Apparatus for producing long-chain olefins, and method for producing long-chain olefins

Abstract

To provide a manufacturing apparatus and method for long-chain olefins that can produce long-chain olefins with high productivity and low raw material costs. [Solution] A apparatus and method for producing long-chain olefins, comprising: a raw material gas supply unit; a first hydrocarbon production unit for producing hydrocarbons containing long-chain olefins; a first gas-liquid separation unit for separating a first gaseous component such as CO2 from a first liquid component such as long-chain olefins; a second hydrocarbon production unit for producing hydrocarbons containing long-chain olefins; a second gas-liquid separation unit for separating a second gaseous component such as CO2 from a second liquid component such as long-chain olefins; a water supply unit for supplying H2O to a steam reforming unit; a steam reforming unit for generating CO2, etc.; a water-gas shift unit for generating CO2, etc.; and a gas-water separation unit for separating CO2, etc. from H2O, wherein the first hydrocarbon production unit produces hydrocarbons from a raw material gas containing CO2 and H2 separated in the gas-water separation unit.

Description

[Technical Field]

[0001] This disclosure relates to an apparatus for producing long-chain olefins and a method for producing long-chain olefins. [Background technology]

[0002] In recent years, concern about global warming has increased, and the Conference of the Parties (COP) to the United Nations Framework Convention on Climate Change, which discusses international frameworks for reducing greenhouse gas emissions, aims to keep the increase in average temperature since the pre-industrial era well below 2°C as a common long-term global goal, and to suppress peak emissions as early as possible and reduce them rapidly in accordance with the latest science. The COP21 Paris Agreement states that all countries should strive to formulate and submit long-term low-emission greenhouse gas development strategies. The European Green Deal includes moves to strengthen policies through legislation, such as achieving carbon neutrality by 2050 and raising reduction targets at the interim stage. In Japan, the government has also declared its aim for carbon neutrality by 2050. In response to these developments, the development of countermeasures technologies for reducing carbon dioxide emissions is being actively pursued in various places. As one such countermeasure technology, several attempts have been proposed to convert emitted carbon dioxide (CO2) into liquid hydrocarbons by chemically reacting it with hydrogen (H2) under a catalyst.

[0003] In the production of hydrocarbons that are liquid at room temperature, there are two main processes: one that primarily produces long-chain paraffins (paraffins that are liquid at room temperature) for fuel use, and another that primarily produces long-chain olefins (olefins that are liquid at room temperature) for use as raw materials for chemical products.

[0004] The following technologies are examples of techniques for efficiently producing liquid hydrocarbons from CO2 through chemical reactions. For example, Patent Document 1 discloses a hydrocarbon production apparatus comprising a reverse shift reaction section that reduces carbon dioxide to carbon monoxide by a reverse shift reaction using carbon dioxide and hydrogen as raw material gases to obtain a synthesis gas containing carbon monoxide and hydrogen, a hydrocarbon production section that produces hydrocarbons using the synthesis gas, a gas-liquid separation section that separates a gas component containing hydrogen, carbon dioxide and light hydrocarbons having 4 or less carbon atoms and a liquid component containing hydrocarbons having 5 or more carbon atoms from the effluent from the hydrocarbon production section, a first separation section that separates hydrogen and carbon dioxide and light hydrocarbons from the gas component, and a catalytic reaction section that receives the supply of the light hydrocarbons separated by the first separation section and generates hydrogen and carbon monoxide using the light hydrocarbons. The reverse shift reaction section receives the supply of hydrogen and carbon dioxide separated by the first separation section and uses the hydrogen and carbon dioxide also for the production of the synthesis gas. The hydrocarbon production section receives the supply of hydrogen and carbon monoxide generated by the catalytic reaction section and uses the hydrogen and carbon monoxide also for the production of the hydrocarbons. 5+ The component of hydrocarbons having 5 or more carbon atoms (C

[0005] Patent Document 2 discloses a carbon dioxide reduction catalyst apparatus that hydrogenates carbon dioxide to reduce carbon dioxide and produce hydrocarbons, having a first catalyst containing Fe and at least one of Ga or Zr as a catalyst metal, and a second catalyst containing Fe and Co as a catalyst metal, wherein the second catalyst is arranged downstream of the first catalyst, and the carbon dioxide reduction catalyst apparatus can preferably produce hydrocarbons having 8 to 16 carbon atoms.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] Among liquid hydrocarbons, long-chain olefins for chemical raw materials are considered to have a higher added value per unit production volume than long-chain paraffins for fuels. However, in the production of long-chain olefins from CO2, it is preferable to have high productivity of long-chain olefins. The higher the productivity, the less catalyst is required, and the reactors per unit can be miniaturized. Also, it is preferable that the raw material cost is low. The raw material H2 needs to be derived from renewable energy for carbon neutrality, but this is very costly. The lower the raw material cost, the more possible it is to suppress the total production cost. On the other hand, there is no known device for producing long-chain olefins from CO2 with high productivity and low raw material cost.

[0008] Therefore, an object of the present disclosure is to provide a long-chain olefin production apparatus and a long-chain olefin production method capable of producing long-chain olefins with high productivity and suppressing raw material costs.

Means for Solving the Problems

[0009] The inventors have found that a long-chain olefin production apparatus and a long-chain olefin production method including specific steps can produce long-chain olefins with high productivity and low raw material costs, leading to the present disclosure.

[0010] That is, the long-chain olefin production apparatus and the long-chain olefin production method according to the present disclosure are as follows.

