Chemical Technology of

Organic Materials II

Univ.-Prof. Dipl.-Ing. Dr. Christian Paulik

SS 2011
Crude oil distillation

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Catalytic cracking

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 Catalytic cracking

Advantages of catalytic over thermal cracking:

1.  Lower production of C1 and C2 hydrocarbons to the credit of higher yields

of C3 and C4 hydrocarbons, which can be used for the manufacture of
isoparaffins for motor gasoline via alkylation and polymerization processes.

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 Catalytic cracking

Advantages of catalytic over thermal cracking:

2.  Lower cracking temperatures which result in a reduced production of

diolefins, thus improving the oxidation stability of the gasoline fractions

3.  Higher octane ratings of gasoline by increased formation of branched

alkanes, naphthenes (cycloalkanes) and aromatics.

4.  Higher cracking reaction rates, allowing smaller dimensioning of plant

equipment.

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 Catalytic cracking

•  The conversion reactions of oil distillates in the catalytic cracking process

occur mainly in the vapor phase at elevated temperatures in the presence
of a cracking catalyst

•  Originally of the montmorillonite type, currently synthetic crystalline

zeolites

•  The cracking reactions occurring at the active sites of the catalysts

proceed via a carbenium ion mechanism that predominantly effects the
formation of olefins, isomeric components, and aromatics (the latter via
intermediate formation of cycloolefins.)

•  The formation of low boiling olefins, branched alkanes, and aromatics

favors the production of gasolines with high octane levels

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 Hydrotreating

•  The most important function of hydrotreating is the removal of sulfur

components (hydrodesulfurization, HDS) by reaction with hydrogen in the
presence of a suitable catalyst, to form hydrogen sulfide.

•  Hydrogen sulfide is removed from the process gas stream using a solvent
(e.g., amine) wash and is then converted into elemental sulfur in a Claus
plant.

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Distillate hydrotreating

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 Desulfurizing by adsorption

Philips Petroleum Co. (S-Zorb)

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 Catalytic reforming

•  In the reforming processes, gasoline fractions (naphthas) with a low

octane number are converted into a high-octane reformate (blending
product for motor gasolines).

•  The most valuable byproduct is hydrogen, as the catalytic reformer is the

only hydrogen source of the refinery.

•  The other important byproduct is liquefied petroleum gas.

•  Straight-run or possibly hydrocracked naphthas usually have octane

numbers of only 35 – 65. Therefore these products are unsuitable for
direct gasoline blending.

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 Catalytic reforming

•  With the development and introduction of noble metal catalysts at the

beginning of the 1950s, the catalytic process displaced other (mainly
thermal) reforming processes.

•  Because the catalytic conversion produces higher liquid yields — together

with higher octane numbers — and hydrogen.

•  Catalytic reforming is chiefly based on the catalytic conversion of normal

paraffins and cycloparaffins into aromatics and isoparaffins.

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 Semiregenerative reformer

•  The plant has three or four reactors that are arranged side by side

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 Hydrocracking

•  The hydrocracking (HC) process was developed to produce high yields of

distillates with better qualities than can be obtained by fluid-bed
catalytic cracking

•  Hydrocracking feedstocks are typically flashed distillates from vacuum

distillation, from cat and thermal cracking, or deasphalted oils

•  Operating conditions in the reactor section of hydrocrackers are usually

about 400 °C and 8 – 15 Mpa

•  The reactions take place on metal sulfide catalysts in the presence of

hydrogen

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Hydrocracking

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Oil refining process

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 Residue conversion processes

In addition to the distillate conversion processes, the conversion of residues

and heavy crudes is of growing importance:

1.  Drastic oil price increase - growing economic need to recover more light,
high-value products from the crude oil barrel at the expense of the
residue

2.  Substitution of heavy fuel oil by other fuels

3.  The relative amount of residues also increases when the crude slate
becomes heavier

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Residue conversion processes

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Residue conversion processes

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 Residue conversion processes

•  To obtain lighter products that are richer in hydrogen, two options exist

1.  Hydrogen addition (“H-in”) processes

2.  Carbon rejection (“C-out”) processes

•  Additional processes for particular cases are the extraction of

asphaltenes and the oxidation to synthesis gas or hydrogen

•  A combination of different process steps is often necessary because of

special conditions in the plant and varying process solutions

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 Residue conversion processes – H-in

