Method for preparing olefins and aromatics through catalytic decomposition of liquid hydrocarbon raw material

Abstract

The present invention relates to a method for preparing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material and, more specifically, to a method for preparing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, in which, in preparing olefin-based and aromatic-based hydrocarbons by decomposing a hydrocarbon raw material, catalytic decomposition is carried out by using, as a raw material, a primary liquid product of CO(1)2(2) Fischer-Tropsch synthesis generated under specific conditions or a liquid hydrocarbon having a specific composition, under specific reaction conditions in the presence of a catalyst, thereby improving the yield of olefins and the selectivity for aromatics.

Description

Method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials

[0001] The present invention relates to a method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material, and more particularly, to a method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material, which improves the yield of olefins and the selectivity for aromatics by performing catalytic cracking using a primary liquid product of CO2 Fischer-Tropsch synthesis produced under specific conditions or a liquid hydrocarbon of a specific composition as a raw material in producing olefin-based and aromatic hydrocarbons by cracking the liquid hydrocarbon raw material.

[0002] Naphtha cracking is a petrochemical process that breaks down heavy petroleum molecules into lighter ones, primarily to produce fuels and chemical feedstocks. Naphtha cracking primarily produces olefinic hydrocarbons, such as ethylene, propylene, butylene, and butadiene, as well as aromatic hydrocarbons, such as benzene, toluene, and xylene.

[0003] The above olefin hydrocarbons are used as raw materials in the manufacture of plastics, rubber products, solvents, detergents, and personal hygiene products, and aromatic hydrocarbons are used as raw materials in the manufacture of plastics, fibers, paints, adhesives, and solvents, and thus olefin and aromatic hydrocarbons are used as key raw materials in many industries closely related to modern life, and thus the demand for olefin and aromatic hydrocarbons and the global market are continuously growing.

[0004] Accordingly, naphtha cracking center (NCC) technology for naphtha cracking holds a key position in the petrochemical industry and is continuously being researched and developed. Currently, thermal cracking and catalytic cracking are two methods in use.

[0005] Pyrolysis is a process that breaks down large hydrocarbon molecules into smaller molecules by inducing a chemical reaction at high temperatures. This process usually does not use a catalyst, but simply increases the temperature to break intramolecular bonds. Since it does not use a catalyst, the process design and operation are relatively simple, and the reaction at high temperatures occurs very quickly, which has the advantage of being advantageous for mass production. However, it consumes a lot of energy to maintain the high temperature, the equipment is subject to severe corrosion and wear, which means high maintenance costs. In addition, various byproducts are generated during the pyrolysis process, which requires processes and costs for post-treatment.

[0006] In contrast, catalytic cracking, a process that decomposes hydrocarbon molecules with the aid of a catalyst, allows for effective decomposition even at lower temperatures. Because the catalyst enables reactions at lower temperatures, this process consumes less energy than thermal cracking, resulting in higher energy efficiency. The catalyst can also selectively increase the production of desired chemicals. Furthermore, the catalytic action reduces byproducts, thereby reducing post-processing costs.

[0007] The present invention proposes a method for producing olefinic and aromatic hydrocarbons from hydrocarbon raw materials such as naphtha by using catalytic cracking as described above, wherein, instead of using general petroleum naphtha as a raw material, a primary liquid product produced through CO2 Fischer-tropsch synthesis under specific conditions is used as a raw material, thereby improving the yield for olefins and the selectivity for aromatics by catalytic cracking.

[0008] As prior art in the technical field of the present invention, Chinese published patents CN 116083121 A, CN 116083122 A, and CN 104152174 A disclose methods for producing low-carbon olefins or light aromatic hydrocarbons from heavy hydrocarbons using catalytic cracking. However, Fischer-Tropsch synthetic oil is only mentioned as one of various raw materials listed as raw materials for hydrocarbons to be subjected to catalytic cracking, and there is no disclosure at all about improving the production efficiency of light olefins and aromatic hydrocarbons from hydrocarbons such as naphtha produced through Fischer-Tropsch synthesis.

[0009] Accordingly, the present invention proposes a new method capable of improving the production efficiency of light olefins and aromatic hydrocarbons by catalytically decomposing a primary liquid product produced through CO2 Fischer-Tropsch synthesis under specific conditions as a raw material under specific conditions.

