UNIT-II

SULFUR AND NATURAL PRODUCTS

 SULFUR
• Sulfur is the basic raw material for manufacture of H2SO4 which is
considered the barometer of India’s industrial progress.
• Current production is at the same level as that of the USA in about
1900 and the per capita consumption of acid in India is only 4% of
that in the USA.
Pertinent properties of Sulfur
i. It exist as rhombic crystals, m.p. 112.80C and as monoclinic
crystals, m.p. 1190C and it boils at 4440C.
ii. The specific gravity at 180C of rhombic form is 2.07 and of the
monoclinic form is 1.96.
iii. The liquid has a specific gravity of 1.803.
iv. It is insoluble in water and soluble in organic solvent and liquid
ammonia.
Contd…
(v) Sulfur exist in the following forms ---
rock, lump, molten, ground powder and
sublimed powder (flowers of sulfur).
Consumption pattern
i. 80-90% of sulfur-containing raw materials are converted to
these commercial oxidized form:
Sulfur dioxide (SO2)
Sulfur trioxide (SO3)
Sulfuric acid (H2SO4)
Oleum (H2SO4+SO3)
Contd…
End uses for elemental sulfur are:
• 85-90% for sulfuric acid manufacture
• Rest for production of:
SO2,SO3,CS2, and P2S5;
Rubber vulcanization agents;
Gunpowder, sulfur dyes;
Putties, sulfur concrete;
Paper--- 7% to paper and pulp,3% to CS2
manufacture.
Contd…
The applications spectrum for sulfuric acid in USA:
• Phosphate fertilizer – 70
• Petroleum refining -- 5
• Inorganic chemicals and pigments -- 4
• Copper leaching --- 3
• Synthetic rubber and plastics -- 2.5
• Industrial organic chemicals -- 2.5
• Pulp and paper -- 2
• Others --- 11
• Raw Materials
• Sulfuric acid may be produced from elemental sulfur,
pyrites (sulfides of iron), hydrogen sulfide as contained
in sour gas and petroleum, waste gases from the
burning of fuel and smelting operations such as pyrites
of copper, iron, zinc and lead.
• Elemental sulfur, pyrites and sulfides are the basic raw
materials for production of sulfuric acid in India.
• Sulfuric acid produced by burning of fuel and smelting
operations is called by-product sulfuric acid.
Contd…
• Classification of processes
i. Elemental sulfur mining from salt domes (USA)
ii. Hydrogen sulfide conversion from natural gas and industrial
gases (Indian and US refineries)
iii. Iron pyrites from Amjhore in Bihar state
• Elemental sulfur mining (Frasch process), reference
flowsheet (Fig. IIA-1), chemical reaction-none
• Raw material
i. Sulfur deposites in salt domes
ii. Large supply of hot water
Contd…
• Quantitative requirements
a. Basis: 1 metric ton of sulfur, water (1600C) 6tons
b. Dome operating capacity: 500-8000 tons/day of sulfur
• Process description
 Major Engineering Problems
a. Heat transfer in melting and shipping operations
b. Finding suitable sources of treated water
c. Corrosion
 Oxidation-reduction of H2S
• Ref. flow sheet: Fig. IIA-2
• Chemical reactions
• 2H2S+3O2 rev.rxn 2SO2+2H2O, Enthalpy = -247.89Kcal
• 2H2S+2SO2 gives S6(g)+4H2O, Enthalpy = -42.24Kcal
• Raw materials
• H2S from natural gas and petroleum refinery streams.
Recovered by scrubbing with ethanolamines and high-temp.
stripping.
• Read the following from books
• (i) Raw materials, (ii) process description, (iii) major
engineering problems
Elemental Sulfur from Pyrites (Finish
Process)
 Sulfuric Acid
• Pertinent Properties (Pure 100% H2SO4)
• Mol. Wt. = 98.08, M.P. 10.50C, B.P. = 3400C (decomposition)
• Solubility – Completely miscible with H2O with large heat of
solution. SO3 soluble in H2SO4 to give varying percentage of
Oleum.
• Methods of production
• Contact process
• Chamber process
• Both process are based on SO2. Chamber process was developed
first (1746) but produced acid of concentration less than 80%.
• Contact process yield 98% H2SO4 and higher which can be diluted,
if necessary. Chamber process is virtually obsolete.
 Contact H2SO4 Process
• Reference flow sheet: Figure IIA-4
• Chemical reactions
a. S(s) + O2(g) → SO2 (g), ∆H = -70.9 Kcal
b. SO2 (g) + 1/2O2 (g) ↔ SO3 (g), ∆H = -23 Kcal
• Raw materials
a. Sulfur
b. Pyrites
c. CuS, ZnS, PbS, MoS
d. Waste H2SO4
e. H2S sources
Contd…
• Catalyst
• Mostly widely used catalyst is vanadium pentoxide dispersed
on a porous carrier in pellet form.
• Platinum catalyst was previously used but suffers from easy
poisoning, fragility, rapid heat deactivation, high initial
investment.
• Characteristics of catalyst
