KR102549406B1 - Process of desulfurization and denitrification of heavy oil using water - Google Patents

Abstract

The present invention relates to upgrading of heavy oil, and more particularly, to a catalyst for removing sulfur and nitrogen from heavy crude oil and process by-products using steam, and to a desulfurization and denitrification treatment process including using the catalyst. .

Description

Desulfurization and denitrification of heavy oil using water {Process of desulfurization and denitrification of heavy oil using water}

The present invention relates to upgrading of heavy oil, and more particularly, to a catalyst for removing sulfur and nitrogen from heavy crude oil and process by-products using steam, and to a desulfurization and denitrification treatment process including using the catalyst. .

Crude oil refining can be largely divided into simple refining and advanced refining. Simple refining is usually separated by heating crude oil to 340 ° C. or higher using the difference in boiling points of components contained in crude oil, and an Atmospheric Distillation Unit or Crude Distillation Unit (ADU / CDU) is a typical example. On the other hand, the advanced refining process is a process of producing gasoline, diesel, kerosene, etc. through processes such as processing, decomposition, and desulfurization of heavy oil.

The advanced refining process can be further divided into a heavy oil cracking process and a heavy oil desulfurization process. Among them, the heavy oil cracking process produces gasoline, kerosene, diesel, etc. by causing a chemical reaction with high sulfur heavy oil using a hydrogenation catalyst. The heavy oil cracking process is divided into hydrocracking and catalytic cracking. In the case of catalytic cracking, since hydrogen is not added, heavy oil must be supplied after desulfurization.

Hydrocracking involves cracking heavy oil by adding hydrogen at high temperature, high pressure, and the presence of a catalyst and then separating the components. Since it is difficult to secure and cracks heavy oil using expensive hydrogen, processing costs increase.

Recently, in order to solve this problem, a technology for processing heavy oil using inexpensive water, which is easy to secure, instead of hydrogen, has been in the limelight. It can be divided into three types according to the processing temperature. The first is to completely lighten heavy oil by reacting heavy oil and water at high temperature, and the second is to heat heavy oil and water near the visbreaking temperature of heavy oil that does not produce coke. It is a technology to process heavy oil by reacting it, and finally, a technology to reduce the viscosity of heavy oil by reacting near the temperature of the steam injected in the drilling process of heavy oil or bitumen.

An example of the first technology is to lighten heavy oil by reacting heavy oil with water and an iron-based catalyst at 470 ° C or higher, such as US4743357 and JP2002-129171. An iron-based catalyst is mainly used, and the reaction must be performed at a relatively high temperature There is a downside to doing it. In addition, there is a problem that a large amount of coke is generated as water, which is less reactive than hydrogen, is used.

An example of the second technology is hardening by reacting with water in the presence of a catalyst containing an alkali metal and nickel at a relatively low temperature of 430 ° C. , the degree of hardening is low.

As such, there is a demand for the development of a process that can have a high sulfur and nitrogen removal rate while using water, which is easily secured instead of hydrogen.

US registered patent 4,743,357 (1988.05.10) Japanese Patent Publication 2002-129171 (2002.05.09) Japanese Patent Publication 2006-007151 (2006.01.12) Japanese Patent Publication 2012-121977 (2012.06.28) Korean Patent Publication 2014-0065511 (2014.05.30)

The present invention has been made to solve the above problems, and in detail, a desulfurization and denitrification treatment process for heavy oil that efficiently removes sulfur and nitrogen components in the presence of a catalyst using steam, thereby reducing the viscosity of heavy oil. It is about.

In addition, an object of the present invention is to provide a heavy oil desulfurization and denitrification treatment process that can be carried out at a low temperature and can efficiently suppress the generation of coke while using water with 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 range of 200 to 420 ° C. The reaction produces a compound having the structure of Formula 1 below Provided is a method for desulfurization and denitrification treatment of heavy oil using water, characterized in that it is carried out in the presence of a sulfurized catalyst.

[Formula 1]

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

(In Formula 1, M1 and M2 are different from each other and are any one metal element selected from the group VIIIA element group, and the weight ratios of a, b, c, and d are 0 ≤ a ≤ 0.4, 0 ≤ b ≤ 0.4, 0, respectively. < c ≤ 0.2 and 0 < d ≤ 0.2, except when a and b are 0 at the same time.)

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

In the desulfurization and denitrification treatment method for heavy oil using water according to an embodiment of the present invention, the compound may satisfy Equation 1 below.

