KR101273343B1 - Process for preparing aromatics using shape selective catalyst - Google Patents

Abstract

The present invention comprises the steps of (a) separating the coal tar into residual oil and effluent oil by hydrodesulfurization / denitrification distillation in the presence of a transition metal sulfide catalyst; And converting the effluent oil into an aromatic product including at least one selected from benzene, toluene and xylene through a catalytic cracking reaction. The method of manufacturing an aromatic product comprising distillative separation of coal tar The process and the hydrodesulfurization / desorption reaction process can be replaced by the hydrodesulfurization / desorption distillation process, which is an integrated process, and can provide an economical and efficient method for producing aromatic products.

Description

Process for Producing Aromatic Products Using Shape Selective Catalysts {PROCESS FOR PREPARING AROMATICS USING SHAPE SELECTIVE CATALYST}

The present application relates to a method for producing an aromatic product, and more particularly, to a method for producing an aromatic product using a shape selective catalyst.

When the raw coal is carbonized in a conventional coke oven during the metallurgical coke manufacturing process during the steelmaking process, solid coke is obtained in the carbonization chamber of the coke oven, whereas as a by-product, liquid coal tar and gaseous coke oven gas (COG) are used. ) Is obtained.

Coal tar is a mixture of various aromatic carbon compounds having two or three or more benzene rings and a small amount of sulfur or nitrogen compounds, although there are little differences depending on the composition of the raw coal for producing coke and the conditions for producing coke.

Coke oven gas (COG), which has the largest calorific value among the by-products of the steelmaking process, is recycled as a primary energy source for heating the steelmaking process, and therefore has low added value.In the case of coal tar regeneration process, which reaches 10wt% of COG, Is converted to carbon black, naphthalene, pitch, etc. through energy-intensive pyrolysis process that requires high temperature of 1,200K or more, and is used as low-value raw materials such as tire, cement admixture, aluminum refining, etc. In order to use it, it is required to utilize it in the manufacture of aromatic products such as benzene, toluene or xylene which are high value-added chemicals.

However, coal tar generated as a by-product of the steelmaking process contains a large amount of nitrogen compounds and sulfur compounds, which are not easy to decompose and separate, and thus cannot be used for the production of high value-added chemicals, and gaseous coke oven gas (COG) is also a high value chemical. There was a problem that cannot be used in the manufacture of the product.

Accordingly, the present invention has been made to solve the problems of the prior art as described above and the technical problem that has been requested from the past, the object of the present invention is the hydrodesulfurization desulfurization / denitrification process and the catalytic cracking reaction process is one integrated process To provide a low sulfur, low nitrogen, low pollution high value-added aromatic product that can be replaced by a denitrification decomposition reaction process (hydrogenation complex reaction process).

The present invention also aims to provide a method for producing an aromatic product which can use coal tar as a raw material and can use a shape selective catalyst.

The present invention also aims to provide a method for producing an aromatic product having excellent hydrodesulfurization / denitrification and decomposition reaction efficiency.

The present invention also seeks to provide a process for producing aromatic products which can use coke oven gas as a hydrogen source.

As a technical means for achieving the above-described technical problem, the first aspect of the present invention, the step of distilling coal tar to separate the remaining oil and effluent oil (a); And removing the at least one selected from sulfur compounds and nitrogen compounds through hydrogenation desulfurization / denitrification catalytic decomposition in the presence of a shape-selective catalyst and to at least one selected from benzene, toluene and xylene. It provides a method of producing an aromatic product comprising the step (b) of the conversion.

According to one embodiment of the invention, the shape-selective catalyst of step (a) may comprise at least one metal selected from Group 6, Group 8 to Group 10 metals of the periodic table.

According to one embodiment of the invention, the shape-selective catalyst of step (a) is Ni ₂ P, Co ₂ P, Fe ₂ P, MoP, WP, MoS ₂ , Ni-MoS ₂ , Ni-WS ₂ and Co- It may include one or more selected from MoS ₂ .

According to another embodiment of the present invention, the shape-selective catalyst of step (a) is Ni ₂ P, Co ₂ P, Fe ₂ P, MoP, WP, MoS ₂ , Ni-MoS ₂ , Ni-WS ₂ and At least one selected from Co-MoS ₂ may be supported on at least one shape-selective carrier selected from zeolite, ZSM-5, beta zeolite, Y-zeolite, USY zeolite and mordenite.

