JPH07194974A - Porous alumina and its preparation - Google Patents

Abstract

PURPOSE: To obtain with high conversion a liq. hydrocarbon low in metal and sulfur contents and capable of being distilled in the case when the subject alumina is used as the supporting body of a catalyst for the hydrogenation conversion of a heavy hydrocarbon. CONSTITUTION: The alumina has 0.65-1.30 ml/g total fine pore volume, and 2-20% fine pores per the total fine pore volume have a pore size of 100,000-10,000 Å, and the 5-30% fine pores have a pore size of 10,000-1,000 Åand 50-93% a pore size of 1,000-30 Å.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to alumina catalysts and their use in a process for converting heavy hydrocarbons into lighter hydrocarbons. More specifically, the present invention relates to removing sulfur and contaminated metals during hydrocarbon conversion.

[0002]

BACKGROUND OF THE INVENTION Economic considerations dictate the upgrading of heavy or residual oils obtained during petroleum refining to higher economic value cuts. It is desirable to convert bitumen or heavy crudes to lower boiling synthetic crudes so that they can be processed by conventional downstream operations. This can be done by hydrogenating these materials at elevated temperature and pressure. Typically, an upflow of liquid feedstock is carried out in a boiling bed in contact with the catalyst present in the form of extrudates with a diameter of 0.7-1.6 mm.

Those skilled in the art have attempted to improve catalyst systems used in various processes for hydrogenating this heavy oil. A representative of the prior art attempts to develop improved catalysts is noted as follows.

US Pat. No. 4,657,665 discloses highly macroporous catalysts. Total pore volume (TPV) is 0.85-1.5 ml / g;
0.15-0.40 ml / g of which are contained in the pores having a diameter of 1,200Å or more. The final composition contains 3.5 to 5% Group VIB metal (as oxide).

US Pat. No. 4,395,328 discloses that at least 0.8 ml / g of TPV is contained in pores having a diameter of 0 to 120Å and at least 0.1 ml / g of 1,
Disclosed is a catalyst contained in pores having a diameter of 200 to 50,000Å.

US Pat. No. 4,328,127 discloses that 40-75% of TPV is contained in pores having a diameter of 150-200Å and up to 5% of TPV is 1,000Å.
Disclosed are catalysts contained in pores having diameters in excess of 1.

US Pat. No. 4,309,278 discloses a catalyst in which TPV not exceeding 0.2 ml / g is contained in pores having a diameter exceeding 400 Å.

US Pat. No. 4,297,242 discloses a catalyst in which at least 95% of the TPV is contained in pores having a diameter of less than 130Å.

US Pat. No. 4,225,421 discloses a catalyst in which 3 to 30% of the TPV is contained in the pores having a diameter of more than 600 liters.

US Pat. No. 4,089,774 discloses that at least 45% of TPVs are contained in pores having a diameter of 30 to 150Å and at least 10% of TPVs are in pores having a diameter of at least 300Å. Disclosed are the included catalysts.

US Pat. No. 4,082,695 discloses a catalyst in which at least 5% of the TPV is contained in pores having a diameter of at least 500Å.

US Pat. No. 3,630,888 discloses that 20-80% of TPV is contained in pores having a diameter of less than 100 liters, and 10-40% of TPV is 100-1,000.
Included in Å pores, 10-40% of TPV is 1,000
Disclosed is a catalyst contained in pores with a diameter exceeding Å.

[0013]

It is an object of the present invention to provide a support for catalysts of improved properties for the hydroconversion of heavy hydrocarbons to obtain distillable liquid hydrocarbon products. It is to be. Other purposes will be apparent to those skilled in the art.

[0014]

The present invention, according to its particular aspect, has a total pore volume of about 0.65 to 1.30 ml / g, with about 2 to 20% of the total pore volume. About 100,000
The shape of the first macropores having a diameter of ˜10,000Å, wherein about 5-30% of the total pore volume is about 10,000
A shape of second macropores having a diameter of 0 to 1,000Å, wherein about 50 to 93% of the total pore volume is about 1.00
The composition is oriented in the form of mesopores having a pore size of 0 to 30Å.

