JP2004358326A - Catalyst for hydrogenation treatment and its using method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for hydrogenation treatment excellent as a catalyst for pretreatment of fluidized catalytic cracking (FCC). <P>SOLUTION: A porous alumina based carrier is carried with (1) 0.1-7 wt% of titanium oxide; (2) 15-25 wt% of oxide of Group 6a metal in the periodic table; (3) 3-7 wt% of oxide of Group 8 metal in the periodic table; and (4) 0.1-7 wt% of phosphorus oxide in terms of P<SB>2</SB>O<SB>5</SB>as catalyst components based on the weight of the catalyst. (a) A specific surface area of the catalyst is 180-300 m<SP>2</SP>/g and (b) a total pore volume is 0.4-0.6 ml/g. In the catalyst for hydrogenation treatment of hydrocarbon oils, in the catalyst manufacturing step, after the carrier is fired/carried with the catalyst component (1), the component (2)-(4) are fired/carried. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００３０】
〔ＩＩ〕水素化処理
水素化処理を行う炭化水素油として、下記の表２に記載された性状の原油を分留して得られた減圧軽油（ＶＧＯ） を原料油として使用した。
この原料油は硫黄含有量が約２．５重量％、全窒素含有量が約１６００重量ｐｐｍ含有するものである。
【００３１】
【表２】

【００３２】
上記実施例１〜２、比較例１〜２で製造した触媒それぞれについて水素化処理を行った。触媒を固定床に備えた反応装置に充填した。
表２に記載した性状の原料油を液相中、５．０ＭＰａで、全液空間速度（Ｌｉｑｕｉｄ Ｈｏｕｒｌｙ Ｓｐａｃｅ Ｖｅｌｏｃｉｔｙ ： ＬＨＳＶ） ２．０ｈｒ^−１及び平均温度３６０及び３８０℃で、供給する水素と原料油の比（Ｈ_２／Ｏｉｌ）を３００Ｎｌ／ｌとして固定床に導入し、生成油を得た。
生成油を捕集し分析して水素化によって脱離された硫黄（Ｓｕｌｆｕｒ）、及び窒素（Ｎｉｔｒｏｇｅｎ）重量比を算出し、下記計算式に基づいて比活性（Ｒｅｌａｔｉｖｅ Ｖｏｌｕｍｅ Ａｃｔｉｖｉｔｙ； ＲＶＡ）を求め、表３に示した。
比活性（ＲＶＡ）は、比較例１の触媒の水素化脱硫（ＨＤＳ）、水素化脱窒素反応にて、反応次数を用いて計算される反応速度定数ｋと実施例との比とした。
【００３３】
【数１】

ここで、ｋ＝（ＬＨＳＶ／ｒ）×（１／ｙ^{（ｒ−１）}−１／Ｘ^{（ｒ−１）}）（ｒ≠１）
ｋ＝ＬＨＳＶ×ｌｎ（ｘ／ｙ）（ｒ≠１）
上記式中、ｋは反応速度定数
ｒは反応次数
ｘは原料油中の硫黄、または窒素の重量割合
ｙは生成油中の硫黄、または窒素の重量割合
なお、ｌｎは自然対数の表記である。
【００３４】
【表３】

【００３５】
〔ＩＩＩ〕ＦＣＣ評価
本実施例及び比較例で得られた処理油を用いて、改良ＭＡＴ（マイクロアクティビティテスト）装置（大倉理研製）を用いて、流動床式接触分解（ＦＣＣ）の評価を行った。評価条件を表４に、評価結果を表５に示した。
【００３６】
【表４】

