WO2019045150A1 - Procédé de production sélective de composés aromatiques btx à partir de phénols, qui sont générés par pyrolyse de lignine, par réaction d'hydrodésoxygénation dans des conditions douces à l'aide d'un catalyseur fereo_x/zro2_2 - Google Patents

Procédé de production sélective de composés aromatiques btx à partir de phénols, qui sont générés par pyrolyse de lignine, par réaction d'hydrodésoxygénation dans des conditions douces à l'aide d'un catalyseur fereo_x/zro2_2 Download PDF

Info

Publication number
WO2019045150A1
WO2019045150A1 PCT/KR2017/009564 KR2017009564W WO2019045150A1 WO 2019045150 A1 WO2019045150 A1 WO 2019045150A1 KR 2017009564 W KR2017009564 W KR 2017009564W WO 2019045150 A1 WO2019045150 A1 WO 2019045150A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
zro
lignin
reaction
fereo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2017/009564
Other languages
English (en)
Korean (ko)
Inventor
박영권
서로스 리자이푸야
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry Cooperation Foundation of University of Seoul
Original Assignee
Industry Cooperation Foundation of University of Seoul
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industry Cooperation Foundation of University of Seoul filed Critical Industry Cooperation Foundation of University of Seoul
Publication of WO2019045150A1 publication Critical patent/WO2019045150A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/04—Benzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/06—Toluene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • 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.
  • biomass is becoming more important as it is the only carbon source of renewable energy as well as an energy source.
  • 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.
  • Bio-oils 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.
  • 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.
  • 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.
  • 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.
  • the endothermic reaction upon adsorption the inactivation of zeolite at low temperatures becomes more problematic.
  • 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.
  • 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.
  • 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).
  • NZ natural zeolite
  • 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.
  • 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.
  • 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.
  • 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.
  • the Zr oxide is ZrO 2
  • 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.
  • 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.
  • FIG. 2 shows the measurement results of the X-ray diffraction apparatus of the catalysts according to the present invention.
  • FIGS. 3, 4 and 5 are pore size distributions according to nitrogen adsorption-desorption isotherm curves of catalysts according to the present invention
  • FIGS. 3, 4 and 5 are pore size distributions of HBeta, Si-MCM-41 and ZrO 2 , respectively.
  • FIG. 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.
  • FIG. 9 is a graph showing the BTX yields depending on the temperatures of Fe / HBeta, Fe / ZrO 2 , and FeReO x / ZrO 2 catalysts.
  • FIG. 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.
  • 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.
  • 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 °C 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.
  • 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.
  • the crystallinity of the catalyst was confirmed by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • 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
  • 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.
  • TPD Temperature-programmed desorption
  • 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.
  • TEM Transmission electron microscopy
  • 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 ⁇ ⁇ to 750 ⁇ ⁇ at a rate of 10 ⁇ ⁇ 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.
  • the activity of the catalyst was measured using a pyrolysis reactor apparatus (Rx-3050TR, Frontier Laboratories Ltd.) capable of treating micro-weight samples.
  • a pyrolysis reactor apparatus Rx-3050TR, Frontier Laboratories Ltd.
  • 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.
  • 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.
  • 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.
  • the reactants are separated by passing through a capillary column (UA-5, 30 m length ⁇ 0.25 mm i.d. ⁇ 0.25 ⁇ m film thickness) in GC and quantitatively and qualitatively analyzed by MSD and FID.
  • a capillary column U-5, 30 m length ⁇ 0.25 mm i.d. ⁇ 0.25 ⁇ m film thickness
  • 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.
  • 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).
  • 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.
  • Figure 6 shows the ammonia-TPD results.
  • 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.
  • 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.
  • ZrO 2 is a more excellent support than Si-MCM-41 in terms of dispersion of iron oxide.
  • 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.
  • Table 2 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.
  • Fe / MCM-41 has a much lower BTX yield than Fe / HBeta.
  • the yield of Fe / MCM-41 increased rapidly from 3.6% to 8.03% when ReO x was added to increase the acidity.
  • high acidity has a good effect on the yield of BTX.
  • the BTX yields of guaiacol at 350 °C were Fe / HBeta> FeReO x / MCM-41> Fe / ZrO 2 > Fe / MCM-41.
  • 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.
  • 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 .
  • 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.
  • FeReO x / MCM-41 and Fe / ZrO 2 show higher yields than Fe / HBeta even at high temperatures.
  • 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.
  • 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.
  • 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.
  • 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.
  • wt% which represents the yield, means a value calculated on the weight basis of the material produced as compared with the input.
  • 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 ⁇ , which accounts for 50.55% by weight of Fe / HBeta higher than 500 ⁇ .
  • the abrupt decrease of the yield in the comparative catalyst is presumed to be caused by the deactivation of the catalyst by adsorption.
  • 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.
  • the generated vapor was passed through the catalyst layer at 350 ° C.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de conversion de phénols, qui sont générés en tant que produit de pyrolyse de lignine, en composés aromatiques de benzène, toluène et xylène par une réaction d'hydrodésoxygénation catalytique de FeReOx/ZrO2. La réaction d'hydrodésoxygénation de la présente invention est réalisée dans des conditions douces dans lesquelles la température et la pression sont inférieures à celles dans des conditions normales. La présente invention présente les avantages d'avoir un rendement de production de BTX beaucoup plus élevé, d'environ 50 %, qu'une technique classique, et permettant d'effectuer une réaction de conversion même dans des conditions douces de basse température et de pression atmosphérique. De plus, en utilisant un processus HDO de basse température et de pression atmosphérique, la présente invention peut être appliquée à un nouveau processus, qui est efficace et économique et peut produire du BTX à partir de lignine.
PCT/KR2017/009564 2017-08-31 2017-08-31 Procédé de production sélective de composés aromatiques btx à partir de phénols, qui sont générés par pyrolyse de lignine, par réaction d'hydrodésoxygénation dans des conditions douces à l'aide d'un catalyseur fereo_x/zro2_2 Ceased WO2019045150A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020170111134A KR101999567B1 (ko) 2017-08-31 2017-08-31 FeReO_X/ZrO_2 촉매를 이용한 온화한 조건의 수첨탈산소 반응에 의한 리그닌 열분해 생성 페놀로부터 BTX 방향족의 선택적 생산방법
KR10-2017-0111134 2017-08-31

