KR100931036B1 - Catalyst for Hydrocracking of Crude Oil and Hydrocracking Method Using the Same - Google Patents

Abstract

The present invention relates to a catalyst for hydrocracking crude oil and a hydrocracking method using the same, and more particularly to a foam form having a specific pore volume, pore surface area, pore wall thickness, pore diameter, and pore diameter / thickness. A catalyst in which an active metal is supported on a porous support of the present invention. The catalyst relates to a catalyst for hydrocracking of crude oil having an API (American Petroleum Institute) specific gravity index in the range of 1 to 30 degrees. The present invention relates to a hydrocracking method that can be effectively hydrocracked under conditions, which is environmentally friendly, and can reduce energy and process costs.

Description

Catalyst for hydrocracking crude oil and hydrocracking method using same {Catalysts for hydrocracking of heavy crude oil and hydrocracking method using the same}

According to the present invention, by adding a catalyst for hydrocracking of crude oil having a low specific gravity index (API) and the catalyst, it is possible to hydrocrack under conditions of low temperature and low pressure than before, which is environmentally friendly, and can reduce energy and process costs. The present invention relates to a hydrocracking method.

With the influence of modernization and industrialization around the world, the energy problem used has emerged as the most important problem. In particular, the recent rise in oil prices has highlighted the importance of abundant and cheaper energy sources rather than existing oil resources.

Oil sand is a material that typically contains about 10 to 20% by weight of bitumen in the sand, which is typically useful when the sand is removed and only the bitumen component is extracted and upgraded. Synthetic crude oil (SCO) is a resource. These oil sands are so richly buried that it is possible to secure low-cost raw materials and stable crude oil supply through the related technology and mines. The technology related to oil sands is Canada's most advanced technology, as described above, and its facilities are mainly concentrated in Canada Alberta. These companies include oil sand extraction and oil sand upgrading technology.

Bitumen, which is obtained through the extraction method of oil sands on the ground or underground, is a representative type of super heavy oil or heavy oil, its density is 1000 kg / m ³ or more, high density, API (American Petroleum Institute) specific gravity index is 15 or less It is a substance containing a large amount of impurities such as S, V, and Ni. Such a non-man is basically required to upgrade (upgrading), the typical technology of such a coking (coking) process and hydrocracking (hydrocracking) process. In particular, the hydrocracking process cracks Vitman in a high-temperature and high-pressure hydrogen atmosphere of 500-1000 ° C., and simultaneously causes hydrogenation reaction.

As the catalyst used for the hydrocracking reaction, metal salt form materials such as metal oxides such as Ni, Mo, Fe, Co, V, Cu, Ru, Pt, and Zn, sulfides or phosphates are used. In addition, carriers such as silica and alumina having a high surface area are widely used as the carrier, and are used by dispersing the catalyst on the carrier. However, even in the case of using such a catalyst, the reaction conditions are very severe in high temperature, high pressure, and hydrogen atmosphere, which causes problems in the design, maintenance, and safety of the reactor.

In addition, in the case of crude oil of heavy oil and super heavy oil having a very complicated molecular structure and high molecular weight, high viscosity and low reactivity as a non-man material, it is very important technology to increase the reactivity of the catalyst.

For the hydrocracking reaction of general hydrocarbon oils, techniques for applying a porous catalyst are disclosed in Korean Patent Laid-Open Nos. 2001-31671, 1990-1313, 2004-68161, 2007-73758, 2005-84122, and the like. Known. However, most of the catalysts have a relatively small pore diameter of 1.5 to 30 nm, a surface area of 200 to 1000 m ² / g, and uniformity of pores was not an important factor. That is, as a porous catalyst having a small pore size and a high surface area, the known catalyst is difficult to apply to the hydrocracking of super heavy oil having a low API specific gravity index, such as B2M. There is a need for a hydrocracking process.

It is an object of the present invention to provide a catalyst for hydrocracking crude oil having a low API specific gravity index.

In addition, an object of the present invention is to provide a hydrocracking method that is environmentally friendly and can reduce energy and process costs.

