KR102097283B1 - Method for preparing synthetic natural gas having improved caloric value and application for the same - Google Patents

Abstract

In the present invention, a synthetic natural gas is produced using synthetic gas obtained from coal, biomass, and solid carbon fuels, but a part of the synthetic gas is separated to synthesize a hydrocarbon compound such as liquefied petroleum gas and dimethyl ether. , It relates to a method for producing a synthetic natural gas having an increased calorific value to mix it with the synthetic natural gas.
At this time, the present invention collects carbon dioxide generated in the process of manufacturing a synthetic natural gas, reacts the carbon dioxide back to produce carbon monoxide, and then mixes the carbon monoxide with a part of the synthetic gas separated for the synthesis of hydrocarbon compounds Therefore, it is characterized by being used as a raw material advantageous for the synthesis of the desired hydrocarbon compound.

Description

METHOD FOR PREPARING SYNTHETIC NATURAL GAS HAVING IMPROVED CALORIC VALUE AND APPLICATION FOR THE SAME

The present invention relates to a method for manufacturing a high caloric synthetic natural gas with increased calorific value using syngas obtained from coal, biomass, and solid carbon fuel, and an apparatus used therein, in detail By separating a part of the synthetic gas to synthesize a hydrocarbon compound such as liquefied petroleum gas (LPG), dimethyl ether (dimethyl ether, DME) having a high calorific value, the calorific value is increased by mixing it with the synthetic natural gas It relates to a method for manufacturing a synthetic natural gas (high caloric SNG) and the apparatus used therein.

In the case of coal among fossil fuels, research has been actively conducted to convert coal to Synthetic Natural Gas (SNG) worldwide due to its rich reserves and less local ubiquity compared to other resources.

Among them, coal gasification refers to a technology that gas is used to generate synthetic gas (H ₂ , CO) by gasifying coal with high heat. When high heat is applied to coal, it changes in the order of solid, liquid, and gas, and the synthetic gas produced in this way can replace some of the natural gas, which is a fuel for power generation.

However, because only the synthesis gas (syngas) does not reach the heat of the natural gas, the synthesis gas (Methanation reaction) of the synthesis gas (Methanation reaction) to produce a synthetic natural gas (SNG) to compensate for the insufficient heat. However, methane is the heat 9,400kcal / m ^3, this also does not reach the standard in calorie 10,400kcal / m ³ of liquefied natural gas supplied from the Korea Gas Corporation (liquified natural gas, LNG).

Accordingly, various attempts have been made to manufacture high-quality synthetic natural gas (SNG) having a heat equivalent to liquefied natural gas (LNG).

Republic of Korea Patent Publication No. 10-2014-0087254 (Patent Document 1) is a process in which a methanation reaction and a Fischer-Tropsch synthesis reaction are simultaneously performed to produce synthetic natural gas having a high calorific value, and Fe, Co, and Zr used in the above process , Ce and Ga-based catalysts and a method of manufacturing the same are presented.

Republic of Korea Patent Registration No. 10-1508263 (Patent Document 2) is a fuel for low-grade coal or solid fuel is injected to combine the fluidized bed reactor and the fixed bed reactor to efficiently use energy to produce synthetic gas for producing synthetic natural gas. A pyrolysis gasification system was presented.

In Korean Patent Publication No. 10-2010-0121423 (Patent Document 3), the molar ratio of syngas required for the methanation process using water gas shift (WGS, Water Gas Shift) (H ₂ -CO ₂ ) / (CO + CO After adjusting ₂ ) to greater than 3.00, a method for producing synthetic natural gas (SNG) was presented.

As described above, most of the conventional methods are intended to produce synthetic gas from coal and solid fuel, and to produce synthetic natural gas having a high calorific value by methaneizing the synthetic gas. However, the synthesis gas generated through coal gasification has a molar ratio H ₂ / CO in the range of 0.5 to 0.8, which is far less than 3.0, the molar ratio H ₂ / CO for the methanation reaction.

Accordingly, a method was developed to increase the molar ratio H ₂ / CO of synthetic gas through a water gas conversion (WGS) reaction as in Patent Document 3, but the water gas conversion reaction produces hydrogen and at the same time produces carbon dioxide, a greenhouse gas. It significantly increases the carbon dioxide emissions of the process. In accordance with the new climate system, which has been drawn up through the recent COP21 agreement, it is necessary to achieve greenhouse gas emission reductions compared to the 2030 Greenhouse Gas Emission Forecast (BAU). There is a limit.

