Method for preparing oxo-alcohol by using partial oxidation reaction products

Abstract

The present invention provides a method for preparing an oxo-alcohol by using partial oxidation reaction products.

Description

Method for producing oxo alcohol using partial oxidation reaction product

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0117716, filed August 30, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a method for producing oxo alcohols from partial oxidation (POX) reaction products.

[0004] The hydroformylation reaction is a reaction in which various olefins are reacted with synthesis gas containing carbon monoxide (CO) and hydrogen (H2) in the presence of a hydroformylation catalyst under appropriate temperature and pressure conditions to produce an aldehyde with one more carbon atom than the olefin.

[0005] The hydrogenated alcohol of an aldehyde produced by a hydroformylation reaction is called an oxo-alcohol, and the hydroformylation reaction is also called an OXO reaction. Oxo-alcohols are widely used industrially as solvents, additives, raw materials for various plasticizers, and synthetic lubricants.

[0006] Meanwhile, steam reforming and partial oxidation (POX) reactions are commonly used as methods for producing synthesis gas containing carbon monoxide (CO) and hydrogen (H2). Steam reforming is an endothermic reaction in which a feed gas containing methane (CH4) reacts with steam in the presence of a steam reforming catalyst to produce carbon monoxide (CO) and hydrogen (H2). Partial oxidation (POX) is an exothermic reaction in which a synthesis gas containing hydrogen and carbon monoxide is produced by supplying less oxygen than is required to oxidize hydrocarbons to water and carbon dioxide.

[0007] The POX reaction can produce synthesis gas containing carbon monoxide (CO) and hydrogen (H2) more energy-efficiently than the steam reforming reaction, but it has the problem of accelerating global warming by generating a large amount of carbon dioxide (CO2) as a reaction byproduct.

[0008] One object of the present invention is to provide a method for producing oxo alcohols by using a synthesis gas containing hydrogen and carbon monoxide, which are products of a partial oxidation (POX) reaction, as a reactant of a hydroformylation reaction.

[0009] Another object of the present invention is to provide a method for controlling the molar ratio of hydrogen / carbon monoxide for the hydroformylation reaction and reducing greenhouse gas emissions by combining the partial oxidation (POX) reaction product with a methane dry reforming (DRM) reaction and / or a water gas shift (WGS) process when applying the product to the hydroformylation reaction.

[0010] However, the technical problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the description below.

[0011] The present invention provides a method for producing an oxo alcohol using a partial oxidation reaction product, the method comprising: generating a first mixed gas containing hydrogen, carbon monoxide, and carbon dioxide through a partial oxidation (POX) reaction of a hydrocarbon; separating carbon dioxide from the first mixed gas; generating a second mixed gas containing hydrogen and carbon monoxide through a dry reforming of methane (DRM) reaction with at least a portion of the carbon dioxide separated from the first mixed gas; and generating an oxo alcohol by hydroformylating a reaction gas containing the first mixed gas with an olefin.

[0012] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, wherein the second mixed gas further includes unreacted carbon dioxide, and the method further includes a step of separating carbon dioxide from the second mixed gas.

[0013] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, further comprising a step of subjecting at least a portion of the carbon dioxide separated from the second mixed gas to a methane dry reforming reaction.

[0014] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, wherein the reaction gas further includes a second mixed gas.

[0015] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, further comprising a step of adding hydrogen to the reaction gas so that the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the reaction gas becomes 0.97 to 1.15.

[0016] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, further comprising a step of producing a third mixed gas containing hydrogen and carbon monoxide by subjecting at least a portion of the second mixed gas to a water gas sift reaction with water vapor.

[0017] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, wherein the reaction gas includes the first mixed gas and the third mixed gas, and the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the reaction gas is 0.97 to 1.15.

[0018] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, wherein the third mixed gas further includes carbon dioxide, and the method further includes a step of separating carbon dioxide from the third mixed gas.

[0019] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, further comprising a step of discharging into the atmosphere an off gas containing carbon dioxide separated from the first mixed gas and not used in a dry reforming of methane reaction.

[0020] The present invention provides a method for producing oxo alcohol using a partial oxidation reaction product, wherein the ratio of the total amount of carbon dioxide in the off-gas to the total amount of the reaction gas is 0.1 or less.

[0021] When using the method of the present invention, a method is provided for synthesizing oxo alcohols in an economical manner by utilizing a synthesis gas containing hydrogen and carbon monoxide, which are products of a partial oxidation (POX) reaction, as a reactant of a hydroformylation reaction.

