JPH04277031A - Novel hydrogenation catalyst having precious metal deposited thereon and hydrogenating method using same - Google Patents

Abstract

PURPOSE: To provide an improved hydrogenation catalyst having a high activity to a heavy feedstock for removing nitrogen atoms from a heavy feedstock as well as a hydrogenating method utilizing the same catalysts. CONSTITUTION: A catalyst composition comprises about 0.005 to 5.0 wt.% of Pt, Pd, Rh or Ir, about 0.5 to 5 wt.% of Ni and/or Co, about 3 to 18 wt.% of Mo and alumina. Pt, Pd, Rh or Ir is supported on alumina in the catalyst composition by utilizing a precursor selected from dithiocarbametes, dithiophosphates, dithiophosphinates, xanthates or thioxanthates. Also a method for removing nitrogen atoms from a hydrocarbon feedstock utilizing the catalyst composition is provided.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to catalysts for removing heteroatoms, particularly nitrogen atoms, from petroleum and synthetic fuel feedstocks. The catalyst comprises at least one group V on a refractory support.
a Group III metal, at least one Group VI metal, and 1
Contains various precious metals. The noble metals are supported on the support by using specific noble metal precursors such as xanthates and dithiocarbamates. The invention also relates to a hydrotreating method using the catalyst.

0002

BACKGROUND OF THE INVENTION Hydrotreatment of petroleum feedstocks and their various boiling point fractions is becoming increasingly important due to ever more demanding product quality requirements. Moreover, the oil industry anticipates a time when it will have to switch to relatively high boiling point feedstocks derived from materials such as coal, tar sands, oil shale, and heavy crude oil. Raw materials derived from such materials generally contain significant more harmful components such as sulfur, nitrogen, oxygen, halogens and metals. As a result, considerable quality improvements are required to reduce the content of such components, thereby
It is necessary to make it more suitable for further steps such as fluid catalytic cracking and/or pyrolysis and/or catalytic reforming.

Hydroprocessing of hydrocarbonaceous feedstocks is well known in the art and typically involves treating the feedstock with hydrogen in the presence of a supported catalyst under hydroprocessing conditions. . The catalyst typically comprises a Group VI metal on a refractory support with one or more Group VIII metals as promoters. Hydrogenation catalysts that are particularly suitable for hydrodesulfurization or hydrodenitrogenation generally contain molybdenum on alumina and are promoted with metals such as cobalt, nickel and iron. Cobalt-promoted molybdenum on alumina is most widely used for hydrodesulfurization, while nickel-promoted molybdenum on alumina catalyst is most widely used for hydrodenitrogenation.

Hydrotreating catalysts containing platinum are also known. U.S. Patent No. 3,422,000 states:
Hydrotreating with a catalyst consisting essentially of 0.005-5% by weight platinum-based metal and 4-30% by weight molybdenum oxide supported on alumina is disclosed, the catalyst being resulfurized. . Catalysts containing molybdenum along with nickel, cobalt, or both are widely available today, but nevertheless have limitations in removing heteroatoms from heavy feedstocks such as heavy coking gas oils and coal-derived gas oils. be. As the feedstock becomes heavier, the content of aromatic hydrocarbons condensed and uncondensed with heteroatoms increases. These condensed aromatic compounds can strongly adsorb onto the catalyst sites, slowing down the rate and reducing the extent of heteroatom removal. Therefore, there is a need in the art for improved hydrogenation catalysts that have high activity for such heavy feedstocks, especially when the heteroatom to be removed is nitrogen.

[0005]

OBJECTS OF THE INVENTION The object of the present invention is to provide an improved hydrogenation catalyst having high activity for heavy raw materials and hydrogenation treatment using the same for removing heteroatoms from heavy raw materials. The purpose is to provide a method.

