KR101726502B1 - Method for forming furfural - Google Patents

Method for forming furfural Download PDF

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KR101726502B1
KR101726502B1 KR1020150093130A KR20150093130A KR101726502B1 KR 101726502 B1 KR101726502 B1 KR 101726502B1 KR 1020150093130 A KR1020150093130 A KR 1020150093130A KR 20150093130 A KR20150093130 A KR 20150093130A KR 101726502 B1 KR101726502 B1 KR 101726502B1
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furfural
ion
yield
alginic acid
iii
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KR1020150093130A
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KR20170003028A (en
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김도희
전원진
반충현
박건우
우희철
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서울대학교산학협력단
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    • 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
    • C07D307/38—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 with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • 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

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

Abstract

A furfural formation process is provided. The furfural forming method includes a step of hydrothermal treatment by mixing an alginic acid compound and a metal ion. Furfural can be selectively formed from the alginic acid compound by a simple process.

Description

METHOD FOR FORMING FURFURAL [0002]

The present invention relates to a furfural forming method, and more particularly, to a method for forming furfural from an alginate compound through hydrothermal treatment using a metal ion catalyst.

Furfural is an important regenerative and non-petroleum derived chemical used in the production of high value-added chemicals such as fuels. This useful furfural can be used in a wide range of applications such as plastics, pesticides, pharmaceuticals, perfumes and fuel additives. Despite a wide range of applications, there is no known synthetic method that can be used to produce furfural except for the conversion of woody fiber biomass.

In order to solve the above problems, the present invention provides a method of forming furfural.

The present invention provides a method for selectively forming furfural from alginic acid compounds.

The present invention provides a method of forming furfural by a simple process.

Other objects of the present invention will become apparent from the following detailed description and the accompanying drawings.

The furfural forming method according to the embodiments of the present invention includes a step of hydrothermal treatment by mixing an alginic acid compound and a metal ion.

The alginic acid compound may include at least one of alginic acid and alginate.

The metal ion may include a transition metal ion. The transition metal ion may include at least one of Cu (II) ion and Fe (III) ion. The metal ion may include at least one of Cu (II) ion, Fe (III) ion, and Pb (II) ion.

The metal ion may be a Cu (II) ion and the concentration of the Cu (II) ion may be 0.005 to 0.02 M.

The temperature of the hydrothermal treatment may be 160 to 220 ° C.

The electronegativity of the metal ion may be 1.5 to 1.91.

According to the embodiments of the present invention, furfural can be selectively formed from an alginic acid compound by a simple process, and the productivity of furfural can be improved.

Figure 1 schematically depicts a furfural shaped process according to one embodiment of the present invention.
Figure 2 shows the catalytic performance of metal ions to convert alginic acid to furfural.
Figure 3 shows the relationship between the electronegativity of metal ions and the yield of furfural.
Figure 4 shows the relationship between the ionic radius of metal ions and the yield of furfural.
Figure 5 shows the relationship between furfural yield and formic acid yield.
Figure 6 shows the relationship between reaction time and reaction temperature and yield of furfural.
Figure 7 shows the relationship between the concentration of Cu (II) ion catalyst and the yield of furfural.
FIG. 8 shows the results of GPC analysis of the liquid product according to the Cu (II) ion catalyst and the Y (III) ion catalyst.

Hereinafter, the present invention will be described in detail with reference to examples. The objects, features and advantages of the present invention will be easily understood by the following embodiments. The present invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments disclosed herein are provided so that the disclosure may be thorough and complete, and that those skilled in the art will be able to convey the spirit of the invention to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

The furfural forming method according to embodiments of the present invention may include a step of hydrothermal treatment by mixing an alginic acid compound and a metal ion.

The alginic acid compound may include at least one of alginic acid and alginate.

The metal ion may include a transition metal ion. The transition metal ion may include at least one of Cu (II) ion and Fe (III) ion. The metal ion may include at least one of Cu (II) ion, Fe (III) ion, and Pb (II) ion. The metal ions may be mixed in the form of metal nitrate compounds. For example, the metal nitrate compound may include Cu (NO 3 ) 2 .3H 2 O, Fe (NO 3 ) 3 .9H 2 O, Pb (NO 3 ) 2 and the like.

The metal ion may be a Cu (II) ion and the concentration of the Cu (II) ion may be 0.005 to 0.02 M. Preferably, the concentration of the Cu (II) ion may be 0.01M. The temperature of the hydrothermal treatment may be 160 to 220 ° C. Preferably, the temperature of the hydrothermal treatment may be 200 ° C.

The electronegativity of the metal ion may be 1.5 to 1.91.

