WO2009008092A1

WO2009008092A1 - Process for produciton of synthesis gas in the process of manufacturing kerosene and gas oil from natural gas

Info

Publication number: WO2009008092A1
Application number: PCT/JP2007/064043
Authority: WO
Inventors: Fuyuki Yagi; Kenichi Kawazuishi; Ryuichiro Kajiyama
Original assignee: Chiyoda Corporation
Priority date: 2007-07-10
Filing date: 2007-07-10
Publication date: 2009-01-15
Also published as: AU2007356234B2; AU2007356234A1; CN101657523A; CN101657523B

Abstract

The invention aims at re-utilizing light hydrocarbon generated as a by-product of low added value in the process of manufacturing kerosene and gas oil from natural gas and thereby providing a novel process for the production of synthesis gas which brings about improvement in the consumption unit of raw material. In order to attain the aim, light hydrocarbon separated by distillation in the upgrading step, which is a by-product of low added value in the process of manufacturing kerosene and gas oil from natural gas, is recycled to the step of producing synthetic gas as the raw material for the production of synthesis gas.

Description

Description Method for producing synthetic gas in the process for producing kerosene from natural gas Technical Field

The present invention relates to a method for producing synthesis gas in a kerosene production process from natural gas, which has a synthesis gas production process, a Fischer-Tropsch oil production process, and an upgrading process.

Background art

Syngas production process for producing syngas from natural gas, Fischer-Roush process for producing heavy hydrocarbons by synthesizing the syngas into a Fischer-Ros push reaction, and production fuel oil by hydrotreating heavy hydrocarbons In the kerosene production process from natural gas that has a grading process, the final target product is kerosene, so light carbonization of LPG, naphtha, etc. that is separated and produced as a by-product other than kerosene in the upgrade process Hydrogen has low added value due to its properties.For example, whether to remanufacture it as a light hydrocarbon or to use it as a raw material for an existing process is determined taking into account various factors such as market value and economic efficiency. It can be said that this is the case.

By the way, if light hydrocarbons, which are a by-product with low added value in the process of producing kerosene from natural gas, can be taken back into the process and reused as raw materials, the basic unit of raw materials can be increased. Seems to be advantageous. However, there is currently no technology that proposes how to handle it as a specific process.

The present invention was devised under such circumstances, and its purpose is to concretely reuse light hydrocarbons, which are by-products with low added value, in the process of producing kerosene from natural gas. It is an object of the present invention to provide a new synthetic gas production method that can increase the raw material intensity. Disclosure of the invention In order to solve the above-described problems, a method for producing synthesis gas in a process for producing kerosene from natural gas according to the present invention is a synthesis method for producing synthesis gas by a reforming reaction between natural gas and steam and carbon dioxide. A gas production process, a Fischer-Tropsch oil production process for producing a Fischer-Tropsch oil by separating a gaseous product from a Fischer-Tropsch reaction product after the synthesis gas is subjected to a Fischer-Tropsch reaction. The Fischer-Tropsch oil is hydrorefined, and the resulting hydrorefined product is distilled to separate light hydrocarbons and kerosene oil, which is the final product, and an upgrading step, from natural gas having In the kerosene production process, light hydrocarbons separated by distillation in the upgrading process are synthesized. As a raw material for gas production, it is configured to be recycled in the synthesis gas production process.

Further, as a preferred embodiment of the present invention, in the synthesis gas production process, when the number of moles of hydrocarbon-derived carbon in the mixed raw material of natural gas and light hydrocarbons used in circulation is represented by C, per mole of carbon H ₂ OZ C (molar ratio) force 0 · 0 to 3 · 0 and C 0 ₂ ZC (molar ratio) is in the range of 0.0 to 1.0.

Further, as a preferred embodiment of the present invention, in the synthesis gas production process, the ratio of the number of carbon atoms in the light hydrocarbons used in circulation to the number of carbon atoms in the hydrocarbons of the natural gas raw material supplied is 1 It is set to be 0 to 3 5%.

