CN104480148A - Process for synthesizing vanillin by adopting bio-enzyme catalytic oxidation method - Google Patents
Process for synthesizing vanillin by adopting bio-enzyme catalytic oxidation method Download PDFInfo
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- CN104480148A CN104480148A CN201410770545.0A CN201410770545A CN104480148A CN 104480148 A CN104480148 A CN 104480148A CN 201410770545 A CN201410770545 A CN 201410770545A CN 104480148 A CN104480148 A CN 104480148A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
Abstract
The invention relates to a method for synthesizing vanillin by adopting a bio-enzyme catalytic oxidation method. The method comprises the following steps: sequentially adding a solvent, a primer coniferyl alcohol/coniferyl aldehyde/ferulic acid, lipase, binary acid or a binary acid derivative and urea hydrogen peroxide in a reaction kettle, wherein lipase accounts for 1-4wt% of the primer isoeugenol, the molar mass of the binary acid or the binary acid derivative is 0.75-1.5 times that of the primer; the molar mass of urea hydrogen peroxide is 1-2 times that of the primer, wherein the adding temperature of urea hydrogen peroxide is 15-35 degrees, the reaction temperature is 20-40 degrees and the reaction time is 14-36 hours; filtering, separating and recycling urea and an enzyme-catalyst, diluting the filtrate by water, extracting by using an organic solvent, recrystallizing by edible alcohol and drying to obtain vanillin; and complexing the mother liquor extracted by the organic solvent by virtue of sodium hydrogen sulfite or sodium sulfite to recover the byproduct of aldehyde. The vanillin yield of the method can reach 85% and the method is simple in reaction step, mild in condition, strong in catalytic specificity, hard to generate byproducts, high in product yield, environmentally friendly and easy to amplify.
Description
Technical field
The present invention relates to a kind of technique adopting biological enzyme synthesis of vanillin.
Background technology
Vanillin food grade,1000.000000ine mesh (Vanillin), have another name called Vanillin, 4-hydroxyl-3-methoxylbenxaldehyde etc., it is the main component in the blue beans of fragrant folder, chemical name is Vanillin, relative molecular weight is 152.1, outward appearance is white extremely micro-yellow needle-like crystals or powder, presents the distinctive fragrance of bean pod of Herba vanillae Planifoliae, micro-sweet.Vanillin food grade,1000.000000ine mesh is one of spices that output is maximum, purposes is the widest in the world.Be widely used in the food such as chocolate, ice-creams, candy and cigarette, beverage and the cosmetics of super quality.It not only can be used as sweetener, also in food, be used as sanitas, preservation agent, antioxidant, correctives or fixative, wherein the food consumption such as beverage, candy, cake, biscuit, bread and roasted seeds and nuts is in the majority, and in other industry, as medicine, plating, agricultural etc. also have larger application.
The production method of current vanillin food grade,1000.000000ine mesh mainly contains plant extraction method, chemical synthesis and biological synthesis process.Plant extraction method produces the beanpod of raw material from Herba vanillae Planifoliae of vanillin food grade,1000.000000ine mesh.Vanillin food grade,1000.000000ine mesh only containing 2% ~ 3% in the beanpod of Herba vanillae Planifoliae, Herba vanillae Planifoliae is not easily planted and is mainly distributed in minority torrid areas.Owing to being subject to the beanpod supply quantitative limitation of starting material Herba vanillae Planifoliae, this makes the natural vanillin only extracted from Herba vanillae Planifoliae can not meet Demand in World Market far away.Vanillin food grade,1000.000000ine mesh products most is in the market by chemosynthesis, as methyl catechol and oxoethanoic acid condensation process, although processing unit is simple, product purity is high, and raw material sources is extensive, but there is serious defect, such as environmental pollution is serious, product fragrance is single, and be easy to doping, the security of synthetic perfume is also under suspicion.