Figure 1 schematically depicts a furfural shaped process according to one embodiment of the present invention. In FIG. 1, a process of forming furfural from alginic acid is shown, but not limited thereto. Furfural can be formed from an alginate compound such as alginate, for example, alginate.

Referring to FIG. 1, the alginic acid monomer has a carboxyl group and provides Bronsted acid (H + ) in an aqueous reaction medium. The acidic reaction medium can function as an acidic catalyst in the conversion of alginic acid to furfural and can promote hydrolysis and dehydration. In the hydrothermal conversion of xylose to furfural, Bronsted acid can enhance the productivity of furfural by promoting dehydration of xylose. Removal of the carboxyl group is necessary to form furfural from alginic acid. The reaction pathway for the catalytic conversion of alginic acid to furfural involves decarboxylation and dehydration. As the carbon bonds at the C-1 and C-2 positions of the monomers are decomposed, the decarboxylation proceeds. For this purpose, it is necessary to form a carbonyl group by dehydroxylation of the hydroxyl group at the C-2 position. The carbonyl group may be formed by keto-enol tautomerization. The metal ion can function as a catalyst to promote ketoene glycol isomerization under hydrothermal conditions. In the hydrothermal reaction of alginic acid, Cu (II) ions promote the tautomerization and induce the formation of carbonyl groups at the C-2 position. After the dicarboxylation, the intermediate is transformed into a ring compound, and furfural is formed by sequential dehydration of the ring compound. In the conversion of alginic acid to furfural, the tautomerization promoted by the metal ions is a critical reaction step that affects the yield of furfural. Based on the correlation between the electronegativity and the furfural yield, a high electronegativity is advantageous to ketoenol isomerization since the electrons of the oxygen atom can be easily attracted to the negative metal ion.

Figure 2 shows the catalytic performance of metal ions to convert alginic acid to furfural. Figure 2 shows the metal ions used as catalyst and the furfural yields for each metal ion in the hydrothermal conversion of alginic acid to furfural for 30 minutes at 200 < 0 > C.

Referring to FIG. 2, the Cu (II) ion catalyst showed the highest furfural yield (13.19%) and was more than twice as high as that of a blank test without metal ions. The yield of furfural was higher when Cu (II), Fe (III), and Pb (II) ions were used than the furfural yield of the control experiment. II) showed no significant difference in the furfural yield. Y (III) showed the lowest furfural yield of 2.5%. Generally, xylose obtained by hydrolysis of hemicellulose forms furfural by sequential dehydration in the hydrothermal conversion of hemicellulose. On the other hand, glucose, which is a monomer of cellulose, has a tendency to be converted to hydroxymethylfurfural (HMF) rather than furfural because it has more alcohol functional groups than xylose. Likewise, to form furfural from alginic acid, the cariolic groups of mannuronic acid and guluronic acid must be removed. That is, dicarboxylation and dehydration are important for the conversion of alginic acid to furfural, which is influenced by metal ions.

FIG. 3 shows the relationship between the electronegativity of metal ions and the yield of furfural, and FIG. 4 shows the relationship between the ion radius of metal ions and the yield of furfural. FIG. 3 and FIG. 4 show the furfural yield when hydrothermal reaction was performed using metal ions for 30 minutes at 200.degree.

Referring to FIG. 3, the furfural yields were found to be proportional to the electronegativity using a transition metal and a post-transition metal. Since the negative metal ions attract electrons to themselves and promote electron transfer in the reaction, the negative metal ions can function as a Lewis acid catalyst in the conversion of the alginic acid to hydrothermal water. Lewis acid plays a role in promoting dehydration in the conversion of alginic acid to furfural, where the strength of the Lewis acid is proportional to the electronegativity of the metal ion. On the other hand, when the lanthanide metal ion (lanthanide) is used, the furfural yield increases as the electronegativity decreases. This means that the lanthanide metal ion participates in the hydrothermal reaction through a different pathway unlike the transition metal ion.

Referring to FIG. 4, the furfural yield increases linearly with the ion radius for lanthanide metal ions, but the furfural yield is not high. The furfural yield is also proportional to the ionic radius for the post-transition metal. Pb (III) ion (119 pm) with the largest ionic radius shows the highest furfural yield (7.12%) among the post-transition metals. On the other hand, there is no correlation between ionic radius and furfural yield in transition metals. Overall, the yield of furfural is higher in transition metals than in post-transition metals and lanthanide-based metals.

