DAIRY – PROCESS - WASTEWATER TREATMENT

DEMAND - SUPPLY GAP

Activity of Dairy Plant

Collect Milk from Producers
Process Milk for making end products

Dairy plant size

Types of manufactured products

Dairy products: Milk, Cheese, Butter, Milkpowder, Condensate

wastewater characteristic = f (product that is produced)

DAIRY – PROCESS - WASTEWATER TREATMENT

DAIRY PROCESSING
Milk receiving
Milk is delivered and stored

Liquid milk products

Decreaming of raw milk
Pasteurized or sterilized of decreamed milk
Products: consumer milk, chocolate milk, custard etc.

Fermentation of milk
Preparation curd
Production of butter
Production of buttermilk
DAIRY – PROCESS - WASTEWATER TREATMENT

Cheese / Whey / Curd

Cheese: food made from pressed curds of milk

About 500 varieties of cheese
Composition of the wastewater varies from variety to variety

Whey : The watery liquid left when milk forms curd

For hard cheeses the quantity of whey produced is high ( = milk)
For soft cheeses whey production is much lower

Butter/Ghee
Butter is made from cream that has been churned
Ghee from Butter
DAIRY – PROCESS - WASTEWATER TREATMENT

Condensate/Cream/Khoa

Condensed milk and cream

a portion of the water is removed by evaporation.

Khoa
produced by thermal evaporation of milk to 65-70% solid state

Milk Powder
DAIRY – PROCESS - WASTEWATER TREATMENT
DAIRY – PROCESS - WASTEWATER TREATMENT

WASTEWATER
Sources of Wastewater from dairy industry

Milk receiving
Wastewater results from tank, truck and storage tank washing,
pipe line washing and sanitizing
It contains milk solids, detergents, sanitizers and milk wastes

Whole milk products

Wastewater is mainly produced during cleaning operations
When different types of product are produced in a specific
production unit,
Clean-up operations between product changes

The main problem is pollution through spoilage of milk

 DAIRY – PROCESS - WASTEWATER TREATMENT

WASTEWATER
Cheese/Whey/Curd
Mainly from the production of whey, wash water, curd particles etc.
The amount of fine particles in the wash water increases if
mechanical washing processes are used

Butter/Ghee
Butter washing steps produce wash water containing buttermilk
Continuous butter production process materially reduces the
potential waste load

Milk powder
High energy consumption (= emission of CO2, CO etc.),
Cleaning

Condensed milk/Cream/Khoa
High energy consumption during the evaporation process

The main suspended solids mentioned in the literature are coagulated

milk and fine particles of cheese curd.
DAIRY – PROCESS - WASTEWATER TREATMENT

WASTEWATER
Organic Wastewater
Easily biodegradable
Demands Oxygen – Depletion of D.O

Fresh – Alkaline

Acidic - when lactose is decomposed into lactic acid

DAIRY – PROCESS - WASTEWATER TREATMENT

An Overview Of The Waste Production Data For The Dairy Industry.

Reference (1) (2)
Average Range Average Range

Wastewater prod. 2400 100 – 12400 2400 100 – 7100

BOD 6 0.2 - 71.2 5.5 0.2 - 7.1

SS (2.0) (0.06 - 10.8)

Nitrogen (0.15) (0.002 - 0.43)

Phosphorus (0.012) (0.007 - 0.16)

 DAIRY – PROCESS - WASTEWATER TREATMENT

Type of product Wastewater volume BOD

Average Range Average Range
Milk 3250 100 - 5400 4.2 0.20 - 7.8
Condensed milk 2100 1000 - 3000 7.6 0.20 - 13.3
Butter 800 0.85
Milkpowder 3700 1500 - 5900 2.2 0.02 - 4.6
Cottage cheese 6000 800 - 12400 34.0 1.30 - 71.2
Milk (canned) 320 - 1870 0.02 - 1.13
Condensed milk 800 - 7290 0.17 - 1.48
Butter 800 - 6550 0.19 - 1.91
Natural cheese 200 - 5850 0.30 - 4.04
Cottage cheese 830 - 12540 1.30 - 42
DAIRY – PROCESS - WASTEWATER TREATMENT