[0010] [Prior Art Literature]

[0011] [Patent Document]

[0012] (Patent Document 1) Chinese Publication No. CN 116083121 A (Published on May 9, 2023)

[0013] (Patent Document 2) Chinese Publication No. CN 116083122 A (Published on May 9, 2023)

[0014] (Patent Document 3) Chinese Publication No. CN 104152174 A (Published on November 19, 2014)

[0015] The present invention was created to solve the above-mentioned problem, and the purpose of the present invention is to provide a method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product, which can improve the yield for olefins and the selectivity for aromatics by catalytically decomposing a primary synthetic liquid product or a liquid hydrocarbon of a specific composition produced through a CO2 Fischer-Tropsch synthesis reaction under specific reaction conditions in the presence of a catalyst under specific reaction conditions when producing olefin-based and aromatic hydrocarbons by decomposing a hydrocarbon raw material.

[0016] A method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material according to one embodiment of the present invention comprises the steps of: (a) performing a Fischer-Tropsch synthesis reaction using a gaseous reactant including carbon dioxide and hydrogen as raw materials in the presence of a CO2 Fischer-Tropsch synthesis catalyst, in the presence of a mixed metal oxide catalyst including Fe, Cu, Al, and K as a Fischer-Tropsch synthesis catalyst, under reaction conditions of a pressure range of 20 to 30 barg and a temperature range of 280 to 320°C, to produce a Fischer-Tropsch primary synthesis product; and (b) performing catalytic cracking using a liquid hydrocarbon having a carbon number of C4 or more among the Fischer-Tropsch primary synthesis products produced in step (a) as a raw material.

[0017] In addition, as an embodiment of the present invention, the catalyst for Fischer-Tropsch synthesis is characterized in that the weight ratio of Fe, Cu, Al, and K is 11 to 15 parts by weight of Cu, 10 to 14 parts by weight of Al, and 10 to 20 parts by weight of K based on 100 parts by weight of Fe.

[0018] In addition, as one embodiment of the present invention, the step (a) is characterized in that the reverse water gas shift reaction and the Fischer Tropsch synthesis reaction are simultaneously performed in one catalyst and reactor by introducing gaseous reactants including carbon dioxide and hydrogen in the presence of a catalyst for the reverse water gas shift reaction and the Fischer Tropsch synthesis.

[0019] In addition, as one embodiment of the present invention, the step (a) is characterized in that the molar ratio of hydrogen / carbon dioxide (H2 / CO2) is in the range of 5:1 to 1:1.

[0020] In addition, as an embodiment of the present invention, in step (a), the gas space velocity (GHSV) of the carbon dioxide and hydrogen mixed gas is 200 to 10,000 mL / g. cat It is characterized by / h.

[0021] In addition, a method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material according to another embodiment of the present invention, wherein the liquid hydrocarbon raw material is a hydrocarbon having 4 or more carbon atoms, and includes 16 to 23 wt% of paraffinic hydrocarbons, 8 to 12 wt% of isoparaffinic hydrocarbons, 60 to 70 wt% of olefinic hydrocarbons, 2 to 4 wt% of naphthenic hydrocarbons, and 1 to 3 wt% of aromatic hydrocarbons.

[0022] In addition, as an embodiment of the present invention, the liquid hydrocarbon is characterized by being obtained by a CO2 Fischer-Tropsch synthesis reaction.

[0023] In addition, as an embodiment of the present invention, the CO2 Fischer-Tropsch synthesis reaction is characterized in that the reverse water gas shift reaction and the Fischer-Tropsch synthesis reaction are simultaneously performed in one catalyst and reactor by introducing gaseous reactants including carbon dioxide and hydrogen in the presence of a catalyst for the reverse water gas shift reaction and the Fischer-Tropsch synthesis.

[0024] In addition, as an embodiment of the present invention, the content of hydrocarbons having 4 to 7 carbon atoms in the liquid hydrocarbon is 13 wt% to 19 wt%, the content of hydrocarbons having 8 to 10 carbon atoms is 45 wt% to 55 wt%, and the content of hydrocarbons having 11 or more carbon atoms is 30 wt% to 37 wt%.

