WO2019045150A1 - Method for selectively producing btx aromatics from phenols, which are generated through lignin pyrolysis, by mild condition hydrodeoxygenation reaction using fereo_x/zro_2 catalyst - Google Patents

Abstract

The present invention relates to a method for converting phenols, which are generated as a pyrolysis product of lignin, into aromatics of benzene, toluene and xylene by a FeReOx/ZrO2 catalyst hydrodeoxygenation reaction. The hydrodeoxygenation reaction of the present invention is carried out under mild conditions in which the temperature and the pressure are lower than those under normal conditions. The present invention has advantages of having a much higher BTX production yield, of approximately 50%, than a conventional technique, and enabling a conversion reaction to be carried out even under mild conditions of low temperature and atmospheric pressure. In addition, by using an HDO process of low temperature and atmospheric pressure, the present invention can be applied to a novel process, which is efficient and economical and can produce BTX from lignin.

Description

Selective Production of BTX Aromatics from Phenol Producing Lignin Pyrolysis by Hydrothermal Oxygenation under Mild Conditions with FeReO_X / ZrO_2 Catalysts

The present invention relates to a process for selectively producing a BTX aromatic from phenol using hydrodeoxygenation (hereinafter referred to as 'HDO') reaction. More specifically, phenol generated as a pyrolysis product of lignin is reacted with FeReO _x / ZrO ₂ catalyst To a BTX aroma using an HDO reaction. The HDO reaction of the present invention proceeds under mild conditions at lower temperatures and pressures than conventional conditions.

Renewable biomass is attracting attention as an energy source to replace fossil fuels in order to deal with environment-related international treaties that become more stringent. However, biomass is becoming more important as it is the only carbon source of renewable energy as well as an energy source.

Pyrolysis during the thermochemical conversion process of biomass is a method to obtain liquid fuel and carbon source. Bio-oil obtained through pyrolysis is very likely to be used as carbon neutral, eco-friendly, renewable alternative fuel and chemical raw material.

Biomass is the most abundant in woody crops and crops, among which lignin is extracted and separated by pretreatment of woody biomass. However, the large amount of lignin that is generated during the pre-treatment process is classified as waste and processed by simple incineration. In particular, there is no clear reuse method for lignin, which occurs in large quantities in the paper industry.

Recently, researches for recycling lignin through rapid pyrolysis, supercritical fluid liquefaction, gasification, etc. have been actively conducted. When the lignin is pyrolyzed by the above-mentioned method, the bio-oil can be produced. Bio-oils, however, contain aldehydes, ketones, furans, phenols, and the like, which have various functional groups including oxygen. Also, due to various mixtures and uneven composition, it is difficult to use as a raw material for the petroleum industry. In order to solve these problems, there is a great interest in the process of converting lignin into phenol through rapid thermal decomposition and then converting it into BTX through a subsequent process using a catalyst, such as benzene, toluene and xylene.

BTX is the backbone of the petrochemical industry, producing and consuming enormous amounts worldwide. BTX is used as an additive to increase the octane number of gasoline, or as a raw material for various chemical products. Currently, most of the BTX is produced through the decomposition or conversion process using crude naphtha as a catalyst. Given the ever-increasing demand for BTX, environmental concerns as well as the depletion of fossil fuels such as oil, it is necessary to develop alternatives to sustainable and reusable production of BTX.

Catalysts are the most important catalysts for the conversion of lignin into BTX through the rapid pyrolysis of phenol after conversion. Since the binding force between the aromatic carbon and oxygen of the phenol molecule is very strong, the reaction energy for deoxygenation is very high as 468 kJ / mol, so that the conversion reaction is not easy. The HDO reaction, which is proposed as a solution, is a reaction with a catalyst with hydrogen and a bifunctionality, in which the compounds of the phenols are assumed to be converted to cyclohexadieneon via a tautomerization reaction. The intermediate product is hydrogenated and dehydrated by the two routes shown in FIG. 1, and in the HDO reaction for the BTX conversion of phenol, development and securing of a dual-functional catalyst having both a metal and an acid capable of both hydrogenation and dehydration More important than anything else.