The porous alumina of the present invention has a triple mode (t
rimodal) pore size distribution, and in particular when the pore volume (as a percentage of the total pore volume TPV) is plotted as a function of pore size (Å), the macropore area (about 1.0
2 different peaks in pores with diameters over 00Å),
It is characterized by containing one peak in the mesopore region (about 30 to 1,000 Å).

The triple mode porous alumina of the present invention is typically characterized as follows.

(I) The first macropores in the area of 100,000 to 10,000Å have a total pore volume of 2 to 2 in total.
A pore volume of 0.02-0.15 ml / g corresponding to 0% is given. Preferably, this first macropore region is 4
0.04 to 0.08 ml of pores in the range of 20,000 to 20,000Å, equivalent to 5 to 12% of the total pore solution
/ g to give a pore solution. In a preferred embodiment, the first macropore area is 40,000.
To give a pore volume of 0.06 ml / g corresponding to 7% of the total pore volume in the region of 0 to 20,000 Å, 60,000
0-20,000Å, preferably 40,000-20,
It may have a pore mode of 000Å, for example 30,000Å (ie the pore size corresponding to the maximum peak when the logarithmic derivative of the penetration (ml / g) is plotted as a function of the pore diameter).

(Ii) The second macropores in the range of 10,000 to 1,000Å have a total volume of 5 to 30% of the total pore volume.
To give a pore volume of 0.05 to 0.27 ml / g. Preferably, this second macropore region is 6,0
Porosities in the region of 00-20,00Å will be contained to give a pore volume of 0.1-0.2 ml / g, which corresponds to a total of 15-28% of the total pore volume. In a preferred embodiment, the second macropore region is 6,000-2,000.
In the area of 0Å, 0.19 corresponding to 22% of the total pore volume
7,000-2,000 to give a pore volume of ml / g
It may have a pore mode of 0Å, preferably 5,000 to 2,000Å, for example 4,000Å.

(Iii) The mesopores in the region of 1,000 to 30 Å correspond to 50 to 93% of the total pore volume in total, which is 0.
It gives a pore volume of 58 to 0.88 ml / g. Preferably,
This mesopore region has pores in the region of 130 to 70Å,
0.48 ~, which corresponds to 60-82% of the total pore volume in total
It will be included to give a pore volume of 0.62 ml / g. In various preferred implementations, the mesopore region ranges from 140 to
To give a pore volume of 0.60 ml / g, which corresponds to 71% of the total pore volume in the area of 80Å, a total volume of 140-80
It may have a pore mode of Å, preferably 110-120 Å, eg 110 Å.

It will be appreciated by those skilled in the art that when the pore volume (actually the logarithmic derivative of the infiltration (ml / g)) is plotted as a function of pore diameter, the curve will be characterized by three peaks. Would be obvious. The mesopore peaks are highest, indicating that the largest part of the pore volume is contained in the smallest (less than 1,000Å) pores. The first macropore region and the second macropore region are lower, and the first macropore region is generally lower than the second pore region.

When the cumulative infiltration (ml / g) was plotted as a function of pore size, the curve showed three flats:
It is characteristic of the trimodal alumina of the present invention.

(I) The first macropore area is 0.2 ml.
It is characterized by a plateau in the region of 100,000 to 10,000Å corresponding to / g.

(Ii) The second macropore area is 0.3 to
It is characterized by a plateau in the region of 10,000-1,000 Å which corresponds to 0.5 ml / g.

(Iii) The mesopore region is characterized by the flat part of the region of 1,000 to 30 Å corresponding to 0.8 ml / g.

Cumulative infiltration and cumulative pore volume are the values actually measured (as a function of pore size) when quantifying pore volume by mercury porosimetry. Unit is ml / g
Is. For mercury porosimetry measurements, a sample (eg alumina) is placed in contact with a mass of mercury in a cell. The pressure applied to the cell is changed and the volume of mercury is measured. The pressure value is converted to a diameter value by the well-known Washburn equation, which indicates the pore size as a function of pressure. Cumulative infiltration at a given pressure is easily converted to pore volume.

