KR20210125348A - Low temperature process for bio-gas reforming - Google Patents

Abstract

According to one embodiment of the present invention, provided is a low-temperature process for bio-gas reforming. The low-temperature process for bio-gas reforming comprises: a first step of introducing a mixture gas including a biogas into a reactor; and a second step of reforming the mixture gas using a catalyst compound to produce a reformed gas. The reformed gas contains methane in an amount greater than that of methane contained in the mixture gas. At least a part of the methane contained in the mixture gas is reformed into a C2 to C4 hydrocarbon compound. The second step is carried out at a temperature of 550-850℃, and the catalyst compound is a metal oxide catalyst including at least one selected from the group consisting of Sr, Ti, La, and Al, or a metal oxide supported catalyst including at least one selected from the group consisting of Na_2WO_4 and Mn.

Description

Low-temperature biogas reforming process {LOW TEMPERATURE PROCESS FOR BIO-GAS REFORMING}

The present invention relates to a method for producing high-energy gaseous fuel including hydrocarbon compounds such as ethane and propane by reforming biogas at a low temperature.

Biogas is a gas mixture produced through anaerobic digestion of organic matter or organic waste resources such as food waste and sewage sludge, methane (CH ₄ ) 50-70%, carbon dioxide (CO ₂ ) 30-50%, and a trace amount of hydrogen sulfide (H ₂ S), nitrogen (N ₂ ), oxygen (O ₂ ), and the like. After removing carbon dioxide, hydrogen sulfide, and the like from biogas, purified biomethane can be produced, which can be mixed with LNG and used as gaseous fuel. Biomethane obtained from biogas can replace fuels such as LNG, but its calorific value is low compared to natural gas containing paraffin compounds such as ethane and propane in addition to methane, so its utility as a fuel may be insufficient. Therefore, in order to increase the calorific value, it is necessary to mix a compound derived from petroleum or natural gas to obtain fuel properties similar to those of conventional natural gas. Therefore, a commercialized process for reforming methane, which is a major component of biogas, is required.

Existing methane conversion processes mostly produce various hydrocarbon compounds from syngas containing carbon monoxide (CO) oxidized to methane. Traditionally well-known chemical processes such as the DME production technology and the Fischer-Tropsch process are methods for producing dimethyl ether or alkyl hydrocarbons from syngas. Many of these processes have been developed and commercialized processes exist. It can be said that it is an indirect conversion technology of methane that produces other high value-added chemical products by producing partially oxidized carbon monoxide from methane. On the other hand, a method for directly converting methane to produce high value-added chemicals is also being developed.

However, there is a disadvantage in that it is difficult to stably operate the conversion reaction process to hydrocarbons for a long time due _{to H 2} S, which is a reducing gas in the biogas. _{Therefore, a process for separating H 2} S before the reaction step is necessarily added, which causes an increase in process cost. For this reason, there is a need for a biogas reforming process that can be stably performed without separating _{H 2 S at an early stage.}

In one aspect, the present specification provides a method for producing paraffin and olefin through the oxidation dimerization reaction of methane contained in biogas, and producing a mixed gas fuel including methane, ethane, ethylene, propane, propylene, etc. aim to do

In another aspect, the present specification provides a catalyst for a mixed oxide biogas conversion reaction comprising at least one component of Sr, Ti, La, Al or Na ₂ WO ₄ , a metal oxide containing Mn-supported biogas on a silicon oxide carrier An object of the present invention is to provide a catalyst for a conversion reaction.

According to an embodiment of the present invention, a first step of introducing a mixed gas containing biogas into the reactor; and a second step of reforming the mixed gas using a catalyst compound to produce a reformed gas, wherein the reformed gas includes a greater amount of methane (CH ₄ ) than the mixed gas, and methane included in the mixed gas At least a portion of the C2 to C4 hydrocarbon compound is reformed, the second step is performed at 550° C. to 850° C., and the catalyst compound is a metal containing at least one or more from the group consisting of Sr, Ti, La, and Al. A low-temperature biogas reforming process is provided, which is an oxide catalyst or a metal oxide supported catalyst including at least one from the group consisting of _{Na 2 WO 4 and Mn.}

According to an embodiment of the present invention, the mixed gas contains methane (CH ₄ ) 50% to 70% by volume based on the total volume of the mixed gas, and 1 volume of methane included in the mixed gas after the second step % to 10% by volume is converted to at least one selected from a C2 to C4 hydrocarbon compound, carbon monoxide, and carbon dioxide, a low-temperature biogas reforming process is provided.