•  The term hydrotreating is also used for the catalytic hydrogen processing
of residues if the main effect is an extensive removal of sulfur and
nitrogen compounds (> 90 %) as well as of heavy metals, at a relatively
low conversion rate (5 – 35 %)

•  Hydrocracking means the operation under more severe conditions with the
objective of high conversion rates of ca. 60 – 90 %

•  The hydrogenation processes use high pressures (5 – 20 MPa) and are

expensive; the principal cost factors are the technical equipment of the
plants, the expensive hydrogen supply, and the catalysts

•  An advantage of H-in processes — especially of hydrocracking — is the

recovery of pure, high-grade products in high yields

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 Residue Hydrotreating

Demetallization, Desulfurization, Denitrification

•  The individual processes differ mainly in the type and number of reactors
(1 – 4 in series) and in catalyst types required for the special purpose

•  In most cases Co-, Ni-, and Mo-containing catalysts are applied, similar
to those used for distillate hydrogenation

•  The objective of “mild” hydrotreating processes is to obtain low-sulfur

residues which can be further processed catalytically (by FCC) or used as
nonpolluting fuel oils

•  The main market for these processes has been in Japan, where “low-sulfur
fuels” are mandatory

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Residue Hydrotreating

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 Residue Hydrocracking

Hydroconversion

•  Despite the advantage of a high yield of clean light distillates, residue

hydrocracking is used worldwide in only a few plants, because of the high
plant cost and the high hydrogen consumption of 300 – 400 m3 per cubic
meter of residue

•  The catalysts used are either expensive metal catalysts (ca. 0.5–1 kg Co
– Mo or Ni – Mo catalyst are used per ton of raw material) which are
continuously withdrawn and regenerated

•  Or cheap, so-called “throwaway” catalysts, which are removed from the

system in a once-through operation, processes with coal-based catalysts

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 Residue Hydrocracking

Hydroconversion - Veba-Combi-Cracking (VCC)

•  Liquid-phase cracking combined with gas-phase hydrogenation of the

conversion products formed

•  Both processes are performed at the same high-pressure level

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Residue Hydrocracking

Hydroconversion - Veba-Combi-Cracking (VCC)

•  In the first (liquid) stage (3 – 4 reactors),

thermal cracking and hydrocracking
reactions occur simultaneously in the
fluidized bed at ca. 15 – 25 MPa and 430 –
470 °C

•  Oil residue, hydrogen, and catalyst are

introduced at the bottom of the reactor, and
a fluidized bed forms

•  The second (gas) stage consists of a fixed-

bed reactor of conventional construction

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 Residue conversion processes

•  To obtain lighter products that are richer in hydrogen, two options exist

1.  Hydrogen addition (“H-in”) processes

2.  Carbon rejection (“C-out”) processes

•  Additional processes for particular cases are the extraction of

asphaltenes and the oxidation to synthesis gas or hydrogen

•  A combination of different process steps is often necessary because of

special conditions in the plant and varying process solutions

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 Residue conversion processes – C-out

•  The carbon rejection processes are designed as purely thermal or —

increasingly — as catalytic processes

•  In these “C-out” processes, excess carbon is deposited as coke and the

distillates, which still contain unsaturated hydrocarbons, must undergo
further processing

•  Disadvantages of these coking processes include the unwanted amount of

low priced coke formed and the high gasification rate

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 Residue conversion processes – C-out

Thermal Processes (Visbreaking, Coking)

•  Visbreaking and coking (with delayed and fluid coking and Flexicoking as
variants)

•  Visbreakers are available from, e.g., Foster Wheeler, IFP, Kellogg, and
Lummus Crest

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 Residue conversion processes – C-out

Thermal Process – Flexicoking

•  Advantage of continuous operation

•  The cracking reactions occur at 500 – 550 °C in the reactor in a fluid bed
of coke particles into which the residue feed is injected

•  Coke fines are removed from the cracked vapors in cyclone separators
before fractionation

•  The coke formed in the reactor flows continuously to the heater, where it
is heated up to 600 – 650 °C by partial combustion in a fluid bed, from
where the net coke production is withdrawn

•  Another part of the heated coke particles is returned to the reactor

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 Residue conversion processes – C-out

Thermal Process – Flexicoking

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 Residue conversion processes – C-out

Catalytic Processes (Residue Cat Cracking)

•  The residue cat cracking processes represent a further development of

the well-known FCC technology

•  The primary objective is maximum gasoline production; the C3 – C4 gases

which are formed in increased yield are also converted to high-grade
alkylate gasoline