[0006]

SUMMARY OF THE INVENTION According to the present invention, approximately 0.
005 to 5.0% by weight of a noble metal, about 0.5 to 5% by weight of at least one Group VIII metal, and about 3 to 18% by weight of at least one Group VIII metal.
A catalyst composition is provided that includes a weight percent Group VI metal and a refractory support. Here, the noble metal is supported on a refractory carrier by using a precursor represented by ML2 when it is Pt or Pd, and a precursor represented by ML3 when it is Rh or Ir. be done. M is a noble metal, L is a ligand selected from dithiocarbamate, dithiophosphate, xanthate, thioxanthate, and L has a sufficient number of carbon atoms to dissolve the noble metal complex in the oil. It is an organic group with

[0007] Also, according to the present invention, about 0.005 to 5
．． Using a catalyst composition comprising 0% by weight of a noble metal, about 0.5-5% by weight of at least one Group VIII metal, and about 3-18% by weight of a Group VI metal, and a refractory support. An improved hydroprocessing method for removing heteroatoms from a hydrocarbonaceous feedstock is provided, wherein the feedstock is treated at hydroprocessing conditions in the presence of hydrogen. Here, the noble metal is a precursor represented by ML2 when it is Pt or Pd, and ML3 when it is Rh or Ir.
It is supported on a refractory carrier by using a precursor represented by: M is a noble metal, L is a ligand selected from dithiocarbamate, dithiophosphate, xanthate, thioxanthate, and L has a sufficient number of carbon atoms to dissolve the noble metal complex in the oil. It is an organic group with

In a preferred embodiment of the invention, the noble metal is platinum and the platinum precursor is a xanthate or a dithiocarbamate. In another preferred embodiment of the invention, the catalyst is about 5 to 15
% by weight of Mo, 1-5% by weight of Ni(Co), and 0.5% by weight.
01-2.5% by weight of platinum.

[0009] Hydrocarbon fractions and unfractionated feedstocks (whol
A variety of feedstocks, including e-feeds, can be hydrotreated by the catalyst of the present invention. Non-limiting examples of such feedstocks include petroleum residue feedstocks, as well as organic solvents, light, medium and heavy petroleum distillates; other feedstocks include coal derived liquids, shale oil and tar sands. There is derived heavy oil.

In practicing the present invention, a heteroatom-containing feedstock, particularly a high nitrogen content feedstock, is contacted with hydrogen under hydrodenitrogenation conditions in the presence of the supported catalyst of the present invention. The catalyst is composed of one noble metal, at least one Group VIII metal, and at least one Group VI metal supported on an inorganic oxide support. The noble metal is present in an amount of about 0.005 to about 5% by weight, preferably about 0.01 to about 2.5%, most preferably 0.1% by weight, based on the total weight of the catalyst.
Present in an amount of ~1% by weight.

Suitable noble metals include platinum, palladium, rhodium, and iridium. Platinum and rhodium are preferred, and platinum is more preferred. The Group VIII metal is present at about 0.5-5% by weight, preferably about 1-4% by weight. Preferred Group VIII metals include Ni, F
e, and Co, with Ni being the most preferred. A preferred Group VI metal is Mo, about 3-20% by weight, preferably about 5-15%, more preferably about 8-14% by weight.
Present in % by weight.

[0012] In the preparation of the catalyst of the present invention, the use of certain noble metal precursors is essential. Noble metal precursors suitable for use in the present invention are: ML2 when M is Pt or Pd;
When it is h or Ir, it is expressed as ML3.

L is a ligand selected from dithiocarbamates, dithiophosphates, xanthates, and thioxanthates. Here, L is an organic group having a sufficient number of carbon atoms to make the noble metal complex soluble or highly dispersed in the hydrocarbon solvent or feedstock. For example, the organic group may be selected from alkyl, aryl, substituted aryl, and ether groups. Generally, the number of carbon atoms in the organic group is about 4-30. Dithiocarbamates and xanthates are preferred. Examples of preferred xanthates have the formula:

[0014]

[Chemical formula 3] (R1 —O-R2 —O-
CSS) nMm [wherein, R1 is an alkyl group (linear, branched or cyclic); an alkoxy-substituted alkyl group; an aryl group; or a substituted aryl group, and R2 is a linear or branched alkylene group , M is a noble metal, m is the oxidation number of the noble metal, and n is an integer of 1 to 4, preferably 2 to 3. ] It is an alkoxyalkyl xanthate represented by

