WO2019059515A1 - Catalyseur pour la polymérisation d'un composé à base de furane dérivé de biomasse, et procédé de préparation de polymère de composé à base de furane dérivé de biomasse à l'aide de celui-ci - Google Patents

Catalyseur pour la polymérisation d'un composé à base de furane dérivé de biomasse, et procédé de préparation de polymère de composé à base de furane dérivé de biomasse à l'aide de celui-ci Download PDF

Info

Publication number
WO2019059515A1
WO2019059515A1 PCT/KR2018/008707 KR2018008707W WO2019059515A1 WO 2019059515 A1 WO2019059515 A1 WO 2019059515A1 KR 2018008707 W KR2018008707 W KR 2018008707W WO 2019059515 A1 WO2019059515 A1 WO 2019059515A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
group
furan
acid
methylfuran
Prior art date
Application number
PCT/KR2018/008707
Other languages
English (en)
Korean (ko)
Inventor
서정길
니거스 게브레실라스말렛
전형빈
Original Assignee
명지대학교 산학협력단
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
Priority claimed from KR1020170123273A external-priority patent/KR101968762B1/ko
Priority claimed from KR1020180088763A external-priority patent/KR102126004B1/ko
Application filed by 명지대학교 산학협력단 filed Critical 명지대학교 산학협력단
Publication of WO2019059515A1 publication Critical patent/WO2019059515A1/fr

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
    • B01J21/08—Silica
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members

