JPS6138629A - Hydrogenation catalyst and metal removal and desulfurization of hydrocarbon residue using the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a hydrogenation catalyst and a method for demetallizing and desulfurizing asphalt-containing hydrocarbons using the same, more specifically,
The present invention relates to the production of a molybdenum hydrogenation catalyst with a controlled amount of feed macropores interconnecting catalytically active micropores and the use of this catalyst in the demetalization and desulfurization of asphalt-containing hydrocarbons.

(Prior Art) ``Removal of metals and sulfur from an asphalt-containing hydrocarbon fraction of petroleum by treating the fraction with hydrogen under high temperature and high pressure while bringing it into contact with a catalyst containing a hydrogenation component is as follows: - Well known in the world.

Typically, Group I and Group II metals, or their oxides and sulfides, were used as the metal component of the catalyst. For example, the catalyst used commercially for the hydrodesulfurization of asphalt-containing crude oil feeds is nickel-cobalt supported on alumina.
It is a molybdenum catalyst. Such catalysts and hydrodesulfurization methods are described, for example, by Carlson et al.
al., U.S. Patent No. Re 29315. The lifetime of conventional hydrodesulfurization catalysts, such as those mentioned above, decreases in proportion to the concentration of metals found in heavy oil. These metals are absorbed onto the catalyst and fill the pores.
re) and deactivate the hydrodesulfurization catalyst.

Hydrogenation catalysts used as conventional demetalization catalysts, such as those described in U.S. Pat. To achieve this, 404°C (
760° F.) or higher.

The recognition that large catalyst pores can be useful for simultaneous demetalization and desulfurization of heavy oils is shown in US Pat. No. 3,898,155 to Geoffrey R. Wilson. This reference discloses that heavy oil containing at least 50 ppm of metals is simultaneously demetallized using a catalyst composition comprising a Group VIB metal and at least one Group II metal in combination with alumina. and desulfurizing, and the catalyst composition is
10-40% of the total pore volume in the pores has a diameter greater than 600 nanometers, and 60-90% of the total pore volume in the pores has an average pore diameter of θ
~600 micropores in diameter and a small micropore volume in the pores (both 80% and at least 100%
It is described as having a diameter of a person.

A process for hydrodemetalization and hydrodesulfurization of asphaltothene-containing hydrocarbons using a nimodic catalyst is also described in US Pat. No. 4,225,421.

In this reference, VI
A catalyst deposited with Group B metals, and about 60-95% of its micropore volume is in micropores having a diameter in the range of about 50-200 pores, and 0 to about 15% of its micropore volume is in the range of about 200-600 pores. micropores with diameters within the human range, and approximately 3-30% of the total pore volume is 60
Catalysts located in macropores with diameters of 0 or more are described.

(Summary of the Invention) According to the present invention, molybdenum and at least one
A catalyst comprising a group metal in combination with alumina, and the catalyst has a mercury content of at least 0.4 c as measured by mercury permeation method.
c/g total pore volume, a macropore volume in the range of 0.02 to 0.2 cc/catalyst volume cc and at least 0.12 cc/g.
A catalyst having a micropore volume of cc/catalyst volume cc,
Optimal demetalization and desulfurization of asphalt-containing hydrocarbons is obtained by use under hydrogenation conditions.

DESCRIPTION OF THE INVENTION It has been determined that the demetalization and desulfurization of asphalt-containing hydrocarbons may be optimized by using a catalyst composition with controlled molybdenum addition and controlled macropore volume and micropore volume distribution.

As used herein, the term "macropore volume" refers to the A37M Bulletin
tk236゜Winslow in February 1959
The total pore volume contained in pores having a pore size in the range of 1,000 to 10,000 pores, as measured by the test method described in "Pore Size Distribution Measuring Apparatus by Mercury Penetration" by J. Low and Shapiro. Say the percentage.

