KR20180045136A - Process of desulfurization and denitrification of heavy oil using water - Google Patents

Abstract

The present invention relates to a desulfurization and denitrification method for heavy crude oil, and more specifically, to a catalyst which removes sulfur and nitrogen from heavy crude oil and process by-products by using water, and to a desulfurization and denitrification process including the use of the catalyst. The desulfurization and denitrification process according to the present invention can remove sulfur and nitrogen in an efficient manner through a reaction of heavy crude oil and steam, and shows removal efficiency comparable to when using hydrogen, and thus has the advantage of reducing the process cost incurred by the use of hydrogen.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for desulfurization and denitrification of heavy oil using water,

The present invention relates to the upgrading of heavy oil, and more particularly, to a desulfurization and denitrification process involving the use of a catalyst for removing sulfur and nitrogen in heavy crude oil and process by-products using water vapor .

The refining of crude oil can be roughly divided into simple refining and upgrading refining. Simple refining is typically performed by heating the crude oil to 340 ° C or higher and separating it using the difference in boiling point of the components contained in the crude oil. An atmospheric distillation unit or a crude distillation unit (ADU / CDU) is typical. On the other hand, the advanced refining process is a process to produce gasoline, diesel oil, kerosene, etc. through processes such as processing, decomposition and desulfurization.

The advanced refining process can be divided into a heavy oil separation process and a heavy oil desulfurization process. The heavy oil separation process is a process of producing a gasoline, a kerosene, and a light oil by causing a chemical reaction with heavy sulfur oil using a hydrogenation catalyst. The cracking process of heavy oil is divided into hydrocracking and catalytic cracking. In case of catalytic cracking, it is not a reaction to add hydrogen, so the heavy oil should be supplied by desulfurization.

Hydrogenolysis is disadvantageous in that it decomposes the heavy oil by adding hydrogen in the presence of high temperature, high pressure and catalyst and then separates the components, which is difficult to secure and decomposes the heavy oil by using expensive hydrogen.

In order to solve these problems, a technique of treating heavy oil by using water which is easy to obtain instead of hydrogen and which is inexpensive water is getting popular. The first is to react the heavy oil and water at high temperature to complete the hardening of the heavy oil. The second is to remove the heavy oil and water from the visbreaking temperature of the heavy oil which does not produce coke And the final step is to reduce the viscosity of the heavy oil by reacting near the temperature of the steam injected in the drilling process of the heavy oil or the bithumen.

Examples of the first technique include a method in which heavy oil is reacted with water and an iron-based catalyst at 470 DEG C or higher, such as US4743357 and JP2002-129171, to harden the heavy oil, and the reaction is preferably carried out at a relatively high temperature . Also, there is a problem that a large amount of coke is generated due to the use of water which is less reactive than hydrogen.

An example of the second technique is to react with water in the presence of a catalyst containing an alkali metal and nickel at a relatively low temperature of 430 ° C to harden the catalyst. The catalyst is in the form of an emulsion, which does not generate coke , And the degree of hardening is low.

Thus, it is required to develop a process capable of having a high sulfur and nitrogen removal rate while using water that can be easily secured instead of hydrogen.

United States Patent 4,743,357 (May 5, 1988) Japanese Unexamined Patent Publication No. 2002-129171 (May, 2002) Japanese Patent Laid-Open No. 2006-007151 (Jan. 12, 2006) Japanese Patent Application No. 2012-121977 (June 28, 2012) Korean Patent Publication No. 2014-0065511 (2014.05.30)

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a desulfurization and denitration treatment process of heavy oil which efficiently removes sulfur and nitrogen components in the presence of a catalyst using steam, .

Another object of the present invention is to provide a process for desulfurization and denitrification of heavy oil which can be carried out at a low temperature and which can effectively suppress the production of coke while using water having low reactivity.

