chapter!1!| !natural!products!!!

CH0204 Organic Chemical Technology

Chapter 1 | Natural Products

Balasubramanian S Assistant Professor (OG) Department of Chemical Engineering

24/01/12 Balaubramanian S 1

Chapter 1 NATURAL PRODUCTS

Edible and EssenJal oils

Soaps and Detergents; Glycerin

1

2

Overview of topics


Overview of topics

Plant and Animal kingdom

Fats and Oils

Edible oil and EssenJal Oils

Soaps and Detergents


Fats and Oils

Fats and oils are found widely distributed in nature, in both the plant and animal

kingdom.

Fats and oils are the mixtures of the glycerides of various faUy acids.

By the industrial terminology, the oils are all liquids and fats are solid at normal

temperatures.

The degree of satura3on

The degree of saturaJon of the acids involved affects the melJng points of the ester

mixture; the more unsaturated give esters with lower melJng points and these are

the chief consJtuents of oil.

The more the saturated esters on the other hand are consJtuents of fats.

Fats and Oils


Edible Oils

Edible oils are naturally-‐occurring compounds based on long chain

faUy acids and esters (parJcularly glyceride esters), as well as

derivaJves such as glycerin, long chain faUy alcohols, surfactants and

sulfonates.

The term “Vegetable Oils” is used as synonym for “Edible Oils”.

Example: Palm oil, Coconut oil, Rice bran oil, Soybean bean oil and so on.

Uses

These oils are used in food, sanitaJon and in the paint industries.

The degree of satura3on

The degree of saturaJon of the acids involved affects the melJng

points of the ester mixture; the more unsaturated give esters with

lower melJng points and these are the chief consJtuents of oil.

The more the saturated esters on the other hand are consJtuents of

fats.

Edible Oils


Group of organic compounds which are pleasantly odoriferous are

called essenJal oils.

EssenJal oils may also defined as volaJle, odoriferous oils of vegetable

origin.

“EssenJal Oil” does not mean “Most necessary” but rather the

concentrated characterisJcs or quintessence of a natural flavor or

fragrance.

EssenJal oil


Essen3al oil

EssenJal oil are, in the main, insoluble in water, and soluble in organic

solvents, although enough of the oil may dissolve in water to give an

intense odor to the soluJon.

Example: Lemon oil, Jasmine oil, Rose oil, Sandal wood oil and so on.

Uses

These oils are widely used in costumes, perfumes, soaps and

medicine.

EssenJal oil


Vegetable (or edible) oils

Olive oil

Palm oil

Palm kernel oil

Peanut oil

Sun flower seed oil

Coconut oil

Soybean oil

Major vegetable (or edible) oils


Olive Oil Palm Oil




Palm Kernal oil Peanut or Groundnut oil




Sunflower seed oil Coconut oil




Soybean Oil




Methods of production – Edible and Essential Oils

Methods

Mechanical

Hydraulic press Screw Press

Solvent ExtracJon and PurificaJon (AlkylaJon )


Soybean oil production

hUp://www.wishh.org/aboutsoy/composiJon.html

ComposiJon of Soybean

24/01/12 14

Production Process – Soybean oil Process

Process

Seeds

Solvent

Water

Steam

Alkali

Oil

Cake

Yield of oil Mechanical (i)  Hydraulic = 14.5 kg/100 kg = 81% (ii)  Screw expeller = 15.3 kg/100 kg = 85% Solvent ExtracJon = 18.2 kg/100 kg = 98%


Production Process-Block diagram Mechanical Method

Dehuller Crushing DIgestor Expeller

Water Steam

Oil

Cake

Upstream Process Downstream process


Production Process-Block diagram

Dehuller Crushing Extractor DesolvenJzer/ Toaster

Hexane

Flash Evaporator

Solvent recycle

Vacuum Stripper

Solvent recycle

Oil

Solvent recycle

Upstream Process

Downstream process

Solvent Extrac3on Method


Production Process-Block diagram Purifica3on

AlkylaJon Centrifuge AdsorpJon

Fullers earth carbon

Rotary Filter

Oil from Mechanical methods and solvent extracJon

Alkali such as Sodium Carbonate and Sodium hyroxide

“Foots” to manufacture soap.

Oil

Cake


Mechanical Method

Dehuller Crushing Digester Expeller

Water Steam

Oil

Cake

Extractor DesolvenJzer/ Toaster

Hexane

Flash Evaporator Solvent recycle

Vacuum Stripper

Solvent recycle

Solvent extracJon

Alkali Centrifuge AdsorpJon

Fullers earth carbon

Rotary Filter

Alkali such as Sodium Carbonate and Sodium hyroxide

“Foots” to manufacture soap.