[0022] In addition, in the present invention, by performing a methane dry reforming reaction (DRM) prior to applying the product of the partial oxidation (POX) reaction to the hydroformylation reaction, the amount of greenhouse gases such as carbon dioxide generated by the partial oxidation reaction can be reduced while the amount of hydrogen and carbon monoxide produced can be increased.

[0023] Furthermore, the present invention can increase the yield of the hydroformylation reaction by controlling the molar ratio of hydrogen and carbon monoxide in the mixed gas by additionally including a water gas shift (WGS) process, and can further increase economic efficiency by eliminating the need to additionally inject hydrogen or carbon monoxide gas for control.

[0024] Figures 1 and 2 are diagrams showing embodiments of the present invention.

[0025] Figure 3 is a diagram showing a comparative example of the present invention.

[0026] Hereinafter, the present specification will be described in more detail.

[0027] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0028] In this specification, 'p to q' or 'p~q' means 'p or more and q or less'.

[0029] In this specification, 'n' means a number arbitrarily described to distinguish substances having different but identical names.

[0030] In this specification, 'syngas' means a mixed gas of carbon monoxide (CO) and hydrogen (H2).

[0031] According to one embodiment of the present invention, there is provided a method for producing an oxo alcohol using a partial oxidation reaction product, the method comprising: generating a first mixed gas containing hydrogen, carbon monoxide, and carbon dioxide through a partial oxidation (hereinafter, 'POX') reaction of a hydrocarbon; and generating an oxo alcohol by reacting a reaction gas containing the first mixed gas with an olefin.

[0032] The above "partial oxidation (POX) reaction of hydrocarbons" is a reaction represented by the following reaction formula 1. The POX reaction is ΔH o 298 = -36 kJ / mol, it is an exothermic reaction and thus energy-saving. Nickel or cobalt catalysts are known as catalysts for the POX reaction, and nickel catalysts, which are highly active, are representatively used in the production of synthesis gas.

[0033] [Reaction Formula 1]

[0034] CH4+ ½O2→ CO + 2H2

[0035] Furthermore, the POX reaction exhibits increased methane conversion and increased selectivity for CO and H2 as the temperature increases in the range of 500 K to 1120 K. In particular, very high synthesis gas conversion is observed at temperatures around 1050 K. Because an increase in the methane / oxygen ratio decreases methane conversion and pushes the reaction further away from complete combustion, the methane / oxygen ratio is often increased to enhance synthesis gas selectivity.

[0036] The hydrocarbon reactant of the above POX reaction contains methane (CH4) as its main component, and although pure methane can be preferably used, vacuum residual oil (VR) generated during the distillation process of crude oil can be used. Here, the "vacuum residual oil (VR)" refers to the bottom oil remaining after vacuum distillation (VDU) of atmospheric residue (AR) generated by atmospheric distillation (CDU) of crude oil. The vacuum residual oil is used as a raw material for the heavy oil hydrodesulfurization process and the asphalt oxidation process.

[0037] Vacuum residue, which corresponds to heavy oil, can be made into light oil through advanced processes such as the RFCC (Residue Fluid Catalytic Cracking) process, which is a catalytic cracking process that reacts with a catalyst, and hydrocracking, which cracks by adding hydrogen.

[0038] In theory, during the POX reaction of the above hydrocarbon, only a mixed gas of hydrogen and carbon monoxide should be produced. However, in the actual process, a large amount of carbon dioxide (CO2) and water (H2O) are produced as some of the reactants are completely combusted. Therefore, the method may further include a step of separating carbon dioxide from the first mixed gas, when a first mixed gas containing carbon dioxide along with hydrogen and carbon monoxide is produced through the POX reaction.

[0039] The method for separating carbon dioxide from the first mixed gas may include, without limitation, a low-temperature separation method, an absorption method, a membrane separation method, an adsorption method, and the like, as long as it is a method commonly known in the relevant field. Preferably, an absorption method or an adsorption method may be used, and more preferably, an absorption method may be used. Here, the absorption method is a method using an absorbent (solvent), and the adsorption method utilizes the principle that a gas mixture is selectively adsorbed on the surface of an adsorbent (solid) having micropores.

[0040] When using vacuum residue (VR) as a reactant in the above POX reaction, the first mixed gas may contain a trace amount of sulfur components. Therefore, the step of separating the carbon dioxide may further include a step of removing sulfur from the first mixed gas. Here, the method for removing the sulfur may be performed by a wet desulfurization process using an absorbent, a dry desulfurization process, or a semi-dry desulfurization process, but is not limited thereto.

