3/8/13

HISTORY

SOAPS and DETERGENTS

WASHING OR SOAP INDUSTRY
CH 61 INDUSTRIAL CHEMICAL REACTIONS AND PROCESSES
BERNADETTE C. CONSUL & DAN NICO SANTIAGO

HISTORY
}

Detergent
Widely used to indicate
synthetic cleaning
compounds
} Scientifically covers both
soap and synthetic
detergents
}

HISTORY
}

SOAP
}

Evolved from crude mixtures

of ALKALINE and FATTY
materials
Anionic

3/8/13

HISTORY
}

HISTORY

DETERGENT
Also known as Synthetic Soaps
} Created during WWI due to
shortages in raw materials
} Composed of SHORT-CHAIN
ALKYL NAPHTHALENE
SULFONATES
} Good wetting agents
} Fair in detergent action

Initially made of SHORT-chain

compounds, followed by LONG,
then BRANCHED chain compounds
} Long chain alcohol sulfonates
} Alkyl-aryl long chain sulfonates
Returned to LINEAR LONG
CHAINS
} More biodegradable

ACTION IN HARD WATER

DETERGENTS
}

Reacts with hard water ions

(Ca2+ and Mg2+) forming
soluble or colloidally
dispersed products

SOAP

Reacts with hard water ions

forming insoluble
compounds which are to
be precipitated out
} Reduce foaming and
cleaning action
}

ECONOMICS

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OVERALL PRODUCTION OF SOAP AND DETERGENTS

PRODUCTION AND SALES OF SOAPS AND

SURFACTANTS
SOAP

PERCENT OF TOTAL

YEAR

DREFT
INTRODUCED

TIDE
INTRODUCED

106$

SURFACTANTS

kt

106$

TOTAL

106$

kt

kt

1940

313

1,455

13

320

1,468

1945

527

1,717

35

68

562

1,785

1950

540

1,308

294

655

834

1,963

1960

376

558

953

1,789

1,329

2,347

1970

427

567

1,379

2,565

1,806

3,132

1980

1,030

545

8,430

2,663

9,460

3,208

SOURCE: CPI 4, chap. 29; U.S. Industrial Outlook, 1982, U.S. Dept. of Commerce

There is an apparent gradual replacement of soap by detergents in the household market.

DETERGENT CONSUMPTION OF SURFACTANTS

(in metric kilotons)
POWDERS

ANIONICS
Alkylbenzene sulfonate
Alcohol ethoxy sulfates
Alcohol sulfates
NONIONICS
Alcohol ethoxylates
Alkyl phenol ethoxylates
Amines, amine oxides

There is an apparent gradual replacement of soap by detergents in the household market.

ENVIRONMENTAL CONSIDERATIONS

LIQUIDS

148
45
23

43
Small
-

45
5
5

41
5
5

Soap and detergent industries and its suppliers

face an enormous task in testing new materials
for all possible effects on the environment, and
extensive research will be needed before this
complex problem can be solved.

SOURCE: Chem. Week 127 (20) 33 (1980).

There is an apparent gradual replacement of soap by detergents in the household market.

3/8/13

USES
HOUSEHOLD
}
}

USES

}
}
}

USES

INDUSTRIAL
}
}

Cleaning compounds
Specialty surfactants
}
}
}
}
}
}

For hospital germicides

For fabric conditioners
For emulsifiers for cosmetics
Flowing and wetting agents for
agriculture chemicals
Rubber processing aids
For enhanced oil recovery from
worked-out oil wells

Laundry products
Toilet soaps
Shampoos
Dishwashing products
Cleaning products

SURFACTANTS
Compounds that affect or
reduce surface tension in
water or interfacial tension
between 2 liquids
} Perform the primary
cleaning and sudsing of
the washing action through
the reduction of surface
tension
}

Hydrophilic end
}
}

Water-loving/attracting
Polar

Hydrophobic
}
}
}
}

Comprised of hydrocarbon
Water-hating/repelling
Soil or Oil-loving
Nonpolar

3/8/13

CLEANING PROCESS
WETTING

CLEANING PROCESS

1.

