JP2021036011A - Treatment method of a plurality of base oils - Google Patents
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Abstract
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本発明は、オレフィン性不飽和結合を有する化合物を含有する原料油の水素化処理と、硫黄原子を有する化合物を含有する原料油の脱硫処理とを、工業的に効率的に行う複数の原料油の処理方法に関する。 The present invention is a plurality of raw material oils for industrially efficiently performing hydrogenation treatment of a raw material oil containing a compound having an olefinically unsaturated bond and desulfurization treatment of a raw material oil containing a compound having a sulfur atom. Regarding the processing method of.
従来、石油精製プロセスにおける１−ブテン、２−ブテンを主成分とするＣ４留分は、アルコールケトン製造の原料として用いられ、水添反応、脱硫反応を経て生成される留分中には、ジイソブチレン及びトリイソブチレンが多く含まれている。これらは、蒸留にて分離され、ジイソブチレンは、イソノナン原料や樹脂原料に、トリイソブチレンは、水素化された後、溶剤として使用される。 Conventionally, C4 fractions containing 1-butene and 2-butene as main components in petroleum refining processes have been used as raw materials for alcohol ketone production, and distillates produced through hydrogenation and desulfurization reactions are mixed. It is rich in isobutylene and triisobutylene. These are separated by distillation, diisobutylene is used as a raw material for isononan and a resin raw material, and triisobutylene is used as a solvent after being hydrogenated.
トリイソブチレン等のオレフィン性不飽和結合を有する化合物の水素化には、通常、白金、ニッケル、パラジウム、ルテニウム、コバルト、モリブデン等の金属担持触媒が用いられる。 A metal-supported catalyst such as platinum, nickel, palladium, ruthenium, cobalt, or molybdenum is usually used for hydrogenation of a compound having an olefinically unsaturated bond such as triisobutylene.
例えば、特許文献１には、ニッケル、パラジウム、白金といった水素化触媒の存在下でジイソブチレンを水素化してイソオクタンを生成させる方法が開示されている。 For example, Patent Document 1 discloses a method of hydrogenating diisobutylene to produce isooctane in the presence of a hydrogenation catalyst such as nickel, palladium, or platinum.
ところが、特許文献１等の白金、ニッケル、パラジウム等の金属担持触媒を用いる、オレフィン性不飽和結合を有する化合物の水素化には、高価な触媒を用いなければならないことや、オレフィン性不飽和結合を有する化合物を含有する原料油の水素化用の触媒が充填されたオレフィン部の水素化専用の反応塔を設ける必要があること等のため、これらがオレフィン性不飽和結合を有する化合物の水素化のコストアップに繋がるという問題があった。 However, an expensive catalyst must be used for hydrogenation of a compound having an olefinically unsaturated bond using a metal-supporting catalyst such as platinum, nickel, or palladium of Patent Document 1 or the like, or an olefinically unsaturated bond. Since it is necessary to provide a reaction tower dedicated to hydrogenation of the olefin portion filled with a catalyst for hydrogenation of the raw material oil containing the compound having an olefinically unsaturated bond, hydrogenation of the compound having an olefinically unsaturated bond. There was a problem that it led to an increase in the cost of.
従って、本発明の目的は、安価にオレフィン性不飽和結合を有する化合物の水素化を行うことができる処理方法を提供することにある。 Therefore, an object of the present invention is to provide a treatment method capable of hydrogenating a compound having an olefinically unsaturated bond at low cost.
上記課題は、以下の本発明により解決される。
すなわち、本発明（１）は、ａ）コバルト及びニッケルから選ばれる１種以上の金属と、モリブデン及びタングステンから選ばれる１種以上の金属とを含有する水素化脱硫触媒が充填されている触媒塔に、オレフィン性不飽和結合を有する化合物を含有し、窒素分が５．０質量ｐｐｍ以下、臭素価が１．０〜１４２．０ｇ−Ｂｒ2／１００ｇ、硫黄含有量が１００．０質量ｐｐｍ未満である第一原料油と、水素ガスと、を供給して、該第一原料油の水素化処理を行い、該第一原料油のオレフィン部水素化処理油を得るオレフィン部水素化工程と、ｂ）該触媒塔に、硫黄含有量が０．０１０〜２．０００質量％である第二原料油と、水素ガスと、を供給して、該第二原料油の脱硫処理を行い、該第二原料油の脱硫処理油を得る脱硫工程と、を、同一の該水素化脱硫触媒を用いて、交互に繰り返すことを特徴とする複数の原料油の処理方法を提供するものである。
The above problem is solved by the following invention.
That is, the present invention (1) is a catalyst tower filled with a hydrodesulfurization catalyst containing one or more metals selected from cobalt and nickel and one or more metals selected from molybdenum and tungsten. to contain a compound having an olefinically unsaturated bond, nitrogen content of 5.0 mass ppm or less, bromine number 1.0~142.0g-Br 2 / 100g, a sulfur content of less than 100.0 ppm by weight The olefin part hydrogenation step of supplying the first raw material oil and hydrogen gas to obtain the olefin part hydrotreated oil of the first raw material oil by hydrogenating the first raw material oil. b) The second raw material oil having a sulfur content of 0.010 to 2.000% by mass and hydrogen gas are supplied to the catalyst tower, and the second raw material oil is desulfurized. (Ii) Provided is a method for treating a plurality of raw material oils, which comprises repeating a desulfurization step of obtaining a desulfurization treatment oil for a raw material oil alternately using the same hydrodesulfurization catalyst.
