Chemical Technology (CH2100)

Course Synopsis
References mentioned correspond to DRYDENS Outlines of Chemical Technology unless stated

Unit operations and unit processes (p.15 - 31)

Filtration:
Laminar flow across the filter: = =
A: area of filtering surface
Rm, Rc : resistances due to filter medium and cake respectively

: thickness of filter paper
: DArcys filter cake permeability
For incompressible cake :
specific cake resistance

For compressible cake: =
constant related to size & shape of particle forming cake
S: cake compressibility (0.1-0.8)
Design criteria for reactor systems (p.42-43)
Space velocity (SV) = represents the relation between volumetric flow and reactor volume
(or catalyst bed volume).
Volume hourly space vel.(VHSV):

Weight hourly space vel.(WHSV):

Holding time = volume/flow rate.
Mean residence time:
Choice between alternative processes (p. 47-51)
Reaction Kinetics

WATER:
Plant location factors related to water (p. 236-238)
Boiler water:
Lowest possible hardness and silicilic acid content
Free from substances promoting the formation of stable forms like oil, resinous, organic
matter
Free from dissolved CO2.oxygen, Mgcl2
Max. Content of dissolved oxygen for low pressure boiler- 3mg/l
Technical water:
Textile &paper industry: Free from Fe, Mn, unwanted coloration organic matter cl-
 Silk & drying : Free from iron and drying matter
Tanneries: soft water and free from purifying bacteria.

Treatment of water
Impurities to be removed (p.239)
Conditioning methods:
Filtration: done on sand filters
Coagulation : treatment with special reagent which enlarges particles to promote the
precipitation
Ex. Al2(SO4)3
Optimum dose of coagulation (Dc)
Turbid water: turbidity of water in mg/lit.
Coloured water: ..colour in degrees in Pt-Co scale
For excess coagulant add lime
Dlime =
Wa = alkalinity of water (mg eq./lit)
L excess lime in mg/lit
Required dose of Al2(SO4)3 =
a = optimum dose of Al2(SO4)3 mg/lit
b = Al2O3 content of product used %
optimum dose of lime =
a1 = optimum dose of CaO mg/lit
b1 = CaO content of product used %

Disinfection: add Cl- chlorine compounds, iodine, and ozone.

Active chlorine (%)=( n*M/Mo )*100
n: no. of hypochlorite ions
M: molecular mass of chlorine
Mo: molecular mass of the chlorine compound
Ultra sound :
Piezoelectric effect : The piezoelectric effect is understood as the linear
electromechanical interaction between the mechanical and the electrical state in
crystalline materials with no inversion symmetry
Stability of H2O: stable water doesnt dissolve caco3
Factors influencing stability
Presence of co2
Low PH
Oversaturation
Increase concentration of sulphates & chlorides
Stability index (C) =
If C>1CaCO3 Precipitates
If C<1aggressive
 Stability (I)= PH0-PHs
PHs = f1(T)-f2(Ca2+)-f3(A)+f4(P) functions can be calculated from nonograms
I= 0 stable
I= + ve H2O will precipitate CaCO3
I= -ve aggressive to metal and concrete
A: alkalinity
P: total salt content mg/l
T: Temperature of H2O
Alkalinity is the mg equivalent of acid required to neutralize OH- ions contained in one
litre of water.
Checks dis in book some more info.
Height of packing material (H) =
Hardness: due to dissolved salts of Ca, Mg
Total hardness: conc. Of Ca2+, Mg2+,Fe2+(mg. equi/lit)
Temporary hardness: Part of total hardness removed by boiling (ca2+,mg2+ bicarbonates)
Permanent hardness: part of total hardness remained in water after boiling it.
Carbonate hardness: part of total hardness for carbonates and bicarbonates of ca, mg
Non-carbonate: total hardness carbonate hardness
Permutit zeolite
Artificial zeolite: Na2.Al2O3.nSiO2.xH2O N=8, x=4
Natural zeolite AlxSiO2(x+y)

Regeneration

Exchange capacity: EC(g Eq./ions) =1000

H: hardness in mg eq./lit
V = total quantity of water passed through the filter till the first Ca2+ appears in the
filtrate
V1 = volume of cation exchange resin expressed in ml
Gas pipe line:

Factors : Pressure, temperature and consumption of gas pipe line geometry

Line pack: amount of gas the pipe line is holding in nm3 at any point of time.
Optimization of pipe lines: not to overshoot maximum erosion and noise velocity

Example: For APIRPIYE, velocity should not exceed

e: empirical constant (FPS)

: Density (lb/ft3)
Range: 100-200.
Minimum fluid velocity=3m/s.(below which flow instability exists).

