JP5695548B2 - Method for producing pre-sulfided regenerated hydrotreating catalyst, method for producing regenerated hydrotreating catalyst, method for selecting regenerating treatment conditions for hydrotreating catalyst, and method for producing petroleum product - Google Patents
Method for producing pre-sulfided regenerated hydrotreating catalyst, method for producing regenerated hydrotreating catalyst, method for selecting regenerating treatment conditions for hydrotreating catalyst, and method for producing petroleum product Download PDFInfo
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、予備硫化済み再生水素化処理用触媒の製造方法、再生水素化処理用触媒の製造方法、石油製品の製造方法、及び水素化処理用触媒の再生処理条件の選別方法に関する。 The present invention relates to a method for producing a presulfided regenerated hydrotreating catalyst, a method for producing a regenerated hydrotreating catalyst, a method for producing a petroleum product, and a method for selecting a regenerating treatment condition for a hydrotreating catalyst.
原油には含硫黄化合物、含窒素化合物、含酸素化合物等が不純物として含まれ、原油を分留して得られる各石油留分中にもこれら不純物が含まれる。これら石油留分中の前記不純物は、水素の存在下に水素化活性を有する触媒に接触せしめる水素化処理と呼ばれる工程により、その含有量を低減することが行われている。特に含硫黄化合物の含有量を低減する脱硫がよく知られている。最近は環境負荷低減の観点から、石油製品中の含硫黄化合物をはじめとする前記不純物の含有量に対する規制、低減の要求が一層厳しくなっており、所謂「サルファー・フリー」と呼ばれる石油製品が多く生産されている。 Crude oil contains sulfur-containing compounds, nitrogen-containing compounds, oxygen-containing compounds and the like as impurities, and these impurities are also contained in each petroleum fraction obtained by fractionating crude oil. The content of the impurities in these petroleum fractions is reduced by a process called hydrotreating which is brought into contact with a catalyst having hydrogenation activity in the presence of hydrogen. In particular, desulfurization for reducing the content of sulfur-containing compounds is well known. Recently, from the viewpoint of reducing environmental impact, regulations on the content of impurities, including sulfur-containing compounds in petroleum products, and demands for reduction have become more stringent, and there are many so-called “sulfur-free” petroleum products. Has been produced.
石油留分の水素化処理に使用する水素化処理用触媒は、一定の期間使用されるとコークや硫黄分の沈着等により活性が低下することから、交換が行われる。特に上記「サルファー・フリー」が求められるようになり、灯油、軽油、減圧軽油といった留分の水素化処理設備において、高い水素化処理能力が求められている。その結果、触媒交換頻度が増大し、結果として触媒コストの上昇や触媒廃棄量の増加をもたらしている。 The hydrotreating catalyst used in the hydrotreating of petroleum fractions is exchanged because its activity decreases due to the deposition of coke and sulfur when used for a certain period of time. In particular, the above-mentioned “sulfur-free” has been demanded, and high hydrotreating capacity is demanded in hydrotreating equipment for fractions such as kerosene, light oil and vacuum gas oil. As a result, the frequency of catalyst replacement increases, resulting in an increase in catalyst cost and an increase in the amount of catalyst discarded.
この対策として、これらの設備においては使用済みの水素化処理用触媒を再生処理した再生触媒（再生水素化処理用触媒）の使用が一部行われている（例えば、特許文献１、２を参照）。 As a countermeasure, a part of the regenerated catalyst (regenerated hydrotreating catalyst) obtained by regenerating a spent hydrotreating catalyst is used in these facilities (for example, see Patent Documents 1 and 2). ).
従来の再生処理においては、水素化処理用触媒の使用中に生じる活性低下の主原因がコークの沈着にあるとして、再生処理条件はコークの沈着物を除去できるか否かという観点から再生処理条件を選定することが一般的であった。例えば、従来の再生処理においては、処理温度をなるべく高温とし、処理温度をなるべく長時間とすることがよいとの考えがあった。 In the conventional regeneration process, assuming that the main cause of the decrease in activity that occurs during the use of the hydrotreating catalyst is the deposition of coke, the regeneration process condition is the condition of whether or not the deposit of coke can be removed. It was common to select For example, in the conventional regeneration process, there has been an idea that the processing temperature should be as high as possible and the processing temperature as long as possible.
しかし、沈着したコークの除去の問題とは別に、再生処理自体が、触媒上に担持された活性金属の構造（活性金属と酸素原子との配位形態等）を変化せしめる等して、触媒活性を低下させてしまうことがある。すなわち、過度な再生処理には、水素化処理触媒を損傷させ、水素化処理用触媒が本来有する活性を低下させてしまうという問題がある。 However, apart from the problem of removing the deposited coke, the regeneration process itself changes the structure of the active metal supported on the catalyst (coordination form of the active metal and oxygen atoms, etc.). May be reduced. That is, excessive regeneration treatment has a problem that the hydrotreating catalyst is damaged, and the activity inherent to the hydrotreating catalyst is reduced.
なお、水素化処理用触媒はその使用前に水素化処理活性を高めるため、予備硫化により触媒中の金属元素を硫化物としておくことが好ましい。 In addition, in order to improve the hydrotreating activity before using the catalyst for hydrotreating, it is preferable that the metal element in the catalyst is made into sulfide by presulfiding.
本発明の目的の一つは、使用済みの水素化処理用触媒から安定して高い水素化処理活性を有する予備硫化済み再生水素化処理用触媒を製造することが可能な、予備硫化済み再生水素化処理用触媒の製造方法を提供することにある。 One of the objects of the present invention is to prepare a presulfided regenerated hydrogen that can stably produce a presulfided regenerated hydrotreating catalyst having high hydrotreating activity from a used hydrotreating catalyst. Another object is to provide a method for producing a catalyst for chemical treatment.
また、本発明の目的の一つは、使用済みの水素化処理用触媒から、予備硫化した際の水素化処理活性が高い再生水素化処理用触媒を安定して製造することが可能な、再生水素化処理用触媒の製造方法を提供することにある。 In addition, one of the objects of the present invention is that a regenerated hydrotreating catalyst having a high hydrotreating activity when pre-sulfided can be stably produced from a used hydrotreating catalyst. It is providing the manufacturing method of the catalyst for hydroprocessing.
また、本発明の目的の一つは、予備硫化した際の水素化処理活性が高い再生水素化処理用触媒を安定して製造することが可能となるような、再生処理条件の選別方法を提供することにある。 In addition, one of the objects of the present invention is to provide a method for selecting a regeneration treatment condition that makes it possible to stably produce a regeneration hydrotreating catalyst having high hydrotreating activity when presulfided. There is to do.
また、本発明の目的の一つは、上記製造方法により製造された予備硫化済み再生水素化処理用触媒を用いた石油製品の製造方法を提供することにある。 Another object of the present invention is to provide a method for producing a petroleum product using the presulfided regenerated hydrotreating catalyst produced by the above production method.
本発明の一側面は、石油留分の水素化処理に用いられた水素化処理用触媒であって、周期表第６族元素から選ばれる金属元素を有する触媒を用意する第１の工程と、上記第１の工程で用意した上記触媒の一部について再生処理及び予備硫化を行うとともに、再生処理及び予備硫化を経た上記触媒について上記金属元素の硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる再生処理条件及び予備硫化条件を求める第２の工程と、上記第１の工程で用意した上記触媒の他部について、上記第２の工程に基づいて決定された再生処理条件及び予備硫化条件で再生処理及び予備硫化を行う第３の工程と、を備える、予備硫化済み再生水素化処理用触媒の製造方法に関する。 One aspect of the present invention is a hydrotreating catalyst used for hydrotreating a petroleum fraction, the first step of preparing a catalyst having a metal element selected from Group 6 elements of the periodic table; A part of the catalyst prepared in the first step is subjected to regeneration treatment and preliminary sulfidation, and the average number of crystal layers of the metal element sulfide crystal layer is observed for the catalyst that has undergone the regeneration treatment and preliminary sulfidation. Based on the second step, the second step for obtaining the regeneration treatment condition and the presulfurization condition in which the average number of layers is 1.6 or more and the other part of the catalyst prepared in the first step And a third step of performing regeneration treatment and preliminary sulfidation under the determined regeneration treatment conditions and preliminary sulfidation conditions.
このような予備硫化済み再生水素化処理用触媒の製造方法によれば、使用済みの水素化処理用触媒から安定して高い水素化処理活性を有する予備硫化済み再生水素化処理用触媒を製造することができる。 According to such a method for producing a pre-sulfided regenerated hydrotreating catalyst, a pre-sulfided regenerated hydrotreating catalyst having a stable and high hydrotreating activity is produced from a used hydrotreating catalyst. be able to.
また、本発明の一側面は、石油留分の水素化処理に用いられた水素化処理用触媒であって周期表第６族元素から選ばれる金属元素を有する触媒を再生処理して、再生触媒を得る第１の工程と、上記第１の工程で得た上記再生触媒の一部について予備硫化を行うとともに、予備硫化を経た上記再生触媒について上記金属元素の硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる予備硫化条件を求める第２の工程と、上記第１の工程で得た上記再生触媒の他部について、上記第２の工程に基づいて決定された予備硫化条件で予備硫化を行う第３の工程と、を備える、予備硫化済み再生水素化処理用触媒の製造方法に関する。 Another aspect of the present invention is a regenerated catalyst obtained by regenerating a catalyst having a metal element selected from Group 6 elements of the periodic table, which is a hydrotreating catalyst used for hydrotreating a petroleum fraction. And the average number of the crystal layers of the metal element sulfide crystal layers of the regenerated catalyst that has undergone presulfidation. And the second step for obtaining the presulfidation condition in which the average number of layers is 1.6 or more, and the other part of the regenerated catalyst obtained in the first step is based on the second step. A pre-sulfided regenerated hydrotreating catalyst comprising: a third step of performing pre-sulfiding under the pre-sulfiding conditions determined in the above.
このような予備硫化済み再生水素化処理用触媒の製造方法によれば、使用済みの水素化処理用触媒から安定して高い水素化処理活性を有する予備硫化済み再生水素化処理用触媒を製造することができる。 According to such a method for producing a pre-sulfided regenerated hydrotreating catalyst, a pre-sulfided regenerated hydrotreating catalyst having a stable and high hydrotreating activity is produced from a used hydrotreating catalyst. be able to.
本発明の一態様において、上記第１の工程における上記再生処理は、上記再生触媒のカーボン含有量が０．１５〜３．０質量％となる条件で行うことができる。このような条件で再生処理された再生触媒について、上記第２の工程に基づいて決定された予備硫化条件で予備硫化を行うことにより、水素化処理活性に一層優れる予備硫化済み再生水素化処理用触媒が得られる。 In one aspect of the present invention, the regeneration treatment in the first step can be performed under the condition that the carbon content of the regenerated catalyst is 0.15 to 3.0% by mass. For the regenerated catalyst regenerated under such conditions, by performing presulfidation under the presulfidation conditions determined based on the second step, the presulfided regenerated hydrotreating process having further excellent hydrotreating activity A catalyst is obtained.
また、本発明の一側面は、石油留分の水素化処理に用いられた水素化処理用触媒であって、周期表第６族元素から選ばれる金属元素を有する触媒を用意する第１の工程と、上記第１の工程で用意した上記触媒の一部について再生処理を行うとともに、再生処理後の上記触媒を予備硫化したときの上記金属元素の硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる再生処理条件を求める第２の工程と、上記第１の工程で用意した上記触媒の他部について、上記第２の工程に基づいて決定された再生処理条件で再生処理を行う第３の工程と、を備える、再生水素化処理用触媒の製造方法に関する。 Moreover, one aspect of the present invention is a first step of preparing a catalyst for hydrotreating used in hydrotreating a petroleum fraction, the catalyst having a metal element selected from Group 6 elements of the periodic table. And regenerating part of the catalyst prepared in the first step, and observing the average number of crystal layers of the sulfide of the metal element when the catalyst after the regeneration process is presulfided. Then, the second step for obtaining the regeneration treatment condition in which the average number of layers is 1.6 or more and the other part of the catalyst prepared in the first step were determined based on the second step. And a third step of performing a regeneration process under a regeneration process condition.
このような再生水素化処理用触媒の製造方法によれば、水素化処理活性が高い再生水素化処理用触媒を安定して製造することができる。 According to such a method for producing a regenerated hydrotreating catalyst, a regenerated hydrotreating catalyst having high hydrotreating activity can be produced stably.
