KR20190031388A - Catalyst precursor for hydrocracking and method for hydrocracking of heavy oil using thereof - Google Patents

Abstract

The present invention relates to a catalyst precursor for a hydrocracking reaction having a structure represented by chemical formula 1: Mo(CO)_6-x-2yL_xL′_y, and reacting with sulfur in heavy oil to produce a molybdenum disulfide catalyst. In chemical formula 1, a compound of chemical formula 1 contains at least one of L or L′, L is a ligand of coordination number 1 containing phosphorus as a central element, L′ is a ligand of coordination number 2 containing phosphorus as a central element, x is an integer of 0 to 6, and y is an integer of 0 to 3.

Description

TECHNICAL FIELD The present invention relates to a catalyst precursor for hydrocracking reaction and a method for hydrocracking a heavy oil using the catalyst precursor.

The present invention relates to a catalyst precursor which reacts with sulfur in heavy oil to form a molybdenum disulfide catalyst.

Generally, the coke used in the steel industry is produced by carbonizing coking coal. At this time, a high-boiling point organic material having a high carbon ratio is obtained. This is called coal tar. Generally, carbon black, naphthalene, and pitch are produced through pyrolysis at a high temperature of 1200 K or more in order to recycle the produced coal tar. Carbon black, naphthalene, pitch and the like produced in this way are generally used as a tire or cement admixture. However, such carbon black, naphthalene, pitch and the like have relatively low added value and have a limited use range.

Therefore, various studies have been conducted on a method of using higher value added coal tar from the steel industry. In addition, due to the increase in crude oil heaviness and impurity content worldwide, the production cost of residual oil from refinery facilities is also increasing, resulting in a heavy burden on post-treatment processes such as existing desulfurization equipment . On the other hand, referring to the world energy demand prediction report provided by the Organization of Petroleum Exporting Countries, it is expected that the demand of the residue fuel will greatly decrease, while the demand of light oil will greatly expand. Therefore, there is a great interest in the slurry-phase hydrocracking reaction technology as a technology for upgrading the low-grade heavy crude oil which has no restriction on the impurity content and can ensure a high yield.

Commercial catalysts applied to such slurry phase hydrocracking can be largely classified into heterogeneous iron oxide based superabsorbent and homogeneous organometallic dispersing catalysts depending on the type of mixing with high-grade oil. In case of heterogeneous iron oxide-based catalyst, economical catalyst supply is possible but the reaction pressure and reaction temperature controlled by excess hydrogen supply can be optimized under relatively severe conditions, resulting in problems of high capital investment cost and operating cost . To solve this problem, a catalyst composed of an organic compound ligand which has a uniform distribution in the transition metal and the reactant has been devised. Fuel, 186, 442-448 (2016) discloses a heavy oil degradation reaction using a catalyst in which palladium is supported on magnetite. However, in the case of the conventional transition metal complex catalysts, the impurity coke is about 3 wt% There is a problem that it is produced in large quantities.

Fuel, 186, 442-448 (2016)

It is an object of the present invention to provide a catalyst precursor capable of increasing the selectivity to low boiling point liquid products during the hydrogenolysis of heavy oils and inhibiting the production of toluene insoluble by-products.

Another object of the present invention is to provide a catalyst precursor capable of producing a high yield liquid product using heavy crude oil as a raw material.

The catalyst precursor for the hydrogenolysis reaction according to the present invention has a structure represented by the following Formula 1 and reacts with sulfur in the heavy oil to produce a molybdenum disulfide catalyst.

[Chemical Formula 1]

Mo (CO) _6-x-2y L _x L ' _y

The compound of formula (1) comprises at least one L or L '

L is a ligand of coordination number 1 containing phosphorus as a central element,

L 'is a ligand of coordination number 2 including phosphorus as a central element,

x is an integer of 0 to 6 and y is an integer of 0 to 3.]

In the catalyst precursor for hydrocracking reaction according to an embodiment of the present invention, the compound of Formula 1 may be a compound represented by Formula 2 or Formula 3 below.

(2)

[In the formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is an integer of 1 to 6.