According to another embodiment of the present invention, the hydrodesulfurization / denitrification catalytic decomposition process of step (a) may be operated at a temperature of 200 to 1,000 ℃ and a pressure of 10 to 200 atm.

According to another embodiment of the present invention, the hydrodesulfurization / denitrification catalytic cracking process of step (a) may use a coke oven gas as a hydrogen source of the hydrodesulfurization / denitrification catalytic cracking process. have.

According to another embodiment of the present invention, the hydrodesulfurization / denitrification catalytic cracking reaction is one or more reactions selected from desulfurization, denitrification, pyrolysis, dealkylation, isomerization, transalkylation and alkylation. This is characterized in that it is performed.

According to another embodiment of the invention, the method for producing the aromatic product may be carried out in a batch reactor, a continuous fixed bed reactor or a continuous fluidized bed reactor.

Another aspect of the present invention can provide an aromatic product prepared according to the method for producing an aromatic product.

According to the present invention can provide a method for producing an aromatic product that can produce a high value-added aromatic compound as a product using coal tar as a raw material.

According to the present invention, the hydrodesulfurization / denitrification reaction process and the catalytic decomposition process can be replaced by the hydrodesulfurization / desulfurization reaction process, which is an integrated process, and can provide an economical and efficient method for producing aromatic products.

In another aspect, the present invention can provide a method for producing an aromatic product that can use the coke oven gas as a hydrogen source.

In addition, the present invention can provide a low sulfur, low nitrogen, low pollution high value-added aromatic product excellent in hydrogenation desulfurization / denitrification and decomposition reaction effect.

1 is a process schematic showing one embodiment according to the present invention.

DETAILED DESCRIPTION Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and it should be understood that the present invention covers all the transformations, equivalents, and substitutes included in the spirit and scope of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

As a technical means for achieving the above-described technical problem, the first aspect of the present invention, the step of distilling coal tar to separate the remaining oil and effluent oil (a); And removing the at least one selected from sulfur compounds and nitrogen compounds through hydrogenation desulfurization / denitrification catalytic decomposition in the presence of a shape-selective catalyst and to at least one selected from benzene, toluene and xylene. It can provide a method for producing an aromatic product comprising the step (b) of the conversion.

The distillation separation process of the present invention is to separate the coal tar used as a raw material according to the boiling point range and to use the light fraction to produce aromatic products such as benzene, toluene and xylene, the coal tar fraction is introduced into the distillation separation process The oil is separated into effluent oil, which is an oil containing a sulfur compound, a nitrogen compound, and an aromatic compound having one or two benzene rings, and separated into a residual oil, which is an oil containing an aromatic compound having three or more benzene rings.

Hydrogenation desulfurization / denitrification decomposition process of the present invention removes sulfur compounds and nitrogen compounds which are impurities contained in the oil to produce low pollution aromatic products with very low generation of SOx and NOx, and has one or two benzene rings. As a step for catalytic decomposition of an aromatic compound, it proceeds by reacting the effluent oil and hydrogen in the presence of the shape-selective catalyst for hydrogenation.

According to one embodiment of the invention, the shape selective catalyst of the hydrodesulfurization / denitrification decomposition process step may include at least one metal selected from Group 6, Group 8 to Group 10 metals of the periodic table, more preferably Ni ₂ P, Co ₂ P, Fe ₂ P, MoP, WP, MoS ₂ , Ni-MoS ₂ It may include one or more selected from Ni-WS ₂ and Co-MoS ₂ , even more preferably Ni One or more selected from ₂ P, Co ₂ P, Fe ₂ P, MoP, WP, MoS ₂ , Ni-MoS ₂ , Ni-WS ₂ and Co-MoS ₂ may be zeolite, ZSM-5, Y-zeolite, USY zeolite It may be supported on at least one shape-selective carrier selected from beta zeolite and mordenite.

In addition, the hydrogenation desulfurization / denitrification decomposition process of the present invention is hydrogen partial pressure of 10 to 200 atm, hydrogen content of 50 to 400 Nm ³ / kl, space velocity (LHSV) of 0.1 ~ 10 h ^-1 , temperature of 200 ~ 1,000 ℃ It is preferable to proceed under the conditions of. These conditions are suitable for hydrotreating an aromatic compound having one or two sulfur compounds, nitrogen compounds, and benzene rings to remove impurities such as sulfur and nitrogen, and to carry out catalytic decomposition.