The present invention relates to a process for desulfurization and denitrification of heavy oil using water, wherein heavy oil and water are introduced into a reactor and then reacted at a temperature in the range of 200 to 420 ° C, The present invention also provides a method for treating desulfurization and denitrification of heavy oil using water, which is carried out in the presence of a sulfurized catalyst.

[Chemical Formula 1]

(Mo) a (W) b (M1) c (M2) d

(Wherein M1 and M2 are different from each other and are any metal element selected from the Group VIII A element group, and the weight ratios of a, b, c and d are 0? A? 0.4, 0? B? 0.4, <c ≤ 0.2 and 0 <d ≤ 0.2, except when a and b are 0 at the same time.)

In the method of treating desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, M ¹ and M ² are each independently Fe, Co, Ni, Pd ), And platinum (Pt).

In the method for treating desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, the compound may be one satisfying the following formula (1).

0.5? (A + b) / (c + d)? 12

(In the above formula 1, a, b, c and d are the same as the weight ratio in the formula (1).)

In the desulfurization and denitration treatment method of heavy oil using water according to an embodiment of the present invention, the catalyst comprises a) a precursor containing molybdenum, tungsten or a mixture thereof, Impregnating the substrate with a first impregnation solution comprising a promoter metal precursor to provide an element-impregnated support; b) calcining the element-impregnated support; c) impregnating the second impregnation solution comprising the promoter metal precursor including molybdenum, tungsten, or a mixed component thereof and a promoter metal precursor including the? And d) calcining the c) step support, followed by heating with a mixed gas of hydrogen sulfide and hydrogen to produce a catalyst.

In the method for treating desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, the support may be any one selected from alumina, silica, silica-alumina, magnesia, zirconia, boria and titania, .

In the method of treating desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, the reaction is carried out at a pressure of 20 to 200 bar under a pressure of 200 to 200 bar for supplying heavy oil and water to the reactor, Heating to 420 DEG C and separately treating the heavy oil, sulfur oxide and nitric oxide.

In the method of treating desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, the carrier gas may be a mixed gas of steam and nitrogen or water vapor and hydrogen.

The desulfurization and denitrification process of heavy oil using water according to the present invention can efficiently reduce sulfur and nitrogen through the reaction of heavy oil with water vapor and particularly, However, the reduction efficiency is almost the same as that in the case of using hydrogen, which is advantageous in reducing the process cost due to the use of hydrogen.

Further, the amount of generated coke can be drastically reduced as compared with the conventional water-based reforming technique, viscosity of the treated heavy oil can be reduced, and the treated heavy oil can be easily handled and transported.

Hereinafter, the process for desulfurization and denitrification of heavy oil using water according to the present invention will be described in detail. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined. Also, unless otherwise specified throughout this specification, &quot; comprising &quot; or &quot; containing &quot; refers to including any element without limitation, and is not to be construed as excluding the addition of other elements.

The terms "treatment", "treated", "upgrading", "upgrading" and "upgraded" are used in conjunction with the heavy oil feedstock in the present invention, Reducing the molecular weight of the hydrogenated or hydrotreated heavy or heavy oil feedstock, reducing the boiling point range of the heavy oil feedstock, decreasing the asphaltene density, reducing the hydrocarbon free radical density, or reducing the sulfur and nitrogen, oxygen, Quot; means a product or crude product that has reduced the same impurities. Here, hydrogen means a compound which reacts in the presence of hydrogen or a compound thereof or a heavy oil feed and a catalyst to provide hydrogen.

Also, in the present invention, the term "process" is referred to as being "hydroprocessing", (hydrocracking or hydroconversion), and the hydrogenation treatment may be hydrogen conversion, hydrogenolysis, hydrogenation, hydrogenation, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodewaxing, hydrodesulfurization, hydrodesulfurization, And hydrogenolysis, including selective hydrogenolysis, but is not limited thereto, and refers to any process carried out in the presence of hydrogen.

The periodic table referred to in the present invention is a table approved by IUPAC and the US National Bureau of Standards, for example, the Periodic Table of the Elements according to the Los Alamos National Laboratory's Chemistry Division, published in October 2001.