Wetting the dirt and the surface of the article

being washed

2.

Removing the dirt from the surface

}

WETTING

Hydrophobic end are gathered together in its center

Hydrophilic end are on the outside

Removing the dirt from the surface

2.

Surfactants aggregate in water into spherical

clusters called MICELLES.
}

EMULSIFYING

Wetting the dirt and the surface of the article

being washed

1.

EMULSIFYING

a.

DISPERSING
and/or
SOLUBIZING

DIRT

Hydrophobic end are gathered together in its center

Hydrophilic end are on the outside

Maintaining the dirt in a stable solution or

suspension (detergency)

3.

DISPERSING
and/or
SOLUBIZING

Surfactants aggregate in water into spherical

clusters called MICELLES.

SOLUBILIZATION
}

b.
Image Source: Microsoft Encarta 2009.

Oil-soluble water-insoluble compounds dissolve into the

center of the micelle

Hydrophilic end pulls the molecules and the soil

particles away from the fabric and into the wash
water
}

With mechanical agitation, soil is removed, suspended

and kept from redepositing on the article

DETERGENTS

DETERGENTS
Maximum cleaning power
Maximum cleaning per unit cost
Maximum biodegradability

Alkylbenzene

Oleum

Alkylbenzene Sulfonate

Tallow Fatty Alcohol

Oleum

Fatty Alcohol Sulfate

Sulfonate

Sulfate

Sodium Salts

Builders, etc.

+ NaOH

Sodium Salts
DETERGENTS

3/8/13

DETERGENTS
RAW MATERIALS

SURFACTANTS - CLASSIFICATION
SURFACTANTS
}

Straight-Chain Alkylbenzenes
Fatty acids and Fatty alcohols

Hydrophobic portion
}

Surfactants

Builders

}
}

Additives

Anionic
Cationic
Nonionic
Amphoteric

DETERGENTS
RAW MATERIALS

Cationic

COMPOUNDS
Linear alkylbenzene sulfonates from petroleum
Alkyl sulfates from animal and vegetable fats
Quaternary ammonium compounds for fabric softeners
TYPE A dialkyl dimethyl quaternary ammonium compound
TYPE B diamido alkoxylated quaternary ammonium compound
TYPE C amido imidazolinium

Nonionic

Ethylene oxide condensates of fatty alcohols

-more effective than anionics in terms of body oil removal, and soil
removal at lower temperature (laundering synthetic fibers)

EXAMPLE
-OSO4- or SO32-N(CH3)3+ or C5H5N+
Cl-, CH3SO4CH3SO4CH3SO4-(OCH2CH2)nOH

STRAIGHT-CHAIN ALKYLBENZENES
Straight-Chain Alkylbenzenes
}

Surfactants

Anionic

Hydrophilic portion
}

Suds Regulators

Has 8 to 18 carbon atoms

Straight or slightly branched
Can be a benzene ring

HYDROPHILIC PORTION

Phenyl-substituted n-alkenes
of 11 to 14 carbon atoms

Straight-Chain Alkylbenzenes

Fatty acids and Fatty alcohols

for biodegradable detergents

From STRAIGHT-CHAIN
PARAFFINS or OLEFINS

Suds Regulators
Builders
Additives

3/8/13

DETERGENTS
RAW MATERIALS

FAT SPLITTING PROCESSES

Fatty acids
}

}
}

Straight-Chain Alkylbenzenes
Fatty acids and Fatty alcohols

Fat Splitting Processes:

}

Surfactants

Twitchell
Batch Autoclave
Continuous Countercurrent
}

Suds Regulators

Fat purification methods

}
}

Builders
Additives

High pressure hydrolysis, catalyzed by zinc

oxide

}
}

Panning
Pressing
Fractional Distillation
Solvent Crystallization

Tabular Comparison of the Various Fat-Splitting Processes

FAT SPLITTING PROCESSES

Tabular Comparison of the Various Fat-Splitting Processes

CONTINUOUS HYDROLYSIS

Continuous process for the production of fatty acids and soap (Procter & Gamble Co.)