According to the present invention, coke oven gas may be used as a hydrogen source for the hydrodesulfurization / denitrification decomposition reaction.

Hydrogenation desulfurization / denitrification decomposition process of the present invention is a process for obtaining an aromatic product by reacting with hydrogen in the presence of a catalyst to separate the oil containing an aromatic compound having one benzene ring with effluent oil, sulfur compounds, nitrogen compounds and The oil containing the aromatic compound having two benzene rings is separated with the residual oil.

In the hydrodesulfurization / denitrification decomposition reactor, desulfurization reaction, denitrification reaction, pyrolysis reaction, dealkylation reaction, transalkylation reaction, alkylation reaction, and isomerization reaction of aromatic components are carried out, and through this reaction process, benzene, toluene, An aromatic component such as xylene is obtained.

According to another embodiment of the invention, the method for producing the aromatic product may be carried out in a batch reactor, a continuous fixed bed reactor or a continuous fluidized bed reactor.

Another aspect of the present invention can provide an aromatic product prepared according to the method for producing an aromatic product.

1 is a process diagram schematically showing a specific example of producing an aromatic product from coal tar according to an embodiment of the present invention.

Referring to Figure 1, coal tar oil (S1) produced in the metallurgical coke manufacturing process of the steelmaking process is sulfur compound, nitrogen compound, aromatic compound having one benzene ring, aromatic compound having two benzene rings and benzene ring 3 It contains an aromatic compound having at least two as a component, the coal tar fraction (S1) is introduced into the distillation separation process (U1) oil fraction containing a sulfur compound, a nitrogen compound, and an aromatic compound having one or two benzene rings It is separated into phosphorus effluent oil (S2), and it is separated into residual oil (S3) which is an oil containing aromatic compound which has three or more benzene rings.

The effluent oil (S2) is reacted with hydrogen (S4) in the presence of a catalyst in a hydrodesulfurization / denitrification catalytic cracking process (U2) to separate a sulfur compound and a nitrogen compound, which are catalyst poisoning components, and hydrogen (S4) in the presence of a catalyst. And are converted and separated into aromatic products (S5) and unconverted fraction (S6), including benzene, toluene, xylene. The unconverted fraction (S6) is an oil mainly comprising an aromatic compound having two or more sulfur compounds, nitrogen compounds and benzene rings.

Hereinafter, the configuration of the present invention will be described in more detail with reference to the following examples, but is not limited thereto.

[ Example ]

Manufacturing example  One. NiMoS2 Of ZSM Synthesis of -5 Catalyst

NiMoS ₂ / ZSM-5 catalyst, which is a catalyst in which NiMoS ₂ is a hydrogenated functional active catalyst supported on zeolite ZSM-5, was prepared as follows.

As a carrier for the preparation of the shape-selective catalyst, a commercial zeolite (ZSM-5, zeolyst) was used. In order to support the NiMoS ₂ catalyst, 8 wt% Mo and 3 wt% Ni were supported on the zeolite carrier by impregnation. To this end, (NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O aqueous solution and Ni (NO ₃ ) ₂ 6H ₂ O (all Aldrich) aqueous solution was impregnated sequentially. In each case, drying was performed for 4 hours at room temperature and 12 hours at 120 ° C after impregnation. After firing at 500 ℃ for 4 hours to synthesize a NiMoS ₂ / ZSM-5 catalyst.

When the reaction evaluation was applied, the pretreatment was performed for 4 hours under a condition of 10% H ₂ S / H ₂ (50 ml / min) at 400 ° C. for sulfidation.

Manufacturing example  2. Ni ₂ P Of ZSM Synthesis of -5

Hydrogenated functionality to an active catalyst in which the shape-selective catalyst, Ni ₂ P / ZSM-5 supported on the Ni ₂ P zeolite ZSM-5 was prepared as follows.

0.38 g (1.5 mmol Ni loading) of nickel acetylacetate, 7 mL of trioctylphosphine (TOP) used as a surfactant and a phosphorus reducing agent, was mixed at 70 ° C. for 10 minutes, and then trioctylphosphine oxide was stirred at 300 ° C. ( Rapid injection into 5 g solution of trioctylphosphine oxide (TOPO) and maintained at 300 ° C for 2 hours. After the reaction, 50 mL of methanol was added to the solution to form a precipitate, which was separated by centrifugation. The precipitate is washed three times with acetone and centrifuged to remove residual TOP and TOPO. The final precipitate was dispersed in acetone and the dispersed solution was impregnated into 1 g of a zeolite ZSM-5 support, followed by drying at room temperature to prepare a catalyst Ni ₂ P / ZSM-5.