Further, as a preferred embodiment of the present invention, in the synthesis gas production step, the ratio of the number of carbon atoms in the kerosene oil that is the final product to the number of carbon atoms in the hydrocarbon of the natural gas raw material supplied is 60 It is set to be ~ 80%.

Further, as a preferred embodiment of the present invention, in the synthesis gas production step, the catalyst layer outlet temperature is 80 to 95 ° C, the catalyst layer outlet pressure is 1.5 to 3. OMP a G, GHSV (gas hourly space velocity) is set to 5 0 0 to 5 0 0 0 hr ^_1 .

As a preferred embodiment of the present invention, in the synthesis gas production step, the hydrocarbon feed gas supplied as a natural gas feed is a hydrocarbon having 1 to 6 carbon atoms containing at least 60 mol% of methane. Configured. The present invention relates to a synthesis gas production process for producing a synthesis gas by a reforming reaction of natural gas and steam or carbon dioxide, and after causing the synthesis gas to undergo a Fischer-Tropsch reaction, a Fischer-Tropsch reaction product A Fischer-Tropsch oil production process for producing a Fischer-Tropsch oil by separating a gaseous product from the product, hydrorefining the Fischer-Tropsch oil, and distilling the resulting hydrofinished product to produce light hydrocarbons. In the process for producing kerosene oil from natural gas, which is separated into kerosene oil, which is the final product, the light hydrocarbons separated by distillation in the upgrade process are made from synthesis gas. As a raw material for construction, it is configured to be recycled for use in the synthesis gas production process. The kerosene and gas oil manufacturing process from the gas, achieving a specific reuse light quality hydrocarbon added value is low by-product, it expressed extremely excellent effect that it is possible to increase the raw material unit consumption. Brief Description of Drawings

FIG. 1 is a scheme showing a method for producing synthesis gas in the process for producing kerosene from natural gas according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described.

The present invention relates to a method for producing synthesis gas in a process for producing kerosene oil from natural gas as a target product (product).

FIG. 1 is a scheme showing a method for producing synthesis gas in the process for producing kerosene from natural gas according to the present invention.

As shown in Fig. 1, the process for producing kerosene oil from natural gas consists of a synthesis gas production process 10, a Fischer-Tropsch oil production process (FT synthesis process) 20, and an upgrade process 30. It is configured.

In such a process for producing kerosene from natural gas, the main part of the present invention is the production of synthesis gas using light hydrocarbons separated by distillation in the upgrading step 30 as a raw material for producing synthetic gas. Recycled (recycled) in the process It is in the point which is constituted. The state of the light hydrocarbon recycling (recycling) process is indicated by reference numeral 40 in FIG.

If light hydrocarbons are recycled (recycled) to the Fischer-Tropsch oil production process (FT synthesis process), the circulation hydrocarbons cannot be used as raw materials, and the synthesis gas partial pressure decreases. As a result, there is a disadvantage that the reaction rate of Fischer-Tropsch synthesis decreases, which is not preferable.

First, each step constituting the process for producing kerosene from natural gas in the present invention will be described in detail.

[Syngas production process]

The synthesis gas production process is a process for producing synthesis gas (CO and H ₂ ) by a reforming reaction (reforming reaction) of natural gas supplied as a raw material with steam and / or carbon dioxide. That is, using hydrocarbon raw material gas containing methane as the main component, CO and H ₂ by steam (H ₂ 0) and Z or carbon dioxide (C 0 ₂ ) reforming in the presence of a catalyst for synthesis gas production Is a process for producing a synthesis gas containing as a main component.

However, in the present invention, in addition to the natural gas supplied as a raw material, the light hydrocarbons separated in the upgrading process 30 as described above are recycled to the synthesis gas manufacturing process to be used for syngas production. It is added as a raw material (see light hydrocarbon recycling (recycling) process 40 in Figure 1). Therefore, further necessary explanation of the synthesis gas production process including the light hydrocarbons to be recycled will be described in detail after the upgrade process 30 described later.

Explanation of synthesis gas production catalyst used for reforming reaction

The catalyst for syngas production has a carrier (carrier) as a base material and a catalytic metal supported on the carrier.

