KR101935529B1 - System for producing naphtha - Google Patents

Abstract

The present invention relates to a bio-ethanol feeder comprising: a supply part for supplying bio-ethanol; A first reactor for producing a liquid product comprising a C ₄ -C ₁₂ oxygen-containing compound under a reaction condition for converting the bioethanol into a supercritical state under a first catalyst supported on a carbon support by a metal active component; And a second reactor for deoxidizing the liquid material under a second catalyst comprising zeolite to separate into a hydrocarbon layer containing naphtha and a water layer, wherein the naphtha production system comprises reacting ethanol directly with a solid acid catalyst It is possible to provide a naphtha production system that improves the yield of produced naphtha by enabling two sequential processes.

Description

A system for producing naphtha {System for producing naphtha}

The present invention relates to a system for producing naphtha, which is a main raw material for gasoline, using ethanol derived from biomass.

Here, background art relating to the present disclosure is provided, and they are not necessarily meant to be known arts.

Recently, the production of bioethanol by the bioconversion process of biomass such as corn and cereal is continuously increasing, and as the price of raw material of bioethanol is rising, research on high value added bioethanol is continuing.

Currently, there is a policy to add a small amount of ethanol (5 ~ 10%) to gasoline, which is a fuel for transportation. However, ultimately, a method of using ethanol itself as fuel should be sought. Therefore, by producing naphtha of high purity from ethanol, And naphtha obtained from ethanol can be converted into high value-added petrochemical products in addition to transportation fuel.

Studies on the catalytic reaction for the production of hydrocarbons from ethanol have been carried out steadily, mainly using zeolite catalysts with strong acid sites (HZSM-5). However, the zeolite catalyst used in the process of directly producing naphtha from ethanol accelerates not only the production of hydrocarbon but also the coking phenomenon due to high reactivity, so that the deactivation of the catalyst is rapidly proceeded. .

1. US registered patent US 8017818 (September 23, 2011) 2. Korea registered patent KR0891001 (Mar. 23, 2009) 3. Japanese Unexamined Patent Publication JP2001348204 (Dec. 18, 2001)

The present invention provides a system for improving the yield of naphtha produced through two sequential process reactors without reacting ethanol directly with a solid acid catalyst.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a naphtha production system using bio-ethanol derived bio-ethanol, comprising: a supply unit for supplying bio-ethanol; A first reactor for producing a liquid product comprising a C ₄ -C ₁₂ oxygen-containing compound under a reaction condition for converting the bioethanol into a supercritical state under a first catalyst supported on a carbon support by a metal active component; And a second reactor for deoxidizing the liquid material under a second catalyst comprising zeolite to separate into a hydrocarbon layer containing naphtha and a water layer.

Further, the first catalyst is characterized in that a metal containing magnesium (Mg), nickel (Ni) and molybdenum (Mo) is supported on the carbon support as the active component.

The first reactor is a high-pressure reactor, and includes a heating device and a cooling device. The first reactor is charged with the bioethanol supplied from the supply unit to the first reactor, and the first reactor is controlled to a high pressure state The heating device is stopped when the temperature of the first reactor reaches the reaction temperature, and quenching is performed through the cooling device.

The naphtha production system may further include a pressure regulator, wherein the first reactor is controlled to a high pressure state to exhibit an initial pressure of 25 to 35 bar.

The second reactor may further include a heating device, wherein the liquid containing the oxygen-containing compound supplied from the first reactor and the second catalyst are introduced into the second reactor, To a reaction temperature and then maintained for a certain period of time.

The second catalyst is characterized in that the zeolite catalyst or zeolite contains a catalyst on which a metal containing nickel is supported.

Also it characterized in that the second reactor, the reactor for separating the layer containing a hydrocarbon layer and a water-containing aromatic hydrocarbon group wherein the C ~ ₇ using a zeolite catalyst as the second catalyst C _11.

Also, in the second reactor, a catalyst containing a nickel-containing metal is supported on the zeolite as the second catalyst, and a hydrocarbon layer containing C ₁₃ or higher alkane and alkene and a layer containing moisture are separated And the like.

Further, the naphtha production system may further include a filter for separating the used first catalyst from the liquid containing the oxygen-containing compound produced in the first reactor so that the separated first catalyst is washed, dried and reused .