1. Porous carrier
2. Active catalytic agent
3. Promoter : alkali, and/or metallic compound added in trace
amount to enhance activity of catalytic agent.
Contd…
• Advantage of V2O5 catalyst
i. Relatively immune to poisons
ii. Low initial investment and only 5% replacement per year
iii. Require only 10 kg of catalyst mass containing 7-8% V2O5 per
daily ton of 100% acid.
• Disadvantages of V2O5catalyst
i. Must use dilute SO2 input (7-10%); as catalyst is less active
and requires high O2/SO2 to give economic conversion.
Larger converters and higher initial investment are
necessary.
Contd…
• Quantitative requirements
a. Basis: 1 ton of 100% H2SO4
SO2 0.67 ton
Air 1450-2200Nm3
(b) Plant capacity: 50-1000 tons/day of 100% acid
Process description
i. Air-SO2 gas containing 7-10% SO2 and 11-14% O2 is
preheated by converter gas, if necessary and sent to first
stage reactors of steal construction.
ii. This is the high tem.(500-6000C) stage, containing 30% of
total catalyst and converts about 80% of SO2.
Contd…
(iii) The converter product is cooled by heat exchange at 3000C
and fed to a second stage where total yield is increased to
97% by operating at 400-4500C for favorable equilibrium.
(iv) High yield product gases are cooled to 1500C by water and
air heat exchangers and absorbed in oleum fed at a rate to
allow not over a 1% rise in acid strength.
(v) Final scrubbing is done with a lower strength (97%) acid.
(vi) Oleum concentrations up to 40% can be made by tower
absorption. Higher strength oleum is prepared by distilling
20% oleum.
Contd…
• Major Engineering Problems
i. Design of multistage catalytic converter for highly
exothermic reaction.
ii. Optimization of space velocity in catalyst chamber.
iii. Corrosion problems
iv. Adaptation of process to various types of gas feeds.
v. Removal of heat of absorption of SO3 in acid.
Economics
 Edible and essential oils
• Edible oils are naturally-occurring compound based on long chain
fatty acids and esters(particularly glyceride esters) as well as
derivatives such as glycerin, long chain fatty alcohols, sulfates and
salfonates.
• Products from these compounds are used for food, sanitation,
polymers and in the paint industry.
• The per capita consumption of all such products is about 7.5 kg per
year in India versus 15.5 as a world average.
• Another group of organic compound which are pleasantly
odoriferous is the essential oils used in cosmetics, perfumes, soaps
and medicines.
• India ranks high among the oilseed producing countries in the world
with, perhaps, the largest number of commercial varieties of oilseed.
Contd…
Worldwide vegetable oil production
(in 106 tons)
1990
Soya oil 16.9
Palm oil 10.6
Rape oil 8.1
Sunflower oil 8.0
Coconut oil 3.1
Total = 46.7
Contd…
• There are other oil sources including:
• Animal sources:
Lard from hog fat
Tallow from beef and mutton fat
Ocean sources:
Menhaden fish
Sperm whale
Codfish
These are not much significant
Contd…
• End uses of vegetable oils have been estimated as follows:
• Edible
• Liquid oil 57%
• Vanaspati (Hydrogenated oil) 19
• Soaps and detergents 10
• Cosmetics 9
• Paints and varnishes 2
• Miscellaneous 1
• Chemical composition and physical properties of vegetable oils
• Fats and oils: mixtures of glycerides of fatty acids where R1,R2 and R3
are not necessarily the same
Contd…
R1 . CO . O. CH2
Ι
R2 . CO . O . CH
Ι
R3 . CO . O . CH2
By terminology of the industry, oils are all liquid and fats are
solid at normal temperatures.
Waxes: mixed esters of polyhydric alcohols other than glycerin.
Usually solid at room temperature.
Effect of degree of saturation: number of double bonds in the
fatty acid radical (R) controls the melting point and chemical
reactivity as shown in the following table:
Contd…
Contd…
• Methods of extracting vegetable Oils (Flow
Chart)
 Hydrogenation of Oils
• Hydrogenation is a unit process which is used in the fat and oil
industry to remove double bonds, raise the melting point of
the fat, and improve its resistance to rancid oxidation.
• The major end product in India is Vanaspati, a solidified
household oil for cooking.
• Other products are vegetable ghee, hardened industrial oils,
and partially hydrogenation liquid oil.
• Reference flow sheet: Figure IIIA-2
• Chemical reactions (* indicates activated catalytic state)
Ni* catalyst

