Project Report on Extraction of Synthetic Vanillin from Bagasse

Introduction
Vanilla is a climbing terrestrial orchid grown in warm humid tropics. It is the second most expensive flavouring spice after saffron. Vanilla planifolia is the commercially grown variety. Growing of vanilla beans is quite complicated and labour intensive and its processing is a slow process requiring skills. Quality of vanilla beans depends on the vanillin content (minimum 1.8-2.0% normally) and presence of 250 aromatics. Vanilla has a wide application. Beans are used for producing extracts, flavours, oleoresins and powders and have a wide range of use in dairy products, ice creams, for flavouring tobacco, liquors, beverages and confectionaries, savoury applications, medicinal purposes, health and personal care products and as an odour maskant in tires, paints, industrial chemicals etc.

Indian Vanilla: Road Ahead

India is currently producing 100MT of cured beans, which is likely to rise to 400 MT by 2006 as many growers in Karnataka, Kerala and Tamil Nadu have taken up vanilla cultivation as monocrop as well as intercrop in the year 2001-02. In the absence of demand for natural vanilla concentrates in India and large-scale natural vanillin extraction facilities in India, almost entire production of cured beans is exported to other countries in particular to USA, UK, France and Germany for further processing and extraction of natural vanillin. Indias domestic market for vanillin is completely dominated by synthetic vanillin due to its low price and easy availability. India imports around 600-700 MT of synthetic vanillin, which is mostly consumed by food and beverages industry (200 MT), ice-cream industry alone consuming about 130 MT. Hence instead of letting Indian Money flow outside the country we can capture it right here at convenient prices.

Indian vanilla, according to industrial sources is at par with Madagascar Bourbon vanilla in terms of vanillin content and quality, which made importers source vanilla beans from India in order to meet the demand of natural vanillin. In 2003-04, India exported 26 MT of cured vanilla beans at

Rs. 36.06 crore (US$ 8 million) registering a phenomenal annual average growth rate of 92 % between 1999-2003. According to certain latest estimates by Spices Board, vanilla exports from India have posted a 90% increase in quantity and a higher average price than Madagascar at US$ 47.30 a kg of cured beans during last fiscal. India came into the market with a small production last year at about 50 MT only. Currently India has 100MT of cured beans to offer to the international vanilla market.

Since the last season Indian growers has been fetching Rs. 900 (US$ 20) per kg of cured vanilla beans and on an average of Rs. 250 275 (US$ 5.5-6) for a kg of green beans. As per industry sources, currently Indian vanilla has been enjoying fairly good demand in the US, France, Germany, the Netherlands, UK and Japan. Considering the export potential, Spices Board has been encouraging vanilla cultivation as an intercrop to coconut, arecanut, coffee, cardamom and other spices in the states of Tamil Nadu, Karnataka and Kerala and also intends to provide support facilities for the expansion of area under the cultivation of vanilla, as an intercrop, to the states of Andhra Pradesh, Maharashtra, Madhya Pradesh, Orissa, West Bengal, Andamans and North Eastern States.

Vanilla Trade
Vanilla is internationally traded as pods or cured beans and its is the largest importer of the cured beans and extractors of natural vanilla extracts followed by EU and Japan. The type or category, of vanilla used determines how ice cream is labelled in the USA: Category 1: Natural vanilla extract. Two-fold vanilla is commonly used. Ice cream products must be labelled as vanilla ice cream. Category 2: Vanilla-vanillin extract. This is considered natural and artificial (N&A), where the natural component is the characterizing flavour. Ice cream products must be labelled as vanilla flavoured ice cream. Category 3: Natural and artificial vanilla flavours or artificial vanilla flavours, where the artificial component predominates. Ice cream products must be labelled artificially flavoured vanilla ice cream.

Vanillin: the compound responsible for the taste of vanilla.

