JP4538014B2 - Catalyst for hydrorefining - Google Patents
Catalyst for hydrorefining Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 170
- 239000011148 porous material Substances 0.000 claims description 108
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052753 mercury Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 238000001465 metallisation Methods 0.000 claims description 17
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- 238000001179 sorption measurement Methods 0.000 claims description 14
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
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- 238000010304 firing Methods 0.000 description 6
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、石油留分などの炭化水素の水素化精製に用いられる触媒及びその製造方法に関し、特に、原油、タールサンド、シェールオイル、石炭液化油などの重質油を常圧蒸留または減圧蒸留することにより得られる各種の重質留分及び残渣油などを水素化脱金属するために用いられる触媒及びその製造方法に関する。 The present invention relates to a catalyst used for hydrorefining of hydrocarbons such as petroleum fractions and a method for producing the same, and in particular, heavy oil such as crude oil, tar sand, shale oil, and coal liquefied oil is subjected to atmospheric distillation or vacuum distillation. The present invention relates to a catalyst used for hydrodemetallation of various heavy fractions, residual oils, and the like obtained by the above and a method for producing the same.
常圧蒸留または減圧蒸留の残渣油などの重質油には、ニッケル、バナジウムなどの金属分が多く含まれている。この金属分は、脱硫、脱窒素、分解などのための水素化精製触媒を被毒し、触媒活性を低下させるため、予め、脱金属を目的とした水素化精製用触媒（以下、脱金属触媒ともいう）で処理を行っている。 Heavy oil such as residual oil obtained by atmospheric distillation or vacuum distillation contains a large amount of metal such as nickel and vanadium. This metal component poisons a hydrorefining catalyst for desulfurization, denitrogenation, decomposition, etc., and lowers the catalytic activity. (Also called).
かかる脱金属触媒は、同程度の中央細孔直径を有し且つ同じ活性金属種が担持されていても、脱金属活性及び金属堆積容量（触媒が活性を失うまでに細孔内に堆積可能な金属量）が大きく異なることがわかっている。これは、細孔径分布またはその他の触媒構造が相違するためであると考えられる。例えば、脱金属触媒として細孔直径６０ｎｍ以下の細孔にほとんどの細孔容積を有する触媒を用いた場合、脱金属活性は高まるが、細孔入口近傍に多くの金属が堆積し、細孔入口を閉塞するために金属堆積容量が小さくなってしまう。これに対し、細孔直径６０ｎｍ以下の細孔群（メソポア）を有するとともに、細孔直径６０ｎｍを超える細孔群（マクロポア）を有する触媒（バイモーダル型触媒）を用いた場合には、金属堆積容量を大きくすることができるが、相対的に脱金属活性は低下してしまう。 Such demetallization catalysts have the same central pore diameter and are supported by the same active metal species, but can be deposited in the pores before the catalyst loses activity. It is known that the amount of metal is greatly different. This is thought to be because the pore size distribution or other catalyst structures are different. For example, when a catalyst having most pore volumes in pores having a pore diameter of 60 nm or less is used as a demetallation catalyst, the metal removal activity is increased, but a large amount of metal is deposited near the pore inlet, Therefore, the metal deposition capacity is reduced. In contrast, when a catalyst having a pore group (mesopore) having a pore diameter of 60 nm or less and a pore group (macropore) having a pore diameter exceeding 60 nm (macropore) is used, metal deposition is performed. Although the capacity can be increased, the metal removal activity is relatively lowered.
従来、上記のようなバイモーダル型触媒として、特公昭６０−４９１３５号（ローヌ・プーラン・アンデュストリ）及び特開平６−８８０８１号（テキサコ・デベロップメント・コーポレーション）が知られている。しかしながら、本発明との関係において、前者は球状担体を開示しているが、触媒が脱金属反応に用いられることは何ら言及していない。後者の文献は、全細孔容積が０．５〜０．８ｃｍ３／ｇの担体を教示しているが、触媒の金属堆積容量は高くない。 Conventionally, Japanese Patent Publication No. 60-49135 (Rhône-Poulean Andustri) and Japanese Patent Application Laid-Open No. 6-88081 (Texaco Development Corporation) are known as such bimodal catalysts. However, in the context of the present invention, the former discloses a spherical support, but does not mention that the catalyst is used for the demetallation reaction. The latter document teaches a support with a total pore volume of 0.5 to 0.8 cm 3 / g, but the metal deposition capacity of the catalyst is not high.
すなわち、従来、脱金属活性と金属堆積容量の両方が高い水素化精製触媒は存在していなかった。 That is, heretofore, there has not been a hydrorefining catalyst having both high metal removal activity and high metal deposition capacity.
本発明の目的は、脱金属活性と金属堆積容量がともに高い水素化精製触媒及びその製造方法を提供することである。 An object of the present invention is to provide a hydrorefining catalyst having a high metal removal activity and a high metal deposition capacity, and a method for producing the same.
本発明の第１の態様に従えば、耐火性多孔質担体に水素化活性金属成分を担持した水素化精製用触媒において、
窒素吸着法により測定した中央細孔直径が８〜２０ｎｍであり；
窒素吸着法により測定した細孔容積が０．５６ｃｍ３／ｇ以上であり；且つ
水銀圧入法により測定した５０ｎｍ以上の細孔直径を有する細孔の細孔容積が０．３２ｃｍ３／ｇ以上であることを特徴とする水素化精製用触媒が提供される。
According to the first aspect of the present invention, in a hydrorefining catalyst in which a hydrogenation active metal component is supported on a refractory porous carrier,
The median pore diameter measured by nitrogen adsorption method is 8-20 nm;
The pore volume measured by the nitrogen adsorption method is 0.56 cm 3 / g or more; and the pore volume of the pore having a pore diameter of 50 nm or more measured by the mercury intrusion method is 0.32 cm 3 / g or more. There is provided a hydrorefining catalyst characterized by that.
本発明の水素化精製用触媒は、中央細孔直径と、窒素吸着法により測定した細孔（概ね６０ｎｍ以下の細孔直径を有する細孔）の細孔容積と、水銀圧入法により測定した細孔であって５０ｎｍを超える細孔直径を有する細孔の細孔容積とを前記規定範囲の値とすることにより、水素化精製、特には、水素化脱金属において、脱金属活性及び金属堆積容量をいずれも高くすることができ、それゆえ、長期間に渡って高い金属分除去率を維持することができる。例えば、本発明の水素化精製用触媒は、後に定義した条件の下で１００ｇの新触媒に対して７０ｇ以上の有効メタル堆積量を示すことが分かった。本発明の触媒は、重質油の脱金属または脱アスファルテンに特に好適に用いられる。 The hydrorefining catalyst of the present invention comprises a central pore diameter, a pore volume measured by a nitrogen adsorption method (a pore having a pore diameter of approximately 60 nm or less), and a fine pore size measured by a mercury intrusion method. By setting the pore volume of pores having a pore diameter exceeding 50 nm to a value within the above specified range, in hydrorefining, particularly hydrodemetallation, demetalization activity and metal deposition capacity Therefore, it is possible to maintain a high metal content removal rate over a long period of time. For example, it has been found that the hydrorefining catalyst of the present invention exhibits an effective metal deposition amount of 70 g or more with respect to 100 g of the new catalyst under the conditions defined later. The catalyst of the present invention is particularly preferably used for heavy metal demetalization or deasphaltenization.
本発明の水素化精製触媒は、一層良好な脱金属活性を有するためには、水銀圧入法により測定して０．８７ｃｍ３／ｇ以上の細孔容積を有するのが好ましい。また、水素化精製触媒は、充分な機械的強度が得られるという理由から、水銀圧入法により測定して１０００ｎｍ以上の細孔直径を有する細孔の細孔容積が０．２ｃｍ３／ｇ以下であることが望ましい。また、本発明の触媒は、脱金属活性が高いのでかさ密度を０．５２ｃｍ３／ｇ以下にすることができる。これにより、触媒が充填された反応器の荷重を減らすことができ、差圧が多少高くても反応器の耐久性を向上させ得る。 The hydrorefining catalyst of the present invention preferably has a pore volume of 0.87 cm 3 / g or more as measured by a mercury intrusion method in order to have a better metal removal activity. Moreover, the hydrorefining catalyst has a pore volume of 0.2 cm 3 / g or less having a pore diameter of 1000 nm or more as measured by a mercury intrusion method because sufficient mechanical strength is obtained. It is desirable to be. Further, since the catalyst of the present invention has a high metal removal activity, the bulk density can be reduced to 0.52 cm 3 / g or less. Thereby, the load of the reactor filled with the catalyst can be reduced, and the durability of the reactor can be improved even if the differential pressure is somewhat high.
