JP2005270937A5

JP2005270937A5 -

Info

Publication number: JP2005270937A5
Application number: JP2004092531A
Authority: JP
Filing date: 2004-03-26
Publication date: 2006-09-14
Anticipated expiration: 2024-03-26

Description

脱硫活性については、以下の方法で解析した。
３６０℃で反応装置を運転し、２０日経過した時点で生成油を採取し、生成油中の硫黄分と原料油の硫黄分および液空間速度から、脱硫反応速度定数（Ｋｓ）を求めた。このＫｓ値の求め方を以下に示す。
生成油の硫黄分（Ｓｐ）の減少量に対して、１．５次の反応次数を得る反応速度式の定数を脱硫反応速度定数（Ｋｓ）とする。
なお、反応速度定数が高い程、触媒活性が優れていることを示している。
脱硫反応速度定数＝２×〔１／（Ｓｐ）^０．５−１／（Ｓｆ）^０．５〕×（ＬＨＳＶ）
式中、Ｓｆ：原料油中の硫黄分（質量％）
Ｓｐ：反応生成油中の硫黄分（質量％）
ＬＨＳＶ：液空間速度（ｈｒ^−１）
脱硫比活性（％）＝各脱硫反応速度定数／比較触媒ｇの脱硫反応速度定数×１００ The desulfurization activity was analyzed by the following method.
The reaction apparatus was operated at 360 ° C., and the produced oil was sampled after 20 days. The desulfurization reaction rate constant (Ks) was determined from the sulfur content in the produced oil, the sulfur content of the raw material oil, and the liquid space velocity. The method for obtaining this Ks value is shown below.
The desulfurization reaction rate constant (Ks) is defined as a constant in the reaction rate equation that obtains a reaction order of 1.5 with respect to the amount of reduction in the sulfur content (Sp) of the product oil.
The higher the reaction rate constant, the better the catalytic activity.
Desulfurization reaction rate constant = 2 × [1 / (Sp) ^0.5 −1 / (Sf) ^0.5 ] × (LHSV)
In formula, Sf: Sulfur content (mass%) in raw material oil
Sp: Sulfur content (mass%) in reaction product oil
LHSV: Liquid space velocity (hr ⁻¹ )
Desulfurization specific activity (%) = desulfurization reaction rate constant / desulfurization reaction rate constant of comparative catalyst g × 100

Claims

無機酸化物担体上に触媒基準、酸化物換算で周期律表第６族金属から選ばれた少なくとも１種を１０〜３０質量％、周期律表第８族金属から選ばれた少なくとも１種を１〜１５質量％、リンを０．８〜８質量％、炭素を２〜１４質量％含み、さらにリチウムを０．1〜０．８質量％担持してなる、比表面積１１０〜３００ｍ^２／ｇ、細孔容積０．３５〜０．６ｍ１／ｇ、平均細孔直径約６５〜１８０Åであることを特徴とする炭化水素油の水素化処理触媒。 10-30% by mass of at least one selected from Group 6 metals of the Periodic Table on the basis of catalyst on an inorganic oxide support, and 1 at least one selected from Group 8 metals of the Periodic Table on an oxide basis Specific surface area of 110 to 300 m ² / g, comprising 15 to 15% by mass, 0.8 to 8% by mass of phosphorus, 2 to 14% by mass of carbon, and 0.1 to 0.8% by mass of lithium. Hydrocarbon oil hydrotreating catalyst having a pore volume of 0.35 to 0.6 m1 / g and an average pore diameter of about 65 to 180 mm.

マイクロカロリメトリー法にて測定した１００〜２００ＫＪ/ｍｏｌのアンモニア吸着熱を発する酸点を、触媒１ｇ当り、２７０〜３８０μｍｏｌの範囲で有していることを特徴とする請求項１記載の炭化水素油の水素化処理触媒。 2. The hydrocarbon oil according to claim 1, wherein the hydrocarbon oil has an acid point which generates an ammonia adsorption heat of 100 to 200 KJ / mol measured by a microcalorimetry method in a range of 270 to 380 μmol per 1 g of the catalyst. Hydroprocessing catalyst.