Total Pore Volume TPV of Triple Mode Alumina
Is 0.65-1.3 ml / g, preferably 0.80-0.
It may be 90 ml / g, for example 0.85 ml / g.

According to a particular embodiment of the invention, the triple mode alumina can be formulated by admixing the raw alumina characterized by the desired properties. Obviously, the raw alumina to be mixed is characterized by its desired pore mode.

For example, the triple mode alumina of the present invention can be formed by the following mixing.

(I) Three separate single modes (monom) each characterized by a desired value of pore mode.
odal) Mix the alumina. In this case, for example, a single mode alumina having a pore mode of 110Å, a pore mode of 4,0
00Å single mode alumina and pore mode 20,0
It is possible to mix 00Å single mode alumina.

In some cases, more than three single mode aluminas may be mixed. In this case, at least 2
Alumina will be characterized by similar pore modes. This may be useful when the two similar pore mode aluminas are characterized by other desirable properties such as surface area.

(Ii) In addition to one single mode alumina, a bimodal alumina is mixed. In this case, the pore modes of the single mode alumina are such that the product is ultimately characterized by a triple mode pore distribution,
It is different from the pore mode of the dual mode alumina.

Once again, at least some of the alumina has a pore mode similar to the others, so that the product is ultimately characterized by a triple mode pore distribution.
It is possible to use more than one single mode alumina and / or more than one dual mode alumina.

The single mode alumina may be characterized by an acid dispersibility of less than 15%, typically 0-10%, for example 3%. Acid dispersibility is acidified slurry (250 meq HNO ₃ for 100 g alumina)
Was centrifuged (1,800 rpm / 5 min), the suspension-retained fraction was decanted, and the remaining solid was stored at 104 ° C.
Measured by drying at (220 ° F), baking at 400 ° C (750 ° F), and weighing.

(Iii) Mixing two different dual mode aluminas having one common pore mode and different second pore modes. For example, one dual-mode alumina has 110 Å mesopore mode and 30,000 Å first
The second dual-mode alumina has a mesopore mode of 110Å and 5,0
It may be characterized by a second pore mode of 00Å. When mixed, alumina will be characterized by a pore mode called the triple mode.

When the triple mode alumina is prepared using the dual mode alumina, the dual mode alumina is always the mesopores and at least one of the first or second macropores, preferably the second fine pores. It should be noted that it contributes to pores. If the triple mode alumina is formed by mixing the dual mode alumina with the single mode alumina, the latter will provide the first macropores. If the triple mode alumina is formed by two dual mode aluminas, each typically has mesopores, one mainly in the first macropore and the other in the other. It will contribute mainly to the second macropores.

It will be apparent to those skilled in the art that other formulations may also be used. For example, by mixing the triple mode alumina with a single mode alumina characterized by a pore mode corresponding to the peak of the first macropore mode of the triple mode alumina, the peak of the first macropore mode is It is desirable to increase.

The alumina used as a raw material to form the triple mode product may be any alumina suitable for the method used. This is α-, δ-, γ
It may include-, χ-, η- or θ-alumina, pseudo-boehmite, boehmite, alumina trihydrate, amorphous alumina and the like. These raw material aluminas may typically be in the form of particles having an average particle size of 40 to 100Å.

An example of the single mode alumina used is:
Includes the following: (1) α-alumina having a pore mode of about 100,000 Å, a total pore volume of 0.4 ml / g, a total surface area of 4 m ² / g and an acid dispersibility of less than 10%; (2) 4,000 Å Α-alumina having a pore mode of 0.6 ml / g, a total pore volume of 0.6 ml / g, a total surface area of 6 m ² / g and an acid dispersibility of less than 10%; (3) 110 Å pore mode, 0.7 ml / Alumina trihydrate having a total pore volume of g, a total surface area of 254 m ² / g and an acid dispersibility of 85%; (4) 90 Å pore mode, 0.72 ml / g total pore volume, 320 m Pseudo-boehmite having a total surface area of ² / g and an acid dispersibility of 75%; and (5) a pore mode of 70Å, a total pore volume of 0.77 ml / g, a total surface area of 350 m ² / g and 85%. Pseudo-boehmite with acid dispersibility.