また、本発明（２）は、前記第一原料油のトリイソブチレン含有量が１．０〜１００．０容量％であり、沸点が４０〜２２０℃であることを特徴とする（１）の複数の原料油の処理方法を提供するものである。 Further, the present invention (2) is characterized in that the triisobutylene content of the first raw material oil is 1.0 to 100.0% by volume and the boiling point is 40 to 220 ° C. It provides a method for treating the raw material oil of the above.
また、本発明（３）は、前記水素化脱硫触媒が、０〜６０．０質量％のイオン交換したゼオライトと、４０．０〜９５．０質量％のアルミナ又はアルミナ含有物と、を含有する担体に、該水素化脱硫触媒全質量に対し、酸化物換算で０．５〜１５．０質量％のコバルト及びニッケルから選ばれる１種以上の金属と、該水素化脱硫触媒全質量に対し、酸化物換算で２．０〜３０．０質量％のモリブデン及びタングステンから選ばれる１種以上の金属と、が担持されている触媒であることを特徴とする（１）又は（２）の複数の原料油の処理方法を提供するものである。 Further, in the present invention (3), the hydrodesulfurization catalyst contains 0 to 60.0% by mass of ion-exchanged zeolite and 40.0 to 95.0% by mass of alumina or an alumina-containing substance. The carrier contains one or more metals selected from cobalt and nickel in an oxide equivalent of 0.5 to 15.0% by mass based on the total mass of the hydrodesulfurization catalyst, and the total mass of the hydrodesulfurization catalyst. The catalyst according to (1) or (2), wherein one or more metals selected from 2.0 to 30.0% by mass of molybdenum and tungsten in terms of oxide are supported. It provides a method for treating raw material oil.
本発明によれば、水素化脱硫触媒を有効に活用することができる原料油の処理方法を提供することで、触媒活性の低下が抑制され、触媒の交換時期を延長することができるので、安価にオレフィン性不飽和結合を有する化合物の水素化を行うことができる処理方法を提供することができる。 According to the present invention, by providing a method for treating a raw material oil that can effectively utilize a hydrodesulfurization catalyst, a decrease in catalytic activity can be suppressed and a catalyst replacement period can be extended, so that the cost is low. Can provide a treatment method capable of hydrogenating a compound having an olefinically unsaturated bond.
本発明の複数の原料油の処理方法は、コバルト及びニッケルから選ばれる１種以上の金属と、モリブデン及びタングステンから選ばれる１種以上の金属とを含有する水素化脱硫触媒が充填されている触媒塔に、オレフィン性不飽和結合を有する化合物を含有し、窒素分が５．０質量ｐｐｍ以下、臭素価が１．０〜１４２．０ｇ−Ｂｒ2／１００ｇ、硫黄含有量が１００．０質量ｐｐｍ未満である第一原料油と、水素ガスと、を供給して、該第一原料油の水素化処理を行い、該第一原料油のオレフィン部水素化処理油を得るオレフィン部水素化工程と、該触媒塔に、硫黄含有量が０．０１０〜２．０００質量％である第二原料油と、水素ガスと、を供給して、該第二原料油の脱硫処理を行い、該第二原料油の脱硫処理油を得る脱硫工程と、を、同一の該水素化脱硫触媒を用いて、交互に繰り返すことを特徴とする複数の原料油の処理方法である。 The method for treating a plurality of raw material oils of the present invention is a catalyst filled with a hydrodesulfurization catalyst containing one or more metals selected from cobalt and nickel and one or more metals selected from molybdenum and tungsten. the tower contains a compound having an olefinically unsaturated bond, nitrogen content of 5.0 mass ppm or less, bromine number 1.0~142.0g-Br 2 / 100g, a sulfur content of 100.0 ppm by weight In the olefin part hydrogenation step of supplying less than the first raw material oil and hydrogen gas and performing the hydrogenation treatment of the first raw material oil to obtain the olefin part hydrotreated oil of the first raw material oil. , The second raw material oil having a sulfur content of 0.010 to 2.000% by mass and hydrogen gas are supplied to the catalyst tower to desulfurize the second raw material oil, and the second raw material oil is subjected to the desulfurization treatment. A method for treating a plurality of raw materials oil, which comprises alternately repeating a desulfurization step of obtaining a desulfurization treatment oil for a raw material oil using the same hydrodesulfurization catalyst.