PETROLEUM
Refinery crude petroleum classification (P.379).
Paraffin Base (k=12.15-12.9)
Naphthalene Base (k=10.5-11.45)
Intermediate Base (k=11.5-12.1)
Base of crude oil determined by characterisation factor
characterisation factor(k) =
: specific gravity at 15.50C
R: average boiling point(k)
Correlation Index (C.I) :
C.I =
T: Metal boiling point(k)
: Specific gravity.
For Paraffins CI=0.
For Aromatics CI=100.
Cloud and pour points indicate relative amount of wax in oil.
Cloud point: temperature at which dissolved solids are no longer completely soluble
Pour point: the lowest temperature at which it will pour or flow under prescribed conditions
Exploration methods (P.382).
Methods of production (P.382).
Petroleum Refinery Production (P.383).
Gas fraction:
Primary object: fuel
Secondary object: synthetic gas, natural gas.
Light gas: C1 and C2
Light ends:
Major product: petrol with aviation spirit, motor spirit, vaporizing oil.
Characteristics of petrol
 Gum Content: due to polymerisation, the particular component is insoluble.
Oxidation stability: to know its explosive nature.
Copper strip corrosion test: petrol should not corrode the copper
Anti-knocking compounds added to slow down the burning rate (iso octane 2,2,4 trimethyl
pentane)
Octane no.
Power no. proportional to power extracted from engine
Octane no. =
Cetane number
CI = 45.2 + 0.0892T10N + [0.131 + 0.901B]T50N + [0.0523 + 0.420B]T90N + 0.00049[T210N - T290N] +
107B + 60B2
Where: D = density at 15C [g/mL] B = [ e( -3.5 ) ( D - 0.85 ) ] -1,
T10 = 10% distillation temperature [C] determined by Test Method ASTM D 86 and
corrected to standard barometric pressure
T10N = T10 - 215,
T50 = 50% distillation temperature [C] determined by Test Method ASTM D 86 and
corrected to standard barometric pressure,
T50N = T50 - 260,
T90 = 90% distillation temperature [C] determined by Test Method ASTM D 86 and
corrected to standard barometric pressure,
T90N = T90 310
Diesel Index =
= Aniline gravity constant/100
=
Aniline point: lowest temperature at which oil is completely miscible with an equal volume of
aniline
Specific gravity of an oil expressed as 0API =
Additives to petrol:
Tetra ethyl lead.
Anti-oxidant.
Metal deactivation.
Pre ignition inhibitor.
Anti-icing.
Dyes.
Decolourisers.
Unit operations in Refinery process (p.387)
Distillation
Absorption
Extraction
Adsorption
Crystallisation
Heat transfer
Fluid flow
Refinery conversion operations ( p. 387-405 )
 Pyrolysis and cracking ( p. 388 )
Background
Used to crack larger molecules to smaller ones
Catalysts are used for higher selectivity and to permit low temp. and pressures
Reactions
Thermal pyrolysis mechanism
Thermal cracking free radical theory
Thermal polymerization
Coke formation
Catalytic cracking mechanism
Produces no C1 and C2 fractions
Isomerises to secondary and tertiary hydrocarbons
Relatively little coke is formed
Reaction conditions
Catalytic cracking process design and operation
Intro
Cracking on acidic catalysts is endothermic
Coke is deposited on the catalysts (deactivation)
By oxidation of coke reactivation is done (regeneration)
Selection of catalysts
Regenerative properties
Burning rate should be high and CO2/CO rates low
Poisoning
Permanently poisoned by metals (group IV)
Aging
Reduction in surface area from continued steam reactivation causes catalyst
reactivity loss
SiO2 compositions are more susceptible to aging
Process variables
Process characteristics
Equipment design
Fluidized bed
Using a dense phase fluidization
Regenerative heat to reaction section
Moving bed
Catalysts pellets move at a fixed rate by gravity flow downward through the
reactor regeneration in succession
Elevated to reactor by a gas lift
Petroleum coking process design and operation
Yields: Petrol (20%), gas oil (60-65%), coke (10-15%), remaining light ends
Equipment design
Delayed coking
Fluid bed
 Moving bed
Reforming ( p. 392-396 )
Background
Used to convert hydrocarbons to aromatics
To supply the aromatic feedstocks for the petrol industries
Feedstock are hydrocarbon fractions just above petrol(virgin naphtha, coking
naphtha, catalytic naphtha)
Reactions
Dehydrogenation
Isomerization
Cyclization
Hydrocracking
Catalysts
Platinum is best in terms of selectivity, lack of hydrocracking, and activity but
expensive
Reforming is done at high pressure, so that catalyst poisons like S & N are
hydrogenated and consequently removed from surface
Pb and As permanently damage Pt. catalyst
Reaction conditions
Product characteristics
No olefins and are oxidation resistant, high in octane no. and low in sulphur and gum
Reforming process design and operation
Low pressure Pt. catalyst process has higher octane ceiling
Catalyst can be regenerated by burning off the carbonaceous deposit with mixtures
of steam, air and flue gas
Polymerization ( p. 396-399 )
Background
Combining of two or more olefin molecules
Reactions: Highly exothermic
Carbonium ion formation
Addition
Regeneration
Isomerization
Catalysts
Acid catalysts are required Ex. 65% H2SO4
Solid catalysts are favoured
Reaction conditions
Product characteristics
Polymer motor spirits are stable after mild hydrogenation with octane nos from 80-
85
Polymerization process design and operation
Feeds are preheated with alkali to remove H2S and mercaptans
For solid acid catalyst processes mild steel is used as the material of construction
Alkylation ( p.400-403 )
 Background
Adds any alky group to a compound
High quality petrol blending because it is comprised of stable, saturated branched
paraffins
Reactions
Carbonium ion formation
Addition
Regeneration
Catalysts
Sulphuric acid
Hydrogen fluoride
Reaction conditions
Product characteristics
Alkylates are denser than the reactants
Butene alkylates have octane ratings from 92-97
These ratings can be raised by removing 5-10% of heavy ends of which have octane
no. around 80
Alkylation process design and operation
Caustic wash to remove sulphur compounds
Simple shell and tube heat exchanger is used only for HF units because of the high
viscosity, low heat transfer coefficient of the H2SO4 emulsion at low temp.
Isomerization ( p.403 )
Background
n paraffins to isomers for alkylation feedstock
Catalyst
Aluminium trichloride HCl promoted
Reaction conditions
Isomerization process design and operation
Removal of light ends by flashing, followed by HCl stripping, caustic soda wash, &
fractionation are standard processes
Hydrogenation
Hydro de alkylation
Sulphur removal