Further, the naphtha production system may further include a filter for separating the second catalyst used from the two-phase liquid phase containing the hydrocarbon layer containing naphtha produced in the second reactor and the water layer, And dried and then reused.

In the present invention, the reaction proceeds on the supercritical ethanol, and the first reactor in which the condensation reaction of ethanol occurs and the second reactor in which the deoxidization reaction occurs are sequentially formed, so that the hydrocarbon of the naphtha range can be obtained in high purity. Thereby controlling the structure of the hydrocarbons produced.

The present invention also provides the effect that a further complicated separation process is not necessary since the hydrocarbon layer and the water layer are naturally separated by the difference in density of the final product.

FIG. 1 shows a process diagram of a naphtha manufacturing system according to an embodiment of the present invention.
FIG. 2 shows a method for producing naphtha from ethanol according to an embodiment of the present invention.
FIG. 3 shows the result of analyzing the composition of the gaseous product produced after the first reaction.
FIG. 4 shows the result of analyzing the composition of the liquid product produced after the first reaction.
FIG. 5 shows the results of analyzing the composition of the gaseous products according to the type of the second catalyst.
FIG. 6 shows an image of the shape of the solid residue and the catalyst after the reaction.
Fig. 7 shows the main components of the liquid product obtained when the catalyst was not used.
Fig. 8 shows the distribution of the major components of the liquid product and the carbon number distribution of the heavy hydrocarbons obtained when the alumina catalyst was used.
FIG. 9 shows the carbon number distribution of the upper layer (hydrocarbon) among the liquid products obtained when the HZSM-5 catalyst was used and the main components of the lower layer portion.
FIG. 10 shows the carbon number distribution of the upper layer (hydrocarbon) among the liquid products obtained when the Ni / HZSM-5 catalyst was used and the main components of the lower layer portion.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

A system for producing naphtha from ethanol according to an embodiment of the present invention includes a supply unit for supplying bioethanol as shown in FIG. 1, a supply unit for supplying the bioactive ethanol to the carbon support in a supercritical state, A first reactor which condenses under a first catalyst to produce a liquid product comprising a C ₄ -C ₁₂ oxygenated compound and a second reactor which deoxidizes the liquid product under a second catalyst comprising zeolite to form a hydrocarbon layer comprising naphtha And a second reactor for separating into a water layer.

The first reactor is supplied with bioethanol through the supply unit, and the bioethanol is made into a supercritical state in the presence of the first catalyst and condensation reaction is performed to produce a liquid material containing a C ₄ -C ₁₂ oxygen-oxygen compound, The gaseous products produced in the reactor are separated and the resulting liquid product is fed to a second reactor.

The first reactor in the second condensation reaction takes place in the C ₂ ethanol using a first catalytic reaction in the supercritical condition with Oxygenated compounds of C ₄ -C _12.

As the first catalyst, a catalyst in which a metal containing magnesium (Mg), nickel (Ni), and molybdenum (Mo) is supported on a carbon support as an active material may be used.

The carbon support may be a carbon support capable of supporting a metal including magnesium-nickel-molybdenum, and may be activated charcoal (AC), mesoporous carbon, graphite, carbon nanotube carbon nanotube, graphene, fullerene, or a mixture thereof, preferably activated charcoal.

In addition, the carbon support easily supports magnesium-nickel-molybdenum and can have a wide reaction surface area, and may be a carbon support including a plurality of pores having a size of 10-100 Å.

The first catalyst preferably comprises 15 to 25% by weight of nickel (Ni), 5 to 20% by weight of molybdenum (Mo) and 1 to 5% by weight of magnesium (Mg), based on the total weight of the carbon support And the metal may be supported on the carbon support in the form of a metal salt. More preferably, it may comprise 18 to 23% by weight of nickel (Ni), 8 to 15% by weight of molybdenum (Mo) and 1 to 3% by weight of magnesium (Mg) based on the total weight of the carbon support have.

The first catalyst may be prepared through a carrying step in which the precursor solution of the active material is successively carried on a carbon support, and an activation step in which the precursor solution is activated by drying, calcination and reduction.

