CN103805647B - A kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA - Google Patents
A kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA Download PDFInfo
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- CN103805647B CN103805647B CN201410038034.XA CN201410038034A CN103805647B CN 103805647 B CN103805647 B CN 103805647B CN 201410038034 A CN201410038034 A CN 201410038034A CN 103805647 B CN103805647 B CN 103805647B
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- furfural
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical class O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000001580 bacterial effect Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 239000001963 growth medium Substances 0.000 claims abstract description 53
- 230000001954 sterilising effect Effects 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002609 medium Substances 0.000 claims abstract description 15
- 238000011218 seed culture Methods 0.000 claims abstract description 14
- 229920001817 Agar Polymers 0.000 claims abstract description 10
- 239000008272 agar Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000855 fermentation Methods 0.000 claims abstract description 8
- 230000004151 fermentation Effects 0.000 claims abstract description 8
- 241000589220 Acetobacter Species 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 25
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 20
- 239000008103 glucose Substances 0.000 claims description 19
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 18
- 229930006000 Sucrose Natural products 0.000 claims description 18
- 239000005720 sucrose Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 235000009508 confectionery Nutrition 0.000 claims description 17
- 229930091371 Fructose Natural products 0.000 claims description 16
- 239000005715 Fructose Substances 0.000 claims description 16
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 16
- 229940041514 candida albicans extract Drugs 0.000 claims description 16
- 239000012138 yeast extract Substances 0.000 claims description 16
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000001888 Peptone Substances 0.000 claims description 12
- 108010080698 Peptones Proteins 0.000 claims description 12
- 235000019319 peptone Nutrition 0.000 claims description 12
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 10
- 239000012137 tryptone Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 2
- 241001460542 Gluconobacter oxydans DSM 2003 Species 0.000 claims 1
- 241000121507 Komagataeibacter hansenii ATCC 23769 Species 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 235000015097 nutrients Nutrition 0.000 description 7
- 244000235858 Acetobacter xylinum Species 0.000 description 6
- 235000002837 Acetobacter xylinum Nutrition 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000011534 incubation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000589232 Gluconobacter oxydans Species 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229940050410 gluconate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 241000589216 Komagataeibacter hansenii Species 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The present invention relates to a kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA, comprise: get in a ring acetobacter access liquid seed culture medium from preserving the agar slant culture-medium of bacterial classification (1), at 20-30 DEG C, cultivate 12-24 hour, with activated spawn; (2) seed liquor is linked in liquid fermentation medium, cultivates or leave standstill cultivation 12～48h in 20-30 DEG C of shaking table; (3) treat have a large amount of floccules to generate in liquid fermentation medium, in culture medium, add furfural and the derivative solution thereof through sterilising filtration, make the final concentration of furfural in culture medium and derivative thereof reach 1-50mmol/L, cultivate or leave standstill in 20-35 DEG C of shaking table and cultivate after 0.5～7 day, to obtain final product. Conversion yield of the present invention is higher, can reach 75-98%, and reaction condition gentleness, environmental protection, have a good application prospect.
Description
Technical field
The invention belongs to the preparation field of furancarboxylic acid and 5-HMFA, particularly one is utilized bacterial oxidation furfural derivatives systemThe method of standby furancarboxylic acid and 5-HMFA.
Background technology
Furancarboxylic acid claims again α-furyl carboxylic acid, 2-furancarboxylic acid or furancarboxylic acid, is commonly used for anticorrisive agent, bactericide, also can be used as organicSynthesize and medicine intermediate, to be converted into the derivatives such as ester, acyl chlorides, acid anhydrides, acid amides, for the manufacture of spices and medicine etc.,In plastics industry, can be used for plasticizer, thermosetting resin etc. Chemically generally taking furtural (furfural) as raw material, through oxidationOr Cannizaro reaction (Cannizzaroreaction) is produced. Taking furfural when raw material is prepared furancarboxylic acid, at strongly basic medium with urgeUnder agent exists, furfural can make furancarboxylic acid through air oxidation, sulfuric acid acidation, but in reaction, has a large amount of byproduct furfuryl alcohols to produce.5-HMFA (5-hydroxymethylfurfural, HMF) is called again 5-methylol-2-furancarboxylic acid, can be by oxidationDeng reaction preparation, it is also important fine chemical material.