The term "micropore volume" is the term used in "Analytical Chemistry" Volume 32, P532.
The total pores contained in pores with diameters in the range of 100 to 600 nanometers, as measured by the nitrogen adsorption method described by Dollen et al. The test methods that refer to the percentage of pore volume and are mentioned herein by reference are hereinafter referred to as the "mercury infiltration" method and the "nitrogen adsorption" method, respectively.

An alumina support is used in the preparation of the novel catalyst of this invention. The alumina of this invention can contain up to about 10% by weight of other components such as silica. Typically, the support is 0.8 cc by mercury permeability measurements.
/g total pore volume, 0.5cc/g nitrogen adsorption volume, 0
．． Consolidated bulk density of 5 g/cc, nitrogen adsorption volume where 95% of the nitrogen adsorption volume resides in pores with diameters in the range of 100-600 mm, BET surface area of 200 rrF/g,
Pore diameter is in the range of 2000-6000, 0.05c
It should have a macropore volume of c/catalyst volume cc and a micropore volume of 0.3 cc/catalyst volume cc.

By adding catalytic metals, the support parameters can be adjusted to produce the catalysts described below.

In catalyst preparation, the alumina can be dried to remove any free water from it, typically at a temperature of 121°C (250°F) for a period of time ranging from 1 to 24 hours.

The catalyst of the present invention contains molybdenum and at least one metal component selected from Group 1.

The molybdenum is deposited on an alumina support, with an addition of at least 0.0005 g, preferably from 0.0006 to 0.0014 g, of molybdenum trioxide per square meter of catalyst surface area, based on molybdenum trioxide. The Group 1 metal is deposited on the support such that the weight ratio of the Group 1 metal to molybdenum is in the range of 0.10 to 0.50, preferably 0.18 to 0.38.

The preparation of the catalysts described below is specifically described as a two-step impregnation of metal into an alumina support, although other preparation methods may also be used. Only one impregnation step can be used or the catalyst can be
of Catalysis) Volume 72 P255-26
265 (1981).

In a two-step impregnation of an alumina support, the alumina presses can be mixed with an aqueous solution of a salt such as ammonium molybdate, ammonium heptamolybdate, molybdenum pentachloride or molybdenum oxalate. The wet impregnated alumina can then be dried, for example, at a temperature of 121°C (250°F) for between 1 and 24 hours.

The molybdenum-impregnated alumina support can then be contacted with an aqueous solution of a Group I metal, such as nickel nitrate. The wet catalyst was then heated at 121°C (250°F) for 1 to 24 hours.
It can be dried in a second drying stage for an hour. The catalyst is then heated to 427-704°C (827-704°C) following a second drying stage.
Calcining can be performed at a temperature within the range of 0.000-1300° F. for a period of 1 to 24 hours.

The hydrogenation metal component of the prepared catalyst can be used in sulfide or non-sulfide form. If the sulfide form is preferred, the catalyst is pre-sulfidized after calcination, or after calcination and reduction, by methods known in the art. For example, sulfidation is
It can be carried out at atmospheric or elevated pressures at temperatures ranging from 204 to 371 degrees Celsius (400 to 700'' F).
It may be convenient to carry out the same conditions used to initiate the demetalization and desulfurization steps. Mixtures of hydrogen and hydrogen sulfide may be used, although the ratio of hydrogen to hydrogen sulfide is not critical.

Elemental sulfur or sulfur compounds such as mercaptans or carbon disulfide may be used in place of hydrogen sulfide.

The catalyst thus prepared and used in the asphalt-containing hydrocarbon demetallization and desulfurization process of this invention has a mercury permeation measurement of at least 0.5 cc/g + preferably 0.
．． The total pore volume is within the range of 60 to 0.75 cc/g, the macropore diameter is within the range of 1000 to 10000,
Macropore volume of 0.02 to 0.20 cc/catalyst volume cc, and at least 0.12, preferably 0.20 to 0
．． It has a macropore volume of 32 cc/catalyst volume CC.

