Chapter 2: PROCESSES TO PRODUCE 7 SECONDARY

PETROCHEMISTRY FEEDSTOCKS
1. Steam cracking
Ethylene

Light hydrocarbons Steam Olefins Propylene

Medium hydrocarbons Cracking Butylenes

Heavy hydrocarbons B, T, X
To: high
P: low

CH3-CH3 CH2=CH2 + H2 DH590oC= +143 kJ

Highly endothermic, being favored at high temperatures and lower pressures

•
R-CH2-CH2-CH2-R R-CH2-CH2-CH2• + R
Instructor: DAO THI KIM THOA • •
R-CH2-CH2-CH2 R-CH2 + CH2=CH2

Cm+nH2(m+n)+2 CmH2m + CnH2n + 2

Steam cracking is a petrochemical process in which saturated hydrocarbons are
broken down into smaller, often unsaturated, hydrocarbons. It is the principal
CH3-CH3 CH2=CH2 + H2 DH590oC = + 143 kJ industrial method for producing the lighter alkenes(or commonly olefins),
including ethene (or ethylene) and propene (or propylene).
• •
R-CH2-CH2-CH2-R R-CH2-CH2-CH2 + R
• • In steam cracking, a gaseous or liquid hydrocarbon feed like Naphtha, LPG or
R-CH2-CH2-CH2 R-CH2 + CH2=CH2
Ethane is diluted with steam and then briefly heated in a furnace (obviously
without the presence of oxygen). Typically, the reaction temperature is very hot —
Bonding energy: C–C ( 345 kJ/mol) and C–H (413 kJ/mol). It is favorable to the
cracking at C–C bonding. around 850 °C—but the reaction is only allowed to take place very briefly. In
modern cracking furnaces, the residence time is even reduced to milliseconds
(resulting in gas velocities reaching speeds beyond the speed of sound) in order to
Unsaturated hydrocarbon is favorable to high temperature than saturated one. improve the yield of desired products. After the cracking temperature has been
üAcetylene is more stable than ethane at T > 1000oC
reached, the gas is quickly quenched to stop the reaction in a transfer line
üEthylene is more stable than ethane at T > 750oC
üBenzene is stable than n-hexane and cyclohexane at 350 - 400oC exchanger.
 The products produced in the reaction depend on the composition of the feed, the
hydrocarbon to steam ratio and on the cracking temperature & furnace residence The process also results in the slow deposition of coke, a form of carbon, on the

time. Light hydrocarbon feeds (such as ethane, LPGs or light naphtha) give product reactor walls. This degrades the efficiency of the reactor, so reaction conditions are
streams rich in the lighter alkenes, including ethylene, propylene, and butadiene. designed to minimize this. Nonetheless, a steam cracking furnace can usually only
Heavier hydrocarbon (full range & heavy naphtha as well as other refinery run for a few months at a time between de-cokings. Decokes require the furnace to
products) feeds give some of these, but also give products rich in aromatic be isolated from the process and then a flow of steam or a steam/air mixture is

hydrocarbons and hydrocarbons suitable for inclusion in gasoline or fuel oil. The passed through the furnace coils at 950 -1050 oC . This converts the hard solid

higher cracking temperature (also referred to as severity) favors the production of carbon layer to Carbon Monoxide and Carbon Dioxide. Once this reaction is
ethene and benzene, whereas lower severity produces relatively higher amounts of complete, the furnace can be returned to service.
propene, C4-hydrocarbons and liquid products.

Reduce partial pressure + Cracking activity is proportional to the hydrocarbon length.