Until now, transition metal catalysts using zeolite as a support were mainly used in the HDO reaction. The transition metal was used as a region for hydrogenation, and the zeolite served as an acid for dehydration. However, lignin pyrolysis phenol usually adsorbs very strongly to zeolite-based catalysts, which dramatically reduces the efficiency of hydrocracking of zeolite catalysts carried out at normal pressure. Moreover, due to the endothermic reaction upon adsorption, the inactivation of zeolite at low temperatures becomes more problematic. In order to solve the problems caused by such adsorption, the HDO reaction has been carried out at a high temperature and a high pressure, all of which consume a large amount of energy.

Patent Document 1 relates to a method for producing a high-carbon bio-oil having a low oxygen content from a pulverulent chopstick containing a high content of lignin or from a garlic garlic using an acidic solid catalyst having nano pores. The high-carbon bio-oil is benzene, toluene, ethylbenzene, xylene or a mixed oil thereof. In Patent Document 1, silica-silicate, titano-silicate or aluminosilicate catalyst is used.

Patent Document 2 relates to a method for producing bio-oil from lignin through two-step catalytic cracking. In Patent Document 2, a natural zeolite (NZ) low acid base catalyst is used in the first stage reaction and HZSM-5 is used in the second stage conversion reaction in order to solve the deactivation of the catalyst in the second reduction or conversion reaction. Respectively. This reduced the inactivation of HZSM-5 used in the 2-step reaction and increased the yield of BTEX (benzene, toluene, ethylbenzene, xylene).

Non-Patent Document 1 is a review paper on a process of cracking a bio-oil / gas generated from biomass pyrolysis using a catalyst, and refers to a technology related to selectivity in which the bio-oil is converted into an aromatic or olefin.

Non-Patent Document 2 describes a method for catalytic pyrolysis of kraft lignin using HZSM-5. In the absence of HZSM-5 catalyst, phenol and guaiacol were mainly formed, and in the presence of catalyst, their formation ratio changed.

However, a BTX production yield is still high enough to be used as a petrochemical raw material, a conversion reaction proceeds at low pressure and low temperature, and a solution for a process without catalyst deactivation due to coke deposition at low temperatures has not been proposed.

(Patent Document 1) Korean Patent Laid-Open Publication No. 2016-0104207 (2016.09.05)

(Patent Document 2) Korean Patent Publication No. 1725178 (Apr.

(Non-Patent Document 1) Pouya Sirous Rezaei et al., &Quot; Production of green aromatics and olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis: A review ", Applied Catalysis A: General, Vol. 469, 490-511, year.

(Non-Patent Document 2) Xiangyu LI et al. "Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons", Front. Environ. Sci. Eng., Vol. 6, No. 3, pp. 295-303, 2012.

(Non-Patent Document 3) G. Zhou, P.A. Jensen, D.M. Le, N.O. Knudsen, A.D. Jensen, Green Chem. 18 (2016) 1965-1975.

(Non-Patent Document 4) P.S. Rezaei, H. Shafaghat, W.M.A.W. Daud, Green Chem. 18 (2016) 1684-1693.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and it is an object of the present invention to improve the efficiency of the HDO reaction by using an acidic support other than zeolite. Also, a catalyst capable of maintaining the activity of the catalyst at a low temperature is constructed. Accordingly, the present invention provides a novel catalyst capable of performing a conversion reaction with a high yield of BTX and a low temperature and a low pressure, and a process using the catalyst. The catalyst according to the present invention will be an economical and efficient way to produce BTX from lignin in the future.

In order to solve the above problems, a first aspect of the present invention provides a catalyst to which a compound containing Fe, Re, and oxygen is added to a Zr oxide support. Specifically, the Zr oxide is ZrO _2, and the compound containing Fe, Re, and oxygen is FeReO _x .