According to an embodiment of the present invention, the mixed gas includes hydrogen sulfide (H ₂ S), and the biogas and the mixed gas are provided in the second step without a hydrogen sulfide removal process, a low-temperature biogas reforming process is provided. .

According to an embodiment of the present invention, the reforming reaction in the second step is performed at a ^{gas Hourly Space Velocity (GHSV) of 1,000 to 30,000 h -1} , a low-temperature biogas reforming process is provided.

According to an embodiment of the present invention, the catalyst compound comprises at least one selected from the group consisting of lanthanum aluminum oxide (LAO), strontium titanium oxide (STO), sodium tungstate-manganese-silica gel (NWM), A low temperature biogas reforming process is provided.

According to an embodiment of the present invention, the catalyst compound is provided in a precursor state, and in the second step, at least some of it has an alpha-cristobalite crystal structure at a temperature of 500° C. or higher, a low-temperature biogas reforming process this is provided

According to an embodiment of the present invention, the catalyst compound is provided in a precursor state, and in the second step, at least a portion is changed to a form having a perovskite crystal structure at a temperature of 500° C. or higher to participate in the reforming reaction. A low-temperature biogas reforming process is provided.

According to an embodiment of the present invention, the low-temperature biogas reforming process is provided, wherein the catalyst compound is provided to have a volume of 0.18 mL to 0.54 mL.

According to an embodiment of the present invention, there is provided a low-temperature biogas reforming process, further comprising a third step of separating C2 to C4 hydrocarbon compounds after performing the second step.

According to an embodiment of the present invention, the biogas and additional oxygen are mixed in the first step,

The volume ratio of the biogas and additional oxygen is 10:1 to 15:1, a low-temperature biogas reforming process is provided.

In one aspect, the technology disclosed herein is a biogas conversion reaction method for producing a hydrocarbon compound containing two or more carbon atoms from methane in a high yield at a low temperature condition of 700° C. or less using the catalyst for biogas reforming has the effect of providing

In another aspect, the technology disclosed herein is a catalyst for a mixed oxide biogas conversion reaction comprising at least one component of Sr, Ti, La, Al or Na ₂ WO ₄ , a metal oxide including Mn is supported on a silicon oxide carrier. It has the effect of providing a catalyst for the biogas conversion reaction.

1 is a block diagram schematically illustrating a biogas reforming process according to an embodiment of the present invention.
2 is a flowchart illustrating a biogas reforming process according to an embodiment of the present invention.
3 is a schematic view of the composition of a biogas reactant and a high-energy mixed gas fuel product of a biogas conversion reaction or methane oxidation dimerization reaction according to an embodiment of the present invention.

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

According to an embodiment of the present invention, biogas can be reformed into a gas raw material having a high calorific value under low temperature conditions. In particular, since the process according to the present invention can be performed without a separate hydrogen sulfide removal process, the process efficiency is excellent.

1 is a block diagram schematically illustrating a biogas reforming process according to an embodiment of the present invention, and FIG. 2 is a flowchart illustrating a biogas reforming process according to an embodiment of the present invention.

1 and 2, the low-temperature biogas reforming process includes a first step (S100) of introducing a mixed gas containing biogas, and a second step (S200) of reforming the mixed gas using a catalyst compound. include

First, in the first step ( S100 ), a mixed gas including biogas (B_G) is introduced into the reactor (RT).

Biogas (B_G) may be a gas mixture obtained through anaerobic digestion of organic matter and organic waste resources. For example, biogas (B_G) may be a gas mixture containing a large amount of methane, which is produced through hydrolysis, acid production, acetic acid production, and methanogenesis steps.