The present invention is a catalyst in which an active metal is supported on a porous support in the form of a foam. The catalyst has a total pore volume of 0.5 to 2.5 cc / g, a pore surface area of 100 to 300 m ² / g, and a pore wall. By providing a catalyst for the hydrocracking of crude oil having an API specific gravity index in the range of 1 to 30 degrees, characterized in that the thickness of 5 to 100 nm, the pore diameter is 30 to 500 nm, the pore diameter / thickness ≥ 2. Solve the problem.

In addition, the present invention is a hydrocracking method characterized in that the hydrolysis of crude oil and hydrogen having an API specific gravity index in the range of 1 to 30 degrees in the presence of the catalyst at a temperature of 100 to 500 ℃ and a pressure of 5 to 200 atm. By providing the above, the above problems are solved.

The present invention provides a catalyst for the hydrocracking of crude oil having a low API specific gravity index, so that hydrocracking is possible under low temperature and low pressure conditions.

In addition, the present invention is capable of hydrocracking the crude oil under conditions of low temperature, low pressure than before, it is environmentally friendly, there is an effect that can reduce the energy and process costs.

The present invention provides a foam having a specific pore volume, pore surface area, pore wall thickness, pore diameter, and pore diameter / thickness in order to provide a catalyst for hydrocracking crude oil having a low specific gravity index (API). Provided is a catalyst in which an active metal is supported on a porous support in a form. In addition, the present invention relates to a hydrocracking method of heavy hydrocarbon oil that can be effectively hydrocracked under low temperature and low pressure conditions by providing the catalyst for hydrocracking of crude oil, which is environmentally friendly and can reduce energy and process cost. .

In the present invention, the crude oil to be hydrocracked has an API specific gravity index of 1 to 30 degrees, and thus, crude oil having a low API specific gravity index has high density, high viscosity, and low reactivity. Therefore, in order to hydrocrack the crude oil, conditions of high temperature and high pressure have been necessary in the past. However, in recent years, the need for abundant and inexpensive energy sources due to the rise in oil prices, the need for a method of hydrocracking crude oil having a low API specific gravity index which is more environmentally friendly, energy and process cost is emerging.

Referring to the present invention in more detail as follows.

The crude oil to be hydrocracked in the present invention has a boiling point of 100 ~ 700 ℃, it is more preferably applicable to those containing a vacuum residue (vacuum residue) in the range of 20 to 70% by weight, the crude oil is more specifically As such, any one selected from Bitumen, oil sand, tar sand, and oil sail may be used.

In the present invention, the crude oil to be subjected to hydrocracking in the present invention has a high molecular weight and high polarity as compared to conventional crude oil. In particular, in the case of Bituman, 20 to 70% by weight of vacuum residue (VR), 2 to 50% by weight of asphaltene, 1 to 10% by weight of sulfur component, and 0.05 to 5% by weight of nitrogen component And relatively high molecular weight components of 0 to 15% by weight of other impurities. These components make hydrocracking reactions involving cracking and hydrogenation reactions very difficult. Conventional catalysts have very small pore volume, surface area and size, so that the conditions for hydrocracking reactions are very severe. There were no drawbacks.

Accordingly, the catalyst for hydrocracking according to the present invention is a catalyst in which an active metal is supported on a porous support in the form of a foam, and the catalyst has a total pore volume of 0.5 to 2.5 cc / g and a pore surface area of 100 to 300. The most technical feature is m ² / g, the pore wall thickness is 5 to 100 nm, the pore diameter is 30 to 500 nm, and the pore diameter / thickness ≧ 2. In this case, when the pore volume is less than 0.5 cc / g, the poor contact with the crude oil of the pores may be difficult to decompose and hydrogenation, and when the volume exceeds 2.5 cc / g, the volume of the catalyst is too large When the pore surface area is less than 100 m ² / g, there may be a problem that the contact surface area with the non-to-man is small, and when exceeding 300 m ² / g may cause a problem of excessive cracking occurs have. In addition, if the thickness of the pore wall is less than 5 nm may cause a problem that the thermal stability of the pores is lowered, if it exceeds 100 nm may cause a problem that the surface area of the pores is too low, the pore diameter is 30 If it is less than nm it may cause a problem that the contact of the high molecular weight, high boiling point of the component of the non-to-man component is bad, and if it exceeds 500 nm may cause a problem that the effective contact surface area becomes small, the above conditions It is advisable to apply a suitable catalyst. In this case, when the pore diameter / thickness is less than 2, a problem may occur in that the porous structure is not sufficiently developed.