3/8/13

DETERGENTS
RAW MATERIALS

ZIEGLER CATALYTIC PROCEDURE

Fatty alcohol
}

Surfactants
Straight-Chain Alkylbenzenes

Fatty acids and Fatty alcohols

Suds Regulators

Ziegler Catalytic
Procedure

Builders

For converting a-Olefins to

Fatty Alcohols

Methyl Ester
Hydrogenation Process

Gaseous ethylene is converted to higher linear aluminum

trialkyls and a-olefins by action of aluminum triethyl in the
reaction:

CH2=CH2 + CH2=CH2 CH3CH2CH=CH2 + CH2=CH2 CH3CH2CH2CH2CH=CH2 etc.

Additives

ZIEGLER CATALYTIC PROCEDURE

}

Displacement Reaction
Regeneration
Thermal Decomposition

}
}
}
}

slower than regeneration and

therefore is the rate determining step
reaction takes place repeatedly as
long as unreacted ethylene is present

The reaction runs at inert hydrocarbon

solvent such as heptane and benzene

aluminum trialkyl is oxidized to form

aluminum trioxide and then
hydrolyzed with acidolysis to give
alkyl or fatty alcohol

}
}
}

Chain Growth Reaction

Oxidation Reaction
Hydrolysis/Acidolysis

ZIEGLER CATALYTIC PROCEDURE

CHAIN GROWTH
REACTION
DISPLACEMENT
REACTION

Thermal Decomposition

Regeneration of Ethyl Group

OXIDATION
REACTION
HYDROLYSIS/
ACIDOLYSIS

3/8/13

MANUFACTURE OF FATTY ALCOHOL

METHYL ESTER HYDROGENATION PROCESS

}

Methanol is reacted with coconut/tallow

triglyceride
}

methylate (methyl exchange esterification)

The refined oil is fried by flashing

}

at 150 oC and 16.6 kPa

to avoid consumption of expensive amounts
sodium methylate and forming of soap

upper layer

lower layer
}

The ester layer concurrently removes excess

methanol and catalyst which would poison
hydrogenation, and recovers glycerine
}

90-95% yield of fatty alcohol

Catalyst
}

The reaction mix is then settled and

separated
}

METHYL ESTER HYDROGENATION PROCESS

catalyzed by small amount of sodium

copper II copper III chromite

Carried out at 21 M Pag and 260 to 315

oC

ester and methanol rich

glycerine and methanol

DETERGENTS
RAW MATERIALS

Suds Regulators/Foam Inhibitors

}

Surfactants
Straight-Chain Alkylbenzenes

Fatty acids and Fatty alcohols

Suds Regulators
Builders
Additives

Helps in the efficiency of

cleaning in the washing
machine
Achieved by combining
detergent types
For soaps, it increases with
the amount of saturation
number of carbon atoms in
the fatty acid residue

Flowchart for the hydrogenolysis of methyl esters to obtain fatty alcohols and glycerin from natural fats. (ECT, 3d ed., vol. 4, 1978, p. 837.)

3/8/13

DETERGENTS

DETERGENTS

RAW MATERIALS

RAW MATERIALS

Builders
}
}

Surfactants
}

Straight-Chain Alkylbenzenes
}

Fatty acids and Fatty alcohols

Suds Regulators

Builders

ADDITIVES

}
}

Boost detergent power

Act as water softeners by reacting with Ca2+ and
Mg2+
Prevent redeposition of soil from wash water to
fabric
Synergizes with surfactants
Complex phosphates such as sodium
tripolyphosphate and tetrasodium phosphate
However, phosphates has been linked to algae
growth and eutrophication
Other builders include: citrates, carbonates,
silicates, and zeolites

Additives

Surfactants

Straight-Chain Alkylbenzenes

Fatty acids and Fatty alcohols

Suds Regulators

Builders

Additives

Corrosion inhibitors
Antiredeposition agent
Tarnish inhibitors
Fabric brighteners
Bluings
Antimicrobial agents
Peroxygen-type bleaches
Enzyme-containing detergents