本発明の水素化精製触媒は、水素化活性金属成分として、モリブデンを２〜６重量％含み得、ニッケルまたはコバルトを０．５〜２重量％含み得る。さらに、水素化精製触媒はリンまたはホウ素を０．５〜１．５重量％含み得る。 The hydrorefining catalyst of the present invention may contain 2 to 6% by weight of molybdenum and 0.5 to 2% by weight of nickel or cobalt as the hydrogenation active metal component. Further, the hydrorefining catalyst may contain 0.5 to 1.5% by weight of phosphorus or boron.
本発明の第２の態様に従えば、水素化活性金属を含む水素化精製用触媒の製造方法であって：γ−アルミナを主成分とし、細孔容積が０．７５ｃｍ３／ｇ以上であり、平均粒子直径が１０〜２００μｍである多孔性の原料粉体を混練して混練物を調製すること；上記混練物を成形及び焼成すること；及び、活性金属成分を混練物または焼成後の混練物に担持させることを含む水素化精製用触媒の製造方法が提供される。本発明の方法では、主成分としてγ−アルミナ粉体を用い、且つ上記規定の細孔容積及び平均粒子径を有する多孔性の粉体を原料として用いているために、脱金属活性と金属堆積容量がともに高い水素化精製触媒及びそれに用いられる触媒担体を容易に且つ低コストで製造することができる。 According to a second aspect of the present invention, there is provided a method for producing a hydrorefining catalyst containing a hydrogenation active metal, comprising γ-alumina as a main component and a pore volume of 0.75 cm 3 / g or more. Kneading a porous raw material powder having an average particle diameter of 10 to 200 μm to prepare a kneaded product; molding and firing the kneaded product; and kneading the active metal component or kneading after firing There is provided a method for producing a hydrorefining catalyst comprising supporting a product. In the method of the present invention, γ-alumina powder is used as a main component, and a porous powder having the above defined pore volume and average particle diameter is used as a raw material. A hydrorefining catalyst having a high capacity and a catalyst carrier used therefor can be easily produced at low cost.
本書において、「γ−アルミナを主成分とする」とは、原料粉体の７０重量％以上がγ−アルミナであることを意味し、残部は、例えば、擬ベーマイトなどのベーマイトにし得る。触媒の脱金属活性と金属堆積容量を一層良好にするには、原料粉体の９０重量％以上、特には、９５重量％以上がγ−アルミナであることが好ましい。さらに、望ましくは、原料粉体のほぼ１００％がγ−アルミナ粉体である。また、本書において、用語「γ−アルミナ」とは、波長０．１５４ｎｍのＸ線回析において、２θ＝４６°及び６７°にピークを有する遷移アルミナである。γ−アルミナ粉体は、ベーマイト粉体を焼成することによって調製するのが好適である。本明細書でベーマイト粉体とは、ベーマイトまたは擬ベーマイトの粉体を意味する。なお、擬ベーマイトは、結晶内に余分の水分子を持つα−アルミナ水和物であり、Ａｌ２Ｏ３・ＸＨ２Ｏで表され、Ｘは１以上２未満である。 In this document, “having γ-alumina as a main component” means that 70% by weight or more of the raw material powder is γ-alumina, and the remainder can be boehmite such as pseudoboehmite. In order to further improve the demetalization activity and metal deposition capacity of the catalyst, 90% by weight or more, particularly 95% by weight or more of the raw material powder is preferably γ-alumina. Further, desirably, almost 100% of the raw material powder is γ-alumina powder. Further, in this document, the term “γ-alumina” is a transition alumina having peaks at 2θ = 46 ° and 67 ° in X-ray diffraction with a wavelength of 0.154 nm. The γ-alumina powder is preferably prepared by firing boehmite powder. In the present specification, boehmite powder means boehmite or pseudoboehmite powder. Pseudoboehmite is α-alumina hydrate having extra water molecules in the crystal, represented by Al 2 O 3 .XH 2 O, and X is 1 or more and less than 2.
本発明の水素化精製触媒の製造方法において、成形コスト及び触媒担体の高空隙率という観点から、例えば、成形器を用いた押出成形により成形するのが好ましい。 In the method for producing a hydrorefining catalyst of the present invention, it is preferable to perform molding by, for example, extrusion molding using a molding machine from the viewpoint of molding cost and high porosity of the catalyst carrier.
以下に本発明の水素化精製触媒及びその製造方法を具体的に説明する。 The hydrorefining catalyst of the present invention and the production method thereof will be specifically described below.
ｉ）触媒の中央細孔直径、細孔容積及び比表面積
本発明の水素化精製触媒において、窒素吸着法により測定された細孔、例えば、１．８〜６０ｎｍの細孔直径を有する細孔の中央細孔直径は、８ｎｍ以上、例えば、８〜２０ｎｍ、好ましくは８〜１５ｎｍ、特に好ましくは８〜１３ｎｍである。水素化精製触媒において、窒素吸着法により測定された細孔、例えば、１．８〜６０ｎｍの細孔直径を有する細孔の細孔容積は、０．５６ｃｍ３／ｇ以上、好ましくは０．５６〜１．０ｃｍ３／ｇ、特に好ましくは０．５６〜０．８ｃｍ３／ｇ、一層特に好ましくは０．６２〜０．８ｃｍ３／ｇである。本発明の触媒の比表面積は、１５０ｍ２／ｇ以上、好ましくは１７０〜３００ｍ２／ｇ、特に好ましくは１８０〜２８０ｍ２／ｇである。上記中央細孔直径、細孔容積及び比表面積は、窒素吸着法により測定される。中央細孔直径は、窒素ガスの脱離過程における相対圧０．９６７の条件で得られる窒素ガスの吸着量を液体として換算した体積の値を細孔容積（Ｖ）とし、ＢＪＨ法によって算出された細孔容積と細孔直径の関係から、細孔直径の大きい側からの累積細孔容積が細孔容積Ｖの半分（Ｖ／２）となる細孔直径として測定することができる。窒素吸着法により細孔直径約２〜６０ｎｍの細孔分布を測定することができる。なお、ＢＪＨ法は、Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，ｖｏｌ．７３，ｐ．３７３〜（１９５１）に開示されている。
i) Central pore diameter, pore volume and specific surface area of catalyst In the hydrorefining catalyst of the present invention, pores measured by a nitrogen adsorption method, for example, pores having a pore diameter of 1.8 to 60 nm are used. The central pore diameter is 8 nm or more, for example, 8 to 20 nm, preferably 8 to 15 nm, particularly preferably 8 to 13 nm. In the hydrorefining catalyst, the pore volume of the pores measured by the nitrogen adsorption method, for example, pores having a pore diameter of 1.8 to 60 nm is 0.56 cm 3 / g or more, preferably 0.56. It is -1.0cm < 3 > / g, Most preferably, it is 0.56-0.8cm < 3 > / g, More preferably, it is 0.62-0.8cm < 3 > / g. The specific surface area of the catalyst of the present invention is 150 m 2 / g or more, preferably 170 to 300 m 2 / g, particularly preferably 180 to 280 m 2 / g. The central pore diameter, pore volume and specific surface area are measured by a nitrogen adsorption method. The median pore diameter is calculated by the BJH method with the volume value of the nitrogen gas adsorption amount obtained under the condition of a relative pressure of 0.967 in the nitrogen gas desorption process converted as a liquid and the pore volume (V). From the relationship between the pore volume and the pore diameter, the cumulative pore volume from the larger pore diameter side can be measured as the pore diameter that is half the pore volume V (V / 2). A pore distribution having a pore diameter of about 2 to 60 nm can be measured by a nitrogen adsorption method. The BJH method is described in Journal of The American Chemical Society, vol. 73, p. 373- (1951).