The pore diameter of the macropore volume is within the range of 2000 to 6000, and the macropore volume is 0.035 to 0.075c.
c/catalyst volume cc, and the pore diameter of the micropore volume is preferably within the range of 100 to 400 pores. Furthermore, the catalyst of the invention has a molecular weight of at least 0.3, preferably 0.3.
Nitrogen adsorption volume of 40-0.55 cc/g, at least 0
．． 4° Consolidation density preferably from 0.50 to 0.70 g/cc - at least 100, preferably from 13'0 to 175
rrF/g and the micropore volume comprises at least 70, preferably 80-95% of the nitrogen adsorption volume.

The effect of catalytic metal concentration in a specific pore structure was
It was determined by preparing seven catalysts according to a stepwise method. The properties of the prepared alumina supported catalyst and the properties of the commercially available catalyst (6) are shown in Table 1 below: Catalysts 1-5 had large macropores (8000); Catalysts 6 and 8 had large macropores Catalyst 7 also had small macropores (800). These catalysts were operated at a hydrogen pressure of 0.4 LH3V, 171 kg/cn cage pressure (2430 ps i g) and a standard liter of hydrogen gas per liter of feedstock ratio of 8901
/ j! (SCF'B: standard cubic feet per barrel = 5000) and a circulation rate of 399°C (750'
F) was screened in an asphalt-containing hydrocarbon demetallization-desulfurization trickle-bed pilot plant operating at temperatures of F). The feedstock used was desalinated Venezuelan crude oil with the following tests: API degree, 'PI 9.1 Sulfur, wt% 3.3 Nitrogen, wt% 0.61 Nickel, ppm 87 Vanadium, p p m 360 carbon residue
15.2 The product quality data obtained after 8 days of operation are shown in Figures 1-3.

Figure 1 reveals that the amount of macropore fraction, i.e., the size, does not affect the sulfur concentration of the product, and that desulfurization increases with increasing molybdenum concentration in 100-600 human diameter pores. Desulfurization is optimized with a molybdenum addition of at least 0.0005 grams of molybdenum trioxide per square meter of surface area.

For these catalysts with pore structures in the 100-600 diameter range, the diffusion of organic sulfur molecules is not a limiting factor.

Figures 2 and 3 reveal the criticality of using large macropores (with pore sizes in the range of 1000 to 10000) in the demetalization of residual hydrocarbon fractions. Although the macropore fraction of catalyst 7 is essentially the same as that of catalysts 1-5, the demetalization effect of catalyst 7 is significantly smaller, demonstrating the significantly better diffusion ability of the large macropores.

To allow large metal-containing molecules to react catalytically on all parts of the catalyst particles, i.e.
With the need for macropores established, experiments were conducted to determine the amount of macropore volume and the optimal size of the pores in the macropore volume. Since increasing the macroporosity is accompanied by a decrease in the catalytically active micropores per unit volume, the amount of macroporosity should be optimized to maintain demetalization and desulfurization catalytic activity.

A series of alumina supported catalysts were prepared using the two-step impregnation method described above. The properties of the prepared catalyst are shown in Table 2 below: Table 2 □, g/cc 0.3960.4290.3590.
3960.7550.2590.2640.286□
1.8B 2.692.211.491.392,73
2.542.476 kg, □ The catalyst in Table 2 was heated at 0.5 LH3V, 141 kg/c4 cage pressure (2000 psig) hydrogen pressure and circulation rate 356
1/N (SCFB2000) and 371℃ (7
The feedstock used was a 1'1exican M
aya) The zAPI degree that was the atmospheric pressure column bottoms, "API
7.5 Sulfur, wt% 4.7 Nickel, ppm 7B Vanadium, ppm The sulfur and metal concentrations for each of the 40B run products are shown in Table 2.

