十分に混合して、得られた混合物をφ１．６ｍｍ、長さ約３ｍｍの円柱状に成型した（シリカジルコニア／アルミナバインダー＝７０／３０（質量比））。得られた成型体を、大気中、５００℃で１時間焼成して担体を得た。この担体に、塩化白金酸の硝酸水溶液を含浸し、担体１００質量部に対して０．６質量部の白金を担持した。これを１２０℃で３時間乾燥し、次いで大気中、５００℃で１時間焼成することで触媒１を得た。 [Preparation of catalyst]
(Catalyst 1)
Silica zirconia (silica / zirconia molar ratio: 0.7) and an alumina binder were sufficiently mixed, and the resulting mixture was molded into a cylindrical shape having a diameter of 1.6 mm and a length of about 3 mm (silica zirconia / alumina binder = 70/30 (mass ratio)). The obtained molded body was fired at 500 ° C. for 1 hour in the air to obtain a carrier. This carrier was impregnated with a nitric acid aqueous solution of chloroplatinic acid, and 0.6 parts by mass of platinum was supported with respect to 100 parts by mass of the carrier. This was dried at 120 ° C. for 3 hours, and then calcined in air at 500 ° C. for 1 hour to obtain Catalyst 1.

（触媒２）
担体に白金を担持する前に、リン酸水溶液を担体に含浸して、担体１００質量部に対して０．２質量部のリンを担持した以外は触媒１の調製と同様にして、触媒２を得た。 (Catalyst 2)
The catalyst 2 was prepared in the same manner as in the preparation of the catalyst 1 except that the carrier was impregnated with an aqueous phosphoric acid solution and 0.2 parts by mass of phosphorus was supported with respect to 100 parts by mass of the carrier before platinum was supported on the carrier. Obtained.

（触媒３）
塩化白金酸の硝酸水溶液を含浸し、担体１００質量部に対して０．６質量部の白金を担持したことに代えて、塩化白金酸及び塩化パラジウムの硝酸水溶液を含浸し、担体１００質量部に対して０．５質量部の白金と０．１質量部のパラジウムとを担持した以外は実施例１と同様にして、触媒３を得た。 (Catalyst 3)
Instead of impregnating a nitric acid aqueous solution of chloroplatinic acid and supporting 0.6 parts by mass of platinum with respect to 100 parts by mass of the carrier, impregnating with nitric acid aqueous solution of chloroplatinic acid and palladium chloride, On the other hand, a catalyst 3 was obtained in the same manner as in Example 1 except that 0.5 parts by mass of platinum and 0.1 parts by mass of palladium were supported.

（触媒４）
シリカジルコニア（シリカ／ジルコニアのモル比：０．７）に代えて、シリカアルミナ（アルミナ量：１４質量％）を用いた以外は触媒１の調製と同様にして、触媒４を得た。 (Catalyst 4)
Catalyst 4 was obtained in the same manner as Catalyst 1 except that silica alumina (alumina content: 14% by mass) was used instead of silica zirconia (silica / zirconia molar ratio: 0.7).

（触媒５）
シリカジルコニア（シリカ／ジルコニアのモル比：０．７）に代えて、アルミナボリア（アルミナ量：８４質量％）を用いた以外は触媒１の調製と同様にして、触媒５を得た。 (Catalyst 5)
Catalyst 5 was obtained in the same manner as in the preparation of catalyst 1 except that alumina boria (alumina content: 84 mass%) was used instead of silica zirconia (silica / zirconia molar ratio: 0.7).

（触媒６）
粒子径が約３ｍｍの球状活性炭からなる担体に、塩化白金酸の硝酸水溶液を含浸し、担体１００質量部に対して０．６質量部の白金を担持した。これを１２０℃で３時間乾燥し、次いで大気中、５００℃で１時間焼成することで触媒６を得た。 (Catalyst 6)
A carrier made of spherical activated carbon having a particle diameter of about 3 mm was impregnated with a nitric acid aqueous solution of chloroplatinic acid, and 0.6 parts by mass of platinum was supported on 100 parts by mass of the carrier. This was dried at 120 ° C. for 3 hours, and then calcined in air at 500 ° C. for 1 hour to obtain catalyst 6.