(3)

[In the formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 Y is a (C1-C5) alkylene, and y is an integer of 1 to 3. The compound of the formula (I)

In the catalyst precursor for a hydrogenolysis reaction according to an embodiment of the present invention, the molybdenum disulfide catalyst may be a molybdenum disulfide disulfide catalyst doped with phosphorus (P).

In the catalyst precursor for a hydrogenolysis reaction according to an embodiment of the present invention, the phosphorus-doped molybdenum disulfide catalyst may contain 0.01 to 0.08 mol of phosphorus per mol of molybdenum atom.

In the catalyst precursor for a hydrogenolysis reaction according to an embodiment of the present invention, the heavy oil may be a hydrocarbon having a hydrogen atom / carbon atom ratio of 1 or less and a sulfur atom content of 0.1 wt% or more.

The present invention also provides a method for hydrocracking heavy crude oil, and a method for hydrocracking heavy crude oil according to the present invention comprises mixing a heavy hydrocarbon oil and a catalyst precursor of Formula 1 to produce a molybdenum disulfide catalyst.

[Chemical Formula 1]

Mo (CO) _6-x-2y L _x L ' _y

The compound of formula (1) comprises at least one L or L '

L is a ligand of coordination number 1 containing phosphorus as a central element,

L 'is a ligand of coordination number 2 including phosphorus as a central element,

x is an integer of 0 to 6 and y is an integer of 0 to 3.]

In the method of hydrolysis of heavy oils according to an embodiment of the present invention, the compound of Formula 1 may be a compound represented by Formula 2 or 3.

(2)

[In the formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is an integer of 1 to 6.

(3)

[In the formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 Y is a (C1-C5) alkylene, and Y is an integer of 1 to 3. " (C 1 -C 20)

In the hydrogenolysis method of heavy oil according to an embodiment of the present invention, the molybdenum disulfide catalyst may be a molybdenum disulfide disulfide catalyst doped with phosphorus (P).

In the method for hydrocracking heavy oil according to an embodiment of the present invention, the catalyst precursor may be added in an amount of 0.01 to 5 wt% of the total reactants.

In the method of hydrocracking a heavy oil according to an embodiment of the present invention, the step of producing the molybdenum disulfide catalyst may be performed at 300 to 500 ° C and 10 to 200 atm.

The catalyst precursor according to the present invention reacts with sulfur in the heavy oil to produce a molybdenum disulfide catalyst doped with phosphorus (P), which improves selectivity for low boiling point liquid products and inhibits the formation of by-products There are advantages to be able to.

FIG. 1 is a graph showing XRD analysis of catalyst components after the reaction of a catalyst precursor for hydrocracking reaction according to an embodiment of the present invention.

Hereinafter, the catalyst precursor for the hydrogenolysis reaction according to the present invention will be described in detail. Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

The present invention relates to a catalyst precursor for a hydrogenolysis reaction having a structure represented by the following general formula (1) and reacting with sulfur in heavy oil to produce a molybdenum disulfide catalyst (MoS ₂ ).

[Chemical Formula 1]

Mo (CO) _{6 - x - 2y} L _x L ' _y

The compound of formula (1) comprises at least one L or L '

L is a ligand of coordination number 1 containing phosphorus as a central element,

L 'is a ligand of coordination number 2 including phosphorus as a central element,

x is an integer of 0 to 6 and y is an integer of 0 to 3.]

When the catalyst precursor according to the present invention is used for the hydrocracking reaction using the catalyst precursor for hydrocracking reaction, the production of coke, which is a by-product, can be suppressed while the ratio of the liquid product is high.

The molybdenum disulfide catalyst according to an embodiment of the present invention may be a molybdenum disulfide disulfide catalyst doped with phosphorus (P). Specifically, when the compound of the formula (1) is mixed with heavy oil, reaction with sulfur contained in the heavy oil occurs to produce molybdenum disulfide (MoS ₂ ). The nanosize particles grown by collecting the molybdenum disulfide are subjected to hydrogenolysis Thereby acting as a catalyst for the reaction. At the same time, in the molybdenum metal complex having a ligand containing phosphorus as a central element, phosphorus (P) is generated while the molybdenum is separated and the resulting phosphorus is mixed with molybdenum disulfide and consequently phosphorus-doped Thereby producing a molybdenum disulfide catalyst. When the hydrogenolysis reaction is carried out using the phosphorus-doped molybdenum disulfide catalyst, the generation of the by-product coke can be reduced by 75% or more, more specifically by 85% or more compared to the case of using only the molybdenum disulfide catalyst There is an advantage. At this time, the molybdenum disulfide disulfide nanosize disulfide serving as a catalyst may be an acicular particle having a particle size of 3 to 50 nm, more specifically, 5 to 20 nm. In this range, the hydrocracking reaction can be performed efficiently have.