【００３７】
【表５】

【００３８】
ガソリン：沸点範囲；Ｃ５−１８０℃
ＬＣＯ （Ｌｉｇｈｔ Ｃｉｒｃｌｅ Ｏｉｌ）：沸点範囲；１８０〜３６０℃
ボトム：沸点範囲；３６０℃以上
コーク：硫黄炭素分析計による測定
【００３９】
【発明の効果】
以上述べたように、本発明は、流動床式接触分解（ＦＣＣ）の前処理で実施例１または２で示される触媒を間接脱硫触媒として使用することにより、ＦＣＣ運転にて経済的付加価値の高いガソリンを従来の触媒を使用した場合よりも１〜１．４重量％増加の高収率とすることができ、ＦＣＣボトム量を相当量低減できることにより、効率的な石油精製を実現することが可能となる。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a hydrotreating catalyst for removing dissolved impurities such as sulfur, nitrogen, and residual carbon contained in a hydrocarbon oil, and a method for using the same.
[0002]
[Prior art]
In general, most of the oil produced from an indirect desulfurization unit (VGO FCC pretreatment) is treated by an FCC (fluid catalytic cracking) unit and supplied to production of FCC gasoline and the like. Until now, indirect desulfurization catalysts for FCC pretreatment have been required to have high desulfurization performance. In recent years, however, there has been an increasing demand for not only desulfurization but also for improving the yield of FCC gasoline and reducing the FCC bottom. .
As a conventional indirect desulfurization catalyst, a catalyst in which a group 6A element such as molybdenum and tungsten or a group 8 element such as nickel and cobalt is supported on a metal oxide carrier such as alumina is widely used. Further, in order to improve the hydrotreating performance by changing the chemical properties of the carrier, attempts have been made to use a composite oxide such as alumina-silica as the carrier. However, even if these methods are used, an indirect desulfurization catalyst capable of simultaneously improving the gasoline yield in an FCC device and reducing the FCC bottom while satisfying the conventional desulfurization performance has not been provided.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that a catalyst for hydrotreating hydrocarbon oils has better hydrotreating (desulfurization, denitrification, and residual carbon) performance than ever before, so that gasoline recovery in FCC units can be improved. An object of the present invention is to provide a catalyst that contributes to an improvement in the yield and a reduction in the FCC bottom yield, and a method for using the catalyst.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above problems, and as a result, after calcining and supporting titanium oxide on a carrier, the catalyst was calcined and supported with another specific metal catalyst component, and a specific ratio was obtained. The present inventors have found that a hydrotreating catalyst having a surface area and a total pore volume is excellent as a pretreatment catalyst for fluidized bed catalytic cracking (FCC), and have completed the present invention.
[0005]
That is, according to the present invention, (1) 0.1 to 7% by weight of titanium oxide is used as a catalyst component on a porous alumina carrier based on the weight of the catalyst.
(2) 15 to 25% by weight of an oxide of a metal of Group 6A of the periodic table;
(3) 3 to 7% by weight of an oxide of a metal belonging to Group 8 of the periodic table, and (4) 0.1 to 7% by weight of phosphorus oxide in terms of P ₂ O _5.
And (a) the specific surface area of the catalyst is 180 to 300 m ² / g, and (b) the total pore volume is 0.4 to 0.6 ml / g.
A catalyst for hydrotreating hydrocarbon oils, characterized in that the catalyst component (1) is calcined and supported on the carrier in the catalyst production step, and then the components (2) to (4) are calcined and supported. is there.
[0006]
The catalyst component (2) is at least one metal selected from the group consisting of chromium, molybdenum and tungsten, and the catalyst component (3) is at least one metal selected from the group consisting of iron, cobalt and nickel. There is a feature.
Further, the calcination temperature during the production of the catalyst is 450 to 600 ° C.
[0007]
Further, the present invention is characterized in that the hydrocarbon oil is brought into contact with the hydrotreating catalyst in the presence of hydrogen under the conditions of a temperature of 350 to 450 ° C., a pressure of 5 to 15 MPa, and a liquid hourly space velocity of 0.1 to 3 hr ^−1. Wherein the hydrocarbon oil is a vacuum gas oil.
[0008]
Further, the present invention is a method for using the above catalyst as a catalyst for pretreatment of fluidized bed catalytic cracking (FCC).
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the above invention will be described in detail. The alumina-based carrier in the present invention has an alumina component in the carrier of 80% by weight or more. Examples of the form of alumina include alumina such as α, θ, δ, κ, η, γ, and χ-type, alumina hydrate such as bayerite, gibbsite, boehmite, and pseudo-boehmite. Can be used. However, gamma alumina is preferred from the viewpoint of economy and practicality. When a composite oxide with alumina is used as a carrier, silica, zinc oxide, zeolite, clay mineral, or the like, or a mixture thereof can be added to the carrier at a ratio of 20% by weight or less.
[0010]
The alumina-based carrier is impregnated with at least one compound selected from magnesium, boron, titanium, zircon, and lanthanum and calcined and supported. Titanium is most preferable from the viewpoint of catalytic activity and economy. The titanium compound used at the time of impregnation is not particularly limited, and includes, for example, titania sol, titanium chloride, titanyl sulfate, alkoxytitanium, peroxotitanic acid, titanium peroxohydroxy acid salt, titanium lactate, and titanium butyrate. The loading amount on the alumina-based carrier is preferably from 0.1 to 7% by weight, more preferably from 0.5 to 6% by weight, based on the catalyst.
