JPS58112049A - Catalyst composition for hydrogenation treatment of light oil under reduced pressure - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst for hydrogenating light oil under reduced pressure, by specifying the pore characteristics of a catalyst prepared by supporting a molybdenum component and a cobalt component by a carrier comparising alumina-baria. CONSTITUTION:The pore characteristics of a catalyst prepared by supporting a cobalt component and a molybdenum component by a carrier comprising alumina-boria are specified as stated hereinbelow. That is, an average pore size of pores within a range between 0-600Angstrom pore size is 70-100Angstrom , the sum of pore volume with of 70-100Angstrom pore size is 70% or more of that of the sum of the volume a pore with 0-600Angstrom pore sizes, the sum of the pore volume with 0-60Angstrom pore sizes, the average size of the pores with 62-600Angstrom pore size is 20% or less of that of the sum of the pore volume of 0-600Angstrom pore sizes measured by a mercury pressure method is 70-100Angstrom , the sum of the pore volumes of pores with an average pore size of + or -10Angstrom is 60% or more of that of the fine pore with a diameter of 62-600Angstrom and the volume of the fine pore with (an average pore size of + or -10Angstrom or more) is 15% or less of that of sum of the pore volume with 62-600Angstrom pore sizes. By this pore characteristics, a highly active hydrogenation catalyst is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses existing vacuum gas oil hydrodesulfurization reaction equipment and reaction conditions to desulfurize heavy oil such as 8 vacuum gas oil, while
The present invention relates to a hydroprocessing catalyst suitable for efficiently obtaining kerosene without increasing the yield of gaseous components and naphtha fraction.

BACKGROUND OF THE INVENTION As crude oil becomes heavier and demand for lighter oils worldwide, there is a noticeable tendency for heavy oils such as so-called vacuum gas oil and atmospheric residual oil to become surplus. Furthermore, from the viewpoint of air pollution, etc., it has become necessary to reduce the sulfur content in product oils. Under these circumstances, there has been a desire to develop a catalyst that has a high desulfurization ability and a high ability to separate heavy oil into light oil J and decompose naphtha into kerosene and gas oil, which requires less hydrogen consumption.

Conventionally, in the case of hydrodesulfurization of heavy oil such as vacuum gas oil, a catalyst carrier made of alumina or amorphous silica-alumina on which Group 6A and Group 8 active metals are supported is generally used. However, this type of catalyst has a low cracking activity because it is prepared to minimize cracking activity and maximize desulfurization activity. on the other hand.

Conventional hydrocracking catalysts have been proposed such as those using an amorphous inorganic oxide as a carrier and those containing crystalline aluminosilicate, but the former mainly has hydrogen cracking ability and therefore has low desulfurization activity. In addition to being insufficient, the hydrogenation resolution itself was not fully satisfactory. In addition, the latter also did not have sufficient desulfurization activity, and since the oil produced by decomposition was mainly naphtha, the amount of hydrogen consumed was large, causing many economical problems. In addition, since conventional hydrocracking catalysts are used under harsh reaction conditions, they are inevitably economically disadvantageous. For example, high-pressure operations do not require expensive thick-walled containers.

There is increased expense due to gas compression, as well as losses due to dissolution of hydrogen into the product liquid.

Based on the above-mentioned points, the inventors of the present invention have conducted intensive research and found that when desulfurizing vacuum gas oil is carried out within the range of existing vacuum gas oil hydrodesulfurization equipment and its conditions.

The carrier that can increase the decomposition activity without reducing the hydrodesulfurization activity is alumina-Girija, which is the best solid acid carrier (#), and if the pore characteristics of the catalyst are controlled, low-value gas and naphtha can be removed. They discovered that it is possible to obtain a hydroprocessing catalyst that reduces the production of fractions and increases the yield of middle distillates such as kerosene and gas oil.

There are still many unknowns as to why alumina-Zeria is particularly superior among solid acid carriers.