Specifically, the phosphorus-doped molybdenum disulfide catalyst according to an embodiment of the present invention may contain 0.01 to 0.08 mol, preferably 0.02 to 0.05 mol, of atoms relative to 1 mol of molybdenum atoms. Due to the excessive amount of phosphorus in the above-mentioned range, it is possible to prevent the degradation of the catalytic activity of the molybdenum disulfide catalyst and to remarkably lower the rate of formation of coke by phosphorus doping.

Specifically, the compound of Formula 1 may be a compound represented by Formula 2 or Formula 3 according to an embodiment of the present invention.

(2)

In formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6- C12) aryl (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is an integer from 1 to 6;

(3)

In formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6- Y is a (C1-C5) alkylene, and y is an integer of 1 to 3. The term " alkyl "

Better,, R ₁ to R ₇ are each (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) aryl (C1-C10) alkyl or (C1-C10) alkyl (C6-C12) aryl days And x may be an integer of 0 to 6, specifically a natural number of 1 to 6, more specifically a natural number of 1 to 3, y is an integer of 0 to 3, specifically a natural number of 1 to 3, More specifically, it may be 1 or 2. There is an advantage that the hydrocracking reaction can be efficiently performed while reducing the impurity content by the molybdenum ligand in the above-mentioned range. More specifically, the ligand of the catalyst precursor for the hydrogenolysis reaction according to an embodiment of the present invention is one or more selected from diphenylphosphinomethane, diphenylphosphinoethane, triphenylphosphine, and diphenyl para- But the present invention is not limited thereto.

The heavy oil according to an embodiment of the present invention may be a hydrocarbon compound in which the ratio of hydrogen atoms / carbon atoms is 1 or less and a large amount of carbon is added to hydrogen. Further, the heavy oil may contain sulfur atoms in an amount of 0.1 wt% May be a hydrocarbon compound containing 0.1 to 5% by weight. More specifically, the heavy oil according to one embodiment of the present invention may be a reduced-pressure residual oil, an atmospheric residue, an oil sand or a non-totemane, but the present invention is not limited thereto.

The present invention also provides a method for the hydrocracking of heavy oils. The method for hydrocracking a heavy oil according to the present invention comprises mixing a heavy oil and a catalyst precursor of Formula 1 to produce a molybdenum disulfide catalyst.

[Chemical Formula 1]

Mo (CO) _{6 - x - 2y} L _x L ' _y

The compound of formula (1) comprises at least one L or L '

L is a ligand of coordination number 1 containing phosphorus as a central element,

L 'is a ligand of coordination number 2 including phosphorus as a central element,

x is a natural number of 0 to 6 and y is a natural number of 0 to 3.]

More specifically, the compound of formula (1) may be represented by the following formula (2) or (3).

(2)

[In the formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is a natural number of 1 to 6.

(3)

[In the formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 Y is a (C1-C5) alkylene, and Y is a natural number of 1 to 3.

Specifically, in the method of hydrogenolysis of heavy oil according to an embodiment of the present invention, the molybdenum disulfide catalyst may be a molybdenum disulfide disulfide catalyst doped with phosphorus (P). As described above, when the hydrogenolysis reaction is carried out using the phosphorus-doped molybdenum disulfide catalyst, the production of the by-product coke is 75% or more, more specifically 85% or more as compared with the case of using only the molybdenum disulfide catalyst % Or more.

Furthermore, in the method of hydrocracking heavy oil according to an embodiment of the present invention, the catalyst precursor may be contained in an amount of 0.01 to 5 wt%, preferably 0.01 to 2 wt%, more preferably 0.05 to 1 wt% . It is possible to prevent the problem that the ligand is detached and contained as an impurity due to the mixing of a large amount of the catalyst precursor, while exhibiting sufficient catalytic activity in the above-mentioned range.