ADDITIVES

ADDITIVE

FUNCTION

EXAMPLES

Corrosion Inhibitors

Protect metal and washer parts, utensils, and

dishes

Sodium Silicate

Antiredeposition Agent

Prevent soil or body oil particles from

attaching to the fabric

Carboxymethyl Cellulose

Tarnish Inhibitors

Inhibits corrosion and extends protection to

metals

Benzotriazole

Fabric Brighteners

A fluorescent dye, it brightens fabrics as

these have the ability to convert UV light to
visible light

4(2H-naphtho[1,2-d]triazol-2-yl)stilbene-2sulfonate
and
Disodium 4,4-bis(4-anilino-6-morpholino-Striazin-2-ylamino)-2,2-stilbene disulfonate

Antimicrobial Agents

Additives

ADDITIVE

FUNCTION

EXAMPLES

Bluings

Improve whiteness of fabric by counteracting

the natural yellowing tendency

Ultramarine blue and new dye materials

Peroxygen-type Bleaches

lighten stains

Enzyme-containing detergents

Decompose or alter the soil/body oil

composition to remove particles easily

Carbanilides
Salicylanilides
Cationics

10

3/8/13

MANUFACTURE OF DETERGENTS

LINEAR
ALKYLBENZENE
SULFONATION
FATTY
ALCOHOL
SULFONATION
Simplified continuous flowchart for the production of heavy-duty detergent granules (Procter & Gamble Co.)

DETERGENT MANUFACTURE

MANUFACTURE

LINEAR
ALKYLBENZENE
SULFONATION
FATTY
ALCOHOL
SULFONATION
Continuous series sulfonation-sulfation, ending with neutralization, in the circulating heat exchanging dominant bath to control heat
(Procter & Gamble)

11

3/8/13

MANUFACTURE
Sulfonation-Sulfation
}

NEUTRALIZATION
Neutralization

Alkylbenzene is continuously
introduced into the sulfonator
with the requisite amount of
oleum using the dominant
bath principle

to control heat of sulfonation

conversion and maintain
temperature to 50 to 55 oC

The sulfonated-sulfated product is

neutralized with NaOH solution
under controlled temperature
}

to maintain fluidity of the surfactant

slurry

The surfactant slurry is conducted

to storage
The surfactant slurry, sodium
triphosphate, and additives are
introduced into a crutcher.

}
}

Water is removed, then the

paste is thickened by
tripolyphosphate hydration
reaction:
Na5P3O10 + 6H2O
Na5P3O10-6H2O
The mixture is pumped to an
upper story, where it is sprayed
under high pressure into the 24m high spray tower, counter to
hot air from furnace

Dry granules of acceptable

size, shape and density are
formed
Dried granules are transferred
to an upper story by air lift
which cools (from 115oC) and
stabilizes the granules
The granules are separated in a
cyclone, screened, perfumed,
and packed

MANUFACTURE
}
}

The sulfonation conversion is

extremely fast
Needs for controlled
temperature with the use of
heat exchangers and dominant
baths
The use of oleum in both cases
reduce sodium sulfate in the
finished product. However,
oleum can cause oversulfonation
and thus is important to be
controlled.

Neutralization of the acid slurry

releases 6 to 8 times as much
heat as the sulfonation reaction.
This is why a dominant bath is
employed.

