KR101555000B1 - Hydrocracking catalysts for heavy oil upgrading - Google Patents

Abstract

The present invention relates to a hydro-cracking catalyst having nickel and molybdenum as active metals supported on a Goethite carrier, a preparation method thereof and a method for hydro-cracking heavy crude oil by using the same. The catalyst of the present invention is useful as a catalyst for a hydro-cracking process where heavy crude oil such as a vacuum residue, an atmospheric residue, oil sands, bitumen, and the like is converted into high value-added low-boiling-point liquid materials (e.g., naphtha, gasoline and the like).

Description

[0001] The present invention relates to a hydrocracking catalyst for heavy oil upgrading,

The present invention relates to a hydrocracking catalyst in which nickel and molybdenum are supported as an active metal on a Goethite carrier, a method for producing the catalyst, and a method for hydrocracking a heavy hydrocarbon using the catalyst.

Demand for low boiling liquid products such as gasoline, kerosene, diesel, medium distillate, and naphtha products in the petroleum industry is steadily increasing. In order to meet the demand for high-quality low-boiling liquid petroleum products, there is a continuing need for the development of technologies for manufacturing light oil products and petroleum chemical raw materials with higher added value by upgrading low-cost heavy oil generated in the refining process of crude oil .

In recent years, attention has focused on the hydrogenolysis method as a method of decomposing heavy oils and obtaining light oils. The reason for this is that by hydrocracking, intermediate distillation products such as kerosene and diesel as well as gasoline can be obtained and the yield of produced oil can be changed according to the operating conditions, It is suitable for high quality.

Hydrocracking technologies are currently being developed in various petroleum industries, such as the VEBA-Combi Cracking (VCC) process developed in Germany, the Micro-Cat technology developed by Exxon Mobil, the HDH technology developed by INTEVEP of Venezuela , Canada's CANMET process and HC3 technology, SOC technology developed in Japan, and Aurabon technology developed by US UOP company. At the core of these technologies is the development of catalysts with high activity, selectivity and economy. However, there are limits to commercial use due to the cost of catalyst synthesis, the amount of catalyst used, severe reaction conditions (temperature, pressure, reaction time, etc.) and coke formation.

Various catalysts have been developed to solve the problems pointed out in the hydrocracking technology at present. For example, in order to solve the problem of coke formation, catalysts in which transition metals are dispersed (U.S. Patent No. 7,691,256; N. Panariti et al. Applied Catalysis A: General 204 (2000) 203-213] has been developed. In order to increase the hydrocracking efficiency of the heavy oil, a catalyst synthesized by sulfiding the transition metal of the VIB group and the VIIV group in an aqueous medium (U.S. Patent No. 4,557,821, No. 4,824,821) has been developed, but the aqueous catalyst or precursor There is another problem that sintering occurs under hydrogenolysis conditions and catalytic activity is poor. In addition, a catalyst containing phosphorus (P) dispersed to a finer size and a catalyst modified with a sulfur flame [US Pat. No. 5,871,638] have been developed for hydrolysis of coal, heavy residues and waste plastics .

As described above, hydrocracking has been developed variously for a long time as a technique for high-heavy-duty oil, but development of a new catalyst having higher activity and selectivity and improvement of reaction conditions are urgently needed.

1) United States Patent No. 7,691,256 2) U.S. Patent No. 4,557,821, 3) United States Patent No. 4,824,821 4) United States Patent No. 5,871,638

N. Panariti et al. Applied Catalysis A: General 204 (2000) 203-213

The present invention provides a catalyst which is applied to a hydrocracking process and has a high catalytic activity and a high selectivity to a liquid product of a low boiling point and which is supported on a Goethite carrier with nickel and molybdenum SUMMARY OF THE INVENTION

It is another object of the present invention to provide a method for producing the above-described novel catalyst.

Another object of the present invention is to provide a hydrocracking method for producing a liquid product at a high yield by using heavy crude oil as a raw material under the above-mentioned novel catalyst.

In order to solve the above problems, the present invention is characterized in that a Goethite carrier is provided with nickel and molybdenum as an active metal supported on a Goethite carrier.