[Equation 1] 0.5 ≤ (a + b) / (c + d) ≤ 12

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

In the desulfurization and denitrification treatment method of heavy oil using water according to an embodiment of the present invention, the catalyst is a) a precursor containing molybdenum, tungsten or a mixture thereof in support particles and ② a group VIIIA component. impregnating with a first impregnating solution comprising a promoter metal precursor to provide an elementally impregnated scaffold; b) calcining the element-impregnated support; c) impregnating the support in step b) with a second impregnation solution containing ① a precursor containing molybdenum, tungsten or a mixture thereof and ② a promoter metal precursor containing a group VIIIA component; and d) preparing a catalyst by calcining the support of step c) and then heating it together with a mixed gas of hydrogen sulfide and hydrogen.

In the method for desulfurization and denitrification of heavy oil using water according to an embodiment of the present invention, the support is any one selected from alumina, silica, silica-alumina, magnesia, zirconia, boria, and titania, or a mixture thereof. can include

In the desulfurization and denitrification treatment method for heavy oil using water according to an embodiment of the present invention, the reaction is performed at a pressure of 200 to 200 bar under a pressure of 20 to 200 bar in the step of supplying heavy oil and water using a carrier gas to a reactor in which a catalyst is stored. It may include a step of heating to 420 ° C. and a step of separating and treating heavy oil and sulfur oxides and nitric oxides.

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

The desulfurization and denitrification treatment process of heavy oil using water according to the present invention can efficiently reduce sulfur and nitrogen through the reaction between heavy oil and water vapor, and in particular, despite using water with low reactivity compared to the existing process using hydrogen, Nevertheless, it has the advantage of reducing the process cost according to the use of hydrogen by showing a reduction efficiency almost equivalent to that of using hydrogen.

In addition, compared to the existing reforming technology using water, the amount of coke generated can be drastically reduced, and the viscosity of the treated heavy oil can be reduced, so that the treated heavy oil can be more easily handled and transported.

Hereinafter, the process of desulfurization and denitrification of heavy oil using water according to the present invention will be described in detail. However, this is presented as an example of the invention, and the scope of the present invention is not necessarily limited thereby, and it is obvious to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention. At this time, unless otherwise defined, the technical terms and scientific terms used have meanings commonly understood by those of ordinary skill in the art to which this invention belongs. In addition, throughout this specification, unless otherwise specified, "include" or "include" refers to including a certain component without particular limitation, and is not construed as excluding the addition of other components.

When the terms "treatment", "treated", "upgrade", "upgrading" and "upgraded" are used in conjunction with a heavy oil feedstock in the present invention, it refers to Heavy oil feedstock that is or has been hydrotreated, or a reduction in the molecular weight of a heavy oil feedstock, a reduction in the boiling range of a heavy oil feedstock, a reduction in the density of asphaltenes, a reduction in the density of free radicals in hydrocarbons, or a reduction in sulfur, nitrogen, oxygen, metals and halides. Refers to the result of reducing the same impurities or crude oil products. Here, hydrogen refers to hydrogen or a compound thereof or a compound that reacts in the presence of a heavy oil feed and a catalyst to provide hydrogen.

In addition, in the present invention, "process" is referred to as "hydroprocessing", (hydrocracking or hydroconversion), and the hydroprocessing is hydroconversion, hydrocracking, hydrogenation ( hydrogenation), hydrotreating, hydrodesulfurization, hydrodenitrification, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodewaxing, and any process carried out in the presence of hydrogen, including but not limited to hydrocracking, including selective hydrocracking.

The periodic table referred to in the present invention is a table approved by IUPAC and the U.S. National Bureau of Standards, and examples thereof include the periodic table of elements by Los Alamos National Laboratory's Chemistry Division published in October 2001.

In the present invention, "metal" may include reagents in their elemental, compound, or ionic form. "Metal precursors" 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, ie Group VIB or promoter metals, but may also include plural forms for mixtures of metals. “In the solute state” means that the metal component is in protic liquid form.

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

In the present invention, "promoter metal" refers to an element, compound, or ionic form of a metal selected from any one component selected from group IVB, group VIIIA, group IIB, group IIA, group IVA, and combinations thereof. it means. The promoter metal increases the catalytic activity of a primary metal such as Mo or W, and may be present in a smaller amount than the primary metal.

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

In the present invention, the group VIIIA element collectively refers to the elements of groups 8 to 10 in the periodic table according to the old IUPAC, iron (Fe), ruthenium (Ru), osmium (Os), hassium (Hs), cobalt (Co), rhodium (Rh), iridium (Ir), meitnerium (Mt), nickel (Ni), palladium (Pd), platinum (Pt), dimstatium (Ds), and the like.

