Professional Documents
Culture Documents
Ethylene
HEINZ ZIMMERMANN, Linde Engineering Division, Pullach, Germany
ROLAND WALZL, Linde Engineering Division, Pullach, Germany
natural gas (! Gas Production, 5. Examples of bioethanol offers a production from renewable
Complex Gas Production Plants, Chap. 1) is raw materials.
converted finally into ethylene. However, none More than half of the production of ethylene
of the alternative technologies has the economics is used for the production of polyethylene
to be a challenge for the well-established steam- (! Polyethylene), one of the most important
cracking process until today. plastic materials today. The market grows con-
With the development of the prices for crude tinuously with an average rate of 4 % worldwide
oil in 2007 and especially 2008, when prices and can be related to the gross national product
increased from approximately 60 US$/bbl to growth in an area or a certain country.
140 US $/bbl [8–10] (Fig. 1), alternative technol- In steam crackers, per ton of ethylene signifi-
ogies for production of ethylene have to been re- cant amounts of CO2 are produced, which range
evaluated. A second aspect that could trigger a from 1 – 1.6 t/t, depending on the raw material
significant change is the CO2 aspect, as the used for cracking. The annual growth of the
production of ethylene produces significant worldwide ethylene production is typically in
amounts of CO2 and will be subject to the range of 5 –6 106 t/a, which translates into
CO2 trading schemes in the future in several additional CO2 emissions of 5 – 9 106 t/a. In
areas. addition, due to the high temperature pyrolisis
These recent changes have started several NOx emissions are produced when using the
developments in the petrochemical industry, conventional technology.
such as shift of huge production capacities to Besides the major industrial applications of
areas with advantaged feedstocks (Middle East, ethylene, a small portion is converted into etha-
South America, Central Asia, etc.) but also nol by hydration and has been a source of syn-
fuelled the search for alternative production thetic ethanol for quite some time. However, with
routes for commercial-scale ethylene production. the increase in oil prices and consequently the
One of the most promising routes is the dehydra- increase of raw material costs for ethylene pro-
tion of ethanol, a reaction known for quite some duction, the reverse reaction has become of
time, but historically not used for large-scale significant interest.
ethylene production, due to economics and avail- Ethylene units are centers of petrochemical
ability of raw materials. However, due to the complexes in which ethylene is transferred into
dramatically increasing production of bioethanol transportable intermediates or semifinished pro-
worldwide, this route has to be reconsidered as an ducts with ethylene capacities of up to 1.5 106
alternative to conventional ethylene production t/a and significant amounts of high-value bypro-
from fossil raw materials. In addition, the depen- ducts. These sizes are required in order to utilize
dence of the ethylene value chain on crude-oil the economy of scale for production of ethylene.
price developments could be interrupted as In a world-scale plant of such scale, ethylene can
Vol. 13 Ethylene 467
at 50 C 1.10 MPa
be produced at much lower specific costs than in at 0 4.27 MPa
smaller units. Explosive limits in air at
Small-scale ethylene production in quantities 0.1 MPa and 20 C
of 100 103 – 200 103 t/a is in most cases lower (LEL) 2.75 vol % or 34.6 g/cm3
upper (UEL) 28.6 vol % or 360.1 g/cm3
not economical as many of the byproducts are Ignition temperature 425–527 C
produced in quantities to small for marketing.
However, world-scale plants for EDC/PVC re-
quire ethylene in quantities of 100 103 –
200 103 t/a only and ethylene supply from 3. Chemical Properties
standalone crackers of this size is not feasible
in most cases. The chemical properties of ethylene result from
the carbon–carbon double bond, with a bond
length of 0.134 nm and a planar structure. Eth-
2. Physical Properties ylene is a very reactive intermediate, which can
undergo all typical reactions of a short-chain
Ethylene is a colorless flammable gas with a olefin. Due to its reactivity ethylene gained
sweet odor. The physical properties of ethylene importance as a chemical building block. The
are as follows: complex product mixtures that have to be sepa-
rated during the production of ethylene are also
due to the reactivity of ethylene.
Ethylene can be converted to saturated hydro-
mp 169.15 C
bp 103.71 C
carbons, oligomers, polymers, and derivatives
Critical temperature, Tc 9.90 C thereof. Chemical reactions of ethylene with
Critical pressure, Pc 5.117 MPa commercial importance are: addition, alkylation,
Critical density 0.21 g/cm3 halogenation, hydroformylation, hydration (see
Density
at bp 0.57 g/cm3 Section 5.4), oligomerization, oxidation, and
at 0 C 0.34 g/cm3 polymerization.
Gas density at STP 1.2603 g/L The following industrial processes are listed
Density relative to air 0.9686 in order of their 2000 worldwide ethylene con-
Molar volume at STP 22.258 L
Surface tension sumption [11]:
at bp 16.5 mN/m
at 0 C 1.1 mN/m 1. Polymerization to low-density polyethylene
Heat of fusion 119.5 kJ/kg (LDPE) and linear low-density polyethylene
Heat of combustion 47.183 MJ/kg
Heat of vaporization
(LLDPE)
at bp 488 kJ/kg 2. Polymerization to high-density polyethylene
at 0 C 191 kJ/kg (HDPE)
Specific heat 3. Addition of chlorine to form 1,2-dichloro-
of liquid at bp 2.63 kJ kg1 K1
of gas at Tc 1.55 kJ kg1 K1
ethane
Enthalpy of formation 52.32 kJ/mol 4. Oxidation to oxirane [75-21-8] (ethylene
Entropy 0.220 kJ mol1 K1 oxide) over a silver catalyst
Thermal conductivity 5. Reaction with benzene to form ethylbenzene
at 0 C 177104 W m1 K1
at 100 C 294104 W m1 K1
[100-41-4], which is dehydrogenated to
at 400 C 805104 W m1 K1 styrene [100-42-5]
Viscosity of liquid 6. Oxidation to acetaldehyde
at mp 0.73 mPa s 7. Hydration to ethanol (Section 5.4)
at bp 0.17 mPa s
at 0 C 0.07 mPa s
8. Reaction with acetic acid and oxygen to form
of gas vinyl acetate
at mp 36104 mPa s 9. Other uses, including production of linear
at 0 C 93104 mPa s alcohols, linear olefins, and ethylchloride
at 150 C 143104 mPa s
Vapor pressure
[75-00-3], and copolymerization with pro-
at 150 C 0.002 MPa pene to make ethylene–propylene (EP) and
at bp 0.102 MPa ethylene–propylene–diene (EPDM) rubber
468 Ethylene Vol. 13
Table 1. Raw materials for ethylene production (as a percentage of total ethylene produced)
Raw material USA 1979 USA 1995 Western Europe 1981 Western Europe 1995 Japan 1981 Japan 1993
Refinery gas 1 4 3
LPG, NGL 65 76 4* 17 10* 3*
Naphtha 14 11 80 71 90 97
Gas oil 20 9 16 9 0 0
*
Including refinery gas
Ethane 29
Propane 8
Butane 3
Naphtha 53
Gas oil 6
Others 1
Figure 2. Feedstocks used for ethylene production
Vol. 13 Ethylene 469
of a feedstock in a simple figure, the quality used for ethylene production are crude oil frac-
factor, which indicates whether yields of the tions in the boiling range of 180–350 C (atmo-
target products are high or low, with aromatic spheric gas oils, AGO) and 350–600 C (vacuum
feedstocks being poor and saturated feedstocks gas oils, VGO). In contrast to naphtha and lighter
being good feedstocks. gas feeds, these feedstocks can not be character-
Quality characterization factors for naphthas ized by individual components.
have been developed, which indicate the aro- Gas chromatography coupled with mass spec-
matics content by empirical correlation. Since trometry (GC–MS) or high performance liquid
aromatics contribute little to ethylene yields in chromatography (HPLC) allow the analysis of
naphtha cracking, a rough quality estimate can be structural groups, i.e., the percentage of paraffins,
made for naphthas with a typical weight ratio of naphthenes, olefins, monoaromatics, and poly-
n- to isoparaffins of 1–1.1. The K factor is defined aromatics in the gas oil, and can be used to
as [14]: determine the quality of the hydrocarbon frac-
tion. If this information is used together with data
ð1:8Tk Þ1=3 such as hydrogen content, boiling range, refrac-
K¼
d tive index, etc., the quality can be determined
where Tk is the molal average boiling point in K. quite accurately. A rough estimate of feed quality
Naphthas with a K factor of 12 or higher are can be made by using the BMCI or the calculated
considered saturated; those below 12 are consid- cetane number of a gas oil. The cetane number,
ered naphthenic or aromatic. The K factor does normally used to calculate the performance of
not differentiate between iso- and n-alkanes. The diesel fuels, is an excellent quality measure, since
U.S. Bureau of Mines Correlation Index (BMCI) it is very sensitive to the n-paraffin content,
[15] can also be used as a rough quality measure which is one of the key parameters for the
of naphthas: ethylene yield. The cetane number CN is calcu-
lated as follows [16]:
BMCI ¼ 48640=Tþ473:7d456:8
CN ¼ 12:822þ0:1164 CIþ0:012976 CI2
where T is the molal average boiling point in K
and d is the relative density d15:6
15:6 . A high value of where CI ¼ 0.9187 (T50 /10)1.26687
BMCI indicates a highly aromatic naphtha; a low (nD =100)
20 1.44227
, where T50 is the volume average
value, a highly saturated naphtha. boiling point in C and n20
D the refractive index at
Gas condensates are very similar to naphthas 20 C
in composition with the main difference of hav-
ing no sharp boiling endpoint. A typical boiling
curve of gas condensates is shown in Figure 3. 5. Production
Gas condensates gain importance as raw material
for ethylene production because they are cheaper 5.1. Ethylene from Pyrolysis
than naphtha. of Hydrocarbons
Gas oils are feedstocks that are gaining im-
portance in several areas of the world. Gas oils The bulk of the worldwide annual commercial
production of ethylene is based on thermal crack-
ing of petroleum hydrocarbons with steam; the
process is commonly called pyrolysis or steam
cracking. The principal arrangement of such a
cracking reactor is shown in Figure 4, a photo-
graph of the furnace section of a modern ethylene
plant in Figure 5. The technology has been
applied for more than 50 years with permanent
improvements in details.