Patent Document 1: Republic of Korea Patent Publication No. 10-2014-0087254 Patent Document 2: Republic of Korea Registered Patent Publication 10-1508263 Patent Document 3: Republic of Korea Patent Publication No. 10-2010-0121423

The present invention is to overcome the above problems and limitations, it has the following object.

The first object of the present invention is to provide a method for producing synthetic natural gas having an increased calorific value using synthetic gas produced through gasification of coal, biomass, and solid carbon fuel.

In addition, the present invention provides a method for converting the molar ratio H ₂ / CO in the synthesis gas to 3 or more through an aqueous gas conversion reaction in order to use the synthesis gas produced through the gasification as a raw material for the methanation process. For the second purpose.

In addition, the present invention separates a part of the gas that has converted the molar ratio H ₂ / CO of the synthesis gas to 3.0 or more through the water gas conversion reaction, and this is the reverse reaction of carbon dioxide generated in excess by the water gas conversion reaction. A method for producing a synthetic natural gas having a liquefied natural gas (LNG) -class heat amount while significantly reducing the emission of carbon dioxide by mixing with carbon monoxide produced through and making it a suitable raw material for synthesizing a high-calorie hydrocarbon compound The third purpose is to provide.

The object of the present invention is not limited to the object mentioned above. The object of the present invention will be more apparent from the following description, and will be realized by means described in the claims and combinations thereof.

The present invention proposes a method for producing a synthetic natural gas with increased calorific value, which includes the following configuration, in order to achieve the above object.

The method for producing synthetic natural gas having an increased calorific value according to the present invention produces synthetic gas by gasifying fuel, converts the synthetic gas into water gas shift, and converts the converted synthetic gas into a first flow and a second flow. Separating and synthesizing the natural gas of the first flow by methanation reaction to produce a synthetic natural gas, before converting the converted synthetic gas into a first flow and a second flow, the converted synthetic gas Separating carbon dioxide from carbon dioxide, preparing carbon monoxide by reverse boudouard reaction of the separated carbon dioxide with a carbon material, preparing the raw material by mixing the carbon monoxide and the syngas of the second flow, and the raw material The reaction may include preparing a hydrocarbon compound and mixing the hydrocarbon compound and the synthetic natural gas.

In a preferred embodiment of the present invention, when the converted syngas is separated into a first flow and a second flow, the volume ratio between the first flow and the second flow may be separated to be 9: 1 to 6: 4.

In a preferred embodiment of the present invention, the reaction temperature of the reverse reaction can be 700 ° C to 2,000 ° C.

In a preferred embodiment of the present invention, the hydrocarbon compound is liquefied petroleum gas (LPG), and the liquefied petroleum gas is a Fischer-tropsch reaction (fischer-tropsch synthesis reaction) as shown in Scheme 4 below. ).

[Reaction Scheme 4]

(2n + 1) H ₂ + nCO → C _n H _{2n +1} + nH ₂ O

The n may be 1 to 20.

A preferred embodiment of the present invention may be to prepare a raw material having a molar ratio H ₂ / CO of 2.0 or more and less than 3.0 by mixing the carbon monoxide and the synthesis gas of the second flow, and reacting the raw material to produce liquefied petroleum gas. have.

In a preferred embodiment of the present invention, the hydrocarbon compound is dimethyl ether (dimethyl ether, DME), the dimethyl ether may be prepared by reacting the raw material as shown in Scheme 5 below.

[Scheme 5]

3H ₂ + 3CO-> CH ₃ OCH ₃ + CO ₂

A preferred embodiment of the present invention may be to prepare a raw material having a molar ratio H ₂ / CO of 1.0 or more and less than 2.0 by mixing the carbon monoxide and the synthesis gas of the second flow, and reacting the raw material to prepare dimethyl ether. .

The apparatus for producing synthetic natural gas having an increased calorific value according to the present invention includes a gasification unit that gasifies fuel to produce a synthetic gas, an aqueous gas conversion unit that reacts by supplying water to the synthetic gas, and converts the converted synthetic gas into a first flow. A synthesis gas separation unit for separating into two flows, and a methanation unit for producing a synthetic natural gas by methanation reaction of the synthesis gas of the first flow, is located between the separation unit and the water gas conversion unit to convert the synthesis A carbon dioxide separation unit for separating carbon dioxide from a gas, an inertial reaction unit for producing carbon monoxide by supplying and reacting carbon dioxide to the separated carbon dioxide, a raw material preparation unit for mixing the carbon monoxide and the synthesis gas of the second flow, and preparing the raw material A reaction unit for producing a hydrocarbon compound by reacting by receiving a raw material from the unit and the hydrocarbon compound And the composite may comprise a mixing unit for mixing the natural gas.