Definitions

  • the present invention relates to a catalyst for polymerizing a furan-based compound derived from biomass and a method for producing a polymer of a biomass-derived furan compound using the same, and more particularly, to a method for producing a biomass-derived furan- And to a method for producing a polymer of a furan-based compound using the novel catalyst.
  • the object of the present invention is also to provide a method for producing a biomass-derived furan-based compound polymer using the catalyst.
  • an embodiment of the present invention provides a catalyst for producing a transportation fuel precursor from a pentane-based furan compound, wherein an acidic functional group is connected to the end of the nanofiber silica.
  • the linking group may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted 2-carbon group having 2 to 20 carbon atoms in which the carbon atom may be substituted with at least one atom selected from O, S, N, A substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, and a substituted or unsubstituted C6-C20 arylene group.
  • the linking group may include a trimethoxysilane group.
  • the pentose may be xylose or arabinose.
  • the furan-based compound may be 2-methylfuran.
  • the present invention also provides a process for producing a transportation fuel precursor comprising contacting the furan-based compound derived from pentane with the catalyst for producing the transportation fuel precursor, and proceeding the hydroxyalkylation and alkylation reaction.
  • the transport fuel precursor may comprise 5,5'-bis (2-methylfuranyl) furan-2-ylmethane.
  • the contact may be carried out at 70 to 90 ⁇ ⁇ , and may be carried out for 0.5 to 2 hours.
  • the acid-containing compound may be at least one selected from chlorosulfonic acid, fluorosulfonic acid, sulfuric acid, and hydrogen peroxide.
  • the present invention also provides a method of preparing a catalyst for producing a transport fuel precursor, further comprising the step of reacting the nanofiber silica with a coupling agent prior to the functionalization step to attach a linker to the surface of the nanofiber silica.
  • the linking group may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted 2-carbon group having 2 to 20 carbon atoms in which the carbon atom may be substituted with at least one atom selected from O, S, N, A substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C3-C20 cycloalkylene group, and a substituted or unsubstituted C6-C20 arylene group.
  • Another embodiment of the present invention provides a catalyst for producing a polymer of a furan-based compound derived from biomass or a derivative thereof, wherein an acidic functional group is connected to the end of the nanofiber silica.
  • the acidic functional group is connected to the end of the nanofiber silica by a linking group, and the linking group includes an ionic liquid.
  • the cation of the ionic liquid is selected from the group consisting of imidazolium, pyridinium, triazolium, thiazolium, piperidinium, pyrrolidinium, ammonium, guanidinium and phosphonium It may be at least one selected.
  • the anion of the ionic liquid may be Br - , Cl - , NO 3 - , SO 4 2- , HSO 4 - , AlCl 3 - , CF 3 COO - , CF 3 SO 2 2- , CF 3 SO 3 - , BF 4 - and PF 6 - .
  • the linking group may be a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted carbonyl group having 1 to 20 carbon atoms in which the carbon atom may be substituted with at least one atom selected from O, S, N, P and Si
  • the acidic functional groups include sulfonic acid, carboxylic acid, phosphoric acid, acetic acid, heteropolyacids, fluoroboric acid and perchloric acid, Lt; / RTI >
  • the furan compound or a derivative thereof may be furan, furfural, 2-methylfuran, furfuryl alcohol, n-butanal, And 2-pentanone.
  • furan furfural, 2-methylfuran, furfuryl alcohol, n-butanal, And 2-pentanone.
  • the polymer may be a transport fuel precursor having a carbon number of 13 or more and may be selected from the group consisting of 5,5-bis (5-methylfuran-2-yl) pentan- Yl) methane, 5,5 '- (butane-1,1-diyl) bis (2-methylpyranyl) (2-methylfuran) (4a) and 6-methyl-6- (5-methylfuran-2-yl) , And 5-dione (4b) tri (furan-2-yl) methane.
  • the furan compound may be 2-methylfuran.
  • the catalyst is preferably used in an amount of 3 to 5% by weight.
  • the present invention also relates to a method for producing a polymer of furan-based compound or derivative thereof, which comprises bringing a furan-based compound derived from biomass or a derivative thereof into contact with the catalyst to carry out a cross-condensation reaction .
  • the furan compound or a derivative thereof may be at least one selected from the group consisting of furan, furfural, 2-methylfuran, furfuryl alcohol, n-butanal ), And 2-pentanone.
  • the contact may be carried out at 55 to 65 ⁇ ⁇ .
  • the present invention also provides a process for preparing a catalyst for producing a polymer of a biomass-derived furan-based compound or derivative thereof, comprising the steps of:
  • the acid-containing compound may be at least one selected from chlorosulfonic acid, fluorosulfonic acid, sulfuric acid, and hydrogen peroxide.
  • the first coupling agent may be (3-mercaptopropyl) trimethoxysilane, (3-aminopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, trimethoxyphenylsilane, trimethoxy (phenylethyl) silane, triethoxyphenylsilane (triethoxyphenylsilane) ), (3-chloropropyl) trimethoxysilane, (chloromethyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane ((3 chloromethyl phenylethyl trimethoxysilane, (4-chlorophenyl) triethoxysilane and 2- (4-pyridyl) trimethoxysilane. Ethyl) triethoxysilane (2- (4-pyridylethy
  • the catalyst for producing a transportation fuel precursor according to the present invention does not use a strong acid such as sulfuric acid, a complicated process for separation and recovery of residual strong acid is not required and it is environmentally friendly.
  • a strong acid such as sulfuric acid
  • the surface area of the catalyst is very wide, it exhibits an excellent conversion ratio, high selectivity of the desired product, and excellent cycle characteristics of the catalyst.
  • an ionic liquid as a linking agent, the acid strength and the degree of hydrophobicity of the terminal acidic functional groups are further strengthened, thereby achieving a higher yield and conversion rate.
  • Figure 3 shows the reaction to produce a transport fuel precursor by a hydroxyalkylation / alkylation reaction and a self-condensation reaction.
  • Figure 4 shows a production flow diagram of a nanofiber silica catalyst according to another embodiment of the present invention.
  • Figure 5 shows a flow chart of the production of a nanofiber silica catalyst according to another embodiment of the present invention.
  • Figure 6 shows the kind of catalyst of another embodiment of the present invention which can be produced according to the kind of the first coupling agent, the ionic liquid, the second coupling agent and the acid-containing compound.