As the carrier, a calcined magnesium oxide molded body is preferably used. Such a molded body is formed by pressure-molding magnesium oxide raw material powder into a predetermined shape using a mold and then firing. Although there are no particular restrictions on the specific shape of the molded body, it is generally desirable to use industrial catalyst forms such as rings, saddles, multi-holes, and pellets. It may be an irregular shape such as a crushed material. The carrier of the magnesium oxide shaped body has a specific surface area of 0.1 to 1. Om ² Zg, preferably 0.2 to 0.5 m ² Zg. When the specific surface area exceeds 1. Om ² Zg, there is a tendency that the rate of formation of force bonbons increases and the catalyst activity decreases. On the other hand, if this value is less than 0.1 m ² Zg, the activity per unit catalyst tends to be insufficient, and there is a tendency that a large amount of catalyst is required. The specific surface area is measured by the so-called “BET” method. In general, the specific surface area of the obtained catalyst or support can be controlled by the calcination temperature and the calcination time.

The carrier magnesium oxide (MgO) can be obtained by firing commercially available magnesium oxide (MgO). The purity of magnesium oxide (MgO) is required to be 98% by weight or more, preferably 99% by weight or more. In particular, components that enhance carbon deposition activity, components that decompose under high temperature and reducing gas atmosphere, such as iron, Mixing of metals such as nickel or silicon dioxide (S ί 0 ₂ ) is not preferable.

Such a carrier supports ruthenium (Ru) as a catalyst metal in a metal conversion amount of 10 to 5000 wt-pm, preferably 100 to 2000 wt-ppm. If the supported amount exceeds 500 Ow t-ppm, the catalyst cost increases and the amount of carbon deposition during production tends to increase. On the other hand, when the supported amount is less than 10 w t -ppm, there is a disadvantage that sufficient catalytic activity cannot be obtained. The amount of Ru metal supported is calculated as a weight ratio with respect to the catalyst support.

Rhodium (Rh) may be used instead of ruthenium (Ru).

A preferred example of a method for preparing a catalyst for syngas production will be described below.

Formation of catalyst support

For example, carbon as a lubricant is mixed with magnesium oxide (MgO) powder, and then pressure-molded into a predetermined shape. Thereafter, the molded product is fired at a firing temperature of 1 000 ° C. or higher, preferably 1 000 to 1 300 ° C., more preferably 1 100 to 1 200 ° C. for 1 to 4 hours. The firing atmosphere is usually performed in the air.

The activity of a normal reforming catalyst is almost proportional to the outer surface area when the type of catalyst is determined, so the catalyst activity increases as the particle size decreases, but the mass rate of the gas The pressure loss increases due to the large degree. Therefore, a cylindrical shape is often adopted.

Catalytic metal (Ru) loading

The carrier formed in this manner is impregnated with an aqueous ruthenium chloride solution, and then dried and calcined so that ruthenium (Ru) is supported on the outer surface of the magnesium oxide molded body.

As a suitable method for impregnating the ruthenium chloride aqueous solution, there are an immersion method and a spray method. Among these, it is particularly preferable to use a spray method in which an aqueous ruthenium chloride solution is sprayed toward a carrier.

The carrier on which Ru is adsorbed is dried at a temperature of 50 to 150 ° C. for about 1 to 4 hours and then calcined at a temperature of 300 to 500 ° C., preferably 350 to 450 ° C. for 1 to 4 hours. The atmosphere for drying and firing may be in the air. By carrying out the calcination, the catalytic metal reaction activity is further increased.

Syngas production method

Based on the presence of the catalyst for producing synthesis gas prepared as described above, natural gas containing methane as a main component as described above (generally a hydrocarbon having 1 to 6 carbon atoms and containing at least 60 mol% of methane) ) And CO and H ₂ by H ₂ 0 and Z or C 0 ₂ reforming, using as a raw material a gas mixture with light hydrocarbons separated and recycled in the upgrade process 30 and used as raw materials for syngas production. Syngas as a component is produced.