More specifically, the supporting step includes the steps of: (i) dissolving a hydrated salt containing an active material as a precursor of the active material in distilled water to prepare a metal precursor solution; (Ii) impregnating the carbon support with a nickel precursor solution and subsequently impregnating the solution with a molybdenum precursor solution and a magnesium precursor solution to produce a catalyst compound wherein the active material is supported on the carbon support in the form of a metal salt, (Iii) drying at 90 to 120 DEG C and atmospheric pressure for 12 hours or more; (Iv) calcining the dried catalyst compound under a nitrogen atmosphere at 450 to 550 DEG C for 2 to 4 hours; And (v) reducing the calcined catalyst compound in a hydrogen atmosphere at 350 to 450 DEG C for 8 hours or more.

Also, the first reactor is operated so that the bioethanol is supercritical to perform a condensation reaction of bioethanol. The first reactor may be a high pressure batch reactor capable of being hermetically sealed, and a heating device and a cooling device . The first reactor is charged with bioethanol and a first catalyst (S11), the first reactor is adjusted to a high pressure state and heated with stirring (S12), and when the first reactor temperature reaches the reaction temperature, the heating is stopped and quenching S13).

The adding step S11 is a step of injecting ethanol and a first catalyst into a first reactor, wherein 1 to 5 parts by weight of a first catalyst is contained in 50 parts by weight of ethanol, And a step of removing air inside the first reactor using nitrogen supplied from the regulator.

The heating step (S12) is a step of reacting bioethanol in the first reactor under a supercritical condition, wherein the first reactor is heated to a high pressure by using a heating device while stirring, and more specifically, Injecting nitrogen from the pressure regulator so that the first reactor exhibits an initial pressure of 25 to 35 bar and heating the first reactor while stirring at a rate of 450 to 550 rpm.

At the temperature and pressure conditions of the heating step (S12), ethanol is supercritical, and the supercritical phase has physical properties different from those of liquid phase and gas phase. Particularly, in the supercritical system, the condensation reaction of ethanol can be more effectively performed because a single-stage reaction is possible and a mass transfer rate is high.

The quenching step S13 is a step of stopping the heating when the temperature of the first reactor reaches the reaction temperature and quenching by using the cooling device. More specifically, when the internal temperature of the first reactor reaches the reaction temperature of 250 to 400 DEG C Immediately stopping the heating of the first reactor and injecting cooling water to lower the temperature to room temperature.

From the ethanol of C ₂ through the condensation reaction in the first reactor, a C ₄ -C ₁₂ oxygen-oxygen compound can be obtained in a yield of 20 to 40% by weight.

Also, the first catalyst used in the first reactor may be separated from the liquid phase using a pressure reducing filter, and the separated first catalyst may be reused in the first reactor after washing and drying.

In the second reactor, the oxygen of the oxygen-containing compound contained in the liquid material obtained through the gas-liquid separation from the first reactor is removed using the second catalyst, and a reaction is performed in which the hydrocarbon layer containing naphtha and the water layer are separated. It is possible to control the structure of hydrocarbons generated according to the kind of the second catalyst to be fed into the second reactor.

A zeolite catalyst is used as the second catalyst. The second catalyst is a structure in which silicon (Si) and aluminum (Al) are mixed with oxygen atoms at a ratio of at least 10 (Si / Al> 10). In the present invention, the molar ratio (Si / 40 < / RTI > By using the second catalyst, the dehydration reaction can be accelerated to increase the ethylene and moisture distribution in the reaction product. Using a solid acid catalyst comprising HZSM-5 as the second catalyst, a C ₇ -C ₁₁ aromatic hydrocarbon can be obtained. When a catalyst containing HZSM-5 as a support and a metal containing nickel (Ni) as an active material is used as the second catalyst, the ring-opening reaction of aromatic hydrocarbons is induced to produce an alkane of C ₁₃ or higher and an alkene ) Can be obtained, and the kind of hydrocarbons generated by controlling the content of nickel (Ni) in the catalyst can be controlled.

The second reactor may be a reactor in which a deoxygenation reaction is performed to remove oxygen from the C ₄ -C ₁₂ oxygen-containing compound contained in the liquid material supplied from the first reactor, and the second reactor may be a closed type batch reactor , A heating device and a cooling device to enable heating and cooling. In the second reactor, a liquid product containing an oxygen-containing compound separated from the product produced in the first reactor is introduced together with the second catalyst (S21), the second reactor is elevated to the reaction temperature, S22) to obtain a two-phase liquid product separated into a hydrocarbon layer containing naphtha and a water layer.

