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Food Preservatives
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Table of Content
Introduction...3 History of food preservatives3 Indian scenario of food processing...3 Classification of Food Preservatives....4 Harmful effects of food preservatives.5 Sodium Benzoate.....5 Sodium Nitrite...7 Citric Acid.....9 References..12
List of Figures
Figure 1: Production Flow Sheet of Sodium Benzoate....6 Figure 2: Production Flow Sheet of Sodium Nitrite.9 Figure 3: Production Flow Sheet of Citric Acid..11
List of Tables
Table 1. Classification of Preservatives4 Table 2. Classification of Artificial Preservatives....4
Table 3. Free Benzoic Acid vs. pH.....5
Table 4. Permitted quantity of Sodium Nitrite and quality..8 Appendix: Table 6. Permitted Quantity of commonly used preservative13
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Introduction:
Other than shelter and clothing, food is the basic requirement of human beings to be alive. Food is very necessary to keep our body working, to satisfy hunger and to get energy to do all the activities. Food is made and kept in specific conditions and climate by adding many chemicals to it. We see that some fruits, vegetables come in specific season, like mango comes in summer whereas custard apple comes in winter. If they are not kept in proper conditions chances of getting spoiled increases. For example, if we keep bread out of refrigerator, after few days, we see that it turns brownish black and smells very bad. When we keep any cooked vegetable outside refrigerator for long time, it gets spoiled.
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Classification of food preservatives: Class-I preservatives Preservatives) (Natural Class-II preservatives Preservatives)
Man-made chemical substance Used in limited quantity
(Artificial
Naturally occurring substances, generally used in kitchen No restriction or limitation on use as naturally occurring No need to be cautious in using them, so better to choose product containing these type of preservatives Salt, Sugar, Vinegar, Alcohol
Preservatives
Antimicrobial agents
Antioxidant
Preserve food by inhibiting atmospheric oxidation and prevent it from breakdown and becoming rancid. Mainly used with the products that contains unsaturated fatty acids, oils and lipids In mechanism, free radical initiates peroxide formation at double bonds of fatty acid. The chain reaction propagates to other double bonds, and aldehyde, ketone, and acidtermination products thus create the rancid off-flavors. Butylated hydroxyanisole, BHA (butter, lard, meats, beer, baked goods, snacks, potato chips, nut products, dry mix for beverages), butylated hydroxytoluene, BHT (fats, oils), Sulfites (beer, wines, dried foods), Vitamin E (fruits and vegetables).
Chelating agent
Prevents the natural ripening process & oxidative deterioration of food by inhibiting the bacteria; parasite, fungi etc. prevent food from becoming brown. Same as antioxidants. They are mixed with anti oxidants to improve their functionality by complexing the metal ions that often initiate free radical formation and prevent metal from oxidation
Definition
Preserve food by preventing the growth of microorganism such as fungi, bacteria, molds, yeasts Reduces moisture content and increases acidity which creates the bad environment for the growth of microorganism. They retain the quality of food like color, smell, texture, nutrients etc. Banzoate (soft drinks, fruit juices, beverages, baked food), Sorbate (dairy product, fermented vegetables, confection, smoked meat and fish, beverages), Propionate (cheese and baked food), Nitrites (meat product)
Mechanism
Examples
Citric acid (foods, beverages, dairy products, pharmaceuticals), EDTA (food processing), Polyphosphates (freshpeeled fruits and vegetables)
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Properties- White powder, transparent in color in conformity with ragulations Purity standard99.0 and 100.5%, halogenide % FeCl3 0.02, Heavy Metal Pb % 0.001, loss on drying (%) 2.0
Solubility in waterPermitted QuantityHighly soluble (61.2 gm. dissolve in 100 gm. at 25 C) 0.1 % by weight (FDA standard)
Method of Production:
Sodium benzoate is produced by the neutralization of benzoic acid with caustic soda. The resulting solution then treated to remove trace impurities as well as color bodies and then dried in steam heated double drum dryers. The product removed from dryers is light and fluffy and in order to reduce shipping and storage space the sodium benzoate is normally compacted. It is then milled and classified into two product forms 1. Dense granular 2. Dense powder It is also available in extruded form. This form is totally dust free. It dissolves more quickly than the dense granular form in both water and antifreeze.