Chemical method prepares that reaction time of furancarboxylic acid and 5-HMFA is longer, and solvent load is large, low conversion rate, and accessory substance is many,Be difficult for separation and purification, cost is high, therefore needs the new technical method of exploitation badly and produces furancarboxylic acid analog derivative.
Summary of the invention
Technical problem to be solved by this invention is to provide one and utilizes bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-methylol chaffThe method of acid, the method conversion yield is higher, can reach 75-98%, and reaction condition gentleness, environmental protection have good applicationProspect.
A kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA of the present invention, comprising:
(1) get in a ring acetobacter access liquid seed culture medium, at 20-30 DEG C from preserving the agar slant culture-medium of bacterial classificationCultivate 12-24 hour, with activated spawn;
(2) by seed liquor by volume percentage 6-10% be linked in liquid fermentation medium, cultivate or leave standstill in 20-30 DEG C of shaking tableCultivate 12～48h;
(3) treat to have in liquid fermentation medium a large amount of floccules to generate, to adding in culture medium through the furfural of sterilising filtration and spreading outBiological solution, makes the final concentration of furfural in culture medium and derivative thereof reach 1-50mmol/L, cultivate in 20-35 DEG C of shaking table orLeave standstill and cultivate after 0.5～7 day, obtain furancarboxylic acid and 5-HMFA.
Acetobacter in described step (1) is that acetic acid Pseudomonas, gluconobacter suboxydans belong to or gluconic acid Acetobacter.
Liquid seed culture medium in described step (1) and (2) and the component of liquid fermentation medium are: sweet mellow wine, grapeSugar, sucrose, glycerine or fructose 25g, peptone or tryptone 3g, yeast extract 5g, water 1L, pH3.5-7.5,121 DEG CSterilizing 20min; Or be: sweet mellow wine, glucose, sucrose, glycerine or fructose 20-100g, yeast extract 5g, peptoneOr tryptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH3.5-7.5,121 DEG C of sterilizing 20min.
In described step (1), in liquid seed culture medium, cultivating is that shaking table is cultivated, and speed is 160～180r/min.
The speed that shaking table in described step (2) and (3) is cultivated is 100-250r/min.
Furfural derivatives in described step (3) is 5 hydroxymethyl furfural.
Beneficial effect
Conversion yield of the present invention is higher, can reach 75-98%, and reaction condition gentleness, environmental protection, with traditional chemical method phase specific energyConsume low, production technology is simple, accessory substance is few, have a good application prospect.
Brief description of the drawings
Fig. 1 is the course figure of acetobacter xylinum (AcetobacterxylinumATCC23770) oxidation conversion variable concentrations furfural; A is trainingThe situation of change of remaining glucose while adding 0-40mmol/L furfural in foster base; B adds 0-40mmol/L furfural in culture mediumTime incubation pH value situation of change; C is the propagation of viable bacteria in incubation while adding 0-40mmol/L furfural in culture mediumSituation; D is the variation of furfural content while adding 0-40mmol/L furfural in culture medium; In figure arrow represent to add furfural timeBetween point;