[0011]
After an oxide such as titanina is formed on the surface of the carrier, Group 6A, Group 8 and phosphorus of the periodic table are supported. Examples of the Group 6A element include chromium, molybdenum, and tungsten, and molybdenum is preferable from the viewpoint of activity and economy. Examples of the Group VIII element include iron, cobalt, and nickel. From the viewpoints of activity and economy, it is preferable to support cobalt or nickel alone or both.
[0012]
It is preferable that the carrying amount of the Group 6A and Group 8 elements of the periodic table including the carrier and the carrier (oxide) is as follows, including the carrier. That is, the Group 6A element is 15 to 25% by weight, preferably 18 to 24% by weight. If the amount is less than 15% by weight, the required catalytic performance is not exhibited. If the amount exceeds 25% by weight, no increase is seen in the catalytic performance. The Group 8 element is 3 to 7% by weight, preferably 4 to 6% by weight. If the amount is less than 3% by weight, the catalyst performance tends not to be exhibited, while if it exceeds 7% by weight, the catalyst performance does not increase.
[0013]
As a method for supporting these elements, a method generally used such as an immersion method or an impregnation method can be used. The order of loading of each element is not particularly limited, and the elements can be loaded sequentially or simultaneously. The solution of the Group 6A element and the Group 8 element used for loading is not particularly limited, but usually a solution of a soluble Group 6A element compound and a Group 8 element compound dissolved in a solvent such as water is used. Also, in order to stabilize the solution, mineral acids such as nitric acid, hydrochloric acid and phosphoric acid and salts thereof, organic acids such as formic acid, acetic acid, oxalic acid, citric acid, malic acid and gluconic acid and salts thereof, or ethylenediamine And various chelates such as EDTA (ethylenediaminetetraacetic acid). When dissolving the Group 6A element compound and the Group VIII element compound using phosphoric acid, the supported amount of phosphorus on the completed catalyst is 0.1 to 7% by weight as an oxide, preferably 0.3 to 7% by weight. 6% by weight.
[0014]
In order to disperse the Group 6A element and the Group 8 element in this aqueous solution, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, and polyvinyl alcohol, and the like are used. Monosaccharides and disaccharides such as ethers, esters, glucose, fructose, lactose and sucrose may be added.
[0015]
After carrying the Group 6A element, the Group VIII element and phosphorus, it is dried and baked. At this time, the atmosphere is not particularly limited, and is usually performed in the air. Drying is performed at 30 to 200 ° C. for about 1 to 3 hours, and the firing step is performed at 450 to 600 ° C. for about 1 to 3 hours.
In order for the catalyst thus obtained to exhibit desired performance in the hydrotreating reaction of hydrocarbon oil, it is necessary to have the following physical properties (specific surface area, pore structure).
[0016]
The specific surface area obtained by the BET equation, 180~300m ² / g is desirable, more preferred range is 190~280m ² / g. If it is less than 180 m ² / g, the catalytic performance is insufficient, and if it exceeds 300 m ² / g, the pore diameter becomes too small, so that pore clogging or the like tends to occur during the reaction. The pore volume obtained by the mercury intrusion method (surface tension: 480 dyn / cm, contact angle: 140 °) is preferably in the range of 0.4 to 0.6 ml / g. If it is less than 0.4 ml / g, the diffusion of hydrocarbon oil into the pores of the catalyst becomes insufficient, and if it exceeds 0.6 ml / g, the catalytic activity decreases due to a decrease in the packing density of the catalyst.
[0017]
The catalyst of the present invention can be used for hydrogenation of hydrocarbon oil in the presence of hydrogen, hydrodesulfurization, hydrodenitrogenation, hydrodenitrification, decarbonization, hydrogen in a fixed bed, boiling bed, moving bed, fluidized bed or other reactor. It is used in a hydrotreating reaction for performing cracking and the like. The following reaction conditions are used: a reaction temperature of 350 to 450 ° C., a hydrogen partial pressure of 5 to 15 MPa, a hydrogen feed oil ratio of 150 to 1500 Nl / l, When a hydrocarbon oil is passed at a liquid hourly space velocity (LHSV) of 0.1 to 3 hr- ¹ , excellent hydrotreating performance is exhibited. The preferred reaction temperature is 340 to 430 ° C., the preferred hydrogen partial pressure is 3 to 20 MPa, the preferred hydrogen feedstock ratio is 200 to 1000 Nl / l, and the preferred liquid hourly space velocity is 0.2 to 2.0 hr ^{− 1.}
[0018]
The hydrocarbon oils to be subjected to the hydrotreating in the present invention include crude oil, atmospheric distillate, vacuum distilled light oil, atmospheric distillation residue oil, vacuum distillation residue, coker gas oil, solvent deasphalted oil, tar sands Oils, shale oils, coal liquefied oils and the like, but preferred hydrocarbon oils are atmospheric distillates and vacuum distilled gas oils.