本発明の水素化精製触媒において、水銀圧入法により測定した細孔の細孔容積は、０．８７ｃｍ３／ｇ以上、好ましくは０．８７〜１．１ｃｍ３／ｇ、特に好ましくは０．８８〜１．０５ｃｍ３／ｇである。また、水銀圧入法により測定した細孔の内、１０００ｎｍ以上の細孔直径を有する細孔の細孔容積は、０．２ｃｍ３／ｇ以下であることが好ましい。なお、水銀圧入法による測定は、水銀の接触角度１４０°、表面張力４８０ｄｙｎｅ／ｃｍとし、２〜４２２５ｋｇ／ｃｍ２（３０．４〜６００００ｐｓｉａ）の範囲で行った。 In the hydrorefining catalyst of the present invention, the pore volume measured by mercury porosimetry is 0.87 cm 3 / g or more, preferably 0.87 to 1.1 cm 3 / g, particularly preferably 0.88. -1.05 cm < 3 > / g. Of the pores measured by mercury porosimetry, the pore volume of pores having a pore diameter of 1000 nm or more is preferably 0.2 cm 3 / g or less. The measurement by the mercury intrusion method was performed in a range of 2 to 4225 kg / cm 2 (30.4 to 60000 psia) with a mercury contact angle of 140 ° and a surface tension of 480 dyne / cm.
本発明において、細孔容積の測定に窒素吸着法と水銀圧入法を用いたのは、当業界で知られたように、前者の方法は細孔壁に吸着した窒素量を測定しているために約６０ｎｍ以下の比較的小さい細孔直径の細孔の細孔容積しか測定することができず、一方、後者では、細孔に充填された水銀の容量を測定するために数ｎｍ以上の広範囲の細孔直径を有する細孔を測定することができるからである。 In the present invention, the nitrogen adsorption method and the mercury intrusion method were used to measure the pore volume because the former method measured the amount of nitrogen adsorbed on the pore wall, as known in the art. Can measure only the pore volume of pores with a relatively small pore diameter of about 60 nm or less, while the latter has a wide range of several nm or more to measure the capacity of mercury filled in the pores. This is because it is possible to measure pores having a pore diameter of.
ｉｉ）触媒のかさ密度
本発明による触媒のかさ密度は、０．５２ｃｍ３／ｇ以下、特には０．４０〜０．５２ｃｍ３／ｇ、さらには０．４２〜０．５２ｃｍ３／ｇが好ましい。これを超えた場合には、脱金属性能が相対的に低下する。本発明の触媒を得るために用いられる触媒用担体のかさ密度は、０．５０ｃｍ３／ｇ以下、特には、０．３５〜０．５０ｃｍ３／ｇが好ましい。かさ密度は、目盛りのついた１００ｃｍ３のシリンダーに触媒又は担体を充填し、１００回振動を与えた後の見かけ上の体積から求めることができる。
ii) Bulk density of the catalyst The bulk density of the catalyst according to the present invention is preferably 0.52 cm 3 / g or less, particularly preferably 0.40 to 0.52 cm 3 / g, more preferably 0.42 to 0.52 cm 3 / g. . When this is exceeded, the metal removal performance is relatively lowered. The bulk density of the catalyst carrier used for obtaining the catalyst of the present invention is preferably 0.50 cm 3 / g or less, particularly preferably 0.35 to 0.50 cm 3 / g. The bulk density can be determined from the apparent volume after a 100 cm 3 cylinder with a scale is filled with a catalyst or a support and subjected to
ｉｉｉ）耐火性多孔質担体
本発明による触媒の好ましい担体は、γ−アルミナを主成分とし、細孔容積が０．７５ｃｍ３／ｇ以上であり、平均粒子直径が１０〜２００μｍである多孔性の原料粉体を混練して混練物を調製し、この混練物を成形・焼成して製造することができる。このγ−アルミナは、触媒重量に対し７０％以上、特には８０％以上含有されていることが好ましい。この触媒は、γ−アルミナ以外にシリカ−アルミナ、ゼオライト、ボリア、チタニア、ジルコニア、マグネシアまたはその他の複合酸化物を含んでもよい。γ−アルミナを主成分として用いるのは、得られる触媒担体がγ−アルミナであれば高活性となるからである。
iii) Refractory porous support A preferred support of the catalyst according to the present invention is a porous support having γ-alumina as a main component, a pore volume of 0.75 cm 3 / g or more, and an average particle diameter of 10 to 200 μm. A kneaded material can be prepared by kneading the raw material powder, and the kneaded material can be formed and fired for production. This γ-alumina is preferably contained in an amount of 70% or more, particularly 80% or more based on the catalyst weight. The catalyst may contain silica-alumina, zeolite, boria, titania, zirconia, magnesia or other complex oxides in addition to γ-alumina. The reason why γ-alumina is used as a main component is that if the obtained catalyst carrier is γ-alumina, the activity becomes high.
担体の製造に用いられる多孔性の原料粉体は、γ−アルミナを主成分とし、細孔容積が０．７５ｃｍ３／ｇ以上、特には０．９〜１．３ｃｍ３／ｇであり、平均粒子直径が１０〜２００μｍ、特には１０〜１５０μｍ、さらには３０〜１５０μｍであることが好ましい。なお、ここでいう細孔容積の値は、窒素ガスの脱離過程における相対圧０．９６７の条件で得られる窒素ガスの吸着量を液体として換算した体積の値として測定できる。また、ここでいう平均粒子直径とは、湿式のレーザー光散乱法で測定される粒度分布のメジアン直径として測定できる。 The porous raw material powder used for the production of the carrier is mainly composed of γ-alumina, and has a pore volume of 0.75 cm 3 / g or more, particularly 0.9 to 1.3 cm 3 / g, average The particle diameter is preferably 10 to 200 μm, particularly 10 to 150 μm, and more preferably 30 to 150 μm. The value of the pore volume mentioned here can be measured as a volume value obtained by converting the adsorption amount of nitrogen gas obtained under the condition of a relative pressure of 0.967 in the desorption process of nitrogen gas as a liquid. The average particle diameter here can be measured as the median diameter of the particle size distribution measured by a wet laser light scattering method.
細孔容積が０．７５ｃｍ３／ｇ未満または平均粒子直径１０μｍ未満の原料粉体を用いると、混練物の可塑性が悪く、これを成形すると成形体の構造に欠陥が生じ、触媒の摩耗強度が低くなる。このような触媒を反応器に充填すると、充填の際に粉が生成し、触媒の空隙を埋めて、差圧増大の原因となる。平均粒子直径が２００μｍを越える原料粉体を用いると、触媒の破壊強度が小さくなり、反応器に充填後、触媒自体の荷重により破壊してしまう。 If a raw material powder having a pore volume of less than 0.75 cm 3 / g or an average particle diameter of less than 10 μm is used, the plasticity of the kneaded product is poor, and if this is molded, defects occur in the structure of the molded product and the wear strength of the catalyst is reduced. Lower. When such a catalyst is filled in the reactor, powder is generated during filling, filling the voids of the catalyst and causing an increase in the differential pressure. When the raw material powder having an average particle diameter exceeding 200 μm is used, the breaking strength of the catalyst is reduced, and after the reactor is filled, it is broken by the load of the catalyst itself.
この原料粉体には、シリカ−アルミナ、ゼオライト、ボリア、チタニア、ジルコニア、マグネシアまたはその他の複合酸化物を含むことができるが、原料粉体の内、担体の重量に対し、７０％以上、特には８０％以上をγ−アルミナとすることが好ましい。細孔直径２〜６０ｎｍの細孔分布における中央細孔直径が８〜１５ｎｍであり、比表面積が２３０〜３３０ｍ２／ｇであることが、高い触媒活性を得るために好ましい。原料粉体の主成分となるγ−アルミナは、擬ベーマイト粉体を４５０〜６５０℃で焼成したものであることが好ましい。 This raw material powder can contain silica-alumina, zeolite, boria, titania, zirconia, magnesia or other complex oxides, but 70% or more, especially with respect to the weight of the carrier in the raw material powder. 80% or more is preferably γ-alumina. In order to obtain a high catalytic activity, it is preferable that the median pore diameter in the pore distribution having a pore diameter of 2 to 60 nm is 8 to 15 nm and the specific surface area is 230 to 330 m 2 / g. The γ-alumina that is the main component of the raw material powder is preferably one obtained by firing pseudo boehmite powder at 450 to 650 ° C.