Prensedt's acid (B acid) t - The solid acid properties of alumina Zelya, which has a large amount, and the increase in hydrogenation activity due to the necessary interaction between alumina Zelya and the active metal component, are effective for decomposition and desulfurization of vacuum gas oil. It is presumed that it is working extremely effectively.

Regarding the pore characteristics of the catalyst, in the present invention, the pore distribution is appropriately controlled, so over-decomposition of feedstock oil is suppressed, and as a result, the production amount of middle distillates such as kerosene and diesel oil increases. It is estimated that

Accordingly, the present invention provides a catalyst composition comprising a molybdenum component and a cobalt component supported on a carrier made of alumina borya, the composition comprising a hydrotreating catalyst that satisfies both conditions 1) and Φ). This is what we provide.

Body) Diameter of 0 to 600 when measured by nitrogen gas adsorption method
The average diameter of the pores in the range of X is 70 to 100X, and the diameter is 70 to 1o.

The volume occupied by the pores on the back is at least 70% of the volume occupied by pores with a diameter of 0 to 600X, and the volume occupied by pores with a diameter of θ to 60X is 20% of the volume occupied by pores with a diameter of θ to 600X. Must be below.

Φ) When measured by mercury intrusion method, the diameter is 62 to 600.
The average diameter of pores in the range of X is 70 to 100 @r:
hF), the volume occupied by pores with average diameter = f = t o @ occupies at least 460% of the volume occupied by pores with diameter 62-600, and the volume occupied by pores with average diameter + IOA or more is at least 460% of the volume occupied by pores with diameter 62-600 ~15% of the volume occupied by 600X pores
Must be below.

The catalyst of the present invention is prepared by mixing a boron compound with aluminum 9 that satisfies both conditions (a) and (b) below, and allowing this mixture to support a molybdenum component and a cobalt component.

(a) When measured by nitrogen gas adsorption method, the diameter is 0~
The average diameter force of the pores in the range of 600X x lc> ~
140X diameter, at least 70% of the volume occupied by pores with a diameter of 10 to 150X, and the volume occupied by pores with a diameter of θ to 600X is 10% or less of the volume occupied by pores with a diameter of 0 to 600X thing.

(b) The diameter is 62 to 6 when measured by the Suizhou press-in method.
The average diameter of pores in the range of 00X is 100-140X
Ashi, the volume occupied by pores with an average diameter of ±10X is a mountain diameter of 6
The volume occupied by pores with a diameter of 2 to 600 times is at least 60%, and the volume occupied by pores with an average diameter of +IOX or more is 10% or less of the volume occupied by pores with a diameter of 62 to 600X.

As mentioned above, the alumina used in the present invention has an average pore size of approximately 100 to 140X, and the pore distribution is in an extremely narrow range. By mixing this aluminum with a boron compound such as boric acid, an alumina carrier having the characteristic pore distribution of the present invention can be obtained. It indicates the nature. Therefore, if the alumina does not satisfy both conditions (a) and Φ), the hydrogenation activity will naturally decrease. Moreover, if the carrier does not have an aluminase composition, naturally the hydrogenation activity will inevitably decrease.

Alumina that satisfies both conditions (1) above is obtained by molding amorphous alumina hydrate, which resembles pseudo-boehmite, with a crystallite size of 40 to 80X, into granules, and thoroughly drying it.
It can be produced by firing at a temperature of °C.

Pseudo-boehmite exists in an aluminate or an amorphous alumina hydrate obtained by neutralizing an aluminum salt with an acid or an alkali, but its crystal size is generally small, usually about 30X. Therefore, in order to grow the crystallite diameter of pseudoboehmite to 40 to 80K, an amorphous alumina hydrate having a concentration of 5 wt% or more, preferably 9 wt% or more as alumina is preferably used (p) 18 to 12.
What is necessary is just to heat it to 50 degreeC or more, preferably 80 degreeC or more, while stirring under weak alkaline conditions of ipH9-11.

The carrier used in the present invention is alumina □-Zelya to which a boron compound is added so as to contain 5 to 30 wt% of boron oxide.