本発明の複数の原料油の処理方法は、オレフィン性不飽和結合を有する化合物を含有する第一原料油の処理と、硫黄含有量が０．０１０〜２．０００質量％である第二原料油の処理と、を、同じ水素化脱硫触媒を用いて、交互に繰り返して行う処理方法である。
つまり、本発明の複数の原料油の処理方法では、本発明の複数の原料油の処理方法に係る水素化脱硫触媒を用いて、所定量、所定時間又は所定回数の第一原料油のオレフィン部の水素化処理を行い、第一原料油のオレフィン部水素化処理油を得るオレフィン部水素化工程を行い、次いで、同一の水素化脱硫触媒を用いて、所定量、所定時間又は所定回数の第二原料油の脱硫処理を行い、第二原料油の脱硫処理油を得る脱硫工程を行い、次いで、同一の水素化脱硫触媒を用いて、所定量、所定時間又は所定回数の第一原料油のオレフィン部の水素化処理を行い、第一原料油のオレフィン部水素化処理油を得るオレフィン部水素化工程を行い、次いで、同一の水素化脱硫触媒を用いて、所定量、所定時間又は所定回数の第二原料油の脱硫処理を行い、第二原料油の脱硫処理油を得る脱硫工程を行うというように、同一の水素化脱硫触媒を用いて、オレフィン部水素化工程と脱硫工程とを交互に繰り返す。
The method for treating a plurality of raw material oils of the present invention includes treatment of a first raw material oil containing a compound having an olefinically unsaturated bond and a second raw material oil having a sulfur content of 0.010 to 2.000% by mass. This is a treatment method in which the above treatment is alternately repeated using the same hydrodesulfurization catalyst.
That is, in the method for treating a plurality of raw material oils of the present invention, the olefin portion of the first raw material oil for a predetermined amount, a predetermined time, or a predetermined number of times is used by using the hydrogenation desulfurization catalyst according to the method for treating the plurality of raw materials oils of the present invention. The olefin part of the first raw material oil is hydrogenated to obtain the olefin part hydrogenated oil, and then the same hydrogen desulfurization catalyst is used to obtain a predetermined amount, a predetermined time, or a predetermined number of times. (Ii) Desulfurization of the raw material oil is performed, a desulfurization step of obtaining the desulfurized oil of the second raw material oil is performed, and then, using the same hydrogenation desulfurization catalyst, a predetermined amount, a predetermined time, or a predetermined number of times of the first raw material oil is used. The olefin part is hydrogenated, and the olefin part hydrogenated step of obtaining the olefin part hydrogenated oil of the first raw material oil is performed, and then a predetermined amount, a predetermined time or a predetermined number of times are used using the same hydrodesulfurization catalyst. Using the same hydrogenation desulfurization catalyst, the olefin part hydrogenation step and the desulfurization step are alternated, such as the desulfurization treatment of the second raw material oil and the desulfurization step of obtaining the desulfurization treatment oil of the second raw material oil. Repeat to.
本発明の複数の原料油の処理方法に係る水素化脱硫触媒、すなわち、オレフィン部水素化工程においてオレフィン部の水素化処理に用いられ、且つ、脱硫工程において脱硫処理に用いられる触媒は、コバルト及びニッケルから選ばれる１種以上の金属と、モリブデン及びタングステンから選ばれる１種以上の金属と、を含有する水素化脱硫触媒であり、好ましくはニッケルとモリブデンを含有する水素化脱硫触媒である。本発明の複数の原料油の処理方法に係る水素化脱硫触媒としては、石油精製プロセスにおいて、原油を常圧蒸留して得られるナフサ留分や灯油留分、軽油留分の脱硫に用いられる水素化脱硫触媒や、常圧蒸留残渣油又は減圧蒸留残渣油の直接脱硫に用いられる水素化脱硫触媒が挙げられる。 The hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention, that is, the catalyst used for the hydrodesulfurization of the olefin part in the olefin part hydrogenation step and used for the desulfurization treatment in the desulfurization step is cobalt and A hydrodesulfurization catalyst containing one or more metals selected from nickel and one or more metals selected from molybdenum and tungsten, preferably a hydrodesulfurization catalyst containing nickel and molybdenum. The hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention is hydrogen used for desulfurization of naphtha distillate, kerosene distillate, and gas oil distillate obtained by atmospheric distillation of crude oil in a petroleum refining process. Examples thereof include a hydrodesulfurization catalyst and a hydrodesulfurization catalyst used for direct desulfurization of atmospheric distillation residual oil or vacuum distillation residual oil.
本発明の複数の原料油の処理方法に係る水素化脱硫触媒におけるコバルト及びニッケルから選ばれる１種以上の金属の担持量は、水素化脱硫触媒全質量に対して、酸化物換算で０．５〜１５．０質量％であり、好ましくは１．０〜１２．０質量％である。なお、水素化脱硫触媒にコバルト及びニッケルの両方が担持されている場合には、上記担持量は、コバルト及びニッケルの合計の担持量を指す。また、本発明の複数の原料油の処理方法に係る水素化脱硫触媒におけるモリブデン及びタングステンから選ばれる１種以上の金属の担持量は、水素化脱硫触媒全質量に対して、酸化物換算で２．０〜３０．０質量％であり、好ましくは７．０〜２５．０質量％である。なお、水素化脱硫触媒にモリブデン及びタングステンの両方が担持されている場合には、上記担持量は、モリブデン及びタングステンの合計の担持量を指す。 The amount of one or more metals selected from cobalt and nickel in the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention is 0.5 in terms of oxide with respect to the total mass of the hydrodesulfurization catalyst. It is ~ 15.0% by mass, preferably 1.0 to 12.0% by mass. When both cobalt and nickel are supported on the hydrodesulfurization catalyst, the supported amount refers to the total supported amount of cobalt and nickel. Further, the amount of one or more metals selected from molybdenum and tungsten in the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention is 2 in terms of oxide with respect to the total mass of the hydrodesulfurization catalyst. It is 0 to 30.0% by mass, preferably 7.0 to 25.0% by mass. When both molybdenum and tungsten are supported on the hydrodesulfurization catalyst, the supported amount refers to the total supported amount of molybdenum and tungsten.