Preferably R1 is a linear alkyl group,
It is a branched alkyl group or an alkoxy-substituted alkyl group. Most preferably R1 is a straight chain alkyl group. The number of carbon atoms in R1 can vary over a very wide range, but typically R1 is about 1 to 24, preferably 2
to 12, more preferably 2 to 8 carbon atoms. Typically R2 has about 2 to 8, preferably 2 to 4 carbon atoms. Most preferably R1 and R2 each have 2 to 4 carbon atoms. R1 and R2 together must contain a sufficient number of carbon atoms to enable the metal alkoxyalkyl xanthate to dissolve in the oil. Examples of suitable substituents in R1 are alkyl, aryl, alkylthio, ether groups, and the like.

Examples of various metal alkoxyalkyl xanthates that can be used in the practice of this invention include platinum bis(ethoxyethyl xanthate), platinum butoxyethyl xanthate, platinum propyloxyethyl xanthate, platinum isopropyloxyethyl xanthate. , platinum 2-hexyloxyethylxanthate, rhodium trisethoxyethylxanthate, rhodium trisbutoxyethylxanthate, rhodium tris(2-ethoxyethylxanthate), and the like. Noble metal dithiocarbamates,
It can be represented by the general formulas ML2 and ML3. Here, L is a dialkyl or monoalkyldithiocarbamate group.

Any suitable support material can be used in the catalyst of the invention. Preferred support materials are alumina and silica lumina. A more preferred support material is alumina. Other refractory inorganic compounds may also be present, including, but not limited to, zinc oxide, titanium oxide, magnesium oxide, and the like. Alumina can be any catalyst conventionally used in hydrotreating catalysts. Such alumina generally has a thickness of about 50 to 200 angstroms, preferably about 70 to 1
Average pore size of 50 angstroms and about 100 to about 35
It is a porous amorphous alumina having a surface area of 0 m2/g, preferably about 200-300 m2/g.

Group VI and Group VIII (Ni, Fe,
Co) metals can be prepared using incipient wetness techniques well known in the art.
can be applied to the carrier using any suitable technique, such as que). However, noble metals are introduced into the catalyst using the precursor complexes previously disclosed in this invention. For example, the catalyst may initially contain Group VI and VII
It may be prepared by impregnating a carrier with an aqueous solution in which a group I metal salt is dissolved. The support may then be dried, calcined, and impregnated with the noble metal precursor in a suitable solvent such as acetone.

The invention can also be practiced by adding the noble metal precursor directly to the feedstock and adding a conventional presulfided Mo and Ni and/or Co hydrotreating catalyst. Another example of a catalyst preparation method of the present invention includes impregnating the presulfided hydrotreated catalyst described above in a solution of the noble metal complex in a suitable organic solvent.

The heteroatom removal conditions, particularly hydrodenitrogenation conditions, will depend on the nature of the feedstock being treated, the nature of the nitrogen atoms being removed, the nature of the complex used, and the desired conversion, if any. It varies considerably depending on things like the degree of the rate. However, in general, the following conditions apply: naphtha boiling at about 25°C to 210°C, about 170°C to 35°C;
Diesel fuel that boils at 0°C, heavy gas oil that boils at about 325°C to 475°C, lubricating oil feedstock that boils at about 290°C to 500°C, or substances that boil at about 575°C or higher.
These are typical conditions applied to the hydrodenitrogenation of resid oils containing from 0 to about 50% by weight.

[0021]

[Table 1]
Table A ──────────
──────────────────────
Raw material temperature Gauge pressure Space velocity Hydrogen gas velocity
°C kg/cm2 (psig) V/V/hr
SCF/B ────────────────
────────────────── Naphtha
100-370 10.5-56.2 (
150-800) 0.5-10 100
-2000 Diesel 200-400
17.6-105.5 (250-1500) 0.
5-6 500-6000 Heavy diesel oil 260-430 17.6-175.8 (2
50-2500) 0.3-4 1000-
6000 Lubricating oil 200-450
7.0-210.9 (100-3000) 0.
2-5 100-10,000 Residual oil
340-450 70.3-351.6
(1000-5000) 0.1-2 2000-
10,000 ────────────────
──────────────────

The following examples are intended to illustrate the invention and are not intended to limit it in any way.