More preferably, a boron compound is added to contain 10 to 20 wt% of boron oxide. The above-mentioned aluminum and neutral carriers can be manufactured by a known method of mechanically mixing a metal hydroxide and a boron compound, followed by drying and firing.

On the carrier thus obtained, molybdenum and conolte are supported as metal hydrides in the form of metal hydrates or metal sulfides, respectively. In this case, it can be supported by a known method such as an impregnation method. The supported amount of the mono-λ nobdenum component is 5 to 24 vt% of the final catalyst composition in terms of metal, preferably 7 to 24 vt%.
16 wt%, :1 Nord component support 11 is 0.5 to 8 wL% of the final catalyst composition in terms of metal, preferably 1.5
~5wt%. The catalyst of the present invention as a whole has a specific surface area of 200 to 400 m"7g and a pore volume of 0.3 to 0.8
It shows the physical property of ml/g.

The catalyst of the present invention has a boiling point of 450'F (232"C) to 11
The catalyst of the present invention is extremely effective as a catalyst for hydrotreating vacuum gas oil in the range of 00"it' (593°C) to crack it and desulfurize it. According to the catalyst of the present invention, existing vacuum gas oil Adopting the hydrodesulfurization equipment and its reaction conditions, specifically, the reaction temperature is about 320-430°C, preferably #i38
0~420℃ 1 reaction pressure approx. 10~200K17cm"
, preferably 50-80 K17cm", liquid hourly space velocity 0.1-5.0, preferably 0.5-2.0. Hydrogen to hydrocarbon ratio 100-1000 Nm"/K1. Preferably 400 to 600 Nm"/Kl (D) By adopting mild hydrotreating conditions, the generation of low-value gas components and naphtha fractions from vacuum gas oil can be suppressed, and middle distillates such as kerosene and gas oil can be produced in high yield. You can get it at

Examples and comparative examples are shown below.

Example (1) Production of alumina A 50% gluconic acid aqueous solution was added to a sodium aluminate solution with a concentration of 5.0% by weight as alumina, and then an aluminum sulfate solution with a concentration of 2.5% by weight as alumina was added. The pH'i of the prepared slurry was adjusted to 7.0. After filtering this alumina slurry with a table filter, it becomes 0.
．． The alumina hydrate containing pseudo-boehmite was prepared by washing with 2 parts by weight of ammonia water. A small amount of ammonia water was added to this alumina hydrate to adjust the alumina hydrate slurry f) H'e to 10.60, and the alumina concentration was adjusted to 8.
．． After adjusting the concentration to 8% by weight, the mixture was stirred under reflux at 95° C. for 20 hours to grow pseudo-boehmite crystallites to a diameter of 65 angstroms. This alumina hydrate was heated and concentrated in a kneader to obtain a kneaded product. This kneaded product) was molded into granules with a diameter Q of 9 mm using an extruder and heated at 110° in air.
C. After drying for 16 hours, it was fired at 550°C for 3 hours. The average diameter of the pores in the range of θ to 600 angstroms determined by the nitrogen adsorption method of the obtained alumina is 134 angstroms, fi, and the pores with diameters in the range of 100 to 150 angstroms are in the range of 0 to 600 angstroms. The number of pores was 84.0, and the pores in the 0-60 angstrom range were 1.2% of the pores in the 0-600 angstrom range. Also, 62 to 600 determined by mercury intrusion method
The average diameter of the pores in the X range is 128X;
if: The pores in the 10i range are 90.4- of the pores in the 62-600X range, and the pores in the 138X or more range are 62-600
The number of pores in the back area was 6.4.

(2) Production of Catalyst A 1.531K An aqueous solution prepared by adding 534 g of 61111 acid and dissolving it under heating was mixed with 5 kg of the above kneaded product, and then mixed in a kneader.
After kneading the product, it was made into an extruded product with a nominal size of 1,725 inches, dried in air at 110° C. for 16 hours, and then calcined at 550° C. for 3 hours to obtain a catalyst carrier having a boron oxide content of 15 wt%. (1 kg of this carrier, 170 g of molybdenum oxide, copal carbonate)
After adding 650+/l- of an aqueous solution containing 75g and impregnating it, the temperature was gradually raised to 250°C and dried.
Calcinate at 0° C. for 1 hour to obtain the catalyst At. The supported amounts of molybdenum and conomalt in this catalyst were 14.0 w1% and 3.7 wt%, respectively, including metal oxides.