Fig. 2 is the course figure of acetobacter xylinum (AcetobacterxylinumATCC23770) oxidation conversion variable concentrations 5 hydroxymethyl furfural;A is the situation of change of remaining glucose while adding 0-40mmol/L5-hydroxymethylfurfural in culture medium; B adds in culture mediumThe situation of change of incubation pH value when 0-40mmol/L5-hydroxymethylfurfural; C adds 0-40mmol/L5-in culture mediumThe propagation situation of viable bacteria in incubation when hydroxymethylfurfural; D is while adding 0-40mmol/L5-hydroxymethylfurfural in culture mediumThe variation of 5 hydroxymethyl furfural concentration; In figure, arrow represents to add the time point of furfural.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention. Should be understood that these embodiment are not only for the present invention is describedBe used for limiting the scope of the invention. In addition should be understood that those skilled in the art can after having read the content of the present invention's instructionSo that the present invention is made various changes or modifications, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) activated spawn
Get ring acetobacter xylinum (AcetobacterxylinumATCC23770) access from preserving the agar slant culture-medium of bacterial classificationLiquid seed culture medium (sweet mellow wine, glucose, sucrose or glycerine 25g, peptone 3g, yeast extract 5g, water 1L,PH3.5,121 DEG C of sterilizing 20min) in, at 30 DEG C, 160 turn cultivation 12 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 6%(v/v) be linked into fluid nutrient medium (glucose, sweet mellow wine, sucrose or glycerine 25g,Peptone 3g, yeast extract 5g, water 1L, pH3.5,121 DEG C of sterilizing 20min) in, in 20 DEG C, 100r/min conditionFor subsequent use after lower shaking table cultivation or standing cultivation 12h;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural (HMF) solution, makes the final concentration of furfural derivatives in culture medium reach 10mmol/L, in 20 DEG C, 100r/min barUnder part, shaking table is cultivated or is left standstill and cultivates after 1 day, detects furfural derivatives in culture medium with high performance liquid chromatography (HPLC)Conversion ratio.
HPLC(Agilent1200series, C18 post is joined UV and DAD detector) detection method: mobile phase is served as reasons containing 2The Milli-Q ultra-pure water of mmol/L formic acid and the gradient elution mobile phase forming containing the acetonitrile of 2mmol/L formic acid: first use 3% secondNitrile is washed 3min, and then in 5min, acetonitrile concentration linearity progressively brings up to 10%. Flow rate of mobile phase: 0.4-0.5mL/min,Column temperature: 40oC, detects wavelength: 254nm.
Result is as the situation of 10mM furfural derivatives in Fig. 1 and Fig. 2. The amount that found that the furfural derivatives being converted reaches100%, the content that is wherein converted into furancarboxylic acid and 5-HMFA accounts for respectively 93 of initial furfural and 5 hydroxymethyl furfural contentWith 88%.
Embodiment 2
(1) activated spawn
Get ring acetobacter xylinum (AcetobacterxylinumATCC23770) access from preserving the agar slant culture-medium of bacterial classificationLiquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 25g, tryptone 3g, yeast extract 5g, water 1L,PH5.5,121 DEG C of sterilizing 20min) in, at 30 DEG C, 160 turn cultivation 18 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 8%(v/v) be linked into fluid nutrient medium (glucose, sweet mellow wine, sucrose or fructose 25g,Tryptone 3g, yeast extract 5g, water 1L, pH5.5,121 DEG C of sterilizing 20min) in, in 30 DEG C, 250r/min barFor subsequent use after shaking table cultivation or standing cultivation 18h under part;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 5mmol/L, shaking table training under 35 DEG C, 250r/min conditionSupport or leave standstill and cultivate after 4 days, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC), inspectionSurvey method is as embodiment 1. In result and Fig. 1 and Fig. 2, the situation of 10mM furfural derivatives is similar. Found that and be convertedThe amount of furfural derivatives reaches 100%, and the content that is wherein converted into furancarboxylic acid and 5-HMFA accounts for respectively initial furfural and 5-95 and 90% of hydroxymethyl furfural content.
