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Chapter 38 P747

Petrochemical Processes
Dr. Hind Barghash
CPI-14

Petrochemical processes are:


1- Lower alkenes
2- Synthesis gases (Syngas)
3- Polymerization
4- Formalin

Lower Alkenes: Petrochemicals-The Origi


Orig
CRUDE OIL
REFINARY
FEEDSTOCKS
Gas, Naphtha, Gas Oil,
Kerosene

PETROCHEMICAL
INDUSTRY
BASIC CHEMICALS
Ethylene, Propylene, 1.3-Butadiene &
BTX,

PETROCHEMICALS
PE,PP,PVC,PS,PBR,MEG,LAB,ACN, AF, PTA, PHA,
MA,CPL

Lower Alkenes: Building block Chemicals


Ethylene
Propylene
Butadiene (1,3)
Benzene
Toulene
Xylenes

Petrochemicals from Ethylene

Petrochemicals from Propylene

Petrochemicals from B
Butadiene
Butadiene
Polybutadiene
Rubber
PBR

Styrene-Butadiene
Rubber SBR

AcrylonitrileButadiene
-Styrene ABS

Specialty
Polymers /
Chemicals

Adiponitrile
ADN

Petrochemicals from Benzene

Petrochemicals from Toluene


Toluene

Benzene

Xylenes

Specialty/
Functionalized
chemicals

Petrochemicals from Xylenes


Xylenes

m-Xylene

p-Xylene

O-Xylene

Iso-phthalic acid

Terephthalic acid
PTA

Phthalic anhydride

PET

Polyesters

Plasticizers

Lower alkenes from oil


Chemical industry uses
- 10% of available petroleum and natural gas as feed
- 5% as fuel
Produced from
steam cracking of various refinery streams.
dehydrogenation reactions.

Example: Lower alkenes or olefins an important feed


for products such as LDPP or HDPP.

Lower alkenes from oil

(CH2=CH-CH=CH2)

C5 olefins

Steam Cracking: Industrial Process


A mixture of HC and steam are passed through tubes
inside a furnace
Heating occurs by convection and radiation
Considerable heat input at a high temperature level
Limited HC partial pressure
Very short residence times (<1 s)
Rapid quench of product to preserve composition
otherwise pyrolysis takes place

Dehydrogenation
Recently, the demand for propenes and butenes has been
increasing.
Direct production for these specific alkenes is important
Selectively dehydrogenate the specific alkane (ie propane
to form propylene)
Alkane dehyrogenation is highly endothermic

Dehydrogenation
Variables in these processes include:
Type of catalyst used
Reactor design
Method of heat supply
Method for catalyst regeneration

Synthesis Gas - Syngas1/2


A mixture of CO and H in varying ratios
Uses:
Refinery hydrotreating, hydrocracking
Ammonia
Alkenes
Methanol, higher alcohols
Aldehydes
Acids

Synthesis Gas - Syngas2/2


Produced from coal, natural gas, etc.
Major processes:
Steam reforming of NG or light HC in the presence of O2
or CO2
Partial oxidation of heavy HC with steam (H2O) and O2
Partial oxidation of coal with steam (H2O) and O2
Raw materials depend on cost and availability

Production of Syngas

Reactions to form Syngas


General reactions
(1) C + H2O CO + H2 (steam reforming, endothermic)
(2) C + O2 CO
(partial oxidation, exothermic)
(3) CO + H2O CO2 + H2
(water gas shift)
NG as a feed:
(1) CH4 + H2O CO + 3H2
(2) CO + H2O CO2 + H2
(3) CH4 + CO2 2CO + 2H2
(4) 2CO C + CO2
(6) CH4 + O2 CO + H2
(7) CH4 + 2O2 CO2 + 2H2O
(8) CO + O2 CO2
(9) H2 + O2 H2O

(steam reforming, endothermic)


(water gas shift)

(partial oxidation)

Steam Reforming1/2
High temperatures
Nickel catalyst contained in tubes heated by a furnace
A mixture of NG and steam are passed through tubes
inside a furnace. May contain 500-600 tubes that are 7-12
m long with ID of 70-130 mm
Heating occurs by convection and radiation
Feed pretreatment required a sulfur removal
Coke deposits can form that deactivate the catalyst and
can block the furnace tubes, so excess steam is used to
prevent coke deposit
Product is cooled in order to separate the condensed