[0023]

[Example] Example 1 Synthesis of platinum bis(2-ethoxyethylxanthate) (PtEEX) A solution of 6.7 g of potassium 2-ethoxyethyl xanthate (KEEX) dissolved in 200 ml of deionized water was stirred with a magnetic stirrer. Stirred and to this was added a filtered solution of potassium tetrachloroplatinate in 150 ml of deionized water. The initially reddish-brown solution became cloudy and a yellow precipitate slowly separated out. 3 of the mixed liquid
After continued stirring for an hour, the precipitate was filtered off and washed well with deionized water. The precipitate was air-dried and recrystallized from acetone-water to give 4.5 g of yellow-orange crystals with a melting point of 83-84°C (yield: 80
%) was obtained.

Example 2 Synthesis of palladium bis(2-ethoxyethylxanthate) (PtEEX) This compound was prepared from 9.5 g of KEEX and 6.52 g of tetrachloropalladate potassium salt following the procedure described above for PtEEX. did. A yellow shiny crystalline solid with a melting point of 70° C. was obtained in a yield of 93%.

Example 3 Synthesis of rhodium tris(2-ethoxyethylxanthate) (RhEEX) This compound was prepared from 1.92 g of sodium hexachlororhodium(III) and 4.2 g of KEEX according to the procedure described above for PtEEX. Prepared. Melting point 75-76℃
An orange-brown crystalline solid was obtained.

Example 4 Samples were presulfided with a commercially available hydrotreating catalyst under the trade name KF-840, sold by Akzo Chemical, and then treated with various concentrations of the above noble metal precursors dissolved in acetone. The final catalyst shown in Table I was obtained. KF-8
The 40 catalyst is an alumina-supported catalyst with approximately 12
．． Contains 7 wt% Mo, 2.5 wt% Ni, and 6.4 wt% P2O5, and has a surface area of about 135 m2/g.
and a pore volume of approximately 0.38 cc/g.

[0027]

[Table 2]
Table I ────────────
────────────────────── Catalyst Additive Catalyst abbreviation
Description of catalyst ────────
──────────────────────────
── A CS2 2.8 g KF-8
40 Commercially available Ni/Mo Al2O
3 catalyst B KF/
Pt KF-840 (3.75
g) + PtEEX (0.404 g) C
KF/Rh
KF-840 (3.75 g) + RhE
EX (0.87 g)D
KF/Pd KF-8
40 (3.75 g) + PdEEX (0.61
5 g) E KF
/Pt500 KF-840 (3.75
g) + PtEEX (0.101 g) F
KF/Pt500(i
mp) KF-840 (3.75 g) + Pt
EEX (0.101 g) ──────────
────────────────────────

[
In all experiments, 32-42 mesh KF-84 was presulfided with 10% H2S of H2.
0 was used. The activity of the catalyst was measured in a gas flow-through autoclave compatible with magnadrive. The reaction temperature was 425°C, and the pressure was 140.6 kg weight/cm2 H2 (20
00 psig H2), residence time was maintained at 4 hours, stirring rate at 1500 rpm, and hydrogen flow rate at 320 cc/min. Each experiment involved 75 g of coal-derived gas oil and 3.75 g of KF-840 (Mo+Ni=
6055 ppm) was used. Catalysts B, C, D and E
That is, the EEX complex of Pt, Rh and Pd was added directly to the feedstock together with pre-sulfided KF-840. Catalyst F
For this purpose, presulfurized KF-840 was impregnated by pore-filling method with an acetone solution of PtEEX. The experiments were carried out in a conventional manner, with all gaseous products analyzed by mass spectrometry and liquid products identified by elemental analysis. The results obtained are shown in Table II.