  • FE-SEM field emission scanning electron microscope
  • FT-IR Fourier transform infrared spectroscopy
  • Figure 11 shows N 2 adsorption-desorption isotherms (a) and pore size distributions (b) of nanofiber silica and sulfonic acid-functionalized nanofiber silica according to one embodiment of the present invention.
  • Figure 13 (c) shows the HPLC results for the liquid product of the hydroxy alkylation / alkylation reaction with KCC-1 SO 3 H catalyst.
  • Figure 14 shows the conversion and selectivity of the hydroxyalkylation / alkylation reactions according to various catalyst types.
  • Figure 18 (e) shows the HPLC results for the liquid product of the self-condensation reaction of 2-methylfuran.
  • Figure 19 shows the conversion and selectivity of the self-condensation reaction of 2-methylfuran according to various catalyst types.
  • FE-SEM field emission scanning electron microscope
  • FT-IR Fourier transform infrared spectroscopy
  • thermogravimetric analysis graph of a nanofiber silica catalyst according to an embodiment of the present invention.
  • 29 shows the conversion and selectivity of the nanofiber silica catalyst according to an embodiment of the present invention, depending on the reaction temperature.
  • the biomass mainly refers to a pentane compound
  • pentane refers to a compound having five carbon atoms contained in the biomass, preferably xylose or arabionose ), And most preferably xylose.
  • the furan-based compounds or derivatives thereof may be used in the group consisting of furan, furfural, 2-methylfuran, furfuryl alcohol, n-butanal and 2-pentanone , Preferably 2-methylfuran, or 2-methylfuran and a furfural.
  • the furan-based compound is polymerized by the catalyst of the present invention to form a polymer, and the polymer formed may be a precursor of a transport fuel having a carbon number of 13 or more.
  • the transport fuel precursor may preferably be a precursor of diesel fuel and is preferably a polymer having a carbon number of at least 13.
  • nanofiber silica means a nanoparticle in which fiber-form silica is covalently bonded to each other by a siloxane linker and arranged in a radial alignment to form a spherical shape.
  • the nanofiber silica described in U.S. Patent No. 8,883,308 Lt; RTI ID 0.0 > nanoparticles. ≪ / RTI >
  • catalysts produced by linking acidic functional groups to the ends of nanofiber silica can be applied to processes for producing transport fuels, particularly diesel fuel precursors, from biomass, especially xylose.
  • the acidic functional groups that can be connected to the ends of the nanofiber silica include sulfonic acid, carboxylic acid, phosphoric acid, acetic acid, heteropolyacids, fluoroboric acid, Perchloric acid and salts thereof, with sulfonic acid functional groups being most preferred.
  • the acidic functional group may be directly connected to the end of the nanofiber silica or may be connected by a linking group.
  • the catalyst of the present invention may have a structure such as [nanofiber silica] - [trimethoxysilane] - [alkylene] - [acidic functional group].
  • the trimethoxysilane can be connected to the three terminal OH groups of the nanofiber silacer.
  • fibrous silica retains a radially aligned spherical shape even when an acidic or alkyl-acidic functional group is attached to the nanofiber silica, and furthermore, the same morphology can be maintained after regeneration of the catalyst .
  • FIG. 1 An exemplary method of making a catalyst for producing a transport fuel precursor according to the present invention is illustrated in FIG.
  • a nanofiber silica catalyst to which an acidic functional group is linked can be prepared by reacting nanofiber silica and an acid-containing compound, and functionalizing the terminal group of the nanofiber silica with an acidic functional group.
  • the acid-containing compound may be selected from, for example, halogenated acids such as chlorosulfonic acid and fluorosulfonic acid, sulfuric acid, hydrogen peroxide, and the like.
  • nanofiber silica is dispersed in a dichloromethane solvent, and chlorosulfonic acid is added and stirred to obtain a sulfonic acid- Silica catalyst can be prepared.
  • the resulting sulfonic acid-functionalized nanofiber silica can be linked in such a way that one -SO 3 H group is attached to the three terminal OH groups of the nanofiber silica.
  • the coupling agent may be selected from the group consisting of 3-chloropropanol, sodium phenolate, (3-mercaptopropyl) trimethoxysilane, (3-aminopropyl) trimethoxy (3-aminopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, 1,3-propane sultone, 1,4-butane sultone
  • 1,4-butane sultone trimethoxyphenylsilane, trimethoxy (phenylethyl) silane, triethoxyphenylsilane, and the like.
  • the nanofiber silica catalyst having an acidic functional group according to the present invention has excellent cycle characteristics. In one embodiment of the present invention, it was confirmed that the catalyst after four cycles not only retained the same structural characteristics, but still exhibited excellent conversion and selectivity. Such a cyclic characteristic is a property that can not be achieved with conventional homogeneous catalysts.
  • the pentose is xylose or arabionose, preferably xylose.
  • the furan-based compound derived from pentane may be selected from the group consisting of furfural, 2-methylfuran and furfuryl alcohol, preferably 2-methylfuran, or 2-methylfuran and furfuralyl have.
  • the transport fuel precursor may preferably be a precursor of a diesel fuel and is preferably a polymer having a carbon number of at least 15.
  • the 2-methylfuran may form a trimer or a tetramer by self-condensation reaction to produce a precursor compound having a carbon number of 15 or more.
  • the precursor compound having a carbon number of 15 or more may be 2, (1a) and 5,5-bis (5-methylfuran-2-yl) pentan-2-one (1b) in the presence of 4,4-tris (5-methylfuran- But is not limited thereto.
  • the first step in the trimerization of 2-methylfuran is ring-opening by hydrolysis between 2-methylfuran and H 2 O. Water can act as a promoter and inhibit the formation of tetramers.
  • the ring-opened 2-methylfuran forms the aldehyde intermediate 4-Oxopentanal.
  • One mole of the intermediate aldehyde can form a C15 trimer by hydroxy alkylation / alkylation with 2 moles of the remaining 2-methylfuran.
  • the self-condensation reaction of 2-methylfuran is preferably carried out at 80 to 90 ° C.
  • the conversion of 2-methylfuran and the selectivity to the 1a compound increase with increasing reaction time. Therefore, in order to obtain a sufficient conversion and selectivity, it is preferable to carry out the self-condensation reaction for 24 hours or more, preferably 48 hours or more.
  • the self-condensation reaction of 2-methylfuran when carried out using a sulfonic acid-functionalized nanofiber silica catalyst, it exhibits 50-60% 2-methylfuran conversion and 75% 1a selectivity.