The present invention also relates to a process for producing a gel by: i) adjusting an iron aqueous solution prepared by dissolving an iron precursor in water to pH 10 to 12; (Ii) aging the resulting gel at 50 to 80 DEG C, filtering and washing, and then drying at 100 to 120 DEG C to obtain Goethite; (Iii) preparing a catalyst in which Goethite, a nickel precursor, and a molybdenum precursor are mixed and stirred in distilled water and then dried to produce a catalyst in which nickel and molybdenum are carried on a Goethite carrier; And iv) calcining the catalyst at 350 to 450 占 폚; And a method for producing the hydrogenolysis catalyst for reforming a heavy oil.

Further, the present invention is characterized by hydrothermal decomposition of heavy oil in the presence of a catalyst in which nickel and molybdenum are supported on a Goethite carrier as an active metal.

The catalyst of the present invention is a multi-metal oxide catalyst in which nickel and molybdenum are supported on a high-temperature support, and exhibits excellent catalytic activity by being applied to hydrocracking reaction of heavy oil.

Therefore, the catalyst of the present invention can be used as a catalyst for the production of high-value-added low-boiling liquid products (for example, gasoline, kerosene, diesel, naphtha, etc.) having a boiling point of 30 ° C to 380 ° C from the vaporization reactors such as vacuum residue, Etc.) in the hydrocracking process.

FIG. 1 is a graph comparing conversion rates and yield changes of the respective products according to the hydrocracking reaction temperature.
FIG. 2 is a graph comparing conversion rates and yield changes of respective products when a hydrocracking reaction is carried out under a single temperature or two-step temperature condition.

The present invention is characterized by a catalyst for reforming a heavy oil, in which nickel and molybdenum are supported as an active metal on a Goethite carrier.

According to a preferred embodiment of the present invention, the catalyst of the present invention contains 1 to 5 wt% of nickel and 3 to 10 wt% of molybdenum based on the total weight of the catalyst.

According to a more preferred embodiment of the present invention, the catalyst of the present invention contains 1 to 3 wt% of nickel and 3 to 8 wt% of molybdenum based on the total weight of the catalyst.

According to another aspect of the present invention, there is provided a process for producing a gel, comprising the steps of: i) adjusting an iron aqueous solution prepared by dissolving an iron precursor in water to pH 10 to 12 to form a gel; (Ii) aging the resulting gel at 50 to 80 DEG C, filtering and washing, and then drying at 100 to 120 DEG C to obtain Goethite; (Iii) preparing a catalyst in which Goethite, a nickel precursor, and a molybdenum precursor are mixed and stirred in distilled water and then dried to produce a catalyst in which nickel and molybdenum are carried on a Goethite carrier; And iv) calcining the catalyst at 350 to 450 占 폚; And a method for producing the hydrogenolysis catalyst for reforming a heavy oil.

The process for preparing the catalyst according to the present invention will be described in detail as follows.

 I) The process is the process of gelling an aqueous solution of iron.

Specifically, an iron precursor is dissolved in water to prepare an iron aqueous solution, and then an aqueous alkali solution is added to the iron aqueous solution to adjust the pH to 10 to 12, thereby producing a gel. The iron precursor used in the present invention is a compound commonly used in the field of catalyst production, and the present invention does not limit the selection of these compounds. Specifically, the iron precursor may be at least one compound selected from iron oxide, iron nitrate, iron sulfate, and the like. The alkali aqueous solution used for gelation may be prepared by dissolving an alkali compound such as a hydroxide, oxide, carbonate, or sulfate of an alkali metal or an alkaline earth metal in water.

Ii) The process is the process of obtaining Goethite.

Specifically, the gel prepared above is aged at 50 to 80 ° C for 12 to 24 hours, filtered and washed, and then dried at 100 to 120 ° C to obtain Goethite.

 Iii) is a process for preparing a catalyst by supporting nickel and molybdenum on a solid support.

Specifically, an aqueous solution prepared by dissolving Goetite, a nickel precursor, and a molybdenum precursor in distilled water is mixed and stirred at room temperature, and then dried to produce a "(Ni, Mo) / Goe "catalyst. At this time, the nickel precursor and the molybdenum precursor used as precursors of the active metal are the compounds commonly used in the field of catalyst production, and the present invention does not limit the selection of these compounds. Specifically, the precursor of the active metal may be at least one compound selected from oxides of metals, halides, alkoxides, nitrate salts, acetate salts, acetoacetonate salts, sulfate salts, ammonium salts and the like. Nickel and molybdenum carried as an active metal may be supported in an amount of 1 to 5 wt% of nickel and 3 to 10 wt% of molybdenum based on the total weight of the catalyst. More preferably from 1 to 3% by weight of nickel and from 3 to 8% by weight of molybdenum based on the total weight of the catalyst.