The term "metal" in the present invention may include reagents in the form of their elemental, compound, or ionic form. The "metal precursor" may also include metal compounds supplied to the process. The term " metal "or" metal precursor "in the singular is not limited to a single metal or metal precursor, i.e., Group VIB or promoter metals, but may also include multiple forms for mixtures of metals. "In the solute state" means that the metal component is in the form of a protic liquid.

In the present invention, "Group VIB metal" may include elemental, compound or ionic forms of chromium, molybdenum, tungsten and combinations thereof.

In the present invention, the term "promoter metal" means an element, compound or ion form of a metal selected from any one of the elements selected from Groups IVB, VIIIIA, IIB, IIA, IVA, it means. The promoter metal increases the catalytic activity of the primary metal such as Mo and W, and may be present in a smaller amount than the primary metal.

In the present invention, the group IVB element refers to a group 14 element in the periodic table according to the former IUPAC, and may include germanium (Ge), tin (Sn), lead (Pb) and the like.

In the present invention, the group VIII A element collectively refers to an element belonging to group 8 to group 10 in the periodic table according to the former IUPAC, and includes iron (Fe), ruthenium (Ru), osmium (Os), hydrosium (Hs), cobalt (Rh), iridium (Ir), manganese (Mt), nickel (Ni), palladium (Pd), platinum (Pt), and diamstantium (Ds).

In the present invention, the group IIB element refers to a group 12 element in the periodic table according to the former IUPAC, and may include zinc (Zn), cadmium (Cd), mercury (Hg), and the like.

In the present invention, the Group IIA element refers to a Group 2 element in the periodic table according to the former IUPAC and may include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium have.

In the present invention, the Group IVA element refers to a Group 4 element in the periodic table according to the former IUPAC and may include titanium (Ti), zirconium (Zr), hafnium (Hf) and the like.

Also, in the present invention, the term "heavy oil feed" or "heavy oil feedstock" may refer to heavy and super crude oil, including residues, coal, bitumen, shale oil, tar sand, But is not limited thereto. In addition, the heavy oil feedstock may be in solution, semi-solid or solid. Examples of the heavy oil feedstock that can be modified in the present invention include Canadian tar sands, Brazilian Santos and decompression residues of Campos basins, Egyptian Gulf of Suez, Chad, Venezuelan Zulia, Malaysia and Indonesia Sumatra. But is not limited to.

The process according to the present invention is a process for desulfurization and denitrification treatment of heavy oil which is carried out in the presence of water and a catalyst. The reactor is charged with heavy oil and water, and then heated to react. In this case, the reaction temperature range is preferably 200 to 420 ° C, preferably 250 to 400 ° C. The water may be used in an amount of 1 to 500 parts by weight based on 100 parts by weight of the heavy oil.

The desulfurization and denitrification process of the heavy oil according to the present invention is characterized in that the compound having the structure represented by the following formula 1 is reacted in the presence of a sulfurized catalyst.

[Chemical Formula 1]

(Mo) _a (W) _b (M ¹ ) _c (M ² ) _d

(Wherein M ¹ and M ² are different from each other and are any metal element selected from the Group VIII A element group, and the weight ratios of a, b, c and d are 0 ≤ a ≤ 0.4, 0 ≤ b ≤ 0.4 , 0 <c? 0.2 and 0 <d? 0.2, except that a and b are 0 at the same time.)

The catalyst may further comprise at least one active metal or active metal precursor with a high loading level which is introduced onto the support. The active metal or metals may be introduced into the support material by any standard solution impregnation method generally known to introduce active metals or metals into or onto the support material. Multiple impregnations can be carried out in combination with additional heat treatment.

In the present invention, in the composition of the compound represented by Formula 1, Mo means molybdenum, which is one of the Group VIB metals, and W means tungsten, which is one of the Group VIB metals.