WASTEWATER
Parameter Value
pH 7.2
Alkalinity 600
TDS 1060
SS 760
BOD 1240
COD 1450
TOTAL NITROGEN 84
P 11.7
OIL & GREASE 290
CHLORIDES 105
DAIRY – PROCESS - WASTEWATER TREATMENT
WASTEWATER REDUCTION

1. Housekeeping practices
2. Water control practices; frequency with which hoses and other
sources of water are left running when not in actual use;
3. Degree of supervision of operations contributing to either the volume
of wastewater or to BOD coefficients;
4. Extent of spillage, pipe-line leaks, valve leaks and pump seals;
5. Extent of carton breakage and product damage in casing, stacking
and cooler operations;
6. Practices followed during the handling of whey;
7. Practices followed in handling spilled curd particles during cottage
cheese transfer and/or filling operations
8. The following of practices that reduce the amount of wash water from
cottage cheese or butter operations;
9. Extent to which the plant uses procedures to segregate and recover
milk solids in the form of rinses and/or products from pasteurization
start-up and product change-over;
10. The procedures used to handle returned products;
11. Management attitude towards waste control.
DAIRY – PROCESS - WASTEWATER TREATMENT

WASTEWATER TREATMENT

SCREEN GREASE GRIT EQL. Primary

S TRAP CHAMBER TANK Clarifier

ASP / TF / AERATED
DISINFECTION LAGOON / DITCH /
ANAEROBIC POND
 TANNERY–PROCESS- WASTEWATER- TREATMENT

Hides - By-product of slaughter activities

Hides are processed into a wide range of end products

The tanning process and wastewater = f( end product)

The chemicals traditionally used for tanning have been derived from
plants

The most common process (nowadays): Combination of chrome salts

(chrome tanning-light leathers) and readily usable vegetable extracts
(vegetable tanning – heavy leathers) (Buljan 1994).

During the tanning process at least ±300 kg chemicals (lime, salt etc.) is
added per ton of hides

In most cases raw hides produced at slaughterhouses are preserved by

pickling and drying for transport to tanneries and further treatment

Animal skin is made of a substance called collagen, which is skin’s main

structural protein.
Since the Stone Age, use of tannins and their
antioxidant capabilities, to make the skin resistant
to the protein cleavage by enzymes (rotting) and
thus conserving the leather

Tannins are “a yellowish or brownish bitter-tasting

organic substance present in some galls, barks,
and other plant tissues, consisting of derivatives of
gallic acid, used in leather production.”
The process of using tannins to preserve collagen
is called tanning

tanning replaces the water molecules in the hide

with the phenolic groups of tannins–the less water,
the less likely it is to rot.
Faster tanning methods make use of minerals
like chromium sulfate (i.e. chrome tanning,
chromexcel), which wasn’t invented until the
mid-nineteenth century.

Basic principle: to cross-link the collagen matrix

to prevent putrefaction and hence
decomposition.

Process: binding chrome salts to the collagen

protein, forming cross-links between the two,
thus creating stable structures of chromium-
protein complexes. The method utilizes large
rotating drums with chromium salt solutions
“washing” the leather.
TANNERY–PROCESS- WASTEWATER TREATMENT
THE TANNING PROCESS
 TANNERY–PROCESS- WASTEWATER- TREATMENT

PRETANNING

Soaking
The preserved raw hides regain their normal water contents.

Dirt, manure, blood, preservatives (sodiumchloride,

bactericides) etc. are removed.

Fleshing and trimming

Extraneous tissue and hair is removed.

Unhairing is done by chemical dissolution of the hair and

epidermis with an alkaline medium of sulphide and lime.

Fleshing is usually precedes unhairing and liming

 TANNERY–PROCESS- WASTEWATER- TREATMENT

Bating:
The unhaired, fleshed and alkaline hides are neutralised (deliming)
with acid ammonium salts and treated with enzymes, similar to
those found in the digestive system,

During this process hair roots, proteins, and pigments are removed
The hides become softer by this enzyme treatment

Pickling:
Pickling increases the acidity of the hide to a pH of 3, enabling
chromium tannins to enter the hide

(Tannin: any of a group of organic compounds found in certaing

tree-barks)

Salts are added to prevent the hide from swelling.

