| IL124800A 1998-06-08 Application filed by Givaudan Roure Int Example 1 250 mL shake flasks containing 50 mL of the following medium were prepared: 103 gL"1 sucrose, 4 gL"1 Na2HP04, 1 gL'1 KH2PO4, 1 gL-1 yeast extract, 0.2 gL'1 NaCl, 0.2 gL"1 MgS04 and 0.05 gL"1 CaCl2. The pH was adjusted to 7.2 using NaOH. A shake flask was inoculated with 2 mL of preculture of Streptomyces setonii ATCC 39116 and cultivated at 37°C, 190 rpm for 16 hours. At the end of the growth phase 0.3 g ferulic acid (purchased from Aldrich, cat. no. 12.870-8, 99%) was added to the culture. For this - 8 -purpose a 10 % w/w solution of the acid substrate in 0.5 M NaOH (final pH of the solution was approximately 7.2) was previously prepared and sterile-filtered. The flask was incubated again at 37°C, 190 rpm. After 31.5 hours of biotransformation (incubation) a vanillin concentration of 3.10 L"l (HPLC) was reached. A molecular yield of 66 mol % was calculated. | DE19532317A1 1995-09-01 Haarmann & Reimer Gmbh Example 3 Production of vanillin in a 10 l fermenter 5 l culture medium (4 g / l glucose, 10 g / l malt extract and 6 g / l yeast extract) were sterilized in a fermenter and after cooling with 100 ml of a Pre-culture of DSM 9992 inoculated according to Example 1. The culture conditions were: 37 ° C, 500 rpm, 5 l air / min. 12.5 hours after 1.634 kg of an approximately 3.7% ferulic acid solution (60.2 g Ferulic acid) added. After 17.5 hours over a period of 10 Hours another 4.377 kg of an approximately 3.7% ferulic acid solution (164.72 g Ferula acid) pumped in. The fermentation was stopped after 32 hours. The concentration on Vanillin was 11.5 g / l and 1 g / l of unreacted ferulic acid was still present. The final volume was 11.29 l. This is an implementation of 77.8% of theory based on converted ferulic acid. |
| WO-2022133274-A1
Biosynthesis of vanillin from isoeugenol Basf
Se, Basf Corporation
2020-12-18
2022-06-23 BACKGROUND OF THE INVENTION Vanilla flavors are among some of the most frequently used flavors worldwide. They are used in the flavorings of numerous foods such as ice cream, dairy products, desserts, confectionary, bakery products and spirits. They are also used in perfumes, pharmaceuticals and personal hygiene products. Natural vanilla flavor has been obtained traditionally from the fermented pods of vanilla orchids. It is formed mainly after the harvest during several weeks of a drying and fermentation process of the beans by hydrolysis of vanillin glucoside that is present in the beans. The essential aromatic substance of vanilla flavor is vanillin (4-hydroxy 3- methoxybenzaldehy de) . Vanillin is one of the most common flavor chemicals and is widely used in the food and beverage, perfume, pharmaceutical, and medical industries. About 12,000 tons of vanillin is consumed annually, of which only 20-50 tons are extracted from vanilla beans, the rest is produced synthetically, mostly from petrochemicals such as guaiacol and lignin. In recent years, increasing demands for natural flavors have led the flavor industry to produce vanillin by bioconversion, as the products of such bioconversion are considered natural by various regulatory and legislative authorities (e.g., European Community Legislation) when produced from biological sources such as living cells or their enzymes, and can be marketed as “natural products”. Natural isoeugenol can be extracted from essential oils and is economical to use for the production of vanillin by enzymatic conversion or microbial bioconversion. Vanillin production via conversion of isoeugenol has been widely reported in a number of microorganisms, including Aspergillus niger, Bacillus subtilis, and Pseudomonas putida. However, the reported titers produced by these microorganisms were very low (less than 2 g/L), significantly limiting the practical application of this approach in the industry. Moreover, the reported bioconversion processes were complicated, further increasing the cost of vanillin production. Accordingly, there is a need in the art for more cost-effective methods for producing vanillin with higher titers and conversion rates. | Example 6: Bioconversion of isoeugenol to vanillin in fermenter
A fermentation process was developed for the bioconversion of
isoeugenol to vanillin using the E. coli strain ISEG-V224 in fermenters.