  • the selectivity to the compound 1a was about 100% in the case of the catalyst in which the sulfonic acid functional group was directly bonded to the nanofiber silica.
  • the catalysts of the present invention may also be used to produce precursor compounds with a carbon number of 15 or greater by hydroxy alkylation / alkylation reactions of 2-methylfuran and furfural.
  • the precursor compounds having 15 or more carbon atoms that can be produced by the hydroxyalkylation / alkylation reaction include but are not limited to 5,5'-bis (2-methylfuranyl) furan-2-ylmethane (2a).
  • the hydroxyalkylation / alkylation reaction of 2-methylfuran and furfural is typically as illustrated in FIG.
  • the catalyst of the present invention serves to accelerate the reaction by providing hydrogen to the polymerization reaction by hydroxyalkylation of 2-methylfuran and furfural, and further, But also acts as a reaction catalyst for providing hydrogen even in the alkylation reaction of the intermediate product and 2-methylfuran.
  • the catalyst of the present invention is preferably added in an amount of 1 to 10 mol%, more preferably 3 to 7 mol%, based on the total reactants.
  • 2-methylfuran and furfural be used in a molar ratio of about 2: 1, since in the hydroxyalkylation / alkylation reaction, 1 mole of the furfural is used relative to 2 moles of 2-methylfuran.
  • the hydroxyalkylation / alkylation reaction is preferably carried out for 0.5 to 2 hours. If the reaction time exceeds 2 hours, a product other than the desired product may be generated, resulting in a problem that the selectivity of the desired product is lowered.
  • the hydroxyalkylation / alkylation reaction is preferably carried out at 70 to 90 DEG C in order to obtain high conversion and selectivity.
  • the hydroxy alkylation / alkylation reaction of 2-methylfuran and furfural using a sulfonic acid-functionalized nanofiber silica catalyst leads to a conversion of 2-methylfuran to greater than 70% It was confirmed that the alkyl-sulfonic acid functionalized catalyst exhibited a conversion of 2-methylfuran of at least 80%.
  • the conversion of furfural is about 79% in the case of the sulfonic acid-functionalized catalyst and 90% or more in the case of the catalyst in which the alkyl chain is connected.
  • the catalyst in which the S and O atoms are substituted in the alkyl chain It was confirmed that it exhibited a perforal conversion of 98% or more.
  • C15 precursor compounds such as 2,4,4-tris (5-methylfuran-2-yl) pentan-1-ol (1a) and 5,5'- 2-methylfuranyl) furan-2-ylmethane (2a) can be converted to a transport fuel such as diesel fuel via processes known in the fuel production art.
  • preferred products 1a and 2a are exemplary compounds and may be a polymer having 15 or more carbon atoms having different functional groups within a predictable range according to the functional groups of the furan-based compound as the starting material.
  • the connector preferably comprises an ionic liquid.
  • ionic liquid refers to a substance in which a cation and an anion exist in a liquid state due to the asymmetry of their size due to the asymmetry of the size thereof. Lt; / RTI > Generally, an ionic liquid means a molten salt composed of an organic cation having a ring structure containing nitrogen and a smaller-sized inorganic anion.
  • the ionic liquid is applied as a linking group between the nanofiber silica and the terminal functional group, thereby not only enhancing the acid strength of the terminal acidic functional group but also imparting hydrophobicity to the catalyst. This can solve the problem that nanofiber silica is not applicable to hydrophobic solvents because it is hydrophilic.
  • the cation of the ionic liquid is at least one selected from the group consisting of imidazolium, pyridinium, triazolium, thiazolium, piperidinium, pyrrolidinium, ammonium, guanidinium and phosphonium And imidazolium or pyridinium is preferred.
  • the anion of the ionic liquid is Br -, Cl -, NO 3 -, SO 4 2-, HSO 4 -, AlCl 3 -, CF 3 COO -, CF 3 SO 2 2-, CF 3 SO 3 -, BF 4 - , PF 6 -, and the like can be applied.
  • the linking group may further include, in addition to the ionic liquid, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, and a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.
  • the carbon atom may be substituted with at least one atom selected from O, S, N, P and Si, and the 'substitution' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano group, , A nitro group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, An alkoxy group and an oxy group.
  • the catalyst of the present invention may have a structure such as [nanofiber silica] - [first connector] - [ionic liquid] - [second connector] - [acidic functional group].
  • the nanofiber silica catalyst can maintain a spherical shape in which the fibrous silica is radially aligned even if an acidic or alkyl-acidic functional group is attached to the end, and the same morphology can be maintained even after regeneration of the catalyst.
  • cationic compound of an ionic liquid means a compound which can be a cation of the above-mentioned ionic liquid.
  • the cationic compound of the ionic liquid may be imidazol. That is, the cationic compound of the ionic liquid usable in the present invention may be at least one selected from the group consisting of imidazole, pyridine, triazole, thiazole, piperidine, pyrrolidine, ammonia, guanidine and phosphine And imidazole or pyridine is preferred.
  • the production method may be carried out by changing the order of steps (a) to (c). For example, a first coupling agent and a cationic compound of an ionic liquid are first reacted to prepare an ionic liquid to which the first coupler is connected, and then the second coupling agent and the nanofiber silica are reacted, , A compound in which an ionic liquid is connected to the end of the first coupler and a second coupler is connected to the ionic liquid can be produced.
  • (3-mercaptopropyl) trimethoxysilane (3-aminopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, trimethoxyphenylsilane, trimethoxy (phenylethyl) silane, triethoxyphenylsilane, (3-chloropropyl (3-chloropropyl) trimethoxysilane, (chloromethyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane, ( Chloromethyl) phenylethyl trimethoxysilane, (4-chlorophenyl) triethoxysilane, and the like.
  • the polymer of the furan compound may be a transport fuel precursor.
  • the biomass is preferably pentane, and more specifically, it is xylose or arabionose, preferably xylose.
  • Perfurans are the most basic form that can be made from xylose in pentoses derived from biomass, and 2-methylfuran is a derivative of furfural. N-butanol and 2-pentanone are produced as by-products in the production process of 2-methylfuran by hydrogenation of the furfural. In the present invention, it is possible to produce a transportation fuel precursor using such a by- Process.