Oil

Cake

Solvent recycle

PurificaJon Oil

Oil

Steam

Steam

Alternate route


Balaubramanian S 20

Mechanical Cleaning and Dehulling

Extractor

Digester

Wet

Meal

Meal to drier

Steam

Alkali

De so

lven

Jzer

Cracking rolls

Recycle stream

Solvent removal

Flash film evapo

rator

Vacuum

strip

ping

Ope

n Steam

Foots to soap mfg.

Fullers Earth Carbon

Water

Steam in

Steam out

Expeller Clear Oil

Oil

Steam in

Steam out

Oil

Cake

Oil 24/01/12

Process Description


Hydrogenation of edible oil Hydrogena3on HydrogenaJon is a unit process which is used in the fat and oil industry to remove the double bonds, raise melJng point of the fat, and improve its resistance to rancid oxidaJon. Hardening of oils Glycerides of unsaturated acids are liquid at room temperature and so are unsuitable for edible fats. By converJng the unsaturated acids into saturated acids, oils are changed into fats by introducJon of hydrogen. This introducJon of hydrogen is known as hardening of oils. The oil is heated and hydrogen is passed under pressure, in the presence of finely divided nickel catalyst. The major end product in India is Vanaspathi, a solidified household oil for cooking. Other products are vegetable ghee, hardened industrial oil, and so on.


Production Process – Hydrogenation of oils

General process

Process

Oil

Catalyst

Fullers Earth Carbon Steam

Oil


Production Process- Block diagram Hardening of oil or HydrogenaJon process

Hydrogenator Filter

Mixer

Oil Make up Catalyst

Recycle catalyst

Vacuum Steam

deodorizer

Adsorber

Fullers Earth Carbon

Filter Oil

Waste Solids

Steam out

Steam in

H2

Oil

Oil + Catalyst Slurry

(C17H31COO) 3C3H5 + 3H2 (C17H33COO) 3C3H5 ΔH = -‐ 420.8 kJ/ kg Ni

Oleic acid or FaUy acids

Hydrogenated oil

Ni(HCOO) 22H2O Ni + 2CO2 +2H2O

Exothermic


Hardening of oil or Hydrogena3on process Process Flow Diagram

Vacuum

Steam

Deo

dorizer

Steam or Water

Hydrogenator

Oil

H2 Catalyst + oil slu

rry

Oil

Make-‐up Nickel Catalyst

Recycle catalyst

Filter aid Fullers Earth Carbon

Steam

H20

Barometer leg

DecolorizaJon Do

wnthe

rm fo

r heaJn

g trays

Steam

Waste Solids

Product Oil 24/01/12 Balaubramanian S 25

Process Description S. No

Process Equipment Unit opera3ons Unit process Objec3ve Opera3ng condi3ons

1. HydrogenaJon (Batch)

(a) Hydrogenator

_______ Hydrogena3on

Remove the double bond to improve the resistance to rancidity

1 – 2 atm 120 -‐160 deg. C

(b) Filter Solid-‐liquid separaJon _______

SeparaJon and recycle of oil and oil slurry with catalyst

_______

(c) Vacuum steam deodorizer

Liquid-‐liquid separaJon _______

Remove volaJle odorous materials by using steam

_______

(d) Adsorber Solid-‐liquid SeparaJon by pressing

_______

Removal of color components using adsorbents

_______

(e) Filter Solid-‐liquid separaJon _______

SeparaJon of oil and solid waste

_______

(f) Catalyst mixer Solid-‐Liquid mixing _______

Mixing of catalyst With oil


End uses of edible and essential oils

Edible oils Food -‐ Hydrogenated oil (Vanaspathi) Soaps and Detergents CosmeJcs Paints and Varnishes

Essen3al oils CosmeJcs Perfumes Soaps Medicines





1

2

Overview of topics


Soaps and Detergents

If an oil is hydrolyzed and or saponified with alkali soaps are obtained. Any metallic salts of faUy acid is soap, but the term soap is applied to water soluble salts. Soaps comprises of the sodium or potassium salts of various faUy acids but chiefly of oleic, stearic, palmiJc, lauric and mysJric acids. The saturated fat gives hard soaps, whereas unsaturated fat gives sor soaps on saponificaJon 24/01/12 Balaubramanian S 30


Soaps comprises of the sodium or potassium salts of various faUy acids but chiefly of oleic, stearic, palmiJc, lauric and mysJric acids. It also comprises of salts of sodium and zinc oxide catalyst.