[0011] <1> A raw material gas supply unit that supplies a raw material gas containing CO2 and H2 to the following first hydrocarbon production unit, A first hydrocarbon production unit that produces a hydrocarbon containing a long-chain olefin having 5 or more carbon atoms from the raw material gas supplied from the raw material gas supply unit, A first gas-liquid separation unit separates a first gas component containing CO2, H2, CO, and light hydrocarbons from the spillage discharged from the first hydrocarbon production unit, and a first liquid component containing the long-chain olefin, H2O, and oxygen-containing compounds. A second hydrocarbon production unit produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation unit, A second gas-liquid separation unit separates a second gas component containing CO2, H2, CO, and light hydrocarbons from the spillage discharged from the second hydrocarbon production unit, and a second liquid component containing the long-chain olefin, H2O, and oxygen-containing compounds. A water supply unit that supplies H2O to the steam reforming unit described below, A steam reforming unit that generates H2 and CO from the second gas component separated in the second gas-liquid separation unit and H2O supplied from the water supply unit, A water-gas shift unit that generates CO2 and H2 from the effluent discharged from the aforementioned steam reforming unit, A gas-water separation unit separates CO2 and H2 from the waste product discharged from the aforementioned water-gas shift unit, and H2O. Equipped with, The first hydrocarbon production unit is a long-chain olefin production apparatus that produces hydrocarbons from the raw material gas containing CO2 and H2 separated in the gas-water separation unit. <2> The first hydrocarbon production unit has a hydrocarbon production catalyst that produces hydrocarbons by coming into contact with the raw material gas supplied from the raw material gas supply unit. The second hydrocarbon production unit has a hydrocarbon production catalyst that produces the hydrocarbon by contacting the first gaseous component separated in the first gas-liquid separation unit. <1> The long-chain olefin manufacturing apparatus described above. <3> The system includes a raw material gas separation unit that separates CO2 and H2, and CO and light hydrocarbons from the second gas component separated in the second gas-liquid separation unit. The steam reforming unit generates H2 and CO from the CO and light hydrocarbons separated in the raw material gas separation unit and H2O supplied from the water supply unit. <1> or <2> The long-chain olefin manufacturing apparatus described above. <4> The system includes an oil-water separation unit that separates the long-chain olefin from the first liquid component separated in the first gas-liquid separation unit and the second liquid component separated in the second gas-liquid separation unit, and recovers the long-chain olefin separated in the oil-water separation unit. <1> ~ <3> A long-chain olefin manufacturing apparatus as described in any one of the items. <5> The oil-water separation unit separates the long-chain olefin, H2O, and oxygen-containing compounds from the first liquid component separated in the first gas-liquid separation unit and the second liquid component separated in the second gas-liquid separation unit. The steam reforming unit generates H2 and CO from the second gas component separated in the second gas-liquid separation unit, the H2O and oxygen-containing compounds separated in the oil-water separation unit, and the H2O separated in the gas-water separation unit. <1> ~ <3> A long-chain olefin manufacturing apparatus as described in any one of the items. <6> The system includes a raw material gas separation unit that separates CO2 and H2, and CO and light hydrocarbons from the second gas component separated in the second gas-liquid separation unit. The steam reforming unit generates H2 and CO from the CO and light hydrocarbons separated in the raw material gas separation unit, the H2O and oxygen-containing compounds separated in the oil-water separation unit, and the H2O separated in the gas-water separation unit. <4> or <5> The long-chain olefin manufacturing apparatus described above. <7> The raw material gas supply unit has a raw material gas preparation unit that prepares the raw material gas to a predetermined molar ratio (H2 / CO2), and supplies the raw material gas prepared in the raw material gas preparation unit to the first hydrocarbon production unit. <1> ~ <6> A long-chain olefin manufacturing apparatus as described in any one of the items. <8> The system includes a purge section for purging a portion of the CO2 and H2 separated in the aforementioned gas-liquid separation section. <1> ~ <7> A long-chain olefin manufacturing apparatus as described in any one of the items. <9> The system includes a purging section for purging a portion of the CO2 and H2 separated in the raw material gas separation section and the gas-water separation section. <3> or <6> The long-chain olefin manufacturing apparatus described above. <10> A raw material gas supply process that supplies raw material gas containing CO2 and H2 to the first hydrocarbon production section described below, A first hydrocarbon production process for producing hydrocarbons containing long-chain olefins having 5 or more carbon atoms from the raw material gas supplied from the raw material gas supply process, A first gas-liquid separation step separates the effluent discharged from the first hydrocarbon manufacturing step into a first gas component containing CO2, H2, CO, and light hydrocarbons, and a first liquid component containing the long-chain olefin, H2O, and oxygen-containing compounds. A second hydrocarbon production step, which produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation step, A second gas-liquid separation step separates a second gas component containing CO2, H2, CO, and light hydrocarbons from the effluent discharged from the second hydrocarbon manufacturing step, and a second liquid component containing the long-chain olefin, H2O, and oxygen-containing compounds. A water supply process that supplies H2O to the steam reforming process described below, A steam reforming step that generates H2 and CO from the second gas component separated in the second gas-liquid separation step and H2O supplied from the water supply step, A water-gas shift process that generates CO2 and H2 from the effluent discharged from the steam reforming process, A gas-water separation step separates CO2 and H2 from the effluent discharged from the aforementioned water-gas shift step. Equipped with, The first hydrocarbon production step is a method for producing long-chain olefins, in which the hydrocarbon is produced from the raw material gas containing CO2 and H2 separated in the gas-water separation step. <11> The first hydrocarbon production step is a step of producing hydrocarbons by contacting the raw material gas supplied from the raw material gas supply step with a hydrocarbon production catalyst, The second hydrocarbon production step is a step of producing hydrocarbons by contacting the first gaseous component separated in the first gas-liquid separation step with a hydrocarbon production catalyst. <10> The method for producing long-chain olefins described above. <12> The system includes a raw material gas separation step that separates CO2 and H2, and CO and light hydrocarbons from the second gas component separated in the second gas-liquid separation step, The steam reforming step generates H2 and CO from the CO and light hydrocarbons separated in the raw material gas separation step and H2O supplied from the water supply step. <10> or <11> The method for producing long-chain olefins described above. <13> The system includes an oil-water separation step for separating the long-chain olefin from the first liquid component separated in the first gas-liquid separation step and the second liquid component separated in the second gas-liquid separation step, and recovering the long-chain olefin separated in the oil-water separation step. <10> ~ <12> A method for producing long-chain olefins as described in any one of the items. <14> The oil-water separation step includes separating the long-chain olefin, H2O, and oxygen-containing compounds from the first liquid component separated in the first gas-liquid separation step and the second liquid component separated in the second gas-liquid separation step. The steam reforming step generates H2 and CO from the second gas component separated in the second gas-liquid separation step, the H2O and oxygen-containing compounds separated in the oil-water separation step, and the H2O separated in the gas-water separation step. <10> ~ <12> A method for producing long-chain olefins as described in any one of the items. <15> The system includes a raw material gas separation step that separates CO2 and H2, and CO and light hydrocarbons from the second gas component separated in the second gas-liquid separation step, The steam reforming step generates H2 and CO from the CO and light hydrocarbons separated in the raw material gas separation step, the H2O and oxygen-containing compounds separated in the oil-water separation step, and the H2O separated in the gas-water separation step. <13> or <14> The method for producing long-chain olefins described above. <16> The raw material gas supply process includes a raw material gas preparation process for preparing the raw material gas to a predetermined molar ratio (H2 / CO2), and supplies the raw material gas prepared in the raw material gas preparation process to the first hydrocarbon production process. <10> ~ <15> A method for producing long-chain olefins as described in any one of the items. <17> The system includes a purging step for purging a portion of the CO2 and H2 separated in the aforementioned gas-liquid separation step. <10> ~ <16> A method for producing long-chain olefins as described in any one of the items. <18> The system includes a purging step for purging a portion of the CO2 and H2 separated in the aforementioned raw material gas separation step and the aforementioned gas-water separation step. <12> or <15> The method for producing long-chain olefins described above. <19> The hydrocarbon catalyst comprises iron, at least one element from the group consisting of lithium, sodium, potassium, rubidium, and cesium, and at least one element from the group consisting of magnesium, aluminum, titanium, manganese, cobalt, copper, zinc, gallium, and zirconium. <11> The method for producing long-chain olefins described above. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide a long-chain olefin manufacturing apparatus and a long-chain olefin manufacturing method that can produce long-chain olefins with higher productivity and lower raw material costs compared to conventional apparatuses and methods for producing long-chain olefins from CO2. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 is a flow chart of an example of a long-chain olefin manufacturing apparatus according to this disclosure (long-chain olefin manufacturing apparatus of Examples 1, 3, and 4). [Figure 2] Figure 2 is a flow chart of another example of the long-chain olefin manufacturing apparatus of this disclosure (the long-chain olefin manufacturing apparatus of Example 2). [Figure 3] Figure 3 shows the flow diagrams for the long-chain olefin manufacturing apparatus of Comparative Examples 1, 3, and 5. [Figure 4]Figure 4 is a flow chart of the long-chain olefin manufacturing apparatus for Comparative Examples 2, 4, and 6. [Modes for carrying out the invention]

[0014] An example embodiment of this disclosure will be described. These descriptions and examples are illustrative and do not limit the scope of the invention. In this specification, a numerical range represented by "~" means a range that includes the numbers before and after "~" as lower and upper limits, unless those numbers are preceded by "greater than" or "less than". If the numbers before and after "~" are preceded by "greater than" or "less than", the numerical range means a range that does not include those numbers as lower or upper limits. In the numerical ranges described stepwise in this specification, the upper limit of one stepwise numerical range may be replaced with the upper limit of another stepwise numerical range, or with the values ​​shown in the examples. Similarly, the lower limit of one stepwise numerical range may be replaced with the lower limit of another stepwise numerical range, or with the values ​​shown in the examples. Furthermore, unless otherwise specified, the percentage (%) used for content refers to "mass%". A percentage of "0" indicates that the component is optional and does not need to be included.

[0015] Each component may contain multiple types of the relevant substance. When referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of those multiple substances present in the composition. The term "process" includes not only independent processes, but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved. A "catalyst for hydrocarbon production" is also simply referred to as a "catalyst."

