U.S. patent application number 16/736263 was filed with the patent office on 2021-01-07 for method for purifying crude 2,5-furandicarboxylic acid composition.
This patent application is currently assigned to FAR EASTERN NEW CENTURY CORPORATION. The applicant listed for this patent is FAR EASTERN NEW CENTURY CORPORATION. Invention is credited to Shu-Wei LIU, Xin-An LU.
Application Number | 20210002243 16/736263 |
Document ID | / |
Family ID | |
Filed Date | 2021-01-07 |
United States Patent
Application |
20210002243 |
Kind Code |
A1 |
LIU; Shu-Wei ; et
al. |
January 7, 2021 |
METHOD FOR PURIFYING CRUDE 2,5-FURANDICARBOXYLIC ACID
COMPOSITION
Abstract
A method for purifying a crude 2,5-furandicarboxylic acid
composition including 2,5-furandicarboxylic acid and 2-furoic acid
is disclosed. The method includes the steps of: (a) mixing the
crude 2,5-furandicarboxylic acid composition with a solvent
solution that includes alcohol so as to obtain a mixture; (b)
heating the mixture to permit full dissolution of the crude
2,5-furandicarboxylic acid composition in the solvent solution; and
(c) cooling the mixture to permit recrystallization of the
2,5-furandicarboxylic acid from the mixture so as to obtain
purified 2,5-furandicarboxylic acid.
Inventors: |
LIU; Shu-Wei; (Taipei City,
TW) ; LU; Xin-An; (Taipei City, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FAR EASTERN NEW CENTURY CORPORATION |
Taipei City |
|
TW |
|
|
Assignee: |
FAR EASTERN NEW CENTURY
CORPORATION
Taipei City
TW
|
Appl. No.: |
16/736263 |
Filed: |
January 7, 2020 |
Current U.S.
Class: |
1/1 |
International
Class: |
C07D 307/68 20060101
C07D307/68 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 2, 2019 |
TW |
108123215 |
Claims
1. A method for purifying a crude 2,5-furandicarboxylic acid
composition, which includes 2,5-furandicarboxylic acid and 2 furoic
acid, the method comprising the steps of: (a) mixing the crude
2,5-furandicarboxylic acid composition with a solvent solution that
includes alcohol and water present in a weight ratio ranging from
5:1 to 5:5 to obtain a mixture; (b) heating the mixture to permit
full dissolution of the crude 2,5-furandicarboxylic acid
composition in the solvent solution; and (c) cooling the mixture to
permit recrystallization of the 2,5-furandicarboxylic acid from the
mixture, so as to obtain purified 2,5-furandicarboxylic acid.
2. The method as claimed in claim 1, wherein the alcohol is
selected from the group consisting of methanol, ethanol,
isopropanol, and combinations thereof.
3. (canceled)
4. (canceled)
5. The method as claimed in claim 1, wherein in step (b), the
mixture is heated to a first temperature ranging from 40.degree. C.
to 120.degree. C.
6. The method as claimed in claim 1, wherein in step (c), the
mixture is cooled to a second temperature ranging from 0.degree. C.
to 30.degree. C.
7. The method as claimed in claim 1, wherein step (c) includes:
recrystallizing the 2,5-furandicarboxylic acid from the mixture;
and separating the 2-furoic acid in the mixture from the
2,5-furandicarboxylic acid.
8. The method as claimed in claim 7, wherein separating the
2-furoic acid in the mixture from the 2,5-furandicarboxylic acid
includes collecting the purified 2,5-furandicarboxylic acid by
filtration, and then drying the purified 2,5-furandicarboxylic acid
at a third temperature ranging from 80.degree. C. to 130.degree. C.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority of Taiwanese Patent
Application No. 108123215, filed on Jul. 2, 2019.
FIELD
[0002] The present disclosure relates to a method for purifying a
crude 2,5-furandicarboxylic acid composition, and more particularly
to a method for purifying a crude 2,5-furandicarboxylic acid
composition that includes 2-furoic acid.