Since a linear relationship exists between product metal and molybdenum content for catalysts with the same amount and size of macropores, and by using the above product data in Table 2, the reactor 100-6 per 100cc volume
The curves shown in FIGS. 4 and 5 can be drawn for a catalyst having 0.50 g of molybdenum in 0.00 mm diameter pores and having a macropore ratio in the range of 2,000 to 6,000 mm. Fourth
Figures 5 and 5 show that when the amount of macropore fraction is less than 0.03 cc/reactor volume cc, diffusion is inhibited;
．． It is shown that macropore ratios above 0.8 cc/cc of catalyst volume have little effect on diffusion enhancement. 0.03
A macropore ratio range of 5 to 0.07'5 cc/cc of catalyst volume optimizes the desired diffusion properties of the catalyst. 6000～
A similar plot for pores in the 10,000 diameter range shows no discernible trend, thereby indicating that 2 as a macropore.
A pore size range of 000 to 6000 diameters is preferred.

Two types of catalysts were prepared to demonstrate the effectiveness of this invention. Catalyst 17 contained 103.96 g of ammonium heptamolybdate (81.5% MOO:+) and 45.4 ml of ammonium hydroxide in 236.0 g of calcined 0.08 cm (1/32 inch) alumina extrudates. It was prepared by impregnating 3fiOml of an aqueous solution. 12 of this material
It was oven dried at 1°C (250°F) and then calcined at 538°C (1000'F) for 10 hours. Then, the calcined material was added (81 nickel nitrate hexahydrate 100.0.9
g and (bl 18.31% TiOz TiC1a stabilized amine aqueous solution 312.69 g).
326 ml) was impregnated. Heat the material to 121°C (250°C)
°F) for approximately 27 hours and finally calcined at 121 °C (1000 °F) for 10 hours.

Catalyst 1 day contains 82.17 g of ammonium heptamolybdate (81.5% MOO3) and 35.9 ml of ammonium hydroxide in 187.0 g of 0.08 cm (1/32 inch) calcined alumina extrudate. 300m of aqueous solution
1 was impregnated. The material was heated to 121℃ (250'
F) in a dryer, then dried at 538°C (
Calcined at 1000°F. Next, Calcination Materials Co., Ltd. (a
) 79.05 g of nickel nitrate hexahydrate and (bl 1
B, 2 of 01χTiO□-TiC14 stabilized aqueous solution
275 ml of aqueous solution containing 48.22 g was impregnated. The material was dried in an oven at 121°C (250°F) for approximately 27 hours, and finally at 538°C (1000°C) for 10 hours.
F) Calcined.

As shown in Table 3 below, the prepared catalysts have the desired amounts of macropore fraction, 0.043 and 0.041 cc/catalyst volume cc, respectively, and micropore fraction, 0.20 and 0.24 cc/catalyst volume cc, respectively. have The catalyst is 0.3
LH3V.

Hydrogen pressure of 169 kg/cn gauge pressure (2400 pisg) and 890 N/jl! (SCFB 5000
Merey Cam
po) Sorted at the pilot plant operated using crude oil feedstock.

Table 3 Hornworm ωr Ministry No. 4
17 18 饋O i M.

i Main yarn surface hand total rope diameter [1- 0C 0C 0C < Water button diameter range 200 [ 400 [ ] 1 Consolidated bulk density, g/cc O, 653,
0,70400c Nie MoO3g/rd O,0010
00,0012710 [20,0012710] The feedstock examination and product oil produced in the operation are shown in Table 4 below. 78. for catalysts 17 and 18, respectively.
1% and 78.9% desulfurization, 83.3% and 8 respectively
A demetalization of 6.9% was obtained.

Table 4 PI degree, 'API 17.8 20.9 2
2.5 Sulfur, wt% 2.28 0.50 0
．． 48 Nitrogen, weight% 0.41 0.34 0
．． 31 Nickel ppm 55 17 1
5 Vanadium ppm 220 29 21 It is desirable that the shape of the catalyst particles used in the demetalization-desulfurization process have a high geometric surface area and a high compaction density for use in the reactor. Although not limited to, 0.0
8 cm (1/32 inch) cylindrical extrudates are preferred.