The hydrolysis step in the biogas (B_G) manufacturing process may be a step in which complexly bound raw materials such as carbohydrates, proteins, and fats are separated into simple organic compounds such as amino acids, monosaccharides, and fatty acids. Hydrolysis can proceed by enzymes released from hydrolyzing bacteria. Next, the acid production step is a process in which the intermediate material produced in the hydrolysis step is converted into lower fatty acids such as acetic acid, propanoic acid, butanoic acid, carbon dioxide, and hydrogen by acid producing bacteria. At this time, small amounts of lactic acid and alcohol may be formed together. Next, the acetic acid production step refers to a process in which the lower fatty acids generated in the acid production step are converted into acetic acid, hydrogen, and carbon dioxide, which are reactants capable of producing biogas by the acetic acid producing bacteria. Finally, the methanogenic step refers to a process in which acetic acid, hydrogen, and carbon dioxide are converted to methane by anaerobic methanogenic bacteria.

Biogas (B_G) may be supplied to the reactor (RT) after being generated through the above-described process. Accordingly, the reactor RT may be connected to the biogas generating reactor in order to receive the biogas B_G. Organic matter and organic waste resources are supplied to the biogas generating reactor, and biogas (B_G) may be generated through the above-described steps of the supplied organic matter and organic waste resources.

Biogas (B_G) may include methane (CH ₄ ), carbon dioxide (CO ₂ ), hydrogen sulfide (H ₂ S), nitrogen (N ₂ ), oxygen (O ₂ ), and the like. Biogas (B_G), in particular, may contain a large amount of _{methane (CH 4} ) and carbon dioxide (CO _{2 ).} Specifically, the biogas (B_G) may include about 50% by volume to about 70% by volume of methane by volume. In addition, it may contain about 30% by volume to about 50% by volume of carbon dioxide.

Biogas (B_G) contains a large amount of methane as described above. Methane is a combustible gas that can be easily combusted. Therefore, biogas (B_G) containing a large amount of methane can be used as a fuel. However, there is a problem in that methane is economical because its volume is large compared to the calorific value. Accordingly, by performing a reforming reaction in which methane is converted into a hydrocarbon having more carbon number, the calorific value of the reformed gas may be increased.

The above-described reforming reaction performed on the biogas (B_G) may be, for example, an oxidation dimerization reaction of methane. The oxidation dimerization reaction of methane may refer to a reaction for producing paraffins, olefins, etc. including two or more carbons such as ethane, ethylene, propane, and propylene from methane. Hydrocarbons with 2 or more carbon atoms (C ₂₊ hydrocarbons) have high high calorific value, which can help fuel biogas (B_G) alone without additives. However, the conversion reaction to hydrocarbons is inhibited due to _{hydrogen sulfide (H 2} S), which is a reducing gas inside the biogas (B_G). Therefore, there is a problem in producing hydrocarbons using biogas (B_G) as a reactant of the oxidative dimerization reaction of methane, and the selectivity and yield of the hydrocarbons are accompanied by many technical difficulties even in slightly increasing them.

According to an embodiment of the present invention, since the reforming reaction of biogas (B_G) can be performed directly in the reactor without removing hydrogen sulfide, process efficiency is excellent. In addition, since the process is performed at a low temperature, the process cost can be reduced.

The above-described reforming reaction of the biogas (B_G) may be performed with the participation of the catalyst compound (CAT) provided in the reactor (RT). Specifically, in the second step ( S200 ), the mixed gas is reformed using the catalyst compound (CAT) to generate the reformed gas.

The catalyst compound (CAT) promotes the reforming reaction of biogas (B_G). For example, the catalyst compound (CAT) promotes the reaction so that methane contained in the biogas (B_G) can be converted into a C2 to C4 hydrocarbon compound.

The catalyst compound (CAT) may, for example, lower the activation energy of at least one of the reactions below, so that the reaction can be carried out more easily.