A hydrocarbon stream is heated by heat
exchange against flue gas in the convection
Figure 3. Boiling curves of liquid cracker feedstocks section, mixed with steam, and further heated to
VGO ¼ Vacuum gas oil; AGO ¼ Atmospheric gas oil incipient cracking temperature (500–680 C,
470 Ethylene Vol. 13
depending on the feedstock). The stream then hydrocarbons in the feedstock are cracked into
enters a fired tubular reactor (radiant tube or smaller molecules; ethylene, other olefins, and
radiant coil) where, under controlled residence diolefins are the major products. Since the con-
time, temperature profile, and partial pressure, version of saturated hydrocarbons to olefins in
it is heated from 500–650 to 750–875 C for the radiant tube is highly endothermic, high
0.1–0.5 s. During this short reaction time energy input rates are needed. The reaction pro-
ducts leaving the radiant tube at 800–850 C are
cooled to 550–650 C within 0.02–0.1 s to pre-
vent degradation of the highly reactive products
by secondary reactions.
The resulting product mixtures, which can
vary widely, depending on feedstock and severity
of the cracking operation, are then separated into
the desired products by using a complex sequence
of separation and chemical-treatment steps.
The cooling of the cracked gas in the transfer-
Color
line exchanger is carried out by vaporization of
Fig high-pressure boiler feed water (BFW, p ¼ 6–
12 MPa), which is separated in the steam drum
and subsequently superheated in the convection
section to high-pressure superheated steam
(HPSS, 6–12 MPa).
tubular reactors, as shown schematically in Molecular kinetic models that use only appar-
Figure 4. These furnaces can be used for all ent global molecular reactions and thus describe
feedstocks from ethane to gas oil, with a limita- the main products as a function of feedstock
tion in the end point of the feedstock of 600 C. consumption have been applied with some suc-
Higher boiling materials can not be vaporized cess to the pyrolysis of simple compounds such
under the operating condition of a cracking as ethane, propane, and butanes.
furnace. For example, cracking of propane can be
Increasing availability of heavy gas oil frac- described as
tions, due to a shift in demand to lighter fractions,
offers cost advantages for processing heavy feed- C3 H8 !a H2 þb CH4 þc C2 H4 þd C3 H6 þe C4 H8 þf C5þ
stocks in some areas of the world. Furthermore,
the availability of large quantities of residual oil where a, b, c, d, e, f are empirical factors depend-
have led some companies to investigate crude oil ing on the conversion of propane.
and residual oils as ethylene sources. Such feed- Gross oversimplification is required if these
stocks cannot be cracked in conventional tubular models are applied to complex mixtures such as
reactors. Various techniques employing fluidized naphthas or gas oils, but some success has been
beds, molten salts, recuperators, and high-tem- attained even with these materials.
perature steam have been investigated, but none Advances have been made in mechanistic
of these have attained commercial significance modeling of pyrolysis, facilitated by the avail-
[17]. Recently cracking of gas condensates in- ability of more accurate thermochemical kinetic
stead of naphthas has gained importance, as some and pyrolysis data and of high-speed computers.
gas condensates offer yield and cost advantages The major breakthrough in this area, however,
compared to naphthas. Some gas condensates are has been the development of methods to inte-
contaminated with Hg or As, which need to be grate large systems of differential equations
removed prior to cracking, as these contaminants [20–22].
could lead to corrosion (Hg) of aluminum Mechanistic models need less experimental
heat exchangers used in the separation section data and can be extrapolated. The accuracy of
or to poisoning (As) of hydrogenation cata- these models is very good for most components,
lysts [18]. but they require permanent tuning of the kinetic
Pyrolysis of hydrocarbons has been studied parameters, especially for computing the
for years. Much effort has been devoted to math- cracked-gas composition for ultrashort residence
ematical models of pyrolysis reactions for use in times. The main application for mechanistic
designing furnaces and predicting the products models is the design of cracking furnaces and
obtained from various feedstocks under different complete ethylene plants. The accuracy of the
furnace conditions. Three major types of model models has been improved, driven by the com-
are used: empirical or regression, molecular, and petition between the contractors for ethylene
mechanistic models [19]. plants. A number of mechanistic models are used
Today, mechanistic computer models, which today in the ethylene industry, describing the
are available from various companies, are used very complex kinetics with hundreds of kinetic
for design, optimization and operation of modern equations [23–25].
olefin plants. Sophisticated regression models To demonstrate the complexity of the chemi-
are also used, mainly by operators, and offer cal reactions, the cracking of ethane to ethylene is
the advantage of a much lower computer perfor- discussed here in detail. A simple reaction equa-
mance requirements than mechanistic models. tion for ethane cracking is:
The regression models are based on a data set,
which can consist of historical data or calculated C2 H6 !C2 H4 þH2 ð1Þ
data. Depending on the quality of the data base
the empirical regression models can be of suffi- If this were the only reaction, the product at
cient accuracy for most operating problems, 100 % conversion would consist solely of ethyl-
within the range of the data field. These models ene and hydrogen; at lower conversion, ethylene,
can be run on small computers and are well suited hydrogen and ethane would be present. In fact,
for process computer control and optimization. the cracked gas also contains methane, acetylene,
472 Ethylene Vol. 13
propene, propane, butanes, butenes, benzene, must be generated (Eqs. 2–4) to start a new chain.
toluene, and heavier components. This reaction Thus, every time a new chain is initiated, a
(Eq. 1) is clearly not the only reaction occurring. molecule of methane is formed (Eq. 3) and a
In the 1930s, the free-radical mechanism for molecule of ethylene is produced (Eq. 4). Other
the decomposition of hydrocarbons was estab- normal and branched-chain alkanes decompose
lished [26]. Although the free-radical treatment by a similar, but more complex, free-radical
does not explain the complete product distribu- mechanism [27]. The number of possible free
tion, even for a compound as simple as ethane, it radicals and reactions increases rapidly as chain
has been extremely useful. Ethane cracking re- length increases.
presents the simplest application of the free- The free-radical mechanism is generally ac-
radical mechanism. Ethane is split into two cepted to explain hydrocarbon pyrolysis at low
methyl radicals in the chain initiation step conversion [26]. As conversion and concentra-
(Eq. 2). The methyl radical reacts with an ethane tions of olefins and other products increase,
molecule to produce an ethyl radical (Eq. 3), secondary reactions become more significant.
which decomposes to ethylene and a hydrogen Partial pressures of olefins and diolefins increase,
atom (Eq. 4). The hydrogen atom reacts with favoring condensation reactions to produce cy-
another ethane molecule to give a molecule of clodiolefins and aromatics. The cracking of hea-
hydrogen and a new ethyl radical (Eq. 5). vy feed, such as naphthas or gas oils, often
Initiation proceeds far enough to exhaust most of the
. .
crackable material in the feedstock.
C2 H6 !CH3 þCH3 ð2Þ The reaction scheme with heavier feeds is
Propagation much more complex than with gaseous feed-
. .
stocks, due to the fact the hundreds of reactants
CH3 þC2 H6 !CH4 þC2 H5 ð3Þ (feed components) react in parallel and some of
those components are formed as reaction pro-
. .
with unreacted ethane. This is not observed. RCH2 CH2 CH2 !RCH2 þC2 H4 ð11Þ
Reactions (3) and (4) terminate if either an This b-scission reaction produces a shorter
ethyl radical or a hydrogen atom reacts with .
H þH !H2
.
C2 H5 þCH3 !C3 H8
.
ð9Þ
(Eqs. 12–14) results in the molecular equation
(Eq. 15):
. . . .
methyl or ethyl radicals or a new hydrogen atom n-C4 H9 !C2 H4 þC2 H5 ð15Þ
Vol. 13 Ethylene 473
. .
reduces the partial pressure of high-boiling, high- Isoalkanes, in general, produce much smaller
molecular-mass aromatics and heavy tarry ma- yields of ethylene and propene than n-alkanes.
terials, reducing their tendency to deposit and They give higher yields of hydrogen and meth-
form coke in the radiant tubes and to foul quench- ane, and of C4 and higher olefins. Isoalkanes tend
exchanger tubes. Steam reduces the fouling of the to produce more propene than ethylene compared
radiant tubes by reacting with deposited coke to to n-alkanes.
form carbon monoxide, carbon dioxide, and hy- Olefin and diolefin yields from cyclopentane,
drogen in a water gas reaction, but as can be seen methylcyclopentane, and cyclohexane have
from the concentration of carbon monoxide in the been reported [27]; methylcyclopentane and
cracked gas (normally ca. 100 ppm), only to a cyclohexane give substantial amounts of
limited extent. butadiene.
The sulfur content of the feed is important, Simple and condensed ring aromatics produce
since sulfur passivates active Ni sites of the no ethylene. Benzene is stable under normal
cracking coil material by forming nickel sulfides, cracking conditions. It is formed during cracking
which do not catalyze coke gasification, in con- and remains unchanged in the feed. Other aro-
trast to nickel metal and nickel oxides. This matics yield primarily higher molecular mass
explains why CO production is high (up to 1 % components. Aromatics with long side chains,
in the cracked gas) if the feedstock is free of such as dodecylbenzene, yield ethylene and other
sulfur. To prevent this effect, ca. 20 ppm of olefins by side-chain cracking. The aromatic
sulfur (e.g., as dimethyl sulfide) are added to nucleus still, however, generally produces pyrol-
sulfur-free feedstocks. ysis fuel oil and tar.
Feedstock composition is another important In summary, maximum ethylene production
consideration in commercial production of ethyl- requires:
ene. Ethylene-plant feedstocks generally contain
straight- and branched-chain alkanes, olefins, . A highly saturated feedstock
naphthenes, and aromatics. Ethylene and other . High coil outlet temperature
olefins are formed primarily from alkanes and . Low hydrocarbon partial pressure
naphthenes in the feed. n-Alkanes are the preferred . Short residence time in the radiant coil
component for high ethylene yields, and those . Rapid quenching of the cracked gases
containing an even number of carbon atoms give
slightly better ethylene yields than odd-numbered These conditions maximize the yield of ole-
ones. n-Alkanes also produce propene, whose fins and minimize the yield of methane and high
yield decreases with increasing chain length. molecular mass aromatic components.