The injecting step (S21) includes a step of sealing 30 to 50 parts by weight of the liquid material containing the oxygen-containing compound and 1 to 5 parts by weight of the second catalyst in a reactor.

The heating step S22 includes a step of raising the internal temperature of the second reactor to a desired reaction temperature of 250 to 400 DEG C using a heating device under atmospheric pressure, and then maintaining the internal temperature for a predetermined time (0 to 8 hours).

The deoxidation in the second reactor can provide a two-phase liquid product separated into an upper layer and a lower layer from a liquid product containing an oxygen-containing compound. Since the hydrocarbon layer (upper layer) including the naphtha and the water layer (lower layer) are automatically separated after the second reaction in the second reactor, there is an advantage that the oil and water separation of the final product is very easy.

The second catalyst used in the second reactor may be separated from the liquid product using a pressure reducing filter, and the separated second catalyst may be reused in the second reactor after washing and drying.

Also, in the system for producing naphtha from ethanol according to an embodiment of the present invention, high-purity naphtha can be obtained through the liquid-liquid phase separation of the liquid phase product of the two phases obtained from the second reactor. Among the resulting two-phase liquid products, the upper layer liquid contains a hydrophobic compound (naphtha) having a low specific gravity and a low water content, and the lower layer liquid contains a water-soluble compound having a high specific gravity and a high water content.

The system for producing naphtha from ethanol according to an embodiment of the present invention may further comprise a filter for separating the liquid generated from the first reactor and the first catalyst, And a filter for separating the two-phase liquid product separated into the hydrocarbon layer containing naphtha and the water layer and the second catalyst, preferably a pressure reducing filter.

According to another aspect of the present invention, there is provided a method for producing naphtha from ethanol, comprising the steps of condensing ethanol to produce a liquid product comprising a C ₄ -C ₁₂ oxygen-containing compound, A deoxidation step (S20) of producing a two-phase liquid product containing C ₄ -C ₁₂ hydrocarbons by deoxygenation of the produced oxygen-containing compound under a zeolite catalyst, and a step And a purifying step (S30) of obtaining high purity naphtha through liquid-liquid phase separation.

Examples and Experimental Examples

(1) Production of first catalyst

Activated carbon (Sigma-aldrich) was purchased and used as a carbon support. Ni (20% of the weight of the support), Mo (10% of the weight of the support) and Mg (5% of the weight of the support) were carried on the carbon support in this order. Of _{Ni (NO 3) 2 · 6H} 2 O as a Ni precursor, a Mo precursor _{(NH 4) 6 Mo 7 O} 24 · to 5H ₂ O, was used as the _{Mg (NO 3) 2 · 6H} 2 O to Mg precursor. The precursor was dissolved in a certain amount of distilled water to prepare a precursor solution, which was then uniformly carried on a carbon support. The supported MgNiMo / C catalyst was dried at 105 ℃ and atmospheric pressure for 12 hours and then calcined in nitrogen atmosphere at 500 ℃ for 3 hours.

(2) Conversion of oxygen to oxygen compounds (primary reaction)

50 g of ethanol and 2 g of the first catalyst prepared above were placed in a 100-mL batch reactor (first reactor), and air in the first reactor was removed using nitrogen. After charging the reactor with nitrogen at 30 bar before the reaction, the stirrer was operated at 500 rpm and the first reactor was started to be heated. The instant when the internal temperature of the first reactor was different from the set temperature was set as the reaction start time (0 min). When the set reaction time (0 to 8 hours) has elapsed, the operation of the heating furnace is stopped and cooling water is injected into the cooling pipe inside the first reactor to lower the temperature of the first reactor to room temperature.

When the reaction was completed, the gas product in the first reactor was collected and subjected to quantitative analysis using a gas chromatography apparatus.

Products other than gaseous products were separated from the liquid product using a vacuum filter. The separated first catalyst was reused after washing and drying.