[0016] <<Long-chain olefin manufacturing equipment / long-chain olefin manufacturing method>> The long-chain olefin manufacturing apparatus of this disclosure is A raw material gas supply unit that supplies raw material gas containing CO2 and H2 to the first hydrocarbon production unit, The first hydrocarbon production unit produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from raw material gas supplied from the raw material gas supply unit, A first gas-liquid separation unit separates the spilled material from the first hydrocarbon production unit into a first gas component containing CO2, H2, CO, and light hydrocarbons, and a first liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. A second hydrocarbon production unit produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation unit, A second gas-liquid separation unit separates the spillage from the second hydrocarbon production unit into a second gaseous component containing CO2, H2, CO, and light hydrocarbons, and a second liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. A water supply unit that supplies H2O to the steam reforming unit, A steam reforming unit generates H2 and CO from the second gas component separated in the second gas-liquid separation unit and H2O supplied from the water supply unit. A water-gas shift section generates CO2 and H2 from the effluent discharged from the steam reforming section, A gas-water separation unit separates CO2 and H2 from H2O in the effluent discharged from the water-gas shift unit. It is equipped with. The first hydrocarbon production unit then produces hydrocarbons from the raw material gas containing CO2 and H2 separated in the gas-water separation unit.

[0017] In the long-chain olefin manufacturing apparatus disclosed herein, A raw material gas supply process that supplies raw material gas containing CO2 and H2 to the first hydrocarbon production process, The first hydrocarbon production process involves producing hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the raw material gas supplied from the raw material gas supply process, A first gas-liquid separation step separates the effluent discharged from the first hydrocarbon manufacturing process into a first gaseous component containing CO2, H2, CO, and light hydrocarbons, and a first liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. A second hydrocarbon production process, which produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation process, A second gas-liquid separation step separates the effluent discharged from the second hydrocarbon manufacturing process into a second gaseous component containing CO2, H2, CO, and light hydrocarbons, and a second liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. A water supply process that supplies H2O to the steam reforming process, A steam reforming process that generates H2 and CO from the second gas component separated in the second gas-liquid separation process and H2O supplied from the water supply process, A water-gas shift process that generates CO2 and H2 from the effluent discharged from the steam reforming process, A gas-water separation process separates CO2 and H2 from the effluent discharged from the water-gas shift process. The long-chain olefin production method of this disclosure, comprising the above, is implemented. The first hydrocarbon production process then produces hydrocarbons from the raw material gas containing CO2 and H2 separated in the gas-water separation process.

[0018] The long-chain olefin manufacturing apparatus and long-chain olefin manufacturing method of this disclosure includes a second hydrocarbon manufacturing section and a second hydrocarbon manufacturing process, and furthermore, the first hydrocarbon manufacturing section and the first hydrocarbon manufacturing process produce hydrocarbons from a raw material gas containing CO2 and H2 separated in the gas-water separation section and gas-water separation process. Therefore, the long-chain olefin manufacturing apparatus and long-chain olefin manufacturing method of this disclosure makes it possible to manufacture long-chain olefins with high productivity and reduced raw material costs.

[0019] Hereinafter, as an example of a long-chain olefin manufacturing apparatus of the present disclosure, the details of a long-chain olefin manufacturing apparatus (see Figures 1 and 2) comprising a raw material gas supply unit having a raw material gas preparation unit, a first hydrocarbon manufacturing unit, a first gas-liquid separation unit, a second hydrocarbon manufacturing unit, a second gas-liquid separation unit, a raw material gas separation unit, an oil-water separation unit (an example of a water supply unit), a steam reforming unit, a water-gas shift unit, a gas-water separation unit, and a purging unit will be described along with the long-chain olefin manufacturing method of the present disclosure. In the following description, since each step of the long-chain olefin manufacturing method of this disclosure is carried out in each part of the long-chain olefin manufacturing apparatus of this disclosure, the description of each step will be omitted.

[0020] In Figures 1 and 2, 10 is the raw material gas supply unit, 10A is the raw material gas preparation unit, 12 is the first hydrocarbon production unit, 14 is the first gas-liquid separation unit, 16 is the second hydrocarbon production unit, 18 is the second gas-liquid separation unit, 16A is the second hydrocarbon production unit A, 16B is the second hydrocarbon production unit B, 18A is the second gas-liquid separation unit A, 18B is the second gas-liquid separation unit B, 20 is the raw material gas separation unit, 22 is the oil-water separation unit (an example of a water supply unit), 24 is the steam reforming unit, 26 is the vaporizer, 28 is the water-gas shift unit, 30 is the gas-liquid separation unit, and 32 is the purging unit. Also, in Figures 1 and 2, C 1-4 C is a light hydrocarbon. 5+ = ROH indicates a long-chain olefin with 5 or more carbon atoms, and ROH indicates an oxygen-containing compound.

[0021] <Raw Gas Supply Department> The raw material gas supply unit supplies raw material gas containing CO2 and H2 to the first hydrocarbon production unit. Specifically, the raw material gas supply unit receives CO2 and H2 from an external source. In addition, the raw material gas supply unit receives CO2 and H2 separated in the raw material gas separation unit and the gas-water separation unit. The raw material gas supply unit then supplies raw material gas containing CO2 and H2 to the first hydrocarbon production unit.

[0022] Here, the raw material gas supply unit includes a raw material gas preparation unit that prepares a raw material gas with a predetermined H2 / CO2 ratio and gas flow rate. The raw material gas supply unit receives CO2 and H2 supplied from an external source, along with CO2 and H2 separated in the raw material gas separation unit and the gas-water separation unit. The raw material gas supply unit then prepares the raw material gas from the supplied CO2 and H2 to a predetermined molar ratio (H2 / CO2) and gas flow rate. By preparing a raw material gas with a predetermined H2 / CO2 ratio and gas flow rate in the raw material gas preparation unit, the productivity of long-chain olefins can be improved.

[0023] The molar ratio (H2 / CO2) of the raw material gas prepared in the raw material gas preparation unit is preferably, for example, 1.0 to 4.0. When the molar ratio of H2 to CO2 is 1.0 or higher, the amount of H2 in the raw material gas is sufficient, so the hydrogenation reaction of CO2 proceeds easily, and productivity is high. On the other hand, when the molar ratio of H2 to CO2 is 4.0 or lower, the amount of CO2 in the raw material gas is sufficient, so productivity is high.

[0024] The raw material gas preparation unit may be provided as an option. In other words, the CO2 and H2 separated in the raw material gas separation unit and the gas-water separation unit, along with the CO2 and H2 supplied from an external source, may be supplied to the first hydrocarbon production unit as raw material gas without adjusting the H2 / CO2 ratio or gas flow rate.

[0025] Here, the CO2 supplied to the raw material gas preparation unit from an external source is not particularly limited, but examples include CO2 directly recovered from the atmosphere by DAC (Direct Air Capture) technology, and CO2 recovered from exhaust gas of steel mills or chemical plants using chemical adsorption methods, etc. Furthermore, while there are no particular restrictions on the H2 supplied from an external source to the raw material gas preparation unit, examples include green hydrogen and blue hydrogen. The CO2 and H2 supplied from external sources refer to CO2 and H2 supplied from equipment other than the long-chain olefin manufacturing apparatus described herein.

[0026] <First Hydrocarbon Manufacturing Department> The First Hydrocarbon Production Department produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from raw material gas supplied from the Raw Material Gas Supply Department. Specifically, the First Hydrocarbon Production Unit receives raw material gas containing CO2 and H2 from the Raw Material Gas Supply Unit. As described above, the raw material gas contains CO2 and H2 separated in the gas-water separation unit and CO2 and H2 separated in the raw material gas separation unit. Then, the First Hydrocarbon Production Department produces the target product, long-chain olefins, from the raw material gas by the FT reaction (Fischer-Tropsch reaction) shown in formula (1) below. Here, for example, the first hydrocarbon production unit has a hydrocarbon production catalyst that produces hydrocarbons by coming into contact with a raw material gas supplied from the raw material gas supply unit, and the first hydrocarbon production unit produces hydrocarbons by coming into contact with the hydrocarbon production catalyst of the raw material gas supplied from the raw material gas supply unit.