[0041] Some of the carbon dioxide separated from the first mixed gas may be released into the atmosphere as off-gas. In this case, if the first mixed gas contains sulfur as described above, the carbon dioxide that has undergone the desulfurization process may be released into the atmosphere. Additionally, during the carbon dioxide separation process, the Claus gas containing sulfur may also be released separately.

[0042] The method may further include a step of producing a second mixed gas containing carbon dioxide, carbon monoxide, and hydrogen by subjecting at least a portion of the carbon dioxide separated from the first mixed gas to a dry reforming of methane (hereinafter referred to as 'DRM').

[0043] The above "dry reforming of methane (DRM) reaction" is one of the methods for converting methane and carbon dioxide into synthesis gas (hydrogen and carbon monoxide) through a reaction represented by the following reaction formula 2.

[0044] [Reaction Formula 2]

[0045] CH4+ CO2→ 2CO + 2H2

[0046] In the present invention, by utilizing carbon dioxide separated from the first mixed gas as a reactant for the DRM reaction, the amount of carbon dioxide emissions can be reduced by 50% or more while the amount of hydrogen and carbon monoxide produced can be increased.

[0047] The above DRM reaction is ΔH o 298 = 261 kJmol, and the reaction efficiency is increased by lowering the reaction temperature using a catalyst. As a catalyst that can be used for the DRM reaction, a metal catalyst including platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), tungsten (W), titanium (Ti), vanadium (V), iron (Fe), nickel (Ni), copper (Cu), etc. can be used, but a catalyst having a perovskite crystal structure supported on a porous metal support can be used. At this time, the porous metal support may be NiFeCrAl, NiCrAl, stainless steel, or inconel, etc., and the perovskite-based catalyst component may include strontium (Sr), titanium (Ti), nickel (Ni), iridium (Y), etc. The above-mentioned perovskite catalyst has inherently excellent resistance to sulfur (S) and carbon (C), and thus can have high resistance to carbon deposition and / or catalyst poisoning.

[0048] In the step of producing oxo alcohol by hydroformylating a reaction gas containing the first mixed gas with olefin, the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the reaction gas may be 0.97 to 1.15, preferably 0.99 to 1.1, and more preferably 0.99 to 1. When synthesizing oxo alcohol through hydroformylation, aldehyde is first produced by the reaction of olefin with hydrogen and carbon monoxide, and at this time, since olefin, hydrogen and carbon monoxide react at a molar ratio of 1:1:1, it is most preferable that the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) in the reaction gas is 1.

[0049] However, since the first mixed gas produced through the POX reaction has a molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of approximately 0.90 to 0.94, which is lower than the molar ratio of the reaction gas suitable for use in the hydroformylation reaction, a step of controlling the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the reaction gas or the mixed gas mixed with the reaction gas may be necessary.

[0050] At this time, methods for controlling the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) include a method of adding hydrogen or a method of utilizing the water gas shift reaction as described below.

[0051] On the other hand, the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) included in the second mixed gas generated by the above DRM reaction has a value close to 1.

[0052] That is, when only the second mixed gas is used as a reaction gas through a separate line, oxo alcohol can be efficiently produced by hydroformylation reaction with olefin without controlling the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO).

[0053] However, in the method of the present invention, the second mixed gas generated by the DRM reaction may be used by being mixed with the reaction gas containing the first mixed gas, and in this case as well, a step of controlling the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the reaction gas or the mixed gas mixed with the reaction gas may be necessary.

[0054] When the second mixed gas is mixed with the first mixed gas and used as a reaction gas, the amount of carbon dioxide generated in the process of producing oxo-alcohol from the POX reaction can be more effectively reduced.

[0055] In addition, when the second mixed gas is mixed with the first mixed gas and used as a reaction gas, the amount of vacuum residue (VR) used can be reduced, and thus the amount of air pollutants such as sulfur compounds (H2S, COS, etc.) and HCN emitted during the POX reaction can be reduced by using vacuum residue (VR). As a result, there is an effect of reducing energy consumption for treating air pollutants.

[0056] Specifically, the method may further include a step of adjusting the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) included in the second mixed gas to a molar ratio of 1.1 to 1.4, 1.15 to 1.35, or 1.2 to 1.3, if necessary, taking into account the efficiency aspect of the hydroformylation reaction to be performed thereafter.