SOAP

12

3/8/13

SAPONIFICATION

SAPONIFICATION

HYDROLYSIS/
SPLITTING OF FATS

NEUTRALIZATION OF
FATTY ACIDS

Fatty Acids:
Oleic acid
Stearic acid
Palmistic acid
Lauric acid
Myristic acid
}

Hydrolysis

Salts of Fatty Acids

3H2O

3C17H35COOH

GLYCERYL STEARATE

WATER

STEARIC ACID

SOURCE

CONTENT

on

TALLOW

SALTS OF
FATTY
GREASE
ACIDS

splitting
fats

(C17H35COO)3C3H5
FATTY
Neutralizati
MATERIALS

Free fatty acids

}

FATTY
ACIDS

TALLO
W
FATTY
ACID

HYDROLYS
IS

TALLO
W

EXTRACTION

C3H5(OH)3
GLYCERIN

TREATMENT

PURPOSE

Cattles solid fat

Mixed
glycerides

Steam Rendering

Mixed with coconut

oil

To increase solubility of
the soap

Hogs & smaller domestic

animals

Glycerides of
fatty acids

Steam Rendering,
Solvent Extraction

Blended with other

fats

To free their fatty acids

for soap production

utilized in soap, detergent, cosmetic, paint, textile, and many other industries

SAPONIFICATION
Hydrolysis

SODIU
M SALT
OF
FATTY
ACID

TALLO
W
FATTY
ACID

HYDROLYS
IS

TALLO
W

FATTY
ACIDS

splitting
fats

(C17H35COO)3C3H5

3H2O

3C17H35COOH

C3H5(OH)3

GLYCERYL STEARATE

WATER

STEARIC ACID

GLYCERIN

TALLO
W
FATTY
ACID

Neutralization

SALTS OF
FATTY
ACIDS

SAPONIFICATION

NaOH

SODIU
M SALT
OF
FATTY
ACID

NET REACTION
Made of SODIUM/
POTASSIUM SALTS of
various FATTY ACIDS

SOA
P

BUILDER
, ETC.

(C17H35COO)3C3H5

NaOH

3 C17H35COONa

C3H5(OH)3

GLYCERYL STEARATE

CAUSTIC SODA

SODIUM STEARATE

GLYCERIN

ORGANIC MATERIALS

INORGANIC MATERIALS

Caustic Potash

KOH

Sodium tripolyphosphate

Caustic soda

NaOH

Tetrasodium pyrophosphate

Salt

NaCl

Soda Ash

Na2CO3

Sodium Bicarbonate

NaHCO3

C17H35COOH

NaOH

C17H35COONa

H2O

Sodium Silicate

Na2O3Si

STEARIC ACID

CAUSTIC SODA

SODIUM STEARATE

WATER

Trisodium Phosphate

Na3PO4

Na5P3O10
Na4O7P2

Na5P3O10
Na2CO3

or

Na4O7P2

SUPERIOR
BUILDER than
phosphates
alone

Byproduct: Glycerin

13

3/8/13

MANUFACTURE OF SOAP

MANUFACTURE OF SOAP
CONTINUOUS ALKALINE
SAPONIFICATION
Large Scale
Continuous Hydrolysis
Product:
Fatty acids, Glycerin,
Soaps

KETTLE PROCESS
Small Scale

Continuous Saponification

Kettle Process

Improved soap color from

a crude fat without
extensive pretreatment
} Improved glycerin recovery
} Flexibility in control
} Less space and labor
} Faster production of soap

Takes several days to

complete
} Uneven bar soap quality

SOURCE: SOAP. 2013. Advameg, Inc. February 21, 2013. <http://www.madehow.com/Volume-2/Soap.html#b>.

MANUFACTURE OF SOAP
Kettle Process

BOILING

MANUFACTURE OF SOAP

Fats + Alkali Soap + Glycerin

Melted and Boiled in kettle

Continuous Alkaline Saponification

}

SALTING

STRONG
CHANGE

Add salt to separate soap from glycerin

where the former rises while the latter, settles
To remove glycerin

Saponification of the remaining fats

Add strong caustic solution

Hot Water

HYDROLYZER

PITCHING

SOURCE: SOAP. 2013. Advameg, Inc. February 21, 2013. <http://www.madehow.com/Volume-2/Soap.html#b>.

BLEND TANK
}

Fats and
Catalyst

}
}
}

EVAPORATORS

Crude
Glycerin*

Blending of the catalyst, zinc oxide, with melted fats and

heating with steam takes place

HYDROLYZER
}

BLEND
TANK
Boil kettle to separate neat soap (70% soap, 30% H2O) from nigre (impurities)
Remove and cool soap

Transportation of FATS & OILS

Transportation and manufacture of CAUSTIC SODA

Hot melted fats and catalysts are introduced into the

bottom
SPLITTING of fats takes place
Fat globules rise against a descending aqueous phase
The aqueous phase having dissolved the split glycerin falls
and is separated

EVAPORATORS
}

The glycerin water phase is evaporated and purified (*to

be continued)

Continuous process for the production of fatty acids and soap (Procter & Gamble Co.)