本発明の複数の原料油の処理方法に係る水素化脱硫触媒における担体は、イオン交換したゼオライトを０〜６０．０質量％含有し、アルミナ又はアルミナ含有物を４０．０〜９５．０質量％含有するものである。 The carrier in the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention contains 0 to 60.0% by mass of ion-exchanged zeolite and 40.0 to 95.0% by mass of alumina or an alumina-containing substance. It contains.
本発明の複数の原料油の処理方法に係るオレフィン部水素化工程は、本発明の複数の原料油の処理方法に係る水素化脱硫触媒が充填されている触媒塔に、オレフィン性不飽和結合を有する化合物を含有する第一原料油と、水素ガスと、を供給して、第一原料油の水素化処理を行い、第一原料油中のオレフィン性不飽和結合を水素化して、第一原料油のオレフィン部水素化処理油を得る工程である。 In the olefin hydrogenation step according to the method for treating a plurality of raw materials oils of the present invention, an olefinically unsaturated bond is formed in a catalyst tower filled with a hydrogenation desulfurization catalyst according to the method for treating a plurality of raw materials oils of the present invention. The first raw material oil containing the compound and hydrogen gas are supplied, the first raw material oil is hydrogenated, and the olefinically unsaturated bond in the first raw material oil is hydrogenated to form the first raw material. This is a step of obtaining a hydrogenated oil in the olefin portion of the oil.
本発明の複数の原料油の処理方法に係る第一原料油の臭素価は、１．０〜１４２．０ｇ−Ｂｒ2／１００ｇ、好ましくは９．０〜９５．０ｇ−Ｂｒ2／１００ｇである。なお、本出願書類における臭素価とは、ＪＩＳ Ｋ ２６０５に準拠して測定される値を意味する。 Bromine number of the first feed oil according to the method of processing a plurality of raw material oil of the invention, 1.0~142.0g-Br 2 / 100g, are preferably 9.0~95.0g-Br 2 / 100g .. The bromine value in the application documents means a value measured in accordance with JIS K 2605.
本発明の複数の原料油の処理方法に係る第一原料油の窒素含有量は、５．０質量ｐｐｍ以下である。なお、本出願書類における窒素含有量とは、ＪＩＳ Ｋ ２６０９に準拠して測定される値を意味する。 The nitrogen content of the first feedstock according to the method for treating the plurality of feedstocks of the present invention is 5.0 mass ppm or less. The nitrogen content in the application documents means a value measured in accordance with JIS K 2609.
本発明の複数の原料油の処理方法に係る第一原料油の硫黄含有量は、１００．０質量ｐｐｍ未満、好ましくは５０．０質量ｐｐｍ未満である。第一原料油は硫黄含有量が少ないので、本発明の複数の原料油の処理方法に係る水素化脱硫触媒を用いて、第一原料油のオレフィン部の水素化処理を行うと、オレフィン部水素化工程での水素化処理中に、水素化脱硫触媒から硫黄原子が失われていく。そして、水素化脱硫触媒から硫黄原子が失われることにより、第一原料油のオレフィン部の水素化処理における触媒のオレフィン部水素化活性が低下する。 The sulfur content of the first feedstock according to the method for treating the plurality of feedstocks of the present invention is less than 100.0 mass ppm, preferably less than 50.0 mass ppm. Since the first raw material oil has a low sulfur content, when the olefin part of the first raw material oil is hydrogenated using the hydrodesulfurization catalyst according to the plurality of raw material oil treatment methods of the present invention, the olefin part hydrogen is hydrogenated. During the hydrogenation process in the hydrogenation process, sulfur atoms are lost from the hydrodesulfurization catalyst. Then, the loss of sulfur atoms from the hydrodesulfurization catalyst reduces the hydrogenation activity of the olefin portion of the catalyst in the hydrogenation treatment of the olefin portion of the first raw material oil.
本発明の複数の原料油の処理方法に係る第一原料油は、オレフィン性不飽和結合を有する化合物を含有し、且つ、臭素価、窒素含有量及び硫黄含有量が上記範囲の原料油であれば特に制限されないが、例えば、エチレン製造装置、流動接触分解装置、水素化分解装置等にて生成する留分を沸点範囲４０〜２２０ ℃で蒸留して得られる留分が挙げられる。 The first raw material oil according to the method for treating a plurality of raw material oils of the present invention may be a raw material oil containing a compound having an olefinically unsaturated bond and having a bromine value, a nitrogen content and a sulfur content in the above ranges. The present invention is not particularly limited, and examples thereof include a fraction obtained by distilling a fraction produced by an ethylene production apparatus, a fluid catalytic cracking apparatus, a hydrocracking apparatus, or the like at a boiling point range of 40 to 220 ° C.
本発明の複数の原料油の処理方法に係る第一原料油に含有されるオレフィン性不飽和結合を有する化合物としては、例えば、イソブチレン、ジイソブチレン、トリイソブチレン等が挙げられる。 Examples of the compound having an olefinically unsaturated bond contained in the first raw material oil according to the method for treating a plurality of raw material oils of the present invention include isobutylene, diisobutylene, triisobutylene and the like.