In the present invention, group IIB elements collectively refer to group 12 elements in the periodic table according to the old IUPAC, and may include zinc (Zn), cadmium (Cd), mercury (Hg), and the like.

In the present invention, group ⅡA elements collectively refer to group 2 elements in the periodic table according to the old IUPAC, and may include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc. there is.

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

In addition, "heavy oil feed" or "heavy oil feedstock" in the present invention may refer to heavy and extra-heavy crude oil, including resid, coal, bitumen, shale oil, tar sand, and the like. However, it is not limited thereto. Also, the heavy oil feedstock may be a solution, semi-solid or solid. Examples of heavy oil feedstocks that can be reformed in the present invention include Canadian tar sands, decompression residues from Brazilian Santos and Campos basins, Egyptian Gulf of Suez, Chad, Venezuelan Zulia, Malaysia, Indonesia Sumatra, etc. Not limited.

The process according to the present invention is a desulfurization and denitrification treatment process for heavy oil carried out in the presence of water and a catalyst. After injecting heavy oil and water into a reactor, the temperature is raised and reacted. At this time, the reaction temperature range is preferably carried out in a temperature range of 200 to 420 ℃, preferably 250 to 400 ℃. In addition, the water is preferably used in an amount of 1 to 500 parts by weight based on 100 parts by weight of heavy oil.

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

[Formula 1]

(Mo) _a (W) _b (M ¹ ) _c (M ² ) _d

(In Formula 1, M ¹ and M ² are different from each other and are any one metal element selected from the group VIIIA element group, and the weight ratio of a, b, c, and d is 0 ≤ a ≤ 0.4, 0 ≤ b ≤ 0.4, respectively. , 0 < c ≤ 0.2 and 0 < d ≤ 0.2, except when a and b are 0 at the same time.)

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

In the present invention, in the compound composition 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 Formula 1, M ¹ and M ² may optionally be present and function as promoter metals among catalyst components. The M ¹ and M ² may each independently be one of group VIIIA metals such as iron, ruthenium, osmium, hassium, cobalt, rhodium, iridium, meitnerium, nickel, palladium, and platinum, preferably iron , it is more preferable to use one of cobalt, nickel, palladium and platinum.

In Formula 1, a, b, c, and d represent total median ratios of each component, and among them, a and b may have a value of 0 to 0.8. That is, the component of the compound may include only any one metal of molybdenum and tungsten. However, the case where both a and b are 0 is excluded. Also, when a and b are both non-zero, 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, the catalyst is

a) impregnating the support with a first impregnating solution containing ① a precursor containing molybdenum, tungsten or a mixture thereof and ② a promoter metal precursor containing a group VIIIA component to provide an element-impregnated support;

b) calcining the element-impregnated support;

c) impregnating the support in step b) with a second impregnation solution containing ① a precursor containing molybdenum, tungsten or a mixture thereof and ② a promoter metal precursor containing a group VIIIA component; and

d) calcining the support of step c) and then heating it together with a mixed gas of hydrogen sulfide and hydrogen to prepare a catalyst.

In this case, the support may be a particle capable of supporting a catalytically active metal component, and an inorganic oxide may be used as the 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 and ZSM-12 , ZSM-21, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SSZ-32, ferrite, SAPO-11, SAPO-31, SAPO-41, MAPO-11 , MAPO-31, X-zeolite, Y-zeolite, L-zeolite, beta-zeolite, SBA-15, MCM-41, MCM-48, etc. may be used.

In the present invention, the support may be impregnated with a catalyst-containing impregnation solution to support the catalyst. In this case, the solution used for impregnation may include a metal precursor including the compound of Chemical Formula 1. The metal precursor is a material soluble and dispersible in oil or water, and may be provided as an elemental metal or metal compound, and the metal precursor included in steps a) and c) may be the same as or different from these.

Preferably, the metal precursor may include an organic acid. For example, acetate, oxalate, citrate, naphthenate, octoate, amine salt, etc. may be used, but is not limited thereto.

The molybdenum metal precursor is preferably an alkali metal or ammonium metal salt of molybdenum such as ammonium molybdate, iso-, feroxo, di-, tri-, tetra-, hepta-, octa-, or tetradeca-molybdate. , ammonium salts of phosphomolybic acid, heteropolyanion compounds of molybdenum-phosphorus, etc. may be used, but are not limited thereto.