[0025] In addition, as an embodiment of the present invention, a method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that the catalytic decomposition is performed in the presence of a ZSM-5 catalyst to which phosphorus (P) is added.

[0026] In addition, as one embodiment of the present invention, the catalytic decomposition is characterized in that it is performed in a pressure range of 0 to 10 barg.

[0027] In addition, as one embodiment of the present invention, the catalytic decomposition is characterized in that it is performed in a temperature range of 650 to 750°C.

[0028] In addition, as an embodiment of the present invention, the mass space velocity (WHSV) during the catalyst decomposition is 1 to 50 h -1 It is characterized by being.

[0029] The present invention has the effect of improving the yield of light olefins by decomposing hydrocarbon raw materials to produce olefin-based and aromatic hydrocarbons, by catalytically decomposing a primary synthetic liquid product produced through a CO2 Fischer-Tropsch synthesis reaction or a liquid product of a specific composition as a raw material under specific reaction conditions in the presence of a catalyst.

[0030] In addition, the present invention has the effect of significantly improving the selectivity of aromatics in a liquid phase through the above-described manufacturing method.

[0031] FIG. 1 is a flow chart illustrating a method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product according to one embodiment of the present invention.

[0032] FIG. 2 illustrates a CO2 Fischer-Tropsch synthesis liquid product and a catalytic cracking reaction product produced according to a method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product according to one embodiment of the present invention.

[0033] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

[0034] Additionally, the terms described below are defined based on their functions within the present invention, and may vary depending on the intent of the user or operator or precedent. Therefore, the definitions of these terms should be based on the overall content of this specification.

[0035] The terms “comprising,” “including,” or “having” used in this specification indicate the presence of features, values, steps, operations, components, parts, or combinations thereof described in the specification, and do not exclude the possibility that other features, values, steps, operations, components, parts, or combinations thereof that are not mentioned may be present or added.

[0036] Hereinafter, a method for producing olefins and aromatics using the CO2 Fischer-Tropsch synthesis liquid product of the present invention will be described with reference to the attached drawings.

[0037] The present invention relates to a method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, and relates to a method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product, which can improve the yield of light olefins and the selectivity of aromatics in the liquid phase by catalytically decomposing a liquid hydrocarbon having a C4 or more carbon number and a C4 or more liquid hydrocarbon of a specific composition synthesized through a CO2 Fischer-Tropsch synthesis reaction under specific reaction conditions in the presence of a catalyst under specific reaction conditions.

[0038] FIG. 1 is a flow chart illustrating a method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product according to one embodiment of the present invention.

[0039] As illustrated in FIG. 1, the method for producing olefins and aromatics using a CO2 Fischer-Tropsch synthesis liquid product according to one embodiment of the present invention comprises: (a) a CO2 Fischer-Tropsch synthesis step; and (b) a CO2 Fischer-Tropsch primary synthesis liquid product catalytic decomposition step.

[0040] More specifically, the step (a) is a step of synthesizing a liquid hydrocarbon, which is a raw material for the step (b), through CO2 Fischer-Tropsch synthesis, by subjecting a gaseous reactant containing carbon dioxide and hydrogen to a Fischer-Tropsch synthesis reaction in the presence of a CO2 Fischer-Tropsch synthesis catalyst to produce a Fischer-Tropsch primary synthesis product.

[0041] At this time, the CO2 Fischer-Tropsch synthesis reaction is performed under reaction conditions of a pressure range of 20 to 30 barg and a temperature range of 280 to 320°C. By maintaining the above reaction conditions, the production efficiency of hydrocarbons can be increased.

[0042] In addition, the step (a) above can simultaneously perform the reverse water gas shift reaction (RWGS) that produces carbon monoxide by introducing carbon dioxide and hydrogen and the Fischer-Tropsch reaction that synthesizes hydrocarbons from the produced carbon monoxide within a single catalyst and reactor.