•  For processing residues in fluid cat crackers it is essential that the

contents of asphaltenes and metals, which deactivate the catalyst, are
kept under a certain level

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 Residue conversion processes – C-out

Catalytic Processes (Residue Cat Cracking)

•  The metals content in the feed should not exceed 10 – 30 ppm, otherwise
pretreatment is necessary

•  Research efforts are being undertaken mainly to develop new catalysts

(use of zeolites, regeneration techniques) and to achieve a reduction of
the residence time (riser know-how)

•  Most large-scale plants process mainly atmospheric residues with

pretreatment of the feedstock

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 Gasoline Upgrading Processes

•  Alkylation

•  Polymerization

•  Isomerization

•  Production of Ethers (MTBE, ETBE)

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 Wiley Online Library: Book Article

Gasoline Upgrading Processes

solves the environmental problem of sulfur, which concentrates in all residues and in coke to such an extent that these residual materials
oxidation the sulfur compounds in the feed materials are completely converted to H2 S which can be processed to sulfur in a Claus plant.

The combinations of residue conversion processes given as examples here represent only some of the possible and useful variations. Th
refinery processing and the more difficult technical problems to be solved, will result in a steep rise in investment and operating costs. In
shortage of crude oil and its poorer quality, as well as growing environmental problems worldwide, mean that the residue problem will in t
Alkylation tasks for crude oil processing.

3.7. Gasoline Upgrading Processes

•  The alkylation process is based on the reaction of isoparaffins (e.g.,
3.7.1. Alkylation

isobutane) with olefins (e.g., propene, butenes, pentenes) to form higher

The alkylation process is based on the reaction of isoparaffins (e.g., isobutane) with olefins (e.g., propene, butenes, pentenes) to form hig
the presence of a strong acid, e.g., sulfuric acid. The alkylation product, or alkylate, is obtained as a mixture of isoparaffins with high rese
an excellent blending component for motor gasolines.
molecular mass branched paraffins in the presence of a strong acid, e.g.,
A typical example of alkylation is the reaction of isobutane (1-methylpropane) with 1-butene to form isooctane (2,2,4-trimethylpentane):

sulfuric acid

•  The alkylation product, or alkylate, is obtained as a mixture of

Alkylation reactions are catalyzed by strong acids. The first generation of commercial units applied sulfuric acid as catalyst. During World
capacities were installed to satisfy the drastic increase in the demand for high-octane gasoline. Alkylation units could easily be installed i
isoparaffins with high research octane numbers, making the product an
available from catalytic cracking units. Isobutane was supplied by LPG streams, e.g., from reformers, and by C4 -isomerization. The newe
hydrogen fluoride ( HF) as catalyst, which has a better regenerability than sulfuric acid.
excellent blending component for motor gasolines
The most commonly applied HF alkylation processes were developed by Phillips Petroleum [44] and UOP [45], [71]. A scheme of the lat
olefin feed and recycle isobutane are contacted with HF in the reactor (a). The reaction product is separated in the settler ( b), from where
34 product is further separa
alkylation product is fractionated in the isostripper (c) together with mixed butane feed. The isostripper overhead
the isobutane is recycled to the feed. The propane product is freed from entrained catalyst in the HF stripper (e). n-Butane is drawn off as
bottom product of the isostripper is alkylate which is supplied to gasoline blending.
 Gasoline Upgrading Processes

Alkylation

•  Alkylation reactions are catalyzed by strong acids

•  The first generation of commercial units applied sulfuric acid as catalyst

•  The newer generation of alkylation units used hydrogen fluoride (HF) as

catalyst, which has a better regenerability than sulfuric acid

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 Gasoline Upgrading Processes

HF-Alkylation

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 Gasoline Upgrading Processes

Polymerization

•  To produce additional gasoline mostly used refineries where excess

amounts of olefins, e.g., propene and butenes from catalytic crackers, are
available

•  The most widely applied process is the UOP polymerization, using

phosphoric acid as catalyst

•  The C3/C4-olefin feed is contacted with the acid in a reactor

•  After separation and stabilization, the polymerate is obtained and used as

a gasoline component

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 Gasoline Upgrading Processes

Polymerization

•  The more recent IFP Dimersol process is a dimerization process for olefins

•  Three types of Dimersol processes are now available for producing gasoline
components

–  Type G: for high-octane gasoline from propene

–  Type X: for octenes from butenes, or for hexenes – heptenes –

octenes mixtures by co-dimerization of propene and butenes

–  Type E: for gasoline from lean ethylene streams

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 Gasoline Upgrading Processes