[0057] That is, in order to increase the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the first mixed gas generated in the POX reaction to an appropriate range, the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the second mixed gas can be adjusted to a value greater than 1 and satisfying the above range.

[0058] Here, the molar ratio of hydrogen and carbon monoxide contained in the second mixed gas can be controlled by adding hydrogen or separating carbon monoxide from the second mixed gas, but the method of adding hydrogen is common.

[0059] In the present invention, in addition to adding hydrogen to the second mixed gas or separating carbon monoxide, the second mixed gas, i.e., the product of the DRM reaction, is reused as a reactant of a water gas shift (hereinafter referred to as 'WGS') reaction, thereby obtaining a mixed gas in which the molar ratio of hydrogen and carbon monoxide (the molar ratio of H2 / CO) is controlled to 1.1 to 1.4, 1.15 to 1.35, or 1.2 to 1.3. Specifically, the method may include a step of generating a third mixed gas containing hydrogen and carbon monoxide by subjecting at least a portion of the second mixed gas and water vapor to a water gas shift (WGS) reaction.

[0060] The above "water gas shift (hereinafter referred to as 'WGS') reaction" is a reaction represented by the following reaction formula 3, and is a reaction in which carbon monoxide and water vapor in the synthesis gas react to produce hydrogen and carbon dioxide. The water gas shift (WGS) reaction is divided into a high temperature shift (HTS) reaction that reacts in the 300-400℃ range and a low temperature shift (LTS) reaction that reacts in the 200-250℃ range depending on the temperature range, and the low temperature shift (LTS) reaction is preferable because it has a high CO conversion rate. A catalyst can be used to increase the reaction rate during the low temperature shift reaction. A representative example of a catalyst that can be used at this time is a copper (Cu)-based catalyst, and more specifically, Cu / ZnO / Al2O3, etc.

[0061] [Reaction Formula 3]

[0062] CO + H2O → CO2+ H2

[0063] If the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the reaction gas can be controlled within a range of 0.97 to 1.15 using the WGS reaction, the step of adding hydrogen or separating carbon monoxide to control the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) in the reaction gas can be omitted.

[0064] The above WGS reaction is ΔH o 298 = -41 kJ / mol, and since the reaction does not consume much energy, it is preferable in terms of energy efficiency to control the molar ratio of hydrogen and carbon monoxide contained in the second mixed gas (molar ratio of H2 / CO) through the WGS reaction rather than adding hydrogen or separating carbon monoxide.

[0065] The method may include a step of producing an oxo alcohol by subjecting a reaction gas including a first mixed gas generated by the POX reaction, a second mixed gas generated by the DRM reaction, and / or a third mixed gas generated by the WGS reaction to a hydroformylation reaction with an olefin.

[0066] That is, the reaction gas may include a first mixed gas, a second mixed gas, and / or a third mixed gas.

[0067] As an example, the first mixed gas generated by the POX reaction can be used as a reaction gas in the hydroformylation reaction.

[0068] As another example, the second mixed gas generated by the DRM reaction can be used as a reaction gas in the hydroformylation reaction.

[0069] As another example, the hydroformylation reaction may include a first mixed gas generated by the POX reaction, and additionally, at least one of a second mixed gas generated by the DRM reaction and a third mixed gas generated by the WGS reaction may be used as a reaction gas.

[0070] As another example, the hydroformylation reaction may use a mixture of a first mixed gas generated by the POX reaction and a second mixed gas generated by the DRM reaction as a reaction gas.

[0071] As another example, the hydroformylation reaction may use a mixture of a first mixed gas generated by the POX reaction and a third mixed gas generated by the WGS reaction as a reaction gas.

[0072] In addition, the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the above-mentioned reaction gases may be 0.97 to 1.15, preferably 0.99 to 1.1, and more preferably 0.99 to 1, as described above.

[0073] However, since the second mixed gas or the third mixed gas may contain unreacted carbon dioxide, the method of the present invention may further include a step of separating carbon dioxide from the second mixed gas or the third mixed gas, if necessary. In this case, the separation of carbon dioxide may be performed before mixing the second mixed gas or the third mixed gas with the first mixed gas, or may be performed after mixing the second mixed gas or the third mixed gas with the first mixed gas.

[0074] Additionally, the method may further include a step of reacting at least some of the carbon dioxide separated from the second mixed gas or the third mixed gas with methane and DRM.