[0043] That is, in the presence of a catalyst for reverse water gas shift reaction and Fischer-Tropsch synthesis, gaseous reactants including carbon dioxide and hydrogen are introduced to simultaneously perform reverse water gas shift reaction and Fischer-Tropsch synthesis reaction within a single catalyst and reactor, thereby improving the yield of carbon monoxide even at a relatively low temperature, thereby improving the yield of hydrocarbon production in the Fischer-Tropsch reaction, and at the same time, the heat generated in the Fischer-Tropsch reaction within the carbon monoxide generation section can be utilized for the reverse water gas shift reaction, thereby improving energy efficiency.

[0044] In addition, when catalytic cracking, which is step (b), is performed using liquid hydrocarbons produced in this manner as raw materials, the efficiency of producing light olefins and aromatics can be further improved.

[0045] More specifically, in step (a), the CO2 Fischer-Tropsch synthesis reaction catalyst includes a mixed metal oxide catalyst including Fe, Cu, Al, and K. At this time, the Fischer-Tropsch synthesis catalyst preferably has a weight ratio of Fe, Cu, Al, and K of 11 to 15 parts by weight of Cu, 10 to 14 parts by weight of Al, and 10 to 20 parts by weight of K based on 100 parts by weight of Fe.

[0046] In addition, the step (a) can supply carbon dioxide gas and hydrogen gas to the reactor at various ratios, and preferably, hydrogen gas and carbon dioxide gas are supplied at a molar ratio of 5:1 to 1:1.

[0047] In addition, the step (a) above can supply a mixture of carbon dioxide and hydrogen gas to the reactor at various flow rates, and the gas hourly space velocity (GHSV) is 100 to 20,000 mL / g. cat / h, preferably 200 to 10,000 mL / g cat / h could be.

[0048] Meanwhile, the present invention may further include a step of removing one or more of by-products such as water and / or gaseous hydrocarbons having less than 4 carbon atoms among the reaction products generated in step (a) and before performing step (b) after step (a).

[0049] In addition, the step (b) is a step of synthesizing ethylene and propylene as light olefins and aromatic hydrocarbons by catalytically decomposing the CO2 Fischer Tropsch primary synthesis liquid product produced in the step (a), and the catalytic decomposition is performed using a liquid hydrocarbon having a carbon number of C4 or more among the Fischer Tropsch primary synthesis products produced in the step (a) as a raw material.

[0050] At this time, the catalytic decomposition in the step (b) is performed under reaction conditions of a pressure range of 0 to 50 barg and a temperature range of 500 to 900°C, more preferably a pressure range of 0 to 20 barg and a temperature range of 600 to 800°C, and even more preferably a pressure range of 0 to 10 barg and a temperature range of 650 to 750°C. Under the above reaction conditions, the yield of light olefins and the selectivity of aromatics in the liquid phase can be improved.

[0051] In addition, in the step (b), the catalyst is not limited as long as it is active for a hydrocarbon decomposition reaction, but may be, for example, an inorganic oxide-supported zeolite, and may include a zeolite having 10-ring structure pores with a SiO2 / Al2O3 molar ratio of 20 to 300 and one or more inorganic oxides selected from the group consisting of Mg, Ca, Sr, Ba, P, Ga, In, Cr, Mn, Fe, Co, Ni and Cu, and preferably may include a ZSM-5 catalyst to which phosphorus (P) is added.

[0052] Additionally, the mass space velocity (WHSV) in the above step (b) is 1 to 50 h -1 , preferably 5 to 25 h -1It could be.

[0053] Meanwhile, the liquid hydrocarbon raw material used in the method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material according to another embodiment of the present invention is characterized by including a hydrocarbon having 4 or more carbon atoms, and comprising 16 to 23 wt% of paraffinic hydrocarbons, 8 to 12 wt% of isoparaffinic hydrocarbons, 60 to 70 wt% of olefinic hydrocarbons, 2 to 4 wt% of naphthenic hydrocarbons, and 1 to 3 wt% of aromatic hydrocarbons based on the total of paraffinic, isoparaffinic, olefinic, naphthenic, and aromatic hydrocarbons. When the composition of the liquid hydrocarbon raw material satisfies the above range, the yield of light olefins and the selectivity of aromatics in the liquid phase can be improved.