Embodiment 3
(1) activated spawn
Get ring acetobacter xylinum (AcetobacterxylinumATCC23770) access from preserving the agar slant culture-medium of bacterial classificationLiquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 25g, tryptone 3g, yeast extract 5g, water 1L,PH5.5,121 DEG C of sterilizing 20min) in, at 30 DEG C, 160 turn cultivation 24 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 10%(v/v) be linked into fluid nutrient medium (sweet mellow wine, glucose, sucrose or fructose 25g,Tryptone 3g, yeast extract 5g, water 1L, pH5.5,121 DEG C of sterilizing 20min) in, in 25 DEG C, 150r/min barFor subsequent use after shaking table cultivation or standing cultivation 48h under part;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 40mmol/L, shaking table under 30 DEG C, 150r/min conditionCultivate or leave standstill and cultivate after 0.5 day, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC),Detection method is as embodiment 1. Result is as the situation of 40mM furfural derivatives in Fig. 1 and Fig. 2. Found that the chaff being convertedThe amount of aldehyde and 5 hydroxymethyl furfural reaches respectively 20% and 30%, and the content that is wherein converted into furancarboxylic acid and 5-HMFA accounts for respectivelyTo 20 and 29% of initial furfural and 5 hydroxymethyl furfural content.
Embodiment 4
(1) activated spawn
Get an epoxidation gluconobacter suboxydans (GluconobacteroxydansDSM from the agar slant culture-medium of preserving bacterial classification2003 or ATCC23773) access liquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 100g, yeastMedicinal extract 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min) in,At 30 DEG C, 160 turn cultivation 12 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 6%(v/v) (glucose, sucrose or fructose 100g, yeast soaks to be linked into fluid nutrient mediumCream 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min) in,Under 20 DEG C, 100r/min condition shaking table cultivate or leave standstill cultivate after 1h for subsequent use;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 50mmol/L, shaking table under 20 DEG C, 100r/min conditionCultivate or leave standstill and cultivate after 0.5 day, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC),Detection method is as embodiment 1. In result and Fig. 1 and Fig. 2, the situation of 40mM furfural derivatives is similar. Found that and be convertedFurfural and the amount of 5 hydroxymethyl furfural reach respectively 50% and 60%, the content that is wherein converted into furancarboxylic acid and 5-HMFA dividesDo not account for 42 and 55% of initial furfural and 5 hydroxymethyl furfural content.
Embodiment 5
(1) activated spawn
Get an epoxidation gluconobacter suboxydans (GluconobacteroxydansDSM from the agar slant culture-medium of preserving bacterial classification2003) access liquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 100g, yeast extract 5g, peptone5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min) in, at 30 DEG C 160Turn and cultivate 14 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 10%(v/v) be linked into fluid nutrient medium (sweet mellow wine, glucose, sucrose or fructose 100g,Yeast extract 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min)In, under 30 DEG C, 250r/min condition shaking table cultivate or leave standstill cultivate after 48h for subsequent use;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 50mmol/L, shaking table under 35 DEG C, 250r/min conditionCultivate or leave standstill and cultivate after 1 day, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC),Detection method is as embodiment 1. In result and Fig. 1 and Fig. 2, the situation of 40mM furfural derivatives is similar. Found that and be convertedFurfural and the amount of 5 hydroxymethyl furfural reach respectively 20% and 30%, the content that is wherein converted into furancarboxylic acid and 5-HMFA dividesDo not account for 30 and 39% of initial furfural and 5 hydroxymethyl furfural content.
Embodiment 6
(1) activated spawn
Get a ring gluconate pyracetobacillus (Gluconacetobacterxylinus from the agar slant culture-medium of preserving bacterial classificationATCC23770 or ATCC53524) access liquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 100g,Yeast extract 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min)In, under 30oC, 160 turn cultivation 12 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 8%(v/v) be linked into fluid nutrient medium (sweet mellow wine, glucose, sucrose or fructose 100g,Yeast extract 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min)In, under 26 DEG C, 140r/min condition shaking table cultivate or leave standstill cultivate after 20h for subsequent use;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 10mmol/L, shaking table under 20 DEG C, 100r/min conditionCultivate or leave standstill and cultivate after 2 days, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC),Detection method is as embodiment 1. Found that the furfural that is converted and the amount of 5 hydroxymethyl furfural all reach 100%, are wherein converted intoThe content of furancarboxylic acid and 5-HMFA accounts for respectively 95 and 87% of initial furfural and 5 hydroxymethyl furfural content.