本発明の一態様において、上記第２の工程における予備硫化は、再生処理後の前記触媒に、０．５〜２．５質量％の硫黄化合物を含む石油留分を、温度２００〜４００℃、液空間速度０．０５〜５ｈ−１、圧力３〜１３ＭＰａ、処理時間５時間以上の条件で連続して接触させて行うことができる。このような条件で予備硫化したときの平均積層数に基づいて、再生処理条件を決定することで、優れた水素化処理活性を有する再生水素化処理用触媒をより確実に製造することができる。 In one aspect of the present invention, the preliminary sulfidation in the second step is carried out by subjecting a petroleum fraction containing 0.5 to 2.5% by mass of a sulfur compound to the catalyst after the regeneration treatment at a temperature of 200 to 400 ° C. The liquid space velocity is 0.05 to 5 h −1 , the pressure is 3 to 13 MPa, and the treatment time is 5 hours or more. By determining the regeneration treatment conditions based on the average number of layers when preliminary sulfidation is performed under such conditions, a regenerated hydrotreating catalyst having excellent hydrotreating activity can be more reliably produced.
また、本発明の一側面は、上記製造方法により製造された再生水素化処理用触媒を予備硫化する工程を備える、予備硫化済み再生水素化処理用触媒の製造方法に関する。このような製造方法によれば、高い水素化処理活性を有する予備硫化済み再生水素化処理用触媒が得られる。 Another aspect of the present invention relates to a method for producing a presulfided regenerated hydrotreating catalyst, comprising a step of presulfiding the regenerated hydrotreating catalyst produced by the above production method. According to such a production method, a presulfided regenerated hydrotreating catalyst having high hydrotreating activity can be obtained.
また、本発明の一側面は、石油留分を処理するための水素化処理用触媒を再生処理するに際し、再生処理条件を選別する方法であって、水素化処理後の水素化処理用触媒について所定の条件で再生処理及び予備硫化を行い、再生処理及び予備硫化を経た上記触媒について上記金属元素の硫化物の結晶層を観測する第２の工程と、上記第２の工程で観測された上記平均積層数に基づいて、再生処理の条件の良否を判定する第３の工程と、を備える、水素化処理用触媒の再生処理条件の選別方法に関する。 Another aspect of the present invention is a method for selecting a regeneration treatment condition when regenerating a hydrotreating catalyst for treating a petroleum fraction, the hydrotreating catalyst after hydrotreating. Regeneration treatment and preliminary sulfidation under predetermined conditions, and a second step of observing the crystal layer of the metal element sulfide with respect to the catalyst that has undergone the regeneration treatment and preliminary sulfidation, and the above-mentioned observed in the second step And a third step of determining whether the conditions of the regeneration process are good or not based on the average number of stacked layers.
このような選別方法によれば、使用済みの水素化処理用触媒から水素化処理活性が高い再生水素化処理用触媒を安定して製造することが可能となる再生処理条件を、容易に選別することができる。 According to such a screening method, it is possible to easily select a regeneration treatment condition that enables stable production of a regenerated hydrotreating catalyst having high hydrotreating activity from a used hydrotreating catalyst. be able to.
また、本発明の一側面は、上記製造方法により製造された予備硫化済み再生水素化処理用触媒を用いて、石油留分の水素化処理を行う工程を備える、石油製品の製造方法に関する。このような製造方法は、高活性な予備硫化済み再生水素化処理用触媒を用いているため経済性に優れる。 One aspect of the present invention also relates to a method for producing a petroleum product comprising a step of hydrotreating a petroleum fraction using the presulfided regenerated hydrotreating catalyst produced by the above production method. Such a production method is economical because it uses a highly active presulfided regenerated hydrogenation catalyst.
本発明によれば、使用済みの水素化処理用触媒から安定して高い水素化処理活性を有する予備硫化済み再生水素化処理用触媒を製造することが可能な、予備硫化済み再生水素化処理用触媒の製造方法が提供される。また、本発明によれば、使用済みの水素化処理用触媒から、予備硫化した際の水素化処理活性が高い再生水素化処理用触媒を安定して製造することが可能な、再生水素化処理用触媒の製造方法が提供される。また、本発明によれば、予備硫化した際の水素化処理活性が高い再生水素化処理用触媒を安定して製造することが可能となるような、再生処理条件の選別方法が提供される。さらに、本発明によれば、上記製造方法により製造された予備硫化済み再生水素化処理用触媒を用いて、経済性に優れる石油製品の製造方法が提供される。 According to the present invention, a presulfided regenerated hydrotreating catalyst that can stably produce a presulfided regenerated hydrotreating catalyst having high hydrotreating activity from a used hydrotreating catalyst. A method for producing a catalyst is provided. In addition, according to the present invention, a regenerated hydrotreating catalyst that can stably produce a regenerated hydrotreating catalyst having high hydrotreating activity when pre-sulfided from a used hydrotreating catalyst. A method for producing a catalyst is provided. In addition, according to the present invention, there is provided a method for selecting a regeneration treatment condition such that a regeneration hydrotreating catalyst having a high hydrotreating activity when presulfided can be stably produced. Furthermore, according to this invention, the manufacturing method of the petroleum product which is excellent in economical efficiency is provided using the catalyst for pre-sulfided regenerated hydrogenation processes manufactured by the said manufacturing method.
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.
（水素化処理用触媒）
本実施形態において、水素化処理用触媒は、周期表第６族元素から選ばれる金属元素を有する。ここで周期表第６族元素から選ばれる金属元素（以下、場合により「金属元素Ｍ」と称する）を有する。ここで、周期表第６族元素から選ばれる金属元素Ｍとしては、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）が挙げられる。なお、ここで周期表とは、国際純正・応用化学連合（ＩＵＰＡＣ）により規定された長周期型の周期表をいう。水素化処理用触媒は、金属元素Ｍとしてモリブデン又はタングステンを有することが好ましく、モリブデンを有することがより好ましい。
(Hydroprocessing catalyst)
In this embodiment, the hydrotreating catalyst has a metal element selected from Group 6 elements of the periodic table. Here, a metal element selected from Group 6 elements of the periodic table (hereinafter sometimes referred to as “metal element M”) is included. Here, examples of the metal element M selected from Group 6 elements of the periodic table include chromium (Cr), molybdenum (Mo), and tungsten (W). Here, the periodic table is a long-period type periodic table defined by the International Union of Pure and Applied Chemistry (IUPAC). The hydrotreating catalyst preferably has molybdenum or tungsten as the metal element M, and more preferably has molybdenum.
水素化処理用触媒としては、例えば、無機担体と、該無機担体に担持された周期表第６族元素から選ばれる金属元素Ｍと、を有する触媒が挙げられる。 Examples of the hydrotreating catalyst include a catalyst having an inorganic carrier and a metal element M selected from Group 6 elements of the periodic table carried on the inorganic carrier.
金属元素Ｍの担持量は、水素化処理用触媒の全質量を基準として、金属元素Ｍの酸化物換算で５〜４０質量％であることが好ましく、１０〜３０質量％であることがより好ましい。 The supported amount of the metal element M is preferably 5 to 40% by mass, more preferably 10 to 30% by mass in terms of the oxide of the metal element M, based on the total mass of the hydrotreating catalyst. .
無機担体としては、例えば、アルミニウム酸化物を含む無機担体を採用できる。このような無機担体としては、例えば、アルミナ、アルミナ−シリカ、アルミナ−ボリア、アルミナ−チタニア、アルミナ−ジルコニア、アルミナ−マグネシア、アルミナ−シリカ−ジルコニア、アルミナ−シリカ−チタニア等が挙げられる。また、各種粘土鉱物（各種ゼオライト、セビオライト、モンモリロナイト等）等の多孔性無機化合物をアルミナに添加した担体を用いることもできる。これらのうち、無機担体としてはアルミナが好ましい。 As the inorganic carrier, for example, an inorganic carrier containing aluminum oxide can be adopted. Examples of such inorganic carriers include alumina, alumina-silica, alumina-boria, alumina-titania, alumina-zirconia, alumina-magnesia, alumina-silica-zirconia, alumina-silica-titania, and the like. In addition, a carrier obtained by adding a porous inorganic compound such as various clay minerals (various zeolites, ceviolites, montmorillonites, etc.) to alumina can also be used. Of these, alumina is preferred as the inorganic carrier.
無機担体上には、周期表第６族元素から選ばれる金属元素以外に、周期表第８〜１０族元素から選ばれる１種又は２種以上の金属元素がさらに担持されていてもよい。周期表第８〜１０族元素から選ばれる金属元素としては、鉄（Ｆｅ）、ルテニウム（Ｒｕ）、オスミウム（Ｏｓ）、コバルト（Ｃｏ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、ニッケル（Ｎｉ）、パラジウム（Ｐｄ）、白金（Ｐｔ）が挙げられる。これらのうち、鉄、コバルト及びニッケルから選ばれる金属元素を含むことが好ましく、コバルト及びニッケルから選ばれる金属元素を含むことがより好ましく、コバルトを含むことがさらに好ましい。本実施形態において、無機担体に担持される金属元素の組み合わせとしては、コバルト−モリブデン、ニッケル−モリブデン、コバルト−モリブデン−ニッケル、コバルト−タングステン−ニッケル等が好ましく用いられる。 In addition to the metal element selected from Group 6 elements of the periodic table, one or more metal elements selected from Group 8 to 10 elements of the periodic table may be further supported on the inorganic carrier. As metal elements selected from Group 8 to 10 elements of the periodic table, iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni) , Palladium (Pd), and platinum (Pt). Among these, it is preferable to include a metal element selected from iron, cobalt and nickel, more preferably to include a metal element selected from cobalt and nickel, and it is more preferable to include cobalt. In the present embodiment, cobalt-molybdenum, nickel-molybdenum, cobalt-molybdenum-nickel, cobalt-tungsten-nickel, or the like is preferably used as a combination of metal elements supported on the inorganic carrier.
周期表第８〜１０族元素から選ばれる金属元素の担持量は、水素化処理用触媒の全質量を基準として、該金属元素の酸化物換算で、０．１〜２０質量％であることが好ましく、０．５〜１０質量％であることがより好ましい。 The loading amount of the metal element selected from Group 8 to 10 elements of the periodic table is 0.1 to 20% by mass in terms of oxide of the metal element based on the total mass of the hydrotreating catalyst. Preferably, it is 0.5-10 mass%.
水素化処理用触媒であって未使用のもの（未使用触媒）としては、例えば、無機担体に、周期表第６族元素から選ばれる金属元素を酸化物として５〜４０質量％、周期表第８〜１０族元素から選ばれる金属元素を酸化物として０．１〜２０質量％、それぞれ担持させて得られる触媒が挙げられる。 Examples of the hydrotreating catalyst that is unused (unused catalyst) include, for example, 5-40% by mass of a metal element selected from Group 6 elements of the periodic table as an oxide on an inorganic carrier. Examples thereof include catalysts obtained by carrying 0.1 to 20% by mass of a metal element selected from Group 8 to 10 elements as oxides.
無機担体に担持する際に用いる金属元素の前駆体としては、例えば、金属元素の無機塩、有機金属化合物等が使用される。これらのうち、好ましくは水溶性の無機塩である。金属元素の担持は、上記前駆体の溶液（好ましくは水溶液）を用いて行うことが好ましい。担持操作としては、例えば、浸漬法、含浸法、共沈法等の公知の方法が好ましく採用される。 Examples of the metal element precursor used for supporting the inorganic carrier include inorganic salts of metal elements, organometallic compounds, and the like. Of these, water-soluble inorganic salts are preferred. The metal element is preferably supported using a solution (preferably an aqueous solution) of the precursor. As the supporting operation, for example, a known method such as an immersion method, an impregnation method, a coprecipitation method, or the like is preferably employed.
金属元素が担持された担体は、乾燥後、好ましくは酸素の存在下に焼成され、金属元素は一旦酸化物とされることが好ましい。さらには、石油留分の水素化処理を行う前に、予備硫化と呼ばれる硫化処理により、金属元素は硫化物とされることが好ましい。 The carrier on which the metal element is supported is preferably dried and then fired in the presence of oxygen, and the metal element is once converted to an oxide. Furthermore, it is preferable that the metal element is converted into a sulfide by a sulfidation treatment called presulfurization before the hydrotreating of the petroleum fraction.
予備硫化は、例えば、石油留分の水素化処理に使用する原料油に硫黄化合物を添加し、これを温度２００〜４００℃、ＬＨＳＶ（液空間速度、Ｌｉｑｕｉｄ Ｈｏｕｒｌｙ Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ）０．０５〜５ｈ−１、水素化処理運転時と同一の圧力、処理時間５時間以上の条件にて、触媒に連続的に接触せしめることが好ましい。原料油に添加する硫黄化合物としては限定されないが、ジメチルジスルフィド（ＤＭＤＳ）、硫化水素等が好ましく、これらを原料油に対して原料油の質量基準で１質量％程度添加することが好ましい。 In the preliminary sulfidation, for example, a sulfur compound is added to a raw oil used for hydrotreating a petroleum fraction, and this is added at a temperature of 200 to 400 ° C. and LHSV (Liquid Space Velocity) 0.05 to 5 h − 1. It is preferable that the catalyst is continuously contacted under the same pressure at the time of hydrotreating operation and a treatment time of 5 hours or more. Although it does not limit as a sulfur compound added to raw material oil, Dimethyl disulfide (DMDS), hydrogen sulfide, etc. are preferable and it is preferable to add these about 1 mass% with respect to the mass of raw material oil with respect to raw material oil.
