KR102147421B1 - System for preparation of synthetic fuel with slurry bubble column reactor operating in two or more FT modes - Google Patents

Abstract

The present invention is a synthetic fuel production apparatus having a slurry bubble column reactor operating in two or more modes; And its use.
The slurry bubble column reactor operating in at least two modes (a) Fe: Cu: K : SiO 2 = 100: 1 ~ 10: 1 ~ 20: 10 ~ 50 weight ratio of the Fischer having-Tropsch iron-based catalyst, or for the synthesis (b ) Fischer-Tropsch synthesis iron-based catalyst with 10 to 100% of iron atoms in the phase fraction of ferrihydrite and 0 to 90% of iron atoms in the phase fraction of hematite with respect to 100% of the number of iron atoms, 250℃ ~ 280 Operate in low temperature FT mode at ℃ to produce synthetic fuel containing C ₁₉₊ as the first wax amount, and operate in high temperature FT mode at 290 ℃ ~ 350 ℃ to make C ₁₉₊ a second wax smaller than the first wax amount. While producing synthetic fuel contained in a large amount, the off-gas emission is greater than that of the low-temperature FT mode, and the synthetic fuel production device is operated in conjunction with the slurry bubble column reactor when operating in the high-temperature FT mode. It is equipped with a combustor, a heat exchanger, a power generator, or a generator that uses gas of high calorific value discharged during operation in the high-temperature FT mode.

Description

Synthetic fuel manufacturing apparatus with slurry bubble column reactor operating in two or more FT modes}

The present invention is a synthetic fuel production apparatus having a slurry bubble column reactor operating in two or more FT mode; And its use.

Due to the Fischer-Tropsch synthesis method (FT synthesis method) developed in 1923 by German chemists Fischer and Tropsch, liquid hydrocarbons are produced from coal, natural gas, biomass, etc. through syngas. It became possible. The process of manufacturing from coal is called Coal-to-liquids (CTL), the process of manufacturing from natural gas is called Gas-to-liquids (GTL), and the process of manufacturing from biomass is called Biomass-to-liquids (BTL). Similar processes are collectively called XTL ("X" rexource-to-liquids).

These processes first convert each raw material into syngas using methods such as gasification and reforming.The composition of syngas suitable for the XTL process to produce liquid fuel is hydrogen as shown in Reaction Formula 1 below. It is known that the ratio of and carbon monoxide is about 2.

[Scheme 1]

CO + 2H ₂ + -[CH ₂ ]- _n → -[CH ₂ ]- _n+1 + H ₂ O

(CO, 2H _{2 ,} -[CH ₂ ]- _n and H ₂ O are respectively carbon monoxide, hydrogen, a hydrocarbon with a chain length of n (carbon number n) and water.)

When the ratio of hydrogen exceeds 2, the selectivity of methane increases, and the selectivity of C ₅₊ (hydrocarbon having 5 or more carbon atoms) is relatively low, which is not suitable. In Scheme 1, not only hydrocarbons having a linear chain of the above form, but also olefins, oxygenates (molecules containing oxygen atoms such as alcohols, aldehydes, ketones, etc.) are produced as by-products.

One of the main objectives of the XTL process is to obtain a liquid fuel, so it is a recent trend to produce linear hydrocarbons, especially C ₅₊ linear hydrocarbons, which are an indicator of productivity, with high selectivity by optimizing the reaction catalyst, ratio of syngas, temperature and pressure. It is a trend.

Fischer-Tropsch cobalt catalyst shows activity in the reduced metal state, so it must be sufficiently reduced before the reaction in any way. In the laboratory scale for catalyst development, the in-situ reduction method is mainly used to raise the temperature to the reduction temperature while flowing the reducing gas while the reactor is filled with the calcined catalyst, but the reduction temperature is usually much higher than the reaction temperature, and a separate reducing gas is injected. Because equipment is required, other methods are sometimes used in commercial reactors. In most commercial processes, a separate catalytic reduction device is provided and reduction is performed by supplying a reducing gas (a mixture of hydrogen and an inert gas with a hydrogen ratio of about 5 to 10%).