Fractionation Processes

Process Name Action Method Purpose Feedstock(s) Product(s)

Atmospheric Separation Thermal Separate Desalted crude Gas, gas oil,

distillation fractions oil distillate,
residual

Vacuum Separation Thermal Separate w/o Atmospheric Gas oil, lube

distillation cracking tower residual stock, residual

Conversion Decomposition Processes

Process Name Action Method Purpose Feedstock(s) Product(s)

Catalytic cracking Alteration Catalytic Upgrade gasoline Gas oil, coke, Gasoline,
distillate petrochemical
feedstock

Coking Polymerize Thermal Convert vacuum Gas oil, coke Gasoline,

residuals distillate petrochemical
feedstock

Hydro-cracking Hydrogenate Catalytic Convert to lighter Gas oil, cracked Lighter,

HC's oil, residual higher-quality
products

Hydrogen steam Decompose Thermal/catalytic Produce Desulfurized gas, Hydrogen, CO,

reforming hydrogen O2, steam CO2

Steam cracking Decompose Thermal Crack large Atm tower heavy Cracked
molecules fuel/ distillate naphtha, coke,
residual

Visbreaking Decompose Thermal Reduce viscosity Atmospheric Distillate, tar

tower residual

Conversion Unification Processes

Process Name Action Method Purpose Feedstock(s) Product(s)

Alkylation Combining Catalytic Unite olefins & Tower Iso-octane

isoparaffins isobutane/cracker (alkylate)
olefin

Grease Combining Thermal Combine soaps & Lube oil, fatty acid, Lubricating
compounding oils alkyl metal grease

Polymerizing Polymerize Catalytic Unite 2 or more Cracked olefins High-octane

olefins naphtha,
petrochemical
stocks

Conversion Alteration or Arrangement Processes

Process Name Action Method Purpose Feedstock(s) Product(s)

Catalytic Alteration/ Catalytic Upgrade low- Coker/hydro- High octane,

reforming dehydration octane naphtha cracker naphtha Reformate/aromatic

Isomerization Rearrange Catalytic Convert straight Butane, Isobutane/

chain to branch pentane, pentane/ hexane
hexane

Treatment Processes

Process Name Action Method Purpose Feedstock(s) Product(s)

Amine treating Treatment Absorption Remove acidic Sour gas, Acid free gases &
contaminants hydrocarbons liquid
w/CO2and H2S hydrocarbons

Desalting Dehydration Absorption Remove Crude oil Desalted crude

contaminants oil

Drying & Treatment Absorption / Remove H2O & liquid Sweet and dry
sweetening thermal sulfur hydrocarbons, hydrocarbons
compounds LPG, alkylation
feedstock