Steam Reforming2/2

Ammonia synthesis1/2
A major product of the CPI
Early sources were natural, or byproduct of coke ovens
Major use in fertilizers (agricultural) and explosives
In 1909 Fritz Haber established the conditions under which
nitrogen, N2(g), and hydrogen, H2(g), would combine using
medium temperature (~500oC)
very high pressure (~250 atmospheres, ~351kPa)
a catalyst such as: 1-a porous iron catalyst prepared by reducing
magnetite, Fe3O4).
2-Osmium is a much better catalyst for the
reaction but is very expensive.
Requires a H2:N2 ratio of 3:1
N2 sources is air, H2 from Syngas
3H2+N2 2NH3
H= -91.44 kJ/ml

Ammonia Synthesis2/2

See chapter 2 for


process description

Uses of Ammonia
Fertiliser

ammonium sulfate, (NH4)2SO4


ammonium phosphate, (NH4)3PO4
ammonium nitrate, NH4NO3
urea, (NH2)2CO

Chemicals

nitric acid, HNO3, which is used in making explosives such as TNT (2,4,6-trinitrotoluene),
nitroglycerine which is also used as a vasodilator (a substance that dilates blood vessels) and
PETN (pentaerythritol nitrate).
sodium hydrogen carbonate (sodium bicarbonate), NaHCO 3
sodium carbonate, Na2CO3
hydrogen cyanide (hydrocyanic acid), HCN
hydrazine, N2H4 (used in rocket propulsion systems)

Explosives

ammonium nitrate (NH4NO3)

Fibres &
Plastics

nylon, -[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and other polyamides

Refrigeration

used for making ice, large scale refrigeration plants, air-conditioning units in buildings and plants

Pharmaceutical used in the manufacture of drugs such as sulfonamide which inhibit the growth and

multiplication of bacteria that require p-aminobenzoic acid (PABA) for the biosynthesis of folic
acids, anti-malarials and vitamins such as the B vitamins nicotinamide (niacinamide) and
thiamine

Pulp & Paper


Mining &
Metallurgy

ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods to be used


used in nitriding (bright annealing) steel,
used in zinc and nickel extraction

Methanol Synthesis1/3
CO+ 2H2 CH3OH
CO2+3H2 CH3OH+H2O
Coupled by: CO+H2O CO2+H2
Second large scale process involving catalyst and high
pressure
Catalyst selectivity is very important, as other products
may form.
Cu/ZnO/Al2O3 catalysts are newer catalysts that enable
lower pressure

Methanol Synthesis2/3
Equilibrium data:

Methanol Synthesis3/3

CO, CO2 & H2 from


steam reforming,

To distillation

Methanol uses
Formaldehyde
Octane booster as Methyl tert-butyl ether
(MTBE)

Polymers & Polymerization


Sources of Polymers
Natural polymers since
prehistoric times are:
Wood
Rubber
Cellulose, rayon

First synthetic polymers:


Phenol formaldehyde resins

Used of polymers
Main component of food:
Starch, protein

Clothes:
Silk, cotton, polyester, nylon

Building materials
Wood, paints, PVC etc.

Polymers

What is a polymer?
The terms polymer and monomer are
part of our everyday speech.
Poly = many Mono = one
Mer is derived from the Greek
meros, meaning part. So, a
monomer is a one part and a
polymer is a many part.

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Polymers
Constructed of monomer units connected by a covalent
bond:

Or

-R-R-R-R[R]n-

R: a bi-functional entity not capable of separate existence


n: degree of polymerization DP
MW: molecular weight, obtained from the MW of the
monomer multiplied by n

Example: Polyethylene
Polyethylene is an example of a synthetic
polymer.
Ethylene, derived from petroleum: is made to
react with itself to form polyethylene.
ethylene unit

