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WO2016005998A1 - Procédé pour l'isolement de la vanilline à partir de paille de riz - Google Patents

Procédé pour l'isolement de la vanilline à partir de paille de riz Download PDF

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Publication number
WO2016005998A1
WO2016005998A1 PCT/IN2015/050059 IN2015050059W WO2016005998A1 WO 2016005998 A1 WO2016005998 A1 WO 2016005998A1 IN 2015050059 W IN2015050059 W IN 2015050059W WO 2016005998 A1 WO2016005998 A1 WO 2016005998A1
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WO
WIPO (PCT)
Prior art keywords
rice straw
vanillin
process according
solvent
acid
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Application number
PCT/IN2015/050059
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English (en)
Inventor
Archana Moni DAS
Abdul Aziz ALI
Dilip Konwar
Tarun Chandra BORA
Manash Protim HAZARIKA
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Council Of Scientific & Industrial Research
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Publication of WO2016005998A1 publication Critical patent/WO2016005998A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/025—Recovery by solvent extraction

Definitions

  • the present invention relates to a process for the isolation of Vanillin (4-hydroxy- 3-methoxy benzaldehyde) by modified convenient process (extraction with organic solvent) of pretreated cellulose from rice straw, a renewable agricultural waste.
  • This invention is also relates to the extraction of vanillin using organic solvents (reusable) in a very cheap and convenient method from a renewable agriculture resource, rice straw. The process does not involve any costly or hazardous chemicals.
  • Vanillin is one of the most important and popular aromatic flavor materials used extensively in foods, beverages, perfumes, cosmetic and pharmaceuticals industries. More than 10 thousand tons per year had been produced by the industries all over the world through chemical synthesis. Demands increasing extensively and existing is not sufficient for the demands. Natural vanillin is mainly obtained from Vanilla planifolia pods which is very much expensive compared to synthetic vanillin derived from various compounds. This 'natural' vanillin, can cover only 1 % of the global demand and the cost is (US $ 4,00.00-500.00 per kilogram) [Virginia Commonwealth University News, 14.04.2003, vcunews@vcu.edu].
  • ferulic acid is first isolated from its source, which is converted to vanillin and vanillic acid using microbes [Synthesis of vanillin from a carbon source; John W. frost, U.S. Pat. No. 6,372,461].
  • the drawback of the method is that the extraction of ferulic acid from paddy straw was carried out via alkaline hydrolysis and was optimized through Central Composite Design (CCD) to give 4.092 g/l corresponding to 0.818% of ferulic acid. Ferulic acid was further utilized as a substrate for the biotransformation of vanillin and resulting in multiple steps.
  • CCD Central Composite Design
  • Vanillin from isoeugenol by using soil stains like Pseudomonas aeruginosa [Use of growing cells of Pseudomonas aeruginosa for synthesis of the natural vanillin via conversion of isoeugenol; Iraj Nahvi et al, Egyptian J.Phar.Res., 10(4), 749-757, 2011]
  • vanillin is prepared from isoeugenol by using soil stains like Pseudomonas aeruginosa.
  • Vanillin from Oryzae sativa by biotransformation method using Aspergillus niger and Phanorochaete [Aromatic benzaldehyde from oryzae sativa; Noor Hasyierah Md. Salleh et al, IPCBEE, 9, 140-144, 201 1]
  • vanillin is Vanillin from Oryzae sativa by biotransformation method using Aspergillus niger and Phanorochaete chrysosporium through two steps of bioengineering.
  • ferulate is extracted from rice straw and that ferulate is oxidized by hydrogen peroxide in the presence of manganese acetate etc. with co-catalyst from salts of cobalt, nickel etc. for conversion of vanillin.
  • the drawback of the method is that it uses ferulate from rice straw, hydrogen peroxide, manganese acetate, salt of cobalt etc. to get vanillin with multi steps reactions and vanillyl alcohol and furfurel present with the vanillin. Also, the yield of the vanillin was 0.012%.
  • biotechnological processes require multi-steps, heavy investment and stringent control to dictate the specific enzymes to work, and have high risk of mutation or inhibition of growth of microorganisms in presence of metabolites and are slow.
  • This invention shows a new method aimed to preparation of vanillin today must concern itself for use of renewable resources and cheap and easily available chemicals.
  • the ideal raw material is the supernatant obtained from the precipitation of lignin from alkali solution (1-3.5%) containing agro-wastes such as rice straw, which is cheap and abundant.
  • the main objective of the present invention is to provide a handy method for the isolation of vanillin from pretreated cellulose of rice straw which obviates the drawbacks of the previously reported methods known prior art as detailed above.
  • Yet another objective of the present invention is to provide a process for the isolation of vanillin by directly from the supernatant of the alkali solution after precipitation of lignin of pretreated cellulose from rice straw thereby reducing the cost of the chemicals to the minimal and avoiding the release of the toxic chemicals to the environment.
  • the present invention provides a method for the preparation of vanillin from rice straw which comprises a. mixing the rice straw with base solution under reflux conditions for a period of 3-10 hours for pretreatment, then cooling to a temperature of about 25- 30° C and separating the solid mass by filtration, collecting the filtrate, b. acidification of the said filtrate to pH 2-3 using mineral acid to separate the lignin part from the liquid by further filtration, c. after filtration extracting the supernatant with an organic solvent followed by removing the moister with anhydrous salts, d. separating the salts from the liquid by filtration, and drying the resultant organic layer to obtain the desired crude product, e.
  • step e purifying, drying and further recrystallizing the crude product by using solvent to get the white crystalline solid product as vanillin
  • step e solvent used in step e is recovered and reused for further experiments
  • g. vanillin obtained from the said process has melting point 82-85 °C, with a yield in the range of 0.1 to 0.2% and has sweet flavor.
  • rice straw is obtained by Cleaning and drying and is cut and milled, which is extracted with ethanol in a soxhlet apparatus to remove fats and coloring materials to obtain the starting material for pretreatment of rice straw.
  • base solution used for pretreatment of the rice straw is selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and sodium carbonate and in the range of 1 % in 200 ml-3.5% in 200 ml per 10 gm of rice straw used.
  • the organic solvent used is selected from the group consisting of dichloromethane, dichloroethane, methanol, ethyl acetate, particularly dichloromethane in the range of 40-80 ml for 10-20 gm of pretreated rice straw used.
  • the mineral acid used is selected from the group consisting of sulphuric acid, hydrochloric acid or perchloric acid etc, particularly sulphuric acid and in the range of 10-20 ml per 10 gm of pretreated rice straw used.
  • temperature used is refluxing condition is in the range of 90-100 °C.