C₂H₄ + 2H₂ G⁰ (1000K) = 40 kJ/mol2CH ₄

C ₂ H ₄ + 2H ₂ G ⁰ (1000K) = 40 kJ/mol

C₂H₆ + H₂ G⁰ (1000K) = 36 kJ/mol2C ₂ H ₄

C ₂ H ₆ + H ₂ G ⁰ (1000K) = 36 kJ/mol

C₂H₄ + 2H₂O G⁰ (1000K) = -152 kJ/mol2CH ₄ + O ₂

C ₂ H ₄ + 2H ₂ O G ⁰ (1000K) = -152 kJ/mol

C₂H₆ + H₂O G⁰ (1000K) = -61 kJ/mol2C ₂ H ₄ + O ₂

C ₂ H ₆ + H ₂ O G ⁰ (1000K) = -61 kJ/mol

The catalyst compound (CAT) may include a mixed oxide catalyst or silicon oxide carrier including at least one component of Sr, Ti, La, and Al; and a catalyst component supported on the carrier, wherein the catalyst component may be a supported catalyst comprising manganese oxide and sodium tungstate. The above-described catalyst compound (CAT) enables the oxidative dimerization reaction of methane to be performed at _{low temperature without removing hydrogen sulfide (H 2 S).}

The catalyst compound (CAT) is provided in a precursor state, and all or part of the mixed oxide may have a perovskite crystal structure at a temperature of about 500° C. or higher. In this case, the catalyst compound (CAT) may be a mixed oxide catalyst, and the mixed oxide catalyst does not specify a structure or crystallinity in a precursor state, and at a temperature of about 500° C. or higher, all or part of the mixed oxide is perovskite. It may have a (perovskite) crystal structure. Specifically, the perovskite crystal may support an alkali metal oxide as an active support. These catalysts show high reaction activity at low temperatures.

The catalyst compound (CAT) is provided in a precursor state, and at a temperature of about 500° C. or higher, all or part of the silicon oxide may have an alpha-cristobalite crystal structure. In this case, the catalyst compound (CAT) may include silicon oxide, and the silicon oxide does not specify a pore structure or crystallinity in a precursor state, and all or part of the silicon oxide is alpha-cristobalite ( alpha-cristobalite) crystal structure. At the reaction temperature of the second step (S200), the catalyst compound (CAT) has an alpha-cristobalite crystal structure, so that the biogas reforming reaction, for example, methane oxidation dimerization reaction, is performed at a high yield even at a relatively low reaction temperature. can be

The catalyst compound (CAT) may include 0.1 to 5 wt%, 3 to 5 wt%, or 1 to 3 wt% of the metal oxide based on the total weight of the catalyst compound (CAT). In another exemplary embodiment, the catalyst compound (CAT) is 0.01 wt% or more, 0.1 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, based on the total weight of the catalyst compound (CAT) , 4 wt% or more, or 5 wt% or more and 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less.

The catalyst compound (CAT) may be provided to have a volume of about 0.18 mL to about 0.54 mL. The catalyst compound (CAT) may be provided in the form of a fluidized catalyst bed. By providing the catalyst compound (CAT) in the above-mentioned range, it is possible to react with high efficiency.

For the reaction of the catalyst compound (CAT) and the biogas (B_G), an additional gas reactant (AR_G) may be supplied into the reactor (RT).

The additional gas reactant AR_G may be, for example, additional oxygen participating in the methane oxidative dimerization reaction. Additional oxygen may be supplied in a ratio of about 10:1 to about 15:1 by volume to biogas. When the additional oxygen is supplied in a volume ratio of more than about 10:1 with respect to the biogas, the oxidation reaction of methane is accelerated, so that the amount of methane converted to carbon dioxide or carbon monoxide may be increased rather than converted to C2-C4 hydrocarbons. In addition, when the additional oxygen is supplied in a volume ratio of less than about 15:1 with respect to the biogas, the methane oxidation dimerization reaction may not sufficiently occur.

The additional gas reactant AR_G may include various gases other than oxygen. For example, it may contain an inert gas such as nitrogen or argon.

The reactor RT may have various shapes. For example, the reactor (RT) may be provided in various forms, such as a continuously stirred tank reactor (CSTR), a plug flow reactor (PFR), a fluidized bed catalytic reactor, and the like.