As a material showing activity in the Fischer-Tropsch synthesis reaction, VIII group metal materials such as iron (Fe), cobalt (Co), nickel (Ni), and ruthenium (Ru) have been reported. Among them, iron (Fe)-based catalysts are particularly suitable for Fischer-Tropsch synthesis reactions linked to indirect coal liquefaction because of their low manufacturing cost, excellent performance, and activity in water-gas shift reactions (WGS, Water-Gas Shift). It shows an advantage. Iron-based catalysts have low methane selectivity at high temperatures, high olefin selectivity among hydrocarbons, and products produce many olefins in addition to liquid fuels.

In the Fe-based catalyst for the FT synthesis reaction, the Fe-based carbide, such as _{ε'-F 2.2 C, χ-} Fe 2 .5 C is known as an active species. However, since the Fe-based catalyst immediately after preparation consists mostly of Fe-based oxides, the activation pretreatment must be performed using a reducing gas including CO before performing the FT synthesis reaction.

In general, iron-based oxide catalysts can be reduced well in a reducing gas consisting only of CO irrespective of pressure, but are not well reduced in a high-pressure syngas atmosphere such as the Fischer-Tropsch synthesis reaction conditions.

In addition, in the Fe-based catalyst, there is a high possibility of re-oxidation and de-carburization of the active species of Fe-based carbides by H ₂ O and CO ₂ generated as by-products during the FT synthesis reaction. The development of reducing and highly carburizing catalysts is very important.

On the other hand, the development of the FT synthesis process was mainly based on the advancement of the reactor along with the catalyst based on the long development experience in Sasol, and from the initial fixed bed reactor (Arge) to a circulating fluidized bed reactor (Synthol) and a fixed fluidized bed reactor (Advanced Synthol) and slurry reactor (Slurry) have gradually progressed in the form of FT reactor (Fig. 1), and in recent Sasol, using a slurry reactor can reduce plant cost by 25-30% compared to the existing multi-tubular fixed bed reactor. I have reported. Since reaction characteristics and product distribution vary depending on the reactor type, it must be appropriately selected according to the target end product.

Fixed bed reactors and slurry reactors are known to be used in low temperature FT (LTFT) processes that mainly produce intermediate oil and wax, and circulating fluidized bed reactors and fixed fluidized bed reactors are known to be used in high temperature FT (HTFT) processes that mainly produce naphtha and olefins. The selectivity of the product in each process is as shown in Table 1 below.

In the low-temperature FT process, more than 60% of hydrocarbons with a higher boiling point than diesel are produced, so diesel is additionally manufactured through a subsequent process such as hydrocracking, and the wax component is converted into a high-quality lubricant base oil through a dewaxing process. Switch to use.

Existing FT process development has focused on the development of a technology that can increase the size of the plant and the unit reactor for this in order to reduce the investment cost. However, in consideration of the local situation where it is difficult to supply such a large-scale plant, development of a customized plant is also required. In particular, small-scale and movable plants have the advantage of having a much more favorable location condition and reducing restrictions on the selection of target gas fields. However, so far, such small CTL plant technology has not been developed at the commercial level.

According to the present invention, (a) Fe:Cu:K:SiO ₂ = 100: 1 to 10: 1 to 20: an iron catalyst for Fischer-Tropsch synthesis having a weight ratio of 10 to 50 or (b) 100% of the number of iron atoms On the other hand, when an iron-based catalyst for Fischer-Tropsch synthesis with 10 to 100% of iron atoms in the phase fraction of ferrihydrite and 0 to 90% of iron atoms in the phase fraction of hematite is used in a slurry bubble column reactor, wax is produced as the main product. It was found that it can be operated in low temperature FT mode at 250°C to 280°C in order to produce fuel oil and high heat emission gas at 290°C to 350°C. The slurry bubble column reactor is in FT mode of 2 or more, depending on the demand of the region where the reactor will be installed. It is designed to be selectively operated, and (ii) unreacted gas discharged from the slurry bubble column reactor and generated C1~C4 gas discharged from the slurry bubble column reactor in connection with the slurry bubble column reactor selectively operable in two or more FT modes through the combustor or It is intended to provide a polygeneration synthetic fuel manufacturing apparatus that simultaneously produces steam or electricity through a generator made of a turbine or gas engine.