Publications (1)

Publication Number Publication Date
WO2019045150A1 true WO2019045150A1 (fr) 2019-03-07

Family

ID=65527674

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/009564 Ceased WO2019045150A1 (fr) 2017-08-31 2017-08-31 Procédé de production sélective de composés aromatiques btx à partir de phénols, qui sont générés par pyrolyse de lignine, par réaction d'hydrodésoxygénation dans des conditions douces à l'aide d'un catalyseur fereo_x/zro2_2

Country Status (2)

Country Link
KR (1) KR101999567B1 (fr)
WO (1) WO2019045150A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140031546A1 (en) * 2012-07-25 2014-01-30 Wenqin Shen Hydrodeoxygenation catalyst
US20140051872A1 (en) * 2012-08-15 2014-02-20 Virent, Inc. Catalysts for hydrodeoxygenation of oxygenated hydrocarbons
KR20140100614A (ko) * 2013-02-05 2014-08-18 한국과학기술연구원 수첨탈산소 반응에 사용되는 탄화몰리브덴 촉매 및 이의 제조 방법
US20140275468A1 (en) * 2013-03-12 2014-09-18 The Procter & Gamble Company Catalysts And Processes For The Production Of Aromatic Compounds From Lignin
CA2928831A1 (fr) * 2013-10-27 2015-04-30 Purdue Research Foundation Procedes de conversion catalytique d'une biomasse, catalyseurs et leurs procedes de fabrication

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030100807A1 (en) * 2001-10-05 2003-05-29 Shabtai Joseph S Process for converting lignins into a high octane additive
US20130079566A1 (en) * 2011-09-27 2013-03-28 Nevada, Catalytic process for conversion of biomass into hydrocarbon fuels
US20150057475A1 (en) * 2013-08-23 2015-02-26 Battelle Memorial Institute Bi-functional catalyst and processes for conversion of biomass to fuel-range hydrocarbons
CN104744204A (zh) * 2015-02-04 2015-07-01 华东理工大学 一种木质素催化加氢脱氧制备芳香烃的方法
KR20160104207A (ko) 2015-02-26 2016-09-05 순천대학교 산학협력단 바이오매스로부터 나노 기공을 가지는 산성 고체 촉매를 이용한 바이오 오일의 제조방법
KR101725178B1 (ko) 2016-03-25 2017-04-10 서울시립대학교 산학협력단 2단계 촉매 열분해를 통한 리그닌으로부터 바이오 오일의 생산