Embodiment 7
(1) activated spawn
Get a ring gluconate pyracetobacillus (Gluconacetobacterhansenii from the agar slant culture-medium of preserving bacterial classificationATCC23769) access liquid seed culture medium (sweet mellow wine, glucose, sucrose or fructose 100g, yeast extract 5g,Peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min) in, at 30 DEG CLower 160 turn cultivation 24 hours, with activated spawn;
(2) bacterium cell that spreads cultivation
To contain seed liquor by 9%(v/v) be linked into fluid nutrient medium (sweet mellow wine, glucose, sucrose or fructose 100g,Yeast extract 5g, peptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH7.5,121 DEG C of sterilizing 20min)In, under 20 DEG C, 100r/min condition shaking table cultivate or leave standstill cultivate after 36h for subsequent use;
(3) add respectively furfural or 5 hydroxymethyl furfural to prepare furancarboxylic acid and 5-HMFA
Treating has a large amount of floccules to generate in culture medium, adds furfural and the 5-methylol through sterilising filtration respectively in culture mediumFurfural solution, makes the final concentration of furfural derivatives in culture medium reach 10mmol/L, shaking table under 25 DEG C, 180r/min conditionCultivate or leave standstill and cultivate after 5 days, detect the conversion ratio of the furfural derivatives in culture medium with high performance liquid chromatography (HPLC),Detection method is as embodiment 1. Found that the furfural that is converted and the amount of 5 hydroxymethyl furfural all reach 100%, are wherein converted intoThe content of furancarboxylic acid and 5-HMFA accounts for respectively 96 and 90% of initial furfural and 5 hydroxymethyl furfural content.
Claims (5)
1. utilize bacterial oxidation furfural derivatives to prepare a method for furancarboxylic acid and 5-HMFA, comprising:
(1) get in a ring acetobacter access liquid seed culture medium, at 20-30 DEG C from preserving the agar slant culture-medium of bacterial classificationCultivate 12-24 hour, with activated spawn; Wherein, acetobacter be AcetobacterxylinumATCC23770,GluconobacteroxydansDSM2003、GluconobacteroxydansATCC23773、GluconacetobacterXylinusATCC53524 or GluconacetobacterhanseniiATCC23769;
(2) by seed liquor by volume percentage 6-10% be linked in liquid fermentation medium, cultivate or leave standstill in 20-30 DEG C of shaking tableCultivate 12～48h;
(3) treat to have in liquid fermentation medium a large amount of floccules to generate, to adding in culture medium through the furfural of filtration sterilization and spreading outBiological solution, makes the final concentration of furfural in culture medium and derivative thereof reach 1-50mmol/L, cultivate in 20-35 DEG C of shaking table orLeave standstill and cultivate after 0.5～7 day, obtain furancarboxylic acid and 5-HMFA.
2. a kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA according to claim 1, itsBe characterised in that: the liquid seed culture medium in described step (1) and (2) and the component of liquid fermentation medium are: sweet mellow wine,Glucose, sucrose, glycerine or fructose 25g, peptone or tryptone 3g, yeast extract 5g, water 1L, pH3.5-7.5,121 DEG C of sterilizing 20min; Or be: sweet mellow wine, glucose, sucrose, glycerine or fructose 20-100g, yeast extract 5g,Peptone or tryptone 5g, citric acid 1.15g, Na2HPO42.7g, water 1L, pH3.5-7.5,121 DEG C of sterilizing 20min.
3. a kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA according to claim 1, itsBe characterised in that: in described step (1), in liquid seed culture medium, cultivating is that shaking table is cultivated, and speed is 160～180r/min.
4. a kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA according to claim 1, itsBe characterised in that: the speed that the shaking table in described step (2) and (3) is cultivated is 100-250r/min.
5. a kind of method of utilizing bacterial oxidation furfural derivatives to prepare furancarboxylic acid and 5-HMFA according to claim 1, itsBe characterised in that: the furfural derivatives in described step (3) is 5 hydroxymethyl furfural.
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