Method for extracting 2,5-furandicarboxylic acid from fermentation broth

Abstract

The present invention relates to the field of microbial fermentation technology, and proposes a method for extracting 2,5-furandicarboxylic acid from a fermentation broth, comprising the following steps: S1, adding activated carbon to the fermentation broth for preparing 2,5-furandicarboxylic acid by fermentation to decolorize, extracting to obtain an extract; S2, stripping the extract to obtain a stripping liquid; S3, crystallizing the stripping liquid, centrifuging, drying, and obtaining a crude product; S4, recrystallizing the crude product, centrifuging, drying, and obtaining 2,5-furandicarboxylic acid; The extractant used during extraction includes a mixture of one or more of toluene, chlorobenzene, 1,2-dichloroethane and (methylthio) methyl sulfoxide methyl ester. Through the above technical scheme, the problem of low yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth in the related art is solved.

Description

Technical Field

[0001] The invention relates to the technical field of microbial fermentation, and in particular to a method for extracting 2,5-furandicarboxylic acid from a fermentation broth. Background Art

[0002] 2,5-Furandicarboxylic acid has extremely wide applications. For example, it can be used to synthesize polyester. Compared with traditional petroleum-based monomers (such as terephthalic acid), the polyester materials prepared from 2,5-furandicarboxylic acid have better thermal stability and mechanical properties. 2,5-Furandicarboxylic acid can also be used to synthesize bio-based packaging materials. The prepared packaging materials have good barrier properties. Compared with traditional petroleum-based packaging materials, the bio-based packaging materials prepared from 2,5-furandicarboxylic acid are more easily biodegradable after disposal, which is in line with the concept of environmental protection.

[0003] The Chinese invention patent with application number 201810376661.2 discloses a method for extracting 2,5-furandicarboxylic acid from a fermentation broth, which specifically comprises: filtering the fermentation broth of 2,5-furandicarboxylic acid prepared by fermentation, decolorizing with activated carbon, extracting with an organic solvent, stripping with alkaline water, and recrystallizing with a combined organic solvent to finally obtain 2,5-furandicarboxylic acid. The organic solvents used in the extraction process are toluene, ethyl acetate, butyl acetate, 1,2-dichloroethane, and chlorobenzene. The effect of extracting 2,5-furandicarboxylic acid is not ideal, resulting in a low yield and purity of the final 2,5-furandicarboxylic acid. Summary of the invention

[0004] The invention provides a method for extracting 2,5-furandicarboxylic acid from a fermentation broth, which solves the problem of low yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth in the related art.

[0005] The technical solution of the present invention is as follows: The method for extracting 2,5-furandicarboxylic acid from a fermentation broth comprises the following steps: S1, adding activated carbon to the fermentation liquid prepared by the fermentation method for 2,5-furandicarboxylic acid to decolorize it, and then extracting it to obtain an extract; S2, stripping the extract to obtain a stripping solution; S3, crystallizing the stripping liquid, centrifuging, and drying to obtain a crude product; S4, recrystallizing the crude product, centrifuging, and drying to obtain 2,5-furandicarboxylic acid; The extractant used in the extraction includes a mixture of one or more of toluene, chlorobenzene, 1,2-dichloroethane and (methylthio)methyl sulfoxide.

[0006] As a further technical solution, the mass volume ratio of the activated carbon to the fermentation liquid is 0.75~1g:1000mL.

[0007] As a further technical solution, the extractant used in the extraction comprises a mixture of 1,2-dichloroethane and (methylthio)methyl sulfoxide in a volume ratio of 1:19 to 19:1.

[0008] The inventors have found that when the extractant is a mixture of 1,2-dichloroethane and (methylthio)methyl sulfoxide in a volume ratio of 1:19 to 19:1, the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth are further improved.

[0009] As a further technical solution, 3 times the volume of the 1,2-dichloroethane is ≥ the volume of the (methylthio)methyl sulfoxide methyl ester.

[0010] The present invention limits the volume of 3 times of 1,2-dichloroethane to be greater than or equal to the volume of methyl (methylthio)methyl sulfoxide, thereby further improving the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth.

[0011] As a further technical solution, the volume ratio of 1,2-dichloroethane to (methylthio)methyl sulfoxide is 1-3:1.

[0012] The volume ratio of 1,2-dichloroethane to (methylthio)methyl sulfoxide is limited to 1-3:1 in the present invention, which further improves the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth.

[0013] As a further technical solution, the amount of the extractant added is 4% to 5% of the volume of the fermentation liquid.

[0014] As a further technical solution, the pH of the decolorized fermentation liquid is adjusted to 6-6.5 before extraction.