The furfural yield and the organic acid yield when the hydrothermal reaction using metal ions were performed at 200 ° C for 30 minutes were measured and are shown in Table 1 below.

catalyst
(0.01M) Yield (mol%) Furfural Glycolic acid Lactic acid Formic acid Control experiment 5.14 0.32 - 2.36 Zn (II) 5.77 3.19 - 2.24 Cr (II) 3.75 5.87 3.34 1.96 Mn (II) 3.44 0.88 - 3.03 Co (II) 5.64 1.85 - 2.42 Ni (II) 5.02 2.44 0.95 2.79 Cu (II) 13.19 0.99 - 1.68 Fe (III) 9.43 1.61 - 1.72 Y (III) 2.5 2.15 - 4.8 Pb (II) 7.12 2.91 2.24 2.31 Ga (III) 3.49 3.76 5.63 3.33 Al (III) 3.24 4.52 6.73 3.08 Ce (III) 3.92 2.53 - 3.73 Pr (III) 3.77 1.54 - 3.97 La (III) 4.31 1.56 1.24 3.6 Nd (III) 3.66 2.60 - 4.24 Gd (III) 2.92 2.67 - 5.37

The hydrothermal reaction of alginic acid forms some organic acids as well as furfural. Table 1 shows the yields of glycolic acid, lactic acid, and formic acid, which are major organic acids formed together with furfural.

Referring to Table 1, in a control experiment, 0.32% glycolic acid and 2.36% formic acid are formed with 5.14% furfural. The Cu (II) ion forms a small amount of organic acid as compared with other metal ions, and exhibits the best catalytic performance with respect to the formation of furfural. This indicates that Cu (II) ion converts alginic acid to furfural more selectively than other metal ions.

Figure 5 shows the relationship between furfural yield and formic acid yield. FIG. 5 shows the furfural yield and formic acid yield when a hydrothermal reaction was performed using metal ions for 30 minutes at 200.degree.

Referring to FIG. 5, the yield of formic acid is inversely proportional to the furfural yield. Furfural is converted to formic acid and non-water soluble fumarate under hydrothermal conditions. When a metal ion such as Gd (III) and Y (III) is used as a catalyst, the furfural is decomposed into formic acid, thereby lowering the furfural yield. However, Cu (II) and Fe (III) ions stably form furfural in acid hydrothermal conditions.

Figure 6 shows the relationship between reaction time and reaction temperature and yield of furfural. FIG. 6 shows the furfural yield when hydrothermal reaction was carried out using Cu (II) ion for 30 minutes at various reaction temperatures.

Referring to FIG. 6, the furfural yield is significantly increased at 200 ° C compared to the results of the control experiment. The maximum yield of furfural (13.19%) is obtained by reaction at 200 ° C for 30 minutes. However, the furfural yield sharply decreases to 5.34% over the next 30 minutes. This is due to the hydrothermal conversion of furfural to formic acid or a fuming compound. The maximum value of the furfural yield does not appear at 220 캜 because the furfural produced during 220 캜 (about 30 minutes) is decomposed or polymerized before it reaches 220 캜. At temperatures lower than 200 ° C the maximum yield of furfural and the rate of formation appear lower than at 200 ° C. For example, the furfural yield reaches a maximum yield of 9.53% at a reaction time of 180 minutes at 160 캜, and then remains constant, indicating that the furfural is thermally stable at 160 캜.

Figure 7 shows the relationship between the concentration of Cu (II) ion catalyst and the yield of furfural.

Referring to FIG. 7, the hydrothermal treatment of alginic acid shows a furfural yield of 13.19% when it is carried out at 200 ° C. using 0.01 M of Cu (II) ion. That is, the optimum concentration of Cu (II) ion for the highest furfural yield is 0.01M. As the concentration of Cu (II) ion increases from 0.0025M to 0.01M, the furfural yield increases, which means that the increasing Cu (II) ion promotes the conversion of alginic acid to furfural as a Lewis acid catalyst . On the other hand, Cu (II) ions at concentrations higher than 0.01 M can inhibit the conversion to furfural. Excess Cu (II) ions may react non-selectively with oxygen atoms of alginic acid to induce adverse reactions. For example, the excess Cu (II) ion can form a bidentate chelate compound that reacts with the oxygen atoms of the carboxyl group of the alginic acid to interfere with the decarboxylation of the alginic acid.

FIG. 8 shows the results of GPC analysis of the liquid product according to the Cu (II) ion catalyst and the Y (III) ion catalyst. FIG. 8 shows the chromatogram of the liquid product when a hydrothermal reaction was carried out using Cu (II) ion and Y (III) ion at 200 ° C. for 30 minutes. The effect of metal ion on the molecular weight change of alginic acid have.