In the above formula (1), M ¹ and M ² may be optionally present and function as a promoter metal in the catalyst component. M ¹ and M ² may each independently be one of Group VIII A metals such as iron, ruthenium, osmium, cesium, cobalt, rhodium, iridium, , Cobalt, nickel, palladium, and platinum.

A, b, c, and d in the above formula (1) represent the total weight ratio of each component, and a and b may have a value of 0 to 0.8. That is, the component of the compound may include only one of molybdenum and tungsten. Provided that a and b are all zero. When both of a and b are not 0, the mixing weight ratio of molybdenum to tungsten is preferably in the range of 9: 1 to 1: 9, more preferably 5: 1 to 1: 5. In addition, the case where both c and d are 0 is excluded.

In the present invention,

a) impregnating the support with a first impregnation solution comprising: a precursor comprising molybdenum, tungsten or a mixture thereof; and a promoter metal precursor comprising a constituent of VIIIIA family, thereby providing an element-impregnated support;

b) calcining the element-impregnated support;

c) impregnating the second impregnation solution comprising the promoter metal precursor including molybdenum, tungsten, or a mixed component thereof and a promoter metal precursor including the? And

d) calcining the c) step support, followed by heating with a mixed gas of hydrogen sulfide and hydrogen to prepare a catalyst.

At this time, the support may be a particle capable of supporting a catalytically active metal component, and an inorganic oxide may be used as a support. The inorganic oxide may include alumina, silica, amorphous silica-alumina, crystalline silica-alumina (zeolite), magnesia, zirconia, boria, titania and mixtures thereof. Specifically, ZSM-5, ZSM-12 31, SAPO-41, MAPO-11, ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SSZ- MAPO-31, X-zeolite, Y-zeolite, L-zeolite, beta-zeolite, SBA-15, MCM-41 and MCM-48.

In the present invention, the support may be impregnated with an impregnation solution containing a catalyst to support the catalyst. At this time, the solution used for the impregnation may include a metal precursor including the compound of the formula (1). The metal precursor may be provided as an elemental metal or a metal compound as a material having solubility and dispersibility in oil or water, and the metal precursors included in steps a) and c) may be the same or different.

Preferably, the metal precursor may comprise an organic acid. For example, acetic acid salts, oxalic acid salts, citric acid salts, naphthenic acid salts, octanoic acid salts, amine salts, and the like can be used, but the present invention is not limited thereto.

The molybdenum metal precursor is preferably an alkali metal or ammonium metal salt of molybdenum, such as ammonium molybdate, iso-, peroxo, di-, tri-, tetra-, hepta-, octa- or tetradeca-molybdate , An ammonium salt of phosphomolybdic acid, a heteropolyanion compound of molybdenum-phosphorus, and the like, but the present invention is not limited thereto.

The tungsten metal precursor may preferably be an alkali metal or ammonium tungstate such as a heteropolyanion compound of tungsten-phosphorus, a heteropolyanion compound of tungsten-silicon, meta-, para-, hexa- or polytungstate But is not limited thereto.

Further, a precursor including both molybdenum and tungsten, such as a nickel-molybdenum-tungsten heteropolyanion compound and a cobalt-molybdenum-tungsten heteropolyanion compound, may be used, but is not limited thereto.

As precursors comprising Group VIII metal in the present invention, metal salts or mixtures selected from nitrate, hydrated nitrate, chloride, hydrated chloride, sulfate, hydrated sulfate, formate, acetate, hypophosphite and mixtures thereof And may be added in a solute state. It is more preferable to be a water-insoluble compound, alloy or water-soluble sulfate solution such as sulfide such as nickel or cobalt, molybdate or tungstate.

The impregnation solution can be divided into a first impregnation solution and a second impregnation solution according to multiple impregnation of the support. However, this classification is based on the number of impregnation, and the number of impregnation may be two or more times. The first impregnation solution and the second impregnation solution may be the same or different from each other.