In addition, in the method of hydrogenolysis of heavy oil according to an embodiment of the present invention, the step of producing the molybdenum disulfide catalyst may be carried out at 300 to 500 ° C under a pressure of 10 to 200 atm. In the above-mentioned range, there is an advantage that the molybdenum disulfide catalyst can be efficiently formed by the reaction of the molybdenum complex with sulfur, and the production cost and catalyst deformation due to the harsh environment can be prevented.

The present invention also provides a process for preparing a catalyst for hydrocracking reaction using a catalyst precursor for hydrocracking according to an embodiment of the present invention. Specifically, the process for preparing a catalyst for hydrocracking reaction according to the present invention comprises reacting a compound of the formula (1) with sulfur contained in a heavy oil to produce a phosphorus-doped molybdenum disulfide catalyst. That is, in the method for preparing a catalyst for hydrocracking reaction according to the present invention, the preparation of the catalyst is carried out in the reaction system, and the catalyst is reacted with the heavy oil as the reactant. In the case of carrying out the hydrocracking reaction of heavy oil using the catalyst prepared by the catalyst production method according to the present invention, it is possible to minimize the production of by-products such as coke and the like and to increase the liquid product such as naphtha, There is an advantage that it can be formed.

Hereinafter, the present invention will be described in detail with reference to examples. The embodiments described below are only for the understanding of the invention, and the present invention is not limited to the embodiments.

[Example 1]

  The materials used as the feedstock in the hydrocracking evaluation are the decompressed residues obtained from Hyundai Oilbank. The properties are summarized in Table 1. In order to analyze the characteristics of the decompressed residual oil, elemental analysis (Model: Thermo Scientific Flash 2000, Detector: X-ray fluorescence analysis, (Thermo / ARL QUANT'X), inductively coupled plasma-atomic emission spectrometry (ICP-AES; Model: Thermo Fisher Scientific iCAP 6500Duo) and SARA (Saturates, Aromatics, Resins and Asphaltenes) Latroscan MK6s) and the boiling point distribution was determined using the ASTM D7169 (GC-SIMDIS) method.

division Composition and Properties of Vacuum Residue Elemental analysis C 83.4 wt% H 10.1 wt% S 5.88 wt% N 0.54 wt% Metal analysis Ni 72.3 ppm V 309 ppm SARA analysis Saturate 5.0 wt% Aromatic 51.8 wt% Resin 18.4 wt% Asphaltene 24.8 wt% Fractional distillation IBP ~ 524 ° C 10.3 wt% 524 to FBP 89.7 wt%

Mo (CO) ₄ (PPh ₃ ) ₂ Complex  synthesis

1 g (3.8 mmol) of Mo (CO) ₆ and 2.2 g (8.37 mmol) of triphenylphosphine are dissolved in 10 ml of THF and 10 ml of diethylene glycol dimethyl ether, and the mixture is reacted at 150 ° C. for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature to remove the supernatant, and the precipitate was washed three times with ether to obtain a catalyst precursor for hydrocracking reaction.

¹ H-NMR (CD ₂ Cl ₂ , ppm): 7.55 (m 8H) 7.37 (m, 12H)

¹³ C-NMR (CD ₂ Cl ₂ , ppm): 212.12 133.10 133.03 129.01 128.06

FT-IR: 1877 cm < ^-1 > (Mo- CO &

Manufactured Complex  Used Hydrocracking reaction

The hydrocracking reaction of vacuum residue (VR) was carried out under the following conditions using the synthesized Mo precursor. 20 g of vacuum residue was placed in a high-temperature high-pressure reactor having a capacity of 100 ml, and a catalyst precursor was charged at about 250 wppm (based on Mo element). The reactor was repeatedly subjected to hydrogen filling and purging three times or more, bar to prepare the hydrogenolysis reaction. After the temperature of the prepared reaction product was raised to 430 ° C, hydrocracking reaction was performed for 1 hour at the same time as stirring (1500 rpm). Upon completion of the reaction, the solution was rapidly cooled to room temperature through a cooling coil. The gaseous components were collected in a Tedlar bag and analyzed by gas chromatography equipped with TCD and FID. The liquid product and the coke were analyzed for solubility in toluene And the liquid product was analyzed for boiling point according to ASTM D7169 (GC-SIMDIS) method. In order to confirm the chemical composition and structure of the precursor after the reaction, the product obtained by pyrolyzing the mixture of the precursor and the raw material was analyzed by XPS and XRD, respectively, and the results are shown in Table 2 and FIG. Are shown in Table 3.

ingredient Content (atom%) C 88.88 O 6.61 P 0.06 S 2.92 Mo 1.53

Referring to Table 2 and FIG. 1, it can be confirmed that phosphorus is doped in the MoS ₂ catalyst.