  • anhydrous salt used is anhydrous sodium sulphate, potassium sulphate, calcium sulphate etc.
  • drying is done by evaporating the solvent under reduced pressure.
  • solvent used in step e of claim 1 is selected from dichloromethane, ethanol, methanol, propanol or acetic acid.
  • the renewable agrowaste used is rice straw.
  • Rice straw a renewable resource, which on treatment under mild reaction conditions- sodium base/ potassium base /calcium hydroxide /sodium carbonate, sulphuric acid/ hydrochloric acid/perchloric acid, extracted with ethyl acetate/chloroform/ dichloromethane/ dichloroethane etc and on refluxing produces vanillin in a easiest method particularly extraction with dichloromethane.
  • This is the new method where vanillin is produced from pretreated cellulose of rice straw a renewable resource which is convenient and cost effective.
  • This method reported in the invention is novel and non-obvious.
  • the filtrate obtained after filtration of lignin was extracted with dichloromethane (40 ml) and washed the organic layer with water for 2-3 times. After that treated with anhydrous sodium sulphate to absorb the moisture content present the organic layer and filtered to separate sodium sulphate.
  • the organic solvent was evaporated under reduced pressure to get the crude product.
  • the solvent used in the method is recovered and reused for further experiments.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure. For recrystallization of the product using methanol to give the white crystalline solid product with sweet flavor, melting point 82-85 °C (Reported 81-83 °C).
  • the vanillin was estimated 10 mg (0.1 %).
  • Dry rice straw 500 grams was extensively washed with distilled water in order to remove impurities (mainly dust).
  • the materials were first dried in sunlight and cut into smaller pieces and milled to pass through a 1-2 mm mesh and extracted with methanol in a soxhlet apparatus to remove fats and coloring materials. This rice straw was preserved and used in subsequent experiments.
  • the filtrate obtained after filtration of lignin was extracted with dichloromethane (40 ml) and washed the organic layer with water for 2-3 times. After that treated with anhydrous sodium sulphate to absorb the moisture content present the organic layer and filtered to separate sodium sulphate.
  • the organic solvent was evaporated under reduced pressure to get the crude product.
  • the solvent used in the method is recovered and reused for further experiments.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure. For recrystallization of the product using methanol to give the white crystalline solid product with sweet flavor, melting point 82-85 °C (Reported 81-83 °C).
  • the vanillin was estimated 14 mg (0.14%).
  • Dry rice straw 500 grams was extensively washed with distilled water in order to remove impurities (mainly dust).
  • the materials were first dried in sunlight and cut into smaller pieces and milled to pass through a 1-2 mm mesh and extracted with petroleum ether (60-80 °C) in a soxhlet apparatus to remove fats and coloring materials. This rice straw was preserved and used in subsequent experiments.
  • the filtrate obtained after filtration of lignin was extracted with dichloromethane (40 ml) and washed the organic layer with water for 2-3 times. After that treated with anhydrous sodium sulphate to absorb the moisture content present the organic layer and filtered to separate sodium sulphate.
  • the organic solvent was evaporated under reduced pressure to get the crude product.
  • the solvent used in the method is recovered and reused for further experiments.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure. For recrystallization of the product using methanol to give the white crystalline solid product with sweet flavor, melting point 82-85 °C (Reported 81-83 °C).
  • the vanillin was estimated 20 mg (0.2%).
  • Dry rice straw 500 grams was extensively washed with distilled water in order to remove impurities (mainly dust).
  • the materials were first dried in sunlight and cut into smaller pieces and milled to pass through a 1-2 mm mesh and extracted with petroleum ether (60-80 °C) in a soxhlet apparatus to remove fats and coloring materials. This rice straw was preserved and used in subsequent experiments.
  • Dry rice straw 500 grams was extensively washed with distilled water in order to remove impurities (mainly dust).
  • the materials were first dried in sunlight and cut into smaller pieces and milled to pass through a 1-2 mm mesh and extracted with methanol in a soxhlet apparatus to remove fats and coloring materials. This rice straw was preserved and used in subsequent experiments.
  • the filtrate obtained after filtration of lignin was extracted with chloroform (40 ml) and washed the organic layer with water for 2-3 times. After that treated with anhydrous pottasium sulphate to absorb the moisture content present the organic layer and filtered to separate pottasium sulphate.
  • the organic solvent was evaporated under reduced pressure to get the crude product.
  • the solvent used in the method is recovered and reused for further experiments.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure. For recrystallization of the product using methanol to give the white crystalline solid product with sweet flavor of melting point 82-85 °C (Reported 81-83 °C).
  • the vanillin was estimated 13 mg (0.13%).
  • the filtrate obtained after filtration of lignin was extracted with methanol (80 ml) and washed the organic layer with water for 2-3 times. After that treated with anhydrous calcium sulphate to absorb the moisture content present the organic layer and filtered to separate calcium sulphate.
  • the organic solvent was evaporated under reduced pressure to get the crude product.
  • the solvent used in the method is recovered and reused for further experiments.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure. For recrystallization of the product using methanol to give the white crystalline solid product with sweet flavor of melting point 82-85 °C (Reported 81-83 °C).
  • the vanillin was estimated 11 mg (0.11 %).
  • the used solvent was recovered by using rotating-evaporator to get the crude (solid) product as well as distilled solvent (36-78 ml) which was used for our further reaction systems. This way we were using the recycled solvents in our reaction systems.
  • the crude product was purified by column chromatography technique using hexane : ethyl acetate :: 10:1 as eluent, and evaporated the solvent to get the desired product under reduced pressure.
  • the vanillin was estimated 20 mg (0.2%).
  • Pretreated cellulose of Agro-waste such as rice straw produces vanillin in a convenient and handy method.
  • the solvent used for the reaction system can be recycled, hence cost effective.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour l'isolement de la vanilline (4-hydroxy-3-méthoxy-benzaldéhyde) par un procédé pratique (extraction avec un solvant organique) sur de la cellulose prétraitée provenant de paille de riz, qui fait partie des déchets agricoles renouvelables. La présente invention concerne l'extraction de la vanilline à l'aide de solvants organiques (réutilisables) d'une manière pratique et très peu coûteuse à partir d'une ressource agricole renouvelable, la paille de riz.
PCT/IN2015/050059 2014-07-08 2015-07-03 Procédé pour l'isolement de la vanilline à partir de paille de riz WO2016005998A1 (fr)