The process iv) is the process of calcining the (Ni, Mo) / Goe catalyst.

Specifically, the Ni, Mo / Goe catalyst prepared by the above method is calcined at 350 to 450 ° C. for 1 to 4 hours to produce the desired catalyst of the present invention.

The above-described catalyst production method of the present invention has an advantage of not including the step of sulfiding the active metal. In the prior art, sulfurization treatment is performed at the time of preparing a catalyst for hydrocracking so as to have resistance to poisoning of the catalyst by the sulfur component contained in the heavy oil. However, the sulfidation treatment is performed by a separate sulfiding step in the process and by a sulfide There is a disadvantage of causing environmental pollution due to device corrosion and leakage. However, according to the production method of the present invention, a catalyst having excellent activity can be produced without any additional sulfiding treatment.

According to another aspect of the present invention, the present invention features a method of hydrocracking a heavy oil in the presence of the above (Ni, Mo) / Goe catalyst.

The (Ni, Mo) / Goe catalyst of the present invention is a high boiling point low boiling point liquid product having a boiling point of 30 ° C to 380 ° C (for example, a reduced pressure residual oil, an atmospheric residual oil, an oil sand, For example, gasoline, kerosene, light oil, naphtha, etc.) and exhibits excellent catalytic activity.

The hydrogenolysis can be carried out by a method well known in the art using a conventional catalytic reactor. In the experimental examples of the present invention, mainly a slurry type reactor is used, but the reactor used in the present invention is not limited thereto. The hydrogenolysis of the present invention can be carried out at a temperature of 400 to 450 DEG C and an initial hydrogen pressure of 5 to 10 MPa.

According to a preferred embodiment of the present invention, the hydrocracking is carried out while raising the temperature from a room temperature to a temperature gradient while the temperature rising period and the maintaining period are repeated twice. Specifically, the hydrocracking may include a first temperature rising period for raising the temperature from room temperature to 400 to 420 ° C, a first holding period for performing hydrocracking while maintaining the temperature of 400 to 420 ° C, A second temperature rising period for raising the temperature to 30 ° C, and a second maintenance period for performing the hydrocracking while maintaining the elevated temperature. It is preferable that the temperature raising rate in the first temperature rising section and the second temperature rising section is maintained in the range of 3 to 20 占 폚 / min. As described above, when hydrocracking is performed by separating the temperature rising period and the temperature holding period when the present invention performs hydrocracking, it is possible to increase the content of the saturate and the liquid product and further improve the yield of the liquid product Can be obtained.

Upon carrying out the hydrocracking described above, the gaseous product is discharged out of the reactor, and the solid or liquid product is separated from the reactor by an effluent process. The solid or liquid product was centrifuged and filtered through a 0.45 μm syringe filter and analyzed using TLC-FID and TGA analysis equipment.

The present invention will now be described in more detail with reference to the following examples and experimental examples. However, the present invention is not limited to the examples and experimental examples.

[Examples] Preparation of Catalyst

Example 1: Preparation of 1% Ni-4.5% Mo / Goe catalyst

To 100 mL of distilled water was added 40 g of Fe (NO ₃ ) ₃ .9H ₂ O as an iron precursor and stirred for 30 minutes. The gel was generated by adding 2M NaOH aqueous solution so that the pH of the reaction solution became 12. The resulting gel was aged at < RTI ID = 0.0 > 70 C < / RTI > The gel was filtered and washed, and then dried in a vacuum oven at 100 ° C for 24 hours to prepare Goethite.

5 g of goethite was added to 50 mL of distilled water and stirred for 1 hour to prepare a carrier solution. 0.25 g of Ni (NO ₃ ) ₂ · 6H ₂ O as a nickel precursor and 0.43 g of (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O as a molybdenum precursor were added to 10 mL of distilled water in a separate vessel and stirred to prepare a precursor solution . The carrier solution prepared above and the precursor solution were mixed, stirred for 1 hour, dried using a rotary evaporator, and calcined at 400 ° C for 2 hours at a rising temperature of 2 ° C / min. As a result, a catalyst having 1 wt% of nickel and 4.5 wt% of molybdenum supported on the basis of the total weight of the catalyst was prepared, which is hereinafter referred to as 1% Ni-4.5% Mo / Goe catalyst.