[0075] The method of the present invention can significantly reduce the amount of carbon dioxide emissions compared to the amount of synthesis gas produced by combining the POX reaction and the DRM reaction. In this regard, in the present invention, some of the carbon dioxide separated from the first mixed gas, the second mixed gas, and / or the third mixed gas can be discharged into the atmosphere as off-gas, and the ratio of the total amount (kg / h) of carbon dioxide in the off-gas to the total amount (kg / h) of the reaction gas (particularly, hydrogen and carbon monoxide) for the hydroformylation reaction can be 0.1 or less, 0.08 or less, or 0.06 or less.

[0076] Figure 1 is a process schematic diagram according to one embodiment of the present invention. First, hydrocarbons (e.g., vacuum residue (VR)) and oxygen (O2) may be introduced into a first reactor (100) to generate hydrogen, carbon monoxide, and a first mixed gas (S1) through a POX reaction. The first mixed gas (S1) may be introduced into a first gas purifier (10) to separate carbon dioxide (CO2) from the first mixed gas (S1). At least a portion (S5) of the separated carbon dioxide may be transported to a DRM pretreatment reactor (200) together with methane (CH4). Components such as dust, H2S, and SO2 mixed in during the process of introducing methane or transporting carbon dioxide may be removed in the DRM pretreatment reactor (200).

[0077] Thereafter, the pretreated mixed gas of methane and carbon dioxide and air can be fed into a third reactor (300). Here, the third reactor may be a reformer. Although not shown in the drawing, the reformer may include a tube side into which the mixed gas is fed and a heater side into which fuel and air are fed.

[0078] The heat required for the DRM reaction of methane and carbon dioxide in the mixed gas is provided by the combustion heat generated through the combustion reaction of air and fuel on the heater side.

[0079] In this way, the DRM reaction of methane and carbon dioxide progresses by the combustion heat generated through the combustion reaction of air and fuel on the heater side, thereby generating a second mixed gas (S10) containing hydrogen and carbon monoxide.

[0080] At this time, the second mixed gas (S10) may contain some unreacted carbon dioxide, and in some cases, may also contain some unreacted methane. If necessary, the second mixed gas (S10) may be fed into a gas purifier (210) to separate the unreacted carbon dioxide. The separated carbon dioxide may be used again in the DRM reaction. For reference, the flue gas generated in the third reactor (300) may be discharged into the atmosphere.

[0081] A mixed gas (S2) of a gas containing hydrogen and carbon monoxide as main components from which carbon dioxide is separated from a first mixed gas (S1) and a second mixed gas (S10) can be supplied to a fourth reactor (400) for a hydroformylation reaction.

[0082] At this time, if the ratio of hydrogen and carbon monoxide (H2 / CO) contained in the mixed gas (S2) is less than 0.97, hydrogen may be added to adjust the ratio of hydrogen and carbon monoxide (H2 / CO) in the reaction gas (S4) for the hydroformylation reaction to satisfy 0.97 to 1.15, most preferably 1. In the fourth reactor (400), the hydroformylation reaction of the reaction gas (S4) may be initiated to synthesize oxo alcohol. Some of the carbon dioxide separated from the first mixed gas (S1) or the second mixed gas (S2) in the first gas purifier (10), or other gases containing other components, may be discharged into the atmosphere, and if necessary, may be added to an additional second gas purifier (20) to remove harmful components such as sulfur, and then the clean purified gas (S7) may be discharged into the atmosphere.

[0083] Figure 2 is a process schematic diagram according to another embodiment of the present invention. First, hydrocarbons (e.g., vacuum residue (VR)) and oxygen (O2) may be introduced into a first reactor (100) to generate hydrogen, carbon monoxide, and a first mixed gas (S1) through a POX reaction. The first mixed gas (S1) may be introduced into a first gas purifier (10) to separate carbon dioxide (CO2) from the first mixed gas (S1). At least a portion (S5) of the separated carbon dioxide may be transported to a DRM pretreatment reactor (200) together with methane (CH4). Components such as dust, H2S, and SO2 mixed in during the process of introducing methane or transporting carbon dioxide may be removed in the DRM pretreatment reactor (200).

[0084] Afterwards, the pretreated mixed gas of methane and carbon dioxide and air can be fed into the third reactor (300), which is a reformer. When the DRM reaction is initiated in the third reactor (300), a second mixed gas (S10) containing hydrogen and carbon monoxide can be generated. The process of generating the second mixed gas (S10) containing hydrogen and carbon monoxide when the DRM reaction is initiated in the third reactor (300) can be applied to the description of Fig. 1.

