CN101333546A - Process for the preparation of 3-hydroxypropanal method for preparing 3-hydroxyl propionaldehyde - Google Patents
Process for the preparation of 3-hydroxypropanal method for preparing 3-hydroxyl propionaldehyde Download PDFInfo
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Abstract
The invention discloses a process for preparing 3-hydroxy-propionaldehyde, which adopts a two-stage process of cultivating microbial thalli firstly and then utilizing the thalli to transform glycerol, and the process comprises the following steps of: (1) preparing an MRS culture medium containing glucose or fructose for cultivating microorganisms that contain glycerol anhydrase and can secrete the 3-hydroxy-propionaldehyde to the outside of cells, and acquiring mass thalli; and (2) utilizing the thalli to serve as a biocatalyst for transforming the glycerol so as to produce the 3-hydroxy-propionaldehyde. The process has advantages of simple separation process, only needing the thalli separation in the transformation process, having no byproduct, saving separation and purification costs, reusable thalli after filtration, washing and activation, reducing the transformation time and improving the production efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of 3-hydroxy propanal.
Background technology
As everyone knows, the 3-hydroxy propanal is a kind of important chemical material, can be used as multiple emerging chemical such as propenal, vinylformic acid, 1, and the precursor of ammediol etc. is used to prepare novel polymer material.The 3-hydroxy propanal can generate vinylformic acid through chemical oxidation, and vinylformic acid is generally obtained by petroleum industry, can be used for producing acrylate, polyacrylic acid and acrylate etc.; 3-hydroxy propanal hydrogenation catalyst can generate 1, ammediol, 1, ammediol and terephthalic acid synthetic polyester PPT (polytrimethylene terephthalate) have incomparable advantage aspect chemical stability, tint permanence, textile printing and dyeing characteristic and the biodegradable, have become international synthon hot of research and development.Simultaneously confirmed that the 3-hydroxy propanal has the broad-spectrum antimicrobial characteristic, can suppress the growth of gram-positive microorganism, Gram-negative bacteria, yeast, mould and protozoon etc., therefore might become new type bactericide and foodstuff additive.Because the aldehyde radical characteristic of 3-hydroxy propanal hydroxy-acid group and amino are had good crosslinked action, and cytotoxicity is lower, being expected substituted epoxide and glutaraldehyde becomes a kind of novel biological linking agent in addition.
At present, the production method of 3-hydroxy propanal has chemical method and biological process.Chemical method mainly contains oxirane carbonyl synthesis method and acrolein hydration method.Oxirane carbonyl is synthetic to be raw material with oxyethane, Preparation of Catalyst difficulty, catalyst system complexity.The acrolein hydration method is a catalyzer with liquid mineral acid or soda acid buffered soln, and the transformation efficiency of propenal is 40%～60%, and 3-hydroxy propanal selectivity is 75%～85%, but reacted product separates difficulty, and catalyzer is difficult to be reclaimed.Generally speaking chemical synthesis has catalyst system complexity, manufacture craft harshness and instability, ligand has severe toxicity, synthesis technique to need problems such as high pressure.
Biological process utilizes cell as catalyzer, directly glycerine converting prepares the 3-hydroxy propanal, and the whole process of production green non-pollution meets the requirement of Sustainable development, and can solve the problem of a large amount of useless glycerine that produce in the biodiesel manufacture process, thereby cause investigator's attention.United States Patent (USP) (patent No. 4962027) discloses a kind of klebsiella spp that utilizes, and adopts aerobic fermentation to produce the method for 3-hydroxy propanal.Chinese patent (application number CN200410036373.0, patent name is " klebsiella spp utilizes the glycerine aerobic fermentation to produce the method for 3-hydroxy propanal ") has also been reported and has been utilized glycerine converting production 3-hydroxy propanal under the klebsiella spp aerobic conditions.But the 3-hydroxy propanal is the intermediate product of klebsiella spp metabolism glycerine, can't secrete outside the born of the same parents generally speaking, so method of above patent disclosure, all need add semicarbazide hydrochloride during the fermentation and regulate metabolic process, and semicarbazide hydrochloride can generate a kind of mixture with the reaction of 3-hydroxy propanal, therefore fermentation back gained is not 3-hydroxy propanal monomer, and later separation extremely bothers, and open report is not arranged at present as yet.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of 3-hydroxy propanal, it is simple that the present invention has sepn process, only need carry out thalline in the conversion process separates, not having other by product produces, save and separate the cost of purifying, and the thalline that uses after filtration, washing, activation back be reusable, reduces transformation time, the characteristics of enhancing productivity.