[0019]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the present invention.
[I] Production of catalyst [Example 1]
(A) Production of Carrier To a tank containing tap water, a certain amount of water glass (29% of SiO ₂ component) was added, and a sodium aluminate solution and an aluminum sulfate solution were simultaneously dropped and mixed. The pH during mixing was 8.0, and the temperature was 60 ° C. A gel of silica-alumina hydrate was formed by such mixing.
[0020]
After separating the silica-alumina hydrate gel obtained in the above step from the solution, a washing treatment was performed using warm water to remove impurities in the gel.
Next, the mixture is kneaded for about 20 minutes using a kneader to improve the gel moldability, and then into a four-leaf shaped particle having a diameter of 1.4 to 1.6 mm and a length of 3.5 mm using a molding machine. Extruded.
Finally, the formed silica-alumina body was fired at 600 ° C. for 2 hours to obtain a particulate silica-alumina support. The amount of silica in the obtained silica-alumina support was 6.0%.
[0021]
(B) Preparation of Catalyst 100 g of a silica-alumina carrier was impregnated with an aqueous solution in which 30 g of titanium lactate (also called titanium butyrate; about 15% as TiO ₂ ) was dissolved as a titanium raw material, and then dried at 120 ° C. for 30 minutes. Calcination was performed at 1.5 ° C. for 1.5 hours to obtain a carrier on which titanium was supported.
Next, 7.2 g of an orthophosphoric acid solution (75% product) was added to 100 ml of a citric acid solution in which 226.5 g of ammonium molybdate tetrahydrate, 3.0 g of nickel carbonate hexahydrate and 9.2 g of cobalt carbonate were dissolved. A solution was prepared. The carrier loaded with titanium was impregnated with the solution to obtain a carrier loaded with molybdenum, nickel and cobalt catalyst components.
Next, the carrier was dried at 120 ° C. for 30 minutes using a dryer, and then calcined at 580 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst are as shown in Table 1 below.
[0022]
[Example 2]
(A) Production of Carrier A sodium aluminate solution and an aluminum sulfate solution were simultaneously added dropwise to a tank storing tap water, followed by mixing. The pH during mixing was 8.0, and the temperature was 60 ° C. This addition and mixing produced a gel of alumina hydrate.
[0023]
After separating the alumina hydrate gel obtained in the above step from the solution, a washing treatment was performed using warm water to remove impurities in the gel.
Next, the mixture is kneaded using a kneader for about 20 minutes to improve the gel moldability, and then into a four-leaf-shaped particle having a diameter of 1.4 to 1.6 mm and a length of 3.5 mm using a molding machine. Extruded.
Finally, the formed alumina body was fired at 600 ° C. for 2 hours to obtain a particulate alumina support.
[0024]
(B) Preparation of Catalyst 30 g of titanium lactate (also known as titanium butyrate; about 15% as TiO ₂ ) was dissolved in 100 g of an alumina carrier, impregnated as an aqueous solution, dried at 120 ° C. for 30 minutes, and then dried at 580 ° C. It was calcined to obtain a titanium-supported carrier.
Next, 7.2 g of an orthophosphoric acid solution (75% product) was added to 100 ml of a citric acid solution to which 226.5 g of ammonium molybdate tetrahydrate, 3.0 g of nickel carbonate hexahydrate, and 9.2 g of cobalt carbonate were added. A solution was prepared. The solution was impregnated with the carrier on which titanium was supported to obtain a carrier on which molybdenum, nickel and cobalt catalyst components were supported.
Next, the carrier was dried at 120 ° C. for 30 minutes using a dryer, and then calcined at 580 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst are as shown in Table 1 below.
[0025]
[Comparative Example 1]
(A) Production of Carrier In the production of the carrier of Example 1 (A), the same molding and firing as in Example 1 were performed to obtain a particulate silica-alumina carrier. The silica content in the obtained carrier was 10% by weight.
[0026]
(B) Preparation of Catalyst 226.5 g of ammonium molybdate tetrahydrate, 3.0 g of nickel carbonate hexahydrate and 9.2 g of cobalt carbonate were prepared to prepare 100 ml of citric acid solution, and 100 g of silica-alumina carrier was added to the solution. Was impregnated.
Next, the carrier was dried at 120 ° C. for 30 minutes using a dryer, and then calcined at 580 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst are as shown in Table 1 below.
[0027]
[Comparative Example 2]
(A) Production of Carrier In the production of the carrier of Example 1 (A), the same molding and firing as in Example 1 were performed to obtain a particulate silica-alumina carrier. The silica content in the obtained carrier was 10% by weight.
[0028]
(B) Preparation of Catalyst Orthophosphoric acid solution (75% product) in 100 ml of citric acid solution in which 226.5 g of ammonium molybdate tetrahydrate, 3.0 g of nickel carbonate hexahydrate and 9.2 g of cobalt carbonate were dissolved. A solution to which 2 g was added was prepared, and this was impregnated with 100 g of a silica-alumina carrier.
Next, the carrier was dried at 120 ° C. for 30 minutes using a dryer, and then calcined at 580 ° C. for 1.5 hours in a kiln to complete the catalyst.
The amounts and properties of each component in the produced catalyst are as shown in Table 1 below.
[0029]
[Table 1]