[0027] In the FT reaction shown in equation (1) below, carbon-carbon chain growth occurs, producing long-chain olefins and H2O as a by-product. In addition, light hydrocarbons with 1 to 4 carbon atoms are also produced as by-products in the FT reaction. nCO2 + 3nH2 → C n H 2n +2nH2O -(1)

[0028] In addition, the FT reaction also produces oxygen-containing compounds such as alcohols and carboxylic acids, in which oxygen derived from CO2 remains in the molecule, depending on the degree of hydrogenation. As an example, the reaction for the production of ethanol as an alcohol is shown in equation (2) below, and the reaction for the production of acetic acid as a carboxylic acid is shown in equation (3) below. Note that oxygen-containing compounds are hydrophilic and therefore readily dissolve in the by-product H2O. 2CO2 + 6H2 → C2H5OH + 3H2O -(2) 2CO2 + 4H2 → CH3COOH + 2H2O -(3)

[0029] The first hydrocarbon production section consists of known FT reactors (fixed-bed reactors, slurry-bed reactors, etc.).

[0030] For the production of long-chain olefins from CO2 and H2, it is preferable to use an iron-based catalyst. For example, an iron catalyst mainly consists of crystalline phases of Fe3O4 and Fe5C2 under the reaction atmosphere. Since Fe3O4 is active in the reverse shift reaction shown in formula (4) below, and Fe5C2 is active in the CO-FT reaction shown in formula (5) below, long-chain olefins can be produced efficiently. CO2 + H2 → CO + H2O - (4) nCO + 2nH2 → C n H 2n +nH2O -(5)

[0031] Furthermore, the catalyst used for producing hydrocarbons from CO2 and H2 preferably contains iron, at least one element from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), and at least one element from the group consisting of magnesium (Mg), aluminum (Al), titanium (Ti), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga), and zirconium (Zr). More preferably, the catalyst used for producing hydrocarbons from CO2 and H2 preferably contains iron, at least one element from the group consisting of sodium (Na), and potassium (K), and at least one element from the group consisting of magnesium (Mg), manganese (Mn), zinc (Zn), gallium (Ga), and zirconium (Zr). By using the above catalyst, long-chain olefins can be produced efficiently.

[0032] The FT reaction conditions are not particularly limited, but FT reaction conditions with a reaction temperature of 250 to 400°C and a reaction pressure of 1.0 to 10 MPa are preferred, and FT reaction conditions with a reaction temperature of 300 to 350°C and a reaction pressure of 3.0 to 7.0 MPa are more preferred. Setting the reaction temperature above 250°C makes it easier to achieve sufficient catalytic activity. Setting the reaction temperature below 400°C suppresses the increase in selectivity of by-products such as methane and the decrease in catalyst lifetime. Therefore, it is preferable to set the reaction temperature within the range of 250 to 400°C. On the other hand, setting the reaction pressure to 1.0 MPa or higher makes it easier to achieve sufficient catalytic activity. Setting the reaction pressure to 10 MPa eliminates the need to set a high pressure resistance design for the plant, thus suppressing increases in equipment costs. Therefore, it is preferable to set the reaction pressure in the range of 1.0 to 10 MPa.

[0033] <First gas-liquid separation section> The first gas-liquid separation unit separates the effluent discharged from the first hydrocarbon production unit into a first gaseous component containing CO2, H2, CO, and light hydrocarbons, and a first liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. Specifically, the first gas-liquid separation unit receives a supply of effluent from the first hydrocarbon production unit, which includes light hydrocarbons, long-chain olefins, CO2, H2, CO, H2O, and oxygen-containing compounds. Then, from the effluent from the first hydrocarbon production section, a first gaseous component containing CO2, H2, CO, and light hydrocarbons is separated from a first liquid component containing long-chain olefins, H2O, and oxygen-containing compounds.

[0034] The first gas-liquid separation unit is composed of a known gas-liquid separator. The separation in the first gas-liquid separation section is carried out, for example, at a temperature of 0 to 80°C. Separation in the first gas-liquid separation section can be performed more efficiently by using the effluent from the first hydrocarbon production section at high pressure without depressurizing it.

[0035] <Second Hydrocarbon Manufacturing Department> The second hydrocarbon production unit produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation unit. Specifically, the second hydrocarbon production unit receives the supply of the first gaseous component. Then, the second hydrocarbon production unit produces the target product, a long-chain olefin, from the first gaseous component by the FT reaction (Fischer-Tropsch reaction) shown in formula (1) above. Unreacted CO2 and H2 from the first hydrocarbon production section react in the second hydrocarbon production section to produce long-chain olefins, thereby improving the one-pass CO2 conversion rate and long-chain olefin productivity. Here, for example, the second hydrocarbon production section has a hydrocarbon production catalyst that produces hydrocarbons by contacting the first gaseous component separated in the first gas-liquid separation section, and the second hydrocarbon production section produces hydrocarbons by contacting the first gaseous component separated in the first gas-liquid separation section with the hydrocarbon production catalyst.

[0036] The difference between the second hydrocarbon production department and the first hydrocarbon production department is that the second hydrocarbon production department includes CO and light hydrocarbons in the reaction gas. CO is consumed in the FT reaction, just like CO2, and light hydrocarbons do not adversely affect the FT reaction. The second hydrocarbon production unit can use the same catalysts and reactors as the first hydrocarbon production unit.

[0037] <Second gas-liquid separation section> The second gas-liquid separation unit separates the effluent discharged from the second hydrocarbon production unit into a second gaseous component containing CO2, H2, CO, and light hydrocarbons, and a second liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. Specifically, the second gas-liquid separation unit receives a supply of effluent from the second hydrocarbon production unit, which includes light hydrocarbons, long-chain olefins, CO2, H2, CO, H2O, and oxygen-containing compounds. The second gas-liquid separation unit then separates the effluent from the second hydrocarbon production unit into a second gaseous component containing CO2, H2, CO, and light hydrocarbons, and a second liquid component containing long-chain olefins, H2O, and oxygen-containing compounds. The second gas-liquid separation unit can perform the same separation as the first gas-liquid separation unit.

[0038] <Number of stages in the second hydrocarbon production section / second gas-liquid separation section> The second production and separation unit, which includes a second hydrocarbon production unit and a second gas-liquid separation unit, may be provided in a single stage, as shown in Figure 1. However, if it is desired to improve the one-pass CO2 conversion rate and the productivity of long-chain olefins, the second manufacturing separation unit may be provided in multiple stages in series, as shown in Figure 2. Figure 2 shows an configuration in which the second manufacturing separation unit is provided in two stages. Specifically, as shown in Figure 2, a second hydrocarbon production section B and a second gas-liquid separation section B are further provided downstream of the second hydrocarbon production section A and the second gas-liquid separation section A, respectively. The second hydrocarbon production unit A produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation unit. The second gas-liquid separation unit A separates a second gas component A, which contains CO2, H2, CO, and light hydrocarbons, from the effluent discharged from the second hydrocarbon production unit A, and a second liquid component A, which contains long-chain olefins, H2O, and oxygen-containing compounds. The second hydrocarbon production unit B produces hydrocarbons containing long-chain olefins with 5 or more carbon atoms from the second gas component A separated in the second gas-liquid separation unit A. The second gas-liquid separation unit B separates the effluent discharged from the second hydrocarbon production unit B into a second gas component B containing CO2, H2, CO, and light hydrocarbons, and a second liquid component B containing long-chain olefins, H2O, and oxygen-containing compounds.