  • the transport fuel precursor may preferably be a precursor of diesel fuel and is preferably a polymer having a carbon number of at least 13.
  • the polymerization reaction of the furan-based compounds of the present invention can be carried out by (i) a self-condensation reaction of 2-methylfuran, (ii) a cross-condensation reaction of 2-methylfuran and furfural, condensation reaction of 2-methylfuran and n-butanol, (iv) a cross-condensation reaction of 2-methylfuran and 2-pentanone, and (v) a cross-condensation reaction of furfural and furan .
  • 2-methylfuran may form a trimer or a tetramer by self-condensation reaction to produce a precursor compound having a carbon number of 15 or more, and the precursor compound having a carbon number of 15 or more (1a) and 2,4,4-tris (5-methylfuran-2-yl) pentan-1-ol (1b) were reacted with 5,5- But are not limited to:
  • the first step in the trimerization of 2-methylfuran is ring-opening by hydrolysis between 2-methylfuran and H 2 O. Water can act as a promoter and inhibit the formation of tetramers.
  • the ring-opened 2-methylfuran forms the aldehyde intermediate 4-Oxopentanal.
  • One mole of the intermediate aldehyde can form a C15 trimer by hydroxy alkylation / alkylation with 2 moles of the remaining 2-methylfuran.
  • the autocondensation reaction of 2-methylfuran is preferably carried out at 55 to 65 ° C.
  • the catalysts of the present invention can also be used to produce precursor compounds with more than 15 carbon atoms by cross-condensation reaction by hydroxy alkylation / alkylation of 2-methylfuran with furfural.
  • the precursor compounds having 15 or more carbon atoms that can be produced by the hydroxyalkylation / alkylation reaction include 5,5'-bis (2-methylfuranyl) furan-2-ylmethane (2a) Methylfuran-2-yl) pentan-2-one (1a).
  • the catalyst of the present invention can also be used to produce a precursor compound having 14 or more carbon atoms by the cross-condensation reaction of 2-methylfuran and n-butanol as in the reaction (iii) in Fig. (iii) the precursor compounds which can be prepared in the reaction are 5,5 '- (butane-1,1-diyl) bis (2-methylfuran) Yl) pentan-2-one (1a).
  • reaction (iii) it is preferable to use 2-methylfuran and n-butanol in a molar ratio of 2: 1 by stoichiometry.
  • the catalyst of the present invention can also be used to prepare a precursor compound having 15 or more carbon atoms by the cross-condensation reaction of 2-methylfuran and 2-pentanone, as in the reaction (iv) of FIG. (iv)
  • the precursor compounds which can be prepared in the reaction are 5,5 '- (pentane-2,2-diyl) bis (2-methylfuran) (4a) and 6-methyl- -Yl) nonane-2,5-dione (4b).
  • 2-methylfuran and 2-phanthanone are preferably used in a molar ratio of 5: 2.
  • the catalyst of the present invention can also be used to prepare precursor compounds having 13 or more carbon atoms by the cross-condensation reaction of furfural and furan, as in the reaction (v) of Fig.
  • the precursor compound that can be prepared in the reaction (v) is tri (furan-2-yl) methane (5b), and di (furan-2-yl) methanol (5a) can be produced as a byproduct.
  • the furfural and furan are preferably used in a molar ratio of 4: 9.
  • the catalyst of the present invention is preferably added in an amount of 1 to 5% by weight, more preferably 3 to 4% by weight, based on the total amount of the reaction product.
  • the combination of 3 wt% of catalyst showed the best combination of conversion and selectivity, and it was confirmed that as the amount of use increased, the conversion increased but the selectivity decreased.
  • the cross-condensation reaction is preferably performed for 60 to 90 minutes, more preferably 80 to 90 minutes. If the reaction is more than 90 minutes, a product other than the desired product may be produced and the selectivity of the desired product may start to deteriorate.
  • the cross-condensation reaction is preferably performed at 55 to 65 ° C, more preferably 58 to 63 ° C. In one embodiment of the present invention, it was confirmed that the best conversion rate and selectivity for a target material can be exhibited at a reaction temperature of 60 ° C.
  • preferred products 1a and 2a are exemplary compounds and may be a polymer having 13 or more carbon atoms having different functional groups within a predictable range according to the functional groups of the furan-based compound as the starting material.
  • HPLC grade solvents such as dichloromethane, diethyl ether, ethyl acetate, methanol, 1-propanol, cyclohexane and toluene were purchased from Across Organics, USA.
  • Sulfuric acid and hydrochloric acid were purchased from Daejung Chemical (Korea), and chlorosulfonic acid and trifluoromethanesulfonic acid were purchased from Sigma-Aldrich.
  • the solid catalysts Amberlyst-15, Amberlyst-36 and Nafion-212 were purchased from Sigma-Aldrich and cut into 2x5 mm pieces of Nafion film (thickness: 51 ⁇ m) Respectively.
  • the nanofiber silica catalyst was synthesized by a slight modification of known synthetic methods.
  • CTAB tetraethoxysilane
  • urea 0.0038 mol
  • the mixture was stirred at room temperature for 1 hour and then transferred to a 200 mL Teflon line hydrothermal reactor.
  • the reactor was placed in an oven at 120 < 0 > C for 6 hours. After cooling the mixture at room temperature, the silica was separated by centrifugation (30 min, 6,000 rpm).
  • the separated solid was washed with deionized water and ethanol, and then dried at 40 ° C for 12 hours.
  • the synthesized silica catalyst was calcined at 550 ⁇ while ramping at 5 ⁇ for 6 hours in air to prepare a nanofiber silica catalyst (KCC-1).
  • the mixture was maintained at room temperature with further stirring for 1 hour.
  • the formed solid catalyst was collected via filtration and washed with diethyl ether (3 x 20 mL).
  • the obtained solid acid catalyst was dried at room temperature for 12 hours to obtain a sulfonic acid-functionalized nanofiber silica catalyst (KCC-1 SO 3 H).
  • Production Example 3 Production of propylsulfonic acid-functionalized nanofiber silica catalyst
  • KCC-1, KCC-1SO 3 prepared in Example H, KCC-1PSO 3 H and KCC-1APSO 3 H catalyst morphology and particle size of the Helios 650 scanned by the electron microscope, the field emission scanning electron microscope (field emission-scanning electron microscopy (FE-SEM) images were recorded.
  • FE-SEM field emission-scanning electron microscopy
  • the SEM image of KCC-1 exhibits a uniform spherical shape of about 420 nm in size.
  • the object is dendrimeric fibers arranged to form a uniform sphere.
  • FE-TEM field emission transmission electron microscope
  • EDX energy-dispersive X-ray
  • FIG. 9 (a) shows TEM images and element mapping results of the KCC-1 catalyst before use
  • FIG. 9 (b) shows the functionalized KCC-1 catalyst
  • FIG. 9 (c) shows TEM images and element mapping results of the KCC-1 catalyst before use
  • FT-IR Fourier transform infrared spectroscopy