IUPAC name 4-Hydroxy-3-methoxybenzaldehyde Other names Methyl vanillin Vanilin Vanillic aldehyde Identifiers CAS number PubChem ChemSpider UNII EC number KEGG MeSH ChEBI ChEMBL RTECS number Beilstein Reference Gmelin Reference 3DMet Jmol-3D images 121-33-5 1183 13860434 CHI530446X 204-465-2 D00091 vanillin CHEBI:18346 CHEMBL13883 YW5775000 472792 3596 B00167 Image 1

Properties Molecular formula Molar mass Exact mass Appearance Odor Density Melting point Boiling point Solubility in water log P Vapor pressure Acidity (pKa) Basicity (pKb) C8H8O3 152.15 g mol1 152.047344122 u White crystals Floral, pleasant 1.056 g cm-3 81-83 354-356 K, 178-181 C, F 285 558 K, 545 C, F 10 g dm-3 1.208 >1 Pa 7.781 6.216 Structure Crystal structure Monoclinic Thermochemistry Std enthalpy of combustion cHo298 Hazards MSDS GHS pictograms hazard.com -3.828--3.828 MJ mol-1

GHS signal word GHS hazard statements GHS precautionary statements

WARNING H302, H317, H319 P280, P305+351+338

EU classification R-phrases NFPA 704 R22

1 1 0
Flash point 147 C Related compounds Related compounds Anisaldehyde Eugenol Phenol

Vanillin is a phenolic aldehyde, an organic compound with the molecular formula C8H8O3. Itsfunctional groups include aldehyde, ether, and phenol. It is the primary component of the extract of the vanilla bean. Synthetic vanillin, instead of natural vanilla extract, is sometimes used as aflavoring agent in foods, beverages, and pharmaceuticals. Lignin-based artificial vanilla flavoring is alleged to have a richer flavor profile than oil-based flavoring; the difference is due to the presence of acetovanillone in the lignin-derived product, an impurity not found in vanillin synthesized from guaiacol.

Biosynthesis
The biosynthesis of vanillin is achieved by the conversion of tyrosine into 4-coumaric acid then into ferulic acid and finally into vanillin. Vanillin is then converted into its corresponding glucose ester.

Uses

Vanilla extract

The largest use of vanillin is as a flavoring, usually in sweet foods. The ice cream and chocolate industries together comprise 75% of the market for vanillin as a flavoring, with smaller amounts being used in confections and baked goods. Vanillin is also used in the fragrance industry, in perfumes, and to mask unpleasant odors or tastes in medicines, livestock fodder, and cleaning products. It is also used in the flavor industry, as a very important key note for many different flavors, especially creamy profiles. Vanillin has been used as a chemical intermediate in the production of pharmaceuticals and other fine chemicals. In 1970, more than half the world's vanillin production was used in the synthesis of other chemicals, but as of 2004 this use accounts for only 13% of the market for vanillin. Additionally, vanillin can be used as a general purpose stain for developing thin layer chromatography (TLC) plates to aid in visualizing components of a reaction mixture. This stain yields a range of colors for these different components.

Bagasse: Our raw material

Bagasse is the fibrous matter that remains after sugarcane or sorghum stalks are crushed to extract their juice. It is currently used as a biofuel and in the manufacture of pulp and paper products and building materials.

Production, storage and composition

For each 10 tonnes of sugarcane crushed, a sugar factory produces nearly 3 tonnes of wet bagasse. Since bagasse is a by-product of the cane sugar industry, the quantity of production in each country is in line with the quantity of sugarcane produced. The high moisture content of bagasse, typically 40 to 50%, is detrimental to its use as a fuel. In general, bagasse is stored prior to further processing. For electricity production, it is stored under moist conditions, and the mild exothermic reaction that results from the degradation of residual sugars dries the bagasse pile slightly. For paper and pulp production, it is normally stored wet in order to assist in removal of the short pith fibres, which impede the papermaking process, as well as to remove any remaining sugar. A typical chemical analysis of bagasse might be (on a washed and dried basis): Cellulose 4555% Hemi cellulose 2025% Lignin 1824% Ash 14% Waxes <1% Bagasse is an extremely inhomogeneous material comprising around 3040% of "pith" fibre, which is derived from the core of the plant and is mainly parenchyma material, and "bast", "rind", or "stem" fibre, which comprises the balance and is largely derived from sclerenchyma material. These properties make bagasse particularly problematic for paper manufacture and have been the subject of a large body of literature.