（水素化処理） (Hydrogenation treatment)
水素化処理は、石油留分（以下、場合により「原料油」という。）を水素の存在下に水素化処理用触媒に接触させることにより行われる。 The hydrotreatment is performed by bringing a petroleum fraction (hereinafter sometimes referred to as “raw oil”) into contact with a hydrotreating catalyst in the presence of hydrogen.
本実施形態において、水素化処理の運転条件は特に限定されない。本実施形態においては、触媒の金属元素が硫化物である状態を維持する目的で、ＤＭＤＳ等の硫黄化合物を原料油に少量添加してもよいが、通常は原料油中に既に含有される硫黄化合物により硫化物である状態を維持することが可能であるので、硫黄化合物は特に添加しないことが好ましい。 In the present embodiment, the operating conditions for the hydrotreatment are not particularly limited. In this embodiment, a small amount of a sulfur compound such as DMDS may be added to the feedstock for the purpose of maintaining the state where the metal element of the catalyst is a sulfide, but usually the sulfur already contained in the feedstock Since it is possible to maintain the state of sulfide by the compound, it is preferable not to add a sulfur compound.
水素化処理における反応器入口における水素分圧は好ましくは３〜１３ＭＰａ、より好ましくは３．５〜１２ＭＰａ、さらに好ましくは４〜１１ＭＰａである。水素分圧が３ＭＰa未満の場合は触媒上のコーク生成が激しくなり触媒寿命が短くなる傾向にある。一方、水素分圧が１３ＭＰａを超える場合は反応器や周辺機器等の建設費が上昇し、経済性が失われる懸念がある。 The hydrogen partial pressure at the reactor inlet in the hydrotreatment is preferably 3 to 13 MPa, more preferably 3.5 to 12 MPa, and still more preferably 4 to 11 MPa. When the hydrogen partial pressure is less than 3 MPa, coke formation on the catalyst becomes intense and the catalyst life tends to be shortened. On the other hand, when the hydrogen partial pressure exceeds 13 MPa, there is a concern that the construction cost of the reactor, peripheral equipment, and the like will increase and the economy will be lost.
水素化処理におけるＬＨＳＶは、好ましくは０．０５〜５ｈ−１、より好ましくは０．１〜４．５ｈ−１、さらに好ましくは０．２〜４ｈ−１の範囲で行うことができる。ＬＨＳＶが０．０５ｈ−１未満である場合には、反応器の建設費が過大となり経済性が失われる懸念がある。一方、ＬＨＳＶが５ｈ−１を超える場合には原料油の水素化処理が十分に達成されない懸念がある。 LHSV in the hydrogenation process is preferably 0.05～5H -1, more preferably 0.1～4.5H -1, more preferably it may be in the range of 0.2~4h -1. When LHSV is less than 0.05 h −1 , there is a concern that the construction cost of the reactor becomes excessive and the economic efficiency is lost. On the other hand, when LHSV exceeds 5h- 1 , there is a concern that the hydrogenation treatment of the raw material oil is not sufficiently achieved.
水素化処理における水素化反応温度は、好ましくは２００℃〜４１０℃、より好ましくは２２０℃〜４００℃、さらに好ましくは２５０℃〜３９５℃である。反応温度が２００℃を下回る場合には、原料油の水素化処理が十分に達成されない傾向にある。一方、反応温度が４１０℃を上回る場合には、副生成物であるガス分の発生が増加するため、目的とする精製油の収率が低下することとなり望ましくない。 The hydrogenation reaction temperature in the hydrotreatment is preferably 200 ° C to 410 ° C, more preferably 220 ° C to 400 ° C, and further preferably 250 ° C to 395 ° C. When the reaction temperature is lower than 200 ° C., the hydrogenation treatment of the raw material oil tends not to be sufficiently achieved. On the other hand, when the reaction temperature exceeds 410 ° C., the generation of a gas component as a by-product increases, which is not desirable because the yield of the target refined oil decreases.
水素化処理における水素／油比は、好ましくは１００〜８０００ＳＣＦ／ＢＢＬ（１７〜１４００ＮＬ／Ｌ）、より好ましくは１２０〜７０００ＳＣＦ／ＢＢＬ（２０〜１２００ＮＬ／Ｌ）、さらに好ましくは１５０〜６０００ＳＣＦ／ＢＢＬ（２５〜１０５０ＮＬ／Ｌ）の範囲で行うことができる。水素／油比が１００ＳＣＦ／ＢＢＬ（１７ＮＬ／Ｌ）未満の場合には、リアクター出口での触媒上のコーク生成が進行し、触媒寿命が短くなる傾向にある。一方、水素／油比が８０００ＳＣＦ／ＢＢＬ（１４００ＮＬ／Ｌ）を超える場合には、リサイクルコンプレッサーの建設費が過大になり、経済性が失われる懸念がある。 The hydrogen / oil ratio in the hydrotreatment is preferably 100 to 8000 SCF / BBL (17 to 1400 NL / L), more preferably 120 to 7000 SCF / BBL (20 to 1200 NL / L), and even more preferably 150 to 6000 SCF / BBL ( 25 to 1050 NL / L). When the hydrogen / oil ratio is less than 100 SCF / BBL (17 NL / L), coke formation on the catalyst proceeds at the reactor outlet, and the catalyst life tends to be shortened. On the other hand, when the hydrogen / oil ratio exceeds 8000 SCF / BBL (1400 NL / L), there is a concern that the construction cost of the recycle compressor becomes excessive and the economy is lost.
水素化処理における反応形式は特に限定されず、固定床、移動床等の種々のプロセスから選ぶことができ、固定床が好ましい。また反応器は塔状であることが好ましい。 The reaction type in the hydrotreatment is not particularly limited, and can be selected from various processes such as a fixed bed and a moving bed, and a fixed bed is preferable. The reactor is preferably tower-shaped.
水素化処理に供される原料油としては、蒸留試験による留出温度が好ましくは１３０〜７００℃、さらに好ましくは１４０〜６８０℃、特に好ましくは１５０〜６６０℃の範囲のものが使用される。留出温度が１３０℃を下回る原料油を用いた場合には水素化処理反応が気相での反応となり、上記の触媒では性能が充分に発揮されない傾向にある。一方、留出温度が７００℃を上回る原料油を用いた場合には、原料油中に含まれる重金属などの、触媒に対する被毒物の含有量が大きくなり、触媒の寿命が大きく低下する場合がある。原料油として用いる石油留分のその他の性状としては特に限定されないが、代表的な性状としては、１５℃における密度が０．８２００〜０．９７００ｇ／ｃｍ３、硫黄含有量１．０〜４．０質量％である。 As the raw material oil to be subjected to the hydrotreating, those having a distillation temperature by distillation test of preferably 130 to 700 ° C, more preferably 140 to 680 ° C, and particularly preferably 150 to 660 ° C are used. When a feed oil having a distillation temperature lower than 130 ° C. is used, the hydrotreating reaction becomes a reaction in the gas phase, and the above-mentioned catalyst tends not to exhibit sufficient performance. On the other hand, when a feedstock having a distillation temperature exceeding 700 ° C. is used, the content of poisonous substances such as heavy metals contained in the feedstock increases with respect to the catalyst, and the life of the catalyst may be greatly reduced. . The other properties of the petroleum fraction used as the feedstock are not particularly limited, but typical properties include a density at 15 ° C. of 0.8200 to 0.9700 g / cm 3 and a sulfur content of 1.0 to 4. 0% by mass.
このような性状を有する原料油としては、灯油留分、軽油留分等の石油留分を好ましく挙げることができる。灯油留分、軽油留分としては、原油の常圧蒸留装置から得られる直留灯油又は直留軽油；常圧蒸留装置から得られる直留重質油や残査油を減圧蒸留装置で処理して得られる減圧軽油、減圧重質軽油あるいは脱硫重油を接触分解して得られる接触分解灯油又は接触分解軽油；減圧重質軽油あるいは脱硫重油を水素化分解して得られる水素化分解灯油又は水素化分解軽油；等が挙げられる。 Preferred examples of the raw material oil having such properties include petroleum fractions such as a kerosene fraction and a light oil fraction. As kerosene fraction and light oil fraction, straight-run kerosene or straight-run light oil obtained from crude oil atmospheric distillation equipment; straight-run heavy oil and residual oil obtained from atmospheric distillation equipment are treated with vacuum distillation equipment Gas cracked kerosene or catalytic cracked light oil obtained by catalytic cracking of vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil obtained by hydrocracking; hydrocracked kerosene or hydrogenation obtained by hydrocracking vacuum heavy gas oil or desulfurized heavy oil Decomposed light oil; and the like.
なお、ここで硫黄含有量とは、ＪＩＳ Ｋ ２５４１に規定する「原油及び石油製品―硫黄分試験方法」の「放射線式励起法」に準拠して測定される硫黄含有量を意味する。また、蒸留試験とは、ＪＩＳ Ｋ ２２５４に規定する「石油製品―蒸留試験方法」の「減圧法蒸留試験方法」または「ガスクロマトグラフ法蒸留試験方法」に準拠して行われるものを意味する。１５℃における密度とは、ＪＩＳ Ｋ２２４９に規定する「原油及び石油製品−密度試験方法及び密度・質量・容量換算表」の「振動式密度試験方法」に準拠して測定される密度を意味する。 Here, the sulfur content means a sulfur content measured in accordance with “Radiation Excitation Method” of “Crude Oil and Petroleum Products—Sulfur Content Test Method” defined in JIS K2541. Further, the distillation test means a test conducted in accordance with “Petroleum product-distillation test method” “depressurization method distillation test method” or “gas chromatographic method distillation test method” defined in JIS K 2254. The density at 15 ° C. means a density measured in accordance with “Oscillating Density Test Method” of “Crude Oil and Petroleum Products—Density Test Method and Density / Mass / Capacity Conversion Table” defined in JIS K2249.
（予備硫化済み再生水素化処理用触媒の製造方法）
本実施形態に係る予備硫化済み再生水素化処理用触媒の製造方法は、石油留分の水素化処理に用いられた水素化処理用触媒であって、周期表第６族元素から選ばれる金属元素Ｍを有する触媒を用意する第１の工程と、第１の工程で用意した触媒の一部について再生処理及び予備硫化を行うとともに、再生処理及び予備硫化を経た触媒について金属元素Ｍの硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる再生処理条件及び予備硫化条件を求める第２の工程と、第１の工程で用意した触媒の他部について、第２の工程に基づいて決定された再生処理条件及び予備硫化条件で再生処理及び予備硫化を行う第３の工程と、を備える。
(Preparation method of pre-sulfided regenerated hydrotreating catalyst)
The method for producing a presulfided regenerated hydrotreating catalyst according to the present embodiment is a hydrotreating catalyst used for hydrotreating a petroleum fraction, and is a metal element selected from Group 6 elements of the periodic table A first step of preparing a catalyst having M, and a regeneration treatment and a preliminary sulfidation are performed on a part of the catalyst prepared in the first step, and the sulfide of the metal element M is formed on the catalyst that has undergone the regeneration treatment and the preliminary sulfidation. Regarding the other part of the catalyst prepared in the first step, the second step of observing the average number of crystal layers and determining the regeneration treatment condition and the presulfurization condition where the average number of layers is 1.6 or more, And a third step of performing the regeneration treatment and the preliminary sulfidation under the regeneration treatment condition and the preliminary sulfidation condition determined based on the second step.
本実施形態において、第２の工程に基づいて決定された再生処理条件及び予備硫化条件は、十分に水素化処理用触媒を再生することができ、過度な再生処理とならず、高い活性を有する予備硫化済み再生水素化処理用触媒が得られる条件である。 In this embodiment, the regeneration treatment condition and the presulfurization condition determined based on the second step can sufficiently regenerate the hydrotreating catalyst, do not become an excessive regeneration treatment, and have high activity. This is the condition under which a presulfided regenerated hydroprocessing catalyst is obtained.
従来、再生処理条件は、コークの沈着物を除去できるか否かという観点から再生処理条件を選別することや、再生処理後且つ予備硫化前の触媒の状態から再生処理条件を選別することが一般的であったのに対し、本実施形態においては、予備硫化後の金属硫化物の結晶層の層構造に基づいて、再生処理条件及び予備硫化条件の組み合せを選別している。このため、本実施形態に係る製造方法によれば、使用済み水素化触媒から、安定して高い活性を有する予備硫化済み再生水素化処理用触媒を製造することができる。 Conventionally, the regeneration process condition is generally selected from the viewpoint of whether or not coke deposits can be removed, or the regeneration process condition is selected from the state of the catalyst after the regeneration process and before the preliminary sulfidation. In contrast, in the present embodiment, the combination of the regeneration treatment condition and the preliminary sulfidation condition is selected based on the layer structure of the metal sulfide crystal layer after the preliminary sulfidation. For this reason, according to the manufacturing method which concerns on this embodiment, the catalyst for pre-sulfurization reproduction | regeneration hydrogenation processes which has a stable high activity can be manufactured from a used hydrogenation catalyst.