[0085] At this time, the second mixed gas (S10) may contain some unreacted carbon dioxide, and in some cases, may also contain some unreacted methane. If necessary, the second mixed gas (S10) may be fed into a gas purifier (210) to separate the unreacted carbon dioxide. The separated carbon dioxide may be used again in the DRM reaction. For reference, the flue gas generated in the third reactor (300) may be discharged into the atmosphere.

[0086] Next, a portion of the second mixed gas (S10) (S11) may be introduced into a WGS reactor (500), and steam may be additionally injected to perform the WGS reaction. Through the WGS reaction, a third mixed gas having a molar ratio of hydrogen and carbon monoxide (H2 / CO) greater than 1 may be generated. When only a portion of the second mixed gas (S10) is introduced into the WGS, a fourth mixed gas (S13) of the third mixed gas and the remainder (S12) of the second mixed gas may be obtained. If necessary, the fourth mixed gas (S13) obtained after the WGS reaction may be introduced into a gas purifier (210) to separate unreacted carbon dioxide. The carbon dioxide thus separated may be used again in the DRM reaction. Carbon dioxide is removed from the first mixed gas (S1) and a mixed gas (S2) containing hydrogen and carbon monoxide as main components and the fourth mixed gas (S13) can be supplied to the fourth reactor (400) for the hydroformylation reaction. Since the molar ratio (H2 / CO) of hydrogen and carbon monoxide contained in the third mixed gas is greater than 1 due to the WGS reaction, the molar ratio (H2 / CO) of hydrogen and carbon monoxide contained in the mixed gas (S2) of the fourth mixed gas (S13) and the first mixed gas (S1) can be approximately 1. Therefore, oxo alcohols can be synthesized by applying the mixed gas (S2) as a reaction gas for the hydroformylation reaction without additionally injecting hydrogen. However, if necessary, additionally injecting hydrogen into the mixed gas (S2) is also included in the scope of the present invention.

[0087] Some of the carbon dioxide separated from the first mixed gas (S1) or the fourth mixed gas (S13) in the first gas purifier (10), or other gases containing other components, can be discharged into the atmosphere, and if necessary, can be fed into an additional second gas purifier (20) to remove harmful components such as sulfur, and then discharge clean purified gas (S7) into the atmosphere.

[0088] Hereinafter, the present invention will be described in detail using examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention is not limited to the examples described below. The examples of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art.

[0089] [Example 1] Synthesis of oxo alcohol using POX reaction product

[0090] By combining the POX reaction and the hydroformylation reaction in the process shown in Fig. 1 to produce oxo alcohols using the POX reaction product, the DRM reaction was additionally combined to reduce the total amount of carbon dioxide generated through the POX reaction and emitted into the atmosphere. Specifically, a first mixed gas (S1) was obtained through the POX reaction of vacuum residue (VR), which contained hydrogen, carbon monoxide, and carbon dioxide, and had a molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of approximately 0.935. Carbon dioxide was separated from the first mixed gas (S1) using a first gas purifier (10). A portion of the separated carbon dioxide was supplied to a DRM pretreatment reactor (200). Methane was also injected into the DRM pretreatment reactor (200) for pretreatment and then transferred to a third reactor (300). Air was injected into the third reactor (300) and the temperature was increased. A second mixed gas (S10) containing hydrogen and carbon monoxide was generated through a DRM reaction in a third reactor (300). The second mixed gas (S10) was transferred to a first gas purifier (10), and unreacted carbon dioxide contained in the second mixed gas (S10) was separated. The separated carbon dioxide was also fed into a DRM pretreatment reactor (200) and used in the DRM reaction. The first mixed gas (S1) from which carbon dioxide was removed and the second mixed gas (S10) were mixed (S2). The molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the mixed gas (S2) was measured to be approximately 0.961, and thus hydrogen was additionally injected into the mixed gas (S2) so that the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) became 1 (S4). In this way, the reaction gas (S4) with the molar ratio of hydrogen and carbon monoxide (H2 / CO) adjusted to 1 was supplied to the fourth reactor (400) to carry out a hydroformylation reaction and produce oxo alcohol.The remainder of the carbon dioxide separated in the first gas purifier (10) that was not used in the DRM reaction was discharged into the atmosphere after undergoing a desulfurization process, etc. in the second gas purifier (20). The carbon dioxide emission rate for the amount of synthetic gas produced calculated through the above process was approximately 0.058.