ｉｖ）混練
混練は、一般に触媒調製に用いられている混練機により行うことができる。上述の原料粉体に水を加えて投入し、攪拌羽根で混合する方法が好適に用いられる。通常、混練の際には水を加えるが、加える液体としては、アルコールやケトンでもよい。また、硝酸、酢酸、蟻酸などの酸やアンモニアなどの塩基、有機化合物、界面活性剤、活性成分等を加えて混練してもよく、特には、水溶性セルロースエーテルなどの有機化合物からなるバインダー成分を原料粉体に対して０．２〜５重量％加えることが好ましい。混練時間及び混練温度は、適宜選択できるが、混線物を直径３３ｍｍ、高さ４０ｍｍの円柱状の試験体にし、重さ１１９２ｇの円盤（直径１２０ｍｍ、高さ７．５ｍｍ）を試験体の底面から１８６ｍｍの高さから落下させ（Ｐｆｅｆｆｅｒｋｏｒｎの可塑性試験機；セラミックスの製造プロセス−粉末調整と成形−、窯業協会編集委員会講座小委員会編、社団法人窯業協会、１９８４）、変形した試験体の高さ（以下、ＰＦ値という）が、１５ｍｍから２５ｍｍとなるまで混練することが好ましい。
iv) Kneading Kneading can be performed by a kneader generally used for catalyst preparation. A method in which water is added to the raw material powder described above and then mixed with a stirring blade is preferably used. Usually, water is added at the time of kneading, but the liquid to be added may be alcohol or ketone. Further, it may be kneaded by adding an acid such as nitric acid, acetic acid or formic acid, a base such as ammonia, an organic compound, a surfactant, an active ingredient, etc., and in particular, a binder component comprising an organic compound such as a water-soluble cellulose ether. Is preferably added in an amount of 0.2 to 5% by weight based on the raw material powder. The kneading time and kneading temperature can be selected as appropriate, but the mixed line is made into a cylindrical specimen having a diameter of 33 mm and a height of 40 mm, and a disk having a weight of 1192 g (diameter of 120 mm and height of 7.5 mm) is taken from the bottom surface of the specimen. Dropped from a height of 186 mm (Pfefferkorn plasticity testing machine; ceramic manufacturing process-powder preparation and molding-edited by the Ceramic Industry Association Editorial Committee Lecture Committee, Ceramic Association of Japan, 1984) It is preferable to knead until the thickness (hereinafter referred to as PF value) is 15 mm to 25 mm.
ｖ）成形・焼成
成形は、プランジャー式押出機、スクリュー式押出機などの装置を用いて、容易にペレット状、ハニカム状などの形状とすることができる。本発明においては、プランジャー式押出機が好適である。通常、０．５〜６ｍｍ径、特には、０．５〜５ｍｍ径の円柱状、中空円筒状、断面が三葉または四葉の柱状などの形状の成形体が用いられる。成形した後、常温〜１５０℃で、特には１００〜１４０℃で乾燥した後、３５０〜９００℃で０．５時間以上、特には５００〜８５０℃で０．５〜５時間焼成することが好ましい。
v) Molding / Firing Molding can be easily formed into a pellet shape, a honeycomb shape, or the like using an apparatus such as a plunger type extruder or a screw type extruder. In the present invention, a plunger type extruder is suitable. Usually, a molded body having a shape of a column having a diameter of 0.5 to 6 mm, particularly a column having a diameter of 0.5 to 5 mm, a hollow cylinder, and a three-leaf or four-leaf cross section is used. After molding, it is preferably dried at room temperature to 150 ° C., particularly 100 to 140 ° C., and then calcined at 350 to 900 ° C. for 0.5 hour or more, particularly 500 to 850 ° C. for 0.5 to 5 hours. .
ｖｉ）水素化活性金属成分
水素化活性金属成分としては、第６族、第８族、第９族及び第１０族元素を、特には、モリブデン、タングステン、ニッケル、コバルトの中から１種、あるいは２種以上組み合わせて用いることが好適である。これらの元素は、触媒中に金属、酸化物あるいは硫化物状態で含有させることが好ましい。これらの元素の含有量は、金属重量の合計として触媒全体中に０．１重量％〜２０重量％の範囲が好ましく、特には、１重量％〜１０重量％の範囲が好ましい。
vi) Hydrogenation active metal component As the hydrogenation active metal component,
水素化活性金属成分を触媒中に含有させる方法としては、担持法、練り込み法などを用いることができる。少なくとも１種類の水素化活性金属成分を練り込み法により含有させることで、脱金属活性を高めることができる。練り込み法としては、水素化活性金属成分を予め原料粉体に含ませておいてもよいし、原料粉体とともに混練して練り込んでもよい。 As a method for containing the hydrogenation active metal component in the catalyst, a supporting method, a kneading method, or the like can be used. By including at least one hydrogenation active metal component by a kneading method, the metal removal activity can be enhanced. As the kneading method, the hydrogenation active metal component may be previously contained in the raw material powder, or may be kneaded and kneaded together with the raw material powder.
また、水素化活性金属成分を触媒担体に担持してもよく、担持する方法としては、通常用いられる含浸法、例えば、ｐｏｒｅ−ｆｉｌｌｉｎｇ法、加熱含浸法、真空含浸法等、浸漬法等の公知の手法を用いることができる。金属成分を担持した後、８０〜２００℃の温度で１０分〜２４時間乾燥し、４００〜６００℃、特には、４５０〜５５０℃の温度で１５分〜１０時間焼成することが好ましい。 In addition, the hydrogenation active metal component may be supported on a catalyst carrier, and as a method for supporting, a commonly used impregnation method, for example, a pore-filling method, a heat impregnation method, a vacuum impregnation method, a dipping method, or the like is known. Can be used. After supporting the metal component, it is preferable to dry at a temperature of 80 to 200 ° C. for 10 minutes to 24 hours and to fire at 400 to 600 ° C., particularly at a temperature of 450 to 550 ° C. for 15 minutes to 10 hours.
ｖｉｉ）他の活性成分
本発明の触媒には、リンおよび／またはホウ素の酸化物を触媒中に元素重量として０．１重量％〜２０重量％、特には、０．２重量％〜５重量％、一層特には０．５重量％〜１．５重量％加えることが好ましく、これにより、脱金属活性が向上する。
vii) Other active ingredients The catalyst of the present invention contains phosphorus and / or boron oxides in an amount of 0.1 to 20% by weight, in particular 0.2 to 5% by weight, in terms of elemental weight in the catalyst. More preferably, it is preferably added in an amount of 0.5 to 1.5% by weight, thereby improving the metal removal activity.
ｖｉｉｉ）水素化精製の対象物
本発明の触媒は、沸点が３５０℃以上の留分を含む重質油、すなわち、原油、タールサンド、シェールオイルあるいは石炭液化油等を常圧蒸留または減圧蒸留することにより得られる各種の重質留分や残渣油、あるいはこれらの分解、異性化、改質、溶剤抽出等の処理を行った重質油に、好ましく用いられるが、特には、減圧残渣油、常圧残渣油など金属分を多く含む、具体的には、ニッケルまたはバナジウムなどを金属重量として４５重量ｐｐｍ以上、特に、５０重量ｐｐｍ以上、さらには６０重量ｐｐｍ以上含む重質油の処理に好適である。また、アスファルテン分を３％以上含む重質油の処理に好適である。なお、代表的なアスファルテン分の測定は、アメリカ鉱山局法（Ａｎａｌ． Ｃｈｅｍ．，Ｖｏｌ．２０，ｐ４６０−，（１９６８））により規定されている。
viii) Object of hydrorefining The catalyst of the present invention distills heavy oil containing a fraction having a boiling point of 350 ° C. or higher, that is, crude oil, tar sand, shale oil, coal liquefied oil, or the like at atmospheric pressure or reduced pressure. It is preferably used for various heavy fractions and residual oils obtained by the above, or heavy oils that have undergone treatments such as decomposition, isomerization, modification, solvent extraction, etc. Suitable for treatment of heavy oil containing a large amount of metal such as atmospheric residue oil, specifically, nickel or vanadium as metal weight of 45 ppm by weight or more, especially 50 ppm by weight or more, and even 60 ppm by weight or more It is. Moreover, it is suitable for processing heavy oil containing 3% or more of asphaltenes. In addition, the measurement of typical asphaltene content is prescribed | regulated by the American Mining Bureau method (Anal. Chem., Vol.20, p460-, (1968)).