[0039] <Raw material gas separation section> The raw material gas separation unit separates CO2 and H2 from CO and light hydrocarbons from the second gas component separated in the second gas-liquid separation unit. Specifically, the raw material gas separation unit receives a supply of a second gas component, including CO2, H2, CO, and light hydrocarbons, from the second gas-liquid separation unit. The raw material gas separation unit then separates CO2 and H2 from CO and light hydrocarbons from the second gaseous component. In the raw material gas separation section, CO2 is separated using at least one of the following methods: chemical adsorption, PSA (Pressure Swing Adsorption), and membrane separation, while H2 is separated using at least one of the following methods: PSA and membrane separation. As a result, CO2 and H2 can be separated from CO and light hydrocarbons in the raw material gas separation section.

[0040] Here, the CO2 and H2 separated in the raw material gas separation section are sent to the raw material gas supply section via the purging section and supplied to the first hydrocarbon production section as raw material gas. The first hydrocarbon production section receives the CO2 and H2 separated in the raw material gas separation section and uses this CO2 and H2 as raw material gas in the production of long-chain olefins. This increases the utilization rate of the raw material gas, thereby reducing raw material costs.

[0041] The raw material gas separation section can be provided as needed. In other words, the second gas component separated in the second gas-liquid separation section may be supplied directly to the steam reforming section, where H2 and CO may be produced from the second gas component separated in the second gas-liquid separation section and H2O supplied from the oil-water separation section (an example of a water supply section), or from the oil-water separation section and the gas-liquid separation section.

[0042] <Oil / water separation section> The oil-water separation unit separates long-chain olefins, H2O, and oxygen-containing compounds from the first and second liquid components. Specifically, the oil-water separation unit receives a supply of a mixed liquid component consisting of a first liquid component and a second liquid component, which includes long-chain olefins separated in the first and second gas-liquid separation units, as well as H2O and oxygen-containing compounds. The oil-water separation unit then separates long-chain olefins, H2O, and oxygen-containing compounds from the first and second liquid components. The oil-water separation unit is composed of a known oil-water separator.

[0043] The long-chain olefins separated in the oil-water separation section are recovered as the target product. On the other hand, the H2O and oxygen-containing compounds separated in the oil-water separation section are sent to the steam reforming section. The H2O and oxygen-containing compounds separated in the oil-water separation section are vaporized by a vaporizer and sent to the steam reforming section.

[0044] Here, the oil-water separation unit is an example of a water supply unit that supplies H2O to the steam reforming unit, and can be provided as is. In other words, the mixed components of the first liquid component and the second liquid component separated in the first gas-liquid separation unit and the second gas-liquid separation unit may be recovered as the target product as is.

[0045] <Steam reforming section> The steam reforming section produces H2 and CO from CO and light hydrocarbons separated in the raw material gas separation section, H2O and oxygen-containing compounds separated in the oil-water separation section, and H2O separated in the gas-water separation section. Specifically, the steam reforming unit receives CO and light hydrocarbons separated in the raw material gas separation unit, H2O and oxygen-containing compounds separated in the oil-water separation unit, and H2O separated in the gas-water separation unit. The H2O and oxygen-containing compounds separated in the oil-water separation section, and the H2O separated in the gas-water separation section, are vaporized by a vaporizer and supplied to the steam reforming section. Then, the steam reforming section generates H2 and CO from H2O, light hydrocarbons, and oxygen-containing compounds through a steam reforming reaction. In steam reforming reactions, H2 and CO are produced from light hydrocarbons and H2O, and H2 and CO are produced from oxygen-containing compounds and H2O. This increases the utilization rate of the raw material gas and reduces raw material costs. Furthermore, CO2 is also produced during the steam reforming reaction, i.e., in the steam reforming section.

[0046] Here, as an example, the steam reforming reaction of methane as a light hydrocarbon is shown in the following equations (6) and (7). In this steam reforming reaction, CO2, H2, and CO are produced from the light hydrocarbon and H2O. CH4 + H2O → CO + 3H2 - (6) CH4 + 2H2O → CO2 + 4H2 - (7) As an example, the steam reforming reaction of ethanol as an oxygen-containing compound is shown in the following equations (8) and (9). C2H5OH + H2O → 2CO + 4H2- (8) C2H5OH + 3H2O → 2CO2 + 6H2- (9)

[0047] Furthermore, if CO and light hydrocarbons are sent directly from the second gas-liquid separation unit to the steam reforming unit without a raw material gas separation unit, unreacted CO2 and H2 will also be sent to the steam reforming unit. Since CO2 and H2 are products in the steam reforming reaction, they act unfavorably in equilibrium, leading to a decrease in the conversion rate of light hydrocarbons. In addition, when raising the temperature of the steam reforming unit to the reaction temperature, CO2 and H2 will also be heated, increasing the required energy. In contrast, the raw material gas separation unit separates CO2 and H2 from CO and light hydrocarbons, thus avoiding the above problem.

[0048] The steam reforming section consists of a known steam reformer. The steam reforming reaction in the steam reforming section may be carried out in two stages. In this case, by carrying out the steam reforming reaction at a reaction temperature of 450-600°C for the first stage and 700-1000°C for the second stage, the amount of unreacted light hydrocarbons can be reduced, and H2 and CO can be efficiently obtained.

[0049] When light hydrocarbons with 2 to 4 carbon atoms are supplied to the steam reforming section, coking due to CO disproportionation is likely to occur in the steam reforming reaction. To prevent this, a methanation section may be provided before the steam reforming section (i.e., between the raw material gas separation section and the steam reforming section). The CO and light hydrocarbons separated in the raw material gas separation section are supplied to the methanation section, where the light hydrocarbons are converted to methane, and then the CO and methane are supplied to the steam reforming section. This allows for the generation of H2 and CO in the steam reforming section while suppressing coking.

[0050] Another method to suppress coking is to set a high S / C ratio (supplied steam / carbon ratio). This suppresses coking by consuming CO, which is the cause of coking, by reacting it with H2O through the reverse reaction of equation (4). On the other hand, setting the S / C ratio too high increases the energy required to heat the water. Therefore, considering economic efficiency, it is preferable to set the S / C ratio between 1.0 and 4.0.

[0051] The catalyst used in the steam reforming reaction is not particularly limited, but it is preferable to use at least one from the group consisting of nickel (Ni), ruthenium (Ru), and rhodium (Rh), and at least one from the group consisting of activated carbon (C), alumina (Al2O3), silica (SiO2), titania (TiO2), and zirconia (ZrO2).

[0052] <Water-gas shift section> The water-gas shift section generates CO2 and H2 from the effluent discharged from the steam reforming section. Specifically, the water-gas shift section receives a supply of effluent from the steam reforming section, which includes CO2, H2, CO, and H2O. Then, the water-gas shift section generates CO2 and H2 from CO and H2O. The water-gas shift reaction is the reverse reaction of equation (4) above.

[0053] The water-gas shift section consists of a known water-gas shift reactor. The water-gas shift reaction in the water-gas shift section may be carried out in two stages, for example. In that case, for example, by carrying out the water-gas shift reaction at a reaction temperature of 450°C for the first stage and 200°C for the second stage, unreacted CO can be reduced and CO2 and H2 can be obtained efficiently.

[0054] Here, CO, like CO2, can be used in the FT reaction, but an increase in CO in the reaction gas leads to a higher H / O ratio (hydrogen / CO2 and oxygen in CO), meaning an excess of H2 and an increase in light hydrocarbons. By providing a water-gas shift section to generate H2 from CO and convert it back to CO2, the H / O ratio can be controlled to a constant level, stabilizing the productivity of long-chain olefins.

[0055] The catalyst used in the water-gas shift reaction is not particularly limited, but it is preferable to use a known high-temperature catalyst such as Fe-Cr catalyst or a known low-temperature catalyst such as Cu / Zn / Al2O3.