  • KCC KCC-1PSO 3 H and 3 H-1APSO catalyst exhibited a peak at around 600cm -1 contraction vibration of the vibration shrinkage and SC binding at around 2,960cm -1 aliphatic CH bond.
  • the peak at 1,650 cm -1 represents water molecules.
  • the sulfur content (wt%), BET surface area, total pore volume and acid content of the catalysts were measured and are shown in Table 1.
  • Catalyst has been carried out the measurement even for KCC-1, KCC-1SO 3 H, KCC-1PSO 3 H and 3 H in addition to the KCC-1APSO commercial catalyst aembeol list -15, -36 and aembeol list Nafion -212, KCC- 41SO 3 H, MCM-41PSO 3 H and MCM-41APSO 3 H, which have the same sulfonic acid functional groups attached to the porous catalysts MCM-41 and MCM-41, respectively, were directly measured.
  • the content of sulfur element was measured using a Flash EA 1112 elemental analyzer.
  • the H ion concentration of the catalyst was determined by inverse titration analysis of the catalyst.
  • NaOH solution (20 mL, 0.1 M) was added to 100 g of catalyst in an Erlenmeyer flask and the solution was stirred for 30 minutes.
  • HCl solution (0.1 M) was added to the titration point of the titration to neutralize excess base.
  • the surface area and pore size of the functionalized catalysts were lower than those of the non-functionalized catalysts.
  • Thermogravimat analysis was performed to analyze the thermal stability and decomposition pattern of the catalyst.
  • Thermogravimetric analysis was carried out with a TGA N 1000 (SCINCO) thermogravimetric analyzer at 20 ° C ramping in a nitrogen atmosphere at 0 to 800 ° C.
  • the TGA graph of the other three types of functionalized catalysts confirms the incorporation of organic functional groups in the silica lattice.
  • the rapid weight loss before 150 ° C corresponds to the loss of water adsorbed on the surface.
  • the additional mass loss at 150 to 450 ⁇ ⁇ is due to the loss of organic functional groups.
  • Example 2 Fuel precursor synthesis by cross-condensation reaction of 2-methylfuran and furfural
  • HAA Hydroxyalkylation / alkylation reactions
  • 2-methylfuran (2-MF) and furfural (FUR) were carried out using commercially available solid catalysts (Amberlyst-15, Amberlyst-36 and Nafion- was carried out using a toluene sulfonic acid (p-TOSH) - a catalyst, para (KCC-1SO 3 H, KCC -1PSO 3 H, KCC-1APSO 3 H) and homogeneous catalyst synthesized in Preparation example.
  • p-TOSH toluene sulfonic acid
  • P-TOSH and Nafion-212 have high conversion rates (2-MF conversion rates of 83% and 72% and 82% and 97% FUR conversion rates, respectively) (98% and 96%), which is believed to be due to the homogeneity of the P-TOSH catalyst.
  • Amberlyst-15 and Amberlyst-36 also showed activity for this reaction, but Nafion-212 showed higher activity. This seems to be due to the structure of Nafion resin. Amberlyst resin is sulfonic acid-functionalized cross-linked polystyrene, whereas Nafion is tetrafluorosulfonic acid. Therefore, the presence of fluorine increases the activity of SO 3 H group .
  • the reactivity of the commercial catalysts was P-TOSH>Nafion-212>Ambalist-36> Ambalist-15.
  • the catalysts of the present invention are superior to commercial solid catalysts and exhibit high conversion and selectivity similar to those of homogeneous catalysts. This excellent activity is explained by the fact that the large surface area of the catalyst and the properties of the fiber structure amplified the reaction of the reactants and acidic points to the maximum.
  • the order of activity catalysts according to the invention is found to KCC-1APSO 3 H> KCC- 1PSO 3 H> KCC-1SO 3 H.
  • KCC-1SO 3 H When Table 1 and 14 together, it was investigated by the KCC-1SO 3 H that has the highest surface area and acid has the content, KCC-1PSO 3 H and KCC-1APSO 3 H catalyst with a higher activity with the alkyl chain . It is interpreted that the presence of the alkyl chain increases the hydrophobicity and activity. The alkyl chain is known to act so that the sulfonic acid is more soluble in the hydrophobic reactants.
  • KCC-1 APSO 3 H showed the highest activity due to the increased hydrophobicity due to the extended alkyl chain and the synergistic effect of increased acidity due to the electronic effect of additional S and O groups.
  • KCC-1 SO 3 H showed the lowest selectivity. This is because water formed in situ due to its surface wettability and low hydrophobicity causes a hydrolysis reaction with 2-methylfuran resulting in the formation of 1a.
  • MCM-41 had a similar tendency to acidic KCC-1 catalyst. As shown in FIG. 14, the activities of MCM-41 supported catalysts were in the order of MCM-APSO 3 H> MCM-PSO 3 H> MCM-SO 3 H.
  • 2-methylfuran and furfural were used in a molar ratio of 2: 1, and 5 mol% of a catalyst was added thereto, and a hydroxyalkylation / alkylation reaction was carried out at a reaction temperature of 70 ° C.
  • the catalyst in which the alkyl linker was present between the silica and the -SO 3 H group showed a higher conversion of 2-methylfuran and furfural in a shorter time. From this, it can be seen that the alkyl group enhances the activity of the catalyst.
  • 2-methylfuran and furfural were used in a molar ratio of 2: 1, and the catalyst was added in an amount of 5 mol% to carry out the hydroxyalkylation / alkylation reaction for 2 hours.
  • the self-condensation reaction of 2-methylfuran (2-MF) was carried out using commercially available solid catalysts (Amberlyst-15, Amberlyst-36 and Nafion-212) It was performed using a (KCC-1SO 3 H, KCC -1PSO 3 H and KCC-1APSO 3 H).
  • MCM-41 catalysts exhibited relatively low conversion, presumably because these catalysts have low solubility for the hydrophobic reactants.
  • CTAB tetraethoxysilane
  • urea 0.0038 mol
  • the mixture was stirred at room temperature for 1 hour, then transferred to a 250 mL round bottom flask and refluxed at 100 < 0 > C for 1 hour.
  • the mixture was then transferred to a 200 mL hydrothermal reactor made of Teflon and reacted at 120 ° C for 6 hours. After cooling the mixture at room temperature, the silica was separated by centrifugation (30 min, 6,000 rpm).
  • the separated solid was washed with deionized water and ethanol, and then dried at 40 ° C for 12 hours.
  • the synthesized silica catalyst was calcined at 550 ⁇ while ramping at 5 ⁇ for 6 hours in air to prepare a nanofiber silica catalyst (KCC-1).
  • KCC-1 means KCC-1 produced in Production Example 5.
  • 1,3-Propanesultone (0.02 mol, 2.44 g) was then added to 3- (3-trimethoxysilylpropyl) -imidazole and stirred under N 2 for 24 hours. After 24 hours, KCC-1 (1.0 g) was added and stirred for 24 hours. After cooling, the mixture was filtered, and the obtained solid was dried at 110 DEG C for 4 hours.
  • the dried solid was added to a solution of ethanol (10 ml) containing H 2 SO 4 (98%, 0.02 mol) and stirred for 10 hours. Washed three times with ethanol and water, filtered, and dried at 100 ° C to obtain a sulfonic acid-functionalized ionic liquid immobilized nanofiber silica catalyst (KCC-1ILHSO 4 ).