[0015] As a further technical solution, the extraction temperature is 30-50°C.

[0016] As a further technical solution, the stripping agent used in the stripping is a strong alkaline aqueous solution.

[0017] The strong alkali aqueous solution includes a sodium hydroxide aqueous solution and / or a potassium hydroxide aqueous solution.

[0018] As a further technical solution, the mass concentration of the strong alkali aqueous solution is 10% to 30%.

[0019] As a further technical solution, the stripping temperature is 30-50°C.

[0020] As a further technical solution, the crystallization comprises the following steps: mixing the stripping liquid with the acid solution to perform crystallization.

[0021] As a further technical solution, the acid solution includes hydrochloric acid solution and / or sulfuric acid solution.

[0022] As a further technical solution, the mass concentration of the acid solution is 10% to 20%.

[0023] As a further technical solution, the pH of the mixed solution is 3-3.5.

[0024] As a further technical solution, the recrystallization agent used in the recrystallization is 1,2-dichloroethane and petroleum ether in a volume ratio of 1:1-5.

[0025] As a further technical solution, the mass volume ratio of the crude product to the solvent is 1g:3~5mL.

[0026] The working principle and beneficial effects of the present invention are: In the present invention, a mixture of one or more of toluene, chlorobenzene and 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester is used as an extractant. By adding (methylthio)methyl sulfoxide methyl ester, since the (methylthio)methyl sulfoxide methyl ester structure contains a strong polar sulfur-oxygen double bond and a sulfide bond, a dipole-dipole interaction can be generated with a polar group carboxyl group in a 2,5-furandicarboxylic acid molecule. After the (methylthio)methyl sulfoxide methyl ester is used in combination with toluene, chlorobenzene and 1,2-dichloroethane, the yield and purity of 2,5-furandicarboxylic acid extracted from a fermentation broth are improved. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] The content of 2,5-furandicarboxylic acid in the fermentation broth for preparing 2,5-furandicarboxylic acid by fermentation in the following examples and comparative examples is 0.0026 g / mL, which is the fermentation broth of Example 1 in Chinese invention patent CN106497957A, wherein the dha β gene of native Klebsiella gene in CN106497957A is a DHA-1 type β-lactamase gene, and the DHA-1 type β-lactamase gene can be found in "DHA-1 type β-lactamase gene cloning and structure, Journal of Huzhou Normal University, Vol. 29, No. 1, pp. 99-102".

[0029] Example 1 S1. Add 5 g of activated carbon to 5000 mL of fermentation broth prepared by fermentation method for 2,5-furandicarboxylic acid, decolorize at 40° C. for 30 min, filter to obtain decolorized fermentation broth, adjust the pH of the decolorized fermentation broth to 6.1, add 200 mL of extractant (the extractant is composed of toluene and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:19), extract at 30° C. for 50 min, let stand, separate layers, and obtain an extract; S2, mixing the extract with a 20 wt % potassium hydroxide aqueous solution until the pH of the mixed solution reaches 11, stripping at 30° C. for 40 min, standing, and layering to obtain a stripping solution; S3, adding 20wt% hydrochloric acid solution to the stripping solution to adjust the pH to 3, performing crystallization, centrifugal separation, and drying to obtain a crude product; S4. Dissolve the crude product in 1,2-dichloroethane, add petroleum ether while stirring, continue stirring for 30 minutes after the addition for recrystallization, centrifuge and dry to obtain 2,5-furandicarboxylic acid, wherein the volume ratio of 1,2-dichloroethane to petroleum ether is 1:1, and the ratio of the volume sum of 1,2-dichloroethane and petroleum ether to the crude product is 3mL:1g.

[0030] Example 2 S1. Add 3.75 g of activated carbon to 5000 mL of fermentation broth for preparing 2,5-furandicarboxylic acid by fermentation, decolorize at 40° C. for 30 min, filter to obtain decolorized fermentation broth, adjust the pH of the decolorized fermentation broth to 6.3, add 250 mL of extractant (the extractant consists of toluene and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:19), extract at 50° C. for 40 min, let stand, separate layers, and obtain an extract; S2, mixing the extract with a 20 wt % sodium hydroxide aqueous solution until the pH of the mixed solution is adjusted to 10, stripping at 50° C. for 40 min, standing, and layering to obtain a stripping solution; S3, adding 10wt% sulfuric acid solution to the stripping solution to adjust the pH to 3.5, performing crystallization, centrifugal separation, and drying to obtain a crude product; S4. Dissolve the crude product in 1,2-dichloroethane, add petroleum ether while stirring, continue stirring for 30 minutes after the addition for recrystallization, centrifuge and dry to obtain 2,5-furandicarboxylic acid, wherein the volume ratio of 1,2-dichloroethane to petroleum ether is 1:5, and the ratio of the sum of the volumes of 1,2-dichloroethane and petroleum ether to the crude product is 5mL:1g.