Vol. 13 Ethylene 475
Cracking conditions and yield structure are Heat requirements for hydrocarbon pyrolysis
often optimized for economic reasons in plant can be divided into three components:
design and operation; even small changes in
cracked gas composition influence the overall
1. The enthalpy required to heat the feedstock,
plant economics dramatically.
including the latent heat of vaporization of
The dilution steam ratio is in most cases at the
liquids
minimum of the range for the specified feedstock,
2. The endothermic heat of cracking
due to the contribution of the dilution steam to the
3. The enthalpy required to heat the cracked gas
production costs.
from the radiant-coil inlet temperature to the
radiant-coil outlet temperature
5.1.2. Heat Requirements for Hydrocarbon
Pyrolysis The first is accomplished in the convection sec-
tion of the furnace; the last two, in the radiant
Primary hydrocarbon pyrolysis reactions are en- section. Enthalpies (1) and (3) can be calculated
dothermic; heat requirements are determined by from standard heat-capacity data; they represent
feedstock and cracking conditions. The temper- 25–60 % of total process heat input in the furnace
ature required to attain a given reaction rate as the feedstock changes from ethane to gas
decreases as the carbon chain length in the feed- oils [27].
stock increases. Thus, the enthalpy required to A typical heat balance for a modern naphtha
reach cracking temperature depends on feed- furnace including the transfer-line exchanger
stock and cracking conditions. (TLE) is shown in Figure 7.
The endothermic heat of cracking is most furnace requires a standardized procedure, espe-
simply calculated from heats of formation by cially if the feedstock is changed from ethane to
the following equation: naphtha and gas oil. A homogeneous sample is
withdrawn from the furnace effluent, quenched,
DHr ¼ DHp DHf
and separated into gaseous and liquid fractions.
where DHr ¼ endothermic heat of cracking, kJ/ These are analyzed separately and then combined
kg; DHp ¼ heat of formation of the cracked to give a complete cracked-gas analysis.
products, kJ/kg; and DHf ¼ heat of formation of The material balance is obtained by matching
the feed, kJ/kg. the hydrogen, carbon, and sulfur content of the
Heats of formation for some alkanes, olefins, feedstock with that of the cracked gas. This type
naphthenes, and aromatics are as follows (in of analysis is time-consuming. In a faster system,
kJ/kg) [31]: gas–liquid separation is eliminated [32] or only a
gas-phase analysis is taken. Due to many sources
Hydrogen 0.0 of errors, series of samples have to be taken and
Methane 5646.3 analyzed. Statistical methods are used to check
Ethane 3548.1 the quality of the results.
Ethylene 1345.3
Acetylene 8540.7
For gas feedstocks, conversion is used as a
Propane 2949.9 measure of the severity of cracking:
Propene 17.9
Methylacetylene 4317.1 Conversion ¼ ðCn;in Cn;out =Cn;in Þ
Propadiene 4496.8
n-Butane 2694.4
where Cn,in ¼ quantity of component n at inlet in
Isobutane 2827.5 kg/h and Cn,out ¼ quantity of component n at
1-Butene 459.4 outlet in kg/h.
cis-2-Butene 649.5 For liquid feedstocks the severity is defined as
trans-2-Butene 668.2
Isobutene 746.5
the ratio of propylene to ethylene (on weight
Ethylacetylene 2720.4 basis) P/E or as ratio of methane to propylene
1,3-Butadiene 1721.8 M/P. Both ratios P/E and M/P are a linear func-
Benzene 783.6 tion of temperature over a wide range and can be
Toluene 243.4
Cyclopentane 1611.3
measured with much higher accuracy than the
Methylcyclopentane 1722.6 apparent bulk coil outlet temperature of a crack-
Cyclohexane 1846.4 ing furnace. The use of P/E and M/P ratios for
Methylcyclohexane 1890.3 severity definition is accepted in industry.
As the alkane chain length increases, the heat Ethane. Ethane is cracked commercially in
of formation approaches 1800 kJ/kg asymptoti- all types of furnaces, from long residence time to
cally. Ethane, the most refractory alkane besides short residence time. However, since ethane is a
methane, has the most endothermic heat of crack- very stable paraffin, cracking temperatures at the
ing, þ4893 kJ/kg. The corresponding figure for coil inlet typically are higher than for other
propane is þ4295 kJ/kg and for a high-molecu- hydrocarbons. For ethane the coil inlet tempera-
lar-mass n-alkane, ca. 1364 kJ/kg. tures are in the range of 650–680 C. Typical
Endothermic heat of cracking increases with conversion ranges of commercial furnaces are
degree of saturation of the feed; as conversion 60–75 %, with 67–70% conversion being a typi-
increases, secondary condensation products in- cal figure for modern designs.
crease. These products have less negative heats Table 3 lists yields for ethane cracking at
of formation than alkanes, or positive heats of various residence times. There is a slight increase
formation. in yield at short residence times. However, as the
run length of short-residence-time ethane fur-
naces is low (Fig. 8) and yield improvement is
5.1.3. Commercial Cracking Yields moderate, application of short-residence-time
furnaces for ethane cracking is not feasible in
Determining the complete yield patterns (gas most cases. In certain economic scenarios with
and liquid products) for a commercial cracking limited quantity of feedstock the application of
Vol. 13 Ethylene 477
short-residence-time coils can make sense, be- with ethane conversions of 40–50 %. Due to the
cause additional ethylene is produced in a short- build up of large recycle streams in such opera-
residence-time coil if a limited amount of feed- tions, co-cracking should be avoided wherever
stock is available. In such scenarios residence possible.
times in the range of 0.25 s are applied in order to
give the advantage of high yield and sufficient Propane is cracked in all types of furnaces
run length. at typical conversions of 90–93 %. The applica-
In naphtha plants the ethane contained in the tion of short-residence-time furnaces for propane
cracked gas is separated and recycled to a segre- cracking has to be evaluated carefully, due to the
gated ethane-cracking furnace, in which cracking reduction in run length between successive de-
is carried out under typical ethane-cracking cokings. In many naphtha plants with propane
conditions. In case the capacity of the ethane recycle, propane is co-cracked together with
furnace is not sufficient to crack all the ethane, naphtha, without a dramatic drop in propane
co-cracking of ethane with naphtha is performed, conversion.
Typical yields for propane cracking for vari-
ous residence times are listed in Table 4. For very
mild propane cracking conditions (70 % conver-
sion) yields of propylene show a maximum at 18–
19 wt % based on propane feed.
The yield increases with decreasing residence Table 10. Properties of AGO and HCR used for yield calculations in
Table 5
time. The maximum benefit of a selective crack-
ing coil is achieved in high-severity cracking, in AGO HCR
which a 5 % feedstock saving can be achieved by
Density at 20 C, g/mL 0.8174 0.8280
using short residence times. However, careful C, wt % 86.20 85.28
analysis is required since, similar to gas cracking, H, wt % 13.64 14.34
shorter run lengths are typical for short-resi- S, wt % 0.18 0.003
dence-time cracking. Maximum annual furnace BMCI 24.8 9.37
Paraffins þ naphthalenes, wt % 80.38 89.4
productivity is achieved with a combination of Monoaromatics, wt % 12.45 7.3
short residence time and long run length. Polyaromatics, wt % 7.17 3.3
Boiling point analysis, C
Gas Oil (AGO; Boiling Range 180– ibp 170 313
cracker has about three times the feedstock parallel in a staggered, double-row tube arrange-
throughput of an ethane cracker, and that naphtha ment. Staggered tubes have nonuniform heat-
cracking shows some sensitivity to short resi- flux distributions because of the shadowing ef-
dence times, whereas ethane crackers are not fect of one coil on its companion. If maximum
very sensitive with respect to feedstock savings capacity and full utilization of the firebox are
as short residence times are applied. A careful desired, tube staggering can be adjusted so that
economic analysis is required to select the opti- the shadowing effect is only marginally greater
mum residence time range for a given feedstock, than with a single-row arrangement.
since shorter residence times lead to reduced Heat transfer to the radiant tubes occurs large-
availability due to shorter run length, as shown ly by radiation, with only a small contribution
for ethane cracking in Figure 8. from convection. Firebox temperature is typical-
ly 1000–1200 C.
The radiant coil of an ethylene furnace is a
5.1.4. Commercial Cracking Furnaces fired tubular chemical reactor. Inlet conditions
must meet the required temperature, pressure,
Furnace Design. Modern cracking furnaces and flow rate. Hydrocarbon feed is heated from
typically have one or two rectangular fireboxes its convection-section entry temperature to the
with vertical radiant coils located centrally be- temperature needed for entry into the radiant
tween two radiant refractory walls. Firebox coils. Dilution steam is introduced into the hy-
heights of up to 15 m and firebox widths of 2– drocarbon stream in the convection section. The
3 m are standard design practice in the industry. combined hydrocarbon and steam stream is then
Firing can be performed with wall- or floor- superheated to the target temperature at the radi-
mounted radiant burners, or a combination of ant coil inlet (crossover temperature, XOT).
both, which use gaseous or combined gaseous Gaseous feeds require only the energy necessary
and liquid fuels. Fireboxes are under slight neg- to heat the feed and steam to the radiant coil inlet
ative pressures with upward flow of flue gas. Flue temperature. Liquid feeds require additional en-
gas flow and draft are established by induced- ergy to heat the liquid to its vaporization temper-
draft fans. In some furnace designs, burners are ature plus its latent heat of vaporization.
mounted on terraced walls. Energy is saved in the convection section by
Firebox length is determined by the total preheating the cracking charge; by using utility
ethylene production rate desired from each fur- preheating, i.e., boiler-feedwater preheating, di-
nace and the residence time of the cracking lution-steam superheating, high-pressure steam
operation. This also determines the number of superheating or by preheating the combustion
individual radiant coils needed, with short resi- air.
dence times requiring many more individual A typical arrangement of furnace elements is
coils than longer residence times for the same shown in Figure 10. In this case, the convection
production capacity. This is due to the shorter section contains six separate zones. As an exam-
lengths of the short-residence-time coils, which ple, the feed could be preheated in the upper zone,
can be as short as 10–16 m per coil. Long-resi- the boiler feedwater in the next, and mixed feed
dence-time coils can have lengths of 60–100 m and dilution steam in the third zone. The process
per coil. The number of coils required for a given steam is superheated in the fourth zone, the HP
ethylene capacity is determined by the radiant (high-pressure) steam is superheated in the fifth
coil surface, which is in the range of 10–15 m2 zone and the final feed and dilution steam are
per tonne of feedstock for liquid feedstocks. preheated in the bottom zone. The number of
Production rate for each coil is determined by zones and their functions can differ according to
its length, diameter, and charge rate, which furnace design. For example, the upper zone
translates into a certain heat flux on the radiant could be used to recover heat for air preheating.