The first aspect of the present invention

(i) a slurry bubble column reactor operating in two or more modes,

(a) Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: 10 to 50 iron-based catalyst for Fischer-Tropsch synthesis having a weight ratio of or (b) ferrihydrite phase with respect to 100% of iron atoms An iron-based catalyst for Fischer-Tropsch synthesis having 10 to 100% iron atoms in the fraction and 0 to 90% iron atoms in the phase fraction of hematite is used,

It is operated in low temperature FT mode at 250℃ ~ 280℃ to produce synthetic fuel mainly containing C ₁₉₊ as the first amount of wax.

It is operated in high temperature FT mode at 290℃ ~ 350℃ to produce synthetic fuel containing C ₁₉₊ in a second amount of wax less than the first amount of wax, while the emission of off-gas is greater than in low temperature FT mode. Phosphorus, slurry bubble column reactor; And

(ii) In connection with the slurry bubble column reactor, from the unreacted gas discharged from the slurry bubble column reactor and the generated C1 to C4 gas, a combustor that produces heat or steam or a turbine or gas engine that produces electricity is provided. generator

A polygeneration capable of providing synthetic fuel and other energy sources at the same time It provides a synthetic fuel manufacturing apparatus.

A second aspect of the present invention provides a method for producing a liquid hydrocarbon from syngas through a low-temperature FT mode and a high-temperature FT mode in a slurry bubble column reactor of the hybrid synthetic fuel production apparatus according to the first aspect.

In the third aspect of the present invention, in the composite synthetic fuel manufacturing apparatus of the first aspect, the slurry bubble column reactor is operated in a low-temperature FT mode and a high-temperature FT mode to produce a liquid hydrocarbon from the synthesis gas, and discharge from the slurry bubble column reactor. To produce heat, steam, and/or electricity from unreacted gases and generated C1-C4 gases. Provides a way.

Hereinafter, the present invention will be described in detail.

In the indirect coal liquefaction system, in general, coal is used as the main raw material through the gasification process -> refining process -> liquefaction process to finally produce a wax-type synthetic fuel. Here, the gasification process is a process of converting coal into a synthetic gas mainly containing hydrogen and carbon monoxide. In addition, the refining process is a process of collecting and desulfurizing the synthetic gas produced through the gasification process, and removing various impurities. Lastly, the liquefaction process is a process of converting the purified synthetic gas into liquid synthetic fuel by reacting it over a catalyst.

As a Fischer-Tropsch synthesis reactor, the slurry bubble column reactor (SBCR reactor) has higher heat transfer efficiency than the fixed bed reactor, and there is no pressure drop and temperature gradient along the axial direction of the reactor (i.e., no hot spot), even during operation. The catalyst can be added/discharged and regenerated, and it is possible to design a larger FT reactor than a fixed bed reactor.

When syngas (CO + H ₂ ) is supplied through the syngas distributor in the slurry bubble column reactor, the syngas becomes bubbles and is uniformly dispersed to form a catalyst for Fischer-Tropsch (FT) synthesis contained in the slurry. In contact with, it produces synthetic fuels such as hydrocarbons, olefins and oxygenates. At this time, liquid hydrocarbons and catalyst particles in the reactor are mixed to obtain a slurry. When the inner liquid level of the reactor rises, the catalyst particles are filtered through a filtration device installed inside and then discharged, and the discharged filtrate is sent to a subsequent process such as upgrading to a high boiling point hydrocarbon such as wax. It is made of fuel. Unreacted gas (CO + H ₂ ), gas generated during the reaction (CO ₂ , C ₂ ~ C ₄ , H ₂ O, etc.), and vaporous hydrocarbons are discharged to the top of the reactor, and gasoline and Low-boiling hydrocarbons such as diesel are recovered. (Figure 2)

The present invention is (a) Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: 10 to 50 with respect to the Fischer-Tropsch synthesis iron catalyst having a weight ratio or (b) 100% of the number of iron atoms In the case of the iron-based catalyst for Fischer-Tropsch synthesis, which has 10 to 100% iron atoms in the phase fraction of ferrihydrite and 0 to 90% iron atoms in the hematite phase fraction, in a slurry bubble column reactor (SBCR reactor) at low and high temperatures. It has been found that it can exert high catalytic activity, and is based on this. The present invention operates the SBCR reactor using the above catalyst in two or more FT modes, operating in low temperature FT mode at 250°C to 280°C to maximize wax production, and at 290°C to 350°C for the purpose of producing diesel or gasoline. It is characterized by operating in high temperature FT mode. Accordingly, the present invention can produce and use various hydrocarbon products by changing the operation mode in the same slurry bubble column reactor.