[0030]
[II] Hydrotreating As a hydrocarbon oil to be subjected to hydrotreating, vacuum gas oil (VGO) obtained by fractionating crude oil having the properties shown in Table 2 below was used as a feedstock oil.
This feedstock has a sulfur content of about 2.5% by weight and a total nitrogen content of about 1600 ppm by weight.
[0031]
[Table 2]

[0032]
Hydrogenation treatment was performed on each of the catalysts produced in Examples 1 and 2 and Comparative Examples 1 and 2. The catalyst was charged to a reactor provided in a fixed bed.
In the liquid phase, a raw material oil having the properties described in Table 2 was supplied at 5.0 MPa at a total liquid hourly space velocity (LHSV) of 2.0 hr ^-1 and at average temperatures of 360 and 380 ° C. with hydrogen and a raw material. oil ratio of _(H 2 / oil) were introduced into a fixed bed as 300 Nl / l, to obtain a product oil.
The product oil is collected and analyzed to calculate the weight ratio of sulfur (Sulfur) and nitrogen (Nitrogen) desorbed by hydrogenation, and to determine a specific activity (Relative Volume Activity; RVA) based on the following formula. The results are shown in Table 3.
The specific activity (RVA) was defined as the ratio between the reaction rate constant k calculated using the reaction order in the hydrodesulfurization (HDS) and hydrodenitrogenation reactions of the catalyst of Comparative Example 1 and the example.
[0033]
(Equation 1)