(a) R1 (C = C)x R2 + (x-y) H2 → R1 (C = C)y R2

Contd…
• Example:
Ni*

(C17H31COO)3 . C3H5 + 3H2 → (C17H33COO)3.C3H5

(b) Nickel catalyst preparation (nickel formate decomposition)
1900C

Ni (HCOO)2 . 2H2O → Ni* + 2CO2 + H2 +2H2O

This produces a finely divided catalyst which is preferred for
well-stirred hydrogenation reactors.
Contd…
• (c) Nickel catalyst preparation (reduced Ni on inert catalyst
support)
• Ni(OH)2 + H2 → Ni* + H2O
• NiCO3 + H2 → Ni* + H2O + CO2
• Nickel salt are precipitated on inert porous carrier such as
kieselguhr or diatomaceous earth and reduced at high temp.
in a hydrogen atmosphere.
(d) Nickel catalyst preparation (Raney or spongy nickel method)
2Al.Ni + 6NaOH → Ni* + 2NaAlO3 + 3H2
alloy (Raney nickel)
• Produces spongy, high-surface area catalyst when the sodium
aluminate is washed out with water
Contd…
• Raw material
• Electrolytic H2O or chlor-alkali
• Steam-iron: reaction of steam on Fe followed by
regeneration with water gas
• Synthesis gas
• Sulfur containing compound (SO2,H2s) are highly poisons
for the hydrogenation catalyst.
these are removed from the last two H2 processes by
cryogenic distillation or a reactive metal guard converter.
Process description:
Contd…
• Batch operation is used because of large residence times (1-3
hours) and variation in oil input and product properties from
day to day.
• Batch hydrogenators can treat 5-30 tons of oil per batch; are
equipped with coils for heating and cooling and turbine
agitators to disperse the injected hydrogen.
• Ghee base oil is hydrogenated at low pressure (1-2 atms.
gage) and high tem.(135-1800C) to yield a fat with melting
point similar to butter.
• Vanaspati shortening is produced by hydrogenating at higher
pressure (2-3.5 atms. gage) and lower temp.(120-1600C) to
maintain higher melting point fats of maximum stability for
cooking purposes.
Contd…
• Major engineering problems
i. Thermodynamics and kinetics
a. Heat of reaction
b. Temperature
c. Kinetic rate factors
ii. H2 handling problems
Hydrogen gas has wide explosive limit range (4.1-74.2%). All
equipment should be leak-tested with freon or helium detectors
before operating. While hydrogen embrittlement is a problem at
high temp. and pressure such as found in the ammonia synthesis
plants, carbon steel can be used throughout for oil hydrogenation.
Economics: Purchasing of raw materials (castorseed, soyabean,rice
bran oil, linseed and coconuts) and selling of products etc.
 Soaps and detergents; Glycerin
• These chemical compound are used for
human comfort, cleanliness and for industrial
surface active applications.
Contd…
• The grease is pulled away from the surface to be cleaned by
the “key’’ mechanism shown.
• The success of any cleansing agent is to supply compounds
with hydrophobic and hydrophilic groups which will also
appreciably decrease surface tension and increase wettability.
Classification of cleansing compound
Soaps:
• The soaps are R. COO.M types of compound, where R. COO.
Is fatty acid radical representing oleic, stearic, palmitic and
myristic.
• These are present in soaps as mixtures based on glyceride
raw materials. M is an alkali element such as Na or K.
Contd…
• Detergents: These are synthetic organic chemicals which
promote better surface tension lowering than soaps. These
are discussed here because of the competitive position with
soaps.
• Where the use of detergent increases to the point of creating
problems in municipal sewerage plants due to excessive
foaming and inability to reduce the organic content of the
sewage effluent, biodegradation of detergent compound
becomes an important factor.
Contd…
• Anionic (give R- in water)
• Sulfated fatty alcohols