(3) Preparation of Catalyst B Catalyst B was prepared in exactly the same manner as Catalyst A except that the active metal carrier was different using the mixture (a). The total content of molybdenum and cobalt in this catalyst was 19.0w1% of the final catalyst as metal oxides.5. Owt% was rare.

Comparative Example (1) Production of Catalyst C Y-type zeolite was placed in a 5% chloride dilute solution (main components: CeCl3.LaCl3°NdC1,), the pH was adjusted to 5 with aqueous ammonia, and the mixture was stirred at 80°C for 30 minutes. This was dehydrated and washed to obtain a rare earth metal-exchanged zeolite (hereinafter abbreviated as fReY zeolite). Next, this R
eY zeolite) 60 wt% and the above alumina blend (X) 40 wt% were mixed and kneaded in a kneader "t" to form an extruded product with a nominal size of 1/25 inch, and heated in air at 110°C for 16 After drying for an hour, it was fired at 550"C for 3 intercostals. WO317 as the final catalyst on the carrier obtained in this way,
Owtchi, the amount to contain Ni04.25wt%,
e. Add an aqueous solution containing ammonium latungstate and nickel nitrate to impregnate.

After drying, it was calcined to obtain catalyst C.

(2) Production of Catalyst Catalyst Ct was produced in exactly the same manner as Catalyst C except that the content of ReY zeolite and alumina admixture was reduced to 40 wt%.

(3) Production of catalyst E (commercially available catalyst) Alumina-silica press (Sin, content 2.5 wt%)
was impregnated with an aqueous solution containing molybdenum oxide and conomalt carbonate, and the same procedure as for catalyst A was followed until the amount of conomalt and molybdenum supported was 3.7 w as metal oxides.
A catalyst B with a concentration of t% and 14.0w1% was obtained.

(4) Production of catalyst F Concentrated U as AI, 03 2. Owt% sodium aluminate solution was added with AI, 0. Concentration as 1. Qwt
% aluminum sulfate solution was added to obtain a slurry with a pIl of 7.0. This slurry was filtered through a table filter, and the filter cake was washed with aqueous ammonia to produce pseudo-boehmite-containing alumina hydrate f, 1111B.

This alumina hydrate was divided into two parts, and a small amount of ammonia water was added to one part to give an AI of 0. Concentration 8.5 wt%, pH
95" without stirring as a slurry of 10.5"
After refluxing at C for 2 hours, the remainder of the alumina hydrate that had been separated into 2 parts was added and spray-dried. Next, aqueous ammonia was added to the obtained powder and the mixture was kneaded to obtain a kneaded product σ) which could be molded. In addition, this kneaded material σ) was molded into a diameter of 0.9 with an extrusion molding machine.
The pore characteristics of the alumina obtained by molding the alumina into granules of 1.0 mm in diameter, drying in air at 110° C. for 16 hours, and then calcining at 550° C. for 3 hours are as follows.

The average diameter of pores in the range of 0 to 600 angstroms, determined by the phoneme adsorption method, is 156 angstroms, which is 10
0 N pores with diameters in the 150 angstrom range
29.8% of the pores in the ~600 angstrom range;
The pores were in the 0 angstrom range. Also, the average diameter of pores in the range of 62 to 600 angstroms, determined by mercury intrusion method, is 151 angstroms.
6 pores of 1 angstrom ± 10 angstrom
There are 591 pores in the range of 2 to 600 angstroms, and 62 to 600 pores in the range of 161 angstroms or more.
It was 22.0% of the pores in the angstrom range.

Catalyst F was prepared in exactly the same manner as catalyst A, except that the above-mentioned kneaded product was used in place of the above-mentioned kneaded product in place of the above-mentioned kneaded product. did.