In order to achieve the above object, technical scheme of the present invention is: the preparation method who utilizes the direct glycerine converting of microorganism resting cell to produce the 3-hydroxy propanal.
A kind of preparation method of 3-hydroxy propanal adopts first culturing micro-organisms thalline, utilizes the two-stage method of thalline glycerine converting then, comprises the steps:
(1) prepares the MRS culture medium culturing that contains glucose or fructose and contain glycerol dehydratase and the 3-hydroxy propanal can be secreted the outer microorganism of born of the same parents, obtain a large amount of thalline;
(2) utilize this thalline to produce the 3-hydroxy propanal as the biological catalyst glycerine converting.
Described culture medium preparation comprises the preparation of the preparation of solid slant culture base, seed culture medium, the preparation of fermention medium.
Described solid slant culture basigamy system comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, agar 15～25g, distilled water 1000ml regulates pH to 5～6 with acetic acid.
The preparation of described seed culture medium comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, distilled water 1000ml regulates pH to 5～6 with acetic acid.
The preparation of described fermention medium comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, glycerine 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, distilled water 1000ml regulates pH to 5～7 with acetic acid.
Described microorganism comprises a kind of in lactobacillus reuteri (Lactobacillus reuteri), enterobacter agglomerans (Enterobacter agglomerans), the colloidal sol Bacterium lacticum (Lactobacilluscollinoides).
The cultivation of described microorganism comprises the steps: that at first the microbe inoculation bacterial classification was cultivated 12～36 hours down at 35～40 ℃ in the solid slant culture base; Then with the inoculation on the inclined-plane in liquid seed culture medium, 35～40 ℃ of following anaerobism were cultivated 12～24 hours, changed seed over to fermention medium again, carried out anaerobism or aerobic under 35 ℃～40 ℃ conditions and cultivated 12～24 hours, and adopting 3～4M alkaline solution or ammoniacal liquor, control pH is 5～6.
The process of glycerine converting is scattered in the aqueous solution for the thalline washing of fermentation being finished the back acquisition, filtration, after centrifugal again in the described step (2), directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 20～60g/L in the aqueous solution, behind 37 ℃ of following stirring reaction 30min～120min, after filtration or can obtain the pure 3-hydroxy propanal aqueous solution behind the centrifugation thalline; It is reusable to separate the thalline that obtains, and also can use the mixing solutions activation of glucose concn 1～5g/L, glycerol concentration 10～20g/L to reuse after 1～3 hour.
Described glycerine is as substrate, derives from a kind of in the raw glycerine of by product raw glycerine in refining glycerine, the production of biodiesel process or soapmaking industry.
Beneficial effect of the present invention is: give full play to the characteristics that each step transforms, obtain a large amount of thalline catalyzer and the segmentation of glycerine converting process is carried out; What obtain at last is the aqueous solution of 3-hydroxy propanal, do not contain other impurity, so sepn process is simple; Only need carry out thalline in the conversion process and separate, not have other by product and produce, can save greatly and separate the cost of purifying; The thalline that uses among the present invention after filtration, washing, activation back be reusable, significantly reduces transformation time, enhances productivity; The present invention can be used for the coupling production of biofuel and 3-hydroxy propanal, improves raw material availability and production efficiency greatly, reduces production costs.