In a preferred embodiment of the present invention, the syngas separation unit can separate the converted syngas so that the volume ratio between the first flow and the second flow is 9: 1 to 6: 4.

In a preferred embodiment of the present invention, the reverse reaction unit may be to react carbon dioxide and carbon materials at a reaction temperature of 700 ° C to 2,000 ° C.

In a preferred embodiment of the present invention, the reaction unit may be a reactor for producing liquefied petroleum gas by Fischer-Tropsch reaction of the raw material as shown in Reaction Scheme 4.

In a preferred embodiment of the present invention, the raw material preparation unit may be a mixture of carbon monoxide and a second flow of synthesis gas so that the molar ratio H ₂ / CO of the raw material is 2.0 or more and less than 3.0.

In a preferred embodiment of the present invention, the reaction unit may be a reactor for producing dimethyl ether by reacting the raw material as shown in Reaction Scheme 5.

In a preferred embodiment of the present invention, the raw material preparation unit may be a mixture of carbon monoxide and a second flow of synthesis gas so that the molar ratio H ₂ / CO of the raw material is 1.0 or more and less than 2.0.

Since the present invention includes the above configuration, according to it can obtain the following effects.

According to the present invention, it is economical and environmentally friendly because it is possible to produce synthetic natural gas with increased calorific value per unit volume of 10,400 kcal / ㎥ or more from coal, biomass, and solid carbon fuels (waste, waste plastic, etc.).

In addition, according to the present invention, synthetic natural gas having a high calorific value can be produced without mixing liquefied petroleum gas (LPG) supplied from the outside with synthetic natural gas produced by methanation reaction of synthetic gas. It is possible to produce synthetic natural gas that is economically and stably increased in calorific value with little reception.

In addition, since the present invention uses carbon dioxide generated in the conversion of water gas in the synthesis gas as a fuel for producing a high-heated hydrocarbon compound, it is possible to significantly reduce the carbon dioxide emission of the entire process, and accordingly, the new climate system greenhouse gas emission forecast It can be a great help to the achievement of.

The effects of the present invention are not limited to the effects mentioned above. It should be understood that the effects of the present invention include all effects that can be deduced from the following description.

1 is a schematic view showing a process for manufacturing a conventional natural gas having a high calorific value.
2 exemplarily shows a method of manufacturing a synthetic natural gas with increased calorific value according to the present invention.
3 exemplarily shows an embodiment of a method for manufacturing a synthetic natural gas with increased calorific value according to the present invention. In detail, the embodiment when the hydrocarbon reaction of FIG. 2 is an LPG synthesis reaction is briefly illustrated.
4 exemplarily shows another embodiment of a method for manufacturing a synthetic natural gas with increased calorific value in the present invention. In detail, the embodiment when the hydrocarbon reaction of FIG. 2 is a DME synthesis reaction is briefly illustrated.

Hereinafter, the present invention will be described in detail through examples. Embodiments of the present invention can be modified in various forms as long as the subject matter of the invention is not changed. However, the scope of the present invention is not limited to the following examples.

If it is determined that the subject matter of the present invention may be obscured, descriptions of well-known structures and functions will be omitted. “Including” in the present specification means that other components may be further included unless otherwise specified.

The present invention relates to a method for manufacturing a synthetic natural gas (high caloric SNG) with an increased calorific value using syngas obtained from coal, biomass, and solid carbon fuel. In detail, a part of the synthetic gas is separated to synthesize a hydrocarbon compound such as liquefied petroleum gas or dimethyl ether having a high calorific value, and is mixed with synthetic natural gas (SNG) to produce a synthetic natural gas having a calorific value of LNG. (SNG) is a method of manufacturing, and more specifically, a part of the synthesis gas; and carbon monoxide obtained by reverse boudouard reaction of carbon dioxide generated in a water gas shift reaction of the synthesis gas; It relates to a method that can produce a synthetic natural gas (high caloric SNG) by increasing the calorific value while significantly reducing the emission of carbon dioxide by synthesizing the hydrocarbon compound as a raw material of the mixture.

Prior to describing the technical features of the present invention in more detail, embodiments of the prior art will be briefly described with reference to FIG. 1.