In order to solve natural vanillin limited source, expensive problem, people have developed the method that biotechnology prepares vanillin food grade,1000.000000ine mesh in recent years, microorganism (bacterium, yeast, fungi) can be utilized to ferment, animal, vegetable cell or their enzyme system produce natural vanillin food grade,1000.000000ine mesh, and gained vanillin food grade,1000.000000ine mesh meets the edible safety requirement of EU and FDA to natural essence.In microorganism, vanillin food grade,1000.000000ine mesh is the intermediate of xylogen, forulic acid, oxymethoxyallylbenzene, isoeugenol degradation pathway, so the research of synthesis of vanillin is a lot of from natural material.At present with forulic acid, lubanol, coniferyl aldehyde for substrate, utilizing biotechnology to prepare vanillin food grade,1000.000000ine mesh, has been one of focus developing direction in recent years.As " mulberry enterobacteria and utilize the method for its biologically transform ferulic acid production forulic acid natural vanillin " (Chinese patent CN103215197A) and " a kind of subtilis and biologically transform ferulic acid thereof produce the method for vanillin food grade,1000.000000ine mesh " (Chinese patent CN102443551A), although reactions steps is simple, mild condition, carbon source, nitrogenous source cost are low, but length consuming time, medium component is complicated, cost is large, and operational path yield not high (50-60%), be difficult to industrialization and amplify.(the US6331655 that and for example " prepared the preparation technology of aromatic carbonyl compounds by alkene ", United States Patent (USP)) and " a kind of method preparing vanillin food grade,1000.000000ine mesh " (Chinese patent, CN102367222) lipase and oxyphorase is adopted to be biological catalyst in respectively, catalysis hydrogen peroxide oxidation isoeugenol prepares vanillin food grade,1000.000000ine mesh, although reactions steps is simple, mild condition, time is short, but due to operational path yield low (40-55%), the shortcomings such as unstable product quality, are difficult to industrialization and amplify.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, providing a kind of reaction conditions gentle, catalysis high specificity, not easily produce by product, product yield is high, can be easy to the lipase-catalyzed method preparing vanillin food grade,1000.000000ine mesh of amplifying, the alternative natural product of the vanillin food grade,1000.000000ine mesh synthesized with this technique.
To achieve these goals, the present invention realizes by following technical scheme: the invention discloses a kind of lipase-catalyzed method preparing vanillin food grade,1000.000000ine mesh, in a kettle., successively through adding the step of solvent, substrate, lipase, diprotic acid or diprotic acid derivative, Urea Peroxide, wherein lipase quality is substrate quality 1%-4%; Diprotic acid or diprotic acid derivative molar mass are 0.75-1.5 times of substrate molar mass; Urea Peroxide molar mass is 1-2 times of substrate molar mass; It is 15-35 degree that Urea Peroxide adds temperature, and temperature of reaction is 20-40 degree, and the reaction times is after 14-36 hour, and filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through water, organic solvent extraction, and edible ethanol recrystallization, obtains vanillin food grade,1000.000000ine mesh after drying.Mother liquor after organic solvent extraction, through sodium bisulfite or S-WAT complexing, reclaims the by product of aldehyde.The vanillin food grade,1000.000000ine mesh yield of present method can reach 85%, and reactions steps is simple, mild condition, and catalysis high specificity, not easily produces by product, and product yield is high, environmentally friendly, can be easy to amplify.
The above substrate is lubanol, coniferyl aldehyde, forulic acid (comprising cis or trans or mixed type);
The above lipase is lipase Novozyme 435;
The above Urea Peroxide is the solid (content of hydrogen peroxide 36%) of commodity purchasing;
Above-described diprotic acid or diester are oxalic acid or oxalic acid two formicesters/diethyl ester, propanedioic acid or dimethyl malonate/bis-
Ethyl ester/, succinic acid or dimethyl succinate/diethyl ester/, oxalic acid methyl monoester/mono ethyl ester, malonic acid monomethyl ester/mono ethyl ester,
Any one or two kinds in monomethyl succinate/mono ethyl ester;
The above organic solvent is toluene or ethylbenzene or methyl tertbutyl ketone or methyl tertiary butyl ether or butylacetate;
The above edible ethanol concentration is 30-95%;
The present invention is with lubanol, coniferyl aldehyde, forulic acid for raw material, and take Urea Peroxide as oxygen source, lipase is catalyzer, carries out oxidizing reaction and prepare vanillin food grade,1000.000000ine mesh under diprotic acid or the effect of diprotic acid derivative.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention take biological enzyme as catalyzer, and reactions steps is simple, and one pot completes reaction, and reaction conditions is gentle, and energy consumption is low, and enzyme catalyst specificity is good, not easily produces by product, and technological operation is easy, and productive rate can reach 85%, is easy to amplify;
2, the present invention take Urea Peroxide as oxygen source, and oxygen source good stability is little to the side effect of biological enzyme, biological enzyme can be made to keep high activity and can reuse, and can reclaim urea, environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to the scope that embodiment represents.