Furfural extraction Solvent Absorption Upgrade mid Cycle oils & lube High quality
extraction distillate & feed-stocks diesel & lube oil
 lubes

Hydro Treatment Catalytic Remove sulfur, High-sulfur Desulfurized

desulfurization contaminants residual/ gas oil olefins

Hydro treating Hydrogenation Catalytic Remove Residuals, cracked Cracker feed,

impurities, HC's distillate, lube
saturate HC's

Phenol extraction Solvent Absorption / Improve Lube oil base High quality lube
extraction thermal viscosity index, stocks oils
color

Solvent Treatment Absorption Remove asphalt Vacuum Tower Heavy lube oil,
deasphalting residual, propane asphalt

Solvent de waxing Treatment Cool/ filter Remove wax Vacuum tower Dewaxed lube
from lube lube oils basestock
stocks

Solvent extraction Solvent Absorption Separate Gas oil, reformate, High-octane

extraction /precipitation unsaturated oils distillate gasoline

Sweetening Treatment Catalytic Remove H2S, Untreated High-quality

convert distillate/gasoline distillate/gasoline
mercaptan
http://www.setlaboratories.com/processe1/tabid/110/Default.aspx

Coal (p. 372 - 378)

Coking of coal (p.372-374)
Raw materials: coking-coal
As temp. Rises, the fluidity of the mass reaches a max. & finally the mass solidifies to
form coke..it has porous nature
Non-coking coal do not soften during heating & the product is known as char
Chemical rxn.

Process description
Carried at 900 -1150oc
The waste gas is then treated to remove sulphur, ammonia, tar and used as fuel in blast
furnace
Engineering problems
Refractories & brickwork maintenance at high temp.
Maintenance of uniform coking
Distillation of coal tar (p.374-376)
Raw materials: light oil from coking process
Process description
Separation of light oil into various phenolic and aromatic compounds
Engineering problems
Corrosion and erosion due to solid particles, ammonia chloride and other chemicals

Gasification of coal (p.374-376)

Raw materials: coke or non-coking coal
Chemical reaction
 4C + O2 + 2H2O 4CO + 2H2
Process description
Koppers Totzek process
Lurgi process
Engineering problems
Availability of tonnage of oxygen
Variation in grades of coal feed
Hydrogenation of coal (p.376-378)
Raw materials
Powdered coal by solvent extraction and hydrogenating the extract
Forming a paste from pulverised coal & heavy oil
Direct powdered coal with steam of hydrogen
Process description
Reaction carried at 400-1000oC
1% tungsten or molybdenum oxide catalyst is used
Engineering problems
Hydrogen embrittlement of reactor steels
Complex separation process
Controlled oxidation and hydrolysis process (p.378)
to produce aromatic derivatives
oxidation reagents like nitric acid, potassium permanganate, ozone and oxygen are used

Nuclear reactor and materials (p. 257 260)

Coolant: Na, NaK, Bi, purified water, heavy water

Moderators: for absorption of neutrons
Pure graphite, heavy water, water, beryllium
Uranium conversion process (p.258-259)

Fertilizers (p. 106)

The major components in fertilizers
Nitrogen during early stage off plant growth
Phosphorus accelerates fruit formation
Potassium to prevent diseases

Urea
The basic process, developed in 1922, is also called the Bosch-Meiser urea process after its
discoverers. The various urea processes are characterized by the conditions under which
urea formation takes place and the way in which unconverted reactants are further
processed. The process consists of two main equilibrium reactions, with incomplete
 conversion of the reactants. The first is an exothermic reaction of liquid ammonia with dry
ice to form ammonium carbamate (H2N-COONH4):

2 NH3 + CO2 H2N-COONH4

The second is an endothermic decomposition of ammonium carbamate into urea and water:

H2N-COONH4 (NH2)2CO + H2O

Both reactions combined are exothermic.

Ammonia (p. 115 - 119)

N2 (g) + 3 H2 (g) 2 NH3 (g) (H = 92.22 kJmol1)

Sulphuric acid (p. 60 65)

Contact process
S (s) + O2 (g) SO2 (g) then
2 SO2 (g) + O2 (g) 2 SO3 (g) (in presence of V2O5)

Lead Chamber process

2 NaNO3 + H2SO4 Na2SO4 + H2O + NO + NO2 + O2
2 NOHSO4 + H2O 2 H2SO4 + NO + NO2

Oils and Fats (p. 285 - 291)

Hydrogenation of oils

Pulp and paper industry (p.351 - 363)

Sulphate (Kraft) pulp process

Polymerisation (p. 594 601)

Polyethylene (p. 594 598)
Polypropylene and polyvinyl chloride (p. 598 601)
Pumps