第２の工程において、金属元素Ｍの硫化物の結晶層の平均積層数は、予備硫化後の触媒を粉砕し、得られた粉末の透過型電子顕微鏡（ＴＥＭ）写真を撮影して、当該ＴＥＭ写真から１００個の結晶層についてその積層数Ｎを測定し、その平均値を算出することによって、求めることができる。なお、金属元素Ｍがモリブデンであるとき、金属元素Ｍの硫化物は二硫化モリブデン（ＭｏＳ２）であり、金属元素Ｍがタングステンであるとき、金属元素のＭの硫化物は二硫化タングステン（ＷＳ２）である。 In the second step, the average number of crystal layers of the sulfide of the metal element M is determined by pulverizing the catalyst after preliminary sulfidation, taking a transmission electron microscope (TEM) photograph of the obtained powder, It can be obtained by measuring the number N of 100 crystal layers from the photograph and calculating the average value. When the metal element M is molybdenum, the sulfide of the metal element M is molybdenum disulfide (MoS 2 ), and when the metal element M is tungsten, the sulfide of the metal element M is tungsten disulfide (WS). 2 ).
以下、第１〜第３の工程について、それぞれ詳述する。
（第１の工程）
第１の工程では、石油留分の水素化処理に用いられた水素化処理用触媒（以下、「使用済み触媒」という。）を用意する。第１の工程で用意された使用済み触媒の一部が第２の工程に供され、他部が第３の工程に供される。
Hereinafter, the first to third steps will be described in detail.
(First step)
In the first step, a hydrotreating catalyst used for hydrotreating a petroleum fraction (hereinafter referred to as “used catalyst”) is prepared. Part of the used catalyst prepared in the first step is provided for the second step, and the other part is provided for the third step.
ここで、使用済み触媒としては、必ずしも一度の水素化処理に同時に使用された水素化処理用触媒のみを示すものではない。使用済み触媒は、同様の又は類似の水素化処理に用いられた、複数の水素化処理用触媒を包含していてもよい。例えば、一回目の水素化処理に用いられた水素化処理用触媒の一部を第２の工程に供し、二回目以降の水素化処理に用いられた水素化処理用触媒を第３の工程に供してもよい。 Here, the spent catalyst does not necessarily indicate only the hydrotreating catalyst that is used simultaneously for one hydrotreating. A spent catalyst may include a plurality of hydrotreating catalysts used in similar or similar hydrotreating. For example, a part of the hydrotreating catalyst used in the first hydrotreating process is used in the second step, and the hydrotreating catalyst used in the second hydrotreating process is used in the third step. May be provided.
（第２の工程）
第２の工程では、再生処理及び予備硫化を経た使用済み触媒において、金属元素Ｍの硫化物の結晶層の平均積層数が１．６以上となる再生処理条件及び予備硫化条件を求める。
(Second step)
In the second step, regeneration treatment conditions and preliminary sulfidation conditions in which the average number of crystal layers of the sulfide of the metal element M is 1.6 or more in the used catalyst that has undergone the regeneration process and the preliminary sulfidation are obtained.
再生処理条件及び予備硫化条件を求める方法は特に限定されず、例えば、再生処理条件及び予備硫化条件をそれぞれ変更して、平均積層数が１．６以上となる再生処理条件及び予備硫化条件の組み合わせを選別することができる。また、下記方法（１）、（２）等の方法で、第２の工程を実施してもよい。 The method for obtaining the regeneration treatment condition and the preliminary sulfidation condition is not particularly limited. For example, the regeneration treatment condition and the preliminary sulfidization condition are respectively changed, and the combination of the regeneration treatment condition and the preliminary sulfidation condition in which the average number of layers becomes 1.6 or more Can be sorted out. Moreover, you may implement a 2nd process by methods, such as the following method (1) and (2).
方法（１）：
使用済み触媒の一部を複数の試料に分け、それぞれの試料について、予備硫化条件は変更せず、再生処理条件を変更して、再生処理及び予備硫化済みサンプルを得る。当該サンプルについて上記平均積層数を求めて、平均積層数が１．６以上となる処理条件を求める。
Method (1):
A part of the used catalyst is divided into a plurality of samples, and the presulfurization conditions are not changed for each sample, but the regeneration treatment conditions are changed to obtain the regenerated and presulfided samples. The said average number of lamination | stacking is calculated | required about the said sample, and the process conditions which an average number of lamination | stacking becomes 1.6 or more are calculated | required.
方法（１）によれば、所定の予備硫化条件で予備硫化を行う場合に、当該予備硫化と組み合わせる再生処理条件を選別することができる。この方法によれば、予備硫化条件（予備硫化を実施するための装置及びその運転条件等）を変更せずに、当該予備硫化条件と組み合せるに好適な再生処理条件を選別することができる。 According to the method (1), when the preliminary sulfidation is performed under a predetermined preliminary sulfidation condition, the regeneration treatment condition combined with the preliminary sulfidation can be selected. According to this method, it is possible to select a regeneration treatment condition suitable for combining with the preliminary sulfidation condition without changing the preliminary sulfidation condition (the apparatus for performing the preliminary sulfidation and the operation condition thereof).
方法（２）：
使用済み触媒を複数の試料に分け、それぞれの試料について、再生処理条件は変更せず、予備硫化条件を変更して、再生処理及び予備硫化済みサンプルを得る。当該サンプルについて上記平均積層数を求めて、平均積層数が１．６以上となる処理条件を求める。
Method (2):
The spent catalyst is divided into a plurality of samples, and for each sample, the regeneration treatment conditions are not changed, and the preliminary sulfidation conditions are changed to obtain the regenerated and presulfided samples. The said average number of lamination | stacking is calculated | required about the said sample, and the process conditions from which an average number of lamination | stacking becomes 1.6 or more are calculated | required.
方法（２）によれば、所定の再生処理条件で再生処理を行う場合に、当該再生処理と組み合わせる予備硫化条件を選別することができる。この方法によれば、再生処理条件（再生処理を実施するための装置及びその運転条件等）を変更せずに、当該再生処理条件と組み合わせるに好適な予備硫化条件を選別することができる。 According to the method (2), when the regeneration process is performed under a predetermined regeneration process condition, it is possible to select the presulfurization condition to be combined with the regeneration process. According to this method, it is possible to select a presulfurization condition suitable for combination with the regeneration process condition without changing the regeneration process condition (the apparatus for performing the regeneration process and its operating condition).
なお、方法（２）において、再生処理条件によっては予備硫化条件を変更しても、平均積層数が１．６以上とならない場合がある。この観点から、方法（２）における再生処理条件は、再生処理後の触媒のカーボン含有量が０．１５〜３．０質量％（より好ましくは０．１５〜１．５質量％）となる条件であることが好ましい。このような再生処理条件で再生処理を行うことにより、適切な予備硫化条件との組み合わせにおいて、上記平均積層数を１．６以上とすることができる。 In the method (2), the average number of stacked layers may not be 1.6 or more even if the preliminary sulfidation conditions are changed depending on the regeneration processing conditions. From this viewpoint, the regeneration treatment condition in the method (2) is such that the carbon content of the catalyst after the regeneration treatment is 0.15 to 3.0% by mass (more preferably 0.15 to 1.5% by mass). It is preferable that By performing the regeneration process under such a regeneration process condition, the average number of stacked layers can be 1.6 or more in combination with an appropriate presulfiding condition.
ここで本願において「カーボン含有量」とは、触媒中に残留するカーボン（コーク）の量を意味し、ＪＩＳ Ｍ８８１９に規定する「石炭類及びコークス類−機器分析装置による元素分析方法」に準拠して測定されるものである。 Here, in the present application, the “carbon content” means the amount of carbon (coke) remaining in the catalyst and conforms to “Coal and cokes—elemental analysis method using an instrument analyzer” defined in JIS M8819. Measured.
金属元素Ｍの硫化物の結晶層の平均積層数は、予備硫化済み再生水素化処理用触媒の水素化処理活性を高めるために、１．６以上であることが必要であり、１．８以上であると好ましく、２．０以上であるとより好ましい。また該平均積層数としては、４．０以下が好ましく、３．０以下がより好ましく、２．５以下がさらに好ましい。平均積層数がこのような上限以下であると、金属元素Ｍの硫化物が高分散されるため、金属元素Ｍの硫化物が水素化処理に有効に活用されるため高い水素化処理活性が得られる。 In order to increase the hydrotreating activity of the presulfided regenerated hydrotreating catalyst, the average number of crystal layers of the metal element M sulfide crystal layer needs to be 1.6 or more, and 1.8 or more. It is preferable that it is, and it is more preferable that it is 2.0 or more. The average number of layers is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. If the average number of layers is less than or equal to such an upper limit, the sulfide of the metal element M is highly dispersed, so that the sulfide of the metal element M is effectively utilized for the hydrogenation treatment, so that high hydrotreatment activity is obtained. It is done.
（第３の工程）
第３の工程では、第２の工程に基づいて決定された再生処理条件及び予備硫化条件で、使用済み触媒の再生処理及び予備硫化を行う。
(Third step)
In the third step, the used catalyst is regenerated and pre-sulfided under the regenerating conditions and pre-sulfiding conditions determined based on the second step.
ここで「第２の工程に基づいて決定された再生処理条件及び予備硫化条件」とは、必ずしも第２の工程で平均積層数が１．６以上となった再生処理条件及び予備硫化条件をそのまま適用することを意味するものではない。 Here, the “regeneration treatment condition and preliminary sulfidation condition determined based on the second step” are the same as the regeneration treatment condition and the preliminary sulfidation condition in which the average number of layers is 1.6 or more in the second step. It does not mean to apply.
例えば、第２の工程において再生処理を行った装置（以下、「処理装置Ａ」）と第３の工程において再生処理を行う装置（以下、「処理装置Ｂ」）とが異なる場合、処理装置Ａと処理装置Ｂとの間の相関関係を予め求めておき、その相関関係と、第２の工程で平均積層数が１．６以上となった再生処理条件と、に基づいて、第３の工程における再生処理条件を決定することができる。 For example, if the apparatus that performed the regeneration process in the second step (hereinafter “processing apparatus A”) and the apparatus that performs the regeneration process in the third process (hereinafter “processing apparatus B”) are different, the processing apparatus A And the processing apparatus B in advance, the third step based on the correlation and the reproduction processing conditions in which the average number of stacks is 1.6 or more in the second step. It is possible to determine the playback processing conditions in
予備硫化についても同様に、第２の工程において予備硫化を行った装置（以下、「処理装置Ｃ」）と第３の工程において予備硫化を行う装置（以下、「装置装置Ｃ」）とが異なる場合、処理装置Ｃと処理装置Ｄとの間の相関関係を予め求めておき、その相関関係と、第２の工程で平均積層数が１．６以上となった予備硫化条件と、に基づいて、第３の工程における予備硫化条件を決定することができる。 Similarly for the preliminary sulfidation, the apparatus (hereinafter referred to as “processing apparatus C”) that has been subjected to preliminary sulfidation in the second process is different from the apparatus that performs preliminary sulfidation in the third process (hereinafter referred to as “apparatus apparatus C”). In this case, a correlation between the processing apparatus C and the processing apparatus D is obtained in advance, and based on the correlation and the preliminary sulfidation condition in which the average number of layers is 1.6 or more in the second step. The presulfiding conditions in the third step can be determined.
なお、処理装置Ａ及び処理装置Ｂ間の相関関係、処理装置Ｃ及び処理装置Ｄ間の相関関係は、それぞれ処理装置以外の条件を同じとしたときの水素化処理活性を比較すること等により求めればよい。 Note that the correlation between the processing apparatus A and the processing apparatus B and the correlation between the processing apparatus C and the processing apparatus D are obtained by comparing the hydrotreating activities when the conditions other than the processing apparatus are the same. That's fine.
当然のことながら、処理装置Ａと処理装置Ｂとが同一の処理装置であったり、同一の再生処理条件を適用できるものである場合には、第３の工程においては第２の工程で決定された再生処理条件と同一の再生処理条件を適用することができる。また、処理装置Ｃと処理装置Ｄとが同一の処理装置であったり、同一の再生処理条件を適用できるものである場合には、第３の工程においては第２の工程で決定された予備硫化条件と同一の予備硫化条件を適用することができる。 As a matter of course, when the processing apparatus A and the processing apparatus B are the same processing apparatus or the same reproduction processing conditions can be applied, the third process is determined in the second process. It is possible to apply the same playback processing conditions as the playback processing conditions. In the case where the processing device C and the processing device D are the same processing device or the same regeneration processing conditions can be applied, the preliminary sulfidation determined in the second step in the third step. The same presulfiding conditions as the conditions can be applied.
（再生処理）
以下、第２の工程、第３の工程における再生処理について詳述するが、再生処理条件は以下の記載に限定されるものではなく、公知の種々の再生処理条件を採用できる。
(Reproduction processing)
Hereinafter, the regeneration process in the second step and the third process will be described in detail. However, the regeneration process condition is not limited to the following description, and various known regeneration process conditions can be adopted.