In addition, the catalyst according to the present invention may be more preferably in the form of a foam (foam).

In particular, the catalyst according to the present invention can perform hydrocracking more preferably when the pore size is uniform and well connected to each other, and the catalyst has an average pore of pores having a pore diameter in the range of 30 to 500 nm. A catalyst having a diameter of 50 to 200 nm and a volume of pores having a pore size within ± 40% of the average pore diameter may be more preferably 50 to 80% by volume of the total pore volume.

On the other hand, the present invention has the above conditions, and relates to a catalyst in which the active metal is supported on the porous support, the porous support is not particularly limited to a general support applied in the art, for example, alumina , Silica or composite oxides thereof can be used. Particularly, in the case of the complex oxide of alumina and silica, when the hydrocracking reaction is performed, the molar ratio of silica to alumina is 0.01 in consideration of the property of providing an acidic site to the reactants to promote the cracking reaction. The thing of the range of -100 can be used more preferably. In addition, a more preferable example of the porous carrier may be selected from MCM-41, MCM-48, SBA-15 and MCF (meso celluar foam).

In addition, the active metal is combined with hydrogen gas to hydrogenate the bitumen when performing a hydrogenation reaction, a single metal selected from Ni, Mo, Fe, Co, Ti, Mn, Ru, Pd, and Pt Alternatively, an active metal selected from two or more metal compounds can be supported on the carrier.

The method of supporting such an active metal on the carrier is not particularly limited to a manufacturing method commonly used in the art, but may be prepared by, for example, the following method.

Firstly, as a carrier, the total pore volume is 0.5 to 2.5 cc / g, the pore surface area is 100 to 300 m ² / g, the pore wall thickness is 5 to 100 nm, the pore diameter is 30 to 500 nm, A single or composite oxide selected from alumina and silica with pore diameter / thickness ≧ 2 and pores arranged regularly or irregularly is prepared.

50 ~ 90.5% by weight of the support and a precursor aqueous solution containing 0.5 to 9% by weight of the active metal selected from a single metal or two or more metal compounds selected from Ni, Mo, Fe, Co, Ti, Mn, Ru, Pd, and Pt After mixing 50% by mass, heat treatment is performed at 300 to 1000 ° C. under atmospheric, nitrogen, or oxygen atmosphere to obtain a catalyst on which an active metal is supported.

The catalyst for hydrocracking according to the present invention may be more preferably applied to the hydrocracking method because the active metal is contained in the range of 0.5 to 50% by weight based on the total catalyst. In this case, when the active metal component is contained too little, the hydrogenation reaction may be weakened. When the amount is contained in an amount of more than 50% by weight, the pores of the catalyst may be blocked or the hydrocracking reaction may occur. Barrier problem may occur, the active metal component is preferably contained in the above range.

The present invention provides a hydrocracking method for contacting crude oil with hydrogen having an API specific gravity index in the range of 1 to 30 degrees in the presence of the catalyst according to the present invention. There is a technical feature in that hydrocracking of the crude oil is carried out even under pressure conditions of 5 to 200 atm.

The catalyst may be added in a range of 0.1 to 100 parts by mass with respect to 100 parts by weight of the crude oil, and more preferably hydrocracked. In this case, when the catalyst is less than 0.1 parts by weight, a problem may occur that the hydrogenation reaction of the hydrocarbon is less, and when it exceeds 100 parts by mass, a problem that less hydrocracking reaction may occur, the content range of the above range It is good to add.

As a result of hydrocracking crude oil having a low API specific gravity index by the hydrocracking method according to the present invention, it was confirmed that the molar ratio of hydrogen to carbon increased by 10% or more. That is, the present invention provides a catalyst in which an active metal is supported on a porous support in the form of a foam having a specific pore volume, pore surface area, pore wall thickness, pore diameter, and pore diameter / thickness. There is an effect capable of hydrocracking under low pressure conditions.