The step of impregnating the support with the impregnation solution may further be carried out under ultrasonic treatment in an inert gas atmosphere.

The support on which the element is impregnated is subjected to a calcination process. At this time, drying can be performed before the calcining step. The calcination step is preferably carried out at a temperature in the range of 250 deg. C to 900 deg. C, preferably 300 deg. C to 800 deg. C, more preferably 350 deg. C to 600 deg. In addition, the calcination temperature and time may be equal to or different from each other, depending on the number of impregnations.

The calcined support is sulfided using a sulfurizing agent. The sulphurizing agent may be a sulfur compound in a form capable of being readily discharged immediately and may be, for example, sulfur, hydrogen sulfide, ammonium sulfide, ammonium thiosulfate, sodium thiosulfate, thiourea, carbon disulfide, dimethyl disulfide, dimethyl sulfide But are not limited to, any one selected from tertiary butyl, polysulfurized terrinonyl, and mixtures thereof. Further, the sulfurizing agent may be at least one selected from alkali or alkaline earth metal sulfides, alkali or alkaline earth metal hydrogen sulfides, and mixtures thereof in addition to sulfur organic substances.

The prepared catalyst may have a content of the VIB group component of 0.5 to 40% by weight and a content of the VIIIIA group content of 0.05 to 20% by weight. If the amount is less than the above range, the desulfurization and denitrification may not be sufficient, and if the amount is outside the above range, the cost may increase due to an increase in cost.

Further, in the present invention, phosphorus, chlorine, bromine, boron, or a mixture thereof may be further added to increase the reaction activity in the production of the catalyst. In the present invention, the addition amount thereof is not limited, but may be 1 to 10% by weight based on the weight of the whole catalyst.

In the present invention, the desulfurization and denitrification treatment of the heavy oil is performed by supplying the heavy oil and water to the reactor containing the catalyst by using the carrier gas, heating the reactor at 200 to 420 ° C under a pressure of 20 to 200 bar, And separating and treating the nitroxide.

The reactor used in the present invention is not particularly limited and can be used as long as it is commonly used. For example, a fixed bed, an ebullated bed, and a moving bed reactor can be used, and the shape, size, and reaction conditions of the reactor can be freely changed and selected according to the process described above .

In the present invention, the carrier gas may be a mixed gas of steam and nitrogen or a mixed gas of steam and hydrogen to supply the raw material heavy oil and water into the reactor. When water vapor is generated by supplying water vapor, it may further include a water vapor generating device before supply. At this time, the supply ratio of steam and heavy oil (steam / heavy oil, weight ratio) may be 0.01 to 5. When the amount of water vapor relative to the heavy oil supplied to the reactor is less than 0.01, the amount of water vapor is insufficient, so that desulfurization and denitrification may not sufficiently occur. If the weight ratio is more than 5, the operation ratio may increase due to excessive water vapor.

When the heavy oil is supplied into the reactor through the carrier gas, the temperature of the reactor is raised and the reaction can proceed. The reaction temperature of the reactor may be 200 to 420 ° C. If the temperature is lower than 200 ° C, the reaction temperature may be low, so that the desulfurization and denitrification may not occur sufficiently. If the temperature exceeds 420 ° C, excessive coke may occur.

Upon completion of the reaction, the treated oil, sulfuric acid, nitric oxide and other products can be recovered after natural cooling.

Although the process according to the present invention is somewhat different depending on the kind of the treated oil, since the activity of the catalyst is high, sulfur and nitrogen can be effectively reduced, the viscosity reduction rate is high, and the content of oil having a specific boiling point is further increased Or reduced.

Hereinafter, the process of desulfurization and denitrification of heavy oil using water according to the present invention will be described in more detail with reference to the following Examples and Comparative Examples. However, the examples and comparative examples are merely examples for explaining the present invention in more detail, but the present invention is not limited thereto.

The physical properties evaluation methods according to Examples and Comparative Examples of the present invention are as follows.