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

In addition, a precursor containing both molybdenum and tungsten may be used, such as a nickel-molybdenum-tungsten heteropolyanion compound or a cobalt-molybdenum-tungsten heteropolyanion compound, but is not limited thereto.

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 may be used as a precursor containing a Group VIIIA metal. and can be added in a solute state. Preferably, it is more preferably a water-insoluble compound, alloy, or water-soluble sulfate solution, such as sulfide such as nickel or cobalt, molybdate, or tungstate.

The impregnation solution may 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 times of impregnation, and it is okay even if the number of times of impregnation is two or more. Also, the first impregnation solution and the second impregnation solution may be the same as or different from each other.

In the step of impregnating the support with the impregnating solution, ultrasonication may be further performed under an inert gas atmosphere.

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

The calcined support is sulfided using a sulfiding agent. The sulfurizing agent may preferably be a sulfur compound in a form that can be released immediately, for example, sulfur, hydrogen sulfide, ammonium sulfide, ammonium thiosulfate, sodium thiosulfate, thiourea, carbon disulfide, dimethyl disulfide, dimethyl sulfide, polysulfide Any one selected from tertiary butyl, polysulfurized tertiary nonyl, and mixtures thereof may be used, but is not necessarily limited thereto. In addition, the sulfiding 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 organic sulfur.

The prepared catalyst may contain 0.5 to 40% by weight of the group VIB component and 0.05 to 20% by weight of the group VIIIA component. If it is less than the above range, desulfurization and denitrification reactions may not be sufficient, and if it exceeds the above range, economic feasibility may decrease due to cost increase.

In addition, in the present invention, phosphorus, fluorine, chlorine, bromine, boron, or a mixture thereof may be further included to increase the reaction activity when preparing the catalyst. Although the amount of these additions is not limited in the present invention, it may include 1 to 10% by weight based on the total weight of the catalyst.

In the present invention, the desulfurization and denitrification treatment of heavy oil includes supplying heavy oil and water to a reactor containing a catalyst using a carrier gas, heating at 200 to 420° C. under a pressure of 20 to 200 bar, and carrying out heavy oil and sulfur oxides and It may include the step of separating and treating nitric oxide.

The reactor used in the present invention may be used without any particular limitation as long as it is commonly used. For example, a fixed bed, an ebullated bed, or a moving bed reactor may be used, and the shape, size, and reaction conditions of the reactor may be freely changed and selected according to the process described above. .

In the present invention, the carrier gas is for supplying heavy oil and water as raw materials into the reactor, and may be a mixed gas of steam and nitrogen or a mixed gas of steam and hydrogen. In the case of generating and supplying steam from sweet water, a steam generator may be further included before supply. At this time, the supply ratio (steam/heavy oil, weight ratio) of steam and heavy oil may be 0.01 to 5. If the weight ratio of steam to heavy oil supplied to the reactor is less than 0.01, desulfurization and denitrification may not occur sufficiently due to insufficient steam, and if the weight ratio exceeds 5, operating costs may increase due to excessive steam use.

When heavy oil is supplied into the reactor through a carrier gas, the temperature of the reactor can be raised and then the reaction can proceed. At this time, the reaction temperature of the reactor may be 200 to 420 ℃. If the reaction temperature is lower than 200 ° C, desulfurization and denitrification may not occur sufficiently, and if the temperature exceeds 420 ° C, excessive coke may occur.

After the reaction is completed, after natural cooling, treated oil, sulfur oxides and nitric oxides, and other products can be recovered.

Although the process according to the present invention has slight differences depending on the type of oil to be treated, sulfur and nitrogen can be effectively reduced due to the high activity of the catalyst, the viscosity reduction rate is high, and the content of oil having a boiling point within a specific range is increased. or may be reduced.

Hereinafter, the desulfurization and denitrification treatment process of heavy oil using water according to the present invention will be described in more detail by way of Examples and Comparative Examples. However, Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited thereto.

Methods for evaluating physical properties according to Examples and Comparative Examples of the present invention are as follows.

(evaluation)

(1) Ingredient content

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

(2) boiling point distribution

It was measured according to the rules of ASTM D-86 using GC-SIMDIS (Gas Chromatography-SIMulated DIStillation) analysis.

(3) Sulfur and nitrogen reduction rate

The sulfur and nitrogen content in the liquid product was measured through Total Sulfur & Nitrogen (TNS) and Elemental Analysis (EA) analysis, and the reduction rate (%) was calculated using Equation 1 below.