[0056] <Sea water separation section> The gas-water separation unit separates CO2 and H2 from H2O from the effluent discharged from the water-gas shift unit. Specifically, the gas-water separation unit receives a supply of effluent from the water-gas shift unit, which includes CO2, H2, and H2O. The gas-water separation unit then separates CO2, H2, and H2O from the effluent from the water-gas shift unit. The gas-liquid separation unit is composed of a known gas-liquid separator.

[0057] Here, the CO2 and H2 separated in the gas-liquid separation section are sent to the raw material gas supply section via the purging section and supplied to the first hydrocarbon production section as raw material gas. The first hydrocarbon production section receives the CO2 and H2 separated in the gas-liquid separation section and uses this CO2 and H2 in the production of long-chain olefins. This increases the utilization rate of the raw material gas, thereby reducing raw material costs. Meanwhile, the H2O separated in the steam-water separation section is vaporized by the vaporizer and sent to the steam reforming section.

[0058] Furthermore, if CO2 and H2 are sent directly from the water-gas shift section to the raw material gas supply section via the purging section, without a gas-water separation section, and then supplied to the first hydrocarbon production section as raw material gas, H2O will also be supplied to the first hydrocarbon production section in the same way. If a large amount of H2O is supplied to the FT reaction catalyst, degradation due to oxidation of the Fe active species will occur, leading to a decrease in productivity. Also, if a large amount of H2O is contained in the reaction gas, the amount of CO2 and H2 flowing per unit time will decrease, which will also lead to a decrease in productivity. In contrast, the gas-liquid separation unit separates CO2 and H2 from H2O, thus avoiding the above problem.

[0059] Here, the gas-water separation unit also serves as the water supply unit that supplies H2O to the steam reforming unit. If an oil-water separation unit is not provided and the H2O separated in the gas-water separation unit is not supplied to the steam reforming unit, a separate water supply unit is provided.

[0060] <Purge section> The purging section purges a portion of the CO2 and H2 separated in the raw gas separation section and the gas-water separation section. Specifically, the purging section receives CO2 and H2 separated in the raw material gas separation section and the gas-water separation section. The purging section then purges a portion of the CO2 and H2 separated in the raw material gas separation section and the gas-water separation section. This controls the amount of impurity gas in the CO2 and H2 gas sent to the raw material gas supply section to be below a certain percentage.

[0061] The purging section can be provided at any time. However, the CO2 and H2 separated in the raw material gas separation section and the gas-water separation section may contain impurity gases such as light hydrocarbons and H2O that cannot be completely removed. Therefore, if the CO2 and H2 separated in the raw gas separation unit and the gas-water separation unit are continuously recycled, impurity gases will accumulate, leading to a decrease in productivity. In contrast, the above problem can be avoided by purging a portion of the recycled CO2 and H2 in a purging section and controlling the amount of impurity gas to below a certain percentage. [Examples]

[0062] Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

[0063] (Method for preparing catalyst) - Catalyst (1)- 12.1 g of iron(III) nitrate nonahydrate (Kanto Chemical), 4.47 g of zinc(II) nitrate hexahydrate (Kanto Chemical), 0.519 g of potassium carbonate (Kanto Chemical), and 21.8 g of urea (Kanto Chemical) were heated to 140 °C while stirring well to obtain a homogeneous solution. Next, the solution was calcined at 550 °C for 5 hours to obtain an iron catalyst (K 20 Fe 80 Zn 40 ).

[0064] - Catalyst (2)- A catalyst support mainly composed of titanium (average pore diameter 10 nm, specific surface area 354 m 2 / g, pore volume 0.89 ml / g), an aqueous solution of iron(III) nitrate, and an aqueous solution of zinc(II) nitrate were mixed. Using urea (urea / Fe molar ratio = 12) as a precipitating agent, the precipitate obtained by stirring at 90 °C for 4 hours was filtered, dried at 120 °C for 12 hours, calcined at 450 °C for 5 hours to obtain Fe 80 Zn8 / Ti 12 . An aqueous solution of potassium nitrate was dropped while irradiating ultrasonic waves to the obtained FeZn / Ti catalyst, dried at 60 °C for 12 hours, and calcined at 450 °C for 5 hours to obtain an iron catalyst (K3 / Fe 80 Zn8 / Ti 12 ).

[0065] - Catalyst (3)- 12.1 g of iron(III) nitrate nonahydrate (Kanto Chemical), 4.47 g of zinc(II) nitrate hexahydrate (Kanto Chemical), 0.399 g of sodium carbonate (Kanto Chemical), and 21.8 g of urea (Kanto Chemical) were heated to 140 °C while stirring well to obtain a homogeneous solution. Next, the solution was calcined at 550 °C for 5 hours to obtain an iron catalyst (Na 20 Fe 80 Zn 40 ).

[0066] (Evaluation of a one-step reaction) The following apparatus was prepared as the reaction apparatus. A tubular fixed-bed reactor was used as the FT reactor in the hydrocarbon production department. After filling the reactor with 0.5g of catalyst (1), catalyst (2), or catalyst (3), a reduction treatment was carried out at 400°C for 8 hours under a flow of pure H2. Under conditions of 330°C and 4.0 MPa, the F (flow rate of raw material gas (H2 / CO2=3.0)) was adjusted in the reactor so that W (catalyst mass) / F (flow rate of raw material gas); (g·h / mol) = 5.0, and hydrocarbons were produced. Furthermore, a separator that cools the piping and traps the condensed water was used as the gas-liquid separation unit, and this was connected to the outlet of the reactor to separate the gaseous and liquid components from the outflow from the hydrocarbon production unit. The separation temperature was set to 40°C. In this manner, hydrocarbons were produced using a reactor having a hydrocarbon production section and a gas-liquid separation section. The composition of the raw material gas and the gaseous components separated in the gas-liquid separation unit after the reaction was completed was determined using online GC-TCD, and the CO2 conversion rate, CO selectivity, and CH4 selectivity were evaluated. Meanwhile, the liquid component separated in the gas-liquid separation section of the ice trap recovered after the reaction was completed was determined by offline GC-FID, and hydrocarbons with 5 or more carbon atoms (C) were identified. 5+ ) Selectivity, long chain olefin (C 5+ = ) Selectivity, long chain olefin (C 5+ = ) Yield, long chain olefin (C 5+ = Productivity was evaluated.

[0067] Here, the CO2 conversion rate, CO selectivity, and the selectivity of each product (CH4 selectivity, hydrocarbons with 5 or more carbon atoms (C)) are shown. 5+ ) Selectivity, long chain olefin (C 5+ = )Selectivity), Long chain olefin (C 5+ = ) yield, and long chain olefin (C 5+ = Productivity was calculated as follows: CO2 conversion rate (%) = (number of moles of CO2 lost / number of moles of CO2 supplied) × 100 CO selectivity (%) = (moles of CO produced / moles of CO2 lost) × 100 • Selectivity of each product (%) = (moles of carbon produced by each product / (total product produced - moles of CO produced)) × 100 However, the number of carbon moles produced by each product (C-mol / kg-cat·h) = the number of moles of molecules produced by each product × the number of carbon atoms in each product. • Long-chain olefins (C 5+ = Yield (%) = (Number of moles of CO2 lost × (Total product generated - Number of moles of CO generated)) / (Number of moles of CO2 supplied × Total product generated) × C 5+ = Selection rate (%) • Long-chain olefins (C 5+ = Productivity (g C5+= / kg cat * h) = (Amount of long-chain olefin produced (g) / (Weight of packing catalyst (g) × Reaction time (h))) × 1000

[0068] (Two-step reaction) The evaluation was carried out in the same manner as for a single-stage reaction, except that a reactor with two stages in series, consisting of a hydrocarbon production section and a gas-liquid separation section, was used.

[0069] (3-step reaction) Except for using a reactor with three stages in series, each consisting of a hydrocarbon production section and a gas-liquid separation section, the evaluation was carried out in the same manner as for a single-stage reaction.