本発明の複数の原料油の処理方法に係る第一原料油のトリイソブチレンの含有量が１．０〜１００．０容量％であり、好ましくは１０．０〜２０．０容量％である。また本発明の複数の原料油の処理方法に係る第一原料油の沸点は４０〜２２０℃であり、好ましくは１７０〜１９５℃である。 The content of triisobutylene in the first raw material oil according to the method for treating a plurality of raw material oils of the present invention is 1.0 to 100.0% by volume, preferably 10.0 to 20.0% by volume. The boiling point of the first raw material oil according to the method for treating a plurality of raw material oils of the present invention is 40 to 220 ° C, preferably 170 to 195 ° C.
本発明の複数の原料油の処理方法に係るオレフィン部水素化工程において、水素化処理時の水素分圧は、０．１０〜１０．００ＭＰａ、好ましくは２．００〜４．００ＭＰａ、特に好ましくは２．４０〜２．８０ＭＰａである。 In the olefin part hydrogenation step according to the method for treating a plurality of raw material oils of the present invention, the hydrogen partial pressure during the hydrogenation treatment is 0.10 to 10.00 MPa, preferably 2.00 to 4.00 MPa, particularly preferably 2.00 to 4.00 MPa. It is 2.40 to 2.80 MPa.
本発明の複数の原料油の処理方法に係るオレフィン部水素化工程において、水素化処理時の温度は、１００〜３５０℃、好ましくは１８０〜３２０℃、特に好ましくは２１０〜３１０℃である。 In the olefin hydrogenation step according to the method for treating a plurality of raw material oils of the present invention, the temperature during the hydrogenation treatment is 100 to 350 ° C., preferably 180 to 320 ° C., particularly preferably 210 to 310 ° C.
本発明の複数の原料油の処理方法に係るオレフィン部水素化工程において、水素化処理時のＬＨＳＶ（液空間速度）は、好ましくは２．０〜９．０ｈｒ-1、より好ましくは４．０〜６．０ｈｒ-1、特に好ましくは４．５〜５．８ｈｒ-1である。 In the olefin hydrogenation step according to the method for treating a plurality of raw material oils of the present invention, the LHSV (liquid space velocity) during the hydrogenation treatment is preferably 2.0 to 9.0 hr -1 , more preferably 4.0. ~ 6.0 hr -1 , particularly preferably 4.5 to 5.8 hr -1 .
本発明の複数の原料油の処理方法に係るオレフィン部水素化工程において、水素化処理時の水素／油比は、好ましくは９０〜７６０ＮＬ／Ｌ、より好ましくは１００〜１３０ＮＬ／Ｌ、特に好ましくは１００〜１１０ＮＬ／Ｌである。 In the olefin hydrogenation step according to the method for treating a plurality of raw material oils of the present invention, the hydrogen / oil ratio during the hydrogenation treatment is preferably 90 to 760 NL / L, more preferably 100 to 130 NL / L, and particularly preferably 100 to 130 NL / L. It is 100 to 110 NL / L.
本発明の複数の原料油の処理方法に係る脱硫工程は、本発明の複数の原料油の処理方法に係る水素化脱硫触媒が充填されている触媒塔に、硫黄含有量が０．０１０〜２．０００質量％の第二原料油と、水素ガスと、を供給して、第二原料油の脱硫処理を行い、第二原料油の脱硫処理油を得る工程である。 In the desulfurization step according to the method for treating the plurality of raw material oils of the present invention, the catalyst tower in which the hydrodesulfurization catalyst according to the method for treating the plurality of raw material oils of the present invention is filled has a sulfur content of 0.010 to 2. This is a step of supplying .000% by mass of the second raw material oil and hydrogen gas to desulfurize the second raw material oil to obtain the desulfurized oil of the second raw material oil.
脱硫工程で脱硫処理される第二原料油の硫黄含有量は、０．０１０〜２．０００質量％、好ましくは０．０１０〜０．０５０質量％である。第二原料油は、硫黄含有量が多いので、オレフィン部水素化工程を行った後の本発明の複数の原料油の処理方法に係る水素化脱硫触媒を用いて、第二原料油の脱硫処理を行うと、脱硫工程での脱硫処理中に、オレフィン部水素化工程を行うことで硫黄分が失われた水素化脱硫触媒に、硫黄原子が導入される。そして、硫黄原子が失われた水素化脱硫触媒に、硫黄原子が導入されることにより、オレフィン部水素化工程を行うことにより失われた、本発明の複数の原料油の処理方法に係る水素化脱硫触媒のオレフィン部水素化活性が回復する。 The sulfur content of the second feedstock oil desulfurized in the desulfurization step is 0.010 to 2.000% by mass, preferably 0.010 to 0.050% by mass. Since the second raw material oil has a high sulfur content, the second raw material oil is desulfurized using the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention after the olefin part hydrogenation step. Then, during the desulfurization treatment in the desulfurization step, sulfur atoms are introduced into the hydrodesulfurization catalyst in which the sulfur content is lost by performing the olefin part hydrogenation step. Then, hydrogenation according to the method for treating a plurality of raw material oils of the present invention, which was lost by performing the olefin portion hydrogenation step by introducing the sulfur atom into the hydrodesulfurization catalyst in which the sulfur atom was lost. The hydrogenation activity of the olefin part of the desulfurization catalyst is restored.