One ml of glycerol stock of ISEG-V224 was inoculated into 100 mL seed
culture medium (Luria-Bertani medium with 5g/L yeast extract, lOg/L
tryptone, lOg/L NaCl, and 50mg/L kanamycin) in 500 mL flasks. The seed
was cultivated in a shaker with shaking speed of 200rpm at 37 °C for 8
hours and then transferred into 2 liter of fermentation medium of
Luria-Bertani medium plus 6 g/L initial glucose, 50mg/L kanamycin in a 5
-liter fermenter.
The present fermentation process has two phases; namely, a cell growth
phase and a bioconversion phase. The cell growth phase was from 0 hour
to 17 hours and is referred as elapsed fermentation time (EFT). During
EFT, the fermentation parameters were set as follows: Air flow: 0.6vvm;
pH was controlled not to go below 7.1 by using 4N NaOH. The growth
temperature was set to 30°C and the agitation speed was set to 300-500
rpm. The level of dissolved oxygen (DO) was maintained above 30%. At EFT
6.5h, IPTG was added to a final concentration of 0.5mM and glucose was
fed at a rate of 0.4 g/L/hour for 17 hours.
The bioconversion phase was from EFT 17 hour to 46.5 hour. The fermentation parameters were set as follows: Air flow: 0.4vvm. pH was controlled not to go below 8.0 with 4N NaOH, and the temperature was kept at 30°C. Agitation was set to 250-500 rpm and DO was maintained above 30%. The feeding of isoeugenol at a rate of 1.5 g/L began at EFT 17 hour and continued for 4 hours. At EFT 21 hours, the isoeugenol feeding rate was reduced to 1 g/L. At EFT 23 hours, the isoeugenol feeding rate was further reduced to 0.6 g/L/hour and maintained for another 8 hours. Samples were collected at specific time intervals, then analyzed by HPLC as described in Example 4. [00126] Referring to FIG. 6, using a 5-liter fermenter, the E. coli strain ISEG-V224 which was transformed with the UmlEM gene was able to produce vanillin using isoeugenol as the substrate at a titer as high as 14.8 g/L. It is also worth noting that the molar conversion rate from isoeugenol to vanillin reaches above 90%. |
| from US4021493A (1975) It is known that vanillin can be made by oxidizing a lignin or lignosulfonate material, such as results from the kraft and sulfite cooking processes for producing pulp. The oxidation is carried out at elevated temperatures and pressures in the presence of an oxygen-containing gas in an alkaline solution. The resulting alkaline aqueous solution contains in addition to the desired vanillin, the unwanted contaminants, such as orthovanillin, acetovanillone, para-hydroxybenzaldehyde and syringaldehyde, which must be removed from the vanillin if the vanillin is to be of high purity and quality. Numerous processes have been proposed for purifying vanillin from alkaline solutions. These include Sandborn U.S. Pat. No. 2,104,701. This patent treats by countercurrent extraction the aqueous alkaline solution of vanillin with a suitable water-immiscible solvent, such as normal butyl alcohol, and recovers the solvent for reuse. The vanillin is removed from the solvent and is subjected to further purification by any known means, such as by distilling the solvent as its water-binary mixture to leave the vanillin compound in an alkaline aqueous solution for further refining. Other patents employing butyl alcohol extractions include U.S. Pat. Nos. 2,399,607, 2,104,701 and 2,489,200. Other patents employ propyl alcohol or isopropyl alcohol as the extractant, such as U.S. Pat. No. 2,721,221. Other patents disclosed purification of vanillin by employing distillation treatments such as U.S. Pat. Nos. 2,506,540 and 2,745,796. While the foregoing treatments are useful in purifying vanillin, it is desired to provide improved processes which more efficiently and effectively isolate and separate vanillin from its chemically related contaminating impurities. Accordingly, it is an object of the present invention to provide an efficient and effective process for removing and purifying vanillin from aqueous alkaline solutions containing contaminants. |  |