Example 2: Preparation of 3% Ni-7.5% Mo / Goe catalyst

A catalyst was prepared according to the procedure of Example 1, except that 0.76 g of Ni (NO ₃ ) ₂ .6H ₂ O as a nickel precursor and (NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O 0.75 g was used. As a result, a catalyst having 3 wt% of nickel and 7.5 wt% of molybdenum supported on the basis of the total weight of the catalyst was prepared, which is hereinafter referred to as '3% Ni-7.5% Mo / Goe' catalyst.

Comparative Example 1: Preparation of 1% Ni-4.5% Mo / γ-Al ₂ O ₃ catalyst

To prepare this catalyst, 5 g of γ-Al ₂ O ₃ (Strem chemical) was added to 50 mL of distilled water and stirred for 1 hour to prepare a carrier solution. 0.25 g of Ni (NO ₃ ) ₂ · 6H ₂ O as a nickel precursor and 0.43 g of (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O as a molybdenum precursor were added to 10 mL of distilled water in a separate vessel and stirred to prepare a precursor solution . The carrier solution prepared above and the precursor solution were mixed and stirred for 1 hour, dried using a rotary evaporator, and finally calcined at 400 ° C for 2 hours under the condition of a rising temperature of 2 ° C / min. As a result, a catalyst having 1 wt% of nickel and 4.5 wt% of molybdenum supported on the basis of the gamma-alumina carrier weight was named as 1% Ni-4.5% Mo / γ-Al ₂ O ₃ catalyst .

Comparative Example 2: Preparation of 1% Ni-4.5% Mo / Fe ₂ O ₃ catalyst

To prepare this catalyst, 5 g of Fe ₂ O ₃ (Sigma-Aldrich) was added to 50 mL of distilled water and stirred for 1 hour to prepare a carrier solution. 0.25 g of Ni (NO ₃ ) ₂ · 6H ₂ O as a nickel precursor and 0.43 g of (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O as a molybdenum precursor were added to 10 mL of distilled water in a separate vessel and stirred to prepare a precursor solution . The carrier solution prepared above and the precursor solution were mixed and stirred for 1 hour, dried using a rotary evaporator, and finally calcined at 400 ° C for 2 hours under the condition of a rising temperature of 2 ° C / min. As a result, a catalyst having 1 wt% of nickel and 4.5 wt% of molybdenum supported on the basis of the weight of the iron oxide carrier was prepared, which is hereinafter referred to as '1% Ni-4.5% Mo / Fe ₂ O ₃ ' catalyst.

[Experimental Example]

The heavy oil used in this experiment is a vacuum residue, and the composition and physical properties of the vacuum residue are summarized in Table 1 below.

division Composition and Properties of Vacuum Residue

Elemental analysis C 84 wt% H 10.71 wt% S 4.84 wt% N 0.14 wt% Other 0.31 wt% Sum 100 wt% H / C mole fraction 1.45
Metal analysis
(ICP analysis) Ni 36.4 ppm V 151 ppm Fe 38.3 ppm Ca 25 ppm Si 198 ppm
SARA analysis
(TLC-FID analysis) Saturate 4 wt% Aromatic 61 wt% Resin 18 wt% Asphaltene 17 wt% Sum 100 wt%


Fractional distillation Room temperature to 150 ° C 0.05 wt% 150-220 C 0.01 wt% 220 to 343 DEG C 4.59 wt% 343-450 DEG C 45.82 wt% 450 to 550 DEG C 34.06 wt% 550 to 900 DEG C 2.01 wt% Residue 13.46 wt% Sum 100 wt%

Experimental Example 1. The yield change of the product according to the hydrocracking reaction temperature

The hydrotreating reaction was carried out at a reaction temperature of 390 to 460 ° C., a hydrogen pressure of 70 bar, and a stirring speed of 600 RPM for 2 hours. The resultant solid, liquid, The yield of gas and the conversion ratio of decompression residual oil are summarized in FIG. The SARA analysis results for the obtained products are shown in Table 2 below.

catalyst Reaction conditions SARA content of product (%) Temperature
(° C) Initial pressure
(bar) time
(h) Appearance Saturate Aromatic Resin Asphaltene

Non-catalyst 390 70 2 Liquid 12 49 14 24 solid N / D N / D N / D N / D 420 70 2 Liquid 20 74 4 N / D solid 5 68 12 14 460 70 2 Liquid 7 86 6 N / D solid N / D 70 23 N / D
1Ni-4.5Mo / Goe
(Example 1) 390 70 2 Liquid 18 60 12 8 solid N / D N / D N / D N / D 420 70 2 Liquid 24 67 7 N / D solid 4 41 17 36 460 70 2 Liquid 15 80 5 N / D solid 3 83 10 2

According to the results of the SARA analysis in Table 2, when the temperature conditions were the same, the content of the saturate product was relatively higher in the catalytic reaction than in the non-catalytic reaction, and the product of the hydrocracking reaction It was confirmed that the most Saturate product content was high. It can be seen that the reaction temperature of 420 ° C is the most optimal temperature in view of the yield and content of the liquid product having a low boiling point.