The properties of the raw materials are as follows: C=88
．． 9%; H=7.99%; S=0.321%; O=1.
85% (calculated value) H/C ratio = 1.05 Boiling point of fraction: ~204°C (400°F) = 0;
343°C (650°F) = 10.8%; 343°C + = 8
9.2%

[0030]

[Table 3]
Table II ──────────
────────────────────────
Catalyst # HDS*
1 HDN*2 H/C
ratio ────────────────────
──────────── A KF-8
40 64.8 80.5
1.254 B KF/Pt
75.5 92.5
1.269 C KF/Rh
80.1 87.2 1.2
69 D KF/Pd 81.
6 82.1 1.269
E KF/Pt500 90
．． 3 94.2 1.267
F KF/Pt500(imp) 9
0.1 94.5 1.32
──────────────────────
──────────── *1 Degree of hydrodesulfurization *2 Degree of hydrodenitrogenation

[0031]
From Table II it is clear that the HDN is very significantly improved for Pt and Rh. Much to my surprise,
Pt has greater advantages at low concentrations than at high concentrations. Furthermore, impregnation also appears to improve the H/C ratio. These results are extremely surprising. Table III below
are comparative data for conversion of C1-C2 and total C1-C4 as well as product liquids at 200°C and 200-340°C.

[0032]

[Table 4]
Table III ────────────
──────────────────────
Catalyst # C1 ~ C4 C1 ~ C2
200℃- 200~340℃ ──────
──────────────────────────
── A 9.5
4.6 12.9 31.
0 B 4.8
2.6 12.4 36.8
C 5.3 2
．． 8 12.9 35.0
D 5.5 2.
8 13.5 32.3
E 3.9 1.4
15.5 36.8
F 7.4 1.8
16.0 38.2
──────────────────────────
───────

Compared with the conventionally used catalyst, that is, KF-840, the HD of the catalyst of the present invention is
The average values of N are clearly different. Furthermore, the catalyst of the present invention produces less gas and increases the yield of naphtha and distillate. The following examples demonstrate the precursor complex PtE
In addition to the method of the present invention using EX, the preparation of platinum-doped KF-840 by a conventional incipient wetness method using inorganic chloroplatinic acid is described.

Example 5 Pt-doped (0
．． Preparation of a 4%) catalyst A 100 g sample of air-exposed KF-840 was stored over water overnight to reach equilibrium moisture. The weight of the sample after exposure was 119.2 g. This was transferred to a filter and covered with water to a 1/8" layer on top of the solids. The sample was bubbled with carbon dioxide for 1 hour. The sample was poured with 16 ml of deionized water. 1.0165 to
g of hexachloroplatinic (IV) acid and 0.0 g of hexachloroplatinic (IV) acid.
216g of concentrated hydrochloric acid was added. Furthermore, carbon dioxide was bubbled for 4 hours. The supernatant was decanted and the sample was air dried. Next, it was dried under reduced pressure at 100°C overnight and calcined at 427°C for 3 hours. The final product was 87.7g. This catalyst was named Catalyst G.

Example 6 Preparation of 0.3% Pt-doped catalyst with PtEEX 10% H2 S/H2 in a porcelain dish at 345°C for 16 hours
0.404g to 50.0g of KF-840 sulfurized with
A solution of PtEEX in 40 ml of acetone was added with manual stirring. The small amount of complex remaining on the porcelain dish was washed off with 5 ml of acetone. The catalyst was air dried for 1 hour and then dried in a vacuum desiccator at 110° C. overnight. This catalyst was named Catalyst H.

Example 7 0.15% Pt in PtEEX
Preparation of Doped Catalyst The title catalyst was prepared according to the method described in Example 6,
It was named Catalyst I.

Example 8 0.05% Pt in PtEEX
Preparation of Doped Catalyst The title catalyst was prepared according to the method described in Example 6,
It was named Catalyst J.

Example 9 In this experiment, the Baton Rouge
Catalysts G, H, J, and KF-840 were compared for improving the quality of light catalyst circulating oil (LCCO). The raw material has the following properties: S = 1.47%; N = 557 ppm; 10.7° AP
I results are shown in Table IV.