An example of the dual mode alumina used is:
Includes the following: (1) 110 Å pore mode and 0.50 ml / g pore volume corresponding to 67% of total pore volume, 4,000 Å pore mode and 0.25 ml corresponding to 33% of total pore volume pseudoboehmite having a pore volume of / g and an acid dispersibility of 50%; (2) a pore mode of 110Å and a pore volume of 1.05 ml / g corresponding to 75% of the total pore volume; Γ-alumina having a pore mode of 000Å and a pore volume of 0.3 ml / g corresponding to 25% of the total pore volume, and an acid dispersibility of less than 10%; (3) 90Å pore mode and total 0.74 ml / g pore volume corresponding to 78% of the pore volume, 40,000Å pore mode and 0.18 ml / g pore volume corresponding to 22% of the total pore volume, and 10% Γ-alumina having an acid dispersibility of less than; and (4) 90 Å pore mode and 90% of the total pore volume Pseudo-boehmite having a pore volume of 0.62 ml / g, a pore mode of 3,000Å and a pore volume of 0.07 ml / g corresponding to 10% of the total pore volume, and an acid dispersibility of 65%.

According to a particular aspect of the invention, the invention comprises
Each of (i) 100,000 to 10,000Å,
(Ii) 10,000 to 1,000Å and (iii) 1,0
Mixing at least two fine-powder raw material aluminas, characterized in that they have at least one pore mode in at least one range from 00 to 30Å, the mixture containing pore modes in each range; A mixture of the above
Add to the acidifying liquid in an amount of about 90-110% of the total pore volume of the mixture; extrude the acidified mixture above; dry the extruded oxide above; and bake the dry mixture above. Orient a method that involves things.

In preparing the alumina of the present invention in accordance with a preferred feature of the present invention, the acid dispersible dual mode pseudo-boehmite alumina is treated with a non-acid dispersible (ie, less than 10% acid dispersible) dual mode. It is preferably mixed with γ-alumina.

When preparing the alumina of the present invention by mixing two dual mode aluminas, it is preferred that they are of different acid dispersibility.

The first dual mode alumina is preferably highly acid dispersible, ie, greater than about 10%, typically 1
It has an acid dispersibility of 0 to 50%, for example about 40%. The second dual mode alumina preferably has low acid dispersibility,
That is, it has an acid dispersibility of less than about 10%, typically 0-10%, such as about 3%.

The formulation of the mixture of aluminas for preparing the preferred triple mode alumina occurs by mixing dry particles of the raw alumina. The amount of each component is easily calculated from the pore size distribution of each alumina in each pore mode.

For example, (i) a TPV containing 110Å pore mode (0.25 ml / g pore volume) mesopores and 4,000Å first macropores.
90 parts of dual mode γ-alumina of 0.87 ml / g,
(2) TPV containing 100% of the second macropores having a pore mode of 40,000Å (pore volume 0.06 ml / g)
Can be mixed with 10 parts of 0.50 ml / g single mode α-alumina to form the desired product.

The mixture containing the alumina source component is typically acidified with an organic acid such as acetic acid, formic acid, propionic acid or oxalic acid; or with an acidifying solution such as an aqueous solution of an inorganic acid such as sulfuric acid or nitric acid. Acidify. Acetic acid is preferably used.

The acid solution is 90 to 11 times the pore volume of the mixture.
An amount of 0%, for example 100%, is used. Typically, the acid (ie, its aqueous solution) is added at 0.75 per mixture.
Use 1 ml / g, for example 0.85 ml / g.