[0031] Example 3 The only difference from Example 1 is that the extractant is composed of chlorobenzene and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:19.

[0032] Example 4 The only difference from Example 1 is that the extractant is composed of 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:19.

[0033] Example 5 The only difference from Example 4 is that the extractant is composed of 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:3.

[0034] Example 6 The only difference from Example 5 is that the extractant is composed of 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 1:1.

[0035] Example 7 The only difference from Example 5 is that the extractant is composed of 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 3:1.

[0036] Example 8 The only difference from Example 5 is that the extractant is composed of 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester in a volume ratio of 19:1.

[0037] Comparative Example 1 The only difference from Example 1 is that the extractant is toluene.

[0038] The 2,5-furandicarboxylic acid obtained in Examples 1 to 8 and Comparative Example 1 was tested for purity by liquid chromatography, and the yield was calculated according to the following formula: Yield = actual mass × purity ÷ theoretical mass × 100%; The results are recorded in Table 1.

[0039] Table 1 Purity and yield of 2,5-furandicarboxylic acid

[0040] It can be seen from Table 1 that the purity of 2,5-furandicarboxylic acid obtained by the method for extracting 2,5-furandicarboxylic acid from a fermentation broth provided by the present invention is above 92.78% and the yield is above 75.6%.

[0041] Compared with Comparative Example 1, the extractants in Examples 1 to 8 are a mixture of one or more of toluene, chlorobenzene, 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester. The purity and yield of 2,5-furandicarboxylic acid obtained in Examples 1 to 8 are higher than those in Comparative Example 1, indicating that a mixture of one or more of toluene, chlorobenzene, 1,2-dichloroethane and (methylthio)methyl sulfoxide methyl ester as an extractant can improve the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth.

[0042] The purity and yield of 2,5-furandicarboxylic acid obtained in Examples 4 to 8 are higher than those in Example 1 and Example 3, indicating that when the extractant is a mixture of 1,2-dichloroethane and (methylthio)methyl sulfoxide in a volume ratio of 1:19 to 19:1, the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth can be further improved.

[0043] The purity and yield of 2,5-furandicarboxylic acid obtained in Examples 5 to 8 are higher than those in Example 4, indicating that the volume of 3 times 1,2-dichloroethane is ≥ the volume of methyl (methylthio)methyl sulfoxide, which can further improve the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth.

[0044] The purity and yield of 2,5-furandicarboxylic acid obtained in Examples 6-7 are higher than those in Examples 5 and 8, indicating that the volume ratio of 1,2-dichloroethane to (methylthio)methyl sulfoxide is 1-3:1, which can further improve the yield and purity of 2,5-furandicarboxylic acid extracted from the fermentation broth.

[0045] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for extracting 2,5-furandicarboxylic acid from a fermentation broth, characterized in that: The following steps are involved: S1, adding activated carbon to the fermentation liquid prepared by the fermentation method for 2,5-furandicarboxylic acid to decolorize it, and then extracting it to obtain an extract; S2, stripping the extract to obtain a stripping solution; S3, crystallizing the stripping liquid, centrifuging, and drying to obtain a crude product; S4, recrystallizing the crude product, centrifuging, and drying to obtain 2,5-furandicarboxylic acid; The extractant used in the extraction includes a mixture of one or more of toluene, chlorobenzene, 1,2-dichloroethane and (methylthio)methyl sulfoxide.

2. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The extractant used in the extraction comprises a mixture of 1,2-dichloroethane and (methylthio)methyl sulfoxide in a volume ratio of 1:19 to 19:

1.

3. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 2, characterized in that: 3 times the volume of the 1,2-dichloroethane ≥ the volume of the (methylthio)methyl sulfoxide methyl ester.

4. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 3, characterized in that: The volume ratio of the 1,2-dichloroethane to methyl (methylthio) methyl sulfoxide is 1-3:

1.

5. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The amount of the extractant added is 4% to 5% of the volume of the fermentation liquid.

6. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: Before extraction, the pH of the decolorized fermentation broth was adjusted to 6-6.

5.

7. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The extraction temperature is 30-50°C.

8. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The stripping agent used in the stripping is a strong alkaline aqueous solution.

9. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The stripping temperature is 30-50°C.

10. The method for extracting 2,5-furandicarboxylic acid from a fermentation broth according to claim 1, characterized in that: The recrystallization agent used in the recrystallization is 1,2-dichloroethane and petroleum ether in a volume ratio of 1:1-5.

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