• These are low priced detergents which are not as stable as

sulfates and require more additives in final compounding to
improve performance. They represent the major ingredient
of compounded detergents.
Contd…
• Sulfated esters and acids
• Good stability in hard water but not under acid and
alkaline conditions.
• Cationic (give R+ in water)
• These have no strong detergent characteristics but
do have germicidal properties.
• Non-ionic
• Alkyl-ethylene oxide derivatives
• Aliphatic polyhydric alcohol esters
• fatty acid amides
Contd…
• Detergent builders
• Phosphate such as sodium tripolyphosphate and
tetrasodium pyrophosphate used as much as 30-50% in
detergent formulations to extend foam
• Sodium carboxycellulose (1-3%) to improve soil and dirt
suspension
• Fluorescent dyes as brightners
• Sodium silicate to avoid aluminum corrosion in washing
machines
• Zeolites as alternative phosphorus-free builders
 Method of soap production
• Batch saponification process:
• Acid hydrolysis of glycerides followed by alkali addition or direct
saponification using strong caustic in batch process operation
are the oldest types of soap manufacture.
• Continuous hydrolysis and saponification process:
• This method is in greater use because it has these advantages
over the batch process:
• Flexibility in control of product distribution
• Higher glycerin yield (>80%)
• Less off-color production during the short time hydrolysis
step
• Require less space and manpower
Contd…
• Reference flow sheet: Figure IIIB-1
• Chemical reactions
• (a) Fat splitting
(R.COO)3.C3H5+3H2O → 3R.COO.H+C3H5(OH)3
triglyceride fatty acid : glycerin
(b) Saponification

R.COO.H+M.OH→ R.COO.M+H2O
soap
Where M is usually an alkali metal such as Na or K

Raw Materials:
• Refined tallow, recovered and refined grease, coconut and palm
oils are the principal fatty constituents. Metal oxides such as ZnO
are frequently added as fat splitting catalyst.
Contd…
• Alkali for saponification and builder-type additives, mainly
rosin.
• Caustic soda and vegetable oil are the two raw materials for
the production of toilet soaps.
• Quantitative requirements
a. Basis: 1 ton of anhydrous soap
Oil or fat 1.1 tons
50% NaOH 0.3 ton
Sodium silicate 6 kg
H2O 0.8 ton
Steam 1.5 ton
(b) Plant capacities: 2-15 tons/day
Process description
 Method of detergent production in India
• Two of the most prominent detergents in use
today will be discussed.
• Sulfated fatty alcohols
High molecular weight alcohols such as the group from lauryl
alcohol (C12H25OH) up to oleyl alcohol (C18H35OH) are derived from
coconut oil by either sodium reduction or catalytic hydrogenation.
• Catalytic hydrogenation of coconut oil
(i) Hydrogenation is done at high temp. (200-3000C) and pressure of
100-200 atms. Using copper salt as catalyst.
(ii) In addition to hydrogenating at the carboxyl linkage, saturation of
double bonds occurs which is not desirable for best detergency
action.
Contd…
• Sodium reduction of coconut oil
• Molten sodium is added slowly to coconut oil in an aliphatic
solvent (xylene or toluene) plus esterifying alcohol such as
amyl alcohol. The reactions occurring are:

• After reaction is completed, the batch is pumped into a water

tank where the mixture settles into three layers---
• The top is the high molecular weight alcohols, the
intermediate layer contains regenerated reducing alcohol and
bottom have caustic soda and glycerin for recovery.
Contd…
• Sulfation of fatty alcohols
• Oleum or an excess of 98% H2SO4 is added to the purified fatty alcohols,
acid sulfate is then converted to sodium salt.
NaOH
R.CH2OH+H2SO4→ R.CH2O.SO3H →R.CH2O.SO3Na (sodium salt of sulfated
fatty alcohols)
Alkyl-Aryl Sulfonates
Compound under this classification are prepared in a three-step process
using cheap petroleum raw materials.
 Glycerin
• Properties:
• Miscible in water and alcohol
• Grades: yellow distilled (99%) for industrial and explosives.
• Consumption pattern: Glycerin has a wide variety of industrial
uses based on its physical properties of moistening and
lubrication and the chemical reactivity of its OH groups.
• End uses:
• Alkyl resins and plastics 35%
• Tobacco humidification 15
• Cellophane plasticizer 12
• Explosives 10
• Food and pharmaceuticals 10
• Reference flow sheet: Figure IIIB-1
 Sucrose
• Pertinent properties of Sucrose
• Chemical formula: C12H22O11 (disaccharide)
• Mol.wt.: 342
• M.P. 186OC (decomposition)
• Density 1.58gm/cc
• Solubility: Very soluble in water, slightly
soluble in methyl and ethyl alcohol
• Forms: powdered, granulated
Contd…
• Method of production
• Classification of processes
i. Extraction of sugar cane to produce crystalline white sugar
ii. Extraction of sugar cane to produce gur, a dark brown sugar concentrate
Extraction of sugar cane for crystalline sugar production
Reference flow sheet: Figure IIID-1
Chemical reactions – none of any importance
Quantitative requirement:
(a) Basis: 1 ton of raw sugar (97% sucrose); yield from cane-95% on sucrose basis,
9.5-15% on cane basis
Sugar can --- 6-10.5 tons of 16-10% sucrose content
Water --- 3-4 tons
Lime --- 12-17 kg
SO2 ---- 6-10 kg
Contd…
(b) Plant capacities: 100-400 tons/day of sugar
• Canes are shredded in crushers and squeezed through a series
of pressure mills containing grooved walls.
• Weak juice and make-up water are added as extract ant fluids
before squeezing to optimize juice yield at 95-97%.
• The juice is treated with calcium phosphate, followed by lime
to precipitate the colloids.
• SO2 is next bubbled through until the pH is 7.0 to 7.1.
• This procedure provides maximum flocculation of impurities
because here SO2 acts as a bleaching agent.
 Starch
• Starch is a high polymer carbohydrate occurring in grains and roots in the
form of granules of 3-100micro size. These granules can be extracted from
the grains by water hydration of the cells.
• Chemical formula: C6H10O5
• Chemical structure ---
 Starch derivatives
• Dextrin: heat and acid depolymerization yields a water soluble
carbohydrate gum which is used in adhesive and gums.
• Chemical reaction: (C6H10O5)n (heat and HCl) → (n/x).(C6H10O5)x
• Dialdehyde Starch: An oxidized form of starch which is used in the paper
industry as a wet-strength additives and in adhesives.
Contd…
• Starch Phosphate: A starch ester which is water soluble, has
excellent freeze-stability, good thickening power. Expected
usage is as thickeners in canned and frozen foods, adhesives,
emulsion paint formulation, pharmaceutical filter and
binders.