[Example 2]

Mo (CO) ₄ (Dppe) complex  synthesis

1 g (3.8 mmol) of Mo (CO) ₆ and DPPE (di (phenylphosphino) ethane) (1.8 g, 4.54 mmol) were dissolved in 10 ml of THF and 10 ml of diethylene glycol dimethyl ether, Deg.] C for 20 h. After the reaction was completed, the supernatant was removed by cooling with RT, and the precipitate was washed three times with ether to obtain a clean compound.

¹ H-NMR (CD ₂ Cl ₂ , ppm): 7.55 (m 12H) 7.37 (m, 18H) 2.54 (m, 4H)

FT-IR: 2010, 1941, 1877 cm -1 (Mo- CO -)

Manufactured Complex  Used Hydrocracking reaction

The hydrocracking reaction was carried out using the complex prepared in the same manner as in Example 1, and the results are shown in Table 3.

[Example 3]

Mo (CO) ₄ (TEP) 2 complex  synthesis

Triethyl phosphite (TEP) (0.19ml, 1.14mmol) was added to 0.1ml (0.38mmol) of Mo (CO) 6 in 5ml of toluene and reacted in a closed vessel at 110 ° C and 200W under microwave for 10 minutes. Export. This reaction was repeated 5 times in total, and after the reaction was completed, the reaction solution was cooled, and the supernatant was removed. The reaction solution was washed three times with hexane and recrystallized.

_{^{1 H-NMR (CDCl 3,}} ppm): 3.996 (m, 6H), 1.264 (m, 9H)

¹³ C-NMR (CDCl ₃ , ppm): 204.83, 59.93, 16.15

FT-IR: 1934, 1897 cm -1 (Mo- CO -)

Manufactured Complex  Used Hydrocracking reaction

The hydrocracking reaction was carried out using the complex prepared in the same manner as in Example 1, and the results are shown in Table 3.

[Comparative Example 1]

Molybdenum 2- Ethylene hexanoate  Preparation of Catalyst

30.0 g of molybdenum acid (Aldrich, MoO3≥85.0%) and 102.2 g of 2-ethylhexanoic acid (Aldrich, 99%) were mixed together in a 300 ml flask by the method of patent KR1396181 and 100 ml while purging with / min of N ₂ was heated at 200 ℃ for 1 hour. Changing the purging of a mixture of 20% H2 and 80% N ₂ and held at 200 ℃ for 12 hours. The reaction yielded molybdenum 2-ethylhexanoate with 14.7 wt% Mo. The results were confirmed by 1 H-NMR and 13 C-NMR, as follows.

¹ H-NMR (CDCl ₃ , ppm): 2.256 (m, 1H), 1.620 (m, 4H), 1.283

¹³ C-NMR (CDCl ₃ , ppm): 183.38, 47.31, 31.58, 29.66, 25.28, 22.74, 13.90, 11.74

Using the prepared catalyst Hydrocracking reaction

The hydrocracking reaction was carried out using the complex prepared in the same manner as in Example 1, and the results are shown in Table 3.

[Comparative Example 2]

The hydrocracking reaction was carried out under the same conditions as in Example 1 except that the molybdenum 2-ethylhexanoate precursor synthesized in Comparative Example 1 was added with one equivalent of PPh _3. The results are shown in Table 3 Respectively.