[0054] The above liquid hydrocarbon raw material may be composed of hydrocarbons having 4 or more carbon atoms, but may mainly have the largest content of hydrocarbons having 8 to 10 carbon atoms. Specifically, the content of hydrocarbons having 4 to 7 carbon atoms may be 13 wt% to 19 wt%, the content of hydrocarbons having 8 to 10 carbon atoms may be 45 wt% to 55 wt%, and the content of hydrocarbons having 11 or more carbon atoms may be 30 wt% to 37 wt%.

[0055] In the present invention, the liquid hydrocarbon raw material may preferably be a primary synthetic liquid product produced through CO2 Fischer-Tropsch synthesis. At this time, the primary synthetic product may be one produced by simultaneously performing a reverse water gas shift (RWGS) reaction in which carbon dioxide and hydrogen are introduced to produce carbon monoxide and a Fischer-Tropsch reaction in which the produced carbon monoxide is synthesized into a hydrocarbon within a single catalyst and reactor. Specifically, when a gaseous reactant containing carbon dioxide and hydrogen is introduced in the presence of a catalyst for the reverse water gas shift reaction and Fischer-Tropsch synthesis, and the reverse water gas shift reaction and the Fischer-Tropsch synthesis reaction are simultaneously performed within a single catalyst and reactor, a liquid hydrocarbon having a specific composition suitable for the present invention can be obtained in a relatively easy manner, so it is preferable to use the primary synthetic liquid product obtained through the CO2 Fischer-Tropsch synthesis as the liquid hydrocarbon raw material of the present invention.

[0056] When catalytic cracking is performed using liquid hydrocarbons produced in this manner as raw materials, the efficiency of producing light olefins and aromatics can be further improved.

[0057] In addition, the catalytic decomposition according to the present invention is performed under reaction conditions of a pressure range of 0 to 10 barg and a temperature range of 650 to 750°C. Under the above reaction conditions, the yield of light olefins and the selectivity of aromatics in the liquid phase can be improved.

[0058] Additionally, in the above catalytic decomposition, the catalyst includes a ZSM-5 catalyst containing phosphorus (P).

[0059] In addition, the mass space velocity (WHSV) in the above catalytic decomposition is 1 to 50 h -1 , preferably 5 to 25 h -1 It could be.

[0060]

[0061] Hereinafter, when describing in detail the principles of a preferred embodiment of the present invention, if it is determined that a specific description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

[0062]

[0063] Example 1 (FTS primary liquid product catalytic decomposition)

[0064] (a) CO2 Fischer-Tropsch synthesis

[0065] The CO2 Fischer-Tropsch synthesis catalyst was prepared by the following co-precipitation-impregnation method.

[0066] A metal solution was prepared by dissolving 50 g of Fe(NO3)3·9H2O, 12.56 g of Al(NO3)3·9H2O, and 3.24 g of Cu(NO3)2·6H2O in 400 ml of distilled water, and an aqueous solution of 34.62 g of K2CO3 dissolved in 400 ml of distilled water was prepared, and then mixed and coprecipitated together. After stirring at 80 °C for 3 hours, it was cooled to room temperature (20 °C). The formed precipitate was precipitated again by mixing with distilled water equivalent to 3 times the amount of the precipitate slurry, discarding the filtrate, and repeating the above process twice more and filtering. After filtering, it was dried at 110 °C for 15 hours and calcined at 550 °C for 5 hours. The above-mentioned sintered product was impregnated with an aqueous solution of 1.7 g of K2CO3 dissolved in 3.2 ml of distilled water per 10 g of catalyst, dried at 110°C for 15 hours, and then sintered at 550°C for 5 hours to produce a 100Fe-13Cu-12Al-15K powder catalyst having a weight ratio of iron, copper, aluminum, and potassium of 100:13:12:15.

[0067] The manufactured CO2 Fischer-Tropsch synthesis catalyst was charged at 0.5 g in a stainless steel reactor, and in order to activate the CO2 Fischer-Tropsch synthesis catalyst, H2 (5%) / Ar gas flow (6000 mL / g) was applied. cat / h), and pretreated at 500 ℃ for 12 hours. 0.5 g of the pretreated CO2 Fischer-Tropsch synthesis catalyst was charged into the reactor, and gaseous reaction gas containing carbon dioxide, hydrogen, etc. was added at 1,800 mL / g so that the molar ratio of carbon dioxide: hydrogen was 1:3. cat After supplying at a flow rate of / h, CO2 Fischer-Tropsch synthesis reaction was performed under the conditions of reaction temperature of 300 ℃ and reaction pressure of 25 barg, thereby producing a liquid hydrocarbon having a composition as shown in Table 1 below.