H2C

n H2C

CH2
CH2

ethylene

-CH2CH2-CH2CH2-CH2CH2-CH2CH2catalyst

-(CH2CH2)- n

polyethylene

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Categories of Polymers1/2
Thermoplastic
Become flexible solids above a certain T
then become rigid again upon cooling below this T
flexible/rigid cycle can be repeated
When flexible it can be molded into shapes
Fibers can be drawn into strands, non fibers cannot
Thermoset resins
Network co-polymers that do not become flexible until the
T is so high thermal decomposition takes place
Synthetic rubber
Deformed by small stresses but regain original shape

Categories of Polymers2/2

Engineered polymers
High % growth
Special properties, replacements for metals, chemical
inertness, etc. used in carpet and tirereinforcement.
Examples:
Acetal (poly-oxy-methylene POM)
Nylons (polyamides)
Polyethylene or poly-butylene terephthalate (PET or PBT)
Polycarbonate PC
Polyphenylene oxide PPO

Polymerization reactions
2 mechanisms: chain growth and step growth
Chain growth (or additional polymer)
Reaction occurs by successive addition of a monomer to the
reactive end
Example, polymerization of a monomers such as ethylene,
propylene, styrene, vinyl chloride
nCH2=CHX
-(-CH2-CHX)nWhere X can be H, CH3, C5H6 or Cl
Initiator or catalyst is required to start the chain growth reaction
High MW product is produced right away (during polymerization)
Polymerization is generally fast, irreversible and moderately to highly
exothermic.

Step growth (or condensation polymerization)


Formed when monomers combine and split out water or
some other simple substance.
Essentially a substitution reaction
Nylon is a condensation polymer.
High MW product is produced from the end of polymerization

Commodity Polymers
Polyethylene (PE)
Polypropylene (PP)
Polyvinylchloride (PVC)
Polystyrene (PS)

Polyethylenes1/2
Classification and properties
linear, unbranched polymers are more densely packed
therefore more ordered
Side branches interfere with alignment of polymer chains
Density can be controlled by operating T, P, catalysts and
co-monomers used
Example: LDPE is produced at high T and high P
higher T results in more side reactions and branching,
thus lower density
Polymer density is degree of crystallinity

Polyethylenes2/2

Applications

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Production of LDPE1/3
Ethylene fed to reactor at high T, P
No catalyst
Initiator can be used (oxygen, peroxide)
Ethylene behaves like a liquid and a solvent
CSTR or tubular reactor

Production of LDPE2/3
Using a tubular reactor: a long pipe heat exchanger with
200-1000 m long, and 2.5-7 cm ID
Reactants heated to 370-470 K
Heat of polymerization means cooling is required by outer
jackets, T is raised up to 520-570 K
Conversions of 15-22%, so recycle stream is employed
Pressure cycling from 3000 to 2000 bar

Production of LDPE3/3

Production of HDPE1/2
There are many processes for production of HDPE such as:
Bulk polymerization
Polymer dissolves in the monomer

Solution polymerization
Polymer and monomer dissolve in HC solvent

Slurry polymerization
Catalyst-polymer particles suspended in HC

Fluidized bed polymerization


Catalyst-polymer particles fluidized in gaseous monomer

Catalytic processes for HDPE and LLDPE are similar

Production of HDPE2/2
Fluidized bed polymerization (gas phase polymerization)
is the most flexible method

Polymer recovery
Unless bulk polymerization, polymer must be
separated from the solvent
Typical separation methods such as crystallization,
distillation.
Precipitation cant normally be used (as polymers are
highly viscous).
Method for precipitation can be done by non solvent
process such as: centrifugation, and removal of
solvent by steam stripping can be used.

Exxon Mobile

Formaldehyde Resins
Is used in the production of two different but related classes of
thermosets:
1- Phenoplast: is called phenolic resins which is produced by
condensation of phenol and formaldehyde.

2- Amenoplast: is prepared from condensation of urea (urea resin) and


formaldehyde

Phenol-Formaldehyde Polymers (Bakelite)


Each formaldehyde molecule reacts with two phenol molecules to
eliminate water. The polymer is then formed.
OH

OH

O
+

C
H

Polymers of this type are


used, in electrical equipment,
because of the insulating and
fire-resistant properties.