The conventional method for producing a synthetic natural gas having an increased calorific value is gasification of a fuel such as coal to produce a synthetic gas (S91), converting the synthetic gas to a water gas (S92), and carbon dioxide from the converted synthetic gas. Separating and discharging (S93), producing a synthetic natural gas by methanation reaction of the separated carbon dioxide synthesis gas (S94), and separating water and carbon dioxide from the synthetic natural gas (S95, S95 ') It is based on. Thereafter, a compound such as liquefied petroleum gas (LPG) is supplied from the outside and mixed with the synthetic natural gas (S96) to produce a synthetic natural gas having a high calorific value.

The conventional method has the advantage of converting the synthetic gas generated by gasifying fuels such as coal into natural gas and supplying it as fuel, but carbon dioxide generated in the process is discharged as it is, and it is not environmentally friendly and is commercially sensitive to oil prices. Compounds such as liquefied petroleum gas (LPG) are supplied from the outside and mixed with synthetic natural gas (SNG) to produce synthetic natural gas with increased calorific value.

The present invention is to solve the problems and limitations of the prior art as described above, without mixing with commercially available liquefied petroleum gas (LPG) supplied from the outside, it is possible to reduce the emission of carbon dioxide generated during the process, the heating value is increased A method for producing synthetic natural gas (high caloric SNG) is presented.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to FIGS. 2 to 4. However, embodiments of the present invention may be modified in different ways depending on the application, and the scope of the present invention is not limited to the embodiments described below.

2 exemplarily shows a method of manufacturing a synthetic natural gas with increased calorific value according to the present invention.

The method for producing synthetic natural gas having an increased calorific value according to the present invention produces synthetic gas by gasifying fuel (S10), converting the synthetic gas to water gas (S20), and removing the converted synthetic gas. Separated into a first flow and a second flow (S30), and the synthesis gas of the first flow is methanized to produce a synthetic natural gas (synthetic natural gas) (S40). Before separating into 2 flows (S30), separating carbon dioxide from the converted syngas (S50), and preparing carbon monoxide by reverse boudouard reaction of the separated carbon dioxide with a carbon material (S60), Preparing the raw material by mixing the carbon monoxide and the synthesis gas of the second flow (S70), preparing a hydrocarbon compound by reacting the raw material (S80) and mixing the hydrocarbon compound and the synthetic natural gas ( S90) It is characterized by including.

Referring to FIG. 2, the method for producing synthetic natural gas having an increased calorific value according to the present inventors starts from producing syngas by coal gasification of fuel (S10).

The fuel may be coal, solid carbon, or the like, and it may be preferable from the economical point of view to use coal obtained from biomass, waste, etc., and solid carbon.

The method of the gasification of the coal is not particularly limited, but a method of thermally decomposing fuels such as coal and solid carbon to make residual carbon and converting the residual carbon into carbon monoxide (CO) and hydrogen (H ₂ ) using water vapor. Can be The molar ratio H ₂ / CO of the syngas produced by the coal gasification is about 0.6 to 0.95.

The present invention may further include the step of purifying the syngas (not shown). Purification of the synthesis gas may be a process such as dust collection, acid gas removal, sulfur compound separation, and the like.

According to the present invention, the purified syngas undergoes a water gas shift reaction (WGSR) (S20), through which some carbon monoxide (CO) of the syngas is water (H ₂₎ It reacts with O) to be converted into hydrogen (H ₂ ) and carbon dioxide (CO ₂ ).

[Scheme 1]

CO + H ₂ O → CO ₂ + H ₂

The molar ratio H ₂ / CO of the syngas can be increased to about 3.0 by consuming some carbon monoxide (CO) of the syngas through the water gas conversion reaction.

The present invention separates carbon dioxide (CO ₂ ) generated by the water gas conversion reaction (WGSR) from the synthesis gas (S50), and synthesizes hydrocarbon compounds without discharging the separated carbon dioxide (CO ₂ ) as it is (S80). It is used to significantly reduce the carbon dioxide emissions of the entire process. Details of this will be described later.

The method for separating the carbon dioxide is not particularly limited, but can be separated by using a temperature swing adsorption (TSA) method, a pressure swing adsorption (PSA) method, or a membrane. .

The present invention separates the synthesis gas in which carbon dioxide is separated into a first flow (A) and a second flow (B) (S30), and the synthesis gas of the first flow (A) is subjected to a methanation reaction to produce a synthetic natural gas (SNG ) (S40), and the synthesis gas of the second flow (B) is used as a raw material for synthesizing a hydrocarbon compound (S70).