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Conditions of reactionReactor Pressure- 200- 700 kPa Reactor Temperature- 136-160 C Cobalt catalyst concentration- 25- 1000 ppm Reactor benzoic acid concentration- 10- 60 wt %
Major Reaction:
C6H5COOH + NaOH NaC6H5CO2 + H2O
Used as preservatives in Sauces, Pickles, cider, fruit juices, wine coolers, syrups and concentrates, mincemeat and other acidic pie fillings, margarine, egg powder, fish, bottled carbonated beverages, fruits preservation, jams, and jellies. Sodium benzoate sensitivity- Persons who have experienced hypersensitivity reactions (atopic allergy), respiratory tract symptoms including asthma, or skin reactions such as hives and eczema, may be particularly vulnerable to benzoate sensitivity. This chemical can damage mitochondria in cells, which leads to neuro-degenerative diseases The following symptoms have been linked to ingesting foods with sodium benzoate: Asthma, Urticarial (hives) and angioedema (tissue swelling), Rhinitis (nasal congestion due to hay fever), Atopic and contact dermatitis, cutaneous vasculitis, Anaphylaxis
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Note- Benzoate ion has essentially no antimicrobial properties; it is due to undissociated benzoic acid that provides the antimicrobial action. Free Benzoic acid Free Benzoic acid pH (%) pH (%) 2.5 98 4.5 32.9 3 93.9 5 13.4 3.5 83 5.5 4.7 4 60.8 6 1.5 4.19 50 6.5 0.15 Table 3. Free Benzoic Acid vs. pH
Consumption in emerging marketPrice US $ 1,340 - 1,355 / Ton Sodium Benzoate pricing is driven by pricing of its core components: sodium hydroxide and benzoic acid. The recent flurry of domestic and global natural disasters has had a significant impact on supply and demand for sodium hydroxide, driving prices to higher than average
levels. During 2006-2009, world capacity for benzoic acid grew very high. In 2009, beverages and food accounted for nearly 43% of the world consumption of benzoic acid in the form of sodium and potassium benzoate, this is mainly due to its use in preservation of food products. This compustions is froeast to grow at an average annual rate of about 3% during 2009-2014.
Storage of sodium benzoate- Slightly hygroscopic and should be stored in sealed containers. Exposure to conditions of high humidity and elevated temperatures should be avoided. Effective Sodium benzoate is most effective below pH 4.5. Lower pH level is required.
Antimicrobial Agent
stable, odorless, pale yellow or straw-colored compound, toxic, Hygroscopic FunctionsOxidizing agent hence acts as corrosion inhibitor but becomes reducing agent to more powerful oxidizer such as KMnO4, K2Cr2O7, on acidification produces nitrous acid which is unstable PriceSpecificationsSolubilityRelative DensityStorageUS $ 500 - 530 / Metric Ton 98.5% purity, powder, white fine crystal Soluble in water but has limited solubility in organic solvent 2.168 Ventilated and dry place against rain heated and isolated under sunlight.
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IncompatibilityToxicity-
Level of sodium nitrite in vegetables is generally in range of 1.1 to 57 mg/kg. Permitted quantity- Human body (0.07 mg of nitrite / kg of body weight per day), Cauliflower (3.49 mg/kg), Fresh meat (0.4-0.5 mg/kg) UsesFormation of dye, rubber chemicals. Most of the uses are because of oxidizing properties. It is used in metal finishing, meat curing. It is used as corrosion inhibitor. Cancer -nitrites can cause some forms of cancer. When proteins break down, they form a chemical known as amines. When amines and nitrites come into contact with each other, they form nitrosamines. These chemicals are linked to an increased risk for colorectal cancer.
Disease caused -
Those people who eat a lot of lettuce and those who have a high rate of conversion of nitrate to nitrite are potentially most at risk to health damage from nitrate Permitted Quantity of Sodium Nitrite:
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Process Description:
Liquid ammonia is oxidized by catalytic air oxidation at a high temperature in catalytic bed, which forms nitrogen oxides (NOx). The stream is sent to the absorption tower and gets contacted with alkaline solution (soda ash or caustic soda). Low temperature and high pressure are required for the absorption to convert NOx completely into Sodium nitrite and thereby minimizing the formation of sodium nitrate. If caustic soda is used, the liquid from the absorption tower is sufficiently concentrated and pure that can be sold directly but if soda ash is used, liquid is highly diluted, thereby water should be removed before selling. Then the slurry is sent to evaporator where it is concentrated and sent to crystallizer. Sodium nitrite crystals form there and sent centrifuged to get pure crystal. Mother liquor is recycled back to the stream going into the evaporator. Since sodium nitrite is corrosion inhibitor, so equipments can be of mild steel. Crystals from centrifuge are treated with anticracking agent to make them free flowing. Uses: formation of dye, rubber chemicals. Most of the uses are because of oxidizing properties. It is used in metal finishing, meat curing. It is used as corrosion inhibitor.