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IN1879/DEL/2014 2014-07-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170549A1 (fr) * 2016-03-29 2017-10-05 東レ株式会社 Procédé de production d'acide hydroxycinnamique
EP4308535A1 (fr) * 2021-03-15 2024-01-24 Specialty Operations France Procédé de purification de vanilline ou d'un dérivé de vanilline obtenus par un procédé biotechnologique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372461B1 (en) 1998-09-18 2002-04-16 Board Of Directors Operating Michigan State University Synthesis of vanillin from a carbon source
WO2007094013A1 (fr) * 2006-02-13 2007-08-23 Council Of Scientific & Industrial Research Procédé de synthèse de vanilline à partir de déchets végétaux agricoles par oxydation catalysée par sel de manganèse et employant du peroxyde d'hydrogène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372461B1 (en) 1998-09-18 2002-04-16 Board Of Directors Operating Michigan State University Synthesis of vanillin from a carbon source
WO2007094013A1 (fr) * 2006-02-13 2007-08-23 Council Of Scientific & Industrial Research Procédé de synthèse de vanilline à partir de déchets végétaux agricoles par oxydation catalysée par sel de manganèse et employant du peroxyde d'hydrogène
US7399889B2 (en) 2006-02-13 2008-07-15 Council Of Scientific And Industrial Research Process for the preparation of vanillin from agricultural waste