(evaluation)

(1) Component content

The content of each component in the catalyst was measured by X-ray fluorescence method.

(2) Non-point distribution

And measured according to ASTM D-86 using GC-SIMDIS (Gas Chromatography-SIMulated DIStillation) analysis.

(3) Reduction rate of sulfur and nitrogen

The contents of sulfur and nitrogen in the liquid product were measured by Total Sulfur & Nitrogen (TNS) and Elemental Analysis (EA) analysis, and the reduction rate (%) was calculated using the following Equation 1.

(Equation 1)

(4) Viscosity reduction rate

The Brookfield rotational viscometer was used to measure the viscosity at 80 DEG C and the viscosity reduction rate (%) was calculated using Equation 2 below.

 (Equation 2)

The used heavy oil is shown in Table 1 below.

Initial boiling point distribution (wt%) Below 170 ℃ 170 ~ 360 ° C 360 to 560 ° C Above 560 ° C LCO 7.1 92.1 0.8 - SLO - 16.2 76.4 7.4 Bituminous - 12.6 32.5 54.9

In the following Examples 1 to 5 and Comparative Examples 1 to 10, the LCO according to Table 1 was used as the heavy oil.

(Example 1)

A catalyst impregnated with zirconia (ZrO ₂ ) support of 3.0 wt% of Ni and 10.0 wt% of Mo was prepared and then subjected to sulphation at 400 ° C for 2 hours using hydrogen gas containing 10% hydrogen sulfide. In a 300 ml batch reactor, 10 g of the sulfided catalyst prepared above was added together with 50 g of LCO and 20 g of water, and the temperature was raised to 400 ° C in a nitrogen atmosphere, and the reaction was carried out for 4 hours. After the reaction, the sulfur reduction rate, the nitrogen reduction rate, the carbon dioxide, the hydrogen sulfide, the hydrogen production amount and the boiling point distribution were measured and are shown in Table 2 below.

(Example 2)

The procedure of Example 1 was repeated except that a catalyst impregnated with alumina (Al ₂ O ₃ ) support of 3.0 wt% of Ni and 9.0 wt% of Mo and then sulfided was used as a catalyst.

(Example 3)

The procedure of Example 1 was repeated except that a catalyst impregnated with 0.98 wt% of Co and 1.0 wt% of Mo in an alumina (Al ₂ O ₃ ) support was prepared and then sulphide was used as a catalyst.

(Example 4)

The procedure of Example 1 was repeated except that USY zeolite was impregnated with 4.5 wt% of Ni and 21.5 wt% of W, and then sulfided.

(Example 5)

The same procedure as in Example 1 was carried out except that a catalyst impregnated with amorphous silica-alumina (SiO ₂ -Al ₂ O ₃ ) support of 3.7 wt% of Ni and 23.6 wt% of W was prepared, Respectively.

(Comparative Example 1)

Was carried out in the same manner as in Example 1 without using a catalyst.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that a catalyst consisting of 82.1 wt% of Fe ₂ O ₃ and 17.9 wt% of Cr ₂ O ₃ was used without a support.

(Comparative Example 3)

The procedure of Example 1 was repeated except that a catalyst consisting of 82.1% by weight of Fe ₂ O ₃ and 17.9% by weight of Cr ₂ O ₃ was prepared without a support and then sulfided in the same manner as in Example 1, Respectively.

(Comparative Example 4)

The procedure of Example 1 was repeated except that 1 g of Mo (CO) ₆ having an Mo content of 1.9 wt% was used as a catalyst without a support.

(Comparative Example 5)

The procedure of Example 1 was repeated except that 1 g of molybdenum naphthalate having a Mo content of 1.0 wt% was used as a catalyst without a support.

(Comparative Example 6)

The procedure of Example 1 was repeated except that 1 g of MoS ₂ was used as a catalyst without a support.