The Fe, Re, and oxygen-containing compounds are impregnated into the Zr oxide support by a wet impregnation method. Specifically, an aqueous solution containing Fe (NO ₃ ) ₃ .9H ₂ O and NH ₄ ReO ₄ is introduced into the Zr oxide support .

A second aspect of the present invention provides a method of using the catalyst for hydrocracking oxygenation. The hydrocracking reaction is a conversion of phenol into benzene, toluene and xylene. As a specific example, a phenol product pyrolyzed with lignin is hydrolyzed.

A third aspect of the present invention provides a method for producing an aromatic compound from lignin using the catalyst. The production process is carried out at atmospheric pressure, at 500 ° C or lower, preferably at 350 ° C, and the main aromatic products are benzene, toluene and xylene.

A fourth aspect of the present invention provides a method for preparing a Zr oxide support comprising: preparing a Zr oxide support through supercritical synthesis; Impregnating the Zr oxide support with an aqueous solution comprising Fe (NO ₃ ) ₃ .9H ₂ O and NH ₄ ReO ₄ ; Drying the impregnated support; And a calcination reaction is carried out on the dried support, wherein a catalyst containing Fe, Re, and oxygen is added to a Zr oxide support. The drying is carried out in two stages at 150 ° C or lower, and the calcination reaction proceeds at 500 ° C or higher.

1 shows the reaction mechanism of the HDO reaction according to the present invention.

FIG. 2 shows the measurement results of the X-ray diffraction apparatus of the catalysts according to the present invention.

3 to 5 are pore size distributions according to nitrogen adsorption-desorption isotherm curves of catalysts according to the present invention, and FIGS. 3, 4 and 5 are pore size distributions of HBeta, Si-MCM-41 and ZrO ₂ , respectively.

6 shows the results of ammonia TPD according to the present invention.

7 shows TEM results of the catalyst according to the present invention. (a), (b), (c), and (d) relate to Fe / MCM-41, FeReO _x / MCM-41, Fe / ZrO ₂ and FeReO _x / ZrO ₂ , respectively.

8 is a graph showing the change in the BTX yield according to the number of times of use of the FeReO _x / ZrO ₂ catalyst according to the present invention.

9 is a graph showing the BTX yields depending on the temperatures of Fe / HBeta, Fe / ZrO ₂ , and FeReO _x / ZrO ₂ catalysts.

10 is a graph showing the yields when BTX is produced by pyrolysis of lignin according to Fe / HBeta, Fe / ZrO ₂ , FeReO _x / MCM-41 and FeReO _x / ZrO ₂ catalysts.

In order to achieve the above object, the present invention was investigated on Fe / HBeta, Fe / MCM-41, Fe / ZrO ₂ , FeReO _x / MCM-41 and FeReO _x / ZrO _{2 which} are various candidate catalyst groups for HDO reaction. As model compounds for lignin, guaiacol, phenol, m-cresol and anisole were used.

Zirconia (ZrO ₂ ) and rhenium oxide (ReO _x ), which are slightly acidic in preparation for HBeta, were also used to determine the extent to which the dehydration step was promoted in the HDO reaction. Iron has been introduced as a catalyst for selectively converting phenol to an aromatic compound.

<Preparation of catalyst>

The catalysts investigated in the present invention are Fe / HBeta, Fe / MCM-41, Fe / ZrO ₂ , FeReO _x / MCM-41 and FeReO _x / ZrO ₂ . HBeta is zeolite beta _{(Zeolyst, CP814C, SiO 2 /} Al 2 O 3 molar ratio: 38) was obtained by the ammonium form of a 12 hour calcination at 550 ℃ reaction (calcination). MCM-41, which is a mesoporous silica, was prepared according to the method described in B.S. Kim, CS Jeong, JM Kim, SB Park, SH Park, J.-K. Jeon, S.-C. Jung, SC Kim, Y.-K. Park, Catal. Today 265 (2016) 184-191. Zirconia is described in J.-R. Kim, K.-Y. Lee, M.-J. Suh, S.-K. Ihm, Catal. Today 185 (2012) 25-34. An Fe catalyst with HBeta, silica, and zirconia as the support was prepared by using incipient wetness impregnation of Fe (NO ₃ ) ₃ .9H ₂ O solution in the support. FeReO _x / MCM-41 and FeReO _x / ZrO ₂ were prepared by using an initial wet co-impregnation method in an aqueous solution containing Fe (NO ₃ ) ₃ .9H ₂ O and NH ₄ ReO ₄ in silica and zirconia. After impregnation, all the catalysts were dried at 60 ° C. for 12 hours and at 110 ° C. for 12 hours. The temperature was then increased to 3 ° C./min and further calcination was carried out at 550 ° C. for 12 hours.