再生処理に用いられる設備は特に限定されないが、石油留分の水素化処理設備とは異なる設備で行われることが好ましい。すなわち、石油留分の水素化処理設備の反応器に触媒を充填したままの状態で再生処理を行うのではなく、反応器より触媒を抜き出し、抜き出された触媒を再生処理のための設備に移動させて、該設備により再生処理を行うことが好ましい。 Although the equipment used for the regeneration treatment is not particularly limited, it is preferably performed in equipment different from the hydrotreating equipment for the petroleum fraction. That is, instead of performing the regeneration process while the catalyst is still filled in the reactor of the hydrotreating equipment for petroleum fractions, the catalyst is extracted from the reactor and the extracted catalyst is used as equipment for the regeneration process. It is preferable to move and perform the regeneration process with the equipment.
使用済み触媒の再生処理を行うための形態は限定されないが、使用済み触媒から、微粉化した触媒や、触媒以外の充填材等を篩い分けにより除去する工程（除去工程）、使用済み触媒に付着した油分を除去する工程（脱油工程）、使用済み触媒に沈着したコーク、硫黄分等を除去する工程（再生工程）からこの順に構成されるものであることが好ましい。 The form for regenerating the used catalyst is not limited, but the process of removing the finely divided catalyst and the filler other than the catalyst by sieving from the used catalyst (removal process) is attached to the used catalyst. It is preferable that the steps are configured in this order from a step of removing the oil component (deoiling step), a step of removing coke deposited on the used catalyst, a sulfur component and the like (regeneration step).
このうち、脱油工程には、酸素が実質的に存在しない雰囲気、例えば窒素雰囲気下に、使用済み触媒を２００〜４００℃程度の温度に加熱することにより油分を揮散せしめる方法などが好ましく採用される。また、脱油工程は、軽質の炭化水素類にて油分を洗浄する方法、あるいはスチーミングによる油分の除去等の方法によるものであってもよい。 Among these, in the deoiling step, a method of volatilizing the oil by heating the used catalyst to a temperature of about 200 to 400 ° C. in an atmosphere where oxygen is not substantially present, for example, a nitrogen atmosphere is preferably employed. The The deoiling step may be performed by a method of washing oil with light hydrocarbons or a method of removing oil by steaming.
再生工程の処理雰囲気、処理温度及び処理時間は、以下のようにすることができる。但し、以下の記載は、処理雰囲気、処理温度及び処理時間が各要件を満たせば必ず再生水素化処理用触媒に十分な触媒活性を付与できることを意味するものではない。あくまで、第３の工程における再生処理は、第２の工程に基づいて決定された再生処理条件によって行われる。 The treatment atmosphere, treatment temperature, and treatment time of the regeneration process can be as follows. However, the following description does not mean that sufficient catalytic activity can be imparted to the regenerated hydrotreating catalyst as long as the processing atmosphere, the processing temperature, and the processing time satisfy the requirements. The reproduction process in the third step is only performed according to the reproduction process condition determined based on the second step.
再生工程における処理雰囲気は、分子状酸素が存在する雰囲気、例えば空気中、特には空気流中とすることが好ましい。 The treatment atmosphere in the regeneration step is preferably an atmosphere in which molecular oxygen exists, for example, in the air, particularly in an air stream.
また、再生工程の処理温度は、使用済み触媒の使用履歴等に応じて異なるが、好ましくは２００〜７００℃、より好ましくは２３０〜５５０℃、さらに好ましくは２４０〜４７０℃、さらにより好ましくは２５０〜４５０℃、より一層好ましくは２５０〜４００℃の範囲で選択される。沈着したコーク、硫黄分等を酸化して除去する方法が好ましく採用される。処理温度が上記下限温度を下回る場合には、コーク、硫黄分等の触媒活性を低下せしめた物質の除去が効率的に進行しない等の傾向にある。一方、処理温度が上記上限温度を超える場合には、触媒中の金属元素が複合金属酸化物を形成する、凝集を起こす等して、得られる再生触媒の活性が低下する場合がある。 Further, the treatment temperature of the regeneration step varies depending on the usage history of the spent catalyst, but is preferably 200 to 700 ° C, more preferably 230 to 550 ° C, further preferably 240 to 470 ° C, and still more preferably 250. It is selected in the range of ˜450 ° C., more preferably 250 to 400 ° C. A method of oxidizing and removing deposited coke and sulfur is preferably employed. When the treatment temperature is lower than the above lower limit temperature, the removal of substances having reduced catalytic activity such as coke and sulfur content tends not to proceed efficiently. On the other hand, when the treatment temperature exceeds the above upper limit temperature, the metal element in the catalyst may form a composite metal oxide, cause aggregation, etc., and the activity of the resulting regenerated catalyst may decrease.
再生工程の処理時間は、好ましくは０．５時間以上、より好ましくは２時間以上、さらに好ましくは２．５時間以上、特に好ましくは３時間以上である。処理時間が０．５時間未満の場合には、コーク、硫黄分等の触媒活性を低下せしめた物質の除去が効率的に進行しない傾向にある。 The treatment time of the regeneration step is preferably 0.5 hours or more, more preferably 2 hours or more, further preferably 2.5 hours or more, and particularly preferably 3 hours or more. When the treatment time is less than 0.5 hours, the removal of substances having reduced catalytic activity such as coke and sulfur content tends not to proceed efficiently.
（予備硫化）
予備硫化は、水素化処理設備とは異なる設備で行ってもよく、水素化処理設備に充填して行ってもよい。特に第３の工程においては、後者の方法で行うことで、予備硫化済み再生触媒を移送せずに、そのまま水素化処理に供することができる。
(Preliminary sulfidation)
The preliminary sulfidation may be performed in a facility different from the hydroprocessing facility, or may be performed by filling the hydroprocessing facility. In particular, in the third step, by performing the latter method, the pre-sulfurized regenerated catalyst can be used as it is without being transferred.
予備硫化の条件は、例えば以下のようにすることができる。但し、以下の記載は、各要件を満たせば必ず予備硫化済み再生触媒に十分な触媒活性を付与できることを意味するものではない。あくまで、第３の工程における予備硫化は、第２の工程に基づいて決定された予備硫化条件によって行われる。 The presulfiding conditions can be set as follows, for example. However, the following description does not necessarily mean that sufficient catalytic activity can be imparted to the presulfided regenerated catalyst if each requirement is satisfied. To the last, the preliminary sulfidation in the third step is performed according to the preliminary sulfidation conditions determined based on the second step.
予備硫化は、例えば、石油留分に硫黄化合物を添加し、これを温度２００〜４００℃、ＬＨＳＶ（液空間速度、Ｌｉｑｕｉｄ Ｈｏｕｒｌｙ Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ）０．０５〜５ｈ−１、水素化処理運転時と同一の圧力（例えば、３〜１３ＭＰａの範囲で選択される圧力）、処理時間５時間以上の条件にて、触媒に連続的に接触せしめることで行うことができる。添加する硫黄化合物としては限定されないが、ジメチルジスルフィド（ＤＭＤＳ）、硫化水素等が好ましく、これらを１質量％程度の濃度（例えば、０．５〜２．５質量％）で石油留分に添加することが好ましい。 In the preliminary sulfidation, for example, a sulfur compound is added to a petroleum fraction, and the temperature is 200 to 400 ° C., LHSV (Liquid Hourly Space Velocity) 0.05 to 5 h −1 , the same as in the hydrotreatment operation. (For example, a pressure selected in the range of 3 to 13 MPa) and a treatment time of 5 hours or more can be performed by continuously contacting the catalyst. Although it does not limit as a sulfur compound to add, dimethyl disulfide (DMDS), hydrogen sulfide, etc. are preferable, and these are added to a petroleum fraction by the density | concentration (for example, 0.5-2.5 mass%) about 1 mass%. It is preferable.
予備硫化条件としては、温度を２００〜４００℃とすることが好ましく、２２０〜３６０℃とすることがより好ましく、２４０〜３４０℃とすることもできる。また、予備硫化条件としては、ＬＨＳＶを０．０５〜５．０ｈ−１としてもよく、より好ましくは０．５〜３．５ｈ−１とすることができ、１．０〜２．０ｈ−１としてもよい。 As preliminary sulfiding conditions, the temperature is preferably 200 to 400 ° C, more preferably 220 to 360 ° C, and can also be 240 to 340 ° C. Moreover, as presulfiding conditions, LHSV may be 0.05 to 5.0 h −1 , more preferably 0.5 to 3.5 h −1, and 1.0 to 2.0 h −1. It is good.
また、予備硫化条件としては、圧力を３〜１３ＭＰａとすることが好ましく、３．５〜１２ＭＰａとすることがより好ましく、４〜１１ＭＰａとすることが更に好ましい。また、予備硫化の処理時間は、好ましくは５時間以上、より好ましくは２４時間以上、さらに好ましくは４８時間以上である。 Moreover, as preliminary sulfiding conditions, the pressure is preferably 3 to 13 MPa, more preferably 3.5 to 12 MPa, and still more preferably 4 to 11 MPa. The presulfiding treatment time is preferably 5 hours or longer, more preferably 24 hours or longer, and further preferably 48 hours or longer.
予備硫化の際に触媒に接触させる石油留分中の硫黄化合物の濃度は、０．５〜２．５質量％であることが好ましく、０．７〜１．７質量％であることがより好ましく、０．８〜１．２質量％であることが更に好ましい。 The concentration of the sulfur compound in the petroleum fraction brought into contact with the catalyst during the preliminary sulfidation is preferably 0.5 to 2.5% by mass, more preferably 0.7 to 1.7% by mass. 0.8 to 1.2% by mass is more preferable.
（予備硫化済み再生水素化処理用触媒）
本実施形態に係る予備硫化済み再生水素化処理用触媒は、上記の製造方法で製造されたものであり、高い活性を有する。
(Pre-sulfurized regenerated hydrotreating catalyst)
The presulfided regenerated hydrotreating catalyst according to this embodiment is produced by the above production method and has high activity.
なお、水素化処理用触媒の活性は、例えば、脱硫活性により評価することができる。脱硫活性は、脱硫活性は、水素化処理前の石油留分中の硫黄分含有量と、水素化処理後の石油留分中の硫黄分含有量と、から得られる脱硫速度定数により評価される。 The activity of the hydrotreating catalyst can be evaluated by, for example, desulfurization activity. The desulfurization activity is evaluated by the desulfurization rate constant obtained from the sulfur content in the petroleum fraction before hydrotreating and the sulfur content in the petroleum fraction after hydrotreating. .
また、再生処理の効率は、使用前の水素化処理用触媒（未使用触媒）の脱硫速度定数Ｓ０と、予備硫化済み再生水素化処理用触媒の脱硫速度定数Ｓ１と、を比較した、比活性（相対活性）Ｓ１／Ｓ０によって評価することができる。本実施形態に係る製造方法によって製造された予備硫化済み再生水素化処理用触媒の比活性Ｓ１／Ｓ０は、好ましくは０．８０以上であり、より好ましくは０．８５以上である。 Also, the efficiency of the regeneration process, compared with the desulfurizing rate constant S 0 of the catalyst for hydrotreating prior to use (unused catalyst), and desulfurization rate constants S 1 of presulfiding spent regeneration hydrotreating catalyst, a, Specific activity (relative activity) can be evaluated by S 1 / S 0 . The specific activity S 1 / S 0 of the presulfided regenerated hydrotreating catalyst produced by the production method according to this embodiment is preferably 0.80 or more, more preferably 0.85 or more.
（予備硫化済み再生水素化処理用触媒の使用法）
予備硫化済み再生水素化処理用触媒は、上述の石油留分の水素化処理の触媒として単独で使用してもよく、未使用触媒と積層して使用してもよい。未使用触媒と積層して使用する場合、再生水素化処理用触媒の割合は特に限定されるものではないが、触媒廃棄量の削減、触媒交換時における触媒の分離し易さ等の観点で未使用触媒１００に対して８０以上（質量比）が好ましく、１２０以上（質量比）がより好ましい。予備硫化済み再生水素化処理用触媒の使用に際し、水素化処理は、上記水素化処理工程と同様にして行うことができる。
(Use of presulfided regenerated hydrotreating catalyst)
The presulfided regenerated hydrotreating catalyst may be used alone as a catalyst for hydrotreating the above-described petroleum fraction, or may be used in a stack with an unused catalyst. In the case of stacking with an unused catalyst, the ratio of the regenerated hydrotreating catalyst is not particularly limited, but it is not used from the viewpoint of reducing the amount of catalyst waste and ease of separating the catalyst when replacing the catalyst. 80 or more (mass ratio) is preferable with respect to the catalyst 100 used, and 120 or more (mass ratio) is more preferable. In using the pre-sulfided regenerated hydrotreating catalyst, the hydrotreating can be performed in the same manner as the hydrotreating step.