Embodiment
Embodiment 1
(1) bacterial classification: lactobacillus reuteri (Lactobacillus reuteri HQU001)
(2) substratum
Solid slant culture base: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, agar 18g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Seed culture medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Fermention medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 25g, glycerine 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58, manganous sulfate 0.28, distilled water 1000ml.Regulate pH to 5.4-6.5 with acetic acid.
(3) cultivate
The cultivation of lactobacillus reuteri thalline: the inoculation lactobacillus reuteri was cultivated 24 hours down at 37 ℃ in the solid slant culture base.Then the inoculation on the inclined-plane was cultivated 12 hours to 37 ℃ of following anaerobism of liquid seed culture medium, then the seed culture fluid adding is contained in the 3L fermentor tank of 2L fermention medium, cultivated 12 hours 37 ℃ of following anaerobism.Adopting 3M alkaline solution control pH is 5.6.
(4) transform
The 400g/L raw glycerine that obtains in the production of biodiesel process is diluted to 20g/L glycerine solution 1L, directly add to filter, the wet thallus 10g after centrifugal, behind 37 ℃ of following stirring reaction 30min, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 16g/L.
Embodiment 2
(1) bacterial classification: lactobacillus reuteri (Lactobacillus reuteri HQU001)
(2) substratum
Solid slant culture base: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, agar 15g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Seed culture medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Fermention medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, glycerine 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
(3) cultivate
The cultivation of lactobacillus reuteri thalline: the inoculation lactobacillus reuteri was cultivated 12 hours down at 35 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 35 ℃ of following anaerobism were cultivated 12 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 35 ℃ of conditions and cultivated 12 hours, and to adopt 3M alkali ammoniacal liquor control pH be 5.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 60g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 120min, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 24g/L.Repeated use after the thalline that separation obtains activates 3 hours with 5g/L glucose and 20g/L glycerine mixing solutions continues the above-mentioned reaction system of adding, and after 37 ℃ 120min was reacted in continuation down, 3-hydroxy propanal concentration of aqueous solution was increased to 40g/L.
Embodiment 3
(1) bacterial classification: lactobacillus reuteri (Lactobacillus reuteri HQU001)
(2) substratum
Solid slant culture base: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, agar 25g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Seed culture medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Fermention medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, glycerine 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 7 with acetic acid.
(3) cultivate
The cultivation of lactobacillus reuteri thalline: the inoculation lactobacillus reuteri was cultivated 36 hours down at 40 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 40 ℃ of following anaerobism were cultivated 4 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 40 ℃ of conditions and cultivated 24 hours, and to adopt 4M alkaline solution control pH be 6.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 40g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 60min, after filtration or can obtain 3-hydroxy propanal concentration of aqueous solution behind the centrifugation thalline and be about 32g/L.
After 2 hours, through washing and filtering, continuing to add concentration is in the 40g/L aqueous glycerin solution with 1g/L glucose and the activation of 10g/L glycerine mixing solutions for thalline that above-mentioned filtering separation obtains, 37 ℃ down behind the reaction 60min, and the 3-hydroxy propanal aqueous solution, concentration is about 28g/L.
It is in the 40g/L aqueous glycerin solution that the filtering separation thalline continues to add concentration, and behind 37 ℃ of following reaction 60min, the concentration of the 3-hydroxy propanal aqueous solution is about 16g/L.
Embodiment 4
(1) bacterial classification: enterobacter agglomerans (Enterobacter agglomerans)
(2) substratum
Solid slant culture base: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, agar 18g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Seed culture medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Fermention medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 25g, glycerine 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58, manganous sulfate 0.28, distilled water 1000ml.Regulate pH to 5.4-6.5 with acetic acid.
(3) cultivate
The cultivation of enterobacter agglomerans thalline: the inoculation enterobacter agglomerans was cultivated 36 hours down at 40 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 40 ℃ of following anaerobism were cultivated 4 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 40 ℃ of conditions and cultivated 24 hours, and to adopt 4M alkaline solution control pH be 6.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 40g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 60min, after filtration or can obtain 3-hydroxy propanal concentration of aqueous solution behind the centrifugation thalline and be about 32g/L.