[0068] The liquid hydrocarbons in Table 1 are some of the products obtained by the above CO2 Fischer-Tropsch synthesis and are liquid hydrocarbons having 4 or more carbon atoms. Among them, the content of hydrocarbons having 4 to 7 carbon atoms is 15.9 wt%, the content of hydrocarbons having 8 to 10 carbon atoms is 50.6 wt%, and the content of hydrocarbons having 11 or more carbon atoms is 33.5 wt%.

[0069]

[0070] (b) CO2 Fischer-Tropsch primary synthesis liquid product catalytic decomposition

[0071] The decomposition reaction catalyst was used as a raw material for liquid hydrocarbons with the composition shown in Table 1 below, and the catalytic decomposition reaction was performed in a MAT (Micro Activity Test) reactor by applying the ASTM D-5154-10 test method.

[0072] The decomposition reaction catalyst was manufactured through the following process.

[0073] 134.7 g of ZSM-5 (Si / Al = 40) and 439.9 g of distilled water were stirred at room temperature for 30 minutes, and then 100.1 g of 85% phosphoric acid and 228.9 g of alumina sol (Al2O3 = 10 wt%) were sequentially added and mixed sufficiently, and stirred for 1 hour using a high-viscosity slurry mixer, and then 196.6 g of clay was added and stirred again for 1 hour to prepare a mixed slurry, and the mixed slurry was spray-dried and calcined at 650°C for 6 hours to prepare a spherical decomposition reaction catalyst.

[0074] 3g of the catalyst manufactured through the above process was charged into a fixed bed reactor, and the primary synthetic product produced in step (a) was cooled to 10℃ or lower to remove by-products such as gaseous hydrocarbons and water, and the collected primary synthetic liquid product was injected into a MAT (Micro Activity Test) reactor at a rate of 73.8 ml / h for 90 seconds to obtain a mass space velocity (WHSV) of 16 h -1 Under the conditions, the catalytic cracking reaction was performed at a reaction temperature of 680 ℃ and a reaction pressure of atmospheric pressure (ASTM D-5154-10 test method), and the results are shown in Tables 3, 4, and 5 below and in Figure 2.

[0075]

[0076] Composition (wt%): Paraffin 19.3, Isoparaffin 10.4, Olefin 65.2, Naphthene 3.1, Aromatic 2.0, Total 100

[0077]

[0078] Comparative Example 1 (Petroleum naphtha thermal cracking)

[0079] The catalytic cracking reaction was performed in the same manner as in step (b) of Example 1, except that petroleum-derived naphtha having the composition shown in Table 2 below was used as a liquid hydrocarbon raw material for the catalytic cracking reaction in step (b) of Example 1, and the results are shown in Table 3 below.

[0080]

[0081] Composition (wt%) Paraffin 44.7 Isoparaffin 34.7 Olefin 3.4 Naphthene 13.7 Aromatic 3.5 Total 100

[0082]

[0083] Comparative Example 2 (Catalytic Cracking of Petroleum Naphtha)

[0084] The decomposition reaction was performed in the same manner as in Comparative Example 1, except that the thermal decomposition reaction was performed without a catalyst, and the results are shown in Table 3 below.

[0085]

[0086] Comparative Example 3 (FTS primary liquid product thermal decomposition)

[0087] Except that the thermal decomposition reaction was performed without a catalyst in step (b) of the above Example 1, the CO2 Fischer-Tropsch synthesis liquid product was thermally decomposed using a hydrocarbon raw material in the same manner as in the above Example 1, and the results are shown in Tables 3, 4, and 5 below.

[0088]

[0089] Olefin yield (wt%) Aromatic selectivity in liquid phase (%) Example 151.263.38 Comparative example 121.410.39 Comparative example 215.66.79 Comparative example 330.117.35

[0090]

[0091] Table 3 above shows the yield of light olefins (ethylene, propylene) produced according to Example 1 and Comparative Examples 1 to 3 and the aromatic selectivity among the liquid products.