coil. Values of 85 kW/m2 for the average heat With the trend to higher capacities per indi-
flux of a coil should be the maximum. vidual furnace a new furnace set-up has been
Radiant coils are usually hung in a single introduced to the industry with great commercial
plane down the center of the firebox. They have success. In this type two fireboxes are connected
also been nested in a single plane or placed to one convection section. This design allows
Vol. 13 Ethylene 483
liquid feedstock cracking furnaces with capaci- 650 C, depending on the feedstock, is necessary
ties of 130 000 200 000 t/a to be installed. to avoid losses of valuable products by secondary
Capacities of gas furnaces are higher and can reactions. This is accomplished by a transfer-line
reach up to 250 000 to 300 000 t/a. This is a result exchanger (see Fig. 10), which cools the cracked
of the general trend to built ethylene plant in gases and recovers much of the heat contained in
much larger scale, which started with the number the cracked gas as high-pressure steam. The
of gas-based projects erected in the Middle East transfer-line exchanger can be a conventional or
in 2000. a linear exchanger as shown in Figure 11. Linear
The induced-draft fans allow complex con- exchangers are preferred today for gas cracking,
vection sections to be designed with very high in order to avoid erosion problems with the very
gas velocities to give optimum heat transfer in the hard coke in gas cracking.
convection section banks. Modern designs in- In all modern furnaces the radiant coils exit
clude integrated catalyst systems for NOx remov- the firebox at the top; the TLEs are top-mounted.
al by SCR (selective catalytic reduction) tech- In older designs coils also leave the bottom of the
nology, whereby the NOx present in the flue gas firebox, with TLEs mounted vertically along the
reacts with ammonia: side of the furnace or horizontally underneath it.
Radiant-coil designs are generally considered
4 NOx þ4 NH3 þO2 !4 N2 þ6 H2 O
proprietary information. All modern designs
The temperature of the cracked gas leaving strive for short residence time, high temperature,
the radiant coils can range from 750 to 900 C. and low hydrocarbon partial pressure. Most coil
Rapid reduction of gas temperature to 500– configurations have two features in common:
484 Ethylene Vol. 13
Color
Fig
Figure 13. Coil with internal fins and improved heat transfer
achieved a major breakthrough in new cracker high aluminum content the material can be ma-
projects. The advantage of chemical treatment is chined, bent, and welded.
that the costly process of deposition by CVD or A different approach is the application of ODS
PVD can be avoided and the dosing can be (oxide dispersion strengthening) leading to
adjusted during operation. A disadvantage is that ‘‘superalloys’’. ODS materials can be used up to
chemicals are introduced that end up in the 1300 C with still good creep resistance but
cracker products and should not influence the despite these ceramic-like properties are duct-
quality of the products significantly. able and weldable like metallic materials. Due to
Another novel development in furnace tech- the non-casting production process based on
nology is the application of new coil materials, metal oxide powders, the costs for such materials
especially 45Ni35Cr steels, offered by many are much higher than those for conventional HP
suppliers. These high-alloy steels are superior to modified or similar materials. The industrial
other HP modified materials and offer advan- breakthrough of ODS in ethylene plants has not
tages with respect to carburization at similar been achieved until today [34].
creep rates as other HP modified materials.
An interesting new material is offered by ABB Lummus Global Furnace. The coil
Schmidt and Clemens (Kaiserau, Germany) un- design of Lummus furnaces has been modified
der the designation Centralloy 60 HT. The prod- in the light of pilot-plant investigations. Several
uct has an increased content of aluminum (6 %) generations of coils SRT-I (short residence time-
and can be operated up to 1200 C. Despite the first model) through SRT-X, have been produced.
The SRT-I model radiant coil is uniform in
diameter. Many SRT-I heaters are still operating,
primarily for cracking ethane, propane, or bu-
tane. All other coils are so-called split coils, with
smaller inlet coils combined into larger outlet
coils. The latest designs – SRT-V SRT-VI and
SRT X – are short residence time coils with
residence times in the range of 0.15–0.20 s. In
the SRT-V coil, 8–12 small coils of ca. 40 mm
internal diameter are headered into a single outlet
Figure 14. Coated radiant coil surface coil of large diameter (150–180 mm). In SRT-VI
486 Ethylene Vol. 13
Color
Fig
For furnaces using gas-turbine integration The Technip furnaces can be paired with a
(GTI) or preheating of combustion air, a floor- common stack and induced-draft fan, or they can
fired, short-residence-time (FFS) design is avail- stand alone. Top outlet coils are preferred.
able. This is completely floor fired, which re- Burners are wall-mounted or wall- and floor-
duces large-volume ductwork to a minimum. mounted.
Coil geometry is similar to USC-U or USC-W
designs, but to maintain a uniform firebox tem- Linde-Pyrocrack Furnace (Linde AG,
perature, more and shorter coil legs are used. Munich, Germany). Linde-Pyrocrack fur-
Overall fuel efficiencies of Shaw furnaces are naces provide capacities of 20 000–300 000 t/
competitive. a. Feedstocks can be all straight-run or pretreated
hydrocarbons from ethane, propane, butane, nat-
Technip Furnace (Technip, Paris, France). ural gas liquids, naphthas, raffinates, gas oils, gas
A number of radiant-coil designs (GK and SMK) condensates and hydrocracked vacuum gas oils.
are available, ranging from a simple serpentine Furnaces are designed for segregated cracking or
coil of constant diameter to GK-1 (gradient ki- co-cracking and for maximum feedstock flexi-
netics, model 1) and GK-6 coils. bility. Linde and its U.S. subsidiary Selas Fluid
Gaseous feed, naphtha, and gas oil can be Processing have installed furnaces with a total
cracked with all coils. Residence times range ethylene capacity > 25 106 t/a.
from 0.15 to 0.5 s. Capacities range up to Pyrocrack coils are all split coils with small
250 000 t/a per furnace. inlet coils headered into a larger outlet coil, with
The GK radiant coil has two thin, parallel residence times from 0.15 to 0.5 s. The three
tubes from the coil inlet to ca. 66 % of the total basic Pyrocrack coil types are shown in
coil length, where they combine to a single, Figure 17. Coil diameters range from ca. 40/
larger tube. The thin tubes can be staggered or 55 mm (inlet/outlet) for Pyrocrack 1–1 coils to
in-line; the larger diameter tubes must be in-line. 100/ 150 mm for Pyrocrack 4–2 coils. Critical
488 Ethylene Vol. 13
venturi nozzles are used to ensure equal distribu- The convection section of Linde Pyrocrack
tion and residence times in all parallel coils of a furnaces contains process heating bundles for
furnace. feed, dilution steam, boiler feedwater, and high-
Today floor firing or a combination of side- pressure steam superheater bundles. Overall
wall and floor firing is used, the latter offering efficiencies of up to 94–95 % (on lower heating
the best distribution of the released heat over the value, LHV) are typical for Linde furnaces.
whole firebox and a excellent radiant efficiency. High-pressure steam systems for heat recovery
Especially for large-capacity furnaces with high have been developed by Linde for up to 14 MPa.
fireboxes the combination of floor and sidewall Linde has built furnaces with SCR-based
firing offer the advantage of an even distribution DeNOx technology integrated into the convec-
of the heat release. Fuel for the radiant burners tion section. The design of the side and front
can be gas or oil or both. Oil firing offers the walls of the convection section provides uni-
opportunity to use a fraction of the pyrolysis fuel form heat distribution and prevents flue gas
oil (i.e., the liquid product of the pyrolysis bypassing. Furnace draft is maintained by an
boiling above 180 C) as fuel and thus of in- induced-draft fan mounted over the convection
creasing the amount of the pyrolysis methane section.
fuel fraction available for export to other con- Linde has introduced with great commercial
sumers. With today’s requirements of low NOx success the Twin Radiant Cell concept, in which
emissions, the application of liquid fuel burners a single high-capacity furnace has two radiant
in ethylene plants is the exception, as the NOx sections, which are connected to a common
emissions for liquid fuels are above the BAT convection section (Fig. 18). The two radiant
levels (best available technique), forming the sections can be operated independently with
basis for local regulations in Europe. Present different feedstocks or even with one firebox
BAT levels in Europe are 80 to 100 mg/Nm3 for in cracking operation and the other in decoke
furnaces in ethylene plants without catalytic operation. This offers the advantage of less ca-
DeNOx systems. Floor firing offers the advan- pacity loss during decoke operation of a large
tage of somewhat lower NOx levels than side- capacity furnace. Other new features are a pro-
wall burners. prietary system for processing gas condensates,
Vol. 13 Ethylene 489
which have an extremely high and variable final low NOx emissions. The mass of steel used in a
boiling point. This system was developed from 400 000 t/a ethylene plant is 30 % lower
the well-established Linde technology for heavy than that used in a 300 000 t/a plant with con-
hydrocracker bottoms and adapted to the require- ventional furnaces. This is achieved by a patented
ments for gas condensates. installation of three radiant coils in the firebox
space normally occupied by one or two
Other Furnaces. The furnaces listed below coils [35].
show some interesting features, but none is of The Mitsubishi Furnace jointly developed by
commercial importance in today’s worldwide Mitsubishi Petrochemical Co. and Mitsubishi
olefin business. Only the furnace designs of the
contractors listed above (ABB Lummus Global,
KBR, Shaw, Technip, and Linde) are considered
to be competitive.
The terraced-wall furnace (Foster & Wheeler
Energy Corp., Livingston, N.J.) uses burners
firing upward from shelves or ledges built into
the walls of the firebox (Fig. 19). A similar
firebox design is used for reformer heaters. This
arrangement apparently gives uniform heating of
the radiant coil. Furnaces are all-gas or all-liquid
fuel fired.