+ With the same number of carbon atom: cracking activity is in order:
Reduce C (formed under high temperature condition) olefin > paraffin > alkyl-naphthene
Steam CH3-CH3 2C + 3H2
C + H2O CO + H2 To: maximum olefin amount and minimum C
Dilution: reduce the contact between hydrocarbon Cracking ethane: 800 oC
and the equipment surface. Cracking naphtha or gas oil: 675-700 oC

Steam: heavy feedstock need more steam

Cracking ethane: steam/ethane = 0.2/1
+ Cracking is remarkable at T > 700 oC Cracking naphtha or gas oil: steam/feed = 1/1.2
+ Dehydrogenation is worthy at 800 - 850 oC
+ Aromatics and coke formation is faster at T > 900 -1000 oC. Long contact and high
temperature are favorable to formation of heavy. Residence time: short to give much olefin
Cracking ethane: 0.5-1.2 s
+ Polymerization of unsaturated hydrocarbons ( olefin, diolefin, acetylene extract) is
fast event at low temperature; However, opposite to cracking, theses reactions are not Cracking naphtha or gas oil: give olefin and B, T, X:
favorable at the pyrolysis condition (by thermodynamics respect). contact time is relatively longer.

(*): 2014 Petrochemical Processes Handbook
Catalytic Cracking takes long molecules and breaks them into much smaller
molecules. The cracking reaction is very endothermic, and requires a large
amount of heat. Another problem is that reaction quickly fouls the Silica (SiO2)
and alumina (Al2O3) catalyst by forming coke on its surface. However, by using a
fluidized bed to slowly carry the catalyst upwards, and then sending it to a
regenerator where the coke can be burned off, the catalyst is continuously
regenerated. This system has the additional benefit of using the large amounts of
heat liberated in the exothermic regeneration reaction to heat the cracking
reactor. The FCC system is a brilliant reaction scheme, which turns two negatives
(heating and fouling) into a positive, thereby making the process extremely
economical.
2. Other processes to produce olefin
• Catalytic cracking (in refinery): give gasoline
• Cracking n-paraffin: C17 – C34 paraffin to give straight a-olefin (C6 – C9, C10
– C13, C14 – C18 used in plasticsizer, surfactant).
• Dehydrogenation n-paraffin.
Fluid catalytic cracking, developed by American engineers Warren K. Lewis and Edwin
R. Gilliand is a commonly used process and a modern oil refinery will typically include
a cat cracker, particularly at refineries in the USA due to the high demand for gasoline.
The process was first used in around 1942, and employs a powdered catalyst. During
the Second World War, it provided Allied Forces with plentiful supplies of gasoline and
artificial rubber that contrasted with the penury suffered by the Axis Forces. Initial
process implementations were based on a low activity alumina catalyst and a reactor
where the catalyst particles were suspended in a rising flow of feed hydrocarbons in a
fluidized bed. Alumina-catalyzed cracking systems are still in use in high school and
university laboratories in experiments concerning alkanes and alkenes. The catalyst is
usually obtained by crushing pumice stones, which contain mainly aluminium oxide
and silicon (IV) oxide into small, porous pieces. In the laboratory, Aluminum oxide (or
porous pot) must be heated.
 During the trip up the riser, the cracking catalyst is "spent" by reactions which deposit
coke on the catalyst and greatly reduce activity and selectivity. The "spent" catalyst is
In newer designs, cracking takes place using a very active zeolite-based catalyst in a disengaged from the cracked hydrocarbon vapors and sent to a stripper where it is
short-contact time vertical or upward sloped pipe called the "riser". Pre-heated feed is contacted with steam to remove hydrocarbons remaining in the catalyst pores. The
sprayed into the base of the riser via feed nozzles where it contacts extremely hot "spent" catalyst then flows into a fluidized-bed regenerator where air (or in some cases
fluidized catalyst at 1230 to 1400 °F (665 to 760 oC). The hot catalyst vaporizes the air plus oxygen) is used to burn off the coke to restore catalyst activity and also provide
feed and catalyzes the cracking reactions that break down the high molecular weight oil the necessary heat for the next reaction cycle, cracking being an endothermic reaction.
into lighter components including LPG, gasoline, and diesel. The catalyst-hydrocarbon The "regenerated" catalyst then flows to the base of the riser, repeating the cycle.
mixture flows upward through the riser for just a few seconds and then the mixture is The gasoline produced in the FCC unit has an elevated octane rating but is less
separated via cyclones. The catalyst-free hydrocarbons are routed to a main fractionator chemically stable compared to other gasoline components due to its olefinic profile.
for separation into fuel gas, LPG, gasoline, light cycle oils used in diesel and jet fuel, Olefins in gasoline are responsible for the formation of polymeric deposits in storage
and heavy fuel oil. tanks, fuel ducts and injectors. The FCC LPG is an important source of C3-C4 olefins
and isobutane that are essential feeds for the alkylation process and the production of
polymers such as polypropylene.