In the second step (S200), the reaction may be carried out at about 550 °C to about 850 °C. The above-mentioned temperature range is lower than the process temperature according to the prior art. In particular, when the reforming reaction is a methane oxidation dimerization reaction, a relatively high process temperature is required according to the prior art. When the temperature of the process is increased, the reaction rate can be increased, but it is difficult to stably operate the process for a long period of time because the catalyst may be denatured at high temperatures. In addition, since a large amount of cost is consumed to maintain the reactor at a high temperature, the process cost is greatly increased. According to the present invention, the reformed gas (RF_G) having a high calorific value can be produced by reforming the biogas (B_G) with high efficiency even at a low temperature.

In the second step (S200), the reaction temperature may be about 550 °C to about 600 °C in some cases. In the above case, the yield of the reforming reaction may be slightly lowered, but since the reaction can be performed in a lower range, there is a great advantage in reactor design, process cost, and the like.

In the second step (S200), the reforming reaction in the second step may be carried out at a gas hourly space velocity (GHSV) ^{of 1,000 to 30,000 h -1 .} By performing the reaction in the above-described gas space velocity range, it is possible to ensure that the supply of reactants and discharge of the product are not delayed while sufficiently performing the reforming reaction in the reactor. Therefore, it is possible to increase process efficiency by operating the process within the above-described range.

The reformed gas RF_G produced after performing the second step S200 may be a gaseous compound in which at least a portion of methane included in the mixed gas is converted into a C2 to C4 hydrocarbon compound.

In the second step (S200), the biogas (B-G) and the mixed gas are provided in the second step (S200) without a hydrogen sulfide removal process. Since the process for the removal or the adsorbent required to remove the hydrogen sulfide contained in the biogas (B_G) can be omitted, the process efficiency is improved. According to the present invention, hydrogen sulfide may be removed in the process of reforming the mixed gas by the catalyst compound (CAT).

After performing the second step (S200), a third step of separating C2 to C4 hydrocarbon compounds may be further included. The separated hydrocarbon compound may be used in various processes, such as further purification processes and polymerization processes.

The reformed gas (RF_G) may be one in which about 1% to about 10% by volume of methane included in the mixed gas is converted to at least one selected from a C2 to C4 hydrocarbon compound, carbon monoxide, and carbon dioxide. Hereinafter, the reformed gas RF_G will be described in more detail.

3 is a schematic view of the composition of a biogas reactant and a high-energy mixed gas fuel product of a biogas conversion reaction or methane oxidation dimerization reaction according to an embodiment of the present invention.

In one exemplary embodiment, the biogas is methane (CH ₄ ) 50-70%, carbon dioxide (CO ₂ ) 30-50%, and less than 10% nitrogen (N ₂ ), oxygen (O ₂ ), hydrogen sulfide (H) ₂ S) and the like.

The hydrocarbon product produced after the biogas reforming reaction may be 80-100% methane, 1-20% paraffin and olefin by volume ratio.

In an exemplary embodiment, the product of the biogas conversion reaction is ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), propane (C ₃ H ₈ ) or propylene (C ₃ H ₆ ) It may include one or more selected from the group consisting of.

As described above, the calorific value of the reformed gas generated by reforming the biogas may be improved. The reformed gas may have a higher calorific value than biogas or mixed gas. For example, the reformed gas may have a calorific value of about 9500 kcal/Nm ³ to about 11000 kcal/Nm ³ .

As described above, by reforming the biogas, a reformed gas having excellent calorific value may be produced. In particular, the process according to the present invention can be directly performed without pretreatment of the raw biogas. As described above, according to the prior art, a process for removing sulfur compounds was required before the biogas reforming process. However, according to the present invention, it is possible to produce a modified gas so as to have a high calorific value from a feed containing a sulfur compound.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Preparation Example 1. Preparation of Lanthanum Aluminum Oxide (LAO) Catalyst

에서 공기 분위기 하에서 건조한 다음 900

에서 5시간 동안 소성하여 제조하였다.14 mL of ethylene glycol and 6.2 g of aluminum chloride hexahydrate are mixed and stirred for about 1 hour. 20 mL of distilled water and 19.3 g of citric acid are added, and each is stirred for about 1 hour. 9.4 g of lanthanum chloride heptahydrate is mixed and stirred for about 12 to 15 hours. The prepared mixed solution in the form of a gel is 250 for 24 hours.

then dried under an air atmosphere at 900

It was prepared by calcination for 5 hours.