Embodiment 1:
1, in 100 milliliters of there-necked flasks, add cis-ferulic oily matter (0.1mol, 19.4 grams), lipase Novozyme 435 (0.19 gram), under stirring, oxalic acid diethyl ester (0.15mol is dripped in 25 degree, 22 grams) Urea Peroxide (0.2mol, 18.8 grams) that dissolves, add complete in 1 hour, keep temperature 35 degree, react 36 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through the aqueous solution, adds N-BUTYL ACETATE extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxoethanoic acid sodium bisulfite affixture by product; Extraction liquid recovery of acetic acid butyl ester, crude product, with edible ethanol crystallization, obtains white needle-like crystals 11.7 grams, yield 77%.
Embodiment 2:
1, in 100 milliliters of there-necked flasks, toluene 20 milliliters is added, coniferyl aldehyde (0.1mol, 17.8 grams), lipase (0.5 gram), under stirring, add oxalic acid (0.15mol, 13.5 grams) in 15 degree, then divide 5 times and add Urea Peroxide (0.18mol, 16.9 gram), each 3.38 grams, temperature remains on 15 degree, adds complete in 2 hours, keep temperature 20 degree, react 16 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through the aqueous solution, adds toluene extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxalic dialdehyde sodium bisulfite affixture by product; Extraction liquid reclaims toluene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12.6 grams, yield 83%.
Embodiment 3:
1, in 100 milliliters of there-necked flasks, methyl tertiary butyl ether 20 milliliters is added, lubanol (0.1mol, 18 grams), lipase (0.4 gram), under stirring, add propanedioic acid (0.075mol, 7.8 grams) in 15 degree, then divide 5 times and add Urea Peroxide (0.15mol, 14.1 gram), each 2.82 grams, temperature remains on 15 degree, adds complete in 2.5 hours, keep temperature 30 degree, react 36 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through the aqueous solution, adds methyl tertiary butyl ether extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is glycollic aldehyde sodium bisulfite affixture by product; Extraction liquid reclaims methyl tertiary butyl ether, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 10.6 grams, yield 70%.
Embodiment 4:
1, in 100 milliliters of there-necked flasks, 20 milliliters, ethylbenzene is added, lubanol (0.1mol, 18 grams), lipase (0.3 gram), under stirring, drips diethyl malonate (0.15mol in 25 degree, 24 grams) Urea Peroxide (0.18mol that dissolves, 16.9 grams), temperature remains on 25 degree, adds complete in 1 hour, keep temperature 40 degree, react 30 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate adds aqueous solution dilution, adds ethylbenzene extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is glycollic aldehyde sodium bisulfite affixture by product; Extraction liquid reclaims ethylbenzene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 11.4 grams, yield 75%.
Embodiment 5:
1, in 100 milliliters of there-necked flasks, 20 milliliters, ethylbenzene is added, coniferyl aldehyde (0.1mol, 17.8 gram), lipase (0.6 gram), under stirring, drips dimethyl succinate (0.1mol in 20 degree, 14.6 grams) Urea Peroxide (0.1mol that dissolves, 9.4 grams), temperature remains on 20 degree, dropwises in 3 hours, slowly be warming up to 25 degree, react 36 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate adds aqueous solution dilution, adds ethylbenzene extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxalic dialdehyde sodium bisulfite affixture by product; Extraction liquid reclaims ethylbenzene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12.2 grams, yield 80%.
Embodiment 6:
1, in 100 milliliters of there-necked flasks, methyl tertbutyl ketone 20 milliliters is added, trans-ferulaic acid (0.1mol, 19.4 grams), lipase (0.6 gram), under stirring, add monomethyl succinate (0.1mol, 13.2 grams) in 30 degree, divide and add Urea Peroxide (0.15mol 5 times, 14.1 gram), each 2.82 grams, temperature remains on 30 degree, adds complete in 3 hours, slowly be warming up to 40 degree, react 36 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate adds aqueous solution dilution, adds the extraction of methyl tertbutyl ketone.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxoethanoic acid S-WAT affixture by product; Extraction liquid reclaims methyl tertbutyl ketone, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12 grams, yield 79%.