In this case, focusing on methane, which is the main component,

(I) if of methane (CH ₄₎ and a method of reacting carbon dioxide (C0 ₂₎ (C0 ₂ reformate timing), the reaction proceeds as represented by the following formula (1). CH ₄ + C0 ₂ 2 CO +2 H ₂ … Formula (1)

(ii) Further, in the case of a method of reacting methane (CH ₄ ) and steam (H ₂ 0) (steam reforming), the reaction proceeds as shown by the following formula (2). CH ₄ + H ₂ 0 CO +3 H ₂ ... Formula (2) Under these reforming reaction conditions, the water gas shift reaction of Formula (3) below proceeds simultaneously with the above two formulas because the catalyst has shift ability. To do.

_{_{CO + H 2 0 <=> C0 2}} + H 2 ... Equation (3) above (1), (2) from the stoichiometry, synthesis of H ₂ CO molar ratio = 1 in C_〇 ₂ reforming of methane In the case of steam reforming of methane, synthesis gas with H ₂ ZCO mole ratio = 3 is generated. Therefore, it is possible to directly synthesize without line Ukoto gas separation such as hydrogen from these syngas product gas of the reaction Li 1-1 ₂ Rei_0 mole ratio = 1-3 by the combining.

That is, it becomes possible to directly synthesize methanol, FT synthesis, and synthesis gas with a H ₂ ZCO molar ratio of 1 to _{2 as} a DME raw material.

However, under the reaction conditions for directly synthesizing such a molar ratio, the produced gas generally has a composition that causes a bonbon deposition on the catalyst surface, resulting in catalyst degradation due to carbon deposition. As the predetermined catalyst capable of solving such problems, the synthesis gas production catalyst described above is used. Furthermore, by using the synthesis gas production catalyst described above, the light hydrocarbons separated by distillation in the upgrading step 30, which is the main part of the present invention, are synthesized as a raw material for synthesis gas production. It becomes feasible to recycle (recycle) the gas production process. In other words, when a synthesis gas production catalyst other than the above is used, if light hydrocarbons are recycled and used in the synthesis gas production process as a synthesis gas production raw material, carbon deposition from the light hydrocarbons becomes significant. As a result, deactivation of the catalyst occurs.

[Fischer Tropus oil production process (FT synthesis process)]

This is a process for producing a Fischer-Tropsch oil by causing the Fischer-Tropsch reaction of the synthesis gas described above and then separating the gaseous product from the Fischer-Tropsch reaction product. The FT synthesis reaction is a reaction that gives a hydrocarbon mixture from the synthesis gas CO and H 2 according to the following formula.

CO + 2 H ₂ → iZn-(CH ₂ ) _n — + H ₂ 0 Examples of catalytic metals include iron (F e), cobalt (Co), ruthenium (R _U ), nickel (N i) etc. are used. When such a catalyst metal is supported on the surface of the support, for example, a support such as silica, alumina, silica alumina, and titania can be used.

The reaction conditions are generally about reaction temperature: 200 to 350 ° C., reaction pressure: normal pressure to about 4.0 MPaG. When an iron catalyst is used, reaction temperature: 250 to 350 ° C, reaction pressure: 2.0 to 4. OMP a G is preferable, and when a cobalt catalyst is used, reaction temperature: 220 to 250 ° C, reaction pressure: about 0.5 to 4.0 MPaG is preferable.

The reaction is a kind of polymerization reaction, and generally it is difficult to keep the degree of polymerization (n number) constant and product. There is a wide range in ~ ^^^. The carbon number distribution of the generated hydrocarbon can be expressed by the chain growth probability in the distribution rule according to the Schulz-Flory distribution rule. For industrial catalysts, the value is about 0.85 to 0.95.

The product of the FT reaction is primarily olefin. -Olefin changes by secondary reaction as follows. That is, production of linear paraffin by hydrogenation, production of lower paraffin such as methane by hydrocracking, or production of higher-grade hydrocarbons by secondary chain growth. It also produces alcohols such as ethanol, ketones such as acetone, and carboxylic acids such as acetic acid, although they are in small quantities.