After 2 hours, through washing and filtering, continuing to add concentration is in the 40g/L aqueous glycerin solution with 1g/L glucose and the activation of 10g/L glycerine mixing solutions for thalline that above-mentioned filtering separation obtains, 37 ℃ down behind the reaction 60min, and the 3-hydroxy propanal aqueous solution, concentration is about 28g/L.
It is in the 40g/L aqueous glycerin solution that the filtering separation thalline continues to add concentration, and behind 37 ℃ of following reaction 60min, the concentration of the 3-hydroxy propanal aqueous solution is about 16g/L.
Embodiment 5
(1) bacterial classification: enterobacter agglomerans (Enterobacter agglomerans)
(2) substratum
Solid slant culture base: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, agar 15g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Seed culture medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Fermention medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, glycerine 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
(3) cultivate
The cultivation of colloidal sol Bacterium lacticum thalline: inoculation colloidal sol Bacterium lacticum was cultivated 24 hours down at 37 ℃ in the solid slant culture base.Then the inoculation on the inclined-plane was cultivated 12 hours to 37 ℃ of following anaerobism of liquid seed culture medium, then the seed culture fluid adding is contained in the 3L fermentor tank of 2L fermention medium, cultivated 12 hours 37 ℃ of following anaerobism.Adopting 3M alkaline solution control pH is 5.6.
(4) transform
The 400g/L raw glycerine that obtains in the production of biodiesel process is diluted to 20g/L glycerine solution 1L, directly add to filter, the wet thallus 10g after centrifugal, behind 37 ℃ of following stirring reaction 30mi n, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 16g/L.
Embodiment 6
(1) bacterial classification: enterobacter agglomerans (Enterobacter agglomerans)
(2) substratum
Solid slant culture base: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, agar 25g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Seed culture medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Fermention medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, glycerine 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 7 with acetic acid.
(3) cultivate
The cultivation of enterobacter agglomerans thalline: the inoculation enterobacter agglomerans was cultivated 12 hours down at 35 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 35 ℃ of following anaerobism were cultivated 12 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 35 ℃ of conditions and cultivated 12 hours, and to adopt 3M alkali ammoniacal liquor control pH be 5.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 60g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 120min, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 24g/L.Repeated use after the thalline that separation obtains activates 3 hours with 5g/L glucose and 20g/L glycerine mixing solutions continues the above-mentioned reaction system of adding, and after 37 ℃ 120min was reacted in continuation down, 3-hydroxy propanal concentration of aqueous solution was increased to 40g/L.
Embodiment 7
(1) bacterial classification: colloidal sol Bacterium lacticum (Lactobacillus collinoides)
(2) substratum
Solid slant culture base: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, agar 18g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Seed culture medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58g, manganous sulfate 0.28g, distilled water 1000ml.Regulate pH to 5.4 with acetic acid.
Fermention medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, glycerine 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 7 with acetic acid.
(3) cultivate
The cultivation of colloidal sol Bacterium lacticum thalline: inoculation colloidal sol Bacterium lacticum was cultivated 12 hours down at 35 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 35 ℃ of following anaerobism were cultivated 12 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 35 ℃ of conditions and cultivated 12 hours, and to adopt 3M alkali ammoniacal liquor control pH be 5.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 60g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 120min, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 24g/L.Repeated use after the thalline that separation obtains activates 3 hours with 5g/L glucose and 20g/L glycerine mixing solutions continues the above-mentioned reaction system of adding, and after 37 ℃ 120min was reacted in continuation down, 3-hydroxy propanal concentration of aqueous solution was increased to 40g/L.
Embodiment 8
(1) bacterial classification: colloidal sol Bacterium lacticum (Lactobacillus collinoides)
(2) substratum
Solid slant culture base: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, agar 15g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Seed culture medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
Fermention medium: beef protein powder 5g, flesh of fish juice 5g, Yeast diffusion juice powder 3g, glucose 10g, glycerine 10g, sodium-acetate 3g, dibasic ammonium citrate 1g, tween 80 0.1g, sal epsom 0.2g, manganous sulfate 0.1g, distilled water 1000ml.Regulate pH to 5 with acetic acid.