In addition, the present invention is capable of hydrocracking crude oil having a low API specific gravity index under conditions of low temperature and low pressure, and is environmentally friendly, and has an effect of reducing energy and process costs.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention.

Example 1

In order to prepare a catalyst for hydrocracking, a meso celluar foam (MCF) silica carrier having a regular porous structure was prepared and prepared according to the literature. AM. CHEM. SOC. 2003, 125, 618-619]

50 wt% of the MCF silica carrier prepared as described above and 50 wt% of Mo metal salt, MoCl ₃ , were mixed, dried at 120 ° C., and calcined at about 500 ° C. for 4 hours. .

As shown in FIGS. 1 and 2, the catalyst had a total pore volume of 1.99 g / cc, a surface area of 256 m ² / g, a diameter of 45 nm, and a foam form. The BJH adsorption curve indicates that the average pore diameter of the pores having a pore diameter in the range of 30 to 500 nm is 45 nm, and the volume of pores having a pore size within ± 30% of the average pore diameter is 80 vol% of the total pore volume. It could be confirmed through analysis. In addition, the hydrocracking catalyst prepared as described above was confirmed to have a pore structure in which pores of a constant size are regularly connected. The analysis results are shown in FIGS. 1, 2, 3 and Table 1 below.

Figure 3 shows the hysteresis curve according to the nitrogen adsorption (sorption profile) of the prepared hydrocracking catalyst, showing a very low hysteresis result at the pressure point of the adsorption-desorption amount, the connection of pores is very It was confirmed that it was excellent.

Based on 100 parts by weight of the catalyst prepared above, 400 parts by weight of Vitman was subjected to hydrocracking at a temperature of 200 ° C. and hydrogen at 10 atm pressure.

At this time, the components of the bitumen carbon, hydrogen, nitrogen, sulfur components of 82.84, 10.4, 1.63, 4.78% by weight, respectively, asphaltene component 15% by weight, vacuum residue 45% by weight, A bitumen taken from Athabasca, Canada. The specific gravity of the API specific gravity of this Beatman was 9.

The result of the reaction is shown in Table 2 and FIG. 2 by performing an elemental analysis, thermal behavior analysis.

Examples 2-4

In order to prepare a catalyst for hydrocracking, the carrier shown in Table 1 was named S2 silica, which was dispersed in an aqueous solution using polystyrene particles having a uniform 400 nm particle size as a template, and TEOS was added thereto as a silica raw material. The thickness of the silica layer was about 20 nm to prepare a material having the pore volume, surface area and diameter as shown in Table 1 below. At this time, the S3 carrier had a pore diameter of 100 nm, was prepared in the same manner as the S2 silica, the S4 carrier had a pore diameter of 30 nm, was prepared in the same manner as S2 silica.

Thus prepared 50% by weight of the carrier and Mo metal salt 50% by weight of MoCl ₃ was mixed, dried at a temperature of 120 ℃, and then fired for 4 hours at a temperature of about 500 ℃ and atmospheric conditions.

The catalyst has a total pore volume, surface area, wall thickness and diameter as shown in Table 1 below, is in the form of a bubble, and has a pore structure in which pores of a constant size are regularly connected.

Hereinafter, hydrocracking reaction of heavy hydrocarbon oil proceeded in the same manner as in Example 1. The result of the reaction is shown in Table 2 by performing an elemental analysis.

pore Kinds Volume (cc / g) Surface area (m ² / g) Wall thickness (nm) Average pore diameter (nm) Diameter / thickness Example 1 1.99 256 10 45 4.5 MCF Silica Example 2 1.20 120 20 400 20 S2 Silica Example 3 1.00 200 20 100 5 S3 Silica Example 4 2.10 300 20 30 1.5 S4 Silica Comparative Example 2 0.004 0.8 50 600 12 Commercial silica Comparative Example 3 1.23 780 5 4.7 0.9 SBA15 Silica

Example  5: change in active metal composition

As the active metal, it proceeded in the same manner as in Example 1 except for using the NiSO ₄ metal salt instead of the Mo metal salt. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Example 6: Change of Catalyst Addition in Hydrocracking Reaction