[0091] [Example 2] Synthesis of oxo alcohol using POX reaction product

[0092] By combining the POX reaction and the hydroformylation reaction in the process shown in Fig. 2 to produce oxo-alcohols using the POX reaction products, and additionally combining the DRM reaction and the WGS reaction, not only was the total amount of carbon dioxide emissions reduced, but also the reaction gas, in which the molar ratio of hydrogen and carbon monoxide (the molar ratio of H2 / CO) was adjusted to approximately 1 without additional hydrogen injection, was used in the hydroformylation reaction to further increase the synthesis yield of oxo-alcohols. Specifically, a first mixed gas (S1) was obtained through the POX reaction of vacuum residue (VR), containing hydrogen, carbon monoxide, and carbon dioxide, and having a molar ratio of hydrogen and carbon monoxide (the molar ratio of H2 / CO) of approximately 0.935. Carbon dioxide was separated from the first mixed gas (S1) using a first gas purifier (10). A portion of the separated carbon dioxide was supplied to the DRM pretreatment reactor (200). Methane was also injected into the DRM pretreatment reactor (200) and pretreated, and then transferred to the third reactor (300). Air was injected into the third reactor (300) and the temperature was increased. A second mixed gas (S10) containing hydrogen and carbon monoxide was generated through the DRM reaction in the third reactor (300). The second mixed gas (S10) was transferred to the first gas purifier (10), and the unreacted carbon dioxide contained in the second mixed gas (S10) was separated. The carbon dioxide thus separated was also injected into the DRM pretreatment reactor (200) and used in the DRM reaction.

[0093] Next, a portion (S11) of the second mixed gas (S10) was introduced into the WGS reactor (500) together with steam to produce a third mixed gas having a ratio of hydrogen and carbon monoxide (H2 / CO) greater than 1. The third mixed gas was mixed again with the remaining gas (S12) of the second mixed gas (S10) that was not introduced into the WGS reactor (500), to obtain a fourth mixed gas (S13) having a molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of approximately 1.28.

[0094] A mixed gas (S2) of a first mixed gas (S1) containing hydrogen and carbon monoxide as main components and a fourth mixed gas (S13) from which carbon dioxide has been removed was supplied as a reaction gas to a fourth reactor (400) for hydroformylation reaction, and the hydroformylation reaction was performed to produce oxo alcohol. At this time, since the molar ratio of hydrogen to carbon monoxide (molar ratio of H2 / CO) in the reaction gas was measured to be approximately 1, no separate hydrogen was injected.

[0095] The remainder of the carbon dioxide separated in the first gas purifier (10) that was not used in the DRM reaction was discharged into the atmosphere after undergoing a desulfurization process, etc. in the second gas purifier (20). The carbon dioxide emission rate for the amount of synthetic gas generated calculated through the above process was approximately 0.060.

[0096] [Comparative Example 1] Synthesis of oxo alcohol using POX reaction product

[0097] Oxo alcohols were produced using a mixed gas obtained from a POX reaction according to the process shown in Fig. 3. Specifically, a first mixed gas (S1) containing hydrogen, carbon monoxide, and carbon dioxide was obtained through a POX reaction of vacuum residue (VR), and having a molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of approximately 0.935. Carbon dioxide was separated from the first mixed gas (S1) using a first gas purifier (10), and an exhaust gas (S5) containing the separated carbon dioxide was discharged into the atmosphere.

[0098] The molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) of the first mixed gas (S2) from which carbon dioxide was removed was measured to be approximately 0.952. Therefore, in order to use the first mixed gas (S2) described above for the hydroformylation reaction, additional hydrogen had to be injected (S4). The reaction gas (S4) in which the molar ratio of hydrogen and carbon monoxide (H2 / CO) was adjusted to 1 was supplied to the fourth reactor (400) to carry out the hydroformylation reaction, thereby producing oxo alcohol.

[0099] Some of the exhaust gas (S6) separated from the first gas purifier (10) was fed into the second gas purifier (20) to separate out harmful components such as sulfur, and the gas from which the harmful components were separated was discharged into the atmosphere as exhaust gas (S7). The carbon dioxide emission rate for the amount of synthetic gas generated calculated through the above process was approximately 0.158.