ｉｘ）水素化精製条件
本発明の触媒を用いて重質油を水素化精製する場合の好ましい条件は、反応温度３００〜４５０℃、水素分圧３０〜２５０ｋｇ／ｃｍ２、液空間速度０．１〜１０ｈｒ−１、水素対重質油の比１００〜４０００Ｌ／Ｌ、より好ましくは、反応温度３５０〜４２０℃、水素分圧８０〜２００ｋｇ／ｃｍ２、液空間速度０．１５〜１．０ｈｒ−１、水素対重質油の比５００〜１０００Ｌ／Ｌである。
ix) Hydrorefining conditions The preferred conditions for hydrorefining heavy oil using the catalyst of the present invention are as follows: reaction temperature 300 to 450 ° C., hydrogen
以下、本発明の水素化精製触媒の製造方法及び触媒を用いた原油の脱金属活性試験について実施例及び比較例を用いて具体的に説明する。 Hereinafter, the method for producing the hydrorefining catalyst of the present invention and the crude metal demetallation activity test using the catalyst will be described in detail with reference to Examples and Comparative Examples.
（１）触媒の調製
実施例１
〔触媒３０５６の調製〕
市販の擬ベーマイトからなる粉体Ａを６００℃で焼成し、γ−アルミナからなる粉体Ｇを作製した。この粉体Ｇの物性は、平均粒子直径が１０１μｍ、比表面積が２６８ｍ２／ｇ、細孔容積が１．０１ｃｍ３／ｇ、中央細孔直径が１２ｎｍであった。ここに示した細孔特性は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡＳＡＰ２４００型測定機を用いて測定した。平均粒子直径は、日機装（株）ＭＩＣＲＯＴＲＡＣ粒度分析計を用い、湿式法で測定した。この分析計は、試料を水中に分散させ、レーザー光を照射し、その前方散乱光により粒度分析を行う。
(1) Preparation of catalyst Example 1
[Preparation of catalyst 3056]
A powder A made of commercially available pseudoboehmite was fired at 600 ° C. to prepare a powder G made of γ-alumina. The physical properties of this powder G were an average particle diameter of 101 μm, a specific surface area of 268 m 2 / g, a pore volume of 1.01 cm 3 / g, and a central pore diameter of 12 nm. The pore characteristics shown here were measured using an ASAP2400 type measuring machine manufactured by Micromeritics. The average particle diameter was measured by a wet method using a Nikkiso Co., Ltd. MICROTRAC particle size analyzer. This analyzer disperses a sample in water, irradiates a laser beam, and performs a particle size analysis using the forward scattered light.
次いで、得られた粉体Ｇ１５００ｇに、イオン交換水２０５８ｇ、水溶性セルロースエーテル１５ｇを加えて混練を行った。スクリュー式押し出し成形機を用いて、混練物を直径１．６ｍｍの円形開口から押し出し、円柱状の成形物とした。この成形物を、乾燥機を用いて１３０℃で１５時間乾燥させた後、空気の気流下で８００℃で１時間焼成を行い、担体とした。 Next, 2058 g of ion-exchanged water and 15 g of water-soluble cellulose ether were added to 1500 g of the obtained powder G and kneaded. The kneaded product was extruded from a circular opening having a diameter of 1.6 mm using a screw-type extrusion molding machine to obtain a cylindrical molded product. The molded product was dried at 130 ° C. for 15 hours using a dryer, and then fired at 800 ° C. for 1 hour in an air stream to obtain a carrier.
この担体に、モリブデン酸アンモニウム水溶液からなる担持液をスプレー法で含浸し、１３０℃で２０時間乾燥した後、硝酸ニッケル水溶液からなる担持液を再度スプレー法で含浸し、１３０℃で２０時間乾燥し、空気の気流下で４５０℃で２５分間焼成を行い、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０５６を調製した。
The carrier was impregnated with a supporting liquid composed of an ammonium molybdate aqueous solution by a spray method and dried at 130 ° C. for 20 hours, and then impregnated with a supporting liquid composed of an aqueous nickel nitrate solution again by a spray method and dried at 130 ° C. for 20 hours. The
実施例２
〔触媒３０６６の調製〕
実施例１で調製した粉体Ｇ１５００ｇに、イオン交換水２１７７ｇ、水溶性セルロースエーテル１５ｇを加えて混練を行った。ＰＦ値が２０ｍｍになるまで混練した。次いで、プランジャー式押し出し成形機を用いて成形し、実施例１と同様の条件で焼成して担体とした。得られた担体に、モリブデン酸アンモニウム、硝酸ニッケル及びリン酸の水溶液からなる担持液をスプレー法で含浸し、１３０℃で２０時間乾燥し、空気の気流下で４５０℃で２５分間焼成を行い、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを０．６重量％含有する触媒３０６６を調製した。
Example 2
[Preparation of catalyst 3066]
To 1500 g of the powder G prepared in Example 1, 2177 g of ion-exchanged water and 15 g of water-soluble cellulose ether were added and kneaded. The kneading was continued until the PF value reached 20 mm. Subsequently, it shape | molded using the plunger type | mold extrusion molding machine, was baked on the conditions similar to Example 1, and was set as the support | carrier. The resulting support was impregnated with a support liquid composed of an aqueous solution of ammonium molybdate, nickel nitrate and phosphoric acid by a spray method, dried at 130 ° C. for 20 hours, and baked at 450 ° C. for 25 minutes in an air stream. A
実施例３
〔触媒３０７０の調製〕
実施例１と同様にして調製した担体に、モリブデン酸アンモニウム及びホウ酸の水溶液からなる担持液をスプレー法で含浸し、１３０℃で２０時間乾燥した後、硝酸ニッケル水溶液からなる担持液を再度スプレー法で含浸し、１３０℃で２０時間乾燥し、空気の気流下で４５０℃で２５分間焼成を行い、モリブデンを３．０重量％、ニッケルを１．０重量％、ホウ素を１．０重量％含有する触媒３０７０を調製した。
Example 3
[Preparation of catalyst 3070]
A carrier prepared in the same manner as in Example 1 was impregnated with a supporting liquid composed of an aqueous solution of ammonium molybdate and boric acid by a spray method, dried at 130 ° C. for 20 hours, and then sprayed again with a supporting liquid composed of an aqueous nickel nitrate solution. Impregnated by the method, dried at 130 ° C. for 20 hours, fired at 450 ° C. for 25 minutes in an air stream, molybdenum 3.0% by weight, nickel 1.0% by weight, boron 1.0% by weight
実施例４
〔触媒３０５７の調製〕
粉体Ｇ１５００ｇに、モリブデン酸アンモニウム水溶液２０６２ｇ、水溶性セルロースエーテル７ｇを加えて混練を行った。スクリュー式押し出し成形機を用いて、混練物を直径１．６ｍｍの円形開口から押し出し、円柱状の成形物とした。この成形物を、乾燥機を用いて１３０℃で１５時間乾燥させた後、空気の気流下で６００℃で１時間焼成を行い、担体とした。
Example 4
[Preparation of catalyst 3057]
Kneading was carried out by adding 2062 g of ammonium molybdate aqueous solution and 7 g of water-soluble cellulose ether to 1500 g of the powder G. The kneaded product was extruded from a circular opening having a diameter of 1.6 mm using a screw-type extrusion molding machine to obtain a cylindrical molded product. The molded product was dried at 130 ° C. for 15 hours using a dryer, and then fired at 600 ° C. for 1 hour in an air stream to obtain a carrier.
この担体に、硝酸ニッケル水溶液からなる担持液をスプレー法で含浸し、１３０℃で２０時間乾燥した後、空気の気流下で４５０℃で２５分間焼成を行い、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０５７を調製した。
This carrier was impregnated with a carrier solution composed of an aqueous nickel nitrate solution by spraying, dried at 130 ° C. for 20 hours, and then fired at 450 ° C. for 25 minutes in an air stream to obtain 3.0 wt% molybdenum,
実施例５
〔触媒３０５８の調製〕
乾燥後の成形物を空気の気流下で８００℃で１時間焼成を行って担体とした以外は、実施例４と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０５８を得た。
Example 5
[Preparation of catalyst 3058]
A catalyst was prepared in the same manner as in Example 4 except that the dried molded product was calcined at 800 ° C. for 1 hour under an air stream to prepare a carrier, and 3.0% by weight of molybdenum and 1.% of nickel. A
実施例６
〔触媒３００９の調製〕
市販の擬ベーマイトからなる粉体Ｂを６００℃で焼成し、γ−アルミナからなる粉体Ｈを作製した。この粉体Ｈの物性は、平均粒子直径が１２μｍ、比表面積が２３６ｍ２／ｇ、細孔容積が０．８２ｃｍ３／ｇ、中央細孔直径が１２ｎｍであった。粉体Ｈ１１３７ｇ及び擬ベーマイトからなる粉体Ｅ３６３ｇに、イオン交換水１６２７ｇを加えて混練を行った。スクリュー式押し出し成形機を用いて、混練物を直径１．６ｍｍの円形開口から押し出し、円柱状の成形物とした。この成形物を、乾燥機を用いて１３０℃で１５時間乾燥させた後、空気の気流下で６００℃で１時間焼成を行い、担体とした。
Example 6
[Preparation of catalyst 3009]
A powder B made of commercially available pseudoboehmite was fired at 600 ° C. to prepare a powder H made of γ-alumina. The physical properties of this powder H were an average particle diameter of 12 μm, a specific surface area of 236 m 2 / g, a pore volume of 0.82 cm 3 / g, and a central pore diameter of 12 nm. To 1363 g of powder H and 363 g of powder E consisting of pseudoboehmite, 1627 g of ion-exchanged water was added and kneaded. The kneaded product was extruded from a circular opening having a diameter of 1.6 mm using a screw-type extrusion molding machine to obtain a cylindrical molded product. The molded product was dried at 130 ° C. for 15 hours using a dryer, and then fired at 600 ° C. for 1 hour in an air stream to obtain a carrier.