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
EKHE, J.D. ET AL.: "ISOLATION AND CHARACTERIZATION OF LIGNIN DEGRADATION PRODUCTS FROM BAGASSE AND RICE STRAW", IPPTA, INDIAN PULP AND PAPER TECHNICAL ASS., vol. 9, no. 2, 1997, pages 21 - 28, XP008079325, ISSN: 0379-5462 *
HERRMANN, W.A. ET AL.: "Methyltrioxorhenium: oxidative cleavage of CC-double bonds and its application in a highly efficient synthesis of vanillin from biological waste", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 153, no. 1-2, 2000, pages 49 - 52, XP002435577, ISSN: 1381-1169, DOI: 10.1016/S1381-1169(99)00370-2 *
IRAJ NAHVI ET AL.: "Use of growing cells of Pseudomonas aeruginosa for synthesis of the natural vanillin via conversion of isoeugenol", IRANIAN J. PHAR. RES., vol. 10, no. 4, 2011, pages 749 - 757
NOOR HASYIERAH MOHD SALLEH ET AL.: "Optimization of alkaline hydrolysis of paddy straw for ferulic acid extraction", INDUSTRIAL CROPS AND PRODUCTS, ELSEVIER, NL, vol. 34, no. 3, 7 June 2011 (2011-06-07), pages 1635 - 1640, XP028381749, ISSN: 0926-6690, [retrieved on 20110613], DOI: 10.1016/J.INDCROP.2011.06.010 *
NOOR HASYIERAH, M. S.; MOHAMED ZULKALI, M. D.; DACHYAR ARBAIN, JIRCAS, vol. 73, 2012, pages 160 - 165
NOOR HASYIERAH, M.S. ET AL.: "Formulation of vanillin derived from paddy straw", JIRCAS WORKING REPORT, MINISTRY OF AGRICULTURE, FORESTRY AND FISHERIES, TSUKUBA, JP, vol. 73, 2012, pages 160 - 165, XP009187147, ISSN: 1341-710X *
SALLEH ET AL.: "Aromatic benzaldehyde from oryzae sativa", IPCBEE, vol. 9, 2011, pages 140 - 144
VIRGINIA COMMONWEALTH UNIVERSITY NEWS, 14 April 2003 (2003-04-14), Retrieved from the Internet <URL:vcunews@vcu.edu>

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170549A1 (fr) * 2016-03-29 2017-10-05 東レ株式会社 Procédé de production d'acide hydroxycinnamique
JP6278163B1 (ja) * 2016-03-29 2018-02-14 東レ株式会社 ヒドロキシ桂皮酸の製造方法
US10519093B2 (en) 2016-03-29 2019-12-31 Toray Industries, Inc. Method of producing hydroxycinnamic acids
AU2017244704B2 (en) * 2016-03-29 2021-07-08 Toray Industries, Inc. Method for producing hydroxycinnamic acid
EP4308535A1 (fr) * 2021-03-15 2024-01-24 Specialty Operations France Procédé de purification de vanilline ou d'un dérivé de vanilline obtenus par un procédé biotechnologique

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