The Mitsui advanced cracker (Mitsui Engi-
neering & Shipbuilding Co., Tokyo, Japan)
offers lower construction costs, smaller land Figure 19. Foster–Wheeler terraced wall furnace
area requirements, high thermal efficiency, and a) Radiant coil; b) Burners
490 Ethylene Vol. 13
. Operating temperature
. Tube service life
. Cost
. Carburization resistance
. Creep-rupture strength
. Ductility
. Weldability
The materials used for cracking coils are high- Stack heat loss is that portion of the heat
alloy steels, e.g. with 45 % Ni, 35 % Cr and released in the radiant firebox which is dis-
several important trace metals (Si, Mn, Nb, Mo, charged to the atmosphere in the flue gas. Stack
W, Ti) [42]. The technical designation of this heat losses are around 5 % of the fired duty. This
most common radiant coil material is HP 40 is the only heat loss that furnace operators can
modified. The new materials offered by the lead- control, given a fixed furnace design, quality of
ing vendors can be operated up to 1150 C. Only a maintenance, feed rate, and coil outlet tempera-
limited number of manufacturers worldwide are ture. Stack heat loss is sensitive to excess com-
able to produce these materials according to very bustion air in the furnace and, thus, to draft, fuel
strict quality standards. composition, and air leakage.
The most common technique for combustion compounds, which are known to deposit coke on
air preheating is the use of hot exhaust gas from the inside surface of the radiant coil [48, 49]. This
gas turbines (GTs). Such plants co-produce elec- coke layer inhibits heat transfer from the tube to
tricity (in the range of 30–60 mWel.), and this has the process gas, raises tube wall temperature, and
a major impact on the plant economy. The GTs reduces the cross-sectional flow area of the tube,
are exclusively used for electricity production. thus increasing the pressure drop along the radi-
Direct driving of large compressors by the GTs is ant coil. Cracking yield is thus lowered because
not feasible, due to the maintenance require- of increasing hydrocarbon partial pressure.
ments for GTs, which require an annual shut- When tube temperature limits are reached, or
down. In modern plants the ethylene plant can pressure limitations of the sonic venturi nozzles
run with and without the GT [47]. The economy used for flow distribution in short-residence-time
of operation with an integrated GT is highly furnaces, the furnace must be shut down to
dependent on the credit for the electricity and remove the coke. During the course of one on-
the increased HP steam production. Scenarios stream cycle, deposited coke can reduce the heat-
that favor GT integration in Japan, Korea, and transfer efficiency of the firebox by 1–2 %, re-
Brazil have existed in the eighties. sulting in a 5 % increase in fuel consumption
Radiant-coil inlet and outlet process tempera- [50]. As radiant efficiency decreases, convection
tures in an ethylene furnace must be the same after section heat transfer increases. This results in an
application of preheated combustion air as they unwanted increase in process crossover temper-
were before, to obtain the same cracking severity. ature and a lower demand for radiant-coil heat
input. After furnace firing equilibration, actual
Convective Heat Transfer and Furnace fuel demand increases by 1–3 %.
Thermal Efficiency. Convective heat transfer Gaseous feedstocks such as ethane yield a
is widely used in isolated green-fields ethylene harder, denser coke with higher thermal conduc-
plants to improve thermal efficiency by preheat- tivity than naphthas or gas oils. Highly aromatic
ing boiler feedwater, generating steam, or super- feeds produce the most coke.
heating HP steam in the convection section of a The mechanism of coil coking is not fully
furnace. Recovered energy must be considered in understood [51]. Two types of coke can be
the overall energy balance for a plant of this type. distinguished, the catalytic coke and pyrolytic
Such techniques can be employed in older plants coke (Fig. 21).
if boiler feedwater, generated steam, or super- The possibility that tube metals such as iron
heated steam can be used. Otherwise, preheating and nickel catalyze coke formation is supported
the combustion air is an alternative. by the observation that sulfur in the feed inhibits
coking. A sulfur content above 400 ppm, how-
ever, may increase coking.
5.1.7. Coking and Decoking of Furnaces
and Quench Coolers Quench-Cooler Coking. Coke deposited in
TLEs reduces both heat transfer and the amount
Radiant-Coil Coking. Hydrocarbon pyrol- of steam generated to such an extent that
ysis produces acetylenic, diolefinic, and aromatic the equipment must be cleaned. Different
shutting down the furnace, disconnecting the radiant coil degrades the value of the cracking
TLE, and removing the coke from the tubes pattern.
mechanically or hydraulically. 4. High heat recovery in the cracked gas, which
The furnace should never be shut down and directly affects operating economics. The
cooled without radiant-coil decoking. Differ- pressure for steam generation is affected by
ences between the coefficients of thermal expan- the cracking feedstock. For light hydrocarbon
sion of the coke and of the metal tube wall are cracking, in which little TLE fouling from
such that the radiant coils may rupture. condensation results, steam of much lower
Off-gas from decoking is usually diverted to a pressure (60 bar) can be generated. With such
decoking system containing a knockout pot feeds, two TLEs can be used in series, one for
equipped with a quench water inlet or a high- generating high-pressure steam, the other for
performance cyclone separator with dry or wet low-pressure steam or other heat recovery.
separation of the coke particles in the effluent. The TLE outlet temperature must be higher
The cleaned, cooled gases are discharged to the for liquid feeds (360 C) because of conden-
atmosphere. Alternatively, the decoke off-gas sation of heavy components in the cracked
can be rerouted to the firebox, where the coke gas; therefore, the pressure of the generated
particles are incinerated. steam can be higher (8–12 MPa). In these
cases, because of the high outlet temperature,
TLEs are generally followed by a direct oil
5.2. Quenching of Hot Cracked Gas quench to lower the gas temperature for entry
into the downstream portion of the plant.
Cracked gases leave the radiant coil of an ethyl- 5. Reasonable TLE run lengths. Fouling of TLE
ene furnace at 750–875 C. The gases should be tubes by condensation and blockage by coke
cooled instantaneously to preserve their compo- increase outlet temperature and pressure drop.
sition. However, this is not practical, so furnaces Ultimately, the system may have to be shut
are designed to minimize residence time of the down and cleaned. The TLE outlet tempera-
hot gas in the adiabatic section between furnace ture usually increases rapidly for several
outlet and quench-system cooling zone. Typical- hours from the start-of-run (SOR) value; the
ly, residence time in this adiabatic zone should increase then falls to a few C per day.
not exceed 10 % of the residence time in the
radiant coil. Figure 23 shows the TLE outlet temperature
The cracked gas is generally cooled by indi- over the run length for ethane, naphtha, and
rect quenching in the TLEs, which permits heat heavy feedstock (AGO, HVGO) cracking in a
recovery at a temperature high enough to gener- modern highly selective furnace.
ate valuable high-pressure steam. Direct quench- The length of run for a TLE in gas cracking
ing by injection of oil has been displaced almost service is limited by coke blockage of the TLE
totally by indirect quenching. inlet tubes [51]. For liquid feeds, TLE run length
Design objectives for transfer-line exchangers is governed by fouling at the outlet end of the
are as follows:
Color
Fig
Figure 26. Details of the Borsig Linear Exchanger Figure 28. Alstom double-pipe transfer-line exchanger
Figure 29. Alstom close coupled linear exchanger surfaces, thereby reducing fouling in the TLE
entry zone. The large USX gas flow tube reduces
zone, but due to the increased length has a higher pressure drop across the exchanger and, thus, the
pressure drop than the conventional exchanger. probability of plugging by coke from the radiant
Figure 29 shows an Alstom close coupled linear coil.
exchanger in the typical U-shape. Feeds for all The USX exchangers can be steam–air de-
Alstom exchangers range from ethane to gas coked; cleaning, when required, is facilitated by
oils [55]. openings at each end of the exchanger.
Shaw Quench System (Shaw, Baton Rouge, KBR Millisecond Primary Quench Ex-
USA). The Shaw proprietary quench system changer (KBR, Houston, Texas). A special
does not rely on a tube sheet. The USX (ultra- primary quench exchanger (PQE) was developed
selective exchanger) quench cooler shown in for use with KBR’s Millisecond furnace. The
Figure 30 is a double-pipe exchanger, with the exchanger has a double-pipe arrangement
inner pipe slightly larger than the radiant-coil (Fig. 31) capable of generating high-pressure
connecting piping. This design can quench the steam.
effluent from one to four radiant coils. The USX A special high-alloy section of tubing is in-
outlet temperature (500–550 C) is higher than in serted to avoid excessive thermal stress at the
most other transfer-line exchanger designs; this high-pressure steam transition piece. This sec-
helps to reduce coking in the exchanger. Nor- tion has the Y-fitting at its base and extends up to
mally, effluents from all USX exchangers on a the boiler feedwater inlet nozzle. A steam bleed
given furnace are combined downstream and fed helps to control thermal gradients and to prevent
to a conventional multitube exchanger where the coke deposition in the annulus between the high-
gases are quenched to a more normal TLE outlet alloy insert and the exchanger inner surface.
temperature. The steam system is a thermosiphon type,
This design, by eliminating the tube sheet and with individual risers and downcomers tied
entry cone, eliminates turbulent eddies and back- together in common headers connecting to a
mixing between the coil outlet and the cooling single steam drum. KBR’s PQEs are normally
498 Ethylene Vol. 13
such as gas oil and hydrocracker bottoms. When . Propane is recycled as a cracking feedstock,
pure ethane is the feedstock, the amount of C3 and used as fuel, or sold.
heavier byproducts is small, and only rarely is the . Propene is sold in various grades.
recovery of heavier products economically fea- . Raw pyrolysis gasoline is sold as motor gaso-
sible. As the concentration of heavier compo- line component after hydrotreatment, or it is
nents increases, recovering them for direct sale used as feedstock for aromatics production.
becomes feasible. Addition of significant . Tar is sold for fuel, used as coke feedstock, or
amounts of propane to ethane feedstock makes diluted with hydrocarbon stocks to produce
a depropanizer necessary and hydrotreating and feedstocks for resins.
fractionation of the C3 cut may be required; . Sulfur is recovered in some plants and sold.
butane feeds make oil and gasoline removal from
the cracked-gas compressor necessary; pentane- 5.3.2. Cracked Gas Processing
range feeds require fractionation of light from
tarry oils, and so on. Many options are available for general process
configuration [56, 59–65]. The sequence for
isolation of hydrocarbon fractions can be varied,
5.3.1. Products depending on plant size, amounts of ethylene and
coproducts, impurities, product range, product
Local market conditions and the degree of inte- purity desired, and other factors.