この担体を用いて、実施例１と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３００９を得た。
Using this carrier, a catalyst was prepared in the same manner as in Example 1 to obtain a
実施例７
〔触媒３０３２の調製〕
乾燥後の成形物を空気の気流下で８００℃で１時間焼成を行った以外は、実施例６と同様にして担体を調製した。得られた担体を用いて、実施例２（触媒３０６６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを１．０重量％含有する触媒３０３２を得た。
Example 7
[Preparation of catalyst 3032]
A carrier was prepared in the same manner as in Example 6 except that the dried molded product was baked at 800 ° C. for 1 hour under an air stream. Using the obtained carrier, a catalyst was prepared in the same manner as in Example 2 (Catalyst 3066), and a catalyst containing 3.0% by weight of molybdenum, 1.0% by weight of nickel and 1.0% by weight of
実施例８
〔触媒３０７６の調製〕
ＰＦ値が１９ｍｍとなるまで混練した混練物を直径１．３ｍｍの円形開口から押し出した以外は、実施例２（触媒３０６６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを０．６重量％含有する触媒３０７６を得た。
Example 8
[Preparation of catalyst 3076]
A catalyst was prepared in the same manner as in Example 2 (Catalyst 3066) except that the kneaded material kneaded until the PF value reached 19 mm was extruded from a circular opening having a diameter of 1.3 mm. A
実施例９
〔触媒３０８７の調製〕
ＰＦ値が１６ｍｍとなるまで混練した混練物を直径１．７ｍｍの四葉状開口から押し出した以外は、実施例２（触媒３０６６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを０．６重量％、それぞれ含有する触媒３０８７を得た。
Example 9
[Preparation of catalyst 3087]
A catalyst was prepared in the same manner as in Example 2 (Catalyst 3066) except that the kneaded material kneaded until the PF value reached 16 mm was extruded from a four-leaf opening having a diameter of 1.7 mm. A
比較例１
〔触媒３０４３の調製〕
市販の擬ベーマイトからなる粉体Ｃを６００℃で焼成し、γ−アルミナからなる粉体Ｉを調製した。この粉体Ｉの物性は、平均粒子直径が１７μｍ、比表面積が２５６ｍ２／ｇ、細孔容積が０．７０ｃｍ３／ｇ、中央細孔直径が１０ｎｍであった。
Comparative Example 1
[Preparation of catalyst 3043]
Powder C made of commercially available pseudoboehmite was fired at 600 ° C. to prepare Powder I made of γ-alumina. As for the physical properties of this powder I, the average particle diameter was 17 μm, the specific surface area was 256 m 2 / g, the pore volume was 0.70 cm 3 / g, and the central pore diameter was 10 nm.
粉体Ｉを用いて、空気の気流下で６００℃で１時間焼成して担体とした以外は、実施例１（触媒３０５６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０４３を得た。
A catalyst was prepared using the powder I in the same manner as in Example 1 (Catalyst 3056) except that it was calcined at 600 ° C. for 1 hour under an air stream to prepare a carrier. A
比較例２
〔触媒３０１０の調製〕
実施例６で用いた粉体Ｈ８０５９及び粉体Ｅ６９５ｇに対して、イオン交換水１５８９ｇを加えて混練を行った。次いで、実施例６（触媒３００９）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０１０を得た。
Comparative Example 2
[Preparation of catalyst 3010]
To the powder H8059 and the powder E695 g used in Example 6, 1589 g of ion-exchanged water was added and kneaded. Next, a catalyst was prepared in the same manner as in Example 6 (Catalyst 3009) to obtain a
比較例３
〔触媒３０９３の調製〕
粉体Ｇ１５００ｇに、イオン交換水２０６８ｇ、水溶性セルロースエーテル１５ｇを加え、ＰＦ値が２５ｍｍになるまで混練した。次いで、実施例２（触媒３０６６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを０．６重量％含有する触媒３０９３を得た。
Comparative Example 3
[Preparation of catalyst 3093]
To 1,500 g of powder G, 2068 g of ion-exchanged water and 15 g of water-soluble cellulose ether were added and kneaded until the PF value became 25 mm. Next, a catalyst was prepared in the same manner as in Example 2 (Catalyst 3066) to obtain a
比較例４
〔触媒３０４１の調製〕
１４５６ｇの粉体Ｉ及び市販の擬ベーマイトからなる粉体Ｆ４４ｇに、イオン交換水４３１ｇ、硝酸水溶液１０００ｇ、ポリビニルアルコール水溶液２５５ｇを加えて混練を行った。次いで、比較例１（触媒３０４３）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０４１を得た。
Comparative Example 4
[Preparation of catalyst 3041]
Kneading was conducted by adding 431 g of ion-exchanged water, 1000 g of nitric acid aqueous solution, and 255 g of polyvinyl alcohol aqueous solution to 44 g of powder F consisting of 1456 g of powder I and commercially available pseudoboehmite. Next, a catalyst was prepared in the same manner as in Comparative Example 1 (Catalyst 3043) to obtain a
比較例５
〔触媒３０２１の調製〕
市販の擬ベーマイトからなる粉体Ｄを６００℃で焼成し、γ−アルミナからなる粉体Ｊを調製した。この粉体Ｊの物性は、平均粒子直径が６６μｍ、比表面積が２９９ｍ２／ｇ、細孔容積が０．９２ｃｍ３／ｇ、中央細孔直径が１１ｎｍであった。
Comparative Example 5
[Preparation of catalyst 3021]
Commercially available powder D made of pseudoboehmite was fired at 600 ° C. to prepare powder J made of γ-alumina. The physical properties of the powder J were an average particle diameter of 66 μm, a specific surface area of 299 m 2 / g, a pore volume of 0.92 cm 3 / g, and a central pore diameter of 11 nm.
粉体Ｊ１５００ｇに、イオン交換水８５４ｇ、硝酸水溶液７５２ｇを加えて混練を行った。次いで、プランジャー式押し出し成形機を用いて成形する以外は、比較例１（触媒３０４３）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０２１を得た。 Kneading was performed by adding 854 g of ion-exchanged water and 752 g of an aqueous nitric acid solution to 1500 g of the powder J. Next, a catalyst was prepared in the same manner as in Comparative Example 1 (Catalyst 3043) except that it was molded using a plunger type extrusion molding machine, and a catalyst containing 3.0% by weight of molybdenum and 1.0% by weight of nickel. 3021 was obtained.
比較例６
〔触媒３０２３の調製〕
粉体Ｊ１１６２ｇ及び粉体Ｅ３３８ｇに、イオン交換水１３８１ｇを加えて混練を行った。次いで、比較例１（触媒３０４３）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％含有する触媒３０２３を得た。
Comparative Example 6
[Preparation of catalyst 3023]
To the powder J1162g and the powder E338g, 1381 g of ion-exchanged water was added and kneaded. Next, a catalyst was prepared in the same manner as in Comparative Example 1 (Catalyst 3043) to obtain
比較例７
〔触媒３０２５の調製〕
粉体Ｊ１５００ｇに、イオン交換水７９２ｇ及び硝酸水溶液７５３ｇを加えて混練を行った。次いで、プランジャー式押し出し成形機を用いて成形する以外は、実施例１（触媒３０５６）と同様にして触媒を調製して、モリブデンを６．０重量％、ニッケルを１．５重量％含有する触媒３０２５を得た。
Comparative Example 7
[Preparation of catalyst 3025]
Kneading was performed by adding 792 g of ion-exchanged water and 753 g of an aqueous nitric acid solution to 1500 g of the powder J. Next, a catalyst was prepared in the same manner as in Example 1 (Catalyst 3056) except that it was molded using a plunger type extrusion molding machine, and contained 6.0% by weight of molybdenum and 1.5% by weight of nickel.