［水素化精製］
（実施例１）
触媒１（１００ｍＬ）を固定床の流通式反応器に充填した。次いで、その触媒１に対して、水素雰囲気下、３４０℃で３時間還元処理を施し、触媒１を活性化した。 [Hydro-refining]
Example 1
Catalyst 1 (100 mL) was charged to a fixed bed flow reactor. Next, the catalyst 1 was subjected to reduction treatment at 340 ° C. for 3 hours in a hydrogen atmosphere to activate the catalyst 1.

続いて、原料であるＦＴ合成法により得られた沸点範囲１４０〜３６０℃の燃料基材（含酸素化合物／オレフィン／イソパラフィン／ノルマルパラフィン＝１０／１４／４／７２質量％）を上記反応器に供給して、反応温度２５０又は３００℃の下で水素化精製を行った。なお、いずれの反応温度の場合も、水素分圧は４．０ＭＰａ、原料の液空間速度は２．０ｈ−１（液流量として２００ｍＬ／ｈ）、水素流量は２５０ＮＬ／ｈ（すなわち、水素／油比は１２５０ＮＬ／Ｌ）とした。 Subsequently, a fuel base material (oxygen-containing compound / olefin / isoparaffin / normal paraffin = 10/14/4/72 mass%) having a boiling point range of 140 to 360 ° C. obtained by the FT synthesis method as a raw material is used in the reactor. The hydrogenation purification was carried out at a reaction temperature of 250 or 300 ° C. At any reaction temperature, the hydrogen partial pressure is 4.0 MPa, the liquid space velocity of the raw material is 2.0 h −1 (200 mL / h as the liquid flow rate), and the hydrogen flow rate is 250 NL / h (that is, hydrogen / oil). The ratio was 1250 NL / L).

反応生成物の蒸留ガスクロマトグラフィー測定を行い、沸点１４０℃未満の軽質留分、含酸素化合物、オレフィン及びイソパラフィンの含有割合を求めた。結果を表１（反応温度２５０℃）、及び表２（反応温度３００℃）に示す。   The reaction product was subjected to distillation gas chromatography measurement, and the content ratio of a light fraction having a boiling point of less than 140 ° C., an oxygen-containing compound, an olefin, and isoparaffin was determined. The results are shown in Table 1 (reaction temperature 250 ° C.) and Table 2 (reaction temperature 300 ° C.).

Figure 2007269885
Figure 2007269885

Figure 2007269885
Figure 2007269885

（実施例２）
触媒１に代えて触媒２を用いた以外は実施例１と同様にして、水素化精製及び反応生成物の分析を行った。結果を表１、２に示す。 (Example 2)
Hydrorefining and analysis of the reaction product were performed in the same manner as in Example 1 except that the catalyst 2 was used instead of the catalyst 1. The results are shown in Tables 1 and 2.

（実施例３）
触媒３（１００ｍＬ）を固定床の流通式反応器に充填した。次いで、その触媒３に対して、水素雰囲気下、３４０℃で３時間還元処理を施し、触媒３を活性化した。 (Example 3)
Catalyst 3 (100 mL) was charged to a fixed bed flow reactor. Next, the catalyst 3 was subjected to a reduction treatment at 340 ° C. for 3 hours in a hydrogen atmosphere to activate the catalyst 3.

続いて、原料である、ＦＴ合成法により得られた沸点範囲１４０〜３６０℃の燃料基材（含酸素化合物／オレフィン／イソパラフィン／ノルマルパラフィン＝１０／１４／４／７２質量％）と、沸点範囲１４０〜３６０℃の石油系の燃料基材である脱硫油とを、７０：３０の質量比で混合して得られた混合油（含酸素化合物／オレフィン／イソパラフィン／ノルマルパラフィン＝７／１１／１５／５２質量％、硫黄分１２質量ｐｐｍ）を上記反応器に供給して、反応温度２５０又は３００℃の下で水素化精製を行った。いずれの反応温度の場合も、水素分圧は４．０ＭＰａ、原料の液空間速度は２．０ｈ−１（液流量として２００ｍＬ／ｈ）、水素流量は２５０ＮＬ／ｈ（すなわち、水素／油比は１２５０ＮＬ／Ｌ）とした。 Subsequently, the fuel base material having a boiling point range of 140 to 360 ° C. obtained by the FT synthesis method (oxygen-containing compound / olefin / isoparaffin / normal paraffin = 10/14/4/72% by mass) as a raw material, and the boiling range A mixed oil obtained by mixing desulfurized oil, which is a petroleum-based fuel base material at 140 to 360 ° C., at a mass ratio of 70:30 (oxygenated compound / olefin / isoparaffin / normal paraffin = 7/11/15 / 52 mass%, sulfur content 12 mass ppm) was supplied to the reactor, and hydrorefining was performed at a reaction temperature of 250 or 300 ° C. In any reaction temperature, the hydrogen partial pressure is 4.0 MPa, the liquid space velocity of the raw material is 2.0 h −1 (200 mL / h as the liquid flow rate), and the hydrogen flow rate is 250 NL / h (that is, the hydrogen / oil ratio is 1250 NL / L).

