Food Preservatives[FOOD PRESERVATIVES] April 12, 2012

NALANDA PUBLIC SCHOOL

CDA , CUTTACK

Food preservatives

Presented by
Archit patnaik
Class xii‘A’
EXTERNAL SIGN:

INTERNAL SIGN:
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Table of Content
Introduction ....................................................................................................... 3
History of food preservatives ................................................................................. 3
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 Preservatives.................................................................... 4
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 preservative ............................... 13
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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.

What are the reasons for all these?

This is mainly due to presence of bacteria, microorganism, insect, and enzymes etc, which get
environment (food, oxygen, moisture and suitable pH) to grow rapidly when food is not kept
under the specified required condition. Other reactions also may occur which cause food
spoiling. It accounts to the cost of food and health problem.

As population is growing very fast, demand of food is rising. We want food to be of good
quality and stay for long time. So to decrease the growth of microorganism, increase the shelf
life of food, making it available anytime anywhere with the same texture, color, smell, food
are preserve either by processing called food preservation or by adding chemical called food
preservatives.

Many food preservation processes are there to preserve food and increase shelf life, these are:
dehydration, salting, pickling, fermentation, drying, freezing, refrigeration, vacuum packing,
jellying etc.

History of food preservatives:

Before chemical preservatives came into picture, foods was kept in the container having water
so that the food remain cool and this work as refrigeration. Some food was placed in clay jars
to keep them away from air and moisture and hence prevent from spoiling. Salt was also a
famous preservative that time as it has desiccating effect, which draws water out of the food.
Modern method involves many other processes and man-made chemical for preservation of
food for long time. All these methods decrease the cost of the food and increase their shelf
life to a great extent.

Indian Scenario of Food Processing:

India is the world’s second largest producer of food next to China. Indian Food Processing
industry is ranked fifth in terms of production, consumption, export and expected growth. The
processed food market accounts for 32% of the total food market. According to the India
Food Report 2008 prepared by leading markets data provider Research and Markets, the
Indian food industry was estimated at over $182 billion, accounting for about two-thirds of
the country's total retail sector.

The turnover of the total food market is approximately Rs.250,000 crores out of which value-
added food products comprise Rs.80,000 crores. The Indian food processing industry is
primarily export orient. India's geographical situation gives it the unique advantage of
connectivity to Europe, the Middle East, Japan, Singapore, Thailand, Malaysia and Korea.

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As the population is growing, food industry in India is rising and the investment in the food
industry is getting more and projected to grow by US$ 100 billion to US$ 300 billion by
2015. Another reason for preservation is long gap between production and actual
consumption of food products.

Classification of food preservatives:

Class-I preservatives (Natural Class-II preservatives (Artificial

Preservatives) Preservatives)
Naturally occurring substances, generally used
in kitchen Man-made chemical substance
No restriction or limitation on use as naturally
occurring Used in limited quantity
No need to be cautious in using them, so better
to choose product containing these type of
preservatives Risk in use as they are chemicals
Salt, Sugar, Vinegar, Alcohol Benzoic acid, sulfite, sorbate
Table 1. Classification of Preservatives

Preservatives Antimicrobial agents Antioxidant Chelating agent

Preserve food by preventing
the growth of microorganism
such as fungi, bacteria,
Definition molds, yeasts
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
Prevents the natural ripening
process & oxidative
deterioration of food by
inhibiting the bacteria;
parasite, fungi etc. prevent
food from becoming brown.

In mechanism, free radical Same as antioxidants. They

Reduces moisture content
and increases acidity which
creates the bad environment
for the growth of
microorganism. They retain
the quality of food like color,
Mechanism smell, texture, nutrients etc.
initiates peroxide formation at
double bonds of fatty acid. The
chain reaction propagates to
other double bonds, and
aldehyde, ketone, and acid-
termination products thus create
the rancid off-flavors.
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

Banzoate (soft drinks, fruit Butylated hydroxyanisole,

juices, beverages, baked
food), Sorbate (dairy
product, fermented
vegetables, confection,
smoked meat and fish,
beverages), Propionate
(cheese and baked food),
Examples Nitrites (meat product)
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).
Citric acid (foods,
beverages, dairy products,
pharmaceuticals), EDTA
(food processing),
Polyphosphates (fresh-
peeled fruits and vegetables)

Table 2. Classification of Artificial Preservatives

Choice of preservatives depends on many factor, like food product that has to be preserved,
climate and conditions, types of spoilage organism endemic to it, period of shelf life, ease of
applications, time lag between production and consumption of food product, cost etc.

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No single preservatives satisfy all the conditions, so combination of many preservatives is

used.

Harmful effects of food preservatives:

Taking large quantity of preservative is also harmful leading to health problem.

People who are sensitive to small amount of particular preservative should not the
same.
Research published in the "Journal of the Egyptian Public Health Association" in
2001 discovered that intake of foods preserved with sodium benzoate and sodium
nitrite among pregnant rats is associated with a higher death rate in offspring. The
results suggest that pregnant women should need caution or avoid the consumption of
foods containing these preservatives.
Preservatives such as EDTA and Nitrites increase the risk of cancer.
Sulfite preservatives may cause asthma symptoms. Nowadays FDA prohibited the
use of sulfites preservatives as it causes respiratory diseases.
According to a 2007 study published in the journal "Lancet." Use of sodium benzoate
causes hyperactivity in children’s.
A number of food preservatives are banned because of severe health problems
associated with them.
Alzheimer's disease, an irreversible neurological disease that causes cognitive
deterioration and metabolic diseases is caused due to excess consumption of
preservatives.