[0039]

[Table 5]
Table IV
Conditions: 315°C; 2.0 LHSV; 3500 S
CF/B; Gauge pressure 84.4 kg/cm2 (1200 psi) ─
──────────────────────────
────────
Catalyst G
Catalyst H
KF-840 (KF-8
40+0.4%Pt)*3 (KF-840+0.3
% Pt/PtEEX) ────────────
────────────────────── Product S% 0.36 0.39
0.38 Product N
, ppm 192 138
101°API
17.1 16.7
16.8 ──────
──────────────────────────
─── *3 K impregnated with 0.4% platinum using hexachloroplatinic acid as a precursor
F-840

As can be seen from this table, the catalyst of the present invention can be prepared using KF-840, which is the state of the art, or a standard catalyst using a precursor such as high concentration platinum but hexachloroplatinic acid. It shows better HDN than KF-840 impregnated with a conventional impregnation method.

Example 10 In this experiment, catalysts H, I, J and KF were tested for improving the quality of light catalyst circulating oil as described in Example 9.
-840 was compared. The purpose of this is to confirm that the method of the present invention is effective even when doping with platinum at a low concentration. The results are shown in Table V.

[0042]

[Table 6]
Table V Conditions: 315°C; 0.85 LHSV; 3500 SCF
/B; Gauge pressure 84
．． 4kg weight/cm2 (1200psig) ────
──────────────────────────
──────
Catalyst H Catalyst I Catalyst J
(KF-84
0+ (KF-840+
(KF-840+
KF-840 0.3%Pt)
0.15%Pt) 0.05
%Pt) ──────────────────
──────────────── Product S%
0.238 0.232
0.232 0.
224 Product N, ppm 17.0
0.3 0.6
3.3 °API
19.0 19.4
19.4 19
．． 4 ──────────────────────
──────────────

As can be seen from the table, all the catalysts of the present invention are significantly more active for HDN than the standard catalyst, ie KF-840. Surprisingly, even at low platinum doping levels, the catalysts still maintain their activity with HDN.

Example 11 A 1.27 cm (1/2 inch) diameter fixed bed counterflow reactor with 5
g of KF-840 was charged. Coal-derived middle distillate feedstock (
0.270% S, 0.958% N distillate) and coal-derived vacuum gas oil (0.318% S, 1.026% N, VGO)
was used to measure the activity of various catalysts. At the start of the test, decanethiol was added to the middle distillate feed to sulfidize the catalyst (4% S uptake). In all cases, the hydrogen pressure was 140.6 kgf/cm2 (2000p
sig) and the processing gas rate is 6000scf/bb
It was maintained at l. Further conditions and results are shown in Table VI. At the end of the test, remove the catalyst from the reactor,
It was replaced with 5 g of presulfurized KF-840 impregnated with 0.15% Pt in PtEEX. Pre-sulfurization is 10% at 340℃
Performed with H2 in H2S. Impregnation was performed by a pore filling method from an acetone solution, followed by drying under reduced pressure to remove residual acetone. The conditions and results are shown in Table VII.

[0045]

[Table 7]
Table VI ────────────
────────────────────────
Raw material Temperature (°C) LHSV N in product
kHDN*4 ──────────
──────────────────────────
Distillate oil 365 0.2 96
0.99 Distillate oil 365 0.1 8
0.74 distillate oil
365 0.8 3526
0.94 Distillate oil 365
0.4 1579 0.
86 Distillate oil 365 0.4
4653 0.68 Distillate oil 400 0.4 70
0.96 Distillate oil 4
25 0.4 50
0.53 VGO 425
0.4 850/2800 0.25/
0.15 VGO 425 0.2
1600/3800 0.09/0.05 ─
──────────────────────────
──────── *4 First-order rate constant of hydrodenitrogenation reaction

[0046]

[Table 8]
Table VII ────────────
────────────────────────
Raw material Temperature (°C) LHSV N in product
kHDN ────────────
────────────────────────
Distillate oil 343 0.4 538
2.40 Distillate oil
343 0.1 22
1.26 Distillate oil 343
0.8 3475
1.75 Distillate oil 365 0.4
227 1.58
Distillate oil 365 0.2 41
1.27 Distillate oil
343 0.4 2118
1.27 Distillate oil 365
0.2 48
1.22 VGO 365 0.
4 3164 0.54
VGO 365 0.2 16
92 0.41 VGO
365 0.1 455
0.37 VGO 400
0.2 253
0.36 VGO 425 0.2
204/916 0.20/0.1
2 ──────────────────────
────────────

The data in the above table shows that the Pt promoted catalyst is superior to the commercially available catalyst in terms of HDN behavior. Furthermore, as shown in Figure 1, a plot of HDN rate constant versus time for oil is
It is shown that promotion by Pt dramatically reduces the rate of catalyst deactivation.