In addition, FIG. 1 shows conversion rates and yield changes of the respective products when the hydrocracking reaction is carried out under catalytic or non-catalytic conditions. According to Fig. 1, the reaction between non-catalytic and catalytic conditions was not converted to a liquid product at a reaction temperature of 390 캜, but was converted to a solid product only. When the reaction temperature was raised to 400 ° C or higher, the yield of the liquid product was increased. In particular, the catalyst conditions were found to be superior to the non-catalytic conditions in the yield of liquid product. For example, when the temperature was elevated to 420 ° C. under the catalytic condition, the conversion of the liquid product was increased to 62%, and the yield of the liquid product tended to decrease to 53% at 460 ° C. And the conversion to solid products was also increased.

Experimental Example 2. Variation of Product Yield According to Temperature Change by Reaction Time

The reduced-pressure residues having the composition shown in Table 1 were prepared under the conditions of a reaction temperature of 410 to 460 ° C, a hydrogen pressure of 70 bar, and a stirring speed of 600 RPM under the conditions of the catalyst (1Ni-4.5Mo / Goe) The hydrocracking reaction was carried out for 6 hours. As a result, the yields of the resulting solid, liquid and gaseous products and the conversions of the reduced pressure residues were summarized in FIG. The SARA analysis results for the obtained products are shown in Table 3 below.

Reaction conditions
(Catalyst: 1Ni-4.5Mo / Goe) SARA content of product (%) Appearance Saturate Aromatic Resin Asphaltene Single stage: 410 ° C, 70 bar, 6 hours Liquid 27 64 7 N / D solid 6 40 15 37 Single step: 420 ° C, 70 bar, 2 hours Liquid 24 67 7 N / D solid 4 41 17 36.03 Single stage: 460 ° C, 70 bar, 2 hours Liquid 15 80 5 N / D solid 3 83 10 2 First section: 410 DEG C, 70 bar, 2.5 hours
Second section: 430 ° C, 70 bar, 1 hour Liquid 26 67 5 N / D solid 5 50 18 26

According to the results of SARA analysis in Table 3, the content ratio of Saturate, Aromatic, Resin, and Asphaltene shows almost the same result even when the hydrocracking reaction is performed in a single temperature range or two temperature ranges. However, when the reaction was carried out while controlling the temperature in the two-step temperature range, the reaction time was significantly shortened compared with the case of the single temperature condition of 410 ° C, and compared with the reaction at the single temperature condition of 460 ° C, There is an effect that the content can be increased.

FIG. 2 shows the conversion rates and the yield changes of the respective products when the hydrocracking reaction is performed under a single temperature or two temperature conditions. FIG. 2 shows that when the reaction is performed by adjusting the temperature condition in two steps, the yield of the liquid product is improved as compared with the single temperature condition. In other words, the conversion rate was 72 ± 5%, which showed similar results at the single temperature or two temperature condition and the gas product yield was similar to 10 ± 2%. However, the yield of the liquid product was 70% higher in the case of performing the reaction under the control of the temperature in the two steps, but it was relatively low in the case of performing the reaction in the single temperature condition.

EXPERIMENTAL EXAMPLE 3: Yield Change of Product by Catalyst

In order to compare the hydrocracking efficiency according to the catalyst, the decompression residue oil having the composition shown in Table 2 was hydrolyzed under the conditions of a reaction temperature of 450 ° C, a hydrogen pressure of 70 bar, a stirring speed of 600 RPM, and a reaction time of 2 hours Respectively. The yields of solid, liquid, and gas produced as a result of the reaction under each catalyst and conversion ratios of reduced pressure residues are summarized in Table 4 below.