[0070] (Comparative Examples 1-2, Examples 1-2) Using catalyst (1), the raw material costs for each example of the long-chain olefin production apparatus were estimated based on the evaluation results of the above one-step to three-step reactions. Specifically, the amount of raw material gas supplied to the first hydrocarbon production section was adjusted so that the raw material gas ratio was kept constant at H2 / CO2 = 3.0. Subsequently, the reaction in the steam reforming section was carried out at 900°C and 1.0 MPa, and the reaction in the water-gas shift section was carried out at 200°C and atmospheric pressure, allowing the reaction to proceed until the equilibrium composition was reached. At this time, the unit consumption of raw material gas required for long-chain olefin production is calculated from "the amount of H2 and CO2 consumed or lost as products in the manufacturing process from the supplied raw material gas / the amount of H2 and CO2 converted to long-chain olefins," and the long-chain olefin (C 5+ = A comparison of raw material costs was conducted using the following as a baseline. Furthermore, "Amount of H2 and CO2 consumed or lost as products in the manufacturing process from the supplied raw material gas / hydrocarbons with 5 or more carbon atoms (C) 5+ From the amount of H2 and CO2 converted to (C), hydrocarbons with 5 or more carbon atoms (C 5+ )Calculate the unit cost of raw material gas required for production, and hydrocarbons with 5 or more carbon atoms (C 5+ A comparison of raw material costs was conducted using the following as a baseline. The raw material cost will be based on Comparative Example 1, which is set at 1.0.

[0071] (Comparative Examples 3-4, Example 3) Using catalyst (2), based on the evaluation results of the above one-step to two-step reactions, the long-chain olefin (C) in the long-chain olefin production apparatus of each example was determined. 5+ = ) and hydrocarbons with 5 or more carbon atoms (C 5+ A comparison of raw material costs was conducted using each of the following as a baseline, in the same manner as in Example 1. The raw material cost for Comparative Example 3 was set to 1.0 as the baseline.

[0072] (Comparative Examples 5-6, Example 4) Using catalyst (3), based on the evaluation results of the above one-step to two-step reactions, the long-chain olefin (C) in the long-chain olefin production apparatus of each example was determined. 5+ = ) and hydrocarbons with 5 or more carbon atoms (C 5+ A comparison of raw material costs was conducted using each of the following as a baseline, in the same manner as in Example 1. The raw material cost for Comparative Example 5 was set to 1.0 as the baseline.

[0073] Here, Figure 1 is a flow chart of the long-chain olefin manufacturing apparatus for Examples 1, 3, and 4. Figure 2 is a flow chart of the long-chain olefin manufacturing apparatus in Example 2. Figure 3 shows the flow diagrams for the long-chain olefin manufacturing apparatus of Comparative Examples 1, 3, and 5. Figure 4 is a flow chart of the long-chain olefin manufacturing apparatus for Comparative Examples 2, 4, and 6. Note that the details of the symbols shown in Figures 3 and 4 are the same as the details of the symbols shown in Figures 1 and 2.

[0074] -Comparative Examples 1, 3, 5- As shown in Figure 3, the long-chain olefin production apparatuses of Comparative Examples 1, 3, and 5 are apparatuses obtained by removing the second hydrocarbon production section, second gas-liquid separation section, steam reforming section, water-gas shift section, and gas-liquid separation section from the long-chain olefin production apparatus of Example 1 shown in Figure 1. In other words, the long-chain olefin production apparatus of Comparative Examples 1, 3, and 5 has a single production separation section with a hydrocarbon production section and a gas-liquid separation section, and does not include a steam reforming section, a water-gas shift section, or a gas-water separation section. Therefore, in the long-chain olefin production apparatus of Comparative Example 1, the CO, light hydrocarbons, oxygen-containing compounds, and H2O generated in the first hydrocarbon production section are not converted to CO2 and H2 and reused as raw material gas.

[0075] -Comparative Examples 2, 4, and 6- As shown in Figure 4, the long-chain olefin manufacturing apparatuses of Comparative Examples 2, 4, and 6 are apparatuses obtained by removing the second hydrocarbon manufacturing section and the second gas-liquid separation section from the long-chain olefin manufacturing apparatus of Example 1 shown in Figure 1. In other words, the long-chain olefin production apparatus of Comparative Examples 2, 4, and 6 has a single production separation section having a hydrocarbon production section and a gas-liquid separation section, and is equipped with a steam reforming section, a water-gas shift section, and a gas-liquid separation section for converting CO, light hydrocarbons, oxygen-containing compounds, and H2O into CO2 and H2 for reuse as raw material gas.

[0076] -Examples 1, 3, and 4- As shown in Figure 1, the long-chain olefin production apparatus of Examples 1, 3, and 4 has a two-stage production separation section having a hydrocarbon production section and a gas-liquid separation section, and is equipped with a steam reforming section, a water-gas shift section, and a gas-liquid separation section for converting CO, light hydrocarbons, oxygen-containing compounds, and H2O into CO2 and H2 for reuse as raw material gas.

[0077] -Example 2- As shown in Figure 2, the long-chain olefin production apparatus of Example 2 has a three-stage production separation section having a hydrocarbon production section and a gas-liquid separation section, and is equipped with a steam reforming section, a water-gas shift section and a gas-liquid separation section for converting CO, light hydrocarbons, oxygen-containing compounds and H2O into CO2 and H2 for reuse as raw material gas.

[0078] The above describes the CO2 conversion rate, CO selectivity, and selectivity of each product (CH4 selectivity, hydrocarbons with 5 or more carbon atoms (C)) in the long-chain olefin production apparatus of Comparative Examples 1-6 and Examples 1-4. 5+ ) Selectivity, long chain olefin (C 5+ = )Selectivity), Long chain olefin (C 5+ = ) yield, and long chain olefin (C 5+ = The productivity and raw material costs are shown in Tables 1 to 3.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Table 3]

[0082] As shown in Tables 1 to 3, a long-chain olefin production apparatus having two or more stages of production separation units, each containing a hydrocarbon production unit and a gas-liquid separation unit, exhibits a higher C5 ratio than a single-stage apparatus.+ = It was confirmed that productivity improved. Furthermore, it was confirmed that the long-chain olefin manufacturing apparatus of the example can produce long-chain olefins with high productivity and low raw material costs. [Explanation of symbols]

[0083] 10. Raw Material Gas Supply Department 10A Raw material gas preparation section 12. First Hydrocarbon Manufacturing Department 14 First gas-liquid separation section 16. Second Hydrocarbon Manufacturing Department 18 Second gas-liquid separation section 20. Raw material gas separation section 22 Oil-water separation unit (an example of a water supply unit) 24 Steam Reforming Section 26 Vaporizer 28 Water-gas shift section 30 Air-water separation section 32 Purge section

Claims

1. CO ２ and H ２ A raw material gas supply unit supplies raw material gas containing the following to the First Hydrocarbon Production Unit, A first hydrocarbon production unit that produces hydrocarbons containing long-chain olefins having 5 or more carbon atoms from the raw material gas supplied from the raw material gas supply unit, From the spilled material from the aforementioned first hydrocarbon production unit, CO ２ H ２ , a first gaseous component including CO and light hydrocarbons, and the long-chain olefin, H ２ A first liquid component containing O and oxygen-containing compounds, and a first gas-liquid separation unit that separates them, A second hydrocarbon production unit produces hydrocarbons containing long-chain olefins having 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation unit, From the spilled material from the aforementioned second hydrocarbon production unit, CO ２ H ２ , a second gaseous component containing CO and light hydrocarbons, and the long-chain olefin, H ２ A second liquid component containing O and oxygen-containing compounds, and a second gas-liquid separation unit that separates them, H ２ A water supply section that supplies O to the following steam reforming section The second gas component separated in the second gas-liquid separation unit and H supplied from the water supply unit ２ O and, from H ２ and a steam reforming unit that generates CO, From the effluent that flowed out from the aforementioned steam reforming unit, CO ２ and H ２ A water-gas shift unit that generates water-gas shift, From the spilled material from the aforementioned water-gas shift section, CO ２ and H ２ And, H ２ A gas-water separation unit that separates O and Equipped with, The first hydrocarbon production unit separates the CO2 separated in the gas-water separation unit. ２ and H ２ A long-chain olefin production apparatus for producing the hydrocarbon from the raw material gas containing the above.