In addition, if the Fischer-Tropsch synthesis is performed in a slurry bubble column reactor using the iron-based catalyst in a low-temperature FT mode and a high-temperature FT mode in accordance with the present invention, the amount of C ₁₉₊ wax generated during high-temperature FT mode operation is low-temperature FT. Less than the amount of C ₁₉₊ wax generated during mode operation, instead, gas products such as methane are 10 wt% or more (based on the total FT product mixture), preferably 15 wt% or more, more preferably 18 wt% or more, even more preferably It is produced in more than 20wt% and can be discharged as off-gas from the slurry bubble column reactor. Therefore, when performing Fischer-Tropsch synthesis in high-temperature FT mode at 290°C to 350°C, the present invention utilizes the energy of the exhaust gas of high calorific value discharged from the slurry bubble column reactor to be used as a heat source, a power source, and/or a power source. Is another characteristic of

The exhaust gas discharged from the slurry bubble column reactor operating in the high-temperature FT mode at 290℃ ~ 350℃ contains not only methane gas but also high calorific gas containing C2~4, so it is burned and used as a heat source or directly gas turbine Or a gas engine to generate power and/or electricity.

Therefore, according to the present invention, using a slurry bubble column reactor operating in two or more modes Synthetic fuel manufacturing equipment can produce various hydrocarbon products through FT mode conversion, in conjunction with coal gasifiers using low-grade coal with ash content of 40 wt% or more, or 50 wt% or more, as well as conversion to high-temperature FT mode. Through the coal mine area where electricity and oil supply infrastructure is insignificant. Fuel for automobiles from coal and Heat, power and/or power using high-calorific gas is determined according to the demand of the region where the reactor will be installed. It can be provided in various ways (Fig. 3).

The synthetic fuel manufacturing apparatus according to the present invention is a polygeneration capable of simultaneously providing synthetic fuel and other energy sources. As a synthetic fuel manufacturing device,

(i) a slurry bubble column reactor operating in two or more modes,

(a) Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: 10 to 50 iron-based catalyst for Fischer-Tropsch synthesis having a weight ratio of or (b) ferrihydrite phase with respect to 100% of iron atoms An iron-based catalyst for Fischer-Tropsch synthesis having 10 to 100% iron atoms in the fraction and 0 to 90% iron atoms in the phase fraction of hematite is used,

It is operated in low temperature FT mode at 250℃ ~ 280℃ to produce synthetic fuel mainly containing C ₁₉₊ as the first amount of wax.

It is operated in high temperature FT mode at 290℃ ~ 350℃ to produce synthetic fuel containing C ₁₉₊ in a second amount of wax less than the first amount of wax, while the emission of off-gas is greater than in low temperature FT mode. Phosphorus, slurry bubble column reactor; And

(ii) In connection with the slurry bubble column reactor, from the unreacted gas discharged from the slurry bubble column reactor and the generated C1 to C4 gas, a combustor that produces heat or steam or a turbine or gas engine that produces electricity is provided. Equipped with a generator.

A heat exchanger and/or power generator may be used instead of or in parallel with the combustor and/or generator, which also falls within the scope of the present invention.

The iron-based catalyst used in the Fischer-Tropsch synthesis reaction of the present invention has 10 to 100% of iron atoms in the phase fraction of ferrihydrite with respect to 100% of the number of iron atoms, and 0 to 90% of the phase fraction of hematite, for example Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: It may have a weight ratio of 10 to 50.