As the reactor for FT synthesis, for example, a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor, a supercritical reactor or the like is used.

Hydrocarbons from FT synthesis are dedusted at the syngas production stage of the raw material, and further refined, such as desulfurization, to protect the catalyst, so the synthesized hydrocarbons contain sulfur and heavy metals. It will be very clean. Hydrocarbons produced by FT synthesis are mostly composed of linear olefin (1-olefin) and linear paraffin.

Separation means for separating the gaseous product from the Fischer-Tropsch reaction product to obtain a Fischer-Tropsch oil (hydrocarbon oil) is not particularly limited, and various known separation means should be used. Can do. As an example, for example, a flash separator may be used.

[Upgrading process]

Hydrotrophic oil (catalytic hydrotreating) obtained from the above Fischer-Tropsch oil production process is hydrorefined, and the resulting hydrorefined product is distilled to produce light hydrocarbons and the final product. Separation into kerosene oil is performed.

The hydrorefining treatment can be carried out using any catalyst bed reactor such as a fluidized bed, moving bed, slurry bed, or fixed bed. The hydrotreating conditions are, for example, a reaction temperature of about 175 to 400 ° C and a hydrogen partial pressure of about 1 to 25 MPaG (10 to 250 atm).

Hydrorefined hydrocarbon fraction is distilled to light hydrocarbons containing LPG and Naphtha as the main components, and to the final products kerosene (Kerosen and Gas Oil). Separated.

In the present invention, light hydrocarbons such as LPG and naphtha that are excluded from final products are recycled and used in the synthesis gas production process as raw materials for synthesis gas production. In other words, LPG and naphtha light hydrocarbons are recycled and introduced into the synthesis gas production process 10 as raw materials for synthesis gas production as shown in Fig. 1. Returning to the synthesis gas production process 10 again, the explanation is as follows.

In the synthesis gas production process 10, when C represents the number of moles of hydrocarbon-derived carbon in the mixed raw material of natural gas, which is the original raw material, and light hydrocarbons that are recycled, H ₂ OZC per mole of carbon (Molar ratio) is adjusted to be within a range of 0.0 to 3.0 and / or CO ₂ / C (molar ratio) force of 0.0 to 1.0.

In particular, a preferable range of H ₂ OZC (molar ratio) is 0.3 to 1.7, and a more preferable range is 0.7 to 1.3. In addition, a preferable range of C0 ₂ ZC (molar ratio) is 0.2 to 0.8, and a more preferable range is 0.4 to 0.6. Furthermore, in the synthesis gas production process 10 of the present invention, the ratio of the number of carbon atoms in the light hydrocarbons used for circulation is 1 to the number of carbon atoms in the hydrocarbons of the natural gas feed to be supplied. It is set to be 0 to 35%, more preferably 15 to 35%, and still more preferably 20 to 300/0. If this value is less than 10 <½, the specific purpose of recycling light hydrocarbons will be reduced, and the original purpose of increasing the raw material intensity will not be sufficiently fulfilled. On the other hand, if this value exceeds 35%, it is easy for force-bon deposition to occur on the surface of the catalyst for syngas production, and catalyst deterioration due to force-bon deposition occurs. Therefore, a value of 10-35% is an important factor in deciding how much light hydrocarbons to circulate should be recycled. In other words, if it is in the range of 10 to 35%, there is no particular problem even if the total amount of light hydrocarbons separated in the upgrade process 30 is recycled, but if the total amount is recycled, it may exceed 35%. For example, a method may be used in which a part of the product is recycled instead of the total amount.

In addition, in the synthesis gas production process 10 of the present invention, the ratio of the number of carbon atoms in kerosene oil, which is the final product, to the number of carbon atoms in the hydrocarbon of the natural gas raw material supplied is 60 to 80%. More preferably, the light hydrocarbon recycling ratio is set to 65 to 80%.

Further, the outlet temperature of the catalyst layer in the synthesis gas production step 10 of the present invention is set to 800 to 950 ° C, preferably 850 to 920 ° C. The catalyst layer outlet pressure is 1.5 to 3. OMPa G. GHSV (gas hourly space velocity) is set to 500 to 500 0 h ¹ .