[Brief explanation of the drawing]

[Figure 1] 140.6kg weight/cm2 H2 (2000p
sig), a commercial alumina-supported Ni/Mo catalyst (KF-84) in a fixed bed counterflow reactor at 427°C (800°F).
0) for the hydrodenitrogenation reaction of vacuum gas oil derived from coal. PtEE
As X, the rate constant of the same catalyst with 0.15% Pt added is also shown. The rate constants reveal that the Pt promoted catalyst is very superior. The horizontal axis represents the number of days, and the vertical axis represents the first-order rate constant.

Claims (10)

[Claims] 1. About 0.005-5.0% by weight of a noble metal, about 0.5-5% by weight of at least one Group VIII metal, and about 3-18% by weight of a Group VI metal. , and a refractory support, wherein the noble metal is Pt.
or a catalyst composition in which the noble metal is supported on a refractory carrier by using a precursor represented by ML2 when the noble metal is Pd, and a precursor represented by ML3 when the noble metal is Rh or Ir. (In the formula, M is a noble metal,
L is a ligand selected from dithiocarbamate, dithiophosphate, dithiophosphinate, xanthate, thioxanthate, and L is an organic ligand having a sufficient number of carbon atoms to dissolve the noble metal complex in oil. It is the basis. ). [Claim 2] The noble metal is selected from Pt and Rh.
A catalyst composition according to claim 1. 3. The Group VI metal is molybdenum,
Catalyst composition according to claim 1, wherein the group VIII metal is Ni and/or Co. [Claim 4] The ligand L has the formula [Formula 1] (R1 —O-R2
-O-CSS)n Mm [wherein, R1 is an alkyl group (linear, branched or cyclic); an alkoxy-substituted alkyl group; an aryl group; or a substituted aryl group, and R2 is a linear or branched M is a noble metal, m is the oxidation number of the noble metal, and n is 1 to 4. The catalyst composition according to claim 1, which is represented by: 5. A catalyst composition according to claim 4, wherein R1 is a straight-chain alkyl group having 2 to 12 carbon atoms. 6. About 0.005-5.0% by weight of a noble metal, about 0.5-5% by weight of at least one Group VIII metal, and about 3-18% by weight of a Group VI metal. , and a refractory support, wherein the noble metal is Pt.
or a catalyst composition in which the noble metal is supported on a refractory carrier by using a precursor represented by ML2 when the noble metal is Pd, and a precursor represented by ML3 when the noble metal is Rh or Ir. (In the formula, M is a noble metal,
L is a ligand selected from dithiocarbamate, dithiophosphate, dithiophosphinate, xanthate, thioxanthate, and L is an organic ligand having a sufficient number of carbon atoms to dissolve the noble metal complex in oil. It is the basis. ) for the removal of heteroatoms from a hydrocarbonaceous feedstock, the method comprising treating the feedstock under hydrotreating conditions in the presence of hydrogen. [Claim 7] The noble metal is selected from Pt and Rh.
The method according to claim 6. 8. The Group VI metal is molybdenum,
7. A method according to claim 6, wherein the group VIII metal is Ni and/or Co. [Claim 9] The ligand L has the formula [Formula 2] (R1 —O-R2
-O-CSS)n Mm [wherein, R1 is an alkyl group (linear, branched or cyclic); an alkoxy-substituted alkyl group; an aryl group; or a substituted aryl group, and R2 is a linear or branched M is a noble metal, m is the oxidation number of the noble metal, and n is 1 to 4. ] The method according to claim 6. 10. The method of claim 6, wherein R1 is a straight-chain alkyl group having 2 to 12 carbon atoms.