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140031546A1 (en) * 2012-07-25 2014-01-30 Wenqin Shen Hydrodeoxygenation catalyst
US20140051872A1 (en) * 2012-08-15 2014-02-20 Virent, Inc. Catalysts for hydrodeoxygenation of oxygenated hydrocarbons
KR20140100614A (ko) * 2013-02-05 2014-08-18 한국과학기술연구원 수첨탈산소 반응에 사용되는 탄화몰리브덴 촉매 및 이의 제조 방법
US20140275468A1 (en) * 2013-03-12 2014-09-18 The Procter & Gamble Company Catalysts And Processes For The Production Of Aromatic Compounds From Lignin
CA2928831A1 (fr) * 2013-10-27 2015-04-30 Purdue Research Foundation Procedes de conversion catalytique d'une biomasse, catalyseurs et leurs procedes de fabrication

Also Published As

Publication number Publication date
KR101999567B1 (ko) 2019-10-01
KR20190024288A (ko) 2019-03-08

Similar Documents

Publication Publication Date Title
Zhang et al. Catalytic upgrading of coal pyrolysis volatiles over metal-loaded HZSM-5 catalysts in a fluidized bed reactor
Huang et al. Lignin-first biorefinery: a reusable catalyst for lignin depolymerization and application of lignin oil to jet fuel aromatics and polyurethane feedstock
Shafaghat et al. Catalytic hydrodeoxygenation of simulated phenolic bio-oil to cycloalkanes and aromatic hydrocarbons over bifunctional metal/acid catalysts of Ni/HBeta, Fe/HBeta and NiFe/HBeta
Sirous-Rezaei et al. Catalytic hydropyrolysis of lignin: Suppression of coke formation in mild hydrodeoxygenation of lignin-derived phenolics
Sirous-Rezaei et al. Insight into the effect of metal and support for mild hydrodeoxygenation of lignin-derived phenolics to BTX aromatics
Cheng et al. Upgrading pyrolysis bio-oil through hydrodeoxygenation (HDO) using non-sulfided Fe-Co/SiO2 catalyst
Ma et al. Selective deoxygenation of lignin during catalytic fast pyrolysis
Sirous-Rezaei et al. Mild hydrodeoxygenation of phenolic lignin model compounds over a FeReO x/ZrO 2 catalyst: Zirconia and rhenium oxide as efficient dehydration promoters
Iliopoulou et al. Catalytic upgrading of biomass pyrolysis vapors using transition metal-modified ZSM-5 zeolite
KR101666089B1 (ko) 임의의 올레핀 재순환과 함께 방향족의 생산을 위한 바이오매스 및 탄화수소성 물질의 촉매 열분해를 위한 시스템 및 방법, 및 촉매 열분해를 위해서 선택된 입자 크기를 지니는 촉매
Wang et al. From biomass to advanced bio-fuel by catalytic pyrolysis/hydro-processing: Hydrodeoxygenation of bio-oil derived from biomass catalytic pyrolysis
Kelkar et al. A survey of catalysts for aromatics from fast pyrolysis of biomass
Ju et al. Efficient hydro-deoxygenation of lignin derived phenolic compounds over bifunctional catalysts with optimized acid/metal interactions
JP5662168B2 (ja) 固体バイオマス、ならびに関連するバイオ燃料、芳香族化合物、およびオレフィン化合物の触媒熱分解
Antonakou et al. Evaluation of various types of Al-MCM-41 materials as catalysts in biomass pyrolysis for the production of bio-fuels and chemicals
Wang et al. Hydrodeoxygenation of bio-oil over Pt-based supported catalysts: Importance of mesopores and acidity of the support to compounds with different oxygen contents
US20150174561A1 (en) Catalyst for selective conversion of oxygenates to aromatics
Bertero et al. Equilibrium FCC catalysts to improve liquid products from biomass pyrolysis
KR102233329B1 (ko) 에탄올 및 이소프로판올을 함유하는 혼합물의 탈수 방법
KR101815056B1 (ko) 금속치환 제올라이트를 활용한 정유 및 석유화학 공정에서 병산되는 다환식 방향족 화합물의 고부가 btx 전환 방법
JP2011514927A5 (fr)
Scaldaferri et al. CO cleavage of diphenyl ether followed by CC coupling reactions over hydrophobized Pd/HY catalysts
Ou et al. Structured ZSM-5/SiC foam catalysts for bio-oils upgrading
Arteaga-Pérez et al. In situ catalytic fast pyrolysis of crude and torrefied Eucalyptus globulus using carbon aerogel-supported catalysts
Wei et al. Hierarchical gallium-modified ZSM-5@ SBA-15 for the catalytic pyrolysis of biomass into hydrocarbons

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17923475

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17923475

Country of ref document: EP

Kind code of ref document: A1