CN103911405B - A kind of method that cell catalysis furfural produces furancarboxylic acid - Google Patents
A kind of method that cell catalysis furfural produces furancarboxylic acid Download PDFInfo
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- CN103911405B CN103911405B CN201410131002.4A CN201410131002A CN103911405B CN 103911405 B CN103911405 B CN 103911405B CN 201410131002 A CN201410131002 A CN 201410131002A CN 103911405 B CN103911405 B CN 103911405B
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Abstract
The invention discloses a kind of method that cell catalysis furfural produces furancarboxylic acid, including: (1) is swaying or in the reaction system of air blow and agitation, with initial substrate concentration less than 10g/L furfural liquid as response matrix, access cell concentration 1.0g/L Gluconobacter oxvdans react；(2) using semicontinuous or filling the most in batches mode to add furfural in reaction system, the furfural content controlled in reaction system is not higher than 10g/L, until furfural adds total amount reaches 39 ~ 40g/L, monitoring in real time and regulation and control pH value are not less than 3.0；(3) reaction is terminated when completing to consume to furfural in reaction system, it is thus achieved that furancarboxylic acid liquid.The present invention need not use metallic catalyst or the acid and alkali reaction condition of harshness, and substrate furfural consumes completely and conversion ratio is high, and furancarboxylic acid product purity is high, it is refined to can be easily separated, and waste water processes simple.The consumption rate of substrate furfural reach 100% and product furancarboxylic acid conversion ratio more than 96% under conditions of, product furancarboxylic acid concentration is more than 40g/L.
Description
Technical field
The present invention relates to furancarboxylic acid preparing technical field, be specifically related to a kind of method that cell catalysis furfural produces furancarboxylic acid.
Background technology
Furancarboxylic acid, also known as α-furyl carboxylic acid, 2-furancarboxylic acid or furancarboxylic acid, it it is a kind of organic synthesis intermediate, the derivants such as ester, acyl chlorides, anhydride, amide can be converted into, for producing 2-methylfuran, furoamide, furoate (salt), plasticizer, thermosetting resin, food industry preservative, coating additive, spice and the synthesis medicine such as furbenicillin and ceftiofur.
The furancarboxylic acid preparation method of existing report is mainly with furfural as raw material, uses Cannizzaro reaction, metal catalysed processes or electrolysis furfural method.As Chinese patent application 200910112526.8 uses " a kind of method preparing sugar alcohol and furancarboxylic acid based on Bipolar membrane water splitting " simultaneously, with netted Zn-Ni alloy as negative electrode, lead electrode is anode, uses high concentration NaOH and MnO2Solution is electrolytic mediator, and furancarboxylic acid maximum output is 85%.Said method also exist furfural convert not exclusively, metallic catalyst consumption, furancarboxylic acid product separates or waste water processes difficulty.Use demand can't be fully met.
Summary of the invention
Goal of the invention: it is an object of the invention to provide a kind of method that cell catalysis furfural produces furancarboxylic acid, can complete to change into furancarboxylic acid by furfural by cell catalysis one step, there is reaction condition simultaneously gentle, the equipment of production process, technique and simple to operate, chemical cost is minimum, waste water processes and the convenient advantage of reuse.
Technical scheme: in order to realize foregoing invention purpose, the technical solution used in the present invention is as follows:
A kind of method that cell catalysis furfural produces furancarboxylic acid, comprises the following steps:
(1) swaying or in the reaction system of air blow and agitation, with initial substrate concentration less than 10g/L furfural liquid as response matrix, access cell concentration be not less than 1.5 g/L Gluconobacter oxvdans (Gluconobacter oxydans) react；
(2) using semicontinuous or filling the most in batches mode to add furfural in reaction system, the furfural content controlled in reaction system is not higher than 10 g/L, until furfural adds total amount reaches 39 ~ 40g/L, monitoring in real time and regulation and control pH value are not less than 3.0；
(3) reaction is terminated when completing to consume to furfural in reaction system, it is thus achieved that furancarboxylic acid liquid.
In prepared furancarboxylic acid liquid, furancarboxylic acid concentration is not less than 40g/L.
In step (1), speed of agitator is 220r/min.
In step (1), initial substrate concentration is 6.5 ~ 7g/L.
In reaction, calcium carbonate is used to control reaction system pH4.0 ~ 7.0.
The cell used is Gluconobacter oxvdans, and all genetic mutagenesis with it as starting strain or gene recombinaton bacterial strain.
Substrate in reaction system is that product is furancarboxylic acid and the arbitary combined product including furfural containing furfural or the arbitary combined reaction substrate that includes furfural.
The preparation method of the present invention is cell catalysis method, and the C-1 position aldehyde radical biological dehydrogenation in orientation bio-catalytical oxidation Furfural Molecule generates C-1 position carboxylate radical；Simultaneously, mode of operation by semicontinuous or continuous filling, achieve effective unification that the cytotoxicity of furfural is controlled to be improved with product furancarboxylic acid concentration, make the yield of the consumption rate of substrate furfural and product furancarboxylic acid all more than 95%, product furancarboxylic acid concentration is more than 40g/L, for the top level of existing furfural class bioconversion report.
Beneficial effect: compared with prior art, the present invention need not use metallic catalyst or the acid and alkali reaction condition of harshness, and substrate furfural consumes completely and conversion ratio is high, and furancarboxylic acid product purity is high, it is refined to can be easily separated, and waste water processes simple.The consumption rate of substrate furfural reach 100% and product furancarboxylic acid conversion ratio more than 96% under conditions of, product furancarboxylic acid concentration, more than 40 g/L, has good practicality, it is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is that under the conditions of semi continuous batch charging, cell catalysis furfural produces the reaction mechanism mechanism of reaction figure of saccharic acid in shaking flask reaction system；In figure, abscissa represents that response time (d), main ordinate represent furfural consumption rate and furancarboxylic acid productivity (%), and secondary ordinate represents furancarboxylic acid concentration and furfural addition (g/L).