(3) Naphtha conversion of oxygen-containing compounds (secondary reaction)

The separated liquid product was put into a 100 mL reactor (second reactor) together with 1 g of the second catalyst. After the second reactor was closed, the internal temperature of the second reactor was raised to 350 ° C using a heating furnace under atmospheric pressure, and then maintained for 4 hours. The type and reaction conditions of the second catalyst used in the second reaction are shown in Table 1 below.

After the reaction was completed, the gaseous products were collected and analyzed for composition using a gas chromatographic apparatus. The liquid product and the second catalyst were separated using a vacuum filter, and the separated liquid product was separated into two phases. Thus, the upper and lower layers were simply separated.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 The second catalyst unused γ-Al ₂ O ₃ HZSM-5 Ni / HZSM-5 Ethanol (g) 50 50 50 50 Catalyst (g) One One One One Temperature (° C) 350 350 350 350 P (bar) at 350 ° C 152.9 159.7 225.8 306.9 P (bar) at 20 ° C 4.3 10.3 19.4 21.0

(4) Analysis of gaseous and liquid products

The composition of the gaseous and liquid products formed after the first reaction was analyzed. The composition of the gaseous products according to the type of the second catalyst was also analyzed. Mass analysis and moisture content analysis of the two phase liquid product were also performed. Mass spectrometry was performed using GC-MS (Agilent 7890A / 5977A) analytical instrument equipped with HP-5MS column and moisture content was measured with a water content meter (Titroline 7750 KF). The shape of the solid residue and the catalyst after the reaction was also photographed.

FIG. 3 shows the result of analyzing the composition of the gaseous product produced after the first reaction. FIG. 4A shows the result of analyzing the composition of the liquid product produced after the first reaction, and FIG. 4B shows the composition of the alcohol in the liquid product formed after the first reaction.

FIG. 5 shows the results of analyzing the composition of the gaseous products according to the type of the second catalyst. The results of mass analysis and moisture content analysis of the liquid product according to the type of the second catalyst are shown in Table 2 below. FIG. 6 shows the shape of the solid residue (when the second catalyst is not used) One image.

The second catalyst unused γ-Al ₂ O ₃ HZSM-5 Ni / HZSM-5 Liquid product-upper phase (g) 46.0 24.8 11.9 14.4 Liquid product-lower phase (g) 15.9 19.8 Water content-upper phase (wt%) 1.6 18.4 0.1 0.1 Water content-lower phase (wt%) 68.3 62.3

As shown in FIG. 5, Table 2 and FIG. 6, in the case of non-catalytic reaction (Blank), most of the ethanol remained unconverted, and hydrogen was generated from ethanol to show a very high distribution of hydrogen in the gaseous products have. In the case of alumina catalyst, about 50% of the mass of the reactant is obtained as a product, which is presumably converted to mostly gaseous products (methane) and some solid residues (coke).

HZSM-5 series catalyst shows high ethylene and moisture distribution. When the catalyst of HZSM-5 series is used, the product is obtained by separating into two liquid phases. In the case of the upper layer existing in the upper part of high water content, it can be presumed that the hydrophobic compound has low specific gravity and moisture content.

(5) Analysis of composition of liquid product

The major components of the liquid product obtained in the second reaction were analyzed.

Fig. 7 shows the main components of the liquid product obtained when the catalyst was not used. As shown in FIG. 7, in the case of the reaction using no catalyst, it is visually colorless and mostly composed of unreacted ethanol.

8 shows the distribution of the major components and the carbon number of the heavy hydrocarbons obtained when the alumina catalyst was used. Table 3 shows the results of hydrocarbons having the top 20 GC-MS peak area ratios among the liquid products obtained using the alumina catalyst Respectively.

Compound name Area percentage (%) Carbon umber Cyclohexene 27.7 6 Heptane, 3-methyl- 8.0 8 Octane 7.1 8 Cyclohexene, 1-ethyl- 5.1 8 Cyclohexane, ethyl- 2.6 8 Decane 2.6 10 Cyclohexene, 1-ethyl- 2.1 8 3-Ethyl-3-methylheptane 1.6 10 4-Octene, (E) - 1.5 8 Nonane, 3-methyl- 1.4 10 Heptane, 4, 4-dimethyl- 1.4 9 Nonane, 3-methyl- 1.4 10 2-Octene, (E) - 1.4 8 Octane, 4-ethyl- 1.3 10 4-Decene 1.2 10 2-Octene, (E) - 1.1 8 2-hexene, 2-methyl- 0.9 7 Bicyclo (3.2.1) oct-2-ene 0.9 8 Nonane 0.9 9 4-Tetradecene (E) - 0.9 14