 (Comparative Example 7)

Except that a catalyst impregnated with 3.0% by weight of Ni and 10.0% by weight of Mo in a zirconia (ZrO ₂ ) support was prepared and then reduced with 400 g of 10% hydrogen gas at 400 ° C for 2 hours. 1. &Lt; / RTI &gt;

 (Comparative Example 8)

Except that a catalyst impregnated with 0.98% by weight of Co and 1.0% by weight of Mo in an alumina (Al ₂ O ₃ ) support was prepared and then reduced with 400 ° C. for 2 hours using 10% hydrogen gas as a catalyst The procedure of Example 1 was repeated.

(Comparative Example 9)

Was prepared in the same manner as in Example 1 except that a catalyst impregnated with 2.4 wt% Ni in an alumina (Al ₂ O ₃ ) support was prepared, and then the catalyst was subjected to reduction at 400 ° C for 2 hours using 10% .

LCO / water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) The product gas (g) Boiling point (wt%) CO ₂ H ₂ S H ₂ Below 170 ℃ 170 ~ 360 ° C 360 ° C to 560 ° C Example 1 50/20 53.5 31.3 0.54 0.24 0.19 11 83.7 4.6 Example 2 59.3 57.8 0.16 0.20 0.15 10.9 81.4 6.6 Example 3 55.2 54.8 0.55 0.46 0.2 11.5 84.1 3.8 Example 4 48.5 65.6 0.08 1.14 0.20 11.3 83.9 4.6 Example 5 19.9 57.1 0.15 2.48 0.09 11.4 83.1 5.5 Comparative Example 1 50/20 5.1 0 0 0 0.10 10.8 84.7 4.6 Comparative Example 2 10.3 15.0 0.63 0 0.25 10.8 83.6 4.7 Comparative Example 3 0 2.4 0.09 0.54 0.14 11.5 83.3 4.4 Comparative Example 4 6.6 1.9 2.74 0 0.28 9 84.4 6.7 Comparative Example 5 17.1 6.2 1.42 0 0.10 10.5 79.7 9.5 Comparative Example 6 4.0 5.3 0.02 0.07 0.17 11 84.3 3.8 Comparative Example 7 11.9 31.6 0.17 0 0.31 9.1 81.6 8.7 Comparative Example 8 17.4 41.4 0.19 0 0.19 10.4 84.7 4.1 Comparative Example 9 9.1 0 0.01 0 0.23 9.3 81.2 8.5

As can be seen from Table 2, Examples 1 to 5 of the present invention exhibited high sulfur and nitrogen reduction ratios. In particular, among the catalysts carrying Examples 2 and 3 and tungsten in the catalyst carrying molybdenum, Example 4 And the efficiency is improved remarkably. On the other hand, the sulfur reduction effect was insufficient in the comparative examples and the sulfur and nitrogen reduction effect was not large even in Comparative Examples 2 to 3 using the iron catalyst, which was expected to exhibit activity in the vapor reaction.

Next, in Example 6 and Comparative Example 13, the process was performed using SLO according to Table 1 as the heavy oil.

(Example 6)

In Example 3, the same procedure as in Example 1 was carried out except that the heavy oil was changed to SLO instead of LCO.

(Comparative Example 13)

The procedure of Example 6 was repeated except that the catalyst was not used.

SLO / water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) Coke Content (%) Boiling point (wt%) Below 170 ℃ 170 ~ 360 ° C 360 ° C to 560 ° C Above 560 ° C Example 6 50/20 54.4 10.3 7.8 2.6 28.5 54.2 14.7 Comparative Example 13 50/20 13.6 3.0 53.3 2.7 35.3 45.3 16.7

As can be seen from the above Table 3, the catalyst used in Example 3, which showed excellent efficiency in the LCO evaluation, showed excellent sulfur and nitrogen reduction rates even in the SLO evaluation. Compared with Comparative Example 13 in which no catalyst was used, not only the reduction ratio of sulfur and nitrogen reduction was further improved but also upgraded to oil having a boiling point of less than 360 ° C while suppressing the formation of coke.