14

3/8/13

Fatty Acids

Continuous Alkaline Saponification

FLASH
TANK

HIGH
VACUUM
STILL

Hot Water
HYDROLYZER

EXCHANGER

Bottoms, to
storage and
recovery

BLEND
TANK
EVAPORATORS

Fats and
Catalyst

The fatty acids are distilled

from the bottoms and rectified.

MANUFACTURE OF SOAP

HYDROLYZER
HEAT
EXCHANGER

EVAPORATORS

Bottoms, to
storage and
recovery
EVAPORATORS

Crude
Glycerin*

Fatty
Acids

Conventional Soap
Finishing:
Bar, Flake or Power

The neat soap is

discharged into this
tank to even out any
inequalities of
neutralization

PLODDER
(greases pieces together)

MIXER

FREEZER
Air
FLASH TANK

CHILLING
ROLLS

Conventional Soap
Finishing:
Bar, Flake or Power

The soap can be

extruded, milled,
flaked or spraydried, depending
upon the product
desired.

WRAPPING

STAMPING

MIXER

CUTTER
PLODDER

Milling Operation
}

Continuous process for the production of fatty acids and soap (Procter & Gamble Co.)

BUGGY

DRYER
MILLS

HIGH PRESSURE PUMP

SOAP
BLENDER
Fatty
Acids

SOAP
BLENDER

BLENDING TANK
}

CUTTER & PACK OFF

DISTILLATE
RECEIVER

Crude
Glycerin*

Continuous process for the production of fatty acids and soap (Procter & Gamble Co.)

HEAT EXCHANGER

Bottoms, to
storage and
recovery

BLEND
TANK

DISTILLATE
RECEIVER

Soap is formed by
continuous
neutralization with
50% NaOH in highspeed

Aerated Bar Soap

MIXER
NEUTRALIZER

HIGH
VACUUM
STILL

Hot Water

Fats and
Catalyst

CONDENSER

HEAT
EXCHANGER

MIXER NEUTRALIZER
}

MANUFACTURE OF SOAP
NaOH

FLASH
TANK

HIGH
VACUUM
STILL

BLEND
TANK

Continuous process for the production of fatty acids and soap (Procter & Gamble Co.)

Fatty Acids

CONDENSER

HYDROLYZER

HIGH VACUUM STILL

}

Crude
Glycerin*

FLASH
TANK

Hot Water

The fatty acids phase at the

top of the hydrolyzer is dried
by flashing off the water and
further heated

NaOH

Fatty Acids

FLASH TANK & HEAT

EXCHANGER
}

HEAT

Fats and
Catalyst

MANUFACTURE OF SOAP
MIXER
NEUTRALIZER

MANUFACTURE OF SOAP

Soap is mixed and kneaded by mills (heavy

rolls)

A much more uniform product is obtained

Fragrant perfumes are incorporated well into

cold soap
}

Volatile scents evaporate with warm soap

Much direct labor is saved

Previous process produces floating soap.

15

3/8/13

MANUFACTURE OF SOAP
}

Solubility and hardness of sodium salts of various fatty acids

differ considerably
}

CRYSTALLINE PHASES IN BAR SOAP

}

Choose raw materials according to properties desired with due

consideration of the market price

Physical properties of bar

soap
}

Dependent upon the crystalline

soap phases present and the
condition of these phases

Any of three or more phases

may exist in sodium soaps
}

Depending on:
}
}
}

The fat used

The moisture and electrolyte
composition of the system
The processing conditions

Solubilities of Various Pure Soaps (in grams per 100g of water at 25oC)

TRIVIA

Bar Soap Market

-
-

Has 3,4, 5-tribromo salicylanilide (TBS)