BACKGROUND
[0003] 2,5-furandicarboxyclic acid (FDCA) is a compound that can be
produced from biomass without requiring chemical refinement, and
thus is production is regarded as adhering to the concepts of green
chemistry. FDCA can be used as a bio-based alternative to
terephthalic acid, which is a raw material in the production of
polyethylene terephthalate (PET). In fact, as compared with PET,
polyethylene furanoate (PEF) , which is a chemical analogue of PET
and is produced from FDCA, exhibits even intrinsically higher gas
barrier properties for oxygen, water vapor, carbon dioxide,
etc.
[0004] Conventionally, the industrial method for synthesizing FDCA
which adheres to the concepts of green chemistry, involves
catalytic oxidation of furan derivatives (e.g.,
5-hydroxymethylfurfural (HMF), 5-(alkoxymethyl)furfural (RMF),
etc.) that are produced from the dehydration of saccharides.
However, the thus obtained crude FDCA (cFDCA) usually contains
impurities of derivatives, particularly monocarboxylic acid species
such as 2-furoic acid (2-FA). If the cFDCA is not further purified,
the impurities of furan derivatives contained therein may cause an
undesirable effect of terminating the chain growth of a polymer,
resulting in a low polymer viscosity of the thus obtained. PEF
which may in turn affect the thermoplastic properties thereof.
[0005] U.S. Pat. No. 8,969,404 B2 discloses a process for purifying
crude FDCA composition by subjecting solvated FDCA composition to
hydrogenation reaction so to form other types of water-soluble
furan derivatives, which are then separated from water-insoluble
FDCA. However, a high temperature (around 170.degree. C.), a high
hydrogen partial pressure and an expensive catalyst such as
palladium on carbon (Pd/C), etc. are indispensible in the
hydrogenation reaction of the purifying process.
SUMMARY
[0006] Therefore, an object of the present disclosure is to provide
a method for purifying a crude 2,5-furandicarboxyclic acid
composition which can alleviate at least one of the drawbacks of
the prior art.
[0007] According to the present disclosure, the crude
2,5-furandicarboxylic acid composition includes
2,5-furandicarboxylic acid and furan derivatives which contain
2-furoic acid. The method includes the steps of: [0008] (a) mixing
the crude 2,5-furandicarboxylic acid composition with a solvent
solution that includes alcohol to obtain a mixture; [0009] (b)
heating the mixture to permit full dissolution of the crude
2,5-furandicarboxylic acid composition in the solvent solution; and
[0010] (c) cooling the mixture to permit recrystallization of the
2,5-furandicarboxylic acid from the mixture so as to obtain
purified 2,5-furandicarboxylic acid.
DETAILED DESCRIPTION
[0011] According to the present disclosure, a method for purifying
a crude 2,5-furandicarboxylic acid composition includes the
following steps (a) to (c). The crude 2,5-furandicarboxylic acid
composition includes 2,5-furandicarboxylic acid and furan
derivatives which contain 2-furoic acid.
[0012] In step (a), the crude 2,5-furandicarboxylic acid
composition is mixed with a solvent solution that includes alcohol
to obtain a mixture.
[0013] In step (b), the mixture is heated to permit full
dissolution of the crude 2,5-furandicarboxylic acid composition in
the solvent solution.
[0014] In step (c), the mixture is cooled to permit
recrystallization of the 2,5-furandicarboxylic acid from the
mixture, so as to obtain purified 2,5-furandicarboxylic acid.
[0015] Examples of the alcohol may include, but are not limited to,
methanol, ethanol, isopropanol, and combinations thereof. In
certain embodiments, the alcohol is ethanol.
[0016] In certain embodiments, the solvent solution further
includes water. In an exemplary embodiment, in the solvent
solution, a weight ratio of the alcohol to water ranges from 5:1 to
5:5.
[0017] In certain embodiments, in step (b), the mixture is heated
to a first temperature ranging from 40.degree. C. to 120.degree.
C.
[0018] In certain embodiments, in step (c), the mixture is cooled
to a second temperature ranging from 0.degree. C. to 30.degree.
C.
[0019] In certain embodiments, the method further includes, after
step (c), a step (d) of removing the 2-furoic acid. In an exemplary
embodiment, step (d) includes the sub-steps of: (d1) collecting the
purified 2,5-furandicarboxylic acid by filtration; and (d2) drying
the purified 2,5-furandicarboxylic acid at a third temperature
ranging from 80.degree. C. to 130.degree. C.