  • a trifluoromethanesulfonic acid-functionalized ionic liquid immobilized nanofiber silica catalyst was prepared according to the procedure described in FIG.
  • KCC-1 (1.0 g) was suspended in toluene (10 ml), and then (3-chloropropyl) trimethoxysilane (0.005 mol, 1.0 g) was added to a 100 ml round bottom flask equipped with a reflux condenser and a gas- Min and stirred at the same time. The mixture was refluxed for 72 hours. The particles were washed with ethanol and water, filtered and dried under vacuum to give chloropropyl-KCC-1.
  • the cooled chloropropyl-KCC-1 was stirred with toluene (10 ml) to which imidazole (0.005 mol, 0.34 g) had been added and the mixture was stirred in a 100 ml round bottom flask equipped with a reflux condenser and a gas injection valve for 24 hours under N 2 gas condition Lt; / RTI > A few drops of triethylamine were added 15 minutes before the reaction was terminated. Washed with acetic acid ether, filtered and dried at 100 < 0 > C to give a solid mixture.
  • the obtained powder was mixed with acetonitrile (10 ml). Trifluorosulfonic acid (0.005 mol, 0.8 g) was slowly dropped while stirring the mixture in an ice bath. The mixture was then cooled to room temperature and stirred for 12 hours. The mixture was washed with water until the pH of the mixture became neutral, filtered, and then dried at 100 ° C. to prepare a trifluoromethanesulfonic acid-functionalized ionic liquid immobilized nanofiber silica catalyst (KCC-1ILCF 3 SO 3 ).
  • the morphology and particle size of the KCC-1, KCC-1ILHSO 4 and KCC-1ILCF 3 SO 3 catalysts prepared in Preparation Examples 5 to 7 were measured using a Helios 650 scanning electron microscope using a field emission-scanning electron microscopy (FE-SEM) images were recorded.
  • FE-SEM field emission-scanning electron microscopy
  • FIG. 22 (a) it can be seen that the SEM image of KCC-1 exhibits a uniform spherical shape with a size of about 750 nm.
  • FIG. 18 (b) it can be seen that the object is dendrimeric fibers arranged to form a uniform sphere.
  • the BET specific surface areas of the catalysts prepared in Production Examples 5 to 7 were measured by N- 2 adsorption-desorption curves at 77K using BELSORP-mini (Bel Japan Inc, Japan) . Preheating pretreatment was carried out in vacuo at 100 ° C for 4 hours to remove physically adsorbed water and impurities.
  • BET Brunauer-Emmett-Teller
  • BJH Barrett-Joyner-Halenda
  • the FT-IR spectra of KCC-1 and KCC-1ILHSO 4 and the FT-IR spectra of KCC-1ILCF 3 SO 3 are shown in FIGS. 24 (a) and 24 (b), respectively.
  • FT-IR Fourier transform infrared spectroscopy
  • Thermogravimat analysis was performed to analyze the thermal stability and decomposition pattern of the catalyst.
  • the TGA graph of the other two types of functionalized catalysts confirms the incorporation of organic functional groups in the silica lattice.
  • the rapid weight loss before 150 ° C corresponds to the loss of water adsorbed on the surface.
  • the additional mass loss at 150 to 450 ⁇ ⁇ is due to the loss of organic functional groups.
  • Example 10 Fuel precursor synthesis by cross-condensation reaction of 2-methylfuran and furfural
  • HAA Hydroxyalkylation / alkylation reactions
  • 2-methylfuran (2-MF) and furfural (FUR) were carried out using commercially available solid catalysts (Amberlyst-15, Amberlyst-36 and Nafion- (KCC-1ILHSO 4 , KCC-1ILCF 3 SO 3 ) synthesized in Production Example and para-toluene sulfonic acid (p-TOSH) as a homogeneous catalyst.
  • P-TOSH and Nafion-212 had a high conversion (78% and 67% 2-MF conversion; and 73% and 76% FUR conversion respectively) (96% and 90%), which is believed to be due to the homogeneity of the P-TOSH catalyst.
  • Amberlyst-15 and Amberlyst-36 also showed activity for this reaction, but Nafion-212 showed higher activity. This seems to be due to the structure of Nafion resin. Amberlyst resin is sulfonic acid-functionalized cross-linked polystyrene, whereas Nafion is tetrafluorosulfonic acid. Therefore, the presence of fluorine increases the activity of SO 3 H group .
  • the reactivity of the commercial catalysts was P-TOSH>Nafion-212>Ambalist-36> Ambalist-15.
  • Example 11 Conversion and selectivity analysis according to reaction time with and without ionic liquid
  • the nanofiber silica catalyst containing the ionic liquid according to the present invention exhibited remarkably excellent conversion and 2a selectivity compared to the nanofiber silica catalyst without ionic liquid.
  • Example 12 Catalytic activity analysis over time
  • Example 13 Catalytic activity analysis according to reaction temperature
  • 2-methylfuran and furfural were used in a molar ratio of 2: 1, and the catalyst was added in an amount of 3 wt% to carry out the hydroxyalkylation / alkylation reaction for 80 minutes.
  • the catalyst was washed three times with methanol after filtration and dried in vacuo at 80 ° C for 8 hours.
  • 2-methylfuran and furfural were used in a molar ratio of 2: 1, and 3 wt% of the catalyst was reacted at 60 DEG C for 80 minutes.
  • the catalyst of the present invention maintained the highest conversion and selectivity up to four cycles, and maintained the highest conversion and selectivity within the error range in five cycles. That is, it can be seen that the catalyst of the present invention has excellent cycle characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne : un nouveau catalyseur de préparation d'un précurseur de carburant de transport à partir d'un composé à base de furane dérivé de biomasse; et un procédé de préparation d'un polymère d'un composé à base de furane à l'aide de celui-ci. Le catalyseur de préparation d'un précurseur de carburant de transport, selon la présente invention, n'utilise pas un acide fort tel que l'acide sulfurique, et ne nécessite donc pas de processus complexe pour la séparation et la récupération d'acide fort restant et est respectueux de l'environnement. De plus, le catalyseur a une surface très large, ayant ainsi un excellent taux de conversion, a une sélectivité élevée pour un produit souhaité et a d'excellentes caractéristiques de cycle. En outre, étant donné que la force acide d'un groupe fonctionnel acide terminal et le degré d'hydrophobicité sont encore renforcés à l'aide d'un liquide ionique en tant que groupe de liaison, un rendement et un taux de conversion plus excellents peuvent être présentés.
PCT/KR2018/008707 2017-09-25 2018-07-31 Catalyseur pour la polymérisation d'un composé à base de furane dérivé de biomasse, et procédé de préparation de polymère de composé à base de furane dérivé de biomasse à l'aide de celui-ci WO2019059515A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0123273 2017-09-25
KR1020170123273A KR101968762B1 (ko) 2017-09-25 2017-09-25 수송연료 전구체 제조용 촉매 및 이를 이용한 수송연료 전구체의 제조방법
KR1020180088763A KR102126004B1 (ko) 2018-07-30 2018-07-30 바이오매스 유래 퓨란계 화합물의 중합용 촉매 및 이를 이용한 바이오매스 유래 퓨란계 화합물의 중합체 제조방법
KR10-2018-0088763 2018-07-30