Preparation Example 2. Preparation of Strontium Titanium Oxide (STO) Catalyst

에서 공기 분위기 하에서 건조한 다음 900

에서 5시간 동안 소성하여 제조하였다.Mix 14 mL of ethylene glycol and 8.8 mL of titanium butoxide and stir for about 1 hour. 20 mL of distilled water and 19.3 g of citric acid are added, and each is stirred for about 1 hour. 6.7 g of strontium chloride hexahydrate is mixed and stirred for about 12 to 15 hours. The prepared mixed solution in the form of a gel is 250 for 24 hours.

then dried under an air atmosphere at 900

It was prepared by calcining for 5 hours.

Preparation Example 3. Preparation of sodium tungstate-manganese-silica gel (NWM) catalyst

0.1280 g of sodium tungstate dihydrate and 0.1309 mL of manganese nitrate hexahydrate were mixed with an aqueous solution of 2 g of silica carrier and 70 g of distilled water and stirred for 30 minutes and mixed for about 3 hours. did. Then, the aqueous solution was dried at 105 °C for 16 hours and then calcined at 800 °C for 5 hours to prepare a sodium tungstate-manganese-silica gel (NWM) catalyst.

Test Example 1.

A biogas reforming reaction was performed using the catalysts prepared in Preparation Examples 1, 2 and 3 using a continuous reactor. The reaction temperature was maintained at ^{600 to 750 o} C or 700 to 850 ^{o C.} The gas mixtures obtained after the reaction were analyzed using gas chromatography.

The reaction conditions of the biogas reforming reaction are as follows. Bio-gas mixture: O ₂ : N ₂ = 27: 2: 1 (v/v/v), GHSV = 3,333 ~ 10,000 mL _feed /h/mL _catalyst , catalyst bed volume = 0.18 ~ 0.54 mL, (Mixture gas = CH ₄ : CO ₂ : H ₂ S = 59.7: 39.8: 0.5 (v/v/v)), Reaction temperature: 600 ~ 750 ^o C (LT), 700 ~ 850 ^o C, ^b 0 °C, at 1 atm. Only hydrocarbon (C _x H _y ) compounds are used in the calculation.

Tables 1 to 3 below show reaction results for various catalysts prepared in Preparation Examples 1, 2 and 3, respectively.

Catalyst of Preparation Example 1 Temperature Furtherance HHV
(Kcal/Nm ³ ) ^b CH ₄ O ₂ N ₂ CO CO ₂ C ₂ H ₂ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ GHSV=10,000
Example 1-1 700 55.0 0.48 4.55 2.06 36.4 0.00 0.75 0.71 0.03 0.00 9694.7 Example 1-2 750 53.1 0.55 4.54 1.98 38.5 0.00 0.53 0.80 0.02 0.00 9687.6 Examples 1-3 800 52.9 0.01 4.47 4.83 37.1 0.00 0.49 0.21 0.01 0.00 9604.8 Examples 1-4 850 50.1 0.01 4.43 8.90 36.3 0.00 0.21 0.03 0.00 0.00 9553.1 GHSV=5,000
Example 2-1 700 53.2 0.09 5.03 2.29 38.1 0.00 0.64 0.61 0.02 0.00 9674.5 Example 2-2 750 53.0 0.01 4.98 1.57 39.6 0.00 0.45 0.43 0.01 0.00 9629.1 Example 2-3 800 52.7 0.01 4.81 5.89 36.2 0.00 0.26 0.09 0.00 0.00 9563.7 Example 2-4 850 48.8 0.01 4.78 10.8 35.4 0.00 0.15 0.02 0.00 0.00 9545.6 GHSV=3,333
Example 3-1 700 52.1 0.03 8.08 2.13 36.2 0.00 0.74 0.75 0.03 0.00 9708.0 Example 3-2 750 53.1 0.01 4.53 1.99 39.2 0.00 0.62 0.52 0.01 0.00 9658.1 Example 3-3 800 50.3 0.01 4.43 6.70 37.7 0.00 0.61 0.16 0.01 0.00 9614.5 Example 3-4 850 48.4 0.01 4.35 9.13 37.9 0.00 0.19 0.02 0.00 0.00 9550.2 GHSV=10,000 (LT)
Example 4-1 600 55.8 0.61 4.58 1.94 36.1 0.00 0.29 0.63 0.01 0.00 9635.2 Example 4-2 650 55.1 2.78 4.37 0.41 37.2 0.00 0.03 0.17 0.00 0.00 9549.9 Example 4-3 700 54.0 1.54 4.39 1.22 38.2 0.00 0.17 0.57 0.00 0.00 9616.8 Example 4-4 750 53.0 0.71 4.43 1.87 38.8 0.00 0.42 0.76 0.01 0.00 9671.1