[Example]

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example 1

Upgrade process of kerosene production process from natural gas as shown in Fig. 1 Recycle all naphtha and LPG by-produced in the process 30 H ₂ ZCO = suitable for FT synthesis 2. 0 synthesis gas was produced. As the synthesis gas production catalyst, a catalyst in which Ru was supported on an _MgO catalyst carrier was used. Catalyst layer outlet temperature in synthesis gas production process 10 900 ° C, catalyst layer outlet pressure 2. OMPaG, GHSV (gas hourly space velocity) 2000 hr ~ H ₂ OZC (molar ratio) = 1.27, C0 ₂ ZC (mole Ratio) = 0.41, and the composition of the raw natural gas is (C 1 ZC2ZC3ZC4 C5 + ZN ₂ = 90. 0/5. 5 2. 5 0. 5/1. 0 / 0.5 (Mornomol)) Met.

Synthetic gas production section inlet and outlet shown in Fig. 1 (Material balance of symbols (1), (2), (3), (4), (5), (7)) shown in Fig. 1 Based on this material balance, the synthesis gas production process in the kerosene production process was evaluated.

As a result, the ratio of the number of carbon atoms in the recycled gas to the number of carbon atoms in the hydrocarbon of the supplied natural gas raw material calculated based on the material balance is 25.8 <½. The ratio of carbon atoms to products (kerosene, light oil) was 67.4 <½. The amount of raw material natural gas was reduced by 17.5% compared to the case without recycling.

Example 2

As shown in Fig. 1, H ₂ ZCO = 2.0 suitable for FT (Fischer's Tropsch) synthesis by recycling only naphtha by-product in the upgrade process 30 of kerosene production from natural gas Synthesis gas was produced. Catalyst gas outlet temperature 900 ° C, catalyst bed outlet pressure in synthesis gas production process 2. OMP a G, GHS V (gas hourly space velocity) 2000 hr "\ H ₂ OZC (molar ratio) = 1.27, C0 ₂ ZC (molar ratio) = 0.41, and the composition of the raw natural gas is (C 1ZC2ZC3ZC4 C5 + ZN ₂ = 90. 0/5. 5/2. 5/0. 5/1. 0/0 5 (mol Z mol)).

As a result, the supply of natural gas raw material supplied based on the material balance The ratio of the number of carbon atoms in the recycled gas to the number of carbon atoms in the hydrocarbon is 24.1%, and the ratio of carbon atoms in the raw natural gas to products (kerosene, light oil) is 66.6 < ½. Feed natural gas amount could be reduced 1 6.40 / ₀ as compared with the case of not performing recycling.

Example 3

H ₂ suitable for FT synthesis by recycling only half of the naphtha produced as a by-product in the upgrade process 30 of kerosene production from natural gas as shown in Figure 1 A synthesis gas with ZCO = 2.0 was produced. Catalyst layer outlet temperature in synthesis gas production process 10 900 ° C, catalyst layer outlet pressure 2. OMPaG, GHSV (gas hourly space velocity) 2000 hr ~ H ₂ OZC (molar ratio) = 1.25, C0 ₂ ZC (mole) Ratio) = 0.44, and the composition of raw natural gas is (C 1 ZC 2ZC 3 / C 4 C 5 + ZN ₂ = 90. 0/5. 5/2. 5Z 0. 5/1-0 / 0.5 (mol mol)).

Synthetic gas production section inlet and outlet shown in Fig. 1 (Material balance of (1), (2), (3), (4), (5), (7)) shown in Fig. 1 Based on this material balance, the synthesis gas production process in the kerosene production process was evaluated.