本発明の複数の原料油の処理方法に係る脱硫工程における第二原料油は、硫黄含有量が上記範囲の原料油であれば、特に制限されない。 The second raw material oil in the desulfurization step according to the method for treating a plurality of raw material oils of the present invention is not particularly limited as long as the raw material oil has a sulfur content in the above range.
本発明の複数の原料油の処理方法に係る脱硫工程における第二原料油としては、例えば、原油を常圧蒸留して得られるナフサ留分、灯油留分、軽油留分、常圧蒸留残渣油や、減圧蒸留装置から得られる減圧蒸留軽油留分、減圧蒸留残渣油等が挙げられる。 Examples of the second raw material oil in the desulfurization step according to the method for treating a plurality of raw material oils of the present invention include naphtha distillate, kerosene distillate, light oil distillate, and atmospheric distillation residual oil obtained by atmospheric distillation of crude oil. Examples thereof include vacuum distillation gas oil distillate obtained from a vacuum distillation apparatus, vacuum distillation residual oil and the like.
本発明の複数の原料油の処理方法に係る脱硫工程において、脱硫処理時の水素分圧は、０．５０〜２５．０ＭＰａ、好ましくは１．００〜４．００ＭＰａ、特に好ましくは１．５０〜２．５０ＭＰａである。 In the desulfurization step according to the method for treating a plurality of raw material oils of the present invention, the hydrogen partial pressure during the desulfurization treatment is 0.50 to 25.0 MPa, preferably 1.00 to 4.00 MPa, particularly preferably 1.50 to 1.50. It is 2.50 MPa.
本発明の複数の原料油の処理方法に係る脱硫工程において、脱硫処理時の温度は、２５０〜４３０℃、好ましくは２５０〜４００℃、特に好ましくは２５０〜３５０℃である。 In the desulfurization step according to the method for treating a plurality of raw material oils of the present invention, the temperature during the desulfurization treatment is 250 to 430 ° C., preferably 250 to 400 ° C., particularly preferably 250 to 350 ° C.
本発明の複数の原料油の処理方法に係る脱硫工程において、脱硫処理時のＬＨＳＶ（液空間速度）は、好ましくは３．０〜７．０ｈｒ-1、より好ましくは４．０〜６．０ｈｒ-1である。 In the desulfurization step according to the method for treating a plurality of raw material oils of the present invention, the LHSV (liquid space velocity) during the desulfurization treatment is preferably 3.0 to 7.0 hr -1 , more preferably 4.0 to 6.0 hr. It is -1.
本発明の複数の原料油の処理方法に係る脱硫工程において、脱硫処理時の水素／油比は、好ましくは５〜２５０ＮＬ／Ｌ、より好ましくは１００〜１２０ＮＬ／Ｌ、特に好ましくは１００〜１１０ＮＬ／Ｌである。 In the desulfurization step according to the method for treating a plurality of raw material oils of the present invention, the hydrogen / oil ratio during the desulfurization treatment is preferably 5 to 250 NL / L, more preferably 100 to 120 NL / L, and particularly preferably 100 to 110 NL / L. It is L.
本発明の複数の原料油の処理方法では、同一の水素化脱硫触媒及び該水素化脱硫触媒が充填されている触媒塔を用いて、オレフィン部水素化工程と脱硫工程とを行う。つまり、本発明の複数の原料油の処理方法では、オレフィン部水素化工程を行った後の本発明の複数の原料油の処理方法に係る水素化脱硫触媒を用いて、脱硫工程を行い、且つ、脱硫工程を行った後の本発明の複数の原料油の処理方法に係る水素化脱硫触媒を用いて、オレフィン部水素化工程を行う。具体的には、本発明の複数の原料油の処理方法に係る水素化脱硫触媒が充填されている触媒塔に、第一原料油を供給して、オレフィン部水素化工程を行い、次いで、該触媒塔に供給する原料油を第二原料油に切り替えて、脱硫工程を行い、次いで、該触媒塔に供給する原料油を再び第一原料油に切り替えて、オレフィン部水素化工程を行い、次いで、該触媒塔に供給する原料油を第二原料油に切り替えて、脱硫工程を行うとのように、複数回、オレフィン部水素化工程及び脱硫工程を繰り返す。 In the method for treating a plurality of raw material oils of the present invention, the olefin portion hydrogenation step and the desulfurization step are performed using the same hydrodesulfurization catalyst and a catalyst tower filled with the hydrodesulfurization catalyst. That is, in the method for treating the plurality of raw material oils of the present invention, the hydrodesulfurization step is performed using the hydrodesulfurization catalyst according to the method for treating the plurality of raw material oils of the present invention after the olefin portion hydrogenation step is performed. , The olefin part hydrogenation step is performed using the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention after the desulfurization step. Specifically, the first raw material oil is supplied to the catalyst tower filled with the hydrodesulfurization catalyst according to the method for treating a plurality of raw material oils of the present invention, the olefin portion hydrogenation step is performed, and then the olefin portion is hydrogenated. The raw material oil supplied to the catalyst tower is switched to the second raw material oil to perform a desulfurization step, and then the raw material oil supplied to the catalyst tower is switched to the first raw material oil again to perform an olefin hydrogenation step, and then The olefin part hydrogenation step and the desulfurization step are repeated a plurality of times, such as switching the raw material oil supplied to the catalyst tower to the second raw material oil and performing the desulfurization step.