When alumina is used as a catalyst, as shown in FIGS. 8 and 3, phase separation does not occur, and yellowish light is visually observed, which means that the content of unreacted ethanol in the product is high, so that hydrophobic hydrocarbons are dissolved. That is, as shown in Table 3, hydrocarbons of C ₆ to C ₁₀ are produced, but the conversion rate of ethanol itself is not high. The resulting hydrocarbons are mainly alkanes or alkenes with alkyl groups.

FIG. 9 shows the distribution of carbon atoms in the upper part (hydrocarbon) and the main components in the lower part of the liquid product obtained when the HZSM-5 catalyst was used. Table 4 shows the upper 20 The distribution of hydrocarbons with GC-MS peak area ratios is shown.

Compound name Area percentage (%) Carbon umber Benzene, 1-ethyl-2-methyl- 6.1 9 Heptane, 3-methyl- 4.1 8 Benzene, 1,4-diethyl- 3.9 10 Benzene, 1-ethyl-3-methyl- 3.7 9 Benzene, 1,2-diethyl- 3.6 10 p-Xylene 3.6 8 Ethane, 1,1-diethoxy- 2.5 Hexane, 2-methyl- 2.3 7 Benzene, methyl- 2.2 7 Hexane, 3-methyl- 2.2 7 Benzene, 4-ethyl-1,2-dimethyl- 2.2 10 Undecane, 2,7-dimethyl- 2.2 13 Heptane 2.1 7 Benzene, 1,4-diethyl-2-methyl- 1.9 11 3-ethyl- (3H) -isobenzofuran-1-one 1.6 9 Decane 1.5 10 Nonane 1.5 9 Pentane, 3-ethyl-3-methyl- 1.5 8 Benzene is reacted with 1-methyl-4- (1-methylpropyl) - 1.5 11 Benzene, ethyl- 1.4 8

When HZSM-5 was used as a catalyst, 11.9 g of a hydrocarbon layer (liquid product of the upper layer) was produced as shown in Table 2, and it was confirmed that it was composed of hydrocarbons having C7 to C11 carbon number .

As shown in Table 4, the produced hydrocarbons accounted for most of the aromatic compounds, and 15.9 g of the liquid product in the lower layer contained about 70 wt% of water, which was obtained by dehydration of ethanol by strong acid catalyst The water obtained is moved to the bottom of the product due to the density difference.

10 shows the carbon number distribution of the upper portion (hydrocarbon) and the main components in the lower portion of the liquid product obtained when the Ni / HZSM-5 catalyst was used, and Table 5 shows the composition of the upper layer liquid The distribution of hydrocarbons having the top 20 GC-MS peak area ratios among the products was shown.

Compound name Area percentage (%) Carbon umber Heptane, 3-methyl- 4.4 8 Heptane 2.0 7 Pentane, 3-ethyl-3-methyl- 1.9 8 Pentane, 3-ethyl- 1.9 7 Hexane, 2-methyl- 1.8 7 Decane 1.8 10 Heptane, 2-methyl- 1.8 8 Hexane, 3-methyl- 1.7 7 Nonane 1.7 9 Heptane, 3-ethyl- 1.6 9 2-hexene, 2-methyl- 1.5 7 Benzene, 1-ethyl-4-methyl- 1.5 9 Dodecane 1.4 12 Decane, 3,8-dimethyl- 1.4 12 Nonane, 3-methyl- 1.4 10 Benzene, 1,4-diethyl- 1.3 10 Heptane, 4-methyl- 1.3 8 Octane, 4-methyl- 1.3 9 Dodecane 1.2 12 Tridecane 1.1 13

In the case of the catalyst carrying Ni on HZSM-5, the overall reactivity is almost the same as that of HZSM-5, but as shown in Table 5, the type of hydrocarbons is changed to alkane and alkene Respectively.

As shown in FIG. 10, when the HZSM-5 catalyst carrying Ni is used, the composition of hydrocarbons having carbon atoms longer than C ₁₃ is high.