Sodium Benzoate – Antimicrobial Agent

Properties- White powder, transparent in color in conformity with

ragulations
Purity standard- ≥99.0 and ≤100.5%, halogenide % FeCl3 ≤ 0.02, Heavy Metal
Pb % ≤ 0.001, loss on drying (%)≤ 2.0
Solubility in water- Highly soluble (61.2 gm. dissolve in 100 gm. at 25 °C)
Permitted Quantity- 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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Process Flow Sheet:

Raw materials - Toluene and air

Figure 1: Production Flow Sheet of Sodium Benzoate

Conditions of reaction-
Reactor 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 market-

Price - 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 it’s 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-
Effective -
Slightly hygroscopic and should be stored in sealed containers.
Exposure to conditions of high humidity and elevated
temperatures should be avoided.
Sodium benzoate is most effective below pH 4.5. Lower
pH level is required.

Sodium Nitrite (NaNO2) Antimicrobial Agent

Properties- stable, odorless, pale yellow or straw-colored compound, toxic,
Hygroscopic
Functions- Oxidizing 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
Price- US $ 500 - 530 / Metric Ton

Specifications- 98.5% purity, powder, white fine crystal

Solubility- Soluble in water but has limited solubility in organic solvent

Relative Density- 2.168

Storage- Ventilated and dry place against rain heated and isolated under
sunlight.

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Packing- Dry product- packed into 22.7 kg or 45.4 kg paper bags, which contain
polyethylene moisture barrier.
Liquid product- 40-42 % NaNO2 and packed in tank cars and tank
trucks
Incompatibility- Incompatible with ammonium salts, thiocyanates, thiosulfates and
strong reducing agents, should be kept away from them.
Toxicity- Toxic in high amounts for animals and humans. To prevent toxicity,
sodium nitrite is sold as a food additive is dyed bright pink to avoid
mistaking it for plain salt or sugar.

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)

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.
Disease caused - 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.

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:

Table 4. Permitted quantity of Sodium Nitrite and quality

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Method of production:

1. Reduction of sodium Nitrate

2. Absorption of Nitrogen oxide into aqueous solution of caustic soda or soda ash
(industrial process)
Raw Materials: Ammonia, Air, Caustic soda or soda ash.

Reaction Involving:
4NH3 + 5O2  4NO + 6H2O
NO + Na2CO3  Na2NO2 +CO2
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.

Process Flow sheet of sodium nitrite production-

Figure 2: Production Flow Sheet of Sodium Nitrite

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Citric Acid -Flavor ingredient (chelating agent), pesticide and fungicide

Price - US $ 900 - 980 / Metric Ton

Specifications of citric acid - Purity 99.5% minimum, white crystal, 8-100mesh

Functions- oxidizing agent, chelating agent or added to antioxidants

to improve their functionality.
Solubility- water-soluble organic solid (576–771 g/l at 20 °C)

Relative Density- 1.665 at 20 °C

Storage of citric acid - Kept in lightproof. Well-closed, dry and cool place

Production- 879,000 MT in 1998 (worldwide)

CAS Registry Number- [77-92-9] – Anhydrous

Toxicity for rats- 1200 mg/kg/d. (experiment was performed on rats)

Disease caused- Irritation in eyes, in the respiratory pathways and on skin

World demand- Soft drinks and beverages account for more than half of the
world demand for citric acid.
Uses- citric 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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From fermentation broth, citric acid is separated using filtration and purified by lime sulfuric
extraction.
In lime sulfuric process, calcium hydroxide slurry is added to fermentation broth, which
precipitates calcium citrate.
After sufficient time, calcium slurry is filtered, filter cake is washed, reslurried and acidified
with sulfuric acid, which form citric acid and calcium sulfate.
Calcium sulfate is insoluble which then removed. Final solution of citric acid is then
deionized to remove trace of calcium, decolorized and other processes are taking place to
improve crystallization.
Aqueous solution of citric acid is then sent to evaporator followed by crystallizer. Crystals of
citric acid forms which are then washed, dried the packed for selling. As aqueous solution of
citric acid is mildly corrosive equipments are made by316 stainless steels
Another process also can be used to recover citric acid from fermentation broth is liquid
extraction. Where hydrocarbon is used as solvent for recovery.
Process Flow sheet of citric acid production-

Figure 3: Production Flow Sheet of Citric Acid

Consumption in world market-

International India
Food, beverages & confectionery 70% 40%
Pharmaceuticals 12% 55%
Industrial application 18% 5%
Table 5. Consumption of Citric Acid
There is a scope of growth in industrial sector in India since we are lagging from international
economy.

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References-
1. 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-food-
preservatives/
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 Paraná, 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:

Acceptable Daily intake

Preservatives (mg/Kg body weight) Commonly used levels (%)

Lactic Acid No limit No limit

Citric acid No limit No limit

Acetic acid No limit No limit

Sodium Diacetate 15 0.3-0.5

Sodium benzoate 5 0.03-0.2

Sodium propionate 10 0.1-0.3

Potassium sorbate 25 0.05-0.2

Methyl paraben 10 0.05-0.1

Sodium nitrite 0.2 0.01-0.02

Sulphur dioxide 0.7 0.005-0.2

Table 6. Permitted Quantity of commonly used preservative

Source FDA, 1991

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