Referring to FIG. 8, Y (III) ion promotes decomposition of alginic acid compared to the control experiment, but the effect of Cu (II) ion on decomposition of alginic acid is not significant. As described above, the Cu (II) ion exhibits the highest furfural yield and the Y (III) ion exhibits the lowest furfural yield. The Y (III) ion promotes the formation of smaller molecules than mannuronic acid and glutaric acid. Y (III) ion is effective for the hydrolysis of alginic acid, but is not effective for the formation of furfural. However, Cu (II) ions are advantageous for the conversion of alginic acid to furfural, despite the low catalytic performance for the degradation of alginic acid.

The average molecular weight (Mw, Mn) and the polydispersity index (PDI) of the liquid product formed when the hydrothermal reaction using Cu (II) ion was performed at 200 ° C for 30 minutes were measured and shown in Table 2 below .

Sample Mw (Da) Mn (Da) PDI Raw alginic acid 240000 - - Cu (II) -0.0025M 1482 658 2.25 Cu (II) -0.05M 1452 666 2.18 Cu (II) -0.01M 1711 712 2.40 Cu (II) -0.02M 1470 937 1.57 Cu (II) -0.04M 1613 1148 1.40

Referring to Table 2 above, samples formed from 0.01 M Cu (II) ions have the highest weight average molecular weight with the highest PDI, indicating that at a concentration of 0.01 M, Cu (II) ) Ion with a broad molecular weight distribution of the liquid product and a relatively low catalytic performance against the decomposition reaction of alginic acid. The relationship between Cu (II) ion concentration and PDI value is similar to the relationship between Cu (II) ion concentration and furfural yield. That is, more furfural is formed when alginate is decomposed into molecules of various sizes than molecules of similar size.

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (8)

Mixing the alginic acid compound with a metal ion and subjecting it to hydrothermal treatment,
Wherein the metal ion comprises a transition metal ion. The method according to claim 1,
Wherein the alginic acid compound comprises alginic acid or alginate. delete The method according to claim 1,
Wherein the transition metal ion comprises at least one of a Cu (II) ion and a Fe (III) ion. Mixing the alginic acid compound with a metal ion and subjecting it to hydrothermal treatment,
Wherein the metal ion comprises at least one of Cu (II) ion, Fe (III) ion, and Pb (II) ion. Mixing the alginic acid compound with a metal ion and subjecting it to hydrothermal treatment,
The metal ion is a Cu (II) ion,
Wherein the concentration of the Cu (II) ion is 0.005 to 0.02 M. 7. The method according to any one of claims 1 to 6,
Wherein the temperature of the hydrothermal treatment is in the range of 160 to 220 占 폚. Mixing the alginic acid compound with a metal ion and subjecting it to hydrothermal treatment,
Wherein the electronegativity of the metal ion is 1.5 to 1.91.
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JP7446239B2 (en) * 2018-04-13 2024-03-08 アーチャー－ダニエルズ－ミッドランド カンパニー Dehydration and cyclization of alpha-,beta-dihydroxycarbonyl compounds to 2-substituted furan derivatives
CN112961126A (en) * 2021-03-01 2021-06-15 安徽金轩科技有限公司 Method for synthesizing furfural

Citations (4)

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Publication number Priority date Publication date Assignee Title
KR101116392B1 (en) 2009-08-12 2012-03-09 한국생산기술연구원 Method of preparing bio fuels from algal galactans
KR101432681B1 (en) 2013-01-16 2014-08-25 한국과학기술원 Method of producing a hydroxymethylfurfural, composition and kit therefor, hydroxymethylfurfural produced therefrom, and method of producing a oxidized product of hydroxymethylfurfural
US20140295508A1 (en) 2011-09-29 2014-10-02 Yasuo Yoshikuni Methods for preparing 2,5-furandicarboxylic acid
CN104327020A (en) 2014-10-15 2015-02-04 暨南大学 Furanone derivative for resisting infection and preparation method and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101116392B1 (en) 2009-08-12 2012-03-09 한국생산기술연구원 Method of preparing bio fuels from algal galactans
US20140295508A1 (en) 2011-09-29 2014-10-02 Yasuo Yoshikuni Methods for preparing 2,5-furandicarboxylic acid
KR101432681B1 (en) 2013-01-16 2014-08-25 한국과학기술원 Method of producing a hydroxymethylfurfural, composition and kit therefor, hydroxymethylfurfural produced therefrom, and method of producing a oxidized product of hydroxymethylfurfural
CN104327020A (en) 2014-10-15 2015-02-04 暨南大学 Furanone derivative for resisting infection and preparation method and use thereof

Non-Patent Citations (2)

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Title
WONJINJEON외,C AT ALYSISTOD AY, AV AIL ABLEONLINE21DECEMBER2015
Zhang, et al. Polymer Degradation and Stability Vol 97, Issue 6, June 2012, pp1034-1040.

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