(6) Measurement of organic element content and calorific value of liquid product

Table 6 shows elemental analysis and calorific value measurement results for the separated upper and lower liquid product. Elemental analysis was performed using an elemental analyzer (EA1110-FISONS). The calorific value was calculated from the following formula (DIN51900 standard) using elemental analysis results.

HHV (MJ / kg) = (34C + 124.3H + 6.3N + 19.3S-9.8O) / 100

Catalyst Carbon (wt%) Hydrogen (wt%) Oxygen (wt%) Nitrogen (wt%) O / C H / C HHV (MJ / kg) γ- Al ₂ O ₃ 74.3 7.9 18.0 0.3 0.18 1.28 33.36 HZSM-5
(upper phase) 84.2 13.9 1.8 0.0 0.02 1.98 45.75 Ni / HZSM-5
(upper phase) 83.0 14.2 2.8 0.0 0.03 2.05 45.6

When alumina was used as a catalyst, hydrocarbons in the naphtha range were produced, but the conversion of ethanol was not high, so that the O / C ratio was significantly higher than that of the HZSM-5 series catalyst.

In the case of HZSM-5 and Ni / HZSM-5 catalysts, the physical properties of the final liquid product were almost similar, but as shown in the mass analysis results, the types of hydrocarbons were remarkably different. It was confirmed that alkane and alkene could be produced by inducing ring-opening reaction of aromatic hydrocarbon.

When the catalyst of HZSM-5 series was used, it was possible to obtain a level of liquid product equivalent to the calorific value of gasoline (47 MJ / kg).

It has been found that the amount of Ni on the catalyst can be controlled to control the kind of hydrocarbons produced.

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims (10)

As a naphtha production system using biomass-derived bioethanol,
A supply unit for supplying bio-ethanol;
In a reaction condition for making the bioethanol into a supercritical state, a condensation reaction is carried out under a first catalyst in which a metal containing magnesium (Mg), nickel (Ni) and molybdenum (Mo) A first reactor for producing a liquid product comprising an oxygen compound; And
And a second reactor for deoxidizing the liquid material under a second catalyst comprising zeolite to separate into a hydrocarbon layer containing naphtha and a water layer.
delete The method according to claim 1,
Wherein the first reactor is a high pressure reactor, comprising a heating device and a cooling device,
The first reactor is charged with the bioethanol supplied from the supply unit and the first catalyst. The first reactor is controlled to a supercritical state by controlling the first reactor to a supercritical state, heated through the heating apparatus while stirring, Wherein the heating device is stopped and quenched through the cooling device when the temperature of the reactor reaches the reaction temperature.
The method of claim 3,
Wherein the naphtha production system further comprises a pressure regulator, wherein the first reactor regulates the high pressure to an initial pressure of 25 to 35 bar.
The method according to claim 1,
Wherein the second reactor comprises a heating device,
The second catalyst is introduced into the second reactor and the liquid containing the oxygen-containing compound supplied from the first reactor is introduced into the second reactor, the second reactor is heated to the reaction temperature through the heating device, The naphtha manufacturing system.
The method according to claim 1,
Wherein the second catalyst comprises a zeolite catalyst or a catalyst in which a metal containing nickel is supported on a zeolite.
The method according to claim 1,
The second reactor to the first reactor of the naphtha production system using a zeolite catalyst as the second catalyst separation with a layer containing a hydrocarbon layer and a water-containing aromatic hydrocarbon group of C ₇ ~ C _11.
The method according to claim 1,
In the second reactor, zeolite is separated into a hydrocarbon layer containing C ₁₃ or more alkanes and alkenes and a layer containing water by using a catalyst carrying a metal containing nickel on the zeolite as the second catalyst A reactor naphtha manufacturing system.
The method according to claim 1,
The naphtha manufacturing system
Further comprising a filter for separating the used first catalyst from the liquid containing the oxygen-containing compound produced in the first reactor, wherein the separated first catalyst is washed, dried and reused.
The method according to claim 1,
The naphtha manufacturing system
Further comprising a filter for separating the second catalyst used from the two-phase liquid phase comprising a hydrocarbon layer comprising naphtha produced in said second reactor and a water layer, wherein said separating catalyst is washed and dried, Manufacturing system.

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