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.
例えば、本発明は、石油留分の水素化処理に用いられた水素化処理用触媒であって周期表第６族元素から選ばれる金属元素Ｍを有する触媒を再生処理して、再生触媒を得る第１の工程と、第１の工程で得た再生触媒の一部について予備硫化を行うとともに、予備硫化を経た再生触媒について金属元素Ｍの硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる予備硫化条件を求める第２の工程と、第１の工程で得た再生触媒の他部について、第２の工程に基づいて決定された予備硫化条件で予備硫化を行う第３の工程と、を備える、予備硫化済み再生水素化処理用触媒の製造方法ということもできる。 For example, the present invention regenerates a catalyst for hydrotreating used in hydrotreating petroleum fractions and having a metal element M selected from Group 6 elements of the periodic table to obtain a regenerated catalyst. Preliminary sulfidation is performed on a part of the regenerated catalyst obtained in the first step and the first step, and the average number of stacked crystal layers of the metal element M sulfide is observed for the regenerated catalyst that has undergone presulfidation, In the second step for obtaining the presulfidation condition in which the average number of layers is 1.6 or more, and for the other part of the regenerated catalyst obtained in the first step, the presulfidation condition determined based on the second step It can also be referred to as a method for producing a presulfided regenerated hydrotreating catalyst comprising a third step of performing presulfidation.
また、本発明は、石油留分の水素化処理に用いられた水素化処理用触媒であって、周期表第６族元素から選ばれる金属元素Ｍを有する触媒を用意する第１の工程と、第１の工程で用意した触媒の一部について再生処理を行うとともに、再生処理後の触媒を予備硫化したときの金属元素Ｍの硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上となる再生処理条件を求める第２の工程と、第１の工程で用意した触媒の他部について、第２の工程に基づいて決定された再生処理条件で再生処理を行う第３の工程と、を備える、再生水素化処理用触媒の製造方法ということもでき、これにより製造された再生水素化処理用触媒を予備硫化する工程を備える、予備硫化済み再生水素化処理用触媒の製造方法ということもできる。 Further, the present invention is a first step of preparing a catalyst for hydrotreating used for hydrotreating a petroleum fraction, the catalyst having a metal element M selected from Group 6 elements of the periodic table; A part of the catalyst prepared in the first step is regenerated, and the average number of the crystal layers of the sulfide of the metal element M when the regenerated catalyst is pre-sulfided is observed. Regeneration processing is performed under the regeneration processing conditions determined based on the second step with respect to the second step for obtaining the regeneration processing conditions for the number of 1.6 or more and the other part of the catalyst prepared in the first step. It can also be called the manufacturing method of the catalyst for regenerated hydrotreating provided with a 3rd process, and the process for presulfided regenerated hydrotreating provided with the process of pre-sulfiding the regenerated hydrotreating catalyst manufactured by this It can also be called the manufacturing method of a catalyst.
また、本発明は、石油留分を処理するための水素化処理用触媒を再生処理するに際し、再生処理条件を選別する方法であって、水素化処理後の水素化処理用触媒について所定の条件で再生処理及び予備硫化を行い、再生処理及び予備硫化を経た触媒について前記金属元素の硫化物の結晶層を観測する第２の工程と、第２の工程で観測された平均積層数に基づいて、再生処理の条件の良否を判定する第３の工程と、を備える、水素化処理用触媒の再生処理条件の選別方法ということもできる。 The present invention also relates to a method for selecting a regeneration treatment condition when regenerating a hydrotreating catalyst for treating a petroleum fraction, the hydrotreating catalyst after hydrotreating being subjected to predetermined conditions. A second step of observing the crystal layer of the sulfide of the metal element with respect to the catalyst that has undergone the regeneration treatment and preliminary sulfidation, and the average number of stacks observed in the second step. And a third step of determining whether or not the conditions for the regeneration treatment are good.
また、本発明は、石油留分の水素化処理に用いられた水素化処理用触媒であって周期表第６族元素から選ばれる金属元素を有する触媒を、上記の決定方法で決定された再生処理条件で再生処理する工程を備える、再生水素化処理用触媒の製造方法ということもできる。 The present invention also provides a catalyst for hydrotreating used in hydrotreating petroleum fractions and having a metal element selected from Group 6 elements of the periodic table, which is determined by the above-described determination method. It can also be said to be a method for producing a regenerated hydrotreating catalyst comprising a step of regenerating under processing conditions.
さらに、本発明は、上記製造方法により製造された予備硫化済み再生水素化処理用触媒を用いて、石油留分の水素化処理を行う工程を備える、石油製品の製造方法であってもよい。このような製造方法によれば、経済性よく石油製品を製造することができる。 Furthermore, the present invention may be a method for producing a petroleum product, comprising a step of hydrotreating a petroleum fraction using the presulfided regenerated hydrotreating catalyst produced by the above production method. According to such a production method, petroleum products can be produced with good economic efficiency.
以下、実施例により本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.
［実施例１］
（使用済み触媒）
活性金属としてモリブデン及びコバルトをアルミナ担体に担持してなる触媒（未使用触媒１）を、灯油の水素化処理設備において水素化処理用触媒として２年間使用したものを使用済み触媒１として用意した。
[Example 1]
(Spent catalyst)
A catalyst obtained by supporting molybdenum and cobalt as active metals on an alumina carrier (unused catalyst 1) as a hydrotreating catalyst in a kerosene hydrotreating facility for 2 years was prepared as a used catalyst 1.
（使用済み触媒の再生処理）
使用済み触媒１の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒１を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、２５０℃で５時間再生処理を行って、再生触媒Ａ１を得た。得られた再生触媒Ａ１のカーボン含有量を測定したところ、１．１６質量％であった。
(Regeneration treatment of spent catalyst)
Part of the used catalyst 1 was deoiled in an electric furnace by heating at 300 ° C. for 3 hours in a nitrogen stream having a flow rate per unit volume of catalyst of 50 NL / h · L. Next, the used catalyst 1 after deoiling is regenerated in an electric furnace at 250 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L, so that the regenerated catalyst A1 Got. The carbon content of the obtained regenerated catalyst A1 was measured and found to be 1.16% by mass.
（再生触媒の予備硫化）
固定床連続流通式反応装置に再生触媒Ａ１を充填し、触媒の予備硫化を行った。具体的には、灯油留分に１質量％のジメチルジスルフィド（ＤＭＤＳ）を添加し、これを反応温度２９０℃、液空間速度２．０ｈ−１、圧力４ＭＰａの条件で、再生触媒Ａ１に対して４８時間連続的に供給して予備硫化処理を行い、予備硫化済み再生触媒Ａ１を得た。
(Pre-sulfurization of regenerated catalyst)
The fixed bed continuous flow reactor was charged with the regenerated catalyst A1, and the catalyst was presulfided. Specifically, 1% by mass of dimethyl disulfide (DMDS) is added to the kerosene fraction, and this is added to the regenerated catalyst A1 under the conditions of a reaction temperature of 290 ° C., a liquid space velocity of 2.0 h −1 , and a pressure of 4 MPa. Pre-sulfiding treatment was performed by continuously supplying for 48 hours to obtain a pre-sulfided regenerated catalyst A1.
（二硫化モリブデン層の平均積層数の測定）
透過型電子顕微鏡（ＴＥＭ）を用いて下記の条件で予備硫化済み再生触媒Ａ１のＴＥＭ写真を撮影した。
電子銃 ：ＬａＢ６
加速電圧：２００ｋＶ
撮影倍率：１５０万倍
得られたＴＥＭ写真から、１００個の二硫化モリブデン層を観察し、各二硫化モリブデン層についてそれぞれ積層数を測定して平均積層数を算出した。予備硫化済み再生触媒Ａ１の二硫化モリブデン層の平均積層数は１．６１であった。
(Measurement of the average number of laminated molybdenum disulfide layers)
A transmission electron microscope (TEM) was used to take a TEM photograph of the presulfided regenerated catalyst A1 under the following conditions.
Electron gun: LaB6
Accelerating voltage: 200kV
Imaging magnification: 1.5 million times From the obtained TEM photograph, 100 molybdenum disulfide layers were observed, and the number of laminated layers was measured for each molybdenum disulfide layer to calculate the average number of laminated layers. The average number of laminated molybdenum disulfide layers of the presulfided regenerated catalyst A1 was 1.61.
図１は、予備硫化済み再生触媒Ａ１のＴＥＭ写真の一部を示す図であり、図２は、図１に示すＴＥＭ写真における二硫化モリブデン層を示す図である。図２中、Ａは、積層数が１の二硫化モリブデン層を示し、Ｂは、積層数が２の二硫化モリブデン層を示し、Ｃは、積層数が３の二硫化モリブデン層を示し、Ｄは、積層数が４の二硫化モリブデン層を示し、Ｅは、積層数が５の二硫化モリブデン層を示す。 FIG. 1 is a view showing a part of a TEM photograph of the presulfided regenerated catalyst A1, and FIG. 2 is a view showing a molybdenum disulfide layer in the TEM photograph shown in FIG. In FIG. 2, A represents a molybdenum disulfide layer having a stack number of 1, B represents a molybdenum disulfide layer having a stack number of 2, C represents a molybdenum disulfide layer having a stack number of 3, and D Represents a molybdenum disulfide layer having a stack number of 4, and E represents a molybdenum disulfide layer having a stack number of 5.
（予備硫化済み再生触媒の調製及び触媒活性の評価）
使用済み触媒１の他部について、上記と同条件で再生処理を行って再生触媒Ｂ１を得て、ついで上記と同条件で予備硫化を行って予備硫化済み再生触媒Ｂ１を得た。得られた再生触媒１のカーボン含有量は１．１６質量％であった。また、予備硫化済み再生触媒Ｂ１における二硫化モリブデン層の平均積層数は１．６１であった。
(Preparation of pre-sulfided regenerated catalyst and evaluation of catalytic activity)
The other part of the used catalyst 1 was regenerated under the same conditions as above to obtain a regenerated catalyst B1, and then presulfided under the same conditions as above to obtain a presulfided regenerated catalyst B1. The carbon content of the obtained regenerated catalyst 1 was 1.16% by mass. Moreover, the average number of laminated molybdenum disulfide layers in the pre-sulfided regenerated catalyst B1 was 1.61.
予備硫化済み再生触媒Ｂ１について、以下のようにして触媒活性を評価した。まず、固定床連続流通式反応装置に予備硫化済み再生触媒Ｂ１を充填し、灯油留分を原料油として、水素分圧４ＭＰａ、液空間速度１．０ｈ−１、水素／油比２００ＮＬ／Ｌ、反応温度３００℃で水素化処理反応を行った。生成油中の硫黄分含有量から、脱硫速度定数を求めた。未使用触媒１の脱硫速度定数を１として、予備硫化済み再生触媒Ｂ１の比活性（脱硫活性）を求めたところ、０．９５となった。 The catalytic activity of the presulfided regenerated catalyst B1 was evaluated as follows. First, a pre-sulfided regenerated catalyst B1 is charged into a fixed bed continuous flow reactor, a kerosene fraction is used as a raw material oil, a hydrogen partial pressure of 4 MPa, a liquid space velocity of 1.0 h −1 , a hydrogen / oil ratio of 200 NL / L, The hydrogenation reaction was performed at a reaction temperature of 300 ° C. The desulfurization rate constant was determined from the sulfur content in the product oil. When the desulfurization rate constant of the unused catalyst 1 was set to 1, the specific activity (desulfurization activity) of the pre-sulfurized regenerated catalyst B1 was determined to be 0.95.
なお、予備硫化済み再生触媒Ａ１についても同様に触媒活性の評価を行ったところ、その比活性（脱硫活性）は０．９５であった。 The catalytic activity of the pre-sulfurized regenerated catalyst A1 was evaluated in the same manner, and the specific activity (desulfurization activity) was 0.95.
［実施例２］
（使用済み触媒の再生処理）
実施例１と同じ使用済み触媒１の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒１を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、３００℃で５時間再生処理を行って、再生触媒Ａ２を得た。得られた再生触媒Ａ２のカーボン含有量を測定したところ、０．４８質量％であった。
[Example 2]
(Regeneration treatment of spent catalyst)
A portion of the same spent catalyst 1 as in Example 1 was heated in a nitrogen stream at a flow rate of 50 NL / h · L per unit volume of the catalyst in an electric furnace at 300 ° C. for 3 hours for deoiling. went. Next, the used catalyst 1 that has been deoiled is regenerated in an electric furnace at 300 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L. Got. The carbon content of the obtained regenerated catalyst A2 was measured and found to be 0.48% by mass.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒Ａ２について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒Ａ２を得た。得られた予備硫化済み再生触媒Ａ２について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は２．４０であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst A2 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst A2. With respect to the obtained pre-sulfided regenerated catalyst A2, TEM photograph analysis was performed in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 2.40.