When the synthesis gas is separated into a first flow (A) and a second flow (B), the volume ratio of the synthesis gas of the first flow and the synthesis gas of the second flow is separated to be 9: 1 to 6: 4. It may be desirable. When the synthesis gas of the first flow is too large and the volume ratio exceeds 9: 1, the amount of the hydrocarbon compound synthesized using the synthesis gas of the second flow may be too small to increase the calorific value of natural gas. On the other hand, when the synthesis gas of the first flow is too small and the volume ratio is less than 5: 4, the amount of synthetic natural gas (SNG) obtained by methanation reaction of the synthesis gas of the first flow is insufficient, so use it as an alternative natural gas. May not be suitable for

In the present invention, a synthetic natural gas (SNG) is prepared by subjecting the synthesis gas of the first flow (A) to a methanation reaction (S40). The synthesis gas of the first flow (A) is a water gas conversion reaction (WGSR), and the molar ratio H ₂ / CO is about 3.0, so it is suitable for the methanation reaction as shown in Reaction Scheme 2 below.

[Scheme 2]

3H ₂ + CO → CH ₄ + H ₂ O

The synthetic natural gas (SNG) means a gas having a component similar to that of natural gas in which methane is the main component, and as described above, the present invention provides syngas from fuels such as coal, biomass, and solid carbon. Prepared, and the synthesis gas by the methanation reaction as shown in Reaction Scheme 2 to obtain a product having methane (methane) as a main component. In the present invention, the product is referred to as a synthetic natural gas (SNG).

Since the synthetic natural gas (SNG) does not reach the standard calorific value of liquefied natural gas (LNG) supplied by the Korea Gas Corporation, 10,400 kcal / m ³ , the present invention provides carbon dioxide separated from water gas converted synthetic gas, Synthetic natural gas having an increased calorific value having a calorific value of LNG by synthesizing a hydrocarbon compound having a high calorific value using the synthetic gas of the second flow (B) and mixing the hydrocarbon compound with the synthetic natural gas (SNG) ( high caloric SNG). It will be described in detail below.

The present invention separates carbon dioxide generated by the water gas conversion reaction from the synthesis gas as described above (S50). The present invention is characterized in that it is used as a raw material for synthesizing a hydrocarbon compound without emitting the carbon dioxide as it is.

The present invention supplies carbon material to the separated carbon dioxide, and prepares carbon monoxide by reverse boudouard reaction as shown in Reaction Scheme 3 below (S60).

[Scheme 3]

C + CO ₂ → 2CO

The reaction temperature of the inverse reaction of Reaction Scheme 3 may be 700 ° C or higher, and more preferably 700 ° C to 2,000 ° C. When the reaction temperature is 700 ° C or higher, the reverse-buffered reaction can be favorably performed compared to the boudouard reaction (2CO → C + CO ₂ ).

The present invention prepares a raw material (C) by mixing the carbon monoxide (CO) and the synthesis gas of the second flow (B) (S70), and reacts the raw material (C) to produce a high-calorific hydrocarbon compound ( S80). Hereinafter, embodiments of the present invention for producing the hydrocarbon compound will be described in detail with reference to FIGS. 3 and 4.

According to an embodiment of the present invention shown in Figure 3, the hydrocarbon compound may be a liquefied petroleum gas (liquified pertoleum gas, LPG), the liquefied petroleum gas (LPG) is the reaction formula 4 below the raw material (C) It can be prepared by Fischer-Tropsch synthesis reaction as shown (S81).

[Reaction Scheme 4]

(2n + 1) H ₂ + nCO → C _n H _{2n +1} + nH ₂ O

The n may be 1 to 20, 2 to 5 in detail, and 3 to 4 in more detail.

In the present invention, the liquefied petroleum gas (LPG) may refer to a hydrocarbon compound mainly having propane and butane having high calorific values.

According to an embodiment of the present invention, the carbon monoxide (CO) is mixed with the synthesis gas of the second flow (B) so that the raw material (C) has a molar ratio H ₂ / CO suitable for the Fischer-Tropsch reaction. You can prepare.

Since the synthesis gas of the second flow (B) has a molar ratio H ₂ / CO of about 3.0, the hydrogen (H ₂ ) is somewhat higher than the carbon monoxide (CO) in the Fischer-Tropsch reaction. Therefore, one embodiment of the present invention is a carbon dioxide (CO) prepared by reacting carbon dioxide back to the synthesis gas of the second flow (B) by mixing carbon monoxide (CO) molar ratio of raw materials (C) H ₂ / CO 2.0 or more and 3.0 Less than, in detail, more than 2.0 and less than 2.5, more specifically, after adjusting to 2.0, it is characterized in that the Fisher-Tropsch reaction proceeds.