2. The first hydrocarbon production unit has a hydrocarbon production catalyst that produces hydrocarbons by coming into contact with the raw material gas supplied from the raw material gas supply unit. The long-chain olefin production apparatus according to claim 1, wherein the second hydrocarbon production unit has a hydrocarbon production catalyst that produces the hydrocarbon by contacting the first gaseous component separated in the first gas-liquid separation unit.

3. From the second gas component separated in the second gas-liquid separation unit, CO ２ and H ２ It is equipped with a raw material gas separation unit that separates CO and light hydrocarbons, The steam reforming unit processes CO and light hydrocarbons separated in the raw material gas separation unit, and H supplied from the water supply unit. ２ O and, from H ２ The long-chain olefin production apparatus according to claim 1, which generates CO.

4. From the first liquid component separated in the first gas-liquid separation unit and the second liquid component separated in the second gas-liquid separation unit, the long-chain olefin and H ２ The long-chain olefin production apparatus according to claim 1, comprising an oil-water separation unit for separating O and oxygen-containing compounds, and for recovering the long-chain olefin separated in the oil-water separation unit.

5. From the first liquid component separated in the first gas-liquid separation unit and the second liquid component separated in the second gas-liquid separation unit, the long-chain olefin and H ２ It is equipped with an oil-water separator that separates O and oxygen-containing compounds. The steam reforming section separates the second gas component separated in the second gas-liquid separation section from the H separated in the oil-water separation section. ２ O and oxygen-containing compounds, and H separated in the gas-water separation section. ２ O and, from H ２ The long-chain olefin production apparatus according to claim 1, which generates CO.

6. From the second gas component separated in the second gas-liquid separation unit, CO ２ and H ２ It is equipped with a raw material gas separation unit that separates CO and light hydrocarbons, The steam reforming unit separates CO and light hydrocarbons separated in the raw material gas separation unit, and H separated in the oil-water separation unit. ２ O and oxygen-containing compounds, and H separated in the gas-water separation section. ２ O and, from H ２ A long-chain olefin production apparatus according to claim 4 or claim 5, which generates CO.

7. The raw material gas supply unit has a predetermined molar ratio (H ２ / CO ２ The long-chain olefin production apparatus according to claim 1 or claim 3, further comprising a raw material gas preparation unit for preparing the raw material gas, and supplying the raw material gas prepared in the raw material gas preparation unit to the first hydrocarbon production unit.

8. CO separated in the aforementioned gas-liquid separation unit ２ and H ２ The long-chain olefin manufacturing apparatus according to claim 1 or claim 4, comprising a purging section for purging a portion of the material.

9. CO separated in the raw material gas separation unit and the gas-water separation unit ２ and H ２ The long-chain olefin production apparatus according to claim 3 or claim 6, comprising a purging section for purging a portion of the material.

10. CO ２ and H ２ A raw material gas supply process that supplies raw material gas containing the following to the first hydrocarbon production section, A first hydrocarbon production process for producing hydrocarbons containing long-chain olefins having 5 or more carbon atoms from the raw material gas supplied from the raw material gas supply process, From the effluent that leaked out from the first hydrocarbon manufacturing process, CO ２ H ２ , a first gaseous component including CO and light hydrocarbons, and the long-chain olefin, H ２ A first gas-liquid separation step separates a first liquid component containing O and oxygen-containing compounds from a first liquid component, A second hydrocarbon production step, which produces hydrocarbons containing long-chain olefins having 5 or more carbon atoms from the first gas component separated in the first gas-liquid separation step, From the effluent that leaked out from the aforementioned second hydrocarbon manufacturing process, CO ２ H ２ , a second gaseous component containing CO and light hydrocarbons, and the long-chain olefin, H ２ A second gas-liquid separation step separates a second liquid component containing O and oxygen-containing compounds from the second liquid component, H ２ A water supply process that supplies O to the steam reforming process described below, The second gas component separated in the second gas-liquid separation step and H supplied from the water supply step ２ O and, from H ２ and a steam reforming process that generates CO, From the effluent released from the aforementioned steam reforming process, CO ２ and H ２ A water-gas shift process that generates, From the effluent that flowed out of the aforementioned water-gas shift process, CO ２ and H ２ And, H ２ A gas-water separation process to separate O and Equipped with, The first hydrocarbon production step involves the CO2 separated in the gas-water separation step. ２ and H ２ A method for producing long-chain olefins, comprising producing the hydrocarbon from the raw material gas containing the above.

11. The first hydrocarbon production step is a step of producing hydrocarbons by contacting the raw material gas supplied from the raw material gas supply step with a hydrocarbon production catalyst, The method for producing long-chain olefins according to claim 10, wherein the second hydrocarbon production step is a step of producing the hydrocarbon by contacting the first gaseous component separated in the first gas-liquid separation step with a hydrocarbon production catalyst.

12. From the second gas component separated in the second gas-liquid separation step, CO ２ and H ２ It also includes a raw material gas separation process that separates CO and light hydrocarbons, The steam reforming step involves using CO and light hydrocarbons separated in the raw material gas separation step, and H supplied from the water supply step. ２ O and, from H ２ A method for producing long-chain olefins according to claim 10, comprising generating CO.

13. From the first liquid component separated in the first gas-liquid separation step and the second liquid component separated in the second gas-liquid separation step, the long-chain olefin and H ２ A method for producing a long-chain olefin according to claim 10, comprising an oil-water separation step for separating O and oxygen-containing compounds, and recovering the long-chain olefin separated in the oil-water separation step.

14. From the first liquid component separated in the first gas-liquid separation step and the second liquid component separated in the second gas-liquid separation step, the long-chain olefin and H ２ It includes an oil-water separation step for separating O and oxygen-containing compounds, The steam reforming step involves separating the second gas component separated in the second gas-liquid separation step from the H separated in the oil-water separation step. ２ O and oxygen-containing compounds, and H separated in the gas-water separation step. ２ O and, from H ２ A method for producing long-chain olefins according to claim 10, comprising generating CO.

15. From the second gas component separated in the second gas-liquid separation step, CO ２ and H ２ It also includes a raw material gas separation process that separates CO and light hydrocarbons, The steam reforming step involves separating CO and light hydrocarbons in the raw material gas separation step and H in the oil-water separation step. ２ O and oxygen-containing compounds, and H separated in the gas-water separation step. ２ O and, from H ２ A method for producing long-chain olefins according to claim 13 or claim 14, comprising generating CO.

16. The aforementioned raw material gas supply process is performed at a predetermined molar ratio (H ２ / CO ２ A method for producing long-chain olefins according to claim 10 or claim 12, comprising a raw material gas preparation step for preparing a raw material gas, and supplying the raw material gas prepared in the raw material gas preparation step to the first hydrocarbon production step.

17. CO separated in the aforementioned gas-water separation step ２ and H ２ A method for producing long-chain olefins according to claim 10 or claim 13, comprising a purging step of purging a portion of the product.

18. CO separated in the aforementioned raw material gas separation step and the aforementioned gas-water separation step ２ and H ２ A method for producing long-chain olefins according to claim 12 or claim 15, comprising a purging step of purging a portion of the product.

19. The method for producing long-chain olefins according to claim 11, wherein the hydrocarbon catalyst comprises iron, at least one from the group consisting of lithium, sodium, potassium, rubidium, and cesium, and at least one from the group consisting of magnesium, aluminum, titanium, manganese, cobalt, copper, zinc, gallium, and zirconium.

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