Preservation: 0.03 - 2 weight percent of fungicides and

bactericides are applied
 TANNERY–PROCESS- WASTEWATER- TREATMENT
TANNING

There are two processes: Chrome tanning

Vegetable tanning

Chrome tanning:
After pickling, when the pH is low, chromium salts (Cr3+) are added

pH is slowly increased through addition of a base

The process of chromium tanning is based on the cross-linkage of

chromium ions with free carboxyl groups in the collagen ( a protein
found in animal tissue)
It makes the hide resistant to bacteria and high temperature.

The chromium-tanned hide contains about 2-3 dry weight percent of

Cr3+.

Wetblue, i.e. the raw hide after the chrome-tanning process, has
about 40 percent of dry matter
 TANNERY–PROCESS- WASTEWATER- TREATMENT
Vegetable tanning:
Vegetable tanning is usually accomplished in a series of vats with
increasing concentrations of tanning liquor

(first the rocker-section vats in which the liquor is agitated

second the lay-away vats without agitation).
Phenol: any of a class of weak acidic organic compounds; molecule
contains one or more hydroxyl groups)

Vegetable tannins are polyphenolic compounds of two types:

Hydrolysable tannins (i.e. chestnut and myrobalan) which are

derivatives of pyrogallols and

Condensed tannins (i.e. hemlock and wattle) which are derivatives

from catechol. (C6H4(OH)2 )

Vegetable tanning probably results from hydrogen bonding of the

tanning phenolic groups to the peptide bonds of the protein chains.

In some cases as much as 50% by weight of tannin is incorporated

into the hide (Ockermann and Hansen, 1988)
 TANNERY–PROCESS- WASTEWATER- TREATMENT
FINISHING

Chromium tanned hides are often re-tanned

Re-tanning process : treated with dye and fat to obtain the proper
filling, smoothness and colour.
Surplus water is removed to make the hides suitable for splitting and
shaving
Drying:
Splitting and shaving is done to obtain the desired thickness of the
hide.
The most common way of drying: vacuum drying

The crust (hard dry formation on the surface) that results after re-
tanning and drying, is subjected to a number of finishing operations.

The purpose of these operations is to make the hide softer and to

mask small mistakes.

The hide is treated with an organic solvent or water based dye and
varnish. The finished end product has between 66 and 85 weight
percent of dry matter.
 TANNERY–PROCESS- WASTEWATER- TREATMENT

WASTEWATER
Over 80 per cent of the organic pollution load in BOD terms
emanates from the beamhouse (pretanning)

Much of wastewater comes from degraded hide/skin and hair

matter.

The pretanning is also the source of all non-limed and limed solid
waste such as fleshing, trimming and waste split.

During the tanning process at least 300 kg of chemicals (lime, salt

etc.) are added per ton of hides.

Excess of non-used salts will appear in the wastewater.

Because of the changing pH, these compounds can precipitate and

contribute to the amount of solid waste or suspended solids
 TANNERY–PROCESS- WASTEWATER- TREATMENT

Every tanning process step, with exception of the crust finishing

operations, produces wastewater. An average of 35 m3 is produced
per ton of raw hide.

This wastewater contains:

salts (Cl), fat, protein, preservatives (soaking)

lime and ammonium salts, ammonia, protein (hair), and sulphides

(fleshing, trimming, bating)

chromium(salts) and polyphenolic compounds (tanning); and

dye and solvent chemicals (wet-finishing)

Solid waste produced consists of fleshings containing lime,

chromium containing ‘wet-blue’ shavings and of trimmings (leather)
 TANNERY–PROCESS- WASTEWATER- TREATMENT

The discharge of solid waste and wastewater containing chromium

is the main environmental problem.

Chromium is a highly toxic compound

Dumping of chromium containing material is restricted to a few

special dumping grounds.

Reduction of chromium discharge is therefore essential

 TANNERY–PROCESS- WASTEWATER- TREATMENT

BOD range: 1000 - 3000 mg/l depending upon the volume of water
used and on other impurities Rajamani (1987)

Precipitated wastewater show a reduction of BOD and COD of 50%

(Pelckmans).

Hence, it is worth precipitating dissolved organic compounds and

treating this as solid waste

Tanneries that perform the complete tanning procedure, produce

mixed wastewater.
 TANNERY–PROCESS- WASTEWATER- TREATMENT

Variation in values for BOD, COD, SS and Cr3+ might be caused by

a high amount (45 m3 per ton of hide) or low amount (25 m3 per ton
of hide) of water used during the tanning process.