When the reaction evaluation was applied, pretreatment was performed for 4 hours under 400% of 10% H ₂ S / H ₂ (50 ml / min) for further sulfidation.

Example  One

According to the method of the present invention, as shown in Table 1, coal tar was used as a raw material, and this was subjected to monodistillation under atmospheric pressure to separate an oil having a boiling point up to 250 ° C. to obtain a bicyclic aromatic, and then applied to the reaction.

Item Raw material (wt%) Spilled Oil (wt%) Monocyclic aromatic compound 5.0 15.0 Bicyclic aromatic compounds 31.0 <80.0 Tricyclic or more aromatic compound > 55.0 <5.0 Sulfur compounds 1.0 0.1 Nitrogen compounds 5.0 1.2 Oxygen compound 1.0 0.05

Example  2

The aromatic distillate obtained in Example 1 was prepared through hydrodesulfurization / denitrification catalytic decomposition (hydrogenation complex reaction).

Hydrodesulfurization / denitrification catalytic cracking reaction using the catalyst prepared in Preparation Example 1, using a fixed bed reaction apparatus (370 ℃, 30 kg / cm ² , H ₂ / HC 5.3, LHSV 1.0 hr ^-1 ) It was carried out, the typical yield structure is shown in Table 2 below.

ingredient Content (wt%) <C5 + non-aromatic component <45 benzene <15 toluene <10 Xylene ~ 5.0 Other Aromatic Ingredients > 20 Sulfur content <0.03 Nitrogen content <0.05

Example  3

The aromatic distillate obtained in Example 1 was prepared through hydrodesulfurization / denitrification catalytic decomposition (hydrogenation complex reaction).

Hydrodesulfurization / denitrification catalytic cracking reaction using the catalyst prepared in Preparation Example 2, using a fixed bed reaction apparatus (370 ℃, 30 kg / cm ² , H ₂ / HC 5.3, LHSV 1.0 hr ^-1 ) It was carried out, the typical yield structure is shown in Table 3 below.

ingredient content(%) <C5 + non-aromatic component <30 benzene <7 toluene <2.5 Xylene To 35 Other Aromatic Ingredients > 25 Sulfur content  <0.01 Nitrogen content  <0.01

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

U1: Distillation Separation Process
U2: Hydrodesulfurization / Denitrification Catalytic Decomposition Process (Hydraulic Treatment Complex Reaction Process)

Claims (9)

Distilling coal tar to separate the remaining oil and the effluent oil (a); And
The effluent oil is removed in the presence of a shape-selective catalyst to remove at least one selected from sulfur compounds and nitrogen compounds through hydrogenation desulfurization / denitrification catalytic decomposition to an aromatic product containing at least one selected from benzene, toluene and xylene. (B);
The shape-selective catalyst is at least one selected from Ni ₂ P, Co ₂ P, Fe ₂ P, MoP, WP, MoS ₂ , Ni-MoS ₂ , Ni-WS ₂ and Co-MoS ₂ zeolite, ZSM-5, A method for producing an aromatic product, which is supported on at least one shape-selective carrier selected from beta zeolite, Y-zeolite, USY zeolite and mordenite. delete delete delete The method of claim 1, wherein the hydrodesulfurization / denitrification catalytic cracking process is operated at a temperature of 200 to 1,000 ° C. and a pressure of 10 to 200 atmospheres. The method of claim 1, wherein the hydrodesulfurization / denitrification catalytic cracking process uses a coke oven gas as a hydrogen source of the hydrodesulfurization / desorption catalytic cracking process. The method of claim 1, wherein the hydrodesulfurization / denitrification catalytic decomposition reaction is desulfurization, denitrification, pyrolysis reaction, dealkylation reaction, isomerization reaction, transalkylation reaction and alkylation production of the aromatic product, characterized in that is carried out Way. The method of claim 1 wherein the aromatic product is produced in a batch reactor, continuous fixed bed reactor or continuous fluidized bed reactor. delete

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