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
In 250mL tool plug triangular flask, add 50mL furfural aqueous solution, furfural initial concentration is 6.5g/L, add 10g/L calcium carbonate and control reaction system pH4.0 ~ 7.0, shaking flask is proceeded to the constant-temperature shaking culture bed of 30 DEG C ± 5, regulation vibration speed of agitator is 220r/min, and accessing Gluconobacter oxvdans to the cell concentration after activation is that 1.0 g/L carry out cell catalysis reaction.
Use semicontinuous filling mode of operation, within every 24 hours, add 6.5 g/L furfurals (based on reactant liquor volume), and add calcium carbonate control reaction system pH4.0 ~ 7.0.After the 6th day, stop filling, amount to and add 39g/L furfural.Continuing to react to the 10th day, stopped reaction, reaction mechanism mechanism of reaction figure is as shown in Figure 1；In figure, abscissa represents that response time (d), main ordinate represent furfural consumption rate and furancarboxylic acid productivity (%), and secondary ordinate represents furancarboxylic acid concentration and furfural addition (g/L)；Detecting through GC-MS or HPLC, substrate furfural is totally consumed, and product furancarboxylic acid concentration is more than 40g/L.
Embodiment 2
In 3 L mechanical ventilation type retort, adding 1.5 L furfural liquid to initial furfural contents is 7.0 g/L, add 20g/L calcium carbonate regulation reaction system pH 4.0 ~ 7.0, maintain temperature of reaction system 30 DEG C ± 5, speed of agitator 350 ~ 500r/min and ventilation 3 ~ 5vvm, holding tank pressure is 0.01 ~ 0.02MPa, and accessing Gluconobacter oxvdans to the cell concentration after activation is that 1.0g/L carries out cell catalysis.
Detecting substrate furfural and the product furancarboxylic acid concentration of reaction system in real time, when furfural content is less than 2g/L, auto-feeding furfural (purity is higher than 97%) is not higher than 10g/L to concentration.To furfural add total consumption reach 40g/L time, stop stream adding furfural continue reaction.Reacting after 92 hours, furfural is totally consumed, and product furancarboxylic acid concentration reaches 41.5g/L, terminates reaction and obtains furancarboxylic acid product liquid.
Claims (3)
1. the method that a cell catalysis furfural produces furancarboxylic acid, it is characterised in that comprise the following steps:
(1) swaying or in the reaction system of air blow and agitation, with initial substrate concentration 6.5～7g/L furfural liquid as response matrix, the Gluconobacter oxvdans accessing cell concentration 1.0g/L reacts；
(2) using semicontinuous or filling the most in batches mode to add furfural in reaction system, the furfural content controlled in reaction system is not higher than 10g/L, until furfural adds total amount reaches 39～40g/L, monitoring in real time and regulation and control pH value are not less than 3.0；
(3) reaction is terminated when completing to consume to furfural in reaction system, it is thus achieved that furancarboxylic acid liquid；
In prepared furancarboxylic acid liquid, furancarboxylic acid concentration is not less than 40g/L.
The method that cell catalysis furfural the most according to claim 1 produces furancarboxylic acid, it is characterised in that: in step (1), speed of agitator is 220r/min.
The method that cell catalysis furfural the most according to claim 1 produces furancarboxylic acid, it is characterised in that: in reaction, use calcium carbonate to control reaction system pH4.0～7.0.
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Citations (3)
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| WO2011026906A2 (en) * | 2009-09-02 | 2011-03-10 | Shell Internationale Research Maatschappij B.V. | Novel microorganism and its use in lignocellulose detoxification |
| CN103602708A (en) * | 2013-11-25 | 2014-02-26 | 华东理工大学 | Method for preparing hydroxyaldehyde by applying microbial cell catalysis method |
| CN103614420A (en) * | 2013-11-25 | 2014-03-05 | 华东理工大学 | Method for oxidizing binary primary alcohol by using alcohol dehydrogenase |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011026906A2 (en) * | 2009-09-02 | 2011-03-10 | Shell Internationale Research Maatschappij B.V. | Novel microorganism and its use in lignocellulose detoxification |
| CN103602708A (en) * | 2013-11-25 | 2014-02-26 | 华东理工大学 | Method for preparing hydroxyaldehyde by applying microbial cell catalysis method |
| CN103614420A (en) * | 2013-11-25 | 2014-03-05 | 华东理工大学 | Method for oxidizing binary primary alcohol by using alcohol dehydrogenase |
Non-Patent Citations (3)
| Title |
|---|
| Microbial biocatalytic preparation of 2-furoic acid by oxidation of 2-furfuryl alcohol and 2-furanaldehyde with Nocardia corallina;Herminia I perez et al;《African Journal of biotechnology》;20090518;第8卷(第10期);全文 * |
| Oxidation of heterocyclic and aromatic aldehydes to the corrsponding carboxylic acids by Acetobavter and serratia strains;Koichi Mitsukura et al;《Biotechnology letters》;20041231;第26卷;第1644页左栏最后1段，图1，表1-2 * |
| 氧化葡萄糖酸杆菌的特性及应用;王端好;《贵州农业科学》;20131030;第41卷(第10期);摘要，图1和2，第115页左栏最后1段 * |
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Effective date of registration: 20200107 Address after: 201199 building 11, no.1288, Zhongchun Road, Minhang District, Shanghai Patentee after: Easy Zhuoxin high energy saving technology (Shanghai) Co., Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee before: Nanjing Forestry University |