(3) cultivate
The cultivation of colloidal sol Bacterium lacticum thalline: inoculation colloidal sol Bacterium lacticum was cultivated 24 hours down at 37 ℃ in the solid slant culture base.Then the inoculation on the inclined-plane was cultivated 12 hours to 37 ℃ of following anaerobism of liquid seed culture medium, then the seed culture fluid adding is contained in the 3L fermentor tank of 2L fermention medium, cultivated 12 hours 37 ℃ of following anaerobism.Adopting 3M alkaline solution control pH is 5.6.
(4) transform
The 400g/L raw glycerine that obtains in the production of biodiesel process is diluted to 20g/L glycerine solution 1L, directly add to filter, the wet thallus 10g after centrifugal, behind 37 ℃ of following stirring reaction 30mi n, after filtration or can obtain the 3-hydroxy propanal aqueous solution behind the centrifugation thalline, concentration is about 16g/L.
Embodiment 9
(1) bacterial classification: colloidal sol Bacterium lacticum (Lactobacillus collinoides)
(2) substratum
Solid slant culture base: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, agar 25g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Seed culture medium: beef protein powder 20g, flesh of fish juice 20g, Yeast diffusion juice powder 7g, glucose 30g, sodium-acetate 7g, dibasic ammonium citrate 3g, tween 80 0.3g, sal epsom 1g, manganous sulfate 0.5g, distilled water 1000ml.Regulate pH to 6 with acetic acid.
Fermention medium: beef protein powder 10g, flesh of fish juice 10g, Yeast diffusion juice powder 5g, glucose 25g, glycerine 20g, sodium-acetate 5g, dibasic ammonium citrate 2g, tween 80 0.1g, sal epsom 0.58, manganous sulfate 0.28, distilled water 1000ml.Regulate pH to 5.4-6.5 with acetic acid.
(3) cultivate
The cultivation of colloidal sol Bacterium lacticum thalline: inoculation colloidal sol Bacterium lacticum was cultivated 36 hours down at 40 ℃ in the solid slant culture base.Then with the inoculation on the inclined-plane in liquid seed culture medium, 40 ℃ of following anaerobism were cultivated 4 hours, changed seed over to fermention medium then, carry out anaerobism or aerobic under 40 ℃ of conditions and cultivated 24 hours, and to adopt 4M alkaline solution control pH be 6.
(4) transform
After fermentation is finished with the thalline washing that obtains, filtration, be scattered in the aqueous solution again after centrifugal, directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 40g/L in the aqueous solution, cell concentration is controlled to be 20g/L, behind the stirring reaction 60min, after filtration or can obtain 3-hydroxy propanal concentration of aqueous solution behind the centrifugation thalline and be about 32g/L.
After 2 hours, through washing and filtering, continuing to add concentration is in the 40g/L aqueous glycerin solution with 1g/L glucose and the activation of 10g/L glycerine mixing solutions for thalline that above-mentioned filtering separation obtains, 37 ℃ down behind the reaction 60min, and the 3-hydroxy propanal aqueous solution, concentration is about 28g/L.
It is in the 40g/L aqueous glycerin solution that the filtering separation thalline continues to add concentration, and behind 37 ℃ of following reaction 60min, the concentration of the 3-hydroxy propanal aqueous solution is about 16g/L.
Claims (9)
1, a kind of preparation method of 3-hydroxy propanal is characterized in that adopting first culturing micro-organisms thalline, utilizes the two-stage method of thalline glycerine converting then, comprises the steps:
(1) prepares the MRS culture medium culturing that contains glucose or fructose and contain glycerol dehydratase and the 3-hydroxy propanal can be secreted the outer microorganism of born of the same parents, obtain a large amount of thalline;
(2) utilize this thalline to produce the 3-hydroxy propanal as the biological catalyst glycerine converting.