Embodiment 7:
1, in 100 milliliters of there-necked flasks, toluene 20 milliliters is added, mixed type forulic acid (0.1mol, 19.4 grams), lipase (0.5 gram), under stirring, add oxalic acid methyl monoester (0.1mol, 10.4 grams) in 20 degree, divide and add Urea Peroxide (0.2mol 5 times, 18.8 gram), each 3.76 grams, temperature remains on 20 degree, adds complete in 2.5 hours, keep temperature 40 degree, react 28 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate adds aqueous solution dilution, adds toluene extraction.Add S-WAT in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxoethanoic acid sodium bisulfite affixture by product; Extraction liquid reclaims toluene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12.6 grams, yield 83%.
Embodiment 8:
1, in 100 milliliters of there-necked flasks, toluene 20 milliliters is added, lubanol (0.1mol, 18 grams), lipase (0.7 gram), under stirring, add oxalic acid mono ethyl ester (0.1mol, 11.8 grams) in 35 degree, divide and add Urea Peroxide (0.11mol 5 times, 10.4 gram), each 2.08 grams, temperature remains on 35 degree, adds complete in 2.5 hours, keep temperature 40 degree, react 26 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate adds aqueous solution dilution, adds toluene extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is glycollic aldehyde sodium bisulfite affixture by product; Extraction liquid reclaims toluene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 11.7 grams, yield 77%.
Embodiment 9:
1, in 100 milliliters of there-necked flasks, methyl tertiary butyl ether 20 milliliters is added successively, coniferyl aldehyde (0.1mol, 17.8 grams), lipase (0.5 gram), under stirring, add dimethyl oxalate (0.15mol, 12.4 grams) in 25 degree, then divide 5 times and add Urea Peroxide (0.15mol, 14.1 gram), each 2.82 grams, temperature remains on 25 degree, adds complete in 2.5 hours, keep temperature 35 degree, react 24 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through the aqueous solution, adds methyl tertiary butyl ether extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxalic dialdehyde sodium bisulfite affixture by product; Extraction liquid reclaims methyl tertiary butyl ether, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12.9 grams, yield 85%.
Embodiment 10:
1, in 100 milliliters of there-necked flasks, toluene 20 milliliters is added successively, coniferyl aldehyde (0.1mol, 17.8 grams), lipase (0.5 gram), under stirring, oxalic acid (0.075mol is added under 25 degree, 6.75 grams), then add the Urea Peroxide (0.15mol that diethyl malonate (0.075mol, 12 grams) dissolves under 25 degree, 14.1 gram), add complete in 3 hours, keep temperature 30 degree, react 30 hours.
2, filtering separation reclaims urea and enzyme catalyst.Filtrate is diluted through the aqueous solution, adds toluene extraction.Add sodium bisulfite in mother liquor after extraction, freezing crystallization, filtered and recycled solid is oxalic dialdehyde sodium bisulfite affixture by product; Extraction liquid reclaims toluene, and crude product, with edible ethanol crystallization, obtains white needle-like crystals 12.2 grams, yield 80%.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (6)
1. adopt a technique for biological enzyme oxidation style synthesis of vanillin, it is characterized in that, comprise the steps:
1) solvent, substrate, lipase, diprotic acid or diprotic acid derivative are added successively in reactor, stir, controlling reactor temperature is 15-35 degree, add Urea Peroxide, be warming up to 20-40 degree, continue stirring reaction 14-36h, filter, Separation and Recovery filtrate, and obtain filtrate;
2) by step 1) filtrate dilute through the aqueous solution, with organic solvent extraction, then be 30-95% edible ethanol recrystallization by mass concentration, after drying, obtain vanillin food grade,1000.000000ine mesh.
2. the technique of employing biological enzyme oxidation style synthesis of vanillin according to claim 1, is characterized in that, by step 2) mother liquor after organic solvent extraction through sodium bisulfite or S-WAT complexing, reclaim the by product of aldehyde.