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Price Specifications of citric acid FunctionsSolubilityRelative DensityStorage of citric acid ProductionCAS Registry NumberToxicity for ratsDisease causedWorld demand-
US $ 900 - 980 / Metric Ton Purity 99.5% minimum, white crystal, 8-100mesh oxidizing agent, chelating agent or added to antioxidants to improve their functionality. water-soluble organic solid (576771 g/l at 20 C) 1.665 at 20 C Kept in lightproof. Well-closed, dry and cool place 879,000 MT in 1998 (worldwide) [77-92-9] Anhydrous 1200 mg/kg/d. (experiment was performed on rats) Irritation in eyes, in the respiratory pathways and on skin Soft drinks and beverages account for more than half of the world demand for citric acid.
Usescitric acid is used mainly in food industry as preservatives, in jam, jellies and candy to suppress the inversion of sucrose and adjust the pH, In salads and meat to prevent enzymatic browning, in frozen food, fats and oils as chelating agent to inhibit metal-catalyzed oxidation, in confections and desserts to enhance flavor and optimize gel-setting characteristic, in dairy products to decrease the viscosity of the mix to make it easy to whip. Citric acid forms complex with many multivalent ions to form chelate as it has ligancy more than one. So, it control metal contamination and prevent metal to undergo any reactions. It does not affect color, stability, and texture of food product. Method of production: Raw material: Molasses, sucrose, and dextrose, calcium hydroxide, sulfuric acid Process Description: (by fermentation of Aspergillus niger microorganism) There are two processes: 1. Surface Fermentation 2. Submerged Fermentation. Submerged process is preferred nowadays as it requires less space, less time, it is less labor intensive and yield is more. This process is used for large volume industrial production. Aspergillus Niger molds is grown under specific conditions (of pH, nutrients). Sterile air is sparged into the fermentor where sugar is converted to citric acid. The process of fermentation is very long and takes 7-8 days.
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Figure 3: Production Flow Sheet of Citric Acid Consumption in world marketInternational Food, beverages & confectionery Pharmaceuticals Industrial application 70% 12% 18% India 40% 55% 5%
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References1. Kirk-Othmer Encyclopedia of Chemical Technology, Volume-3, 6, 12, 22 2. Sodium Nitrite from China and Germany, Investigation Nos. 701-TA-453 (Final) and 731-TA-1136-1137 (Final) 3. http://www.livestrong.com/article/288335-the-most-common-foodpreservatives/ 4. 03_Organic_acids_Mattanovich_1103.pdf 5. Livestrong website article number 467268 http://www.livestrong.com/article/467268-food-preservatives-disease/ 6. Dsir government report on citric acid http://www.dsir.gov.in/reports/techreps/tsr032.pdf 7. http://chemical.ihs.com/nl/Public/2010/1006/1006.html#a= 8. http://www.shreeadditives.com/htmlsite/5a.htm 9. http://www.ihs.com/products/chemical/planning/ceh/benzoic-acid.aspx 10. New Perspectives for Citric Acid Production and Application, Carlos R. Soccol, Luciana P. S. Vandenberghe, Cristine Rodrigues, and Ashok Pandey, Bioprocess Engineering and Biotechnology Division, Department of Chemical Engineering, Federal University of Paran, Curitiba-PR, Brazil, and Ashok Pandey, Biotechnology Division, Regional Research Laboratory, CSIR, Trivandrum 695 019, India 11. http://www.inchem.org/documents/cicads/cicads/cicad26.htm#SubSect ionNumber:11.1.1
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Appendix 1 :
Permitted Quantity of commonly used preservative:
Preservatives Lactic Acid Citric acid Acetic acid Sodium Diacetate Sodium benzoate Sodium propionate Potassium sorbate Methyl paraben Sodium nitrite Sulphur dioxide
Commonly used levels (%) No limit No limit No limit 15 0.3-0.5 5 0.03-0.2 10 0.1-0.3 25 0.05-0.2 10 0.05-0.1
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