反応生成物の蒸留ガスクロマトグラフィー測定を行い、沸点１４０℃未満の軽質留分、含酸素化合物、オレフィン及びイソパラフィンの含有割合を求めた。結果を表１、２に示す。   The reaction product was subjected to distillation gas chromatography measurement, and the content ratio of a light fraction having a boiling point of less than 140 ° C., an oxygen-containing compound, an olefin, and isoparaffin was determined. The results are shown in Tables 1 and 2.

（比較例１）
触媒１に代えて触媒４を用いた以外は実施例１と同様にして、水素化精製及び反応生成物の分析を行った。結果を表１、２に示す。 (Comparative Example 1)
Hydrorefining and analysis of the reaction product were performed in the same manner as in Example 1 except that the catalyst 4 was used in place of the catalyst 1. The results are shown in Tables 1 and 2.

（比較例２）
触媒１に代えて触媒５を用いた以外は実施例１と同様にして、水素化精製及び反応生成物の分析を行った。結果を表１、２に示す。 (Comparative Example 2)
Hydrorefining and analysis of the reaction product were performed in the same manner as in Example 1 except that the catalyst 5 was used instead of the catalyst 1. The results are shown in Tables 1 and 2.

（比較例３）
触媒１に代えて触媒５を用いた以外は実施例１と同様にして、水素化精製及び反応生成物の分析を行った。結果を表１、２に示す。 (Comparative Example 3)
Hydrorefining and analysis of the reaction product were performed in the same manner as in Example 1 except that the catalyst 5 was used instead of the catalyst 1. The results are shown in Tables 1 and 2.

表１、２に示した結果からわかるように、実施例１〜３においては、燃料基材中の含酸素化合物及びオレフィンを十分に低減できると共に、ノルマルパラフィンからイソパラフィンへ十分に異性化できることが確認された。   As can be seen from the results shown in Tables 1 and 2, in Examples 1 to 3, it was confirmed that the oxygen-containing compounds and olefins in the fuel substrate can be sufficiently reduced, and that normal paraffin can be sufficiently isomerized from isoparaffin. It was done.

Claims (4)

水素の存在下、
含酸素化合物、オレフィン及びノルマルパラフィンを含有する燃料基材を、
シリカジルコニアを含有する担体と、その担体に担持された周期律表第ＶＩＩＩ族金属と、を含む水素化精製触媒に
接触させる、燃料基材の水素化精製方法。 In the presence of hydrogen,
A fuel base material containing an oxygen-containing compound, olefin and normal paraffin,
A method for hydrorefining a fuel substrate, comprising contacting a hydrorefining catalyst comprising a carrier containing silica zirconia and a Group VIII metal on the periodic table supported on the carrier. 前記水素化精製触媒は、前記活性金属として、パラジウム及び／又は白金を含む、請求項１記載の水素化精製方法。   The hydrorefining method according to claim 1, wherein the hydrorefining catalyst contains palladium and / or platinum as the active metal. 前記水素化精製触媒はリンを更に含む、請求項１又は２に記載の水素化精製方法。   The hydrorefining method according to claim 1 or 2, wherein the hydrorefining catalyst further contains phosphorus. 前記燃料基材は、フィッシャー・トロプシュ反応により生成した成分を含有する、請求項１〜３のいずれか一項に記載の水素化精製方法。   The hydrorefining method according to any one of claims 1 to 3, wherein the fuel base contains a component generated by a Fischer-Tropsch reaction.
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PCT/JP2007/055703 WO2007119455A1 (en) 2006-03-30 2007-03-20 Process for hydrorefining fuel base material
RU2008143027/04A RU2429278C2 (en) 2006-03-30 2007-03-20 Method for hydrofining fuel base
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