（予備硫化済み再生触媒の調製及び触媒活性の評価）
使用済み触媒１の他部について、上記と同条件で再生処理を行って再生触媒Ｂ２を得て、ついで上記と同条件で予備硫化を行って予備硫化済み再生触媒Ｂ２を得た。得られた再生触媒Ｂ２のカーボン含有量は０．４８質量％であった。また、予備硫化済み再生触媒Ｂ２における二硫化モリブデン層の平均積層数は２．４０であった。
(Preparation of pre-sulfided regenerated catalyst and evaluation of catalytic activity)
The other part of the used catalyst 1 was regenerated under the same conditions as above to obtain a regenerated catalyst B2, and then presulfided under the same conditions as above to obtain a presulfided regenerated catalyst B2. The carbon content of the regenerated catalyst B2 obtained was 0.48% by mass. In addition, the average number of molybdenum disulfide layers in the pre-sulfided regenerated catalyst B2 was 2.40.
予備硫化済み再生触媒Ｂ２について、実施例１と同様にして触媒活性を評価したところ、予備硫化済み再生触媒Ｂ２の比活性（脱硫活性）は０．９８であった。なお、予備硫化済み再生触媒Ａ２についても同様に触媒活性の評価を行ったところ、その比活性（脱硫活性）も０．９８であった。 When the catalyst activity of the pre-sulfided regenerated catalyst B2 was evaluated in the same manner as in Example 1, the specific activity (desulfurization activity) of the pre-sulfided regenerated catalyst B2 was 0.98. The catalytic activity of the presulfided regenerated catalyst A2 was evaluated in the same manner, and the specific activity (desulfurization activity) was 0.98.
［実施例３］
（使用済み触媒の再生処理）
実施例１と同じ使用済み触媒１の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒１を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、３５０℃で５時間再生処理を行って、再生触媒Ａ３を得た。得られた再生触媒Ａ３のカーボン含有量を測定したところ、０．１５質量％であった。
[Example 3]
(Regeneration treatment of spent catalyst)
A portion of the same spent catalyst 1 as in Example 1 was heated in a nitrogen stream at a flow rate of 50 NL / h · L per unit volume of the catalyst in an electric furnace at 300 ° C. for 3 hours for deoiling. went. Next, the deoiled spent catalyst 1 is regenerated in an electric furnace at 350 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L, so that the regenerated catalyst A3 Got. The carbon content of the obtained regenerated catalyst A3 was measured and found to be 0.15% by mass.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒Ａ３について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒Ａ３を得た。得られた予備硫化済み再生触媒Ａ３について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は２．２９であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst A3 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst A3. The obtained pre-sulfided regenerated catalyst A3 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 2.29.
図３は、予備硫化済み再生触媒Ａ３のＴＥＭ写真の一部を示す図であり、図４は、図３に示すＴＥＭ写真における二硫化モリブデン層を示す図である。図４中、Ａは、積層数が１の二硫化モリブデン層を示し、Ｂは、積層数が２の二硫化モリブデン層を示し、Ｃは、積層数が３の二硫化モリブデン層を示し、Ｄは、積層数が４の二硫化モリブデン層を示す。 FIG. 3 is a view showing a part of a TEM photograph of the presulfided regenerated catalyst A3, and FIG. 4 is a view showing a molybdenum disulfide layer in the TEM photograph shown in FIG. In FIG. 4, A represents a molybdenum disulfide layer having a stack number of 1, B represents a molybdenum disulfide layer having a stack number of 2, C represents a molybdenum disulfide layer having a stack number of 3, and D Indicates a molybdenum disulfide layer having a stack number of four.
（予備硫化済み再生触媒の調製及び触媒活性の評価）
使用済み触媒１の他部について、上記と同条件で再生処理を行って再生触媒Ｂ３を得て、ついで上記と同条件で予備硫化を行って予備硫化済み再生触媒Ｂ３を得た。得られた再生触媒Ｂ３のカーボン含有量は０．１５質量％であった。また、予備硫化済み再生触媒Ｂ３における二硫化モリブデン層の平均積層数は２．２９であった。
(Preparation of pre-sulfided regenerated catalyst and evaluation of catalytic activity)
The other part of the used catalyst 1 was regenerated under the same conditions as above to obtain a regenerated catalyst B3, and then presulfided under the same conditions as above to obtain a presulfided regenerated catalyst B3. The carbon content of the obtained regenerated catalyst B3 was 0.15% by mass. Moreover, the average number of laminated molybdenum disulfide layers in the pre-sulfided regenerated catalyst B3 was 2.29.
予備硫化済み再生触媒Ｂ３について、実施例１と同様にして触媒活性を評価したところ、予備硫化済み再生触媒Ｂ３の比活性（脱硫活性）は０．９８であった。なお、予備硫化済み再生触媒Ａ３についても同様に触媒活性の評価を行ったところ、その比活性（脱硫活性）も０．９８であった。 When the catalyst activity of the pre-sulfided regenerated catalyst B3 was evaluated in the same manner as in Example 1, the specific activity (desulfurization activity) of the pre-sulfided regenerated catalyst B3 was 0.98. The catalytic activity of the pre-sulfurized regenerated catalyst A3 was evaluated in the same manner, and the specific activity (desulfurization activity) was 0.98.
［実施例４］
（使用済み触媒）
活性金属としてモリブデン、ニッケル及びコバルトをアルミナ担体に担持した触媒（未使用触媒２）を、灯油の水素化処理設備において水素化処理用触媒として２年間使用したものを使用済み触媒２として用意した。
[Example 4]
(Spent catalyst)
A catalyst in which molybdenum, nickel and cobalt as active metals were supported on an alumina carrier (unused catalyst 2) was used as a catalyst for hydrotreating in a kerosene hydrotreating facility for two years was prepared as a used catalyst 2.
（使用済み触媒の再生処理）
使用済み触媒２の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒２を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、３５０℃で５時間再生処理を行って、再生触媒Ａ４を得た。得られた再生触媒Ａ４のカーボン含有量を測定したところ、２．０９質量％であった。
(Regeneration treatment of spent catalyst)
Part of the used catalyst 2 was deoiled in an electric furnace by heating at 300 ° C. for 3 hours under a nitrogen stream having a flow rate per unit volume of the catalyst of 50 NL / h · L. Next, the deoiled spent catalyst 2 is regenerated in an electric furnace at 350 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L. Got. The carbon content of the obtained regenerated catalyst A4 was measured and found to be 2.09% by mass.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒Ａ４について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒Ａ４を得た。得られた予備硫化済み再生触媒Ａ４について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は２．０４であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst A4 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst A4. The obtained sulfidized regenerated catalyst A4 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 2.04.
（予備硫化済み再生触媒の調製及び触媒活性の評価）
使用済み触媒２の他部について、上記と同条件で再生処理を行って再生触媒Ｂ４を得て、ついで上記と同条件で予備硫化を行って予備硫化済み再生触媒Ｂ４を得た。得られた再生触媒Ｂ４のカーボン含有量は２．０９質量％であった。また、予備硫化済み再生触媒Ｂ４における二硫化モリブデン層の平均積層数は２．０４であった。
(Preparation of pre-sulfided regenerated catalyst and evaluation of catalytic activity)
The other part of the used catalyst 2 was regenerated under the same conditions as above to obtain a regenerated catalyst B4, and then presulfided under the same conditions as above to obtain a presulfided regenerated catalyst B4. The carbon content of the obtained regenerated catalyst B4 was 2.09% by mass. Moreover, the average number of laminated molybdenum disulfide layers in the pre-sulfided regenerated catalyst B4 was 2.04.
予備硫化済み再生触媒Ｂ４について、実施例１と同様にして触媒活性を評価したところ、未使用触媒２の脱硫速度定数を１とした予備硫化済み再生触媒Ｂ４の比活性（脱硫活性）は０．９６であった。なお、予備硫化済み再生触媒Ａ４について同様に触媒活性の評価を行ったところ、その比活性（脱硫活性）も０．９６であった。 The catalytic activity of the presulfurized regenerated catalyst B4 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the presulfided regenerated catalyst B4 with the desulfurization rate constant of the unused catalyst 2 being 1. 96. When the catalytic activity of the presulfurized regenerated catalyst A4 was evaluated in the same manner, the specific activity (desulfurization activity) was 0.96.
［実施例５］
（使用済み触媒の再生処理）
実施例４と同じ使用済み触媒２の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒２を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、４００℃で５時間再生処理を行って、再生触媒Ａ５を得た。得られた再生触媒Ａ５のカーボン含有量を測定したところ、０．１８質量％であった。
[Example 5]
(Regeneration treatment of spent catalyst)
A part of the same spent catalyst 2 as in Example 4 was heated in a nitrogen stream with a flow rate per unit volume of catalyst of 50 NL / h · L at 300 ° C. for 3 hours in an electric furnace for deoiling. went. Next, the used catalyst 2 after deoiling is regenerated at 400 ° C. for 5 hours in an electric furnace under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L, thereby producing a regenerated catalyst A5. Got. It was 0.18 mass% when the carbon content of the obtained regenerated catalyst A5 was measured.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒Ａ５について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒Ａ５を得た。得られた予備硫化済み再生触媒Ａ５について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．８４であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst A5 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst A5. With respect to the obtained pre-sulfided regenerated catalyst A5, TEM photograph analysis was performed in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.84.
（予備硫化済み再生触媒の調製及び触媒活性の評価）
使用済み触媒２の他部について、上記と同条件で再生処理を行って再生触媒Ｂ５を得て、ついで上記と同条件で予備硫化を行って予備硫化済み再生触媒Ｂ５を得た。得られた再生触媒Ｂ５のカーボン含有量は０．１８質量％であった。また、予備硫化済み再生触媒Ｂ５における二硫化モリブデン層の平均積層数は１．８４であった。
(Preparation of pre-sulfided regenerated catalyst and evaluation of catalytic activity)
The other part of the used catalyst 2 was regenerated under the same conditions as above to obtain a regenerated catalyst B5, and then presulfided under the same conditions as above to obtain a presulfided regenerated catalyst B5. The carbon content of the obtained regenerated catalyst B5 was 0.18% by mass. Moreover, the average number of laminated molybdenum disulfide layers in the presulfided regenerated catalyst B5 was 1.84.
予備硫化済み再生触媒Ｂ５について、実施例１と同様にして触媒活性を評価したところ、未使用触媒２の脱硫速度定数を１とした予備硫化済み再生触媒Ｂ５の比活性（脱硫活性）は０．９５であった。なお、予備硫化済み再生触媒Ａ５についても同様に触媒活性の評価を行ったところ、その比活性（脱硫活性）も０．９５であった。 The catalytic activity of the presulfurized regenerated catalyst B5 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the presulfided regenerated catalyst B5 with the desulfurization rate constant of the unused catalyst 2 being 1. 95. The catalytic activity of the presulfided regenerated catalyst A5 was evaluated in the same manner, and the specific activity (desulfurization activity) was 0.95.
［比較例１］
（使用済み触媒の再生処理）
実施例１と同じ使用済み触媒１の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒１を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、４５０℃で５時間再生処理を行って、再生触媒６を得た。得られた再生触媒６のカーボン含有量を測定したところ、０．０９質量％であった。
[Comparative Example 1]
(Regeneration treatment of spent catalyst)
A portion of the same spent catalyst 1 as in Example 1 was heated in a nitrogen stream at a flow rate of 50 NL / h · L per unit volume of the catalyst in an electric furnace at 300 ° C. for 3 hours for deoiling. went. Next, the deoiled spent catalyst 1 is regenerated in an electric furnace at 450 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L. Got. It was 0.09 mass% when the carbon content of the obtained regenerated catalyst 6 was measured.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒６について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒６を得た。得られた予備硫化済み再生触媒６について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．４７であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst 6 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst 6. The obtained pre-sulfided regenerated catalyst 6 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.47.
図５は、予備硫化済み再生触媒６のＴＥＭ写真の一部を示す図であり、図６は、図５に示すＴＥＭ写真における二硫化モリブデン層を示す図である。図６中、Ａは、積層数が１の二硫化モリブデン層を示し、Ｂは、積層数が２の二硫化モリブデン層を示し、Ｃは、積層数が３の二硫化モリブデン層を示し、Ｄは、積層数が４の二硫化モリブデン層を示す。 FIG. 5 is a view showing a part of a TEM photograph of the presulfided regenerated catalyst 6, and FIG. 6 is a view showing a molybdenum disulfide layer in the TEM photograph shown in FIG. In FIG. 6, A represents a molybdenum disulfide layer having a stack number of 1, B represents a molybdenum disulfide layer having a stack number of 2, C represents a molybdenum disulfide layer having a stack number of 3, and D Indicates a molybdenum disulfide layer having a stack number of four.
（触媒活性の評価）
予備硫化済み再生触媒６について、実施例１と同様にして触媒活性を評価したところ、未使用触媒１の脱硫速度定数を１とした予備硫化済み再生触媒６の比活性（脱硫活性）は０．８３であった。
(Evaluation of catalytic activity)
The catalytic activity of the pre-sulfurized regenerated catalyst 6 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the pre-sulfided regenerated catalyst 6 with the desulfurization rate constant of the unused catalyst 1 being 1. 83.