(Equation 1)

(4) Viscosity reduction rate

It was measured at 80 ° C using a Brookfield rotational viscometer, and the viscosity reduction rate (%) was calculated using Equation 2 below.

(Equation 2)

In addition, heavy oil used is shown in Table 1 below.

Distribution of initial boiling point (wt%) less than 170℃ 170 ~ 360℃ 360 ~ 560℃ Above 560℃ LCO 7.1 92.1 0.8 - SLO - 16.2 76.4 7.4 Bitumen - 12.6 32.5 54.9

The following Examples 1 to 5 and Comparative Examples 1 to 10 were processed using LCO according to Table 1 as heavy oil.

(Example 1)

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 sulfided at 400° C. for 2 hours using hydrogen gas containing 10% hydrogen sulfide. In a 300 ml batch reactor, 10 g of the previously prepared sulfurized catalyst was put together with 50 g of LCO and 20 g of water, the temperature was raised to 400 ° C. in a nitrogen atmosphere, and the reaction was carried out for 4 hours. After the reaction was completed, the sulfur reduction rate, nitrogen reduction rate, carbon dioxide, hydrogen sulfide, hydrogen production and boiling point distribution were measured and shown in Table 2 below.

(Example 2)

A catalyst impregnated with 3.0 wt% of Ni and 9.0 wt% of Mo in an alumina (Al ₂ O ₃ ) support was prepared, and the same method as in Example 1 was carried out, except that a sulfurized catalyst was used as the catalyst.

(Example 3)

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 the same method as in Example 1 was carried out except that the sulfurized catalyst was used as the catalyst.

(Example 4)

A catalyst impregnated with 4.5 wt% of Ni and 21.5 wt% of W in USY zeolite was prepared, and the same method as in Example 1 was carried out, except that a sulfurized catalyst was used as the catalyst.

(Example 5)

The same method as in Example 1, except that a catalyst impregnated with 3.7% by weight of Ni and 23.6% by weight of W in an amorphous silica-alumina (SiO ₂ -Al ₂ O ₃ ) support was prepared and then a sulfurized catalyst was used as the catalyst. was carried out.

(Comparative Example 1)

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

(Comparative Example 2)

It was carried out in the same manner as in Example 1 except that a catalyst composed 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)

A catalyst composed 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 sulfurized in the same manner as in Example 1, except that a catalyst was used as the catalyst. conducted.

(Comparative Example 4)

It was carried out in the same manner as in Example 1, except that 1 g of Mo(CO) ₆ having a Mo content of 1.9% by weight was used as a catalyst without a support.

(Comparative Example 5)

It was carried out in the same manner as in Example 1, except that 1 g of molybdenum naphthalate having a Mo content of 1.0% by weight was used as a catalyst without a support.

(Comparative Example 6)

It was carried out in the same manner as in Example 1, except that 1 g of MoS ₂ was used as a catalyst without a support.

(Comparative Example 7)

Examples 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 at 400 ° C. for 2 hours using 10% hydrogen gas as a catalyst. It was carried out in the same way as in 1.

(Comparative Example 8)

Except that a catalyst impregnated with 0.98% by weight of Co and 1.0% by weight of Mo on an alumina (Al ₂ O ₃ ) support was prepared and reduced at 400 ° C for 2 hours using 10% hydrogen gas as a catalyst. It was carried out in the same way as in Example 1.

(Comparative Example 9)

A catalyst impregnated with 2.4% by weight of Ni in an alumina (Al ₂ O ₃ ) support was prepared, and then reduced using 10% hydrogen gas at 400 ° C. for 2 hours. method was carried out.

LCO/water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) Product gas (g) Non-point distribution (wt%) _{CO2 H2S H2} less than 170℃ 170 ~ 360℃ 360℃ ~ 560℃ 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 in Table 2, Examples 1 to 5 of the present invention exhibited high sulfur and nitrogen reduction rates, especially Examples 2 and 3 among catalysts supported by molybdenum and Example 4 among catalysts supported by tungsten. In the case of , it was confirmed that the efficiency was greatly improved. On the other hand, in Comparative Examples, the sulfur reduction effect was insufficient, and in the case of Comparative Examples 2 to 3 using the iron catalyst, which was expected to be active in steam reaction, the sulfur and nitrogen reduction effect was not great.

Next, the following Example 6 and Comparative Example 13 were processed using SLO according to Table 1 as heavy oil.

(Example 6)

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

(Comparative Example 13)

Example 6 was carried out in the same manner as in Example 6, except that no catalyst was used.