(Example 7)

In Example 3, the heavy oil was changed to bitumen instead of LCO, and 10 g of the catalyst used in Example 3 was added to a 300 ml batch reactor together with 80 g of bimodemen and 4 g of water. The temperature was raised to 370 占 폚 in a nitrogen atmosphere, The reaction was carried out for a period of time. After the reaction, the sulfur reduction rate, the nitrogen reduction rate, the carbon dioxide, the hydrogen sulfide, the hydrogen production amount and the boiling point distribution were measured and are shown in Table 2 below.

(Comparative Example 14)

The procedure of Example 7 was repeated except that the catalyst was not used.

Bitumen / water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) Viscosity reduction rate (%) Boiling point (wt%) Below 170 ℃ 170 ~ 360 ° C 360 ° C to 560 ° C Above 560 ° C Example 7 80/4 21.7 12.0 94.2 2.4 21.7 30.5 45.4 Comparative Example 14 80/4 10.8 3.3 85.3 1.7 18.6 32.9 46.8

As can be seen from Table 4, Example 7 showed a high value at the sulfur reduction rate and the nitrogen reduction rate, and the boiling point distribution in which the increase amount of the component having the boiling point of 170 to 360 ° C before the treatment was improved to more than 170% It looked. It was also found that the viscosity reduction rate was higher than other catalysts in terms of transportation of heavy oil after treatment.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken in conjunction with the present invention. Therefore, the contents described in the embodiments are not intended to limit the scope of the present invention defined by the limitations of the claims.

Claims (7)

As a method for desulfurization and denitrification of heavy oil,
The reactor is charged with heavy oil and water and then reacted at a temperature ranging from 200 to 420 ° C,
Wherein the reaction is carried out in the presence of a catalyst having a structure represented by the following general formula (1).
[Chemical Formula 1]
(Mo) _a (W) _b (M ¹ ) _c (M ² ) _d
(Wherein M ¹ and M ² are different from each other and are any metal element selected from the Group VIII A element group, and the weight ratios of a, b, c and d are 0 ≤ a ≤ 0.4, 0 ≤ b ≤ 0.4 , 0 <c? 0.2 and 0 <d? 0.2, except that a and b are 0 at the same time.)
The method according to claim 1,
M ¹ and M ² are each independently selected from the group consisting of desulfurization of heavy oil using water as a metal element selected from among iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd) And a denitration treatment method.
The method according to claim 1,
Wherein the catalyst satisfies the following formula (1).
0.5? (A + b) / (c + d)? 12
The method according to claim 1,
The catalyst may comprise,
a) impregnating the support particles with a first impregnation solution comprising: a precursor comprising molybdenum, tungsten or a mixture thereof; and a promoter metal precursor comprising a constituent of a VIII family; providing an element-impregnated support;
b) calcining the element-impregnated support;
c) impregnating the second impregnation solution comprising the promoter metal precursor including molybdenum, tungsten, or a mixed component thereof and a promoter metal precursor including the? And
d) calcining the c) step support, followed by heating with a mixed gas of hydrogen sulfide and hydrogen to produce a catalyst;
And a denitrification process of the heavy oil using water.
5. The method of claim 4,
Wherein the support comprises desulfurization and denitrification treatment of heavy oil using water comprising any one or a mixture of alumina, silica, silica-alumina, magnesia, zirconia, boria and titania.
The method according to claim 1,
The reaction may include heating the reactor to 200 to 420 DEG C under a pressure of 20 to 200 bar to supply heavy fuel oil and water to the reactor containing the catalyst, and separating and treating the heavy oil, sulfur oxide and nitric oxide A method for desulfurization and denitrification of heavy oil using water.
The method according to claim 6,
Wherein the carrier gas is desulfurization and denitrification treatment of heavy oil using water, which is a mixed gas of water vapor and nitrogen or water vapor and hydrogen.