Table 1 shows the pore characteristics of catalysts A, B, E and F.

Table 1 Examples of Catalyst Usage In order to confirm the effects of the present invention, vacuum gas oil was hydrogenated under the following conditions using the above catalysts A and Fl. The reactor had an inner diameter of 1 g, 4 mm, and was filled with 100 g of catalyst.
A fixed bed reactor with a length of 1.8 m was used.

Reaction conditions Pressure 58 K17cm"G H, / HC50G Nm" / KI L H8V 1.5 hr-' Temperature 415°C Hydrogen concentration 90 mol Raw material oil specific gravity (15/4°C) 0.912C, ~204°C
Distillation 0.9 vo1% 204-343℃ distillation
11.5, vo1% kinematic viscosity @50℃ 29.4
cat Sulfur 1.7 wt Chi Residual carbon Q, 5 wt% Nadium 0.6 ppm Nickel
Desulfurization rate when using 0.3 ppm catalyst AI, dregs components (01 to C4), naphtha fraction (Cs-20
4°C) and middle distillate (204-343°C) tt
When the desulfurization rate and the yield of decomposition products of each catalyst were determined in relative values, the results shown in Table 2 were obtained.

Table 2 Catalyst Desulfurization'$ Ct~C3 naphtha fraction Middle distillate A 100.0 100 100
100B 101.0 98
95 97CB8.9 500
670 75D 96.2 200
300 85B 100.2
92 71 80F 94.
8 170 280 83 In addition, when the reaction temperature was changed and the changes in the above-mentioned gaseous components, naphtha fraction, and middle distillate akt were tracked for catalyst A and catalyst E, it was found that the first to third The results shown in the figure were obtained.

As is clear from Table 2, Catalyst A of the present invention.

Compared to catalysts C and D, which correspond to typical hydrocracking catalysts, B produces less gaseous components and naphtha fractions, and increases the raw H,t of the middle distillate. Furthermore, when compared with Catalyst E, which corresponds to a typical hydrophobic desulfurization catalyst, Catalysts A and B of the present invention have a desulfurization activity that is as good as, if not superior to, Catalyst E.

(See Figures 1 to 3)

Although Catalyst F differs from the catalyst of the present invention only in terms of pore characteristics, the results shown in Table 2 for Catalyst F indicate that the pore characteristics of the catalyst are effective in imparting excellent desulfurization and cracking activity to the catalyst. It shows that it is extremely important.

[Brief explanation of the drawing]

FIGS. 1 to 3 are graphs showing the relationship between the reaction temperature and the amount of gaseous components, naphtha fraction, and middle distillate produced.

Claims (1)

[Claims] 1. A catalyst in which a conomalt component and a molybdenum component are supported on a body made of alumina-2, wherein the pore characteristics of the catalyst satisfy both of the following conditions (5) and 0). A vacuum gas oil hydrotreating catalyst composition characterized in that it satisfies the requirements of the present invention. 4 When measured by the 9-element gas adsorption method, the diameter is θ ~ 600
The average diameter of pores in the range of
At least 70% of the volume occupied by 600X pores is 0, and the volume occupied by 60X pores is θ~60
The volume occupied by 0 K pores should be 20% or less. ■) When measured by mercury porosimetry, the target diameter is 62 to 600.
The average diameter of pores in the range of H is 70 to 100X, and the volume occupied by pores with an average diameter of ±101 is 62 to 6
00 At least 60 tlb of volume occupied by the slot on the back?
: The volume occupied by pores with an average diameter of +10^ or more is 15% or less of the volume occupied by pores with a diameter of 62 to 600X. 2. The catalyst composition according to claim 1, wherein the aluminase contains 5 to 30 wt of *BTO8. 3. The amount of the molybdenum component supported as a metal is 5 to 24 wt% of the catalyst composition, and the amount of the codol component supported as a metal is 0.5 to 8 wt% of the catalyst composition. Catalyst composition according to item 1.