| US20240158329A1 (2021) Method for purifying vanillin or derivatives thereof obtained by a biotechnological method Abstract The present invention relates to a process for purifying a fermentation must (M), obtained via a biotechnological process, comprising biomass and vanillin or derivatives thereof in aqueous solution, for the preparation of a crystallized vanillin or derivatives thereof, characterized in that, throughout the purification process, the vanillin or derivatives thereof in protonated or salified form remain in aqueous solution. |
| PROCESS FOR PURIFYING VANILLIN BY LIQUID-LIQUID EXTRACTION FR2984314B1 Abstract translated from French Worldwide applications 2011 FR 2012 A process for the purification of vanillin, from a solution of vanillin in a solvent S1 containing impurities, is described, comprising the following steps: a) a step of evaporation of the solvent S1 in the presence of water to obtain an aqueous solution vanillin; b) a liquid/liquid extraction step by bringing the aqueous solution obtained at the end of step a) into contact with a solvent S2, at a pH greater than 8 and less than 10, to obtain an organic phase and an aqueous phase containing vanillin and residual solvent S2; c) a step of precipitation, at a pH comprised from 4 to 7.5, of the vanillin contained in the aqueous phase obtained at the end of step b), and d) a step of isolation of the vanillin. |
|
CN111548260A * 2020-06-02 2020-08-18
上海欣晨新技术有限公司 Separation method of 6-methyl vanillin and vanillin Separation method of 6-methyl vanillin and vanillin Abstract The invention provides a separation method of vanillin and impurity 6-methyl vanillin, which realizes the good separation of 6-methyl vanillin and vanillin by extracting the mixed solution containing vanillin, 6-methyl vanillin and other impurities with alcohol water; wherein, an appropriate extractant alcohol aqueous solution is selected, and the mass concentration of alcohol in the alcohol aqueous solution is 20-60%; the weight ratio of the solvent for alcohol-water extraction is (0.5-4): 1; furthermore, the method can well realize the effective separation of vanillin, 6-methyl vanillin and other impurities in the vanillin crystallization mother liquor, so that the vanillin finished product obtained in the separation and refining process can meet higher quality requirements, the loss of vanillin in the separation process is reduced, and the yield of vanillin is improved. |
| DE19532317A1
1995-09-01 1997-03-06 Haarmann & Reimer
Gmbh Process for the production of vanillin and suitable
microorganisms Claims (4) translated from German 1. Amycolatopsis sp. from the genus Pseudonocardia with the in the German Collection for Microorganisms and Cell Cultures GmbH in Braunschweig under the numbers DSM 9991 and DSM 9992 Tribes. 2. Process for the preparation of vanillin from ferulic acid in the presence of Amycolatopsis sp. DSM 9991 or DSM 9992 or its enzymes or of microorganisms with genetic material from Amycolatopsis sp. DSM 9991 or DSM 9992, which are the structural and regulatory genes for the Encodes enzymes that are effective in this reaction. 3. The method according to claim 2, according to which natural as the starting component uses ferulic acid. 4. Use of the produced by the method according to claims 2 and 3 Vanillins for the production of flavors. Example 3 Production of vanillin in a 10 l fermenter 5 l culture medium (4 g / l glucose, 10 g / l malt extract and 6 g / l yeast extract) were sterilized in a fermenter and after cooling with 100 ml of a Pre-culture of DSM 9992 inoculated according to Example 1. The culture conditions were: 37 ° C, 500 rpm, 5 l air / min. 12.5 hours after 1.634 kg of an approximately 3.7% ferulic acid solution (60.2 g Ferulic acid) added. After 17.5 hours over a period of 10 Hours another 4.377 kg of an approximately 3.7% ferulic acid solution (164.72 g Ferula acid) pumped in. The fermentation was stopped after 32 hours. The concentration on Vanillin was 11.5 g / l and 1 g / l of unreacted ferulic acid was still present. The final volume was 11.29 l. This is an implementation of 77.8% of theory based on converted ferulic acid. |
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