&Lt; Identification of catalyst &

The crystallinity of the catalyst was confirmed by X-ray diffraction (XRD). The Rigaku Miniflex diffractometer was used and the analysis conditions were 40 kV, 30 mA, Cu Kα radiation (λ = 1.54443 Å). XRD patterns were measured in the 2 [theta] range of 10-90 [deg.] With 0.017 [deg.] Intervals. X-ray fluorescence (XRF) instrument (ZSX Primus II, Rigaku) was used for the chemical analysis of the samples.

The pore size distribution and surface area of the catalyst were measured by nitrogen isotherm (-196 ° C) adsorption-desorption curves. The device used was Micromeritics ASAP 2020. Temperature-programmed desorption (TPD) was measured using BEL Japan and BELCAT B to determine the activity of the sample. The sample placed in the TPD cell was exposed to 5% NH ₃ /95% He gas at a flow rate of 50 ml / min at 100 ° C for 30 minutes. The sample was then washed with helium for 30 minutes to remove the ammonia that was physically adsorbed. The desorption of ammonia was measured until the temperature of the sample increased by 10 ° C per minute to 600 ° C in an environment in which helium flowed 50ml per minute. Transmission electron microscopy (TEM) measurements were performed at an accelerating voltage of 200 kV using a JEOL JEM-2100F.

Thermogravimetric analysis (TGA) of the catalyst used was carried out by measuring the amount of phenol trapped in the catalyst in the HDO reaction. While flowing 100 ml of nitrogen gas per minute, the sample was heated at 30 占 폚 to 750 占 폚 at a rate of 10 占 폚 per minute and maintained at the final temperature for about 30 minutes. It is analyzed that the weight loss occurring when the temperature is increased is caused by the vaporization of the phenol trapped in the catalyst.

&Lt; Measurement of Catalyst Activity >

The activity of the catalyst was measured using a pyrolysis reactor apparatus (Rx-3050TR, Frontier Laboratories Ltd.) capable of treating micro-weight samples. In the pyrolysis apparatus, two heating units are continuously provided, and pyrolysis or vaporization occurs in the first heating unit, and the catalytic reaction proceeds in the second heating unit. To investigate the HDO reaction characteristics, 1 mg of each of guaiacol, m-cresol and anisole was injected into the first heating part using a syringe. Phenol (1 mg) or kraft lignin (4 mg), a solid sample, was placed in a stainless steel cup and then pyrolyzed or heated by the first heating section.

The temperature of the first heating section was set at 300 ° C and 600 ° C respectively for the vaporization of the phenol model compound and the thermal decomposition of kraft lignin. Vapor from the first heating section is sent to the second heating section for the conversion reaction. In the second heating part, a catalyst (40 mg) is disposed on the glass fiber in the form of a plug to form a fixed layer. Therefore, the ratio of catalyst to raw material is 40, 10 for phenol and lignin conversion, respectively.