The acidified mixture is then thoroughly mixed and extruded in the form of a catalyst-supported extrudate, typically 0.5-5 mm, for example 7 mm long and 0.5 mm in diameter.
Extrudate in air at 15-148 ° C (60-300 °
F), for example, at 65 ° C (150 ° F) for 1 to 24 hours, such as 10 hours. Then, in air, they are 287 to 1,093 ° C (550 to 2,000 °
F), eg, 400 ° C. (750 ° F.) for 1 to 6 hours, eg 3 hours.

The formation of the catalyst is carried out by loading the triple mode alumina support with a metal suitable for carrying out the reaction. If the catalyst is to be used for heavy oil hydrogenation (typically a reaction used in H-oil processes),
The catalyst contains a Group VIB metal (chromium, molybdenum or tungsten) and a non-noble Group VIII metal (iron, cobalt or nickel). Group VIB metal is 3-24% of the support, preferably 8-12%, for example 9.5%.
May be present in an amount of. The Group VIII metal is added to the support in an amount of 0.0 to
7%, preferably 1.2-2.5%, for example 1.5%
May be present in an amount of.

One preferred catalyst is molybdenum9.
It may contain 5% by weight and 1.5% by weight nickel.

The support is immersed in an aqueous solution of ammonium molybdate at pH 2.0 for 0.5 to 12 hours, for example 3 hours, and then immersed at 15 to 148 ° C (60 to 300 ° F), for example 27 ° C (80 ° F). ) For 1 to 24 hours, for example 10
And dried for 287-593 ° C (550-1,1
00 ° F), for example 500 ° C (930 ° F),
The metal can be supported on the support by firing in air for 6 hours, for example 3 hours. afterwards,
The partially supported support is immersed in an aqueous solution of nickel nitrate for 0.5 to 12 hours, for example 3 hours,
~ 148 ° C (60-300 ° F), for example 27 ° C (8
At 0 ° F.) for 1-24 hours, for example 10 hours,
287-593 ° C (550-1,100 ° F), for example 400 ° C (750 ° F), for 1-6 hours, for example 3
Bake for hours.

It is a feature of the present invention that the catalyst metal may be supported on the raw material alumina before, during, or after the mixing. The metals may be separately supported as described above, and may be simultaneously supported from, for example, a solution containing nickel nitrate and ammonium molybdate. When adding the above metals from a single solution, it is preferred to include stabilizers such as hydrogen peroxide, citric acid or phosphoric acid.

Preferably, an aqueous solution of at least one metal compound may be added during the mixing of the alumina.
When doing this, the aqueous acid may be reduced or not used, and in order to improve the quality, the total amount of liquid added during mixing is of the same order of magnitude as the TPV of the mixture,
Preferably equal.

The characteristics of the catalyst prepared using the triple mode alumina of the present invention are as follows.

(I) An amount of 10 to give a pore volume of about 0.03 to 0.15 ml / g, which corresponds to about 2 to 20% of TPV.
First macropores in the range of 10,000-10,000Å. Preferably, the first macropore region is 40,0
In the 00 to 20,000 Å region, an amount of pores is provided which gives a pore volume of about 0.03 to 0.08 ml / g corresponding to about 5 to 10% of TPV. In a preferred embodiment, the first macropore region is about 0.0, which corresponds to about 7% of TPV.
It has a pore mode of about 30,000Å, in an amount that gives a pore volume of 6 ml / g.

It will be noted that the values of the first macropore region for the catalyst are roughly comparable to those for triple mode alumina.

(Ii) An amount of 1 to give a pore volume of about 0.05 to 0.25 ml / g, which corresponds to about 5 to 30% of TPV.
Second macropores in the range of 10,000 to 1,000Å. Preferably, the second macropore area is between 6,000 and
The 2,000Å region contains an amount that provides about 0.08 to 0.20 ml / g of pores, which corresponds to about 17 to 25% of TPV. In a preferred embodiment, the second macropore region has a pore mode of about 4,000Å in an amount that provides a pore volume of about 0.17 ml / g, which corresponds to about 22% of TPV.

It will be noted that the value of the second macropore region for the catalyst is approximately comparable to that for triple mode alumina.