触媒が、予備硫化後において、透過型電子顕微鏡により観察される二硫化モリブデン相の積層数の平均値が２．５〜５であることを特徴とする請求項１または２記載の炭化水素油の水素化処理触媒。 3. The hydrocarbon oil according to claim 1, wherein the catalyst has an average value of 2.5 to 5 of the number of laminated molybdenum disulfide phases observed by a transmission electron microscope after preliminary sulfidation. 4. Hydroprocessing catalyst.

比表面積１６０〜５００ｍ^２／ｇ、細孔容積０．５５〜０．９ｍ１／ｇ、平均細孔直径６０〜１５０Åである無機酸化物担体上に、周期律表第８族金属から選ばれた少なくとも１種を含む化合物、周期律表第６族金属から選ばれた少なくとも１種を含む化合物、有機酸、リン酸、リチウムを含有する溶液を用い、触媒基準、酸化物換算で周期律第６族金属を１０〜３０質量％、周期律表第８族金属を１〜１５質量％、リンを０．８〜８質量％、リチウム０．1〜０．８質量％、炭素を２〜１４質量％となるように担持させ、２００℃以下で乾燥させることを特徴とする請求項１〜３のいずれかに記載の炭化水素油の水素化処理触媒の製造方法。 On an inorganic oxide support having a specific surface area of 160 to 500 m ² / g, a pore volume of 0.55 to 0.9 m 1 / g, and an average pore diameter of 60 to 150 mm, at least selected from Group 8 metals of the periodic table A compound containing at least one compound, a compound containing at least one selected from Group 6 metals in the Periodic Table, a solution containing an organic acid, phosphoric acid, and lithium, using a catalyst standard and an oxide equivalent group 6 10-30% by mass of metal, 1-15% by mass of Group 8 metal of the periodic table, 0.8-8% by mass of phosphorus, 0.1-0.8% by mass of lithium, 2-14% by mass of carbon The method for producing a hydrocarbon oil hydrotreating catalyst according to any one of claims 1 to 3, wherein the catalyst is dried at 200 ° C or lower.

比表面積１６０〜５００ｍSpecific surface area 160-500m ^２2 ／ｇ、細孔容積０．５５〜０．９ｍｌ／ｇ、平均細孔直径６０〜１５０Åである無機酸化物担体上に、リチウムを含有する溶液を用い、リチウムを担持後、乾燥、焼成し、リチウム担持無機酸化物担体を調整後、周期律表第８族金属から選ばれた少なくとも１種を含む化合物、周期律表第６族金属から選ばれた少なくとも１種を含む化合物、有機酸、およびリン酸を含有する溶液を用い、触媒基準、酸化物換算で周期律表第６族金属を１０〜３０質量％、周期律表第８族金属を１〜１５質量％、リンを０．８〜８質量％、リチウムを０．１〜０．８質量％、炭素を２〜１４質量％となるように担持させ、２００℃以下で乾燥させることを特徴とする請求項１〜３のいずれかに記載の炭化水素油の水素化処理触媒の製造方法。/ G, a pore volume of 0.55 to 0.9 ml / g, an inorganic oxide carrier having an average pore diameter of 60 to 150 mm, using a solution containing lithium, after supporting lithium, drying and firing, After preparing the lithium-supporting inorganic oxide carrier, a compound containing at least one selected from Group 8 metals of the periodic table, a compound containing at least one selected from Group 6 metals of the periodic table, an organic acid, and Using a solution containing phosphoric acid, 10 to 30% by mass of Group 6 metal of the periodic table, 1 to 15% by mass of Group 8 metal of the periodic table in terms of oxide, 0.8 to 0.8% of phosphorus 8% by mass, 0.1 to 0.8% by mass of lithium and 2 to 14% by mass of carbon are supported and dried at 200 ° C. or less. The manufacturing method of the hydrotreating catalyst of description hydrocarbon oil.

請求項１〜３のいずれかに記載の触媒の存在下、水素分圧３〜８ＭＰａ、温度３００〜４２０℃、液空間速度０．３〜５ｈｒ^−１の条件で、炭化水素油留分の接触反応を行うことを特徴とする炭化水素油の水素化処理方法。 Contact of a hydrocarbon oil fraction in the presence of the catalyst according to any one of claims 1 to 3 under conditions of a hydrogen partial pressure of 3 to 8 MPa, a temperature of 300 to 420 ° C, and a liquid space velocity of 0.3 to 5 hr- ^1. A method for hydrotreating a hydrocarbon oil, characterized by carrying out a reaction.