Soaps and Detergents Detergents differ from soap in their acJon in hard water.

Detergents may react with hard water ions, but the resulJng

products are either soluble or remain colloidally dispersed in

water.

ScienJfically, the term detergent covers both soap and

syntheJc detergents or “Syndents” but it is widely used to

indicate syntheJc cleaning compound.


Methods of production - Soap


Difference between batch and Continuous process

Batch (Twitchell) Process Con3nuous process

Temperature, deg. C 150 – 175 230 -‐ 250

Pressure, mPa (g) 5.2 – 10 4.1 – 4.9 40 – 45 atm

Catalyst Oxides of calcium, zinc and magnesium i.e. CaO, ZnO, MgO.

Same catalyst or opJonal

Acid used Sulfuric acid __________

Time, h 12 – 48 2 – 3

OperaJon equipment Batch ConJnuous

Hydrolysis 85 – 98 % 97 – 99%

Glycerol obtained 5 – 15% 10 – 25%

Advantages Low temperature, adaptable to small scale

Small floor space, uniform product quality, high yield of acids, high glycerin concentraJon, automaJc control

Disadvantages Catalyst handling; ling reacJon Jme, need more than one stage for good yield

High temperature and pressure, High cost and greater operaJng skill


Production Process – Soap

Con3nuous hydrolysis and Saponifica3on

Process

Fat or Oil

Catalyst

Water

Steam

Soap

CausJc Glycerin-‐ by product


Production Process – Block diagram

Con3nuous Hydrolysis and Saponifica3on

Holding tank (or)

DisJllate receiver

Mixer (NeutralizaJon)

Blender (SaponificaJon)

Ion exchanger

MulJple effect evaporator

SJll

Cooling

Holding Tank

Adsorber

Filter

Blend tank Hydrolyzer

(Fat splitng)

Steam flash tank

Vacuum DisJllaJon Condenser

Waste

Oil or Fat + Catalyst Hot Water Steam out

99% White Glycerin

98% Yellow Glycerin

AcJvated Carbon

CausJc (NaOH)

Steam in

FaUy Acids

Steam Out

Steam in

Steam Out

Soap to final product

Bar Stock Press Chipping rolls

Spray drier to soap powder

Production Process–process diagram

Mixer Hy

drolyser

Fat or Oil and Catalyst

Hot water

Steam Flash Tank

Vacuum

DisJ

llaJo

n

Waste Steam

Ion exchange

Triple Effect Evaporator

FaUy acid product

Holding

tank

Blender

NaOH

Air Water

Holding Tank

SJll

Steam

Heater

Soap to final products

Bar stock press

Chipping rolls Spray drier for soap powder

Filte

r

99% Glycerin 99% Yellow Glycerin

AcJvated Carbon

AdsorpJo

n


Hydrolysis (Fat – SpliWng) (R . COO)3 . C3H5 + 3H20 3R . COO . H + C3H5(OH)3 (Triglyceride) + (Water) FaUy acid + Glycerin (C17H35C00)3 C3H5 + 3H2O 3C17H35COOH + H2O Glyceryl stearate + Water FaUy acid + Glycerin Saponifica3on (Caus3c Addi3on) R . COOH + M . OH R . COO . M + H2O C17H35COOH + NaOH C17H35COONa + H20 (Stearic acid) + (CausJc) Sodium stearate + water

Production Process – Unit process


S. No


1. ConJnuous Hydrolysis and SaponificaJon (ConJnuous Process)

(a) Blend tank Physical blending

__________

Blending of fat or oil and catalyst

__________

(b) Hydrolyzer __________

Hydrolysis Splitng of fats 230 -‐ 250 deg. C 40 – 45 atm

(c) Ion exchanger Ion exchange

__________

SeparaJon of dissolved salts and glycerides collected from the hydrolyzer as the boUom product

__________

(d) Evaporator EvaporaJon

__________

SeparaJon of water and glycerides (or) ConcentraJon of glycerides

__________

Process description


S. No


(e) DisJllaJon sJll

DisJllaJon

__________

Glycerides obtained from the evaporator is purified to produce 99% Yellow Glycerin