The same procedure as in Example 1 was carried out except that 90 wt% of the MCF silica carrier and 10 wt% of the Mo metal salt of Mo metal ₃ were mixed. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Example 7 Effect of Surface Alumina Introduction in Hydrocracking Reaction

About 10% by weight of AlCl ₃ was added to the MCF silica support, and the same procedure as in Example 1 was carried out except that the material, which was oxidized at 500 ° C. and converted to alumina, was used as a catalyst carrier. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Comparative Example 1

The bitumen was placed in a reactor and subjected to hydrocracking at a temperature of 200 ° C. and hydrogen at 10 atm pressure. At this time, the catalyst for hydrocracking was not further added. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Comparative Example 2

As a carrier, a commercially available porous silica (Junsei, 6H1377) having a pore volume, surface area, and diameter shown in Table 1 above was prepared. At this time, 50% by weight of the carrier and 50% by weight of MoCl ₃ , a Mo metal salt, were mixed, dried at a temperature of 120 ° C., and calcined at a temperature of about 500 ° C. and atmospheric conditions for 4 hours.

The catalyst had the total pore volume, surface area, wall thickness and diameter as shown in Table 1 above.

Hereinafter, the hydrocracking reaction of Beaterman was performed in the same manner as in Example 1. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Comparative Example 3

SBA-15 silica carriers having a regular porous structure were prepared and prepared according to the literature for the preparation of catalysts for hydrocracking. [Dongyuan Zhao, et al. Science 279 , 548 (1998)].

50 wt% of the SBA-15 silica carrier thus prepared and 50 wt% of MoCl ₃ , a Mo metal salt, were mixed, dried at a temperature of 120 ° C., and calcined at a temperature of about 500 ° C. and atmospheric conditions for 4 hours.

The catalyst was in the form of a cylinder, the total pore volume, surface area, wall thickness and diameter as shown in Table 1 above.

Hereinafter, the hydrocracking reaction of Beaterman was performed in the same manner as in Example 1. The result of the reaction is shown in Table 2 by performing an elemental analysis.

Test Example 1: Thermal Behavior Analysis

In Example 3, the Vitusman before hydrocracking, that is, the Vitusman (A) in which the other catalyst is not included in the present invention, and the Beatusman (B) in which the catalyst of Example 3 was mixed were prepared. The sample prepared as described above was subjected to a thermogravimetic analysis of the TA instrument TGA Q500 instrument under nitrogen atmosphere at about 10 mg to 1000 ° C., and is shown in FIG. 4.

Figure 4 shows the results of the pyrolysis experiment showing the amount of pyrolysis of the bitumen according to each decomposition temperature interval, in the case of the bitumen (B) mixed with the catalyst prepared according to Example 3 of the present invention, the ratio without the catalyst Compared with Twoman (A), it was confirmed that the amount of the component having a decomposition temperature of 500 ° C. or more was reduced by four times or more.

Test Example 2: Elemental Analysis

Elemental analysis was performed by using the CHNSO Fisons EA-1108 Elemental Analyzer for about 10 mg of the Vitman sample according to the Examples and Comparative Examples of the present invention, the results are shown in Table 2 below.

At this time, the hydrogen / carbon molar ratio means the degree of hydrogenation, the larger the value, means that the hydrocracking reaction is carried out effectively, so that more hydrogen is added.

nitrogen carbon Hydrogen sulfur Hydrogen / carbon molar ratio Example 1 1.34 79.46 10.95 3.46 1.65 Example 2 0.41 77.44 10.49 3.88 1.62 Example 3 0.35 78.63 10.41 4.09 1.59 Example 4 1.36 83.66 10.77 4.58 1.54 Example 5 1.32 79.56 10.38 3.56 1.55 Example 6 1.32 83.54 10.87 4.81 1.56 Example 7 1.32 79.64 10.93 3.32 1.65 Vittoman before hydrocracking 1.63 82.84 10.40 4.78 1.50 Comparative Example 1 1.46 80.22 10.21 4.67 1.51 Comparative Example 2 0.5 82.56 10.54 5.27 1.52 Comparative Example 3 0.58 80.51 10.08 6.46 1.50

As shown in Table 2, the total pore volume is 0.5 ~ 2.5 cc / g, the pore surface area is 100 ~ 300 m ² / g, the pore wall thickness is 5 ~ 100 nm, the pore diameter is 30 ~ 500 nm It was confirmed that the hydrocracking reaction was effectively performed when the pore diameter / thickness ≧ 2.