catalyst Conversion Rate (%) Yield of product (%) solid Liquid gas 1% Ni-4.5% Mo / Goe
(Example 1) 77 29 53 20 3% Ni-7.5% Mo / Goe
(Example 2) 78 24 56 19 1% Ni-4.5% Mo / γ-Al 2 O 3
(Comparative Example 1) 77 22 48 26 1% Ni-4.5% Mo / Fe ₂ O ₃
(Comparative Example 2) 62 38 41 24 Goethite 68 32 47 22 Non-catalyst 69 30 38 31

According to the results shown in Table 4, when the conversion ratios alone were compared, the results of the gelatite supported catalysts of the present invention (Examples 1 and 2) were almost equivalent to those of the alumina supported catalyst (Comparative Example 1) Comparative Example 2). However, when the liquid products are compared, it can be seen that the gelatite supported catalyst of the present invention (Examples 1 and 2) is significantly superior to the alumina supported catalyst (Comparative Example 1). Therefore, it can be confirmed that the (Ni, Mo) / Goe catalyst is suitable for carrying out the hydrocracking reaction in which the present invention produces the desired liquid product at a high yield.

Experimental Example 4. Bottom Distribution of Liquid Product

Hydrogenolysis was carried out by the method of Experimental Example 3 above. The results of the TGA analysis and the SARA analysis to compare the boiling point distribution obtained by collecting the liquid products obtained by carrying out the respective catalytic reactions are shown in Table 5 below.

catalyst Non-point distribution of liquid product SARA content of liquid product (%) Room temperature ~ 220 ℃ 220-990C Saturate Aromatic Resin Asphaltene 1% Ni-4.5% Mo / Goe
(Example 1) 86 14 15 80 5 N / D 3% Ni-7.5% Mo / Goe
(Example 2) 73 27 13 85 2 N / D 1% Ni-4.5% Mo / γ-Al 2 O 3
(Comparative Example 1) 64 36 10 84 6 N / D 1% Ni-4.5% Mo / Fe ₂ O ₃
(Comparative Example 2) 69 31 9 88 3 N / D Goethite 61 39 8 86 6 N / D Non-catalyst 62 38 9 85 6 N / D

According to the above Table 5, it can be seen that the liquid product obtained by using the support of the present invention of the present invention (Examples 1 and 2) has a high content of the low boiling point substance. As a result of SARA analysis of the liquid product obtained by carrying out each catalytic reaction, it was found that the liquid product obtained by using the support of the present invention of the present invention (Examples 1 and 2) High. Therefore, it can be confirmed that the (Ni, Mo) / Goe catalyst is suitable as a catalyst for hydrolysis to produce a target naphtha and a low boiling point substance such as gasoline or diesel.

Claims (8)

A hydrocracking catalyst for reforming a heavy oil, wherein a Goethite carrier is loaded with nickel and molybdenum as an active metal and a liquid product having a boiling point of from room temperature to 220 ° C is obtained from the heavy oil.
The method according to claim 1,
A catalyst for reforming a heavy oil reforming catalyst characterized by comprising 1 to 5 wt% of nickel and 3 to 10 wt% of molybdenum based on the total weight of the catalyst.
I) a step of preparing a gel by adjusting an iron aqueous solution prepared by dissolving an iron precursor in water to a pH of 10 to 12;
(Ii) aging the resulting gel at 50 to 80 DEG C, filtering and washing, and then drying at 100 to 120 DEG C to obtain Goethite;
(Iii) preparing a catalyst in which Goethite, a nickel precursor, and a molybdenum precursor are mixed and stirred in distilled water and then dried to produce a catalyst in which nickel and molybdenum are carried on a Goethite carrier; And
Iv) calcining the catalyst at 350 to 450 占 폚;
Of claim 1, comprising the steps of:
The method of claim 3,
Wherein the catalyst is prepared by supporting 1 to 5 wt% of nickel and 3 to 10 wt% of molybdenum based on the total weight of the catalyst.
A process for hydrocracking a heavy oil which is carried out in the presence of a catalyst as defined in claim 1 or 2.
6. The method of claim 5,
Wherein the hydrogenolysis is carried out at a temperature of 400 to 450 DEG C and an initial hydrogen pressure of 5 to 10 MPa.
The method according to claim 6,
Wherein the temperature of the first holding section is 400 to 420 DEG C, and the temperature of the first holding section and the temperature of the second holding section are increased by repeating the temperature rising section and the temperature holding section twice, And the temperature difference between the holding intervals is 10 to 30 占 폚.
8. The method of claim 7,
Wherein the temperature raising rate in the temperature rising period is maintained in the range of 3 to 20 占 폚 / min.

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