At this time, ferrihydrite is an iron oxy-hydroxide of partially hydrated iron and may mean an iron-based compound represented by the general formula of FeOOH·nH ₂ O (0<n<1). In other words, ferrihydrite may collectively refer to partially hydrated iron hydroxide, in which water molecules are less than 1 mole per mole of iron atoms. Specifically, ferrihydrite is Fe ₅ O ₇ (OH) 4H ₂ O, (Fe ^{3 +} ) ₂ O ₃ 0.5H ₂ O, Fe ₉ O ₂ (OH) ₂₃ , 5Fe ₂ 0 ₃ 9H ₂ 0, Fe ₅ HO ₈ ·4H ₂ 0, and Fe ₂ 0 ₃ ·2FeOOH · 2.6H ₂ 0, etc., and these chemical formulas are essentially equivalent and the general formula FeOOH·nH ₂ O (0< It can be converted to n<1).

Hematite is one of iron oxides and may mean an iron-based compound represented by the general formula of α-Fe ₂ O ₃ . Hematite can be crystallized in a rhombohedral lattice system, and goethite (general formula: α-FeOOH), one of iron oxy-hydroxides, is oxidized and converted to hematite. Can be.

The reaction pressure upon activation of the iron-based catalyst may be the same as the reaction pressure for Fischer-Tropsch synthesis. Preferably, the reaction pressure may be 1 to 3 MPa. In addition, the reaction temperature and space velocity in addition to the reaction pressure may be the same during activation and during Fischer-Tropsch synthesis. Preferably, it may be carried out at a reaction temperature of 240 to 300° C. and a space velocity of 2 to 20 NL/g _(cat) /h.

The iron-based catalyst of a specific phase fraction used in the present invention can be activated by the syngas as a reactant even at high pressure (1.0 to 3.0 MPa) such as the Fischer-Tropsch synthesis reaction conditions, so pure CO or low pressure (normal pressure to 0.5 MPa) Fischer-Tropsch synthesis reaction by activating the iron-based catalyst for Fischer-Tropsch synthesis under Fischer-Tropsch synthesis reaction conditions without a separate catalyst activation process using the synthesis gas of Can be done. Therefore, at the beginning of the reaction Separate device for separate catalyst activation Without it, a new catalyst can be injected into the slurry bubble column reactor and the Fischer-Tropsch synthesis reaction can be started. In addition, during the Fischer-Tropsch synthesis reaction (somewhere along the line), the catalyst is running to compensate for the loss of catalyst without a separate device for catalyst activation. It can be injected directly into the reactor. In addition, when the catalyst is replaced due to deactivation of the catalyst, the catalyst is discharged without a separate device for activating the catalyst, while the unused or regenerated catalyst is operated directly in the reactor. Fischer-Tropsch synthesis reaction can be carried out continuously by injection.

In the Fischer-Tropsch synthesis reaction of the present invention, the synthesis gas may be selected from a mixture of carbon monoxide and hydrogen, or carbon monoxide and hydrogen as impurities, inert gas, methane, or carbon dioxide.

Synthetic gas may be H ₂ /CO adjusted to be 0.7 to 2.5. Preferably, the synthesis gas may be used that additionally contains 0.1 to 20% of CO ₂ based on the volume of the total synthesis gas.

The synthesis gas is a mixture of carbon monoxide and hydrogen in a ratio of 1:1 to 2, and most preferably carbon monoxide and hydrogen in a ratio of 1:1 is good in terms of product yield. Methane or other inert gases may be included. The ratio of carbon monoxide and hydrogen means a volume ratio. In addition, throughout the present invention, the ratio of the synthesis gas in the Fischer-Tropsch reaction means a volume ratio.

The syngas may be supplied within a space velocity of 2.5 to 24.0 NL/g _cat /hr. Even if it is less than the space velocity, there is no great difficulty in the progress of the reaction, but there is a problem in that the productivity per unit time of hydrocarbon is low, and when syngas that is greater than the space velocity is injected, the conversion rate of carbon monoxide may decrease.

The composite synthetic fuel production apparatus of the present invention may operate the slurry bubble column reactor in a low temperature FT mode for the purpose of maximizing wax production, and operate the slurry bubble column reactor in a high temperature FT mode for the purpose of producing diesel or gasoline.

In addition, the composite synthetic fuel production apparatus of the present invention is operated in conjunction with the slurry bubble column reactor, and may further include a reactor for cracking wax.