Catalytic reforming The reaction chemistry

Purpose: produce B,T,X.

1: The dehydrogenation of naphthenes to convert them into aromatics as exemplified in
Feed: heavy naphtha. the conversion methylcyclohexane (a naphthene) to toluene (an aromatic), as shown
Treatment: hydrogenation olefins (olefins form coke, reduce catalyst activity). below:
hydro-desulfurize.
hydro-denitrogenate (S, N: poison catalyst).
Catalyst: bi-functional
- Metal: Pt: hydro – dehydrogenation.
- Carrier: alumina (acid).
 3: The dehydrogenation and aromatization of paraffins to aromatics (commonly called
2: The isomerization of normal paraffins to isoparaffins as exemplified in the dehydrocyclization) as exemplified in the conversion normalheptane to toluene, as
shown below:
conversion of normal octane to 2,5-Dimethylhexane (an isoparaffin), as shown below:

Composition change in a catalytic reformer (%V)

4: The hydrocracking of paraffins into smaller molecules as exemplified by the cracking
of normal heptane into isopentane and ethane, as shown below:
Feed Product
Paraffins 50 35
Naphthenes 40 10
Aromatics 10 55
 Reactor 1: lesser catalyst than the other two: mainly
dehydrogenation naphthene to aromatic
C4 and
lighter Reactor 2 and 3: more catalyst: slow reactions
to form aromatic and iso-paraffin

Recycled H2
Dehydrogenation is endothermic: needed
to be reheat after reactor 1 and 2
catalyst

catalyst

catalyst
naphtha
To: 500 – 525oC
Hydrogen
heater reactors separator stabilizer

Recognize the correlation between the size of reactors and the retention time of those reactions.

Steam reforming

Steam reforming of natural gas, sometimes referred to as steam methane reforming (SMR) is
the most common method of producing commercial bulk hydrogen as well as the hydrogen used
in the industrial synthesis of ammonia. It is also the least expensive method. At high temperatures
(700 – 1100 °C) and in the presence of a metal-based catalyst, steam reacts with methane to yield
carbon monoxide and hydrogen.
CH4 + H2O → CO + 3 H2
The United States produces nine million tons of hydrogen per year, mostly with steam reforming
of natural gas. The worldwide ammonia production, using hydrogen derived from steam
reforming, was 109 million metric tonnes in 2004 (*).
This SMR process is quite different from and not to be confused with catalytic
reforming of naphtha, an oil refinery process that also produces significant amounts of
hydrogen along with high octane gasoline.
A great deal of ethylene is produced by a non-catalytic process called “steam
cracking” which cracks (i.e., reforms) large hydrocarbon molecules into smaller
molecules). In the year 2003, there was 97,000,000 metric tons of ethylene (used to
produce polyethylene and a host of other petrochemical chemicals) manufactured
worldwide by the steam cracking of various hydrocarbons (methane, ethane, LPG,
naphtha, and fuel oils).

(*): Wikipedia
Purpose: produce (CO + H2)
Feed: natural gas, distillates
Catalyst: activated Ni
Steam/natural gas = 4 - 5

To: 700 – 800oC

P: 30 – 50 atm
Products: H2, CO, CO2, CH4 , H2O
Reactions:
CH4 + H2O CO + H2
CH4 + 2 H2O CO 2 + 4 H2

Applications of synthesis gas: Methanol production

NH3 production
Fischer Troopsch hydrocarbons