__________

(f) Cooler (or) Heat exchanger

Cooling or Heat transfer __________

Cool the glycerides obtained from the sJll

__________

(g) Holding tank Storage __________

Cooled glycerides Stored __________

(h) Adsorber AdsorpJon

__________

Removal of color consJtuents using acJvated carbon as the adsorbent

__________

Process description


S. No


(i) Filter FiltraJon

__________

Final separaJon of glycerides

__________

(j) Steam flash tank

Steam separaJon __________

SeparaJon of steam from faUy acid

__________

(k) Vacuum disJllaJon column

DisJllaJon __________

SeparaJon of faUy acids and race impuriJes

__________

(l) Condenser CondensaJon __________

Vapors of faUy acids converted to liquid

__________

(m) Holding tank (or) DisJllate receiver

Storage __________

The disJllate from the condenser is stored

__________

Process description


S. No


(n) Mixer Mixing

__________

NeutralizaJon of faUy acids

__________

(o) Blender Blending SaponificaJon SaponificaJon of neutralized faUy acids

__________

(p) Spray drier Drying __________

Drying of soaps into powder arer saponificaJon.

__________

Process description


Methods of production-Detergents

Two of the most prominent detergents used today are

1.  Sulfated faUy alcohols

2.  Alkyl-‐Aryl sulfonates

Manufacturing method

1. Sulfated faUy alcohols

Deriving higher molecular weight of alcohols from oils of plant origin by

sodium reducJon or hydrogenaJon followed by sulfonaJon. The steps

involved in the manufacture of sulfated faUy alcohols are as follows,

a)  CatalyJc hydrogenaJon of coconut oil

b)  Sodium reducJon

c)  SulfaJon of faUy acids



1. Alkyl-‐Aryl sulfonates

The steps involved in the manufacture of Alkyl-‐Aryl sulfonates are as follows

(a) Conversion of hydrocarbon (paraffin) to alkyl chloride

(b) AlkylaJon of Alkylchloride yields Aryl-‐Benzene compounds

(c) Aryl-‐Benzene compound on sulfonaJon in presence of oleum yields

detergents (Aryl-‐Benzene sulfonate)




Methods of production-Glycerin

Cleaning action of soaps The success of an cleaning agent is to supply compounds with hydrophobic (water

haJng) and hydrophilic (water loving) groups which will also appreciably decrease

surface tension and increase weUability. i.e. surface tension is inversely proporJonal

to the weUability.

In wash water, soaps or detergents increase the wetng ability of water so that it can

more easily penetrate into the fabrics and reach the soil.

Each molecule of the cleaning soluJon may be considered a long chain. One end of

the chain is hydrophilic(Water loving) and the other end of the chain is hydrophobic

(Water haJng or soil loving). The soil loving end are aUracted to a soil parJcle and

surround it.


Cleaning action of soaps

At the same Jme the water loving end pulls molecules and the soil parJcles

away from the fabric and into the wash water.

This is the acJon which, when combined with the mechanical agitaJon of the

washing machine, enables a soap or detergents to remove soil, suspend it,

and keep it from redeposiJng on clothes.



End Uses – Soaps and Detergents; Glycerin A parJal list of soaps and detergents; glycerin is given to show the diversity of applicaJon

Glycerin Alkyl resin and PlasJcs Tobacco humidificaJon Cellulose PlasJcizer Explosives Food and PharmaceuJcals

Soaps and detergents TexJle manufacture SanitaJon Food processing Shaving soaps SyntheJc rubber and plasJcs emulsion polymerizaJon Paints -‐ water emulsion formulaJons Paper -‐ ApplicaJon of sizing


References

1.  Dryden C. E, Outlines of Chemical technoloy – for the 21st Century, 3rd ediJon, East-‐West Press (2004)

2.  AusJn G. T, Shreve’s Chemical Process Industries, 5th ediJon, Mc Graw Hill InternaJonal ediJons (1984)

3.  United States Department of Agriculture, Oil seeds: World markets and trade report.

4.  hUp://www.mapsofindia.com/indiaagriculture/oil-‐seeds/soyabean-‐growing-‐states.html

5.  hUp://www.mapsofindia.com/indiaagriculture/oil-‐seeds/soyabean-‐growing-‐states.html

6.  hUp://www.wishh.org/aboutsoy/composiJon.html 7.  hUp://en.wikipedia.org/wiki/Pliny_the_Elder 8.  hUp://en.wikipedia.org/wiki/Michel_Eugène_Chevreul 9.  hUp://en.wikipedia.org/wiki/Nicolas_Leblanc 10. hUp://en.wikipedia.org/wiki/Ascanio_Sobrero 11. hUp://en.wikipedia.org/wiki/Alfred_Nobel

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