gration of the ethylene units into refining or The following discussion of the recovery
petrochemical complexes influence the desired process is split into two sections:
products and the feedstocks used. Many types of
coproduct can be generated with different equip- 1. Front-end section, including cracked gas
ment [56–58]; only the major product options are compression and associated units
discussed here. 2. Hydrocarbon-fractionation section
The principal ethylene coproducts are as
follows: Difference between the two sections is made for
simplicity reasons. The basic process route for
. Acetylenes (C2 and C3) are hydrogenated to the front-end section is identical for all commer-
ethane, ethylene, propane, and propene; or they cial processes, however major difference exists
may be recovered and sold as products. between gas- and liquid feedstock cracking. For
. Aromatics (various fractions) can be recovered the hydrocarbon fractionation section there are a
or they may remain in the hydrotreated pyrol- large variety of process routes available, while
ysis gasoline. the feedstock type results only in minor differ-
. The C4 fraction can be refined for butadiene, ences of the basic process route.
butene, isobutene, or mixtures thereof. If no C4
products are desired, C4 dienes and olefins are 5.3.2.1. Front-End Section
hydrogenated and recycled to cracking
. C5 olefins can be either recovered and refined The front-end section (Figs. 32, 33) receives the
to give isoprene, piperylene, and cyclopenta- effluent stream from the cracking furnaces. Its
diene, or hydrotreated in the pyrolysis gasoline main task is to cool the cracked gas stream,
fraction. recovering waste heat and providing it to other
. Ethane is recycled as cracking feedstock or plant sections, to condense and to produce dilu-
used as fuel. tion steam, and to remove heavy hydrocarbon
. Fuel oil is used as such or to produce coke or components such as tar, oil, and heavy gasoline.
carbon black. The resulting purified gas is compressed in the
. Hydrogen is purified and used for hydrogena- cracked gas compression section and dried to
tion steps in the plant; excess hydrogen is sold prepare it for further cryogenic separation in the
or used as fuel in the plant. fractionation section. An acid-gas removal step
. Methane is used as fuel or sold. that eliminates all CO2 and H2S from the cracked
. Naphthalene is recovered for sale or left in the gas is incorporated between the final compressor
pyrolysis fuel oil fraction. stages.
500 Ethylene Vol. 13
Figure 32. Simplified process flow diagram for the front-end process of an ethylene plant cracking gaseous feedstocks
The process configuration of this front-end amounts of heavy hydrocarbons present in the
section is fairly independent from licensors as cracked gas can be removed in the water-quench
they all follow the same process principals. column. Furthermore, additional installations are
However there are many variations in detailed required in the water-quench system and in the
design. Major differences are observed between compressor and drying units to treat the larger
plants processing gaseous feedstocks (ethane, amount of pyrolysis gasoline that condenses in
propane, and butane) and those treating liquid these units. The point when oil quench must be
feedstocks like naphtha and heavier fractions. applied is reached, when substantial amounts of
Processing of cracked gas resulting from liquid C4 hydrocarbons are contained in the feedstock
feedstocks is more complex as higher amounts of mixture.
heavy hydrocarbons are condensed and must be
removed in this section. Primary Fractionation. With liquid pyrol-
ysis feedstocks, the primary fractionation col-
Process Description. The main difference umn is the first step in the cracked gas processing
between the process for gaseous feedstock route. Cracked gas enters the column typically at
(Fig. 32) and liquid feedstock (Fig. 33) is the 230 C. In the column it is contacted with circu-
presence of a primary fractionator that by con- lating oil and, at the top of the column, with a
tacting with circulating oil removes tar and oily heavy pyrolysis gasoline fraction obtained from
material (bp > 200 C) from the cracked gas in the subsequent water-quench tower. Cracked gas
the latter. In the case of cracking gaseous feed- leaves the top of the primary fractionator at ca.
stock only, this step is not necessary, as the small 100 C, free of oil but still containing all the
Figure 33. Simplified process flow diagram for the front-end process of an ethylene plant cracking liquid feedstocks
Vol. 13 Ethylene 501
dilution steam. Hot oil, which functions as a heat separation of hydrocarbons and water. Tarry
carrier, is collected at the bottom of the column material with a density similar to water, which
and, after cooling, recirculated as reflux to the is present in small quantities, tends to accumulate
middle section of the primary fractionator and to in the system and to stick to the surface of the
the quench nozzles downstream of the TLEs. column internals. On-line or off-line washing
Most of the heat contained in the cracked gas with high-boiling, aromatic-rich solvents is ap-
leaving the TLEs is removed by the circulating plied to extend the on-stream time of the system
quench oil. Heat is reused for generation of up to five years. There is furthermore a strong
process steam as well as for other purposes such tendency for formation of emulsions, leading to
as preheating of feedstock, preheating of process fouling problems in the generation of dilution
water, or for other energy consumers at an ap- steam and in the processing of the wastewater
propriate temperature level. Excess oil is re- from the system. Emulsification is avoided by
moved from the primary fractionation system careful control of the pH value in the quench-
and sent out as product. Pyrolysis oil is generally water system.
produced as one fraction, containing all hydro- Numerous options exist in the design and
carbons boiling above 200 C. However some operation of the quench column and primary
plants produce two qualities of pyrolysis oil, one fractionator units for removing pyrolysis
called PGO (pyrolysis gas oil) boiling in the tars, recovering various heavy hydrocarbon
range 200–400 C and PFO (pyrolysis fuel oil) streams, and isolating quench oil for recycle
containing the heavier components. [56, 66, 67].
and/or in the quench tower, further processing pressor. After gravity separation from process
requires compression to ca. 3200–3800 kPa. water this gasoline stream is fractionated in a
Some condensation of water and hydrocarbons stripper to remove C4 and lighter components
occurs during compression, and in the later before routing it to a hydrotreating step. Drying is
stages, acidic gases are removed. Compression required for all liquid and gas streams subjected
is typically performed by a turbine-driven cen- to temperatures below 15 C [56, 59, 65, 66].
trifugal compressor in four to five stages with
intermediate cooling. The number of stages de- Acid-Gas Removal. Before further proces-
pends primarily on the cracked-gas composition sing, carbon dioxide and hydrogen sulfide are
the temperature level of the cooling medium, and removed from the cracked gas by once-through
the highest temperature allowed for interstage (caustic wash) and regenerative solvent (MEA)
discharge. Interstage cooling and temperature scrubbing. Sulfur may also be removed from the
control keep the cracked gas below 100 C to cracker feedstock. [56].
prevent diolefin polymerization and subsequent The acid-gas removal system is typically lo-
equipment fouling. Various injection systems, cated between the 3rd and 4th, or between the 4th
using aromatic rich oil or water, are applied to and 5th stages. In all process configurations acid-
reduce fouling of compressor internals and inter- gas removal must be located upstream of
cooling equipment. Interstage cooling usually the drying unit in order to avoid formation of
employs water coolers to minimize inlet temper- ice and hydrates in the following fractionation
ature in the subsequent stages. First-stage steps.
compressor suction is normally maintained Carbon dioxide is removed because it can
somewhat above atmospheric pressure to prevent freeze at low temperature in heat-exchange and
oxygen intrusion. The operating pressure is set to fractionation equipment. Carbon dioxide can
economically balance yield in the cracking coils also be absorbed into ethylene, affecting product
against higher energy consumption for compres- quality and further processing. Hydrogen sulfide
sion [56]. The compressor discharge pressure is is corrosive and a catalyst poison as well as a
set by the choice of process design and by the potential product contaminant [58, 59]. CO2 and
choice of refrigerant. With a high-pressure de- H2S concentrations in the overhead stream of the
methanization methane condenses in the de- caustic wash are typically below 0.2 ppm.
methanizer overhead condenser. Condensation These acid gases are scrubbed with sodium
temperature varies with hydrogen/methane ratio. hydroxide on a once-through basis or in combi-
The discharge pressure, with the coldest ethylene nation with a regenerative chemical. Regenera-
refrigerant level typically at ca. 100 C, is tive pre-scrubbing before final sodium hydroxide
normally 3200–3800 kPa. Processes involving treatment is applied at high-sulfur feedstocks.
low-pressure or medium-pressure demethanizers This reduces sodium hydroxide consumption,
can use discharge pressures of 2000 kPa only, which is desirable for economic and environmen-
however, in such cases the total compression tal reasons, however, it requires the handling of a
power is fairly constant, because the power is sulfur-rich off-gas stream.
just shifted from cracked-gas compression to Regenerative scrubbing can employ alkano-
refrigerant compressors. The criteria used to lamines, but it is not possible with this treatment
determine suction pressure and discharge pres- alone to lower the concentration of CO2 to that
sure are selectivity and energy consumption, and required to meet standard ethylene specifications
equipment costs. [56, 67] (e.g., to 0.2 ppm). In any case a polishing scrub-
Interstage cooler pressure drops must be kept ber consisting of a caustic wash unit is applied to
low, especially in the initial stages, to reduce achieve the required CO2 specification in the
compressor and energy costs. The water and effluent stream. Acid-gas removal systems are
hydrocarbon condensates may be routed to an- frequently subject to fouling, especially at high
other compressor stage, to the quench column concentrations of C4 and C5 diolefins. Insiders
preceding the compressor, or to a fractionation talk about ‘‘yellow oil’’ or ‘‘red oil’’, an unpleas-
tower. In liquid cracking most of the gasoline antly smelling polymeric material. The fouling
fraction containing the C6 to C8 aromatics is process can be controlled by applying special
condensed in the interstage coolers of the com- inhibitors.