Publications (1)

Publication Number Publication Date
WO2019059515A1 true WO2019059515A1 (fr) 2019-03-28

Family

ID=65809683

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/008707 WO2019059515A1 (fr) 2017-09-25 2018-07-31 Catalyseur pour la polymérisation d'un composé à base de furane dérivé de biomasse, et procédé de préparation de polymère de composé à base de furane dérivé de biomasse à l'aide de celui-ci

Country Status (1)

Country Link
WO (1) WO2019059515A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110041953A (zh) * 2019-04-29 2019-07-23 南开大学 一种利用生物质制备液态燃料的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8883308B2 (en) * 2010-03-02 2014-11-11 King Abdullah University Of Science And Technology High surface area fibrous silica nanoparticles
KR101777735B1 (ko) * 2016-03-28 2017-09-12 한국과학기술연구원 5탄당 유래 퓨란계 화합물 및 6탄당 유래 퓨란계 화합물의 중합체 제조용 촉매 및 이를 이용한 중합체 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8883308B2 (en) * 2010-03-02 2014-11-11 King Abdullah University Of Science And Technology High surface area fibrous silica nanoparticles
KR101777735B1 (ko) * 2016-03-28 2017-09-12 한국과학기술연구원 5탄당 유래 퓨란계 화합물 및 6탄당 유래 퓨란계 화합물의 중합체 제조용 촉매 및 이를 이용한 중합체 제조방법

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ABOELHASSAN, M. M.: "Sulfonic acid functionalized silica nanoparticles as catalysts for the esterification of linoleic acid", NEW JOURNAL OF CHEMISTRY, vol. 41, no. 9, 3 April 2017 (2017-04-03), pages 1 - 36, XP055584463 *
BALAKRISHNAN, M.: "Syntheses of biodiesel precursors: sulfonic acid catalysts for condensation of biomass-derived platform molecules", CHEMSUSCHEM, vol. 7, 2014, pages 1078 - 1085, XP055584460 *
CHERMAHINI, A. N. ET AL.: "Production of 5-hydroxymethylfurfural from fructose using a spherically fibrous KCC-1 silica catalyst", RSC ADVANCES, vol. 40, no. 6, 22 March 2016 (2016-03-22), pages 1 - 21, XP055584459 *
GEBRESILLASE, M. N.: "Sulfonic acid functionalized fibrous nano-silica (KCC-1) catalysts for the condensation of furanic p latform molecules to diesel precursors", THEORIES AND APPLICATIONS OF CHEMICAL ENGINEERING, vol. 23, no. 2, 25 October 2017 (2017-10-25), pages 2231, XP055584467 *
GEBRESILLASE, M. N.: "Sulfonic acid functionalized silica-supported catalysts for the condensation of furanic platform molecules to fuel precursors", 3RD GREEN & SUSTAINABLE CHEMSTRY CONFERENCE, 13 May 2018 (2018-05-13), Berlin, Germany, pages 1.11 *
YATI, I.: "Water-promoted selective heterogeneous catalytic trimerization of xylose-derived 2-methylfuran to diesel precursors", APPLIED CATALYSIS A: GENERAL, vol. 495, 2015, pages 200 - 205, XP029124244, DOI: doi:10.1016/j.apcata.2015.02.002 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110041953A (zh) * 2019-04-29 2019-07-23 南开大学 一种利用生物质制备液态燃料的方法

Similar Documents

Publication Publication Date Title
WO2010041909A2 (fr) Polymère et son procédé de préparation
WO2014171755A1 (fr) Dérivé de fullerène, cellule solaire organique l'utilisant, et procédé de fabrication associé
WO2016089153A1 (fr) Membrane électrolytique polymère
WO2016032299A1 (fr) Procédé de préparation de polyimide au moyen d'un sel monomère
WO2009142434A2 (fr) Fibre creuse, composition de solution de dopage pour former une fibre creuse et procédé de fabrication d'une fibre creuse au moyen d'une telle composition
WO2017155311A1 (fr) Procédé de fabrication d'un matelas d'aérogel, et matelas d'aérogel ainsi fabriqué
WO2018236100A1 (fr) Cellule solaire organique
WO2013169024A1 (fr) Solvant de substitution de solvant utilisé dans une fabrication d'aérogel et procédé de fabrication d'aérogel rendu hydrophobe l'utilisant
WO2018034549A1 (fr) Composition catalytique pour la préparation d'un composé de type polycétone, système catalytique mixte à base de palladium, procédé de préparation d'un composé de type polycétone l'utilisant et polymère de polycétone
WO2019004781A1 (fr) Cellule solaire en pérovskite
WO2019059515A1 (fr) Catalyseur pour la polymérisation d'un composé à base de furane dérivé de biomasse, et procédé de préparation de polymère de composé à base de furane dérivé de biomasse à l'aide de celui-ci
WO2017179900A1 (fr) Fibre de graphène et son procédé de fabrication
WO2017171290A1 (fr) Polymère séquencé et membrane électrolytique polymère le comprenant
WO2021075874A1 (fr) Matériau actif d'électrode positive et son procédé de préparation
WO2019083235A1 (fr) Composé hétérocyclique et dispositif électronique organique le comprenant
WO2016175573A2 (fr) Composé et cellule solaire organique le comprenant
WO2021054771A1 (fr) Résine contenant du phosphore à extrémité coiffée d'un groupe insaturé, son procédé de préparation et composition de résine comprenant une résine contenant du phosphore à extrémité coiffée d'un groupe insaturé
WO2023243995A1 (fr) Pastille pour dispositif électroluminescent organique et dispositif électroluminescent organique l'utilisant
WO2015119436A1 (fr) Dérivé de fullerène, cellule solaire organique l'utilisant, et procédé de fabrication associé
WO2015072692A1 (fr) Copolymère poly(benzoxazole-imide) thermiquement réarrangé ayant une structure réticulée, membrane de séparation de gaz le comprenant et son procédé de préparation
WO2019125052A1 (fr) Composition d'aérogel et son procédé de préparation
WO2019172571A1 (fr) Procédé de fabrication de cellule solaire organique et cellule solaire organique fabriquée à l'aide de celui-ci
WO2019098771A1 (fr) Polymère et séparateur polymère le comprenant
WO2021177632A1 (fr) Nouveau composé et dispositif électroluminescent organique l'utilisant
WO2019066338A1 (fr) Composition de revêtement, diode électroluminescente organique l'utilisant et son procédé de préparation

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: 18858049

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: 18858049

Country of ref document: EP

Kind code of ref document: A1