[0020] The present disclosure will be further described by way of
the following examples. However, it should be understood that the
following examples are intended solely for the purpose of
illustration and should not be construed as limiting the present
disclosure in practice.
EXAMPLES
Example 1 (E1)
[0021] First, 49.0 g of methanol was added to 1.0 g of a crude
2,5-furandicarboxylic acid (cFDCA) composition that includes
2,5-furandicarboxylic acid (FDCA) and furan derivatives (i.e,
approximately 526 ppm of 2-furoic acid (2-FA)) in a container, so
as to obtain a mixture. Next, the container was sealed and the
mixture was heated to a first temperature of 40.degree. C., which
was maintained for 10 minutes to permit full dissolution of the
cFDCA composition in the methanol. After that, the heated mixture
in the container was cooled to a second temperature of 0.degree.
C., which was maintained for 30 minutes, so as to recrystallize
FDCA in the mixture. The mixture was subjected to suction
filtration so as to remove liquid portion thereof, and then the
recrystallized FDCA thus collected was dried at a third temperature
of 100.degree. C. to obtain a solid product containing purified
FDCA.
Examples 2 to 4 (E2 to E4)
[0022] The methods of E2, E3 and E4 were similar in procedure to
E1, except that, the amount of methanol used in P2 to P4 were
respectively 24.0 g, 15.7 g and 13.3 g, and the first temperature
applied in. E2 to E4 were 65.degree. C., 80.degree. C. and
95.degree. C., respectively.
Examples 5 and 6 (E5 and E6)
[0023] The methods of E5 and E6 were similar in procedure to E1,
except that methanol was replaced with ethanol, and the first
temperature applied in E5 and E6 were 60.degree. C. and 85.degree.
C., respectively.
Examples 7 and 8 (E7 and E8)
[0024] The methods of E7 and E8 were similar in procedure to E5
except that, the amount of methanol used in E7 and E8 were
respectively 19.0 g and 15.7 g, and the first temperature applied
in E7 and E8 were 100.degree. C. and 110.degree. C.,
respectively.
Example 9 (E9)
[0025] First, 39.0 g of a solvent solution (a weight ratio of
methanol to water was 5:3) was added to 1.0 g of the crude
2,5-furandicarboxylic acid (cFDCA) composition as described in E1,
in a container so as to obtain a mixture. Next, the container was
sealed and the mixture was heated to a first temperature of
65.degree. C., which was maintained for 10 minutes, so as to permit
full dissolution of the cFDCA composition in the solvent solution.
After that, the heated mixture in the container was cooled to a
second temperature of 0.degree. C., which was maintained for 30
minutes, so as to recrystallize FDCA in the mixture. The mixture
was subjected to suction filtration so as to remove liquid portion
thereof, and then the recrystallized FDCA thus collected was dried
at a third temperature of 100.degree. C. to obtain a solid product
containing purified FDCA.
Example 10 (E10)
[0026] The method of E10 was similar in procedure to E9, except
that the amount of the solvent solution was 24.0 g, and the first
temperature was 80.degree. C.
Examples 11 and 12 (E11 and E12)
[0027] The methods of E11 and E12 were similar in procedure to E9,
except that in E11 and E12, methanol in the solvent solution was
replaced with ethanol and a weight ratio of ethanol to water was
5:3. In addition, the first temperature applied in E11 and E12 were
60.degree. C. and 75.degree. C., respectively.
Example 13 (E13)
[0028] The method of E13 was similar in procedure to E11, except
that the amount of solvent solution was 15.7 g, and the first
temperature was 88.degree. C.,
Examples 14 to 17 (E14 to E17)
[0029] The methods of E14 to E17 were similar in procedure to E13,
except that, in E14 to E17, the weight ratio of ethanol to water in
the solvent solution were 5:1, 5:2, 5:4 and 5:5, respectively, and
the first temperature were 90.degree. C., 85.degree. C., 90.degree.