Vol. 13 Ethylene 503
Acid gases liberated from the regenerative 5.3.2.2. Hydrocarbon Fractionation Section
solvent can be incinerated or recovered [56,
59, 66, 67, 69]. Waste caustic, containing sulfides The fractionation section receives the com-
and carbonate in the range of a few % is usually pressed cracked gas at a pressure of 3200–
oxidized and neutralized in a wet caustic oxida- 3800 kPa for further fractionation into different
tion unit or neutralized and stripped, before products and fractions at specified qualities and
feeding it to the sewer system. Spent caustic is battery limit conditions. Over the history of
the most contaminated liquid effluent in the design and construction of ethylene plants many
ethylene plant, because it is the outlet for various different process schemes have been developed
trace components accumulating in the process. In and implemented for this task.
addition to the sulfur and carbonate load the Cryogenic separation is the predominant
stream further carries traces of dissolved hydro- method for cracked-gas separation. Although
carbons, organic acids, ketones, alcohols, and gas separation processes via adsorption, absorp-
aldehydes. tion, or membrane technology has made re-
markable progress in the recent past, it has not
Drying. The cracked gas is saturated with found major application in the ethylene indus-
water before compression and after each inter- try. Rare applications of these methods can be
cooler stage. Moisture must be removed before found in very special cases like revamps or
fractionation to prevent formation of hydrates pretreatment of off-gases from polymerization
and ice. Typically, this is accomplished by chill- plants or from refineries, containing valuable
ing and by adsorption on molecular sieves. Older components, before being sent to the ethylene
plants also used absorption by a glycol scrubbing plant.
system or adsorption on alumina [58]. Drying is Today, three processing routes have gained
arranged before the first fractionation step, typi- commercial importance, with the main charac-
cally after the last compression stage. Before teristics being the first separation step and the
feeding the compressor effluent to the molecular position of the hydrogenation of the acetylene
sieve dryer it is cooled in a water cooler and contained in the cracked gas. These three process
subsequently by propene refrigerant. A tempera- sequences are:
ture of 15 C upstream of the dryer is desirable
for removing as much water as possible to reduce 1. Demethanizer first with tail-end hydrogen-
load on the dryers. However, the temperature ation
must remain above the hydrate-formation point, 2. Deethanizer first with front-end hydrogen-
which lies in the range 10–15 C [56, 66]. Water ation
is adsorbed on molecular sieves, preferably after 3. Depropanizer first with front-end hydrogen-
the highest compression pressure is reached to ation
minimize adsorption costs. Higher pressure al-
lows smaller dryer volume with lower adsorbent These basic processes differ in the configura-
cost and less water removal because the water tion of process steps for any given feedstock, but
content in the gas stream decreases with increas- provide similar overall capabilities for fraction-
ing pressure. Multiple adsorption beds make ation and hydrogenation. The differences are
continuous water removal possible. One or more primarily in the sequence of fractionation and
adsorption beds are in operation while at least hydrotreating steps downstream of cracked-gas
one unit is being regenerated. Regeneration re- compression [56].
quires the use of heated gas that is free of poly-
merizable components. Byproduct methane and Process Description. Compressed cracked
hydrogen used as fuel are typically good choices gas can be:
for this gas [56–59, 66, 67]. In liquid-feedstock
cracking processes large amounts of hydrocar- 1. Condensed and fed to a demethanizer column
bons are condensed at 15 C. If these liquid (front-end demethanizer), as shown in
hydrocarbons are to be fed to the fractionation Figure 34
column they are also dried over molecular sieve 2. Condensed and fed to a deethanizer (front-end
adsorbers. deethanizer), as shown in Figure 35
504 Ethylene Vol. 13
Figure 34. Simplified process flow diagram for the production of ethylene by liquid cracking with a front-end demethanizer
3. Removed from an intermediate compressor vapor are sent to different parts of the plant
stage, condensed, and depropanized in a [66, 62].
column, whereby the light gas is returned to Traditionally the demethanizer first/tail-end
the last compressor stage (front-end depropa- hydrogenation process sequence was used by
nizer), as shown in Figure 36 American contractors. With the need for reduc-
tion of energy consumption in the separation
Combinations are possible; for example, section and process simplification for cost rea-
intermediate compressor stage condensate and sons, the deethanizer first/front-end hydrogena-
Figure 35. Simplified process flow diagram for the production of ethylene by liquid cracking with a front-end deethanizer
Vol. 13 Ethylene 505
Figure 36. Simplified process flow diagram for the production of ethylene by liquid cracking with a front-end depropanizer
tion process, which had long been used by Linde, propadiene, propane, and propene are taken as
was also applied by some American contractors. an overhead stream. This overhead fraction is
A comparison of all routes has shown that hydrogenated to remove methylacetylene and
this sequence seems to have the best energy propadiene, which can also be recovered by
efficiency [70]. New developments in this area distillation or absorption and stripping. In the
are the combination of the advantageous se- propene fractionation step, propene is recovered
quence with special equipment (dephlegmators) for sale and propane for recycle. The propene
[71] and the application of washing steps for product can be of chemical grade or polymer
demethanization [72]. grade with additional purification. Depropanizer
bottoms are sent to a debutanizer for separation
Front-End Demethanizer (Fig. 34). The hy- into other product streams (C4 materials, raw
drocarbon-separation sequence begins with re- pyrolysis gasoline, C5 materials, aromatics, etc.)
moval of methane and lighter components, pri- [56, 58–60, 65, 66].
marily hydrogen, from higher molecular mass
components. Hydrogen may be removed before Front-End Deethanizer (Fig. 35). Deetha-
or after methane. The bottom product is routed to nization of dried cracked gas is used as the first
a deethanizer column where acetylene, ethane, fractionation step to produce an overhead stream
and ethylene are removed as overhead product, of ethane and lighter components, and a bottom
and C3 and heavier components as bottom stream of C3 and heavier materials; subsequently,
product. the lighter components are hydrogenated to re-
Typically, the overhead product from the move acetylene and fractionated cryogenically.
deethanizer is first hydrotreated to convert acet- Because this overhead stream is hydrogen rich,
ylene to ethylene and ethane. This treated over- no supplementation is necessary for hydrogena-
head mixture is then fractionated to ethylene tion. During the chilling and demethanizer oper-
product and ethane recycle. ation, the overhead is separated into hydrogen
The bottom product from the deethanizer is and methane; the bottom stream is fractionated to
depropanized to separate C4 and heavier compo- yield ethylene product and ethane; and the ethane
nents as a bottom stream; methylacetylene, is recycled to the cracking furnaces.
506 Ethylene Vol. 13
The bottom stream from the deethanizer is (ca 10 000 t/a) This quantity, however, on the
treated in the same way as in the front-end other hand is too large to be totally used by the
demethanizer system described above. welding industry.
Front-End Depropanizer (Fig. 36). Depro- Pre-fractionation Feed Chilling. Before be-
panization of dried cracked gas is used as the first ing fed to any of the fractionation towers, dried
fractionation step to produce a propane and cracked gas must be cooled and partially con-
lighter component overhead stream and a C4 and densed. Dried cracked gas is cooled by the re-
heavier bottom stream. The depropanizer over- frigerant systems and by the low-temperature
head stream is compressed and hydrogenated to product and recycle streams leaving the cold
remove acetylene, and to partially hydrogenate fractionation equipment down to a temperature
methylacetylene and propadiene. It is then of typically 140 to 160 C. At this tempera-
chilled and demethanized, and the bottom frac- ture C2 components are entirely removed by
tion of demethanization is deethanized. The partial condensation, and the noncondensed gas
deethanizer overhead components are fraction- stream has a hydrogen concentration of 80–
ated to ethylene product and ethane, which is 95 vol %. The type of refrigerant, number of
recycled as cracking feedstock. Deethanizer bot- refrigeration levels, and the design of the refrig-
tom product is hydrotreated to remove methyla- eration and heat-exchange systems depend on the
cetylene and propadiene, and fractionated to temperature and pressure required in the down-
propene product and propane, which is recycled stream fractionation equipment. Fractionation
to the cracking furnaces. The depropanizer and purification consume much energy. Cryo-
bottom components are fractionated to produce genic purification of methane, ethane, and ethyl-
C4 materials and raw pyrolysis gasoline [59, 60, ene requires costly refrigeration. Design optimi-
65, 66]. zation is complex because:
For all three of the above-mentioned basic
processes numerous process variants exist. For 1. The most efficient routing must be considered
liquid cracking acetylene hydrogenation is al- for the condensates and vapor streams from
ways performed in the C2 stream, in the C2 or in each stage of the cool-down sequence in the
the C3 stream. In the case of cracking gaseous individual refrigeration loops (e.g., 2–6 stages
feedstock with little coproduction of C4 hydro- each)
carbons the hydrogenation step can also be ar- 2. The energy requirements for fractionation
ranged in the total cracked gas stream during or must be determined
just after cracked-gas compression (after or be- 3. The freezing of components, such as acety-
fore drying). This is not feasible for cracked gas lene, butadiene, and benzene, must be avoided
streams resulting from liquid cracking because
1,3-butadiene, typically a valuable byproduct, When acetylene content is high, prevention of
would be cohydrogenated almost completely to freezing and safe hydrogenation are important.
butene and butane. Also of importance from a safety standpoint for
Acetylene may also be recovered for sale by the chilling section and downstream equipment is
an absorption process. This absorption process the choice of appropriate construction materials
step is located in the gas phase upstream of the for cryogenic conditions [56, 58]. Process equip-
ethylene fractionation column. N-methyl-2-pyr- ment that may accidentally be exposed to cryo-
rolidone, acetone, and N,N-dimethylformamide genic conditions should also be carefully studied.
are typical solvents used for acetylene recovery. National standards are available in most coun-
The acetylene absorption tower yields a very tries to assist in making appropriate selections
pure ethylene product, because acetylene is re- [56, 58].
moved practically down to the detection limit.