比較例８
〔触媒ＨＯＰ６０６〕
市販されているバイモーダル触媒ＨＯＰ６０６（オリエントキャタリスト製）を用いた。
Comparative Example 8
[Catalyst HOP606]
A commercially available bimodal catalyst HOP606 (manufactured by Orient Catalyst) was used.
比較例９
〔触媒３０６９の調製〕
粉体Ｉを粉体Ｇの代わりに用いた以外は、実施例２（触媒３０６６）と同様にして触媒を調製し、モリブデンを３．０重量％、ニッケルを１．０重量％、リンを０．６重量％それぞれ含有する触媒３０６９を得た。
Comparative Example 9
[Preparation of catalyst 3069]
A catalyst was prepared in the same manner as in Example 2 (Catalyst 3066) except that Powder I was used instead of Powder G. Molybdenum was 3.0% by weight, nickel was 1.0% by weight, and phosphorus was 0%. A
（２）触媒の物性評価
上記実施例及び比較例で製造した触媒の比表面積、細孔容積及び中央細孔直径を、それぞれ、前述の窒素吸着法で測定した。測定結果を図１の表１−Ａに示す。また、それらの触媒の細孔容積を、前述の水銀圧入法を用いて測定した。水銀圧入法を用いて５０ｎｍ以上の細孔直径の細孔の細孔容積及び１０００ｎｍ以上の細孔直径の細孔の細孔容積についても測定した。それらの水銀圧入法による細孔容積の測定結果を、図２に示した表１−Ｂに示す。
(2) Evaluation of physical properties of catalyst The specific surface area, pore volume and central pore diameter of the catalysts produced in the above Examples and Comparative Examples were measured by the above-mentioned nitrogen adsorption method. The measurement results are shown in Table 1-A in FIG. Moreover, the pore volume of these catalysts was measured using the mercury intrusion method described above. Using the mercury intrusion method, the pore volume of pores having a pore diameter of 50 nm or more and the pore volume of pores having a pore diameter of 1000 nm or more were also measured. The measurement results of the pore volume by the mercury intrusion method are shown in Table 1-B shown in FIG.
なお、表１−Ａには、前述した触媒形状及び寸法、担持した活性成分及び担体重量に対するγ−アルミナの重量比についても合わせて示した。また、触媒のかさ密度の測定結果について、表１−Ｂ中に示した。かさ密度の測定は、内径２８ｍｍ、測定容器１００ｃｍ３のシリンダーを有する測定装置（ＳＥＩＳＩＮ ＴＡＰＤＥＮＳＥＲＫＹＴ−３０００）を用いて測定した。さらに、表１−Ｂには、成形時に用いた押し出し機の種類を、Ｓ（スクリュー式押し出し機）またはＰ（プランジャー式押し出し機）により示した。 In Table 1-A, the catalyst shape and dimensions described above, the supported active ingredient, and the weight ratio of γ-alumina to the weight of the carrier are also shown. The measurement results of the bulk density of the catalyst are shown in Table 1-B. The bulk density was measured using a measuring device (SEISIN TAPDENSERKYT-3000) having a cylinder with an inner diameter of 28 mm and a measuring container of 100 cm 3 . Furthermore, in Table 1-B, the type of the extruder used at the time of molding is shown by S (screw type extruder) or P (plunger type extruder).
表１−Ａ及び１−Ｂの結果より、実施例１〜９の触媒では、窒素吸着法による細孔容積は０．５９ｃｍ３／ｇ以上であり、中央細孔直径が８．２ｎｍ以上であり、水銀圧入法による細孔容積は０．８８ｃｍ３／ｇ以上であり、水銀圧入法により測定した５０ｎｍ以上の細孔直径の細孔の細孔容積は０．３３ｃｍ３／ｇ以上であることがわかる。 From the results of Tables 1-A and 1-B, in the catalysts of Examples 1 to 9, the pore volume by the nitrogen adsorption method is 0.59 cm 3 / g or more, and the central pore diameter is 8.2 nm or more. The pore volume by mercury intrusion method is 0.88 cm 3 / g or more, and the pore volume of pores having a pore diameter of 50 nm or more measured by mercury intrusion method is 0.33 cm 3 / g or more. Recognize.
（３）触媒の脱メタル活性の評価
上記実施例及び比較例で製造した触媒の脱金属活性を評価するために、下記表２に示した性状のボスカン原油とラタウィ残渣油を原料油として用い、下記表３の運転条件で水素化脱金属反応を行った。
(3) Evaluation of catalyst demetallization activity In order to evaluate the demetallization activity of the catalysts produced in the above Examples and Comparative Examples, the properties of Boskan crude oil and Latawi residue oil shown in Table 2 below were used as raw material oils, The hydrodemetallation reaction was performed under the operating conditions shown in Table 3 below.
なお、ラタウィ残渣油は、ラタウィ原油の常圧残渣油５０％と減圧残渣油５０％の混合油である。 The Latawi residue oil is a mixed oil of 50% atmospheric pressure residue oil and 50% reduced pressure residue oil of Latawi crude oil.
硫化処理した各触媒を用いて、表３に示した触媒反応条件下で反応温度３８０℃から３８５℃、３９０℃に昇温して、ラタウィ残渣油を原油油として水素化精製反応を行って精製油のバナジウム及びニッケル濃度を測定した。測定されたバナジウム及びニッケル濃度から３９０℃の１次脱金属反応速度定数を求めて初期脱金属活性として、それらの値を表１‐Ｂに示した。 Using each sulfurated catalyst, the temperature was raised from 380 ° C. to 385 ° C. and 390 ° C. under the catalytic reaction conditions shown in Table 3, and refined by conducting a hydrorefining reaction using Latawi residue oil as crude oil. The vanadium and nickel concentrations of the oil were measured. The primary demetallation rate constant at 390 ° C. was determined from the measured vanadium and nickel concentrations, and the values are shown in Table 1-B as the initial demetallation activity.
実施例２，６，７，８，９及び比較例３，７，８で得られた触媒については、原料油をボスカン原油に切り替えて反応温度３９０℃で水素化精製を継続することにより触媒上のバナジウム及びニッケル金属堆積量の増加及び脱金属率の変化を求めた。その結果を、図３に示した。図３中、縦軸は脱金属率を示し、横軸は新触媒１００ｇに堆積した金属量（ｇ）を示す。
For the catalysts obtained in Examples 2, 6, 7, 8, and 9 and Comparative Examples 3, 7, and 8, the feedstock oil was switched to Boskan crude oil and hydrorefining was continued at a reaction temperature of 390 ° C. The increase of vanadium and nickel metal deposits and the change of metal removal rate were obtained. The results are shown in FIG. In FIG. 3, the vertical axis represents the metal removal rate, and the horizontal axis represents the amount of metal (g) deposited on the
図３からわかるように、使用初期の脱金属率は、ＨＯＰ６０６を除く触媒ではほぼ同じであるが、金属堆積量が増えると、触媒３０２５（比較例７）３０９３（比較例３）は急速に脱金属率が低下して、触媒活性を失ってゆく。これに対して、実施例の触媒は金属堆積量が増えても比較的高い脱金属活性を維持していることがわかる。 As can be seen from FIG. 3, the demetalization rate at the initial stage of use is almost the same for the catalyst except for HOP606, but when the amount of deposited metal increases, the catalyst 3025 (Comparative Example 7) 3093 (Comparative Example 3) rapidly desorbs. The metal ratio decreases and the catalytic activity is lost. On the other hand, it can be seen that the catalyst of the example maintains a relatively high demetalization activity even when the amount of metal deposition increases.