(Iii) an amount giving a pore volume of about 0.44 to 0.66 ml / g, which corresponds to about 50 to 93% of TPV,
Mesopores in the range of 1,000 to 30Å. Preferably, the mesopore region has an amount of 13 to provide a pore volume of about 0.48 to 0.62 ml / g, which corresponds to about 65 to 78% of TPV.
It contains pores in the 0-70Å region. In a preferred embodiment, the mesopore region is in an amount that provides a pore volume of about 0.55 ml / g, which corresponds to about 71% of TPV, of about 105-10.
It has a pore mode of 0Å.

The mesopore region values for the catalyst are (albeit slightly lower) than those for triple mode alumina.
It will be noted that they are almost comparable.

The finished catalyst is 0.6-1.25 ml / g,
Preferably 0.7-0.9 ml / g, eg 0.78 ml / g
TPV of 120-220 m ² / g, preferably 150-
It has a surface area of 200 m ² / g, for example 180 m ² / g.

It is a feature of the triple mode alumina of the present invention that the pore modes of the mesopores may be shifted (ie, increased) to the left if desired. For example, if the finished catalyst is used in a hydrogenation process (eg, H-oil process) fed with a hydrocarbon feedstock containing large amounts of high molecular weight such as asphaltene, this is desirable. Ah

The pore mode of the mesopores may be altered by treatment after mixing and before addition of the catalytic metal.

In practicing the method aspects of the present invention, the pore modes of the mesopores are a mixture of starting alumina or triple mode alumina (before addition of the catalytic metal):
700 to 1,000 in the presence of water vapor, if necessary.
It may be shifted (i.e. increased) to the left by heating to C, e.g. 900 C, for 1 to 5 hours, e.g. 3 hours. This is done during firing.

During this operation, the volume distribution in the macropore region remains largely unchanged. Typically, the mesopore mode is increased by 5 to 50Å, preferably 30 to 50Å, for example 40Å, and the value after the increase is 80 to 120.
Å, preferably 90-110Å, for example 110Å. In a preferred embodiment, the mesopore mode is
It increases from the initial value of 80Å to 110Å.

The characteristics of the catalyst prepared using the triple mode alumina of the present invention are,
A product characterized by (i) a reduced content of heavy metals such as vanadium and nickel, (ii) a reduced sulfur content, and (iii) conversion of asphaltene to a low boiling hydrogenation product. Therefore, it is used for hydrotreatment.

Asphaltene is evaluated by mixing 1 part of the hydrotreated product with 50 parts of cyclohexane or n-heptane, filtering and weighing as cyclohexane or n-heptane insolubles. This is a component which has a rather unfavorable effect on the tendency of heavy oils treated by the process of the invention to form coke and sediment.

These heavy oils typically include vacuum resids having a high boiling point, usually above 1,000 ° F (537 ° C). By using the catalyst of the present invention, these heavy oils, crude distillation column or vacuum distillation column,
Allows conversion to lower quality products, which typically have boiling points less than 1,000 ° F (537 ° C), which are easier to distill.

The conversion of hydrocarbons by the method of the present invention is carried out by converting the starting hydrocarbons into the boiling bed of the catalyst at 400 to 438 ° C. (7
50-820 ° F), for example 427-432 ° C (80
0-810 ° F). The catalyst is
Typically, 6.3% molybdenum and 1.2% nickel on a cylindrical triple mode alumina having a diameter of 1 mm and a length of 7 mm. Hydrogen is in the boiling bed, 10.4-20.8
MPa (1,500-3,000 psig), eg 15.
At an operating pressure of 6 MPa (2,250 psig), 337-1,
An amount of 180 Nm ³ / m ³ (2,000 to 7,000 SCFB), for example 842 Nm ³ / m ³ (5,000 SCFB), is introduced. The space velocity for the reactor feed is 0.10 to 0.5 LHSV, for example 0.37 LHSV, based on the empty reactor.