SLO/water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) Coke content (%) Non-point distribution (wt%) less than 170℃ 170 ~ 360℃ 360℃ ~ 560℃ Above 560℃ 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 in Table 3, the catalyst used in Example 3, which showed excellent efficiency in LCO evaluation, exhibited excellent sulfur and nitrogen reduction rates in SLO evaluation. Compared to Comparative Example 13 in which no catalyst was used, this not only showed a more excellent sulfur and nitrogen reduction rate, but also upgraded to an oil with a boiling point distribution of less than 360 ° C. while suppressing coke formation.

(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 put into a 300 ml batch reactor together with 80 g of bitumen and 4 g of water, and the temperature was raised to 370 ° C. in a nitrogen atmosphere. The reaction proceeded over time. After the reaction was completed, the sulfur reduction rate, nitrogen reduction rate, carbon dioxide, hydrogen sulfide, hydrogen production and boiling point distribution were measured and shown in Table 2 below.

(Comparative Example 14)

Example 7 was carried out in the same manner as in Example 7, except that the catalyst was not used.

Bitumen/water
(g) Sulfur reduction rate (%) Nitrogen reduction rate (%) Viscosity reduction rate (%) Non-point distribution (wt%) less than 170℃ 170 ~ 360℃ 360℃ ~ 560℃ Above 560℃ 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 in Table 4, Example 7 showed high values in the sulfur reduction rate and nitrogen reduction rate, and the boiling point distribution was improved to 170% or more in the increase of components with a boiling point distribution of 170 to 360 ° C. compared to before treatment. looked In addition, it showed a high value in terms of viscosity reduction rate, and it was confirmed that it was superior to other catalysts in terms of transportation of heavy oil after treatment.

Although the preferred embodiments of the present invention have been described above, it is clear that the present invention can use various changes, modifications, and equivalents, and can be equally applied by appropriately modifying the embodiments. Therefore, the content described in the examples does not limit the scope of the present invention, which is defined by the limits of the claims.

Claims (7)

As a desulfurization and denitrification treatment method for heavy oil,
After adding heavy oil and water to the reactor, react at a temperature range of 200 to 420 ° C.
The reaction is carried out in the presence of a catalyst obtained by sulfurizing a compound having the structure of Formula 1 below,
The catalyst is
a) impregnating support particles with a first impregnating solution containing ① a precursor containing molybdenum, tungsten or a mixture thereof and ② a promoter metal precursor containing a group VIIIA component to provide an element-impregnated support;
b) calcining the element-impregnated support;
c) impregnating the support in step b) with a second impregnating solution containing ① a precursor containing molybdenum, tungsten or a mixture thereof and ② a promoter metal precursor containing a group VIIIA component; and
d) calcining the support of step c) and then heating it together with a mixed gas of hydrogen sulfide and hydrogen to prepare a catalyst;
Desulfurization and denitrification treatment method of heavy oil using water, characterized in that produced by including.
[Formula 1]
(Mo) _a (W) _b (M ¹ ) _c (M ² ) _d
(In Formula 1, M ¹ and M ² are different from each other and are any one metal element selected from the group VIIIA element group, and the weight ratio of a, b, c, and d is 0 ≤ a ≤ 0.4, 0 ≤ b ≤ 0.4, respectively. , 0 < c ≤ 0.2 and 0 < d ≤ 0.2, except when a and b are 0 at the same time.)
According to claim 1,
The M ¹ and M ² are each independently desulfurized heavy oil using water, which is any one metal element selected from iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), and platinum (Pt). and a denitrification treatment method.
According to claim 1,
The method of desulfurization and denitrification treatment of heavy oil using water, wherein the catalyst satisfies Formula 1 below.
[Equation 1] 0.5 ≤ (a + b) / (c + d) ≤ 12
delete According to claim 1,
The support is a desulfurization and denitrification treatment method of heavy oil using water containing any one selected from alumina, silica, silica-alumina, magnesia, zirconia, boria and titania or a mixture thereof.
According to claim 1,
The reaction includes supplying heavy oil and water to a reactor containing a catalyst using a carrier gas, heating at 200 to 420 ° C. under a pressure of 20 to 200 bar, and separating and treating heavy oil and sulfur oxides and nitric oxides. Desulfurization and denitrification treatment method of heavy oil using
According to claim 6,
The carrier gas is desulfurization and denitrification treatment method of heavy oil using water, which is a mixed gas of steam and nitrogen or steam and hydrogen.