Here, k = (LHSV / r) × (1 / y ^(r−1) −1 / X ^(r−1) ) (r ≠ 1)
k = LHSV × ln (x / y) (r ≠ 1)
In the above formula, k is a reaction rate constant r is a reaction order x is a weight ratio of sulfur or nitrogen in the feed oil y is a weight ratio of sulfur or nitrogen in the produced oil, and ln is a notation of natural logarithm.
[0034]
[Table 3]

[0035]
[III] Evaluation of FCC Using the treated oil obtained in this example and the comparative example, the fluidized bed catalytic cracking (FCC) was evaluated using an improved MAT (micro activity test) device (manufactured by Okura Riken). Was. Table 4 shows the evaluation conditions and Table 5 shows the evaluation results.
[0036]
[Table 4]

[0037]
[Table 5]

[0038]
Gasoline: Boiling range; C5-180 ° C
LCO (Light Circuit Oil): boiling point range: 180 to 360 ° C
Bottom: Boiling range; 360 ° C. or higher Coke: Measured by sulfur carbon analyzer
【The invention's effect】
As described above, the present invention provides economical added value in FCC operation by using the catalyst shown in Example 1 or 2 as an indirect desulfurization catalyst in the pretreatment of fluidized bed catalytic cracking (FCC). High gasoline can be obtained at a high yield of 1 to 1.4% by weight higher than when a conventional catalyst is used, and the amount of FCC bottom can be considerably reduced, thereby realizing efficient petroleum refining. It becomes possible.

Claims (6)

(1) 0.1 to 7% by weight of titanium oxide as a catalyst component, based on the catalyst weight, on a porous alumina-based carrier;
(2) 15 to 25% by weight of an oxide of a metal of Group 6A of the periodic table;
(3) 3 to 7% by weight of an oxide of a metal belonging to Group 8 of the periodic table; and (4) 0.1 to 7% by weight of phosphorus oxide in terms of P ₂ O _5.
Is supported, and the catalyst has (a) a specific surface area of 180 to 300 m ² / g, and (b) a total pore volume of 0.4 to 0.6 ml / g.
A catalyst for hydrotreating hydrocarbon oils, wherein the catalyst component (1) is calcined and supported on a carrier in the catalyst production step, and then the components (2) to (4) are calcined and supported. The catalyst component (2) is at least one metal selected from the group consisting of chromium, molybdenum and tungsten, and the catalyst component (3) is at least one metal selected from the group consisting of iron, cobalt and nickel. Item 7. The catalyst according to Item 1. The catalyst according to claim 1, wherein the calcination temperature is 450 to 600C. The hydrocarbon oil is brought into contact with the hydrotreating catalyst according to claim 1 in the presence of hydrogen at a temperature of 350 to 450 ° C., a pressure of 5 to 15 MPa, and a liquid hourly space velocity of 0.1 to 3 hr ^−1. Hydroprocessing of hydrocarbon oil. The method according to claim 4, wherein the hydrocarbon oil is a vacuum gas oil. Use of the catalyst according to claim 1 as a catalyst for pretreatment of fluidized bed catalytic cracking (FCC).