According to another embodiment of the present invention shown in Figure 4, the hydrocarbon compound may be dimethyl ether (dimethyl ether, DME), the dimethyl ether (DME) may be prepared through the reaction as shown in Formula 5 below. (S82).

[Scheme 5]

3H ₂ + 3CO-> CH ₃ OCH ₃ + CO ₂

According to another embodiment of the present invention, by mixing the carbon monoxide (CO) in the synthesis gas of the second flow (B), the raw material (C) has a molar ratio H ₂ / CO suitable for the reaction as in Scheme 5 Can be prepared.

For the same reason as the one embodiment, another embodiment of the present invention is a mixture of carbon monoxide (CO) prepared by reacting carbon dioxide with the synthesis gas of the second flow (B) by reverse reaction, and the molar ratio of raw materials (C) H ₂ / After adjusting the CO to 1.0 or more and less than 2.0, in detail to 1.0 or more and less than 1.5, and more specifically to 1.0, it is a technical feature to proceed with the reaction of Scheme 5.

The present invention separates and collects carbon dioxide generated during the manufacturing process of high caloric SNG with increased calorific value, converts it into carbon monoxide through an inverse reaction, and mixes the carbon monoxide with the syngas of the second flow. As a raw material, a hydrocarbon compound capable of increasing the calorific value of synthetic natural gas (SNG) is synthesized. Therefore, it is possible to manufacture a synthetic natural gas having an increased calorific value without receiving liquefied petroleum gas from the outside as in the prior art, and it is possible to significantly reduce the amount of carbon dioxide emitted.

The present invention is a synthetic gas produced by the methanization reaction of the synthesis gas of the first flow (SNG) and a hydrocarbon compound such as liquefied petroleum gas (LPG), dimethyl ether (DME), and heat per unit volume of 9,500 Synthetic natural gas having a high calorific value of kcal / m 3 or higher, preferably 10,400 kcal / m 3 or higher (S90).

The present invention may further perform the step of separating water (S91) and separating the remaining trace amount of carbon dioxide (S92) from the high heat generation synthetic natural gas. Through this, it is possible to finally obtain high-quality synthetic natural gas (SNG) having liquefied natural gas (LNG) -grade heat.

The present invention further provides a manufacturing apparatus that can be used in the method for producing a synthetic natural gas having an increased calorific value as described above.

The apparatus for producing a synthetic natural gas having an increased calorific value according to the present invention is a gasification unit that gasifies fuel to produce a synthesis gas, a water gas conversion unit that reacts by supplying water to the synthesis gas, and the converted synthesis gas in a first flow. And a synthesis gas separation unit for separating into a second flow, and a methanation unit for producing a synthetic natural gas by methanation reaction of the synthesis gas of the first flow, located between the separation unit and the water gas conversion unit, and converted Carbon dioxide separation unit for separating carbon dioxide from the synthesized gas, an inertial reaction unit for producing carbon monoxide by supplying and reacting carbon dioxide to the separated carbon dioxide, a raw material preparation unit for mixing the carbon monoxide and the syngas of the second flow, A reaction unit for producing a hydrocarbon compound by receiving and reacting with a raw material from a raw material preparation unit and the hydrocarbon It may include a mixing unit to mix the compound with the synthesis gas.

Specifically, the reaction unit is a reactor for producing liquefied petroleum gas (LPG) by reacting the raw material with a Fischer-Tropsch reaction as in Scheme 4, or reacting the raw material as in Scheme 5 to produce dimethyl ether (DME). It can be a reactor.

The reaction occurring in each unit and reactor is the same as mentioned in the manufacturing method of the corresponding high-caloric natural gas (high caloric SNG) with the above-described calorific value, so a person skilled in the art will clearly understand the manufacturing apparatus. , In order to avoid duplication of the following description, it will be omitted.

Hereinafter, the present invention will be described in more detail through specific examples. However, these examples are intended to illustrate the present invention and the scope of the present invention is not limited by them.

According to one embodiment of the present invention shown in FIG. 3 and another embodiment of the present invention shown in FIG. 4, when a synthetic natural gas having an increased calorific value is produced, the heat amount per unit volume of the synthetic natural gas (kcal / m 3), The process was simulated using PRO II, a process simulation program, to find out the output per unit time (kmol / hr) and the emission per unit time (kmol / hr) of carbon dioxide emitted during the process.