3. the technique of employing biological enzyme oxidation style synthesis of vanillin according to claim 1, is characterized in that, described substrate is lubanol, coniferyl aldehyde or cis-ferulic/trans-ferulaic acid/hybrid forulic acid.
4. the technique of employing biological enzyme oxidation style synthesis of vanillin according to claim 1, it is characterized in that, lipase quality is substrate quality 1%-4%; Diprotic acid or diprotic acid derivative molar mass are 0.75-1.5 times of substrate molar mass; Urea Peroxide molar mass is 1-2 times of substrate molar mass.
5. the technique of the employing biological enzyme oxidation style synthesis of vanillin according to claim 1 or 4, it is characterized in that, described lipase is lipase Novozyme 435; Described diprotic acid or diprotic acid derivative are C
2-C
4diprotic acid or diprotic acid derivative; Described organic solvent is toluene or ethylbenzene or methyl tertbutyl ketone or methyl tertiary butyl ether or butylacetate.
6. the technique of employing biological enzyme oxidation style synthesis of vanillin according to claim 5, is characterized in that, C
2-C
4diprotic acid or diester class comprise oxalic acid or oxalic acid two formicesters/diethyl ester, propanedioic acid or dimethyl malonate/diethyl ester/, succinic acid or dimethyl succinate/diethyl ester/, oxalic acid methyl monoester/mono ethyl ester, malonic acid monomethyl ester/mono ethyl ester, any one or two kinds in monomethyl succinate/mono ethyl ester.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106754773A (en) * | 2016-12-26 | 2017-05-31 | 波顿（上海）生物技术有限公司 | A kind of isoeugenol monooxygenase operon gene and its recombinant vector and restructuring pseudomonad |
| CN106947755A (en) * | 2017-04-05 | 2017-07-14 | 牡丹江医学院 | The lipase load hollow nano-sphere of vanillic aldehyde is prepared by catalytic oxidation |
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|---|---|---|---|---|
| US5017388A (en) * | 1989-06-20 | 1991-05-21 | Haarmann & Reimer Gmbh | Process for the preparation of vanillin |
| US5712132A (en) * | 1992-07-24 | 1998-01-27 | V. Mane Fils S.A. | Method for the enzymatic preparation of aromatic substances |
| US6331655B1 (en) * | 1999-06-19 | 2001-12-18 | Haarmann & Reimer Gmbh | Process for the preparation of aromatic carbonyl compounds from styrenes |
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2014
- 2014-12-12 CN CN201410770545.0A patent/CN104480148B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5017388A (en) * | 1989-06-20 | 1991-05-21 | Haarmann & Reimer Gmbh | Process for the preparation of vanillin |
| US5712132A (en) * | 1992-07-24 | 1998-01-27 | V. Mane Fils S.A. | Method for the enzymatic preparation of aromatic substances |
| US6331655B1 (en) * | 1999-06-19 | 2001-12-18 | Haarmann & Reimer Gmbh | Process for the preparation of aromatic carbonyl compounds from styrenes |
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| 计立等: "过氧化脲在氧化反应中的应用研究进展", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106754773A (en) * | 2016-12-26 | 2017-05-31 | 波顿（上海）生物技术有限公司 | A kind of isoeugenol monooxygenase operon gene and its recombinant vector and restructuring pseudomonad |
| CN106754773B (en) * | 2016-12-26 | 2020-04-24 | 波顿（上海）生物技术有限公司 | Isoeugenol monooxygenase operon gene, recombinant vector thereof and recombinant pseudomonas |
| CN106947755A (en) * | 2017-04-05 | 2017-07-14 | 牡丹江医学院 | The lipase load hollow nano-sphere of vanillic aldehyde is prepared by catalytic oxidation |
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Application publication date: 20150401 Assignee: Shenzhen xinshengrui Biotechnology Co.,Ltd. Assignor: BOTON (SHANGHAI) BIOTECHNOLOGY Co.,Ltd. Contract record no.: X2022980009383 Denomination of invention: A process for the synthesis of vanillin by biological enzyme catalytic oxidation Granted publication date: 20171208 License type: Common License Record date: 20220705 |
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