[0092] Referring to Table 1 above, when the CO2 Fischer-Tropsch synthesis liquid product was catalytically decomposed using hydrocarbon raw materials according to Example 1, which is the manufacturing method of the present invention,

[0093] Compared to Comparative Example 1, when catalytic cracking was performed using petroleum naphtha as a raw material, the olefin yield was more than twice and the aromatic selectivity in the liquid phase was more than six times. Compared to pyrolysis using CO2 Fischer-Tropsch synthesis liquid product as a raw material, the olefin yield was more than 1.6 times and the aromatic selectivity in the liquid phase was more than three times. Compared to Comparative Example 2, when pyrolysis was performed using petroleum naphtha as a raw material, the olefin yield was more than three times and the aromatic selectivity in the liquid phase was more than nine times.

[0094] That is, when CO2 Fischer-Tropsch synthesis is performed according to the manufacturing method of the present invention and then the primary liquid composite produced thereby or the liquid raw material having the composition of the present invention is catalytically decomposed, the yield of olefins can be improved and the aromatic selectivity in the liquid can be significantly improved.

[0095]

[0096] Table 4 above shows the yield of each hydrocarbon in the products manufactured according to Example 1 and Comparative Example 3.

[0097]

[0098] Yield (wt%) Example 1 Comparative Example 3 Methane 5.3 5.4 Ethylene 23.6 15.6 Ethane 4.3 4 Propylene 27.6 14.6 Propane 2.9 0.6 1-Butene 2.5 4.8 i-Butylene 3.9 1.2 t-2-Butene 2.6 0.9 c-2-Butene 20.7 i-Butane 0.5 0 n-Butane 0.9 0.2 i-Pentane 0.3 0.2 n-Pentane 0.6 5.1 Others 4.3 9.7 Total 8 1.3 6 3 E+P, wt% 5 1.2 3 0.2

[0099]

[0100] As shown in Table 4 above, when the CO2 Fischer-Tropsch synthesis liquid product was catalytically decomposed using hydrocarbon raw materials according to Example 1, which is the manufacturing method of the present invention, it was shown that a yield of 1.5 times or more for ethylene and 1.8 times or more for propylene could be obtained.

[0101] That is, even if the CO2 Fischer-Tropsch synthesis liquid product is used as an olefin synthesis raw material or a raw material according to the composition of the present invention, a higher light olefin yield can be obtained when catalytic decomposition according to the production method of the present invention is used than when thermal decomposition is used.

[0102]

[0103] Table 5 below shows the wt% of the liquid phase of hydrocarbons having a carbon number of C4 or more among the products manufactured according to Example 1, and Table 6 shows the wt% of the liquid phase of hydrocarbons having a carbon number of C4 or more among the products manufactured according to Comparative Example 3. For reference, P represents paraffinic, I represents isoparaffinic, O represents olefinic, N represents naphthenic, and A represents aromatic hydrocarbons.

[0104]

[0105] Carbon NoPIONATotalC4000000C500.550.08000.63C60.050.020.140.055.095.35C70.060.190.310.1226.0326.71C800.530.91.271921.7C900.641 .690.294.216.83C1001.810.040.794.276.91C1100.6800.371.963.0 1C120.321.58002.824.72C13+000000Total0.4363.162.8963.3875.86

[0106]

[0107] Carbon NoPIONATotalC40.1100.12000.23C50.050.311.240.0501.65C60.360.593.620.163.217.94C703.932.030.525.8412.32C80.152.247.422.1 98.320.3C902.461.7004.16C101.2903.73005.02C111.0202.25003.27 C121.6501.63003.28C13+000000Total4.639.5323.742.9217.3558.17

[0108]

[0109] As a result of performing catalytic decomposition according to Example 1 and thermal decomposition according to Comparative Example 3 on the first synthetic liquid product produced in step (a) of Example 1, as shown in Tables 5 and 6, in the case of thermal decomposition, benzene was produced at 3.21 wt%, toluene at 5.84 wt%, and xylene at 8.3 wt%, for a total of 17.31 wt%, and in the case of catalytic decomposition, benzene was produced at 5.09 wt%, toluene at 26.0 wt%, and xylene at 19 wt%, for a total of 50.12 wt%, showing that catalytic decomposition had a selectivity among the liquid phases of benzene, toluene, and xylene in the reaction product that was about 3 times higher than that of thermal decomposition.