The initial distillation temperature of the raw material is 316 to 427 ° C. (60
0-800 ° F), for example 371 ° C (700 ° F),
50% distillation temperature exceeds 537 ° C (1,000 ° F),
When the end point exceeds 537 ° C. (1,000 ° F.), the liquid phase is typically 21-149 ° C. (70-300 ° F.), for example 49 ° C. (120 ° F.) and 0-50 psig, for example 10 psig. The product recovered in the first distillation temperature is 10-
93 ° C (50-200 ° F), for example 49 ° C (120
° F), 50% distillation temperature 400-454 ° C (750-8
50 ° F.), for example 427 ° C. (800 ° F.), and end points 482-565 ° C. (900-1,050 ° F.), for example 537 ° C. (1,000 ° F.).

[0071]

INDUSTRIAL APPLICABILITY According to the present invention, porous alumina having improved properties, which is useful as a support for a catalyst used for hydroconversion of heavy hydrocarbons to obtain a distillable liquid hydrocarbon product. Can be obtained. The catalyst using the porous alumina of the present invention as a support gives a distillable hydrocarbon product with a high conversion and a low metal and sulfur content.

[0072]

The invention will now be further described with reference to the following examples. All parts are parts by weight unless otherwise noted.

Example 1 In this example, which shows the best mode currently known for carrying out the method of the present invention, the starting alumina is as follows.

(A) 80 parts of pseudo-boehmite--that is,
When TPV is 0.85 mlg, (i) the pore mode of 110 Å and 0.5 corresponding to 67% of TPV of the pseudo-boehmite.
Mesopores with a pore volume of 7 ml / g; and (ii) 4,000
It is a dual mode alumina having a pore mode of Å and a second macropore with a pore volume of 0.28 ml / g corresponding to 33% of the TPV of the pseudo-boehmite. The pseudo-boehmite is
It has an acid dispersibility of 40% and a surface area of 196 m ² / g.

(B) 20 parts of γ-alumina--that is,
When TPV is 1.05 ml / g, (i) the pore mode of 110 Å and 0.7 corresponding to 67% of TPV of the γ-alumina.
mesopores with a pore volume of ml / g; and (ii) 30,000
A dual-mode alumina having a pore mode of Å and a first macropore having a pore volume of 0.35 ml / g corresponding to 33% of TPV of the γ-alumina. The γ-alumina has an acid dispersibility of less than 5% and a surface area of 170 m ² / g.

These aluminas are mixed and about 2 g of glacial acetic acid is added to 100 g of alumina. Mixing
Perform in a Sigma® blade mixer for 30 minutes,
During that time a paste was formed. The paste was extruded with a piston extruder to form a cylinder having a diameter of 1 mm and a height of 2 mm. After air drying at 27 ° C (80 ° F) for 12 hours, they were calcined at 500 ° C (932 ° F) for 3 hours.

The calcined triple mode alumina support so formed had a pore volume of 0.82 ml / g and a 178 m ²
Characterized by a surface area of / g. It contains the following pores: (A) A first macropore in the 100,000 to 10,000 Å region, in an amount to provide a pore volume of 0.06 ml / g corresponding to 7% of TPV. The pore mode is about 30,000Å. (B) Second macropores in the 10,000-1,000 Å region in an amount that gives a pore volume of 0.18 ml / g, corresponding to 22% of TPV. The pore mode is about 4,000Å. (C) Mesopores in the 1,000 to 30Å region in an amount that gives a pore volume of 0.58 ml / g corresponding to 71% of TPV.
The pore mode is about 110Å.

This alumina was impregnated with a 12.5% aqueous solution of ammonium molybdate for 24 hours, and kept at 24 ° C. (7
Dry at 5 ° F for 12 hours, and 500 ° C (932 °)
It was baked in F) for 3 hours. Next, nickel nitrate 6.4
% Aqueous solution for 24 hours and 1 at 24 ° C (75 ° F)
It was dried for 2 hours and calcined at 400 ° C (752 ° F) for 3 hours.