Example 1  To Example 8

The process of manufacturing a synthetic natural gas with an increased calorific value shown in FIG. 3 is simulated.

When separating the carbon dioxide separated synthesis gas into a first flow and a second flow, the volume ratios of the first flow and the second flow are 9: 1 (Examples 1 and 5), and 8: 2 (Examples 2 and 6), respectively. ), 7: 3 (Examples 3 and 7), and 6: 5 (Examples 4 and 8).

After mixing the synthesis gas of the second flow (B) and carbon monoxide (CO) prepared through an inverse reaction as shown in FIG. 3, the molar ratio H ₂ / CO of the raw material (C) is 2.0, followed by Liquefied petroleum gas (LPG) was prepared by reacting the Fischer-Tropsch reaction.

The conversion rate and selectivity of the Fischer-Tropsch reaction are shown in Table 1 below, and the reaction is Qianwen Zhang, Direct synthesis of LPG fuel from syngas with the hybrid catalyst based on modified Pd / SiO ₂ and zeolite, Catalysis. It was carried out using catalysts disclosed in Today , 104, 30-36 (2005) (A catalyst: Examples 1 to 4, B catalyst: Examples 5 to 8).

division A catalyst (Examples 1 to 4) B catalyst (Examples 5-8) Conversion rate of carbon monoxide [%] 43.5 74.1
Product yield
hydrocarbon 23.7 40.7 Dimethyl ether 0.0 0.1 carbon dioxide 19.8 33.3

Hydrocarbon composition
[C mol%]
C1 5.2 7.2 C2 6.5 4.3 C3 41.2 14.2 C4 35.8 8.2 C5 8.8 1.4 C6 + 2.5 0.3

Example 9  To Example 12

The process of manufacturing a synthetic natural gas with an increased calorific value shown in FIG. 4 is simulated.

When separating the carbon dioxide separated synthesis gas into a first flow and a second flow, the volume ratios of the first flow and the second flow are 9: 1 (Example 9), 8: 2 (Example 10), and 7: It was set to 3 (Example 11) and 6: 5 (Example 12).

As shown in FIG. 4, after mixing the synthesis gas of the second flow (B) with carbon monoxide (CO) prepared through an inverse reaction, the molar ratio H ₂ / CO of the raw material (C) is 1.0, followed by DME Dimethyl ether (DME) was prepared through a synthetic reaction.

The conversion rate and selectivity of the DME synthesis reaction are shown in Table 2 below, and the reaction is Andres Garcia-Trenco, Direct synthesis of DME from syngas on hybrid CuZnAl / ZSM-5 catalysts: New insights into the role of zeolite acidity, Applied catalysis A: General , 411-412, proceeded using a catalyst (C catalyst) disclosed in 170-179 (2012).

division C catalyst (Examples 9 to 12) Conversion rate of carbon monoxide [%] 93.0
Product yield

hydrocarbon 0.5 Dimethyl ether 65.0 carbon dioxide 31.0 Methanol 3.5

Experiment result

Heat output per unit volume (kcal / ㎥), production volume per unit time (kmol / hr) and emission of carbon dioxide emitted during the process (kmol / hr) per unit volume of synthetic natural gas, which is the final product of the simulation process according to Examples 1 to 12 ) Was measured. The results are shown in Table 3 below.

division Volume ratio
[A: B] catalyst Synthetic natural gas
Per unit volume
calorie
[kcal / ㎥] Synthetic natural gas
Per unit hour
output
[kcal / hr] carbon dioxide
Per unit hour
Emissions
[kmol / hr] Example 1 9: 1 A catalyst 9,548.7 6,188.4 11,536.1 Example 2 8: 2 A catalyst 10,081.5 6,277.6 11,501.2 Example 3 7: 3 A catalyst 10,379.8 6,367.1 11.466.3 Example 4 6: 4 A catalyst 11,447.0 6,456.7 11,431.4 Example 5 9: 1 B catalyst 9,806.9 6,090.0 11,653.8 Example 6 8: 2 B catalyst 10,595.3 6,040.4 11,736.6 Example 7 7: 3 B catalyst 11,464.7 6,011.3 11,819.5 Example 8 6: 4 B catalyst 12,428.5 5,982.3 11,902.3 Example 9 9: 1 C catalyst 9,918.9 6,274.9 11,282.1 Example 10 8: 2 C catalyst 10,685.6 6,450.4 10,993.5 Example 11 7: 3 C catalyst 11,411.5 6,626.4 10,704.7 Example 12 6: 4 C catalyst 12,099.8 6,802.5 10,416.1

Referring to Table 3, in Examples 1 to 12, the heat per unit volume of synthetic natural gas is 9,500 kcal / m 3 or more, and all Examples except Examples 1, 2, 5, and 9 It can be seen from 10,400 kcal / ㎥ or more.