Process for extraction of lignin materials: 1) There are several processes can be used to remove and/or isolate and/or purify the lignin from biomass material cells. The alkaline methods are generally more effective because they are able to solubilize a greater fraction of lignin, also they are more vantage compared to other pretreatment technologies. 2) This method breaks down the hydrogen bonds in the lignocellulosic biomass fractions by removal of the surrounding lignin structure hemicellulose and cellulose and recovering the resulting soluble monomeric.

The Actual Process

Dried sugarcane bagasse

Grounding and screening to prepare 50 mesh powder

Treatment with alkali in autoclave at 75C, for 1 h

Solid residue

Extract

Waste

a) Filtration with 0.55 m pore filters b) Acid treatment with H2SO4(pH 5) c) Filtration with 0.40 m pore filters

HPLC Analysis

1) The pretreated sugarcane bagasse powder was suspended in 100 ml of Alkali solution (with concentration 0.5M) and autoclaved at 75C for 1 h, using 250 ml Pyrex glass bottles with plastic caps. 2) The bagasse extract solutions obtained from alkaline hydrolysis were filtered through filters with 0.55 mm pore diameter and stored at 4 until C analyses were made. 3) Prior to the analysis, all liquid samples were acidified with H2SO4 up to pH 5.0 and filtered through membranes with 0.40 mm pore diameter.

% of main components extracted Bagasse (g) alkaline treatment (M) 0.5 1.0 2.0 3.0 4.0 0.5 1.0 2.0 3.0 4.0 0.5 1.0 2.0 3.0 4.0 0.5 1.0 2.0 3.0 4.0 p-coumaric acid 79.61 76.36 74.01 75.78 76.10 76.83 67.40 69.04 67.27 78.91 83.41 82.13 79.98 80.59 78.79 76.04 73.79 67.00 71.68 71.49 Ferulic acid Syringic acid 16.21 17.58 19.03 18.49 18.78 15.44 18.90 19.26 21.12 15.80 14.96 16.04 17.31 17.33 18.36 19.10 20.59 24.40 21.10 20.23 1.10 1.49 1.81 1.69 1.79 3.19 3.97 3.37 3.95 2.45 0.82 0.97 1.34 1.50 1.82 1.79 2.38 3.31 2.87 3.18 Vanillin 3.08 4.57 5.14 4.05 3.34 4.53 9.72 8.33 7.65 2.85 0.80 0.86 1.37 0.59 1.04 3.07 3.24 5.28 4.35 5.10

1.0

2.0

3.0

5.0

App. Cost of Components:

Alkali: Bagasse: Citric Acid: Electricity: Labour: Rs.20 per kg Rs.5 per kg Rs.40 per kg Rs.5 per hour Rs. 70 per hour

Vanillin that can be obtained after an hour in a 1000 liter boiler = 50 liters Total cost price of all components in 1000 liter boiler = Rs. 13,800 Cost Distribution: Alkali (160kg) Bagasse (500kg) Citric Acid (200kg) Electricity & Labour Miscellaneous Total Cost = Rs.3,200 = Rs.2,500 = Rs. 8,000 = Rs.75 = Rs. 25 = Rs. 13,800

Selling Price of Vanillin (50 liters) = Rs.250 per liter Selling Price of Sodium Citrate (100kg) = Rs.55 per kg Total Income from selling vanillin and sodium citrate = Rs. 18,000 One session will be of 2 hours, 1 hour heating and 1 hour cooling. Difference (Profit) per session of 2hours = Rs. 4,200 Difference (Profit) per day (4 sessions) = Rs. 16,800 Hence our capacity with a 1000 liter tank will be 2 tons per day.