[0110] While the present invention has been described above with reference to the embodiments described herein and illustrated in the accompanying drawings, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent embodiments are possible. Accordingly, the technical protection scope of the present invention should be defined by the following claims.

Claims

In a method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, (a) a step of producing a Fischer-Tropsch primary synthesis product by performing a Fischer-Tropsch synthesis reaction in the presence of a mixed metal oxide catalyst including Fe, Cu, Al and K as a Fischer-Tropsch synthesis catalyst using a gaseous reactant including carbon dioxide and hydrogen as raw materials in the presence of a CO2 Fischer-Tropsch synthesis catalyst under reaction conditions of a pressure range of 20 to 30 barg and a temperature range of 280 to 320°C; and (b) A method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that it comprises a step of catalytically decomposing a liquid hydrocarbon having a carbon number of C4 or more among the Fischer-Tropsch primary synthesis products produced in step (a) as a raw material. In the first paragraph, The above Fischer-Tropsch synthesis catalyst is, A method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that the weight ratio of Fe, Cu, Al and K is 11 to 15 parts by weight of Cu, 10 to 14 parts by weight of Al and 10 to 20 parts by weight of K based on 100 parts by weight of Fe. In the first paragraph, Step (a) above, A method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, characterized in that the reverse water gas shift reaction and the Fischer Tropsch synthesis reaction are simultaneously performed in one catalyst and reactor by introducing gaseous reactants containing carbon dioxide and hydrogen in the presence of a catalyst for the reverse water gas shift reaction and the Fischer Tropsch synthesis. In the first paragraph, Step (a) above, A method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material, characterized in that the molar ratio of hydrogen / carbon dioxide (H2 / CO2) is in the range of 5:1 to 1:

1. In the first paragraph, Step (a) above, The gaseous high-speed space velocity (GHSV) of the carbon dioxide and hydrogen mixture is 200 to 10,000 mL / g. cat A method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, characterized in that the rate is / h. In a method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, The above liquid hydrocarbon raw material is a hydrocarbon having 4 or more carbon atoms, 16 to 23 wt% of paraffinic hydrocarbons, 8 to 12 wt% of isoparaffinic hydrocarbons, 60 to 70 wt% of olefinic hydrocarbons, 2 to 4 wt% of naphthenic hydrocarbons and A method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material, characterized in that it contains 1 to 3 wt% of aromatic hydrocarbons. In paragraph 6, A method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that the liquid hydrocarbon is obtained by a CO2 Fischer-Tropsch synthesis reaction. In paragraph 7, A method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, characterized in that the CO2 Fischer-Tropsch synthesis reaction is performed simultaneously in a single catalyst and reactor by introducing gaseous reactants containing carbon dioxide and hydrogen in the presence of a catalyst for the reverse water gas shift reaction and the Fischer-Tropsch synthesis. In paragraph 6, A method for producing olefins and aromatics through catalytic cracking of a liquid hydrocarbon raw material, characterized in that the content of hydrocarbons having 4 to 7 carbon atoms in the liquid hydrocarbon is 13 wt% to 19 wt%, the content of hydrocarbons having 8 to 10 carbon atoms is 45 wt% to 55 wt%, and the content of hydrocarbons having 11 or more carbon atoms is 30 wt% to 37 wt%. In claim 1 or claim 6, A method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that the catalytic decomposition is performed in the presence of a ZSM-5 catalyst to which phosphorus (P) is added. In Article 10, A method for producing olefins and aromatics through catalytic decomposition of liquid hydrocarbon raw materials, characterized in that the catalytic decomposition is performed in a pressure range of 0 to 10 barg. In Article 10, A method for producing olefins and aromatics through catalytic decomposition of a liquid hydrocarbon raw material, characterized in that the catalytic decomposition is performed in a temperature range of 650 to 750°C. In claim 1 or claim 6, The mass space velocity (WHSV) during the above catalyst decomposition is 1 to 50 h -1 A method for producing olefins and aromatics through catalytic cracking of liquid hydrocarbon raw materials, characterized in that:

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