The experimental examples and examples of the present invention have been described in detail above, and the scope of the present invention is not limited to the experimental examples and examples described above, and the basic concept of the present invention defined in the following claims Various modifications and improvements of those skilled in the art are also included in the scope of the present invention.

Claims (14)

Gas of any one or more of coal, biomass, and solid carbon is gasified to produce synthesis gas, and after converting the synthesis gas into water gas, the converted synthesis gas is separated into a first flow and a second flow. And, by synthesizing the synthesis gas of the first flow to produce a synthetic natural gas (synthetic natural gas),
Separating carbon dioxide from the converted syngas before separating the converted syngas into a first flow and a second flow;
Preparing carbon monoxide by reverse boudouard reaction of the separated carbon dioxide with a carbon material;
Preparing a raw material by mixing the carbon monoxide and the syngas of the second flow;
Reacting the raw material to prepare a hydrocarbon compound; And
And mixing the hydrocarbon compound and the synthetic natural gas.
Separating the converted synthesis gas into a first flow and a second flow is separated so that the volume ratio of the first flow and the second flow is 9: 1 ~ 6: 4,
When the molar ratio H ₂ / CO of the carbon monoxide and the synthesis gas of the second flow included in the raw material is 2.0 or more and less than 3.0, a liquefied petroleum gas is prepared by reacting the raw material as shown in Reaction Scheme 4 below,
When the molar ratio H ₂ / CO of carbon monoxide and the synthesis gas of the second flow included in the raw material is 1.0 or more and less than 2.0, the raw material is reacted as shown in Reaction Scheme 5 below to produce dimethyl ether (DME). Method for producing synthetic natural gas with increased calorific value.
[Reaction Scheme 4]
(2n + 1) H ₂ + nCO → C _n H _{2n + 1} + nH ₂ O
The n is 1 to 20.

[Scheme 5]
3H ₂ + 3CO-> CH ₃ OCH ₃ + CO ₂
delete According to claim 1,
Method for producing a synthetic natural gas with an increased calorific value, characterized in that the reaction temperature of the counter-reaction is 700 ° C to 2,000 ° C.
delete delete delete delete Gasification unit for producing synthesis gas by gasifying any one or more fuels of coal, biomass, and solid carbon, water gas conversion unit for supplying water to react with the synthesis gas, and first and second flows of the converted synthesis gas Synthetic gas separation unit for separating, and comprises a methanation unit for producing a synthetic natural gas by the methanization reaction of the synthesis gas of the first flow,
A carbon dioxide separation unit located between the separation unit and the water gas conversion unit to separate carbon dioxide from the converted synthesis gas;
An inverse reaction unit for producing carbon monoxide by supplying and reacting carbon dioxide to the separated carbon dioxide;
A raw material preparation unit for mixing the carbon monoxide and the syngas of the second flow;
A reaction unit that receives a raw material from the raw material preparation unit and reacts to produce a hydrocarbon compound; And
Includes; a mixing unit for mixing the hydrocarbon compound and the synthetic natural gas,
The syngas separation unit separates the converted syngas so that the volume ratio between the first flow and the second flow is 9: 1 to 6: 4,
When the molar ratio H ₂ / CO of the carbon monoxide and the synthesis gas of the second flow included in the raw material is 2.0 or more and less than 3.0, a liquefied petroleum gas is prepared by reacting the raw material as shown in Reaction Scheme 4 below,
When the molar ratio H ₂ / CO of the carbon monoxide and the synthesis gas of the second flow included in the raw material is 1.0 or more and less than 2.0, the raw material is reacted as shown in Reaction Scheme 5 below to produce dimethyl ether (DME). Synthetic natural gas manufacturing apparatus with increased calorific value.
[Reaction Scheme 4]
(2n + 1) H ₂ + nCO → C _n H _{2n + 1} + nH ₂ O
The n is 1 to 20.

[Scheme 5]
3H ₂ + 3CO-> CH ₃ OCH ₃ + CO ₂
delete The method of claim 8,
The reverse reaction unit is an apparatus for producing synthetic natural gas with an increased calorific value, characterized in that carbon dioxide and a carbon material are reacted at a reaction temperature of 700 ° C to 2,000 ° C.
delete delete delete delete

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