In addition, it was confirmed that an effective hydrocracking reaction occurred in the case of Ni based on the change of the active metal, and an effective hydrocracking reaction was performed even when the amount of the active metal added in the catalyst was 0.5 to 50% by weight in the hydrocracking reaction. I could confirm that it happened.

In the conventional catalyst, the hydrogenation reaction hardly occurred due to the hydrocracking reaction, so that there was no change in the hydrogen / carbon molar ratio [Comparative Examples 1 to 3], whereas the result of the hydrocracking reaction using the catalyst according to the present invention [Examples 1 to 3] 7], the hydrogen / carbon molar ratio was increased by more than 10% was confirmed that the hydrocracking reaction was carried out effectively.

Therefore, by developing a catalyst that is possible even under low-temperature, low-pressure hydrocracking conditions, it is expected to enable energy saving, environmentally friendly and process cost reduction.

Figure 1 shows a pore size distribution graph of the catalyst for hydrocracking prepared according to Example 1 of the present invention.

Figure 2 shows an image of a scanning electron microscope (SEM) of the hydrocracking catalyst prepared according to Example 1 of the present invention, (1) is an image that can confirm the foam (foam) form of the catalyst, (2 ) Is an image that can identify pores inside the catalyst.

3 shows a hysteresis curve according to nitrogen sorption profile of the hydrocracking catalyst prepared according to Example 1 of the present invention.

4 shows the results of pyrolysis experiments showing the amount of pyrolysis of Bitumen according to each decomposition temperature section, R1, R2, R3, R4, R5 are 100 ~ 177, 177 ~ 343, 343 ~ 545, 545 ~ 800 , Temperature range of 800 ~ 1000 ℃.

Claims (12)

A catalyst in which an active metal is supported on a porous support in the form of a foam. The catalyst has a total pore volume of 0.5 to 2.5 cc / g, a pore surface area of 100 to 300 m ² / g, and a pore wall thickness. A catalyst for hydrocracking crude oil having a specific gravity index in the range of 1 to 30 degrees, characterized in that 5 to 100 nm, pore diameter of 30 to 500 nm, and pore diameter / thickness ≥ 2. The catalyst for hydrocracking according to claim 1, wherein the crude oil has a boiling point of 100 to 700 ° C and a vacuum residue in the range of 20 to 70 wt%. 3. The catalyst for hydrocracking according to claim 2, wherein the crude oil is selected from bitumen, oil sand, tar sand, and oil sail. The catalyst for hydrocracking according to claim 1, wherein the porous carrier is alumina, silica or a composite oxide thereof. The catalyst for hydrocracking according to claim 4, wherein the complex oxide has a silica / alumina in the range of 0.01 to 100 molar ratio. The catalyst for hydrocracking according to claim 4, wherein the porous carrier is selected from MCM-41, MCM-48, SBA-15, and MCF. The catalyst for hydrocracking according to claim 1, wherein the active metal is selected from a single metal or two or more metal compounds selected from Ni, Mo, Fe, Co, Ti, Mn, Ru, Pd, and Pt. The catalyst for hydrocracking according to claim 1, wherein the active metal is contained in a range of 0.5 to 50 wt% based on the total catalyst. In the presence of a catalyst for hydrocracking according to any one of claims 1 to 8, crude oil and hydrogen having an API specific gravity index in the range of 1 to 30 degrees and hydrogen at 100 to 500 ℃ and pressure of 5 to 200 atm Hydrocracking method characterized by performing hydrocracking. The hydrocracking method according to claim 9, wherein the catalyst is used in the range of 0.1 to 100 parts by weight based on 100 parts by weight of crude oil. 10. The hydrocracking method according to claim 9, wherein the crude oil has a boiling point of 100 to 700 DEG C and a vacuum residue in the range of 20 to 70 wt%. 10. The hydrocracking method of claim 9, wherein the crude oil is selected from bitumen, oil sand, tar sand, and oil sail.

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