Catalyst of Preparation Example 2 Temperature Furtherance HHV
(Kcal/Nm ³ ) ^b CH ₄ O ₂ N ₂ CO CO ₂ C ₂ H ₂ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ GHSV=10,000
Example 5-1 700 52.3 2.65 4.55 0.46 39.5 0.00 0.14 0.44 0.00 0.00 9598.9 Example 5-2 750 55.3 2.92 4.24 0.50 36.8 0.00 0.05 0.14 0.00 0.00 9547.5 Example 5-3 800 55.1 2.57 4.28 0.50 37.2 0.00 0.14 0.25 0.01 0.00 9571.5 Example 5-4 850 54.5 1.81 4.35 0.40 38.1 0.00 0.45 0.38 0.03 0.00 9625.2 GHSV=3,333
Example 6-1 700 57.0 1.41 5.08 0.63 33.7 0.00 0.99 1.22 0.04 0.00 9773.7 Example 6-2 750 54.2 0.99 5.06 0.99 37.7 0.00 0.50 0.51 0.02 0.00 9645.6 Example 6-3 800 54.5 0.87 4.81 1.04 38.1 0.00 0.28 0.35 0.01 0.00 9601.8 Example 6-4 850 53.3 0.01 4.70 2.56 39.1 0.00 0.09 0.25 0.03 0.00 9574.3 GHSV=10,000 (LT)
Example 7-1 600 57.5 3.26 4.16 0.21 34.8 0.00 0.01 0.07 0.00 0.00 9534.5 Example 7-2 650 55.2 2.97 4.17 0.23 37.3 0.00 0.02 0.08 0.00 0.00 9537.1 Example 7-3 700 55.3 2.90 4.18 0.25 37.2 0.00 0.02 0.10 0.00 0.00 9539.6 Example 7-4 750 55.2 2.83 4.41 0.24 37.2 0.00 0.04 0.14 0.00 0.00 9546.8

Catalyst of Preparation Example 3 Temperature Furtherance HHV
(Kcal/Nm ³ ) CH ₄ O ₂ N ₂ CO CO ₂ C ₂ H ₂ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ GHSV=10,000
Example 8-1 700 54.7 3.21 4.29 0.00 37.5 0.00 0.03 0.18 0.00 0.00 9551.0 Example 8-2 750 54.7 3.09 4.41 0.26 37.0 0.00 0.11 0.40 0.00 0.00 9588.1 Example 8-3 800 53.5 2.33 4.52 0.49 37.7 0.00 0.61 0.80 0.03 0.00 9698.0 Example 8-4 850 50.8 0.01 4.89 0.84 39.8 0.07 2.34 1.06 0.19 0.05 9962.8 GHSV=5,000
Example 9-1 700 54.2 2.91 4.28 0.36 37.4 0.00 0.26 0.66 0.01 0.00 9637.7 Example 9-2 750 54.6 3.23 4.29 0.40 36.6 0.00 0.27 0.66 0.01 0.00 9639.4 Example 9-3 800 52.1 1.78 4.44 0.90 38.4 0.01 1.32 1.04 0.08 0.01 9816.1 Example 9-4 850 50.7 0.01 4.63 1.43 39.8 0.05 2.64 0.52 0.16 0.03 9913.1 GHSV=3,333
Example 10-1 700 53.2 2.67 4.45 0.48 37.8 0.00 0.50 0.89 0.02 0.00 9696.8 Example 10-2 750 53.0 2.48 4.27 0.44 38.4 0.00 0.50 0.89 0.02 0.00 9697.5 Example 10-3 800 50.9 0.11 4.65 1.06 39.7 0.02 2.04 1.33 0.14 0.02 9947.1 Example 10-4 850 50.7 0.01 4.51 1.63 39.9 0.04 2.58 0.43 0.15 0.03 9894.2