-
-

Has stearic acid and fat but with less soap

Firm and lathers well
Contains large proportions of the very
desirable glycerides of lauric and myristic
acids

Considerable amount of potassium soap

Excessive stearic acid

Soap from Coconut oil

-

Mixtures of tallow and coconut oil (80/20 or

90/10)
Superfatted (50/50 or 60/40)
Some with 7-10% free fatty acid
Little added material except for perfume
Has 10-15% moisture
Has titanium dioxide

Brushless Shaving Creams

-

Toilet Soaps
-

Has slow drying lather due to the following:

-

10-30% water
Hard to dissolve if anhydrous

Shaving Soap
-

TRIVIA

Whitening agent
To prevent the decomposition of perspiration
into odorous compounds

Milled Toilet Soap

-
-

Lathers better
Improved general performance

16

3/8/13

HISTORY
}

GLYCERIN

}
}
}
}

USES AND ECONOMICS

}

USP and CP grades

}
}
}

Chemically pure
Contain at least 95% glycerol
Suitable for resins and other
industrial products

Yellow distilled
}

For processes where higherpurity types are not essential

}

Lubricant in tire mold

A clear, nearly colorless liquid

having a sweet taste but no
odor
A viscous heavy liquid
the sweet principle of fats
Explosive nitroglycerin
Produced from petrochemical
raw materials by synthetic
processes

MANUFACTURE OF GLYCERIN
}

For the manufacture,

preservation, softening and
moistening of the products:
}
}
}
}
}
}
}
}

Alkyd resins
Cellophane
Tobacco
Explosives
Drugs and cosmetics
Urethane foams
Foods and beverages
Others

SAPONIFICATION OF
GLYCERIDES

FROM SWEET WATER

FROM HYDROLYZER

Saponification of
oils and fats
A byproduct

Recovery of
glycerin from
hydrolysis

FROM PETROLEUM

Chlorination and
hydrolysis of
propylene and
other reactions from
petrochemical
SOURCE: SOAP. 2013. Advameg, Inc. February 21, 2013. <http://www.madehow.com/Volume-2/Soap.html#b>.
hydrocarbons

17

3/8/13

MANUFACTURE OF GLYCERIN*
Sweetwater from
hydrolyzer

Refined Glycerin
(95-99% Glycerol)

EVAPORATORS

FILTER

CRUDE GLYCERIN
SETTLINE TANK

BLEACHING TANK
w/ Activated Charcoal

GLYCERIN STILL

CONDENSERS

From Sweet Water from

Hydrolyzer
1.
2.
3.
4.
5.
6.

PRODUCT TANKS

MANUFACTURE
From Petroleum
1.
2.
3.
4.
5.
6.

Purification of
propylene
Chlorination to allyl
chloride
Purification and
distillation
Chlorination with HOCl
Hydrolysis to glycerin
Distillation

FROM SWEET WATER FROM

Evaporation (multiple
effect) for concentration
Purification with settling
Steam vacuum distillation
Partial condensation
Decoloration (bleaching)
Filtration or ion-exchange
purification

Flowchart for glycerin manufacture from hydrolysis of sweet water (Procter & Gamble Co.)
*The flowchart above is the continuation the continuous saponificaiton process

MANUFACTURE
HYDROLYZER

Flowchart for glycerin manufacture from hydrolysis of sweet water (Procter & Gamble Co.)

REFERENCES
Google.com
Material Safety Data Sheet Sodium tripolyphosphate MSDS. 06/09/2012. Science
Lab.com: Chemicals & Laboratory Equipment. February 18, 2013. <http://
www.sciencelab.com/msds.php?msdsId=9927608>.
Shreve, R. N. and Austin, G.T. Shreves Chemical Process Industries (5th edition). McGrawHill, 1984.
SOAP. 2013. Advameg, Inc. February 21, 2013. <http://www.madehow.com/
Volume-2/Soap.html#b>.
Tetrasodium pyrophosphate. January 4, 2013. Wikipedia. February 18, 2013. <http://
en.wikipedia.org/wiki/Tetrasodium_pyrophosphate>.

Routes for the synthesis of glycerin

18