OH

OH
H2
C

+ H2O

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Phenolic Resins1/3
Phenolic resins (phenol-formaldehyde polymers), copolymers of
phenol and formaldehyde, were the first fully synthetic polymers
made. They were discovered in 1910 by Leo Baekeland and given
the trade name Bakelite.
Two processes, both involving step growth polymerization, are
used for the manufacture of phenolic resins.
A one-stage resin may be obtained by using an alkaline catalyst
and excess formaldehyde to form linear, low-molecular-weight
called the resol resins. See next slide
Acidification and further heating causes the curing process to give
a highly cross-linked thermoset polymer (ie high molecular
weight) called the resite.

Phenolic Resins2/3
The second process (Fig. 1) uses an acid catalyst and
excess phenol to give a linear polymer (called novolac as
shown next slide) that has no free methylol groups for
crosslinking.
In a separate second part of this two-stage process, a
cross-linking agent is added and further reaction occurs. In
many instances, hexamethylenetetramine is used, which
decomposes to formaldehyde and ammonia.
Other modifications in making phenolic polymers are the
incorporation of cresols or resorcinol as the phenol (Fig.
1) and acetaldehyde or furfural as the phenol.

Phenolic Resins3/3

Urea Resins1/2
Urea resins (urea formaldehyde polymers) are formed by the
reaction of urea with formaldehyde (Fig. 1).
Monomethylolurea (HOH2CNHCONH2) and dimethylolurea
((HOH2CNHCONHCH2OH) are formed first under alkaline
conditions. Continued reaction under acidic conditions gives
a fairly linear, low-molecular-weight intermediate polymer.
A catalyst and controlled temperature are also needed and,
since the amine may not be readily soluble in water or
formalin at room temperature, it is necessary to heat it to
about 80oC to obtain the methylol compounds for many
amine-formaldehyde resins.
Heating for an extended period of time under acidic
conditions will give a complex thermoset polymer of poorly
defined structure including ring formation.

Urea Resins2/2

Formalin Plant (CH2O)

INTRODUCTION
Formalin is the aqueous form of formaldehyde produced
mostly from methanol by an oxidation process.
Recently, the production volume of formaldehyde has
grown rapidly thanks to the every-increasing demand in
the manufacturing sector for resins including phnolic,
urea, melamin, acetal and many additives.
Other additional application areas of formaldehyde
include surface coating, leather tanning, bindery
applications, laminates, insulation materials, etc.

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Processes
There are two processes known to produce formalin from
methanol methanol excess and air excess.
The basic difference between them is the catalyst applied.
1-The methanol excess process, called the silver process,
employs silver as the catalyst,
2-The air excess process, called molybdenum process, uses
metallic oxides of iron and molybdenum.
Second process, is considered a higher investment cost
and more complicated operation than the silver process,
the use the silver process is recommended

Process Description1/2
The evaporated methanol, filtrated air and steam are fed into the
mixer where theses gases are mixed uniformly, and then sent to
reactor.
Most of the methanol is converted into formaldehyde when the
mixed gas passes through the catalyst.
The reacted gas is immediately quenched in the waste heat boiler
integrated with the reactor. At the same time, the waste heat boiler
recovers reaction heat to generate steam, which is effectively used
as heat sources for the methanol evaporator and other heaters, and
as steam supply for the mixer.
The reacted gas is introduced into the absorber where produced
formaldehyde and residual methanol are absorbed by recycling
formalin at the lower section of the absorber.

Process Description2/2
The vent gas from the absorber, containing about 20% of
hydrogen, can be used as boiler fuel to generate steam and
prevent air pollution.
The concentration of formalin produced in the absorber
can be adjusted as required by regulating the treated water
flow rate. The formic acid content in the raw formalin as
produced from the absorber bottom is usually 60~150
ppm, but the lower formic acid content can be obtained by
treating it through the ion-exchanger.
The product yield of the reaction is more than 91% (wt)
and this process requires small utilities and the cost of
catalyst is very low.

Process Flow Diagram

Applications
Phenol Resin and Adhesives / Urea and Melamine
Adhesives
Urea Resin / Melamine Resin /
Hexamethylenetetramine
Pentaerythritol / Paraformaldehyde
Medicines and Agricultural Chemicals as
antiseptic (disinfectant)