50 m3 per ton of hide for traditional manufacturing processes of

Wet-blue

20 m3 per ton of hide when water conservation is practiced (Mulder

and Buijssen 1994).

Per ton of hide approximately a total of 35 m3 wastewater is produced

Some tanneries produce a huge amount of water (about 310 m3

wastewater per ton of raw hides), and high amounts of SS and a
COD of 2500 kg per ton of raw hides (Clonfero, 1990)
 TANNERY–PROCESS- WASTEWATER- TREATMENT

Process step Amount of water pH COD NKj Cr

(m3/ton) - kg COD/m3 kg N/m3 kg Cr/m3

Pretanning:

Soaking 4-6 6-9 30-40 1-1.5 -

Unhairing, liming 5-9 12-13 40-60 3-5 -

Fleshing 1-3 - - - -

Deliming, bating 5-7 8.5-9 5-8 3.5-4 -

Tanning:

Chrome tanning 0.5-1 3.8-4 2-3 0.3-0.6 0.5-5

Pressing 0.4-0.6 3.6-4.5 1.2-1.8 0.11-0.22 0.5-5

Neutralisation 1-1.5 4.5-4.7 2.5-3 0.5-0.8 0-1.0

Painting, fatting 3-4.5 3.8-4.5 5-6 0.2-0.3 0-5.0

Finishing:

Drying 3-6

Finishing 1-2

Cleaning 5
 TANNERY–PROCESS- WASTEWATER- TREATMENT

PREVENTION OF WASTE PRODUCTION

Considerations for the reduction of the amount of polluting value of the

produced wastewater are:

Reduction of the total water use by re-use of produced wastewater

Development of technologies that minimize the quantity of water needed

during the tanning process; and

Reduction of the used chemicals such as lime, salt, sulphide etc

Reduction of chromium

Water conservation ( Higham, 1991):

A reduction of water use can lead to a reduction of the total waste load.

Re-use of wastewater with a minimal harmful or even a moderately

beneficial effect on earlier processes may be considered as an option
 TANNERY–PROCESS- WASTEWATER- TREATMENT
Curing hides and skins
A reduction of the use of salt for preservation can be
considered as an option.
15% of salt on weight basis may preserve the hides for even
6 weeks,
5 % of salt plus biocide lead to a preservation for 2 months

Chilling without salt can preserve hides for a few days

Alternative preservation method is radiation by electron

beam or gamma rays.

Where possible, biodegradable preservatives (insecticides

etc.) should be used instead of derivatives of chlorinated
aromatic hydrocarbons.

The latter persist in the waste and are highly toxic to the
environment.
Beamhouse processes
Hair saving methods are recommended to prevent
degraded keratin from entering the waste streams.
Unhairing/liming fluids can be recycled after
recharging. It is also recommended that the
unhairing and liming stages should be seperated.
Both liquids can be recharged and hair can be
screened out. The intermediate wash can be re-used
as a soak liquid.
 TANNERY–PROCESS- WASTEWATER- TREATMENT
Tanning
Low chrome systems, possibly requiring an aluminium salt for
pretannage will produce a wet-white leather. Splitting and shaving
wastes will contain less chromium. Alternative mineral salts such as
aluminium, zirconium, titanium and iron are might be used as
substitutes for chromium salts. However, under certain conditions
aluminium is known to be more poisonous to aquatic life than
trivalent and even hexavelant chromium. Re-use of chromium is a
more realistic alternative. The unused tanning fluids which contain
chromium can be collected separately. From these fluids and from
the solids that contain chromium, chromium can be recovered. The
remainder may be used as source material for glue and animal
feedstuff. In countries where discharge of chromium is strictly
prohibited, great efforts are made to recover and re-use chrome.
Alternative vegetable tanning methods can replace chrome tanning
to a high degree. An example is the ‘Liritan’ process, developed in
South Africa. A high chemical uptake, low pollution load, uniform
penetration of the tan and a shortened process time with
consequent financial efficiency are claimed to be the main
advantages of this process (Higham, 1991), but little is known on
the practical implications.
 TANNERY–PROCESS- WASTEWATER- TREATMENT

Finishing
A reduction of volatile organic compounds (VOC) can be
accomplished by using aqueous finishes for base and middle
finishing coatings.produced)