The demetalization-desulfurization reaction carried out according to the method of this invention is
After relatively rapidly increasing the starting temperature in the presence of a catalyst for asphalt-containing hydrocarbons, from about 316 to
454°C (600-850°F), preferably 343-850°F
It is carried out at a temperature maintained in the range of 427°C (650-800'F). The reaction is 35.2-211 kg/c
a gauge pressure (500-3000 psig), preferably 105.5-176 kg/ad gauge pressure (150
0-2500 psig) in the presence of a partial pressure of neat hydrogen. Hydrogen gas (at least 60% purity)
159 liters (Harrell) of the feed through the reaction zone
Atasu 28,250~282,000 standard liters (100
0 to 10,000 standard cubic feet), preferably 562
50~168750 standard liter (2000~6000
standard cubic feet) (SCFB).

The liquid volume of oil per volume of catalyst (Ll(S
V) maintaining the space velocity of V) within the reaction zone.

[Brief explanation of the drawing]

Figure 1 is a graph showing the relationship between product sulfur and the concentration of molybdenum in catalyst pores of 100 to 600 diameters.
FIG. 3 is a graph showing the relationship between the vanadium concentration in the hydrocarbon product and the molybdenum concentration in the micropores. FIG. 3 is a graph showing the relationship between the nickel concentration in the hydrocarbon product and the micropore volume. Figure 1! . Figure 2 Figure 3 Ml io kI [toocc ar-, vstm~mAmz
itrermr=prya Soribjiso Medilla A Hibiki (Figure 4 υ51Mo4iLR*'++12000~6000A
m5L'1lIC'A71 Tuna is soft and wise Figure 50.5yMoasz-IT 2o00~e;oooA
MJjL411=8 has -r4 macros.

Claims (1)

[Claims] 1. Molybdenum deposited on an alumina support and VII
a catalyst comprising a Group I metal, wherein said catalyst has a total pore volume of at least 0.4 cc/g by mercury permeation measurements;
A catalyst having a macropore volume of 0.02 to 0.20 cc/cc of catalyst volume and a micropore volume of at least 0.12 cc/cc of catalyst volume. 2. The macropore volume is within the range of 0.035 to 0.075 cc/catalyst volume cc, and the pore diameter of the macropore is 20
The catalyst according to claim 1, wherein the catalyst has a diameter of 00 to 6000 Å. 3. A catalyst according to claim 2, in which the molybdenum is deposited on the alumina support in such a way as to provide a loading of at least 0.0005 g of molybdenum trioxide per square meter of catalyst surface. 4. The catalyst according to claim 3, wherein the addition is in the range of 0.0006 to 0.0014 g of molybdenum trioxide per square meter of catalyst surface. 5. The catalyst according to claim 3, wherein the micropore volume is within the range of 0.20 to 0.32 cc/catalyst volume cc. 6. The catalyst according to claim 5, wherein the pore diameter of the micropore volume is within the range of 100 to 400 Å. 7. The catalyst of claim 3 comprising a Group IVB metal deposited on the alumina. 8. Contacting an asphalt-containing hydrocarbon containing sulfur and metals under hydrogenation conditions with hydrogen and a catalyst comprising molybdenum and Group VIII metals precipitated on an alumina support, and wherein said catalyst was determined by mercury permeation measurements. at least 0
．． Total pore volume of 4cc/g, 0.02-0.20cc/
a macropore volume of catalyst volume cc, and at least 0.1
A method for demetallizing and desulfurizing residual hydrocarbons, characterized in that the catalyst has a macropore volume of 2 cc/cc of catalyst volume. 9. The macropore volume is within the range of 0.035 to 0.075 cc/catalyst volume cc, and the pore diameter of the macropore is 20
9. The method according to claim 8, wherein the thickness is within the range of 00 to 6000 Å. 10. The method of claim 9, wherein the deposition of molybdenum onto an alumina support is carried out in such a way as to provide a loading of at least 0.0005 g of molybdenum trioxide per square meter of catalyst surface. 11. The method of claim 10, wherein said catalyst also includes a Group IVB metal deposited thereon. 12. Micropore volume of catalyst is 0.20~0.32cc
12. The method according to claim 11, wherein the catalyst volume is within the range of cc/catalyst volume.