Using the prepared catalyst Hydrocracking reaction

The hydrocracking reaction was carried out using the complex prepared in the same manner as in Example 1, and the results are shown in Table 3.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Gas product (%) 6.2 7.5 6.7 6.1 6.7 Liquid Product (%)  Naphtha (IBP-177 < 0 > C) 7.1 8.8 8.8 11.7 13.0 ^A MD (177-343 ℃) 20.6 21.2 21.5 25.0 17.0  Gas oil (343-524 DEG C) 38.0 36.4 35.1 37.7 34.4  Residue (524 ° C-FBP) 27.2 25.5 29.7 16.9 15.6 Toluene insoluble (%) 0.5 0.5 0.3 3.0 3.3 Liquid Yield (%) ^b 66.1 66.5 63.3 63.5 64.4 Conversion (%) ^c 72.8 74.5 70.3 71.1 84.4

a. M.D. : Middle distillate

b. 100% -Gas product (%) - Residue (%) - Toluene insoluble (%)

c. 100% -Residue (%)

As described above, referring to Table 2 and FIG. 1, it can be confirmed that phosphorus-doped molybdenum disulfide is formed when a molybdenum complex precursor containing phosphorus as a central element is used. When the hydrogenolysis reaction is carried out using the catalyst precursor containing the phosphorus-doped molybdenum disulfide, the content of the liquid product is high and the production of the toluene-insoluble component (coke), which is a by-product, is remarkably lowered have. In addition, this merit is a phenomenon that occurs when phosphorus is doped in molybdenum disulfide. In the case where a phosphorus compound contained as a ligand in the embodiment is added separately from molybdenum (Comparative Example 2), the advantages similar to those of the present invention are not shown .

Claims (10)

A catalyst precursor for a hydrogenolysis reaction having a structure represented by the following formula (1) and reacting with sulfur in heavy oil to produce a molybdenum disulfide catalyst.
[Chemical Formula 1]
Mo (CO) _{6 - x - 2y} L _x L ' _y
The compound of formula (1) comprises at least one L or L '
L is a ligand of coordination number 1 containing phosphorus as a central element,
L 'is a ligand of coordination number 2 including phosphorus as a central element,
x is an integer of 0 to 6 and y is an integer of 0 to 3.] The method according to claim 1,
Wherein the compound of formula (1) is a compound represented by the following formula (2) or (3).
(2)

[In the formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is an integer of 1 to 6.
(3)

[In the formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 Y is a (C1-C5) alkylene, and y is an integer of 1 to 3. The compound of the formula (I) The method according to claim 1,
Wherein the molybdenum disulfide disulfide catalyst is a molybdenum disulfide disulfide catalyst doped with phosphorus (P). The method of claim 3,
Wherein the phosphorus-doped molybdenum disulfide catalyst comprises 0.01 to 0.08 mol of phosphorus relative to 1 mol of molybdenum atom. The method according to claim 1,
Wherein the heavy oil is a hydrocarbon having a ratio of hydrogen atoms / carbon atoms of 1 or less and containing sulfur atoms in an amount of 0.1 wt% or more. Mixing a heavy oil and a catalyst precursor of formula (1) to produce a molybdenum disulfide catalyst.
[Chemical Formula 1]
Mo (CO) _{6 - x - 2y} L _x L ' _y
The compound of formula (1) comprises at least one L or L '
L is a ligand of coordination number 1 containing phosphorus as a central element,
L 'is a ligand of coordination number 2 including phosphorus as a central element,
x is an integer of 0 to 6 and y is an integer of 0 to 3.] The method according to claim 6,
Wherein the compound of formula (1) is a compound represented by the following formula (2) or (3).
(2)

[In the formula 2, R ₁ to R ₃ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 (C1-C20) alkyl or (C1-C20) alkyl (C6-C12) aryl, and x is an integer of 1 to 6.
(3)

[In the formula 3, R ₄ to R ₇ are each hydrogen, hydroxy, halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C12) aryl, (C6 Y is a (C1-C5) alkylene, and Y is an integer of 1 to 3. " (C 1 -C 20) The method according to claim 6,
Wherein said molybdenum disulfide catalyst is a molybdenum disulfide disulfide catalyst doped with phosphorus (P). The method according to claim 6,
Wherein the catalyst precursor is added in an amount of 0.01 to 5 wt% of the total reactants. The method according to claim 6,
Wherein the step of producing the molybdenum disulfide catalyst is carried out at a temperature of 300 to 500 DEG C and 10 to 200 atm.

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