［比較例２］
（使用済み触媒の再生処理）
実施例１と同じ使用済み触媒１の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒１を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、５００℃で５時間再生処理を行って、再生触媒７を得た。得られた再生触媒７のカーボン含有量を測定したところ、０．０１質量％であった。
[Comparative Example 2]
(Regeneration treatment of spent catalyst)
A portion of the same spent catalyst 1 as in Example 1 was heated in a nitrogen stream at a flow rate of 50 NL / h · L per unit volume of the catalyst in an electric furnace at 300 ° C. for 3 hours for deoiling. went. Next, the deoiled spent catalyst 1 is regenerated in an electric furnace at 500 ° C. for 5 hours under an air flow having a flow rate per catalyst unit volume of 50 NL / h · L. Got. It was 0.01 mass% when the carbon content of the obtained regenerated catalyst 7 was measured.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒７について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒７を得た。得られた予備硫化済み再生触媒７について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．１０であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst 7 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst 7. The obtained pre-sulfided regenerated catalyst 7 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.10.
（触媒活性の評価）
予備硫化済み再生触媒７について、実施例１と同様にして触媒活性を評価したところ、未使用触媒１の脱硫速度定数を１とした予備硫化済み再生触媒７の比活性（脱硫活性）は０．８２であった。
(Evaluation of catalytic activity)
The catalytic activity of the pre-sulfurized regenerated catalyst 7 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the pre-sulfided regenerated catalyst 7 with the desulfurization rate constant of the unused catalyst 1 being 1. 82.
［比較例３］
（使用済み触媒の再生処理）
実施例４と同じ使用済み触媒２の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒２を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、５００℃で５時間再生処理を行って、再生触媒８を得た。得られた再生触媒８のカーボン含有量を測定したところ、０．０１質量％であった。
[Comparative Example 3]
(Regeneration treatment of spent catalyst)
A part of the same spent catalyst 2 as in Example 4 was heated in a nitrogen stream with a flow rate per unit volume of catalyst of 50 NL / h · L at 300 ° C. for 3 hours in an electric furnace for deoiling. went. Next, the spent catalyst 2 that has been deoiled is regenerated in an electric furnace at 500 ° C. for 5 hours under an air flow having a flow rate per unit volume of catalyst of 50 NL / h · L. Got. It was 0.01 mass% when the carbon content of the obtained regenerated catalyst 8 was measured.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒８について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒８を得た。得られた予備硫化済み再生触媒８について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．２６であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst 8 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst 8. The obtained presulfided regenerated catalyst 8 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.26.
（触媒活性の評価）
予備硫化済み再生触媒８について、実施例１と同様にして触媒活性を評価したところ、未使用触媒２の脱硫速度定数を１とした予備硫化済み再生触媒８の比活性（脱硫活性）は０．８０であった。
(Evaluation of catalytic activity)
The catalytic activity of the presulfided regenerated catalyst 8 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the presulfided regenerated catalyst 8 with the desulfurization rate constant of the unused catalyst 2 being 1. 80.
［比較例４］
（使用済み触媒の再生処理）
実施例４と同じ使用済み触媒２の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒２を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、２５０℃で５時間再生処理を行って、再生触媒９を得た。得られた再生触媒９のカーボン含有量を測定したところ、１１．３０質量％であった。
[Comparative Example 4]
(Regeneration treatment of spent catalyst)
A part of the same spent catalyst 2 as in Example 4 was heated in a nitrogen stream with a flow rate per unit volume of catalyst of 50 NL / h · L at 300 ° C. for 3 hours in an electric furnace for deoiling. went. Next, the used catalyst 2 that has been deoiled is regenerated in an electric furnace at 250 ° C. for 5 hours under an air flow at a flow rate of 50 NL / h · L per unit volume of the catalyst. Got. The carbon content of the obtained regenerated catalyst 9 was measured and found to be 11.30% by mass.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒９について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒９を得た。得られた予備硫化済み再生触媒９について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．４３であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst 9 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst 9. The obtained pre-sulfided regenerated catalyst 9 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.43.
（触媒活性の評価）
予備硫化済み再生触媒９について、実施例１と同様にして触媒活性を評価したところ、未使用触媒２の脱硫速度定数を１とした予備硫化済み再生触媒９の比活性（脱硫活性）は０．４２であった。
(Evaluation of catalytic activity)
The catalytic activity of the presulfurized regenerated catalyst 9 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the presulfided regenerated catalyst 9 with the desulfurization rate constant of the unused catalyst 2 being 1. 42.
［比較例５］
（使用済み触媒の再生処理）
実施例４と同じ使用済み触媒２の一部を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである窒素気流下に、３００℃で３時間加熱して脱油を行った。次いで、脱油済みの使用済み触媒２を、電気炉中にて、触媒単位体積当りの流速が５０ＮＬ／ｈ・Ｌである空気流下に、３００℃で５時間再生処理を行って、再生触媒１０を得た。得られた再生触媒１０のカーボン含有量を測定したところ、７．５２質量％であった。
[Comparative Example 5]
(Regeneration treatment of spent catalyst)
A part of the same spent catalyst 2 as in Example 4 was heated in a nitrogen stream with a flow rate per unit volume of catalyst of 50 NL / h · L at 300 ° C. for 3 hours in an electric furnace for deoiling. went. Next, the used catalyst 2 after deoiling is regenerated in an electric furnace at 300 ° C. for 5 hours under an air flow at a flow rate of 50 NL / h · L per unit volume of the catalyst. Got. The carbon content of the obtained regenerated catalyst 10 was measured and found to be 7.52% by mass.
（再生触媒の予備硫化、二硫化モリブデン層の平均積層数の測定）
再生触媒１０について実施例１と同条件で予備硫化を行い、予備硫化済み再生触媒１０を得た。得られた予備硫化済み再生触媒１０について、実施例１と同様にＴＥＭ写真解析を行ったところ、二硫化モリブデン層の平均積層数は１．２７であった。
(Measurement of pre-sulfurized regenerated catalyst and average number of molybdenum disulfide layers)
The regenerated catalyst 10 was presulfided under the same conditions as in Example 1 to obtain a presulfided regenerated catalyst 10. The obtained pre-sulfided regenerated catalyst 10 was analyzed by TEM photograph in the same manner as in Example 1. As a result, the average number of laminated molybdenum disulfide layers was 1.27.
（触媒活性の評価）
予備硫化済み再生触媒１０について、実施例１と同様にして触媒活性を評価したところ、未使用触媒２の脱硫速度定数を１とした予備硫化済み再生触媒１０の比活性（脱硫活性）は０．５８であった。
(Evaluation of catalytic activity)
The catalytic activity of the pre-sulfurized regenerated catalyst 10 was evaluated in the same manner as in Example 1. As a result, the specific activity (desulfurization activity) of the pre-sulfided regenerated catalyst 10 with the desulfurization rate constant of the unused catalyst 2 being 1. 58.
実施例１〜５では、予備硫化済み再生触媒の平均積層数が１．６以上となる再生処理条件及び予備硫化条件を選択することで、未使用触媒に対する比活性の高い予備硫化済み再生触媒が得られた。また、実施例１〜５の予備硫化条件で平均積層数が１．６以上となる再生処理条件は、再生触媒のカーボン含有量が０．１５〜３．０質量％となる再生処理条件であった。一方で、再生触媒のカーボン含有量が０．１５〜３．０質量％の範囲外となる再生処理条件を採用した比較例１〜５では、予備硫化済み再生触媒の平均積層数が１．６未満であり、このような再生処理条件及び予備硫化条件の組み合わせでは、高い比活性を得ることができなかった。
In Examples 1 to 5, by selecting a regeneration treatment condition and a presulfurization condition in which the average number of layers of the presulfided regenerated catalyst is 1.6 or more, a presulfided regenerated catalyst having a high specific activity relative to an unused catalyst is obtained. Obtained. In addition, the regeneration treatment conditions in which the average number of layers is 1.6 or more under the presulfurization conditions in Examples 1 to 5 are regeneration treatment conditions in which the carbon content of the regeneration catalyst is 0.15 to 3.0% by mass. It was. On the other hand, in Comparative Examples 1 to 5 in which the regeneration treatment conditions in which the carbon content of the regenerated catalyst is outside the range of 0.15 to 3.0% by mass are adopted, the average number of layers of the presulfided regenerated catalyst is 1.6. The specific activity cannot be obtained with the combination of the regeneration treatment condition and the presulfurization condition.
Claims (8)
前記第１の工程で用意した前記触媒の一部について再生処理及び予備硫化を行うとともに、再生処理及び予備硫化を経た前記触媒について前記金属元素の硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上４．０以下となる再生処理条件及び予備硫化条件を求める第２の工程と、
前記第１の工程で用意した前記触媒の他部について、前記第２の工程に基づいて決定された再生処理条件及び予備硫化条件で再生処理及び予備硫化を行う第３の工程と、
を備える、予備硫化済み再生水素化処理用触媒の製造方法。 A first step of preparing a catalyst having a metal element selected from Group 6 elements of the periodic table, which is a catalyst for hydroprocessing used for hydrotreating a petroleum fraction;
Regeneration treatment and preliminary sulfidation are performed on a part of the catalyst prepared in the first step, and the average number of stacked crystal layers of the metal element sulfide is observed for the catalyst that has undergone the regeneration treatment and preliminary sulfidation. A second step for obtaining a regeneration treatment condition and a presulfurization condition in which the average number of layers is 1.6 or more and 4.0 or less ,
A third step of performing regeneration treatment and preliminary sulfidation under the regeneration treatment conditions and presulfurization conditions determined based on the second step for the other part of the catalyst prepared in the first step;
A process for producing a presulfided regenerated hydroprocessing catalyst comprising:
前記第１の工程で得た前記再生触媒の一部について予備硫化を行うとともに、予備硫化を経た前記再生触媒について前記金属元素の硫化物の結晶層の平均積層数を観測して、当該平均積層数が１．６以上４．０以下となる予備硫化条件を求める第２の工程と、
前記第１の工程で得た前記再生触媒の他部について、前記第２の工程に基づいて決定された予備硫化条件で予備硫化を行う第３の工程と、
を備える、予備硫化済み再生水素化処理用触媒の製造方法。 A first step of regenerating a catalyst for hydrotreating used in the hydrotreating of petroleum fractions and having a metal element selected from Group 6 elements of the periodic table to obtain a regenerated catalyst;
A portion of the regenerated catalyst obtained in the first step is subjected to presulfidation, and the average number of laminated layers of the sulfide crystals of the metal element is observed for the regenerated catalyst that has undergone presulfidation. A second step for obtaining a presulfidation condition in which the number is 1.6 or more and 4.0 or less ;
A third step of performing preliminary sulfidation on the other portion of the regenerated catalyst obtained in the first step under pre-sulfurization conditions determined based on the second step;
A process for producing a presulfided regenerated hydroprocessing catalyst comprising:
前記第１の工程で用意した前記触媒の一部について再生処理を行って、再生処理後の前記触媒を予備硫化したときの前記金属元素の硫化物の結晶層の平均積層数が１．６以上４．０以下となる再生処理条件を求める第２の工程と、
前記第１の工程で用意した前記触媒の他部について、前記第２の工程に基づいて決定された再生処理条件で再生処理を行う第３の工程と、
を備える、再生水素化処理用触媒の製造方法。 A first step of preparing a catalyst having a metal element selected from Group 6 elements of the periodic table, which is a catalyst for hydroprocessing used for hydrotreating a petroleum fraction;
Regeneration treatment is performed on a part of the catalyst prepared in the first step, and the average number of crystal layers of the metal element sulfide crystal layer when the catalyst after the regeneration treatment is presulfided is 1.6 or more. A second step for obtaining a reproduction processing condition of 4.0 or less ;
A third step of performing a regeneration process on the other part of the catalyst prepared in the first step under a regeneration process condition determined based on the second step;
A method for producing a regenerated hydrotreating catalyst.
水素化処理後の水素化処理用触媒について所定の条件で再生処理及び予備硫化を行い、再生処理及び予備硫化を経た前記触媒について前記金属元素の硫化物の結晶層を観測する第２の工程と、
前記第２の工程で観測された前記平均積層数に基づいて、再生処理の条件の良否を判定する第３の工程と、
を備える、水素化処理用触媒の再生処理条件の選別方法。 A method for selecting regeneration treatment conditions when regenerating a catalyst for hydrotreating a petroleum fraction and having a metal element selected from Group 6 elements of the periodic table ,
A second step of regenerating and presulfiding the hydrotreating catalyst after the hydrotreating under predetermined conditions, and observing the crystal layer of the metal element sulfide with respect to the catalyst that has undergone the regenerating and presulfiding; ,
A third step of determining whether the conditions of the regeneration process are good based on the average number of stacked layers observed in the second step;
A method for selecting a regeneration treatment condition for a hydrotreating catalyst.
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