Acetylene recovery, however, is becoming Demethanization. Demethanization of
more and more a niche application due to the cracked gas separates methane as an overhead
disappearing importance of the acetylene chem- component from C2 and heavier bottom compo-
istry and due to the limited acetylene production nents; concurrently, hydrogen is removed from
rate that can be obtained from a large-scale plant the cracked-gas stream and may be obtained as a
Vol. 13 Ethylene 507
product by purification before or after demetha- The industry offers a large variety of combi-
nization. In case of naphtha cracking hydrogen is nations of process steps to achieve the desired
recovered at high purity because it is needed in separation result. All processes consist of a
the plant itself for various hydrogenation steps combination of cooling steps, partial condensa-
and because any excess can typically be sent out tion, and a demethanizer tower system. Liquids,
when the plant is embedded in a refinery envi- knocked out during cooling are fed to the de-
ronment. In gas-cracking plants hydrogen is only methanizer at an appropriate position. Some
required at low quantities. The bulk of hydrogen licensors apply special equipment like dephleg-
is recovered together with methane, forming the mators or recontactors in this process configu-
tail-gas stream, that is sent to the fuel system after ration to perform a preseparation of the material
expansion. before sending it to the column. Both dephleg-
Methane is typically used as plant fuel or sold; mators and recontactors incorporate an addi-
C2 and heavier components are sent to the recov- tional number of theoretical equilibrium
ery system. This overall fractionation is impor- stages in the cooling train contributing to the
tant from a design and operational standpoint demethanization.
because of its high share of the capital, energy, Demethanizer systems operate in a wide pres-
and fuel consumption of the ethylene plant. sure range between 1000 and 3500 kPa (LP, MP,
Demethanization typically consumes the greatest and HP demethanizers), each of these having
proportion of net energy from the refrigeration their specific characteristics.
system (see Fig. 37 and discussion of refrigera- A special challenge in this process is the
tion, Section Refrigeration) [61, 69]. provision of the respective chilling duty for
In the demethanizer system and the associated individual cooling steps. The classical method
process for the isolation of high-purity hydrogen for generating chilling duty down to a tempera-
the lowest temperatures in the plant (down to ture of 100 C is the refrigerant cascade of
165 C) prevail. ethylene and propene. Temperatures below
Figure 37. Distribution of heat load and work requirement of the refrigeration system in a typical front-end demethanizer
ethylene plant*
A) Distribution of heat load and work requirement
a) Net heat absorbed by the refrigeration system; b) Net work done by the refrigeration system
B) Relative cost of heat absorbed by the refrigeration system at different temperatures
*Reprinted with permission [69].
508 Ethylene Vol. 13
100 C are achieved by one of the following perature, thus reducing fouling in reboilers. As
methods: with the demethanizer, these designs conserve
refrigeration energy but increase capital costs
. Adding another element in the refrigerant and operating complexity. The overhead product
cascade, namely a methane refrigerant condensation temperature is typically ca. 0 to
cycle 50 C, based on a column operating pressure of
. Generation of a light recycle stream, i.e., 1500–2700 kPa [59, 60, 65].
vaporizing condensed cracked gas fractions
and recycling the vapors to the cracked gas Depropanization of cracked gas separates
compressor propane and lighter fractions as overhead com-
. In the case of gas cracking, hydrogen is not ponents from C4þ fractions as bottom compo-
recovered at high pressure and can be depres- nents. Feed streams from compression, and
surized to fuel gas pressure in a turbo-expander, sometimes streams from the gas-chilling section,
generating chilling duty at very low tempe- can be routed to the depropanizer, which, com-
rature pared to other fractionation units, requires less
. Applying a mixed refrigerant cycle that covers refrigeration because of its higher operating
the full temperature range temperature (Fig. 37) [69].
The feed stream to the depropanizer comes
[63, 67]. primarily from the deethanizer when front-end
The demethanizer bottom stream contains C2 demethanization and deethanization are em-
and heavier components. With the front-end ployed. With front-end depropanization, the
demethanizer, components from C2 through py- feedstock is taken from the gas dryers. In the
rolysis gasoline may be present. However, with simplest case, the dried cracked-gas feed stream
front-end deethanization, C3þ components are is separated into a propene–propane overhead
removed, and with front-end depropanization, stream, which contains small amounts of methy-
C4þ components are removed. The demethanizer lacetylene and propadiene, and a bottom stream
design changes significantly as heavier compo- which contains components from C4 materials
nents are eliminated, especially with regard to the to raw pyrolysis gasoline. Energy requirement is
refrigeration needed to condense the incoming reduced by mixing smaller feed streams re-
cracked-gas feed stream and to reboil the bottom moved from intermediate compression or gas-
stream. chilling stages with the main feed stream, or by
having them enter separately at a point in the
Deethanization. Deethanization of cracked depropanizer consistent with the composition of
gas separates acetylene, ethylene, and ethane as column components. Condensate is usually
overhead components from C3þ bottom compo- stripped before entry into the depropanizer
nents. In newer plants, low-pressure fraction- [56, 67].
ation may be used, or feed streams from the Operating pressure and temperature of the
cracked-gas chilling section can be supplied as depropanization step in ethylene plants, even
multiple feeds to the deethanization tower. The downstream of the deethanizer, are kept low to
deethanizer is usually the third largest user of reduce fouling of the fractionator by acetylenic
refrigeration energy in a front-end demethanizer and diolefinic contaminants. Hydrogenation of
ethylene plant (Fig. 37) [56, 66, 67, 69]. cracked gas in the compressor zone lowers the
With front-end demethanization and front- amount of these polymerizing contaminants sub-
end depropanization, the feed stream to the stantially, but also destroys most of the butadiene
deethanizer comes primarily from the demetha- [56, 60, 65].
nizer. With front-end deethanization, the deetha-
nizer feed comes from the chillers that follow the Debutanization. Debutanization of cracked
gas dryers. In the simplest cases, single feed gas separates C4 materials as overhead compo-
streams from these units are separated into over- nents from C5 and heavier fractions as bottom
head and bottom fractions for further processing. components. The feed stream comes typically
[56]. Dual-pressure deethanizer systems improve from the depropanizer column or is a depropa-
energy consumption and reduce the bottom tem- nized condensate stream from the compressor.
Vol. 13 Ethylene 509
The mixed C4 overhead fraction may be sent to an In the case of (1) and (2) any methylacetylene,
extraction unit for removal of 1,3-butadiene and propadiene and butadiene, present in the gas
further processing. The bottom stream and the stream is cohydrogenated. (methylacetylene ca.
debutanized fraction from the compression sec- 80 %, propadiene 30 %, butadiene > 90 %).
tion can be used as pyrolysis gasoline feedstock Although hydrogenation in the cracked gas (1)
or processed to produce aromatics and specialty may offer advantages for the lighter feedstocks,
chemicals feedstocks [56]. disadvantages exist with heavier feedstocks. In
particular, the volume of gas treated at this stage
Acetylene Hydrogenation. Cracked gas is is high; butadiene is hydrogenated and lost; and a
selectively hydrogenated to remove acetylene single hydrogenation to concurrently remove
from ethylene, except when acetylene is recov- acetylene, methylacetylene, and propadiene to
ered for sale. Hydrogenation is performed with the required levels without significant olefin loss
palladium-based catalysts. Ethylene specifica- is not possible. Hydrogenation of individual
tion requires less than 1 ppm of acetylene, thus mixed C2 and C3 streams after deethanization
acetylene content at the outlet of the hydrogena- and depropanization, respectively, appears to
tion must be < 0.5 ppm. Pressure ranges typically permit more efficient use of catalyst and result
from 20 to 35 bar and the temperature from 25 to in higher product yields. However, proponents of
100 C. There are two basic processes for the the front-end deethanization and depropaniza-
hydrogenation of acetylene. tion process with front-end acetylene hydro-
genation report that bed sizes are equivalent for
Tail-End Hydrogenation. Acetylene hydro- that reaction. Higher hydrogen concentration
genation takes place in the gas phase of a pure C2 and improved catalysts allow higher gas space
fraction, consisting of ethylene, ethane, and acet- velocities than can be achieved down-
ylene only. The unit is typically incorporated stream [66].
after demethanization, upstream of the C2 frac- General advantages of the front-end hydro-
tionation tower. Hydrogenation reactors consist genation versus the tail-end hydrogenation unit
of one or two adiabatic beds. Hydrogen is added are: (1) no hydrogen make up is required as
upstream of the reactor at a molar H2/C2H2 ratio hydrogen is already present in the feed stream;
of ca. 1.5–2, resulting in an ethylene gain of up to (2) longer run length between catalyst regenera-
50 % of the acetylene present. Hydrogen and tions; (3) No removal of light ends, as required in
small amounts of methane and CO introduced tail-end hydrogenation, is necessary.
after demethanization must be removed by addi- Front-end hydrogenation is typically con-
tional fractionation. Sometimes purging the light ducted in multistage adiabatic beds with inter-
ends from the overhead ethylene fractionator cooling, or less frequently in a single tubular
condensate is possible, but additional multistage reactor that allows an isothermal reaction.Due to
fractionation is usually required in the ethylene the high concentration of hydrogen and ethylene
fractionator or in a small separate demethanizer. in the process gas front-end hydrogenation re-
A useful design provides five to ten overhead quires a very selective catalyst, that promotes the
stages above the product drawoff point in the hydrogenation of acetylene only.
ethylene fractionator column for further separa- Acetylene hydrogenation requires heat-
tion of the light ends. The overhead condensate is exchange systems for incoming low-temperature
returned to the top of the tower, and the light ends process streams (2) and (3). Hydrogenation in the
are removed from the overhead partial condenser compressor section (1) does not require the heat-
for reprocessing [56, 61, 66, 69]. exchange system necessary for cryogenic
streams. Most of the troublesome polymerizable
Front-End Hydrogenation. Acetylene is components are removed before fractionation,
hydrogenated: although rapid fouling of the hydrogenation
bed must be avoided. Hydrogenation may be
1. In the total cracked gas stream after or before necessary before chilling if a high acetylene
drying concentration in the cracked gas would result
2. In the C3 stream with front-end depropanizer in plugging or in unsafe downstream operation
3. In the C2 stream with front-end deethanizer [56, 58, 66].
510 Ethylene Vol. 13
Although tail-end hydrogenation is the most erant compressor. After compression, propene
common process in currently operating plants, it vapors are condensed in the reboiler, providing
seems there is a strong tendency to increasingly heat duty. By means of this system the propene
apply the front-end hydrogenation system in new refrigerant compressor acts as an indirect heat
projects. This tendency is supported by a contin- pump, shifting heat from the condenser of the
uous improvement of front-end hydrogenation column to the reboiler. The top of the column is
catalysts. New catalysts show an increased oper- equipped with some pasteurization trays to re-
ating temperature window in which only acety- move light ends introduced when acetylene is
lene or dienes are selectively hydrogenated. Fur- hydrogenated in the feed stream to this column.
thermore, new catalysts are less sensitive toward Ethylene product is withdrawn as a liquid side
CO. These improvements result in higher opera- stream some trays below the top, pumped to the
tional stability decreasing the danger of reaction required product pressure, and delivered to bat-
runaway, where in addition to acetylene also tery limits after vaporization and heating.
ethylene participates in the reaction. The shapes
of catalyst particle were typically little spheres, Heat-Pumped C2 Fractionation. In heat-
tablets, or extruded particles of a size of a few pumped C2 fractionation, the column operates