C. and 93.degree. C., respectively.
Comparative Examples 1 and 2 (CE1 and CE2)
[0030] The methods of CE1 and CE2 were similar in procedure to E8,
except that in CE1 and CE2, methanol was replaced with water, and
the first temperature were 90.degree. C. and 170.degree. C.,
respectively. In addition a container used in CE2 is capable of
withstanding a high temperature.
Determination of 2-FA Removal Percentage and FDCA Percentage
Purity
[0031] In order to determine 2-FA and FDCA contents, the cFDCA
composition before purification, and each of the solid products
obtained by the methods of E1 to E17 and CE1 and CE2 were
respectively dissolved in methanol and then subjected
high-performance liquid chromatography analysis (column type: C18
from Waters; mobile phase: acetonitrile and 0.05% phosphoric acid
solution (10%:90%, v/v) in an elution gradient shown in Table 1
below).
TABLE-US-00001 TABLE 1 Time Acetonitrile 0.05% Phosphoric (min) (v
%) acid solution (v %) 0.0 10 90 5.0 10 90 6.0 30 90 13.0 50 50
14.5 100 0 16.0 100 0
[0032] 2-FA removal percentage was calculated using the formula:
[1-(A/B)].times.100%, in which A represents the 2-FA content (ppm)
in the purified solid product, and
[0033] B represents the 2-FA content (ppm) in the cFDCA
composition. FDCA percentage purity was calculated using the
formula: (C/D).times.100%, in which. C represents the weight of
FDCA in the purified solid product, and D represents the total
weight of the purified solid product. The results were shown in
Table 2 below.
TABLE-US-00002 TABLE 2 2-FA removal FDCA percentage percentage (%)
purity (%) E1 85 99.9 E2 81 99.8 E3 69 99.7 E4 55 99.5 E5 92 99.8
E6 92 99.8 E7 88 99.7 E8 81 99.8 E9 88 99.8 E10 80 99.7 E11 >99
99.8 E12 >99 99.9 E13 >99 99.9 E14 91 99.8 E15 94 99.9 P16 96
99.9 E17 88 99.8 CE1 7 99.2 CE2 >99 99.9
[0034] As shown in Table 2, in each of E1 to E17, the 2-FA removal
percentage is higher than 55%, and the percentage purity of FDCA is
higher than 99.5%, indicating that 2-FA was effectively removed
from the FDCA composition, thereby obtaining a highly purified
FDCA. In contrast, the 2-FA removal percentage in CE1 is merely 7%,
and the FDCA percentage purity is 99.2%, indicating that effective
removal of 2-FA during purification of cFDCA composition was not
achieved, and a highly purified FDCA cannot be obtained by the
method of CE1. Although a high 2-FA removal percentage and a high
FDCA percentage purity may be achieved in CE2, complete dissolution
of the cFDCA composition in the solvent solution is required to be
conducted at a relatively high temperature (i.e., 170.degree.
C.).
[0035] In summary, by virtue of the method for purifying cFDCA
composition of the present disclosure, which utilizes simple
procedures and mild conditions, furan derivatives such as 2-FA, can
be effectively removed, thereby obtaining FDCA with high
purity.
[0036] In the description above, for the purposes of explanation,
numerous specific details have been set forth in order to provide a
thorough understanding of the embodiments . It will be apparent,
however, to one skilled in the art, that one or more other
embodiments may be practiced without some of these specific
details. It should also be appreciated that reference throughout
this specification to "one embodiment," "an embodiment," an
embodiment with an indication of an ordinal number and so forth
means that a particular feature, structure, or characteristic may
be included in the practice of the disclosure. It should be further
appreciated that in the description, various features are sometimes
grouped together in a single embodiment, figure, or description
thereof for the purpose of streamlining the present disclosure and
aiding in the understanding of various inventive aspects, and that
one or more features or specific details from one embodiment may be
practiced together with one or more features or specific details
from another embodiment, where appropriate, in the practice of the
disclosure.
[0037] While the present disclosure has been described in
connection with what are considered the exemplary embodiments, it
is understood that this disclosure is not limited to the disclosed
embodiments but is intended to cover various arrangements included
within the spirit and scope of the broadest interpretation so as to
encompass all such modifications and equivalent arrangements.
* * * * *