本発明の複数の原料油の処理方法において、１回当たりのオレフィン部水素化工程での第一原料油の処理量、処理時間又は処理回数は、第一原料油中のオレフィン部の量、硫黄含有量、水素化活性の低下度合、触媒中の金属種又はその含有量等により、適宜選択される。また、本発明の複数の原料油の処理方法において、１回当たりの脱硫工程での第二原料油の処理量、処理時間又は処理回数は、第二原料油の油種、硫黄含有量、触媒中の金属種又はその含有量等により、適宜選択される。 In the method for treating a plurality of raw material oils of the present invention, the treatment amount, treatment time or number of treatments of the first raw material oil in each olefin hydrogenation step are the amount of the olefin part in the first raw material oil and sulfur. It is appropriately selected depending on the content, the degree of decrease in hydrogenation activity, the metal species in the catalyst or the content thereof, and the like. Further, in the plurality of raw material oil treatment methods of the present invention, the treatment amount, treatment time or number of treatments of the second raw material oil in each desulfurization step is determined by the oil type, sulfur content and catalyst of the second raw material oil. It is appropriately selected depending on the metal species in the oil, its content, and the like.
本発明の複数の原料油の処理方法では、オレフィン部水素化工程を行うことによって、水素化脱硫触媒中の硫黄原子が失われて、触媒のオレフィン部水素化活性が低下しても、その後に、その水素化脱硫触媒を用いて脱硫工程を行うことにより、触媒に硫黄原子が導入されるので、触媒のオレフィン部水素化活性を回復させることができる。そのため、本発明の複数の原料油の処理方法では、同一の水素化脱硫触媒を用いて、オレフィン部水素化工程と脱硫工程とを交互に繰り返すことにより、同一の水素化脱硫触媒を用いて、第一原料油のオレフィン部の水素化と、第二原料油の脱硫とを、長期に亘って継続することができる。 In the method for treating a plurality of raw material oils of the present invention, even if the sulfur atom in the hydrodesulfurization catalyst is lost by performing the olefin hydrogenation step and the olefin hydrogenation activity of the catalyst is reduced, after that. By performing the hydrodesulfurization step using the hydrodesulfurization catalyst, sulfur atoms are introduced into the catalyst, so that the hydrogenation activity of the olefin portion of the catalyst can be restored. Therefore, in the method for treating a plurality of raw material oils of the present invention, the same hydrodesulfurization catalyst is used, and the same hydrodesulfurization catalyst is used by alternately repeating the olefin part hydrogenation step and the desulfurization step. Hydrogenation of the olefin portion of the first feedstock oil and desulfurization of the second feedstock oil can be continued for a long period of time.
そして、本発明の複数の原料油の処理方法では、石油精製プロセスにおける原油を常圧蒸留して得られるナフサ留分や灯油留分、軽油留分、常圧蒸留残渣油又は減圧蒸留残渣油を直接脱硫するための直接脱硫触媒及び触媒塔を用いて、オレフィン性不飽和結合を有する化合物を含有する第一原料油のオレフィン部の水素化を行うことができるので、水素化脱硫触媒を有効に活用することができ、安価にオレフィン性不飽和結合を有する化合物の水素化を行うことができる。 Then, in the method for treating a plurality of raw material oils of the present invention, a naphtha distillate, a kerosene distillate, a light oil distillate, an atmospheric distillation residual oil or a vacuum distillation residual oil obtained by atmospheric distillation of crude oil in a petroleum refining process is used. Since the olefin portion of the first raw material oil containing a compound having an olefinically unsaturated bond can be hydrogenated by using a direct desulfurization catalyst and a catalyst tower for direct desulfurization, the hydrodesulfurization catalyst is effective. It can be utilized and hydrogenation of a compound having an olefinically unsaturated bond can be carried out at low cost.
以下に実施例を示して本発明を更に具体的に説明するが、本発明はこれに制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
（触媒の前処理）
流通式反応管にモリブデンとニッケルを酸化物換算でそれぞれ１０．４質量％担持した水素化脱硫触媒を１５ｃｍ3充填し、水素分圧が２．５ＭＰａ、ＬＨＳＶが５．０ｈｒ-1、水素／油が１０６ＮＬ／Ｌの条件下、１００℃で２時間、２５０℃で２時間、３２０℃で２時間、ジメチルジスルフィドを２％含有したイソドデカンを通液し、前処理済み水素化脱硫触媒を得た。
(Catalyst pretreatment)
The hydrodesulfurization catalyst 10.4 wt% on each of molybdenum and nickel in the flow-type reaction tube in terms of oxide to 15cm 3 filled, the hydrogen partial pressure is 2.5 MPa, LHSV is 5.0hr -1, a hydrogen / oil Under the condition of 106 NL / L, isododecane containing 2% of dimethyl disulfide was passed through at 100 ° C. for 2 hours, 250 ° C. for 2 hours, and 320 ° C. for 2 hours to obtain a pretreated hydrodesulfurization catalyst.