脱金属堆積量の値を評価する基準として、以下のようにして有効金属堆積量を定義した。有効金属堆積量は、バナジウム及びニッケル含有量が非常に多いボスカン原油を、反応温度３９０℃、水素圧力１４０ｋｇ／ｃｍ２Ｇ、液空間速度１．０ｈｒ−１、水素オイル比６７０ＮＬ／ＮＬの条件で反応を行い、脱メタル率が５０％まで低下した時点までに、充填時の触媒重量１００ｇに対して、触媒上に蓄積したバナジウム及びニッケルを合計した重量で定義する。触媒上に蓄積したバナジウム及びニッケルの重量は、原料油と精製油のバナジウム及びニッケルの濃度差を経時的に積算することによって求められる。実施例２，６，７，８，９及び比較例３，７，８で得られた触媒についての有効金属堆積量の値を、図３及び表１‐Ｂに示した。有効金属堆積量の値から触媒の寿命を評価することができる。すなわち、実施例に従う触媒は比較例の触媒に比べて、バナジウム及びニッケルが触媒細孔に堆積しても良好な脱金属活性を長期間に渡って維持することができる。 The effective metal deposition amount was defined as follows as a standard for evaluating the value of the metal removal amount. The effective metal deposition amount is Boskan crude oil with a very high vanadium and nickel content under the conditions of a reaction temperature of 390 ° C., a hydrogen pressure of 140 kg / cm 2 G, a liquid space velocity of 1.0 hr −1 , and a hydrogen oil ratio of 670 NL / NL. By the time when the reaction is carried out and the demetallation rate is reduced to 50%, the total weight of vanadium and nickel accumulated on the catalyst is defined with respect to 100 g of the catalyst weight at the time of filling. The weights of vanadium and nickel accumulated on the catalyst are determined by integrating the concentration difference between vanadium and nickel in the feedstock oil and refined oil over time. The values of the effective metal deposition amount for the catalysts obtained in Examples 2, 6, 7, 8, and 9 and Comparative Examples 3, 7, and 8 are shown in FIG. 3 and Table 1-B. The life of the catalyst can be evaluated from the value of the effective metal deposition amount. That is, the catalyst according to the example can maintain a good metal removal activity over a long period of time even when vanadium and nickel are deposited in the catalyst pores, as compared with the catalyst of the comparative example.
なお、表１‐Ｂには、初期脱金属活性と有効金属堆積量の観点から総合評価を示した。評価において、○は両者が高い値を示していることを意味し、×はいずれかが、低い値を示していることを意味する。 Table 1-B shows a comprehensive evaluation from the viewpoint of initial metal removal activity and effective metal deposition amount. In the evaluation, ◯ means that both values are high, and x means that either value is low.
以上のことより、本発明に従う水素化精製触媒は、脱金属活性及び有効金属堆積量のいずれもが従来の水素化精製触媒に比べて優れていることがわかる。 From the above, it can be seen that the hydrorefining catalyst according to the present invention is superior in both the metal removal activity and the effective metal deposition amount as compared with the conventional hydrotreating catalyst.
実施例６及び比較例８については、ボスカン原油を用い、金属堆積量の増加と脱金属率の変化を求める途中で原料油を一時的にラタウィ残渣油に交換して、脱アスファルテン率の変化を求めた。その結果を、図４に示した。図４中、縦軸は脱アスファルテン率を示し、横軸は新触媒１００ｇに堆積した金属量（ｇ）を示す。 For Example 6 and Comparative Example 8, using Boskan crude oil, the raw oil was temporarily replaced with the Latawi residue oil in the middle of obtaining the increase in the amount of deposited metal and the change in the demetallation rate, Asked. The results are shown in FIG. In FIG. 4, the vertical axis represents the deasphalted rate, and the horizontal axis represents the amount of metal (g) deposited on 100 g of the new catalyst.
図４から分かるように、実施例の触媒は、金属堆積量が増えても高い脱アスファルテン率を維持していることがわかる。 As can be seen from FIG. 4, it can be seen that the catalyst of the example maintains a high deasphaltene ratio even when the amount of deposited metal increases.
（４）触媒の摩耗率の評価
実施例２、比較例３及び９の触媒の摩耗率を、標準試験法（ＡＳＴＭ Ｄ４０５８−９２）により求めた。その結果を表１−Ｂに示した。細孔容積が０．７５ｃｍ３／ｇ以上の粉体を用いた触媒は、摩耗率が低く、水素化精製反応器の差圧上昇などを生じないことがわかる。
(4) Evaluation of catalyst wear rate The wear rates of the catalysts of Example 2, Comparative Examples 3 and 9 were determined by a standard test method (ASTM D4058-92). The results are shown in Table 1-B. It can be seen that a catalyst using a powder having a pore volume of 0.75 cm 3 / g or more has a low wear rate and does not cause an increase in the differential pressure of the hydrotreating reactor.
本発明の水素化精製触媒は、脱金属活性が高く、有効金属堆積量が多いために、減圧残渣油、常圧残渣油などニッケルまたはバナジウムなどの金属分を多く含む重質油の脱金属処理に好適である。また、アスファルテン分を３％以上含む重質油の処理にも好適である。また、本発明の水素化精製触媒の製造方法を用いることにより、脱金属活性及び有効金属堆積量に優れた水素化精製触媒を容易に且つ低コストで製造することができる。 Since the hydrorefining catalyst of the present invention has high demetallation activity and a large amount of effective metal deposit, demetallation treatment of heavy oil containing a large amount of metal such as nickel or vanadium such as reduced-pressure residue oil and atmospheric residue oil. It is suitable for. It is also suitable for treating heavy oil containing 3% or more of asphaltenes. Further, by using the method for producing a hydrotreating catalyst of the present invention, a hydrotreating catalyst having excellent metal removal activity and effective metal deposition amount can be produced easily and at low cost.
Claims (6)
窒素吸着法により測定した中央細孔径が８〜２０ｎｍであり；
窒素吸着法により測定した細孔容積が０．５６ｃｍ３／ｇ以上であり；且つ
水銀圧入法により測定した５０ｎｍ以上の細孔直径を有する細孔の細孔容積が０．３２ｃｍ３／ｇ以上であり、
水銀圧入法により測定した細孔容積が０．８７ｃｍ３／ｇ以上であり、
水素化活性金属成分として、モリブデンを２〜６重量％、ニッケルまたはコバルトを０．５〜２重量％含み、
比表面積が１８０〜２８０ｍ２／ｇであることを特徴とする水素化精製用触媒。 In a hydrorefining catalyst in which a hydrogenation active metal component is supported on a refractory porous carrier,
The median pore diameter measured by nitrogen adsorption method is 8-20 nm;
The pore volume measured by the nitrogen adsorption method is 0.56 cm 3 / g or more; and the pore volume of the pore having a pore diameter of 50 nm or more measured by the mercury intrusion method is 0.32 cm 3 / g or more. Yes,
The pore volume measured by the mercury intrusion method is 0.87 cm 3 / g or more,
As a hydrogenation active metal component, it contains 2 to 6% by weight of molybdenum, 0.5 to 2% by weight of nickel or cobalt,
A catalyst for hydrorefining having a specific surface area of 180 to 280 m 2 / g.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092906A (en) * | 1973-12-19 | 1975-07-24 | ||
| JPS5740588A (en) * | 1980-07-02 | 1982-03-06 | Catalyse Soc Prod Francais | Hydrogenation purification of hydrocarbon residue |
| JPS58252A (en) * | 1981-06-17 | 1983-01-05 | アモコ コ−ポレ−シヨン | Improved catalyst and carrier and production and use thereof |
| JPS6265750A (en) * | 1983-12-19 | 1987-03-25 | インテヴエツプ，エス・エイ・ | Catalyst for hydrogenation treatment of heavy oil, etc. and manufacture thereof |
| JPH06154598A (en) * | 1992-11-20 | 1994-06-03 | Sumitomo Metal Mining Co Ltd | Manufacture of gamma-alumina catalyst carrier |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092906A (en) * | 1973-12-19 | 1975-07-24 | ||
| JPS5740588A (en) * | 1980-07-02 | 1982-03-06 | Catalyse Soc Prod Francais | Hydrogenation purification of hydrocarbon residue |
| JPS58252A (en) * | 1981-06-17 | 1983-01-05 | アモコ コ−ポレ−シヨン | Improved catalyst and carrier and production and use thereof |
| JPS6265750A (en) * | 1983-12-19 | 1987-03-25 | インテヴエツプ，エス・エイ・ | Catalyst for hydrogenation treatment of heavy oil, etc. and manufacture thereof |
| JPH06154598A (en) * | 1992-11-20 | 1994-06-03 | Sumitomo Metal Mining Co Ltd | Manufacture of gamma-alumina catalyst carrier |
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