In addition, the hybrid synthetic fuel manufacturing apparatus of the present invention can provide fuel for automobiles from coal, and high calorific emission gas containing methane and C2-4 to supply heat, power and/or power.

According to the present invention, an iron-based catalyst for Fischer-Tropsch synthesis having 10 to 100% of iron atoms in the phase fraction of ferrihydrite with respect to 100% of iron atoms and 0 to 90% of iron atoms in the phase fraction of hematite was used as a slurry bubble column reactor. If used, it can be operated interchangeably in low temperature FT mode at 250℃ ~ 280℃ and high temperature FT mode at 290℃ ~ 350℃.

As described above, the synthetic fuel production apparatus using a slurry bubble column reactor operating in two or more modes according to the present invention can produce various hydrocarbon products through FT mode conversion in connection with a coal gasifier, as well as conversion to high temperature FT mode. Through this, it is possible to provide heat, power, and/or power using automobile fuel and high calorific gas from coal to coal mine areas where the electricity and oil supply infrastructure is insignificant.

The exhaust gas discharged from the slurry bubble column reactor operating in the high-temperature FT mode at 290°C to 350°C is a high calorific gas containing not only methane gas but also C2~4, so it is burned to form steam or directly gas turbine or gas. Engines can be turned to generate power and/or electricity.

1 shows the types of FT reactor types used for high temperature FT and low temperature FT.
2 is a schematic conceptual diagram of a system using a slurry bubble column reactor for producing synthetic fuel.
3 is a diagram using a slurry bubble column reactor operating in two or more FT modes according to an embodiment of the present invention. The hybrid synthetic fuel manufacturing device is linked to the coal gasifier, and the conversion to the high-temperature FT mode allows the It is an overall process diagram showing the process of providing power using high calorific emission gas.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

[Slurry according to the present invention Bubble tower Reactor Synthetic Fuel Manufacturing]

As shown in FIG. 2, an FT reactor was designed in the form of a slurry bubble column reactor (SBCR), and a coal gasifier was connected thereto to construct a system for producing synthetic fuel. At this time, the slurry bubble column reactor used an iron-based catalyst having a weight ratio of Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: 10 to 50.

Example 1 to 3: high temperature FT Mode Synthetic fuel production by driving

In the synthesis of FT, the reaction temperature was set to 290°C, 310°C, and 325°C, respectively, and synthetic fuels were prepared under the conditions shown in Tables 2 to 4 below.

The results of analyzing the hydrocarbon composition of the synthetic fuels prepared in Examples 1 to 3 are shown in Table 5 below.

According to Table 5, when the Fischer Tropsch synthesis reaction was performed under the conditions of 290°C, 310°C, and 325°C higher than the operating conditions previously used in the SBCR reactor according to the present invention, prepared according to Examples 1 to 3 It is confirmed that the proportion of C _5-11 hydrocarbons is 29% by weight or more, the proportion of C _12-18 hydrocarbons is 8 to 15% by weight, and the proportion of C ₁₉₊ hydrocarbons is 20% by weight or less based on the total product weight in the synthetic fuel. As a result, it can be seen that the production of diesel and gasoline among all synthetic fuels increased and the production of wax decreased. In addition, instead of the reduced C ₁₉₊ hydrocarbon, methane (based on the total FT product mixture) is produced in an amount of 15 wt% or more, and can be discharged as off-gas from the slurry bubble column reactor. Therefore, when the Fischer-Tropsch synthesis is performed in the high-temperature FT mode, the energy of the exhaust gas containing C _1-4 containing high calorific value discharged from the slurry bubble column reactor can be utilized as a heat source, a power source, and/or a power source.

Example 4: Production of synthetic fuel by operating in low temperature FT mode

In the low-temperature FT mode, the reaction temperature was set to 260°C, and a synthetic fuel was prepared under the conditions shown in Table 6 below.

The hydrocarbon composition of the synthetic fuel prepared in Example 4 was analyzed. The results are shown in Table 7 below.

According to Table 7 above, when the Fischer Tropsch synthesis reaction was performed under 260°C as the operating conditions of the SBCR reactor in the low-temperature FT mode, C _5-11 hydrocarbons based on the total product weight of the synthetic fuel prepared according to Example 4 It can be seen that the ratio of is less than 25% by weight, the ratio of C _12-18 hydrocarbons is 15% by weight, and the ratio of C ₁₉₊ hydrocarbons is more than 30% by weight, and thus the ratio of gas, diesel and gasoline among the total synthetic fuels It can be seen that production decreased and wax production increased.