As a result, the ratio of the number of carbon atoms in the recycled gas to the number of carbon atoms in the hydrocarbons of the natural gas raw material supplied calculated based on the material balance is 11.0%. The ratio of carbon atoms to products (kerosene, light oil) was 60.6 <½. The amount of raw material natural gas was reduced by 8.2% compared to the case without recycling. (Comparative Example 1)

H ₂ ZCO suitable for FT (fisher's 卜 robsch) synthesis without recycling PG as naphtha by-product in the upgrade process 30 of kerosene production from natural gas as shown in Figure 1 = 2.0 Syngas was produced. Catalyst layer outlet temperature in synthesis gas production process 10 900 ° C, catalyst layer outlet pressure? OMP aG, GHSV (gas hourly space velocity) 2000 hr ¹ , H ₂ OZC (molar ratio) = 1.24, C0 ₂ ZC (molar ratio) = 0.46, and the composition of raw material natural gas is ( C 1ZC2ZC3ZC4ZC5 + N ₂ = 90. 0/5. 5 2. 5/0. 5/1. 0 / 0.5 (mol mol)).

Synthetic gas production section inlet and outlet shown in Fig. 1 (reference (1), (2), (3), (4), (5), (7)) shown in Fig. 1 Based on the material balance, the synthesis gas production process in the kerosene production process was evaluated.

As a result, the ratio of carbon atoms in the raw natural gas calculated based on the material balance to products (kerosene, light oil) was 55.6%. From the above results, the effect of the present invention is clear. That is, in the present invention, light hydrocarbons separated by distillation in the upgrading process are configured to be recycled and used in the synthesis gas production process as a synthesis gas production raw material. In the kerosene oil production process, light hydrocarbons, which are by-products with low added value, can be reused concretely, resulting in an extremely excellent effect that the raw material consumption can be increased. Industrial applicability

It is used in industries that produce synthetic gas for the chemical conversion of natural gas to produce methanol, DME, and synthetic petroleum.

Claims

The scope of the claims

1. a synthetic gas production process for producing synthetic gas by a reforming reaction of natural gas with steam and Z or carbon dioxide;

A Fischer-Tropsch oil production process for producing a Fischer-Tropsch oil by separating the gaseous product from the Fischer-Robsch reaction product after the synthesis gas is subjected to a Fischer-Mouth push reaction;

An upgrade process for hydrorefining the Fischer-Tropsch oil and distilling the resulting hydrorefined product into light hydrocarbons and kerosene oil, which is the final product. In the kerosene production process of

In a process for producing kerosene oil from natural gas, characterized in that light hydrocarbons separated by distillation in the upgrade process are recycled to the synthesis gas production process as a raw material for the production of synthesis gas. A method for producing synthesis gas.

2. In the synthesis gas production process, when the number of moles of carbon derived from hydrocarbons in the mixed raw material of natural gas and light hydrocarbons used in circulation is represented by C, H ₂ OZ C (molar ratio) per mole of carbon In the process for producing kerosene oil from natural gas according to claim 1, in the range of 0.0 to 3.0 and Z or C 0 ₂ / C (molar ratio) force 0.0 to 1.0. A method for producing synthesis gas.

3. In the synthesis gas production process, the ratio of the number of carbon atoms in the light hydrocarbons used in circulation to the number of carbon atoms in the hydrocarbons of the natural gas feed supplied is 10 to 35 <½. The method for producing synthesis gas in a process for producing kerosene from natural gas according to claim 1, which is set to be as follows.

4. In the synthesis gas production process, the ratio of the number of carbon atoms in kerosene oil, which is the final product, to 60 to 80% of the number of carbon atoms in the hydrocarbon of the natural gas feed to be supplied. The method for producing synthesis gas in a process for producing kerosene from natural gas according to claim 1, wherein

5. In the synthesis gas production process, the catalyst layer outlet temperature is 800 ~ 950 ° C, the catalyst bed outlet pressure is 1.5 ~ 3. OMPaG.GHSV (gas hour I y space velocity) is 500 ~ 5000 hr. The method for producing synthesis gas in the process for producing kerosene from natural gas according to claim ^1, which is 1.

6. From the natural gas according to claim 1, wherein the hydrocarbon raw material gas supplied as the natural gas raw material in the synthesis gas production process is a hydrocarbon having 1 to 6 carbon atoms and containing at least 60 mol% of methane. Of syngas in the kerosene oil production process.