2, the preparation method of 3-hydroxy propanal as claimed in claim 1 is characterized in that: described culture medium preparation comprises the preparation of the preparation of solid slant culture base, seed culture medium, the preparation of fermention medium.
3, the preparation method of 3-hydroxy propanal as claimed in claim 2 is characterized in that: described solid slant culture basigamy system comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, agar 15～25g, distilled water 1000ml regulates pH to 5～6 with acetic acid.
4, the preparation method of 3-hydroxy propanal as claimed in claim 2, it is characterized in that: the preparation of described seed culture medium comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, distilled water 1000ml regulates pH to 5～6 with acetic acid.
5, the preparation method of 3-hydroxy propanal as claimed in claim 2 is characterized in that: the preparation of described fermention medium comprises and takes by weighing beef protein powder 5～20g, flesh of fish juice 5～20g, Yeast diffusion juice powder 3～7g, glucose 10～30g, glycerine 10～30g, sodium-acetate 3～7g, dibasic ammonium citrate 1～3g, tween 80 0.1～0.3g, sal epsom 0.2～1g, manganous sulfate 0.1～0.5g, distilled water 1000ml regulates pH to 5～7 with acetic acid.
6, the preparation method of 3-hydroxy propanal as claimed in claim 1 is characterized in that: described microorganism comprises a kind of in lactobacillus reuteri (Lactobacillus reuteri), enterobacter agglomerans (Enterobacter agglomerans), the colloidal sol Bacterium lacticum (Lactobacillus collinoides).
7, the preparation method of 3-hydroxy propanal as claimed in claim 1 is characterized in that: the cultivation of described microorganism comprises the steps: that at first the microbe inoculation bacterial classification was cultivated 12～36 hours down at 35～40 ℃ in the solid slant culture base; Then with the inoculation on the inclined-plane in liquid seed culture medium, 35～40 ℃ of following anaerobism were cultivated 12～24 hours, changed seed over to fermention medium again, carried out anaerobism or aerobic under 35 ℃～40 ℃ conditions and cultivated 12～24 hours, and adopting 3～4M alkaline solution or ammoniacal liquor, control pH is 5～6.
8, the preparation method of 3-hydroxy propanal as claimed in claim 1, it is characterized in that: the process of glycerine converting is scattered in the aqueous solution for the thalline washing of fermentation being finished the back acquisition, filtration, after centrifugal again in the described step (2), directly add pure glycerin in the aqueous solution of mycetome, glycerol concentration is controlled at 20～60g/L in the aqueous solution, behind 37 ℃ of following stirring reaction 30min～120min, after filtration or can obtain the pure 3-hydroxy propanal aqueous solution behind the centrifugation thalline; It is reusable to separate the thalline that obtains, and also can use the mixing solutions activation of glucose concn 1～5g/L, glycerol concentration 10～20g/L to reuse after 1～3 hour.
9, the preparation method of 3-hydroxy propanal as claimed in claim 8 is characterized in that: described glycerine is as substrate, derives from a kind of in the raw glycerine of by product raw glycerine in refining glycerine, the production of biodiesel process or soapmaking industry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013518573A (en) * | 2010-02-02 | 2013-05-23 | バイオガイア・エイ・ビー | Improvement of immunomodulatory properties of Lactobacillus strains |
| WO2024077181A1 (en) * | 2022-10-06 | 2024-04-11 | Microbyre, Inc. | Methods of producing reuterin and propenoic acid using an isolated strain of lactobacillus reuteri |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013518573A (en) * | 2010-02-02 | 2013-05-23 | バイオガイア・エイ・ビー | Improvement of immunomodulatory properties of Lactobacillus strains |
| WO2024077181A1 (en) * | 2022-10-06 | 2024-04-11 | Microbyre, Inc. | Methods of producing reuterin and propenoic acid using an isolated strain of lactobacillus reuteri |
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