（実施例１）
臭素価が６６．０ｇ−Ｂｒ2／１００ｇ、窒素含有量が２．３質量ｐｐｍ、硫黄含有量が１．３質量ｐｐｍの炭化水素油とイソドデカンを１：９で混合した混合油を第一原料油として、上記前処理済み水素化脱硫触媒を用いて、温度２７０℃、水素分圧が２．４９ＭＰａ、ＬＨＳＶが５．４ｈｒ-1、水素／油が１０６ＮＬ／Ｌの条件下、４日間、水素化反応を行った。
その後、硫黄含有量が１９０質量ｐｐｍのヘビーナフサを第二原料油として、上記前処理済み水素化脱硫触媒を用いて、温度２７０℃、水素分圧が２．０８ＭＰａ、ＬＨＳＶが５．４ｈｒ-1、水素／油が１０６ＮＬ／Ｌの条件下、３日間、脱硫反応を行った。
上記第一原料油を用いた反応と上記第二原料油を用いた反応の２反応を１サイクルとして、３１サイクルを行い、各サイクルにおける第一原料油の水素化処理油の臭素指数を測定した。その結果を図１に示す。
(Example 1)
Bromine number 66.0g-Br 2 / 100g, a nitrogen content of 2.3 mass ppm, sulfur content 1 1.3 mass ppm of hydrocarbon oil and isododecane: The combined mixed oil in 9 first material Using the pretreated hydrodesulfurization catalyst as the oil, hydrogen was used for 4 days under the conditions of a temperature of 270 ° C., a hydrogen partial pressure of 2.49 MPa, an LHSV of 5.4 hr -1 , and a hydrogen / oil of 106 NL / L. The conversion reaction was carried out.
Then, using heavy naphtha having a sulfur content of 190 mass ppm as a second raw material oil, using the pretreated hydrodesulfurization catalyst, the temperature was 270 ° C., the hydrogen partial pressure was 2.08 MPa, and the LHSV was 5.4 hr -1 . The desulfurization reaction was carried out for 3 days under the condition of hydrogen / oil of 106 NL / L.
31 cycles were performed with the two reactions using the first feedstock oil and the reaction using the second feedstock oil as one cycle, and the bromine index of the hydrotreated oil of the first feedstock oil was measured in each cycle. .. The result is shown in FIG.
（比較例１）
上記第一原料油を用いた反応を１サイクルとして１７サイクルを行う以外は、実施例と同様の条件で実施し、各サイクルにおける第一原料油の水素化処理油の臭素指数を測定した。
(Comparative Example 1)
The reaction was carried out under the same conditions as in Examples except that 17 cycles were carried out with the reaction using the first feedstock oil as one cycle, and the bromine index of the hydrotreated oil of the first feedstock oil was measured in each cycle.
実施例１は、全３１サイクルにおいて臭素指数が２０ｍｇ−Ｂｒ2／１００ｇ以下で推移していることから、水素化脱硫触媒のオレフィン部水素化活性は長期間に渡って維持されていることがわかる。一方、比較例１は、反応サイクルが増えるに従い、臭素指数が６９ｍｇ−Ｂｒ2／１００ｇまで単調に増加していることから、水素化脱硫触媒のオレフィン部水素化活性は徐々に低下していることがわかる。
このことから、本発明の方法を用いることにより、触媒の活性を維持したまま原料油の水素化処理を行うことができることがわかる。
Example 1, since the bromine index has remained below 20mg-Br 2 / 100g in total 31 cycles, it is understood that the olefin unit hydrogenation activity hydrodesulfurization catalyst is maintained over a long period of time .. On the other hand, Comparative Example 1, in accordance with the reaction cycle is increased, the bromine index since it has increased monotonically to 69mg-Br 2 / 100g, olefin unit hydrogenation activity of hydrodesulfurization catalysts are gradually decreased I understand.
From this, it can be seen that by using the method of the present invention, the hydrogenation treatment of the raw material oil can be performed while maintaining the activity of the catalyst.
Claims (3)
ｂ）該触媒塔に、硫黄含有量が０．０１０〜２．０００質量％である第二原料油と、水素ガスと、を供給して、該第二原料油の脱硫処理を行い、該第二原料油の脱硫処理油を得る脱硫工程と、
を、同一の該水素化脱硫触媒を用いて、交互に繰り返すことを特徴とする複数の原料油の処理方法。 a) An olefinically unsaturated bond is formed in a catalyst tower packed with a hydrodesulfurization catalyst containing one or more metals selected from cobalt and nickel and one or more metals selected from molybdenum and tungsten. contains a compound having a nitrogen content of 5.0 ppm by mass or less, and a bromine number is first feedstock 1.0~142.0g-Br 2 / 100g, a sulfur content of less than 100.0 ppm by weight , Hydrogen gas, and hydrogenation treatment of the first raw material oil to obtain the olefin part hydrogenation treatment oil of the first raw material oil, and the olefin part hydrogenation step.
b) The second raw material oil having a sulfur content of 0.010 to 2.000% by mass and hydrogen gas are supplied to the catalyst tower to desulfurize the second raw material oil, and the second raw material oil is subjected to the desulfurization treatment. (Ii) Desulfurization process for obtaining desulfurized oil for raw material oil, and
A method for treating a plurality of raw material oils, which comprises alternately repeating the above with the same hydrodesulfurization catalyst.
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