Claims (12)

(i) a slurry bubble column reactor operating in two or more modes,
(a) Fe: Cu: K: SiO ₂ = 100: 1 to 10: 1 to 20: 10 to 50 iron-based catalyst for Fischer-Tropsch synthesis having a weight ratio of or (b) ferrihydrite phase with respect to 100% of iron atoms An iron-based catalyst for Fischer-Tropsch synthesis having 10 to 100% iron atoms in the fraction and 0 to 90% iron atoms in the phase fraction of hematite is used,
By operating in low-temperature FT mode at 250℃ ~ 280℃, producing synthetic fuel mainly containing C ₁₉₊ in the first wax amount from synthesis gas,
By operating in high temperature FT mode above 300℃ and below 350℃, producing synthetic fuel containing C ₁₉₊ in a second wax amount smaller than the first wax amount from the synthesis gas, and off-gas compared to the low-temperature FT mode The discharge of the large, slurry bubble column reactor; And
(ii) In connection with the slurry bubble column reactor, from the unreacted gas discharged from the slurry bubble column reactor and the generated C1 to C4 gas, a combustor that produces heat or steam or a turbine or gas engine that produces electricity is provided. generator
A polygeneration capable of providing synthetic fuel and other energy sources at the same time Synthetic fuel manufacturing equipment.
The method of claim 1, wherein the slurry bubble column reactor is operated in a low temperature FT mode for the purpose of maximizing wax production,
Synthetic fuel manufacturing apparatus characterized by operating a slurry bubble column reactor in high temperature FT mode for the purpose of producing diesel or gasoline.
The synthetic fuel manufacturing apparatus according to claim 1, characterized in that it provides fuel for automobiles from coal, and methane and C2-4 containing high calorific emission gas to supply heat, power and/or power.
The synthetic fuel production apparatus according to claim 1, which is operated in conjunction with the slurry bubble column reactor and further comprises a reactor for cracking wax.
The method of claim 1, wherein at the beginning of the reaction Separate device for separate catalyst activation Injecting the new Fischer-Tropsch synthesis iron-based catalyst as specified in claim 1 into the slurry bubble column reactor without starting the Fischer-Tropsch synthesis reaction. Synthetic fuel manufacturing device characterized by that.
The catalyst according to claim 1, wherein the catalyst is operated to compensate for the loss of the catalyst without a separate device for catalyst activation somewhere along the line. Synthetic fuel production device characterized by direct injection into the reactor.
The method of claim 1, wherein when the catalyst is replaced due to deactivation of the catalyst, the unused or regenerated catalyst is directly transferred to the reactor while discharging the catalyst without a separate device for activating the catalyst. Synthetic fuel production apparatus characterized by continuously performing the Fischer-Tropsch synthesis reaction by injection.
The apparatus of claim 1, wherein the ferrihydrite is FeOOH·nH ₂ O (0<n<1).
The synthetic fuel manufacturing apparatus according to claim 1, wherein the synthesis gas is adjusted so that H ₂ /CO is 0.7 to 2.5.
In the slurry bubble column reactor of the composite synthetic fuel production apparatus according to any one of claims 1 to 9, the synthesis gas through a low temperature FT mode of 250°C to 280°C and a high temperature FT mode of more than 300°C and 350°C or less A method of producing a liquid hydrocarbon from
The method of claim 10, wherein the slurry bubble column reactor is operated in a low temperature FT mode to produce wax as a main product,
A method characterized by producing oil for fuel by operating a slurry bubble column reactor in high temperature FT mode.
In the composite synthetic fuel manufacturing apparatus according to any one of claims 1 to 9,
The slurry bubble column reactor was operated in a low temperature FT mode of 250°C to 280°C and a high temperature FT mode of more than 300°C and not more than 350°C to produce a liquid hydrocarbon from syngas,
To produce heat, steam, and/or electricity from the unreacted gas discharged from the slurry bubble column reactor and the generated C1-C4 gas Way.

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