[0100] In order to confirm that the amount of carbon dioxide emissions is significantly reduced when using the method according to the present invention, the amount of carbon dioxide emissions for the amount of synthesis gas produced in the processes of Examples 1 and 2 and Comparative Example 1 was compared and is shown in Table 1 below.

[0101] For reference, the processes of Examples 1 and 2 and Comparative Example 1 are the results of simulations using AspenPlus V12.1, a commercial petrochemical process simulator.

[0102] Example 1 Example 2 Comparative Example 1 Total amount of carbon dioxide emitted / Total amount of synthesis gas 0.060 0.058 0.158

[0103] As can be seen from the results in Table 1 above, it was confirmed that the amount of carbon dioxide emissions was reduced by 63% and 62%, respectively, in the case of Examples 1 and 2 combining the DRM reaction according to the present invention, compared to the case of Comparative Example 1.

[0104] In addition, in Example 2, by additionally carrying out a WGS reaction in addition to the DRM reaction, the molar ratio of hydrogen and carbon monoxide (H2 / CO) in the reaction gas for the hydroformylation reaction can be adjusted to 1, thereby significantly increasing the synthesis yield of oxo alcohol and omitting additional injection of hydrogen gas, thereby reducing costs.

[0105] In this way, when the method of the present invention is used, not only can the synthesis gas containing hydrogen and carbon monoxide, which are products of the POX reaction, be utilized as a reactant for the hydroformylation reaction, but also the amount of carbon dioxide emissions, which have been problematic due to the large amount generated through the POX reaction, can be significantly reduced through the DRM reaction. In addition, by further performing the WGS process at the later stage of the DRM reaction, not only can more hydrogen and carbon monoxide gases that can be used for the hydroformylation reaction be generated, but also the molar ratio of hydrogen and carbon monoxide in the hydroformylation reaction gas can be adjusted to 1 through mixing with the product gas of the POX reaction from which carbon dioxide has been removed, thereby enabling the synthesis of oxo alcohols in an economical and efficient manner.

Claims

1. A step of generating a first mixed gas containing hydrogen, carbon monoxide, and carbon dioxide through a partial oxidation (POX) reaction of hydrocarbon; A step of separating carbon dioxide from the first mixed gas; A step of producing a second mixed gas containing hydrogen and carbon monoxide through a dry reforming of methane (DRM) reaction of at least a portion of the carbon dioxide separated from the first mixed gas; and A step of producing oxo alcohol by hydroformylating a reaction gas containing the first mixed gas with olefin, A method for producing oxo alcohol using a partial oxidation reaction product.

2. In paragraph 1, The second mixed gas further contains unreacted carbon dioxide, The method further comprises a step of separating carbon dioxide from the second mixed gas. A method for producing oxo alcohol using a partial oxidation reaction product.

3. In paragraph 2, Further comprising a step of subjecting at least a portion of the carbon dioxide separated from the second mixed gas to a methane dry reforming reaction. A method for producing oxo alcohol using a partial oxidation reaction product.

4. In paragraph 1, The above reaction gas further comprises a second mixed gas, A method for producing oxo alcohol using a partial oxidation reaction product.

5. In paragraph 4, A step of adding hydrogen to the reaction gas to adjust the molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the reaction gas to 0.97 to 1.15 is further included. A method for producing oxo alcohol using a partial oxidation reaction product.

6. In paragraph 1, Further comprising a step of generating a third mixed gas containing hydrogen and carbon monoxide by performing a water gas sift reaction with at least a portion of the second mixed gas and water vapor. A method for producing oxo alcohol using a partial oxidation reaction product.

7. In paragraph 6, The above reaction gas includes the first mixed gas and the third mixed gas, The molar ratio of hydrogen and carbon monoxide (molar ratio of H2 / CO) contained in the above reaction gas is 0.97 to 1.

15. A method for producing oxo alcohol using a partial oxidation reaction product.

8. In paragraph 6, The third mixed gas further contains carbon dioxide, The method further comprises a step of separating carbon dioxide from the third mixed gas. A method for producing oxo alcohol using a partial oxidation reaction product.

9. In paragraph 1, Further comprising a step of discharging into the atmosphere an off gas containing carbon dioxide that is not used in the dry reforming of methane reaction among the carbon dioxide separated from the first mixed gas. A method for producing oxo alcohol using a partial oxidation reaction product.

10. In paragraph 9, The ratio of the total amount of carbon dioxide in the off-gas to the total amount of the reaction gas is 0.1 or less, A method for producing oxo alcohol using a partial oxidation reaction product.

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