The catalyst was 9.53% by weight of MoO ₃ and 1.5.
It contained 0% by weight of NiO. Surface area is 158 m ² / g
And the pore volume was 0.78 ml / g.

A 300 ml continuous flow Robinson-Mah of this catalyst was used.
I put it in the oney reactor. Pre-sulfiding with carbon disulfide to 3
Performed at 16 ° C (600 ° F). The reaction was carried out according to Examples 1, 2
And 427 ° C. (800 ° F.) in Comparative Example 1, Example 3
At 430 ° C (806 ° F). Hydrogen 842Nm
^It was introduced at a space velocity of ³ / m ³ (5,000 SCFB). The space velocity of the feed was 34 ml / h, corresponding to a LHSV of 0.37. The catalyst space velocity was 0.96.

The characteristics of the feedstock and product were as shown in Table 1.

[0082]

[Table 1]

Examples 2, 3 and Comparative Example 1 A series of tests were conducted to evaluate the feed conversion (wt%) of Example 1 as a function of catalyst catalyst age (barrels / pounds). A comparative experiment was conducted. In the experiments of Examples 2 and 3, the catalyst was similar to Example 1. In Comparative Example 1 for comparison, the catalyst had the characteristics of Table 2 and was named American Cya under the trade name HDS-1443B.
It was a commercially available HDS catalyst sold by Namide.

[0084]

[Table 2]

The characteristics of the product are shown in Table 3.

[0086]

[Table 3]

It will be apparent from the above table that, at any cumulative throughput, the triple mode catalysts of the present invention provide lower total metal content and insoluble content in the total liquid product. Moreover, the triple-mode catalyst can be operated under severe conditions while keeping the insoluble content in the liquid product approximately equal to the comparative catalyst (at low temperature). In addition to reducing the content of heteroatoms in the liquid, operating at high temperatures also results in distillable liquids with considerably higher yields.

For example, the metal content of the product of Example 3 was slightly less than 61 ppm in Comparative Example 1, even after operation at 0.2 m ³ / kg (0.566 barrels / lb). It was 50 ppm. From Example 2, the sulfur content is
It can be seen that the value of 1.29% in Comparative Example 1 was lowered to 1.22%.

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Claims (4)

[Claims] 1. A total pore volume of 0.65 to 1.30 ml / g, (i) 2 to 20% of the total pore volume is 100,000 to 1
The shape of the first macropores having a pore size of 10,000Å; (ii) 5-30% of the total pore volume is 10,000-1,
A second macropore shape having a pore size of 000Å; and (iii) 50-93% of the total pore volume is 1,000-30.
Porous alumina in the form of mesopores with a pore size of Å. 2. Porous alumina according to claim 1, characterized in that the plot of cumulative penetration (ml / g) as a function of pore size (A) shows the following three flats: (I) a flat part of the first macropores in the 100,000 to 10,000Å region; (ii) a flat part of the second macropores in the 10,000 to 1,000Å region; and (iii) 1, The flat part of the mesopores in the 000 to 30Å region. 3. An amount of (i) 4 giving an amount of pore volume of 0.04 to 0.08 ml / g corresponding to 5 to 12% of the total pore volume.
First macropores having a pore size of 20,000 to 20,000Å; (ii) 0.1 to 15 to 28% of the total pore volume.
An amount of 6,000 to 2, which gives a pore volume of 0.2 ml / g.
Second macropores with a pore size of 000 Å; and (iii) 0.48-corresponding to 60-82% of the total pore volume.
130-70Å in an amount that gives a pore volume of 0.62 ml / g
The alumina according to claim 1, containing mesopores having a pore size of. 4. Each of (i) 100,000 to 1
The mixture is characterized by having at least one pore mode in at least one range of 10,000 Å, (ii) 10,000 to 1,000 Å and (iii) 1,000 to 30 Å. Of at least two finely divided raw aluminas, containing about 90-110 of the total pore volume of the mixture.
%, In addition to the acidifying liquor; extruding the acidified mixture; drying the extruded oxide; and calcining the dried mixture. .