Polymerization – Dimerisol process

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 Gasoline Upgrading Processes

Isomerization

•  Isomerization of low molecular mass n-paraffins has been used for a long
time (particularly for isomerizing n-butane to isobutane) in order to
produce makeup feedstock for alkylation units

•  Isomerization gained importance after the introduction of lead-free

gasolines, to compensate for the reduction in octane number

•  Was achieved by isomerizing C5 and C6 n-paraffin fractions to the

corresponding isoparaffins

•  Led to the development of various catalytic isomerization processes that

used hydrogen and operated at moderate reaction conditions

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 Gasoline Upgrading Processes

Isomerization – Hysomer process

The C5/C6-rich light gasoline feed is heated up together with hydrogen in

the furnace (a) and isomerized in the reactor (b) containing a noble metal
catalyst.
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 Gasoline Upgrading Processes

Isomerization

•  MTBE’s high octane rating of RON 117 and its rather low boiling point of
55 °C made it a valuable gasoline component

•  The ether is produced by reaction of isobutene with methanol at 40 to 70

°C on an acidic ion exchange resin followed by distillative separation

•  The presence of water in the reaction mixture leads to the formation of

tert-butanol (TBA), another excellent gasoline component

•  In a similar way ethyl tert-butyl ether (ETBE) can be produced from

isobutene with ethanol as reactant

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 Gasoline Upgrading Processes

Isomerization

•  As the utilization of ethanol from agricultural production is promoted due

to political reasons, an MTBE plant can be modified to produce ETBE

•  In the USA production of tert-amyl methyl ether (TAME) is favored with

methylbutenes as unsaturated hydrocarbon reactants

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 Gasoline Upgrading Processes

TAME

•  While the blending properties of these ethers are extremely good, their
chemical constitution is a disadvantage

•  All ethers contain a tertiary carbon atom, resulting in a very slow

biological decomposition

•  Soil which has accidentally been contaminated can not be cleaned easily

•  For this reason the ethers have been banned from gasoline in sensitive
areas of the USA
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 Emissions

•  Environmental problems arise in dealing with crude oil and its products
because the petroleum industry maintains exploration, transport, and
refining installations for crude oil that are scattered over the entire globe

•  Since the geographical location of crude oil fields does not coincide with
that of the large consuming and refining regions, enormous transportation
distances exist

•  The annual refining capacity in 2004 was about 4 109 t in more than 650
refineries worldwide

•  Industry needs to take precautions in all areas with regard to air emissions,
water and soil pollution and, to a lesser degree, noise

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•  The problems of introducing uniform
standards are caused by legal
standards which differ from country
to country

•  Depending on the local

concentrations of industrial areas
with their corresponding
environmental pollution and
population density

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 Emissions - Sulfur

•  Sulfur and its compounds are catalyst poisons and adversely affect
atmospheric emissions

•  Hydrogen sulfide, mercaptans, and disulfides are odor nuisances, and sulfur
dioxide is formed during the combustion of crude oil products

•  Therefore, sulfur and its compounds must be removed or their contents

reduced

•  The light refinery products, liquefied petroleum gas and gasoline, must be
almost completely sulfur-free; for diesel fuels and light heating oils, a
substantial sulfur reduction to 0.1 – 0.5 % is required by recent legislation

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 Emissions - Sulfur

•  Serious problems exist with heavy fuel which is used almost exclusively as
fuel in large industrial furnaces and power stations and leads to
considerable SO2 emissions

•  Many countries have established a maximum sulfur content in fuels of 1 – 2

wt %

•  This value can be reached without additional treatment only with a few,
low-sulfur crude oils

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 Emissions - Sulfur

•  Sulfur is generally removed from distillates by hydrodesulfurization,

whereby the chemically bound sulfur is converted to hydrogen sulfide

•  The H2S is removed from the reaction gas stream in a gas scrubber,
converted to elemental sulfur in the downstream Claus process, and
supplied to the chemical industry as a raw material

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 Consumer related emissions

•  The emissions of SO2 and NOx from the combustion of refinery products
outside the refinery are much greater than the emissions during refining
itself

•  In addition, the HC emissions in the transportation field, both in refueling

and in running motor vehicles, are also considerably greater than in the
steps from production to the filling station

Hydrocarbon emissions in the

petroleum field
(Western Europe 1986)

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