Referring to Tables 1 to 3, when the process according to an embodiment of the present invention is used, it can be seen that the calorific value of the reformed gas generated at a process temperature of about 700° C. is the highest. The calorific value of the reformed gas produced at the process temperature of about 750 °C, about 800 °C, and about 850 °C was lower than the calorific value of the reformed gas produced at the process temperature of about 700 °C. A high calorific value means a high rate of reforming of methane gas into C2-C4 hydrocarbon compounds.

Accordingly, it can be seen that the process according to the present invention can be carried out at 700° C. or less, thereby reducing the cost required to increase the process temperature, and having higher efficiency than performing the reaction at a higher process temperature. can

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art or those having ordinary knowledge in the technical field will not depart from the spirit and technical scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (10)

A first step of introducing a mixed gas containing biogas into the reactor;
A second step of reforming the mixed gas using a catalyst compound to produce a reformed gas,
The reformed gas contains a greater amount of methane (CH ₄ ) than the mixed gas,
At least a portion of the methane contained in the mixed gas is reformed into a C2 to C4 hydrocarbon compound,
The second step is carried out at 550 ° C. to 850 ° C.,
The catalyst compound is a metal oxide catalyst containing at least one or more from the group consisting of Sr, Ti, La, Al or Na ₂ WO4, a metal oxide supported catalyst containing at least one or more from the group consisting of Mn, low-temperature biogas reforming process. According to claim 1,
The mixed gas contains _{50% to 70% by volume of methane (CH 4} ) based on the total volume of the mixed gas,
After the second step, 1% to 10% by volume of methane included in the mixed gas is converted to at least one selected from C2 to C4 hydrocarbon compounds, carbon monoxide, and carbon dioxide, a low-temperature biogas reforming process. According to claim 1,
The mixed gas includes hydrogen sulfide (H ₂ S),
The biogas and the mixed gas are provided in the second step without a hydrogen sulfide removal process, a low-temperature biogas reforming process. According to claim 1,
In the second step, the reforming reaction is performed at a gas Hourly Space Velocity (GHSV) ^{of 1,000 to 30,000 h -1 , a low-temperature biogas reforming process.} According to claim 1,
The catalyst compound is a low-temperature biogas reforming process comprising at least one selected from the group consisting of lanthanum aluminum oxide (LAO), strontium titanium oxide (STO), and sodium tungstate-manganese-silica gel (NWM). 6. The method of claim 5,
The catalyst compound is provided in a precursor state,
In the second step, at least a portion at a temperature of 500° C. or higher has an alpha-cristobalite crystal structure, a low-temperature biogas reforming process. 6. The method of claim 5,
The catalyst compound is provided in a precursor state,
In the second step, at least a portion of at least a portion of which is changed to a form having a perovskite crystal structure at a temperature of 500° C. or higher to participate in the reforming reaction, a low-temperature biogas reforming process. According to claim 1,
The catalyst compound is provided to have a volume of 0.18 mL to 0.54 mL, low-temperature biogas reforming process. According to claim 1,
After performing the second step, the low-temperature biogas reforming process further comprising a third step of separating C2 to C4 hydrocarbon compounds. According to claim 1,
Mixing the biogas and additional oxygen in the first step,
The volume ratio of the biogas and additional oxygen is 10:1 to 15:1, low-temperature biogas reforming process.

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