The temperature of the second heating section can vary from 250 ° C to 500 ° C. 100 ml of hydrogen per minute was used as the carrier gas and all reactions proceeded at atmospheric pressure. Prior to the reaction, the catalyst was reduced at 350 ° C or 500 ° C for 1 hour. The gas converted by the reaction was transferred to a gas chromatograph (7890A, Agilent Technologies, hereafter referred to as 'GC') for analysis via the heating section (320 ° C). Prior to GC analysis, the reaction passes through a MicroJet Cryo Trap (MJT-1030E, Frontier Laboratories Ltd.), a cooling trap maintained at -196 ° C. Subsequently, the reactants are separated by passing through a capillary column (UA-5, 30 m length × 0.25 mm i.d. × 0.25 μm film thickness) in GC and quantitatively and qualitatively analyzed by MSD and FID.

In the cyclohexanol dehydration reaction, a 40 mg catalyst was placed in a second heating zone at 350 DEG C, and 0.4 mg of cyclohexanol was injected at 300 DEG C in the first heating zone. 30 ml of helium per minute was used as the carrier gas. Prior to the reaction, the catalyst was reduced on 100 ml of pure hydrogen per minute for 1 hour.

<Examples>

<1. Identification of catalyst >

The ratio of each metal (Fe or Re) in the Fe / HBeta, Fe / MCM-41, Fe / ZrO ₂ , FeReO _x / MCM-41 and FeReO _x / ZrO ₂ catalysts measured by XRF is about 4 wt% to be. The zirconia synthesized in the present invention has a monoclinic crystalline structure (see FIG. 2).

3 to 5, Si-MCM-41 and ZrO ₂ are mesoporous supports each having an average diameter of BJH adsorption pores of 2.8 to 18.9 nm, and HBeta is a fine A pore channel (0.66x0.67nm, 0.56x0.56nm is a zeolite.

As can be seen below in the physical and chemical properties of the catalysts shown in Table 1, ZrO _2, and a catalyst to the Si-MCM-41 as a support or respectively the smallest <greatest ((100㎡g ^-1 800㎡g)> ^{- 1} ) surface area. In addition, ZrO ₂ and Si-MCM-41 supported catalysts showed very small volume due to micropores, whereas Fe / HBeta was mostly due to micropores.

Figure 6 shows the ammonia-TPD results. According to FIG. 6, the total acidity of each catalyst is as follows. _{Fe / HBeta> FeReO x / ZrO} 2> FeReO x / MCM-41> Fe / ZrO 2> Fe / MCM-41. As can be seen from FIG. 6, when ReO _x is added to Fe / ZrO ₂ and Fe / MCM-41, the adsorption amount of ammonia increases sharply as the acidity increases. This is because ReO _x is an acid- It can be seen that it shows a very strong effect with increasing the acidity in the catalytic reaction.

As can be seen from the TEM results in FIG. 7, it can be seen that ZrO ₂ is a more excellent support than Si-MCM-41 in terms of dispersion of iron oxide. As can be seen in FIG. 7 (a), the iron oxide appears as a black dot in the cluster form in the Si-MCM-4 support, but in the case of ZrO ₂ , it is dispersed evenly and does not appear as a separate cluster.

<2. Check activity>

<2.1 Comparative Example Results>

Table 2 below shows the HDO yields of guaiacol, m-cresol, anisole and phenol by Fe / MCM-41, Fe / HBeta, Fe / ZrO ₂ and FeReO _x / MCM-41.

In the case of guaiacol, Fe / MCM-41 has a much lower BTX yield than Fe / HBeta. However, the yield of Fe / MCM-41 increased rapidly from 3.6% to 8.03% when ReO _x was added to increase the acidity. In other words, in case of guaiacol, high acidity has a good effect on the yield of BTX.

On the other hand it is also higher than the Fe / yield of the ZrO ₂ Fe / MCM-41, as was seen in 7 appears to be on the dispersion of the Fe much better viscosity influence from the ZrO ₂ support.

The BTX yields of guaiacol at 350 ℃ were Fe / HBeta> FeReO _x / MCM-41> Fe / ZrO ₂ > Fe / MCM-41. On the other hand, the BTX yield of guaiacol in the temperature-reduced 300 ° C reaction was in the order of FeReO _x / MCM-41> Fe / ZrO ₂ > Fe / HBeta. That is, Fe / HBeta having a high acidity is advantageous for the reaction when the temperature is high, but the yield of Fe / HBeta is low because the phenol having a hydroxy group is adsorbed better at a low temperature at the Fe / HBeta having a high acidity . In addition, the Fe / HBeta catalyst is interpreted to have a lower yield due to the reduction of diffusion in the micropores as the temperature decreases because the catalyst has only micropores.

The BTX yield results for the other model compounds phenol, m-cresol, anisole, etc. are also shown in Table 2. Unlike guaiacol, FeReO _x / MCM-41 and Fe / ZrO ₂ show higher yields than Fe / HBeta even at high temperatures. In other raw materials, the pH of the catalyst is less influenced by the acidity of the catalyst because the hydroxyl value of the phenol is lower than that of the former. In this way, the BTX yield by reaction with HDO is slightly different for each catalyst and each reactant.

&Lt; 2.2 Results of Example &

The results of HDO reaction of guaiacol and m-cresol using FeReO _x / ZrO ₂ catalyst according to the present invention are shown in Table 3. As shown in Table 3, it can be seen that the FeReO _x / ZrO ₂ catalyst according to the present invention has a much higher BTX yield than other catalysts of the comparative examples. It can be interpreted that the catalyst of the present invention has a higher yield due to the incorporation of the acid sites of other catalysts such as the acid sites according to the ReO _x moiety and the acid sites by the ZrO ₂ moiety into one system.

As can be seen in Table 1, the FeReO _x / ZrO ₂ catalyst according to the present invention has an acidity of 0.24 mmol / g, while the Fe / HBeta has an acidity of 0.49 mmol / g. However, the FeReO _x / ZrO ₂ catalyst of the present invention exhibits significantly higher BTX yields compared to Fe / HBeta even at 350 ° C. favorable to high acidity. From this point of view, the catalyst according to the present invention is interpreted as having excellent properties against HBeta in addition to the effect of acidity and dispersion, and this is an unpredictable result. As can be seen from Fig. 8, the FeReO _x / ZrO ₂ catalyst shows very little inactivation by phenol even in continuous use. Although it has been reused more than 160 times, it maintains a similar value to the initial BTX yield. In the present invention, wt%, which represents the yield, means a value calculated on the weight basis of the material produced as compared with the input.

On the other hand, FIG. 9 shows the effect of FeReO _x / ZrO ₂ , Fe / ZrO ₂ and Fe / HBeta catalysts on the temperature. Figure 9 shows the BTX yields according to the reaction temperature in the HDO reaction of m-cresol. FIG. 9 shows that the FeReO _x / ZrO ₂ catalyst according to the present invention has very excellent temperature characteristics as compared to other catalysts. The FeReO _x / ZrO ₂ catalyst maintains a constant high value without dropping the yield even when the temperature drops to 250 ° C, but other catalysts show a rapid decrease from 300 ° C. The BTX yield of the catalyst according to the present invention is very good even at a low temperature of 250 캜, which accounts for 50.55% by weight of Fe / HBeta higher than 500 캜. The abrupt decrease of the yield in the comparative catalyst is presumed to be caused by the deactivation of the catalyst by adsorption.

<3. Yield associated with pyrolysis of lignin>

Kraft lignin was used to characterize the catalysts associated with pyrolysis of Fe / HBeta, Fe / ZrO ₂ , FeReO _x / MCM-41 and FeReO _x / ZrO ₂ lignin. After the lignin was pyrolyzed at 600 ° C, the generated vapor was passed through the catalyst layer at 350 ° C. As can be seen in FIG. 10, the HDO activity of the catalysts was in the order of FeReO _x / ZrO ₂ > FeReO _x / MCM-41> Fe / ZrO ₂ > Fe / HBeta. Toluene, benzene, xylene, trimethylbenzene, pentamethylbenzene, and naphthalene were the major products when the FeReO _x / ZrO ₂ catalyst according to the present invention was used, and the yields of BTX and the total aromatic compound were 4.61 and 6.87%, respectively.

Compared with the prior art, it can be seen that the FeReO _x / ZrO ₂ catalyst according to the present invention converts lignin pyrolysis vapor to BTX very efficiently at 350 ° C. under atmospheric pressure. This low temperature conversion reaction is a surprising effect that has not been reported in the past. Catalytic pyrolysis of lignin typically proceeds above 500 ° C. It has also been reported in many literature that the production of hydrocarbons increases at a temperature higher than 600 ° C. Non-Patent Document 3 mentioned that a high temperature of 600 ° C or higher is required, and an aromatic hydrocarbon was obtained from lignin by using HZSM-5 catalyst at a yield of 4.0 wt%. In Non-Patent Document 4, lignin was catalytically cracked using Fe / HBeta under an oxygen-free condition at 500 ° C, and the yield of the aromatic compound was 5.13% by weight.

The yield of the catalyst FeReO _x / ZrO ₂ at 350 ° C according to the present invention is 6.87% by weight, which is higher than the yield at high temperature in the conventional literature. As can be seen from Tables 2 and 3 of the present invention, the FeReO _x / ZrO ₂ catalyst according to the present invention exhibits a yield of 4.2 times higher than that of the conventional Fe / HBeta catalyst at 350 ° C. The catalyst according to the present invention has a mild condition It can be deduced that it will exhibit very excellent characteristics in comparison with the conventional literature.

As described above, the catalyst according to the present invention exhibits a very good BTX conversion ratio at 350 ° C., which is a mild condition, as compared with the conventional catalyst, and thus it is economical and very close to commercial commercialization conditions.

The present invention is advantageous in that the BTX production yield is as high as about 50% as compared with the conventional technology, and the conversion reaction can be performed even under mild conditions of low temperature and normal pressure. Due to the low temperature and atmospheric HDO processes, the present invention can be applied to new economical and efficient processes for producing BTX from lignin.

Claims (13)

1. A catalyst to which a compound containing Fe, Re, and oxygen is added to a Zr oxide support.
2. The method according to claim 1,

   The Zr oxide is ZrO ₂

   Compound comprising the Fe, Re, and oxygen is FeReO _x catalyst.
3. The method according to claim 1,

   Wherein the Zr oxide support is impregnated with a compound containing Fe, Re, and oxygen by a wet impregnation method.
4. The method of claim 3,

   The method of wet impregnating a compound comprising Fe, Re, and oxygen comprises impregnating the Zr oxide support with an aqueous solution comprising Fe (NO ₃ ) ₃ .9H ₂ O and NH ₄ ReO ₄ .
5. Use of a catalyst according to any one of claims 1 to 4 for hydrotreating oxygenation.
6. 6. The method of claim 5,

   Wherein said hydrocracking reaction is a conversion of phenol to benzene, toluene and xylene.
7. 6. The method of claim 5,

   Wherein the hydrocracking reaction is a hydrocracking reaction of pyrolysis products of lignin.
8. A process for producing an aromatic compound from lignin using the catalyst according to any one of claims 1 to 4.
9. 9. The method of claim 8 wherein the process produces an aromatic compound from lignin that proceeds at or below atmospheric pressure.
10. 10. The process of claim 9, wherein the process is conducted at atmospheric pressure at 350 DEG C and the main product is an aromatic compound produced from benzene, toluene, xylene, lignin.
11. Preparing a Zr oxide support through supercritical synthesis;

    Impregnating the Zr oxide support with an aqueous solution comprising Fe (NO ₃ ) ₃ .9H ₂ O and NH ₄ ReO ₄ ;

    Drying the impregnated support;

    Conducting a baking reaction on the dried support;

    A method for producing a catalyst to which a compound containing Fe, Re, and oxygen is added to an included Zr oxide support.
12. 12. The method of claim 11,

    Wherein the drying is carried out in two stages at 150 DEG C or lower.
13. 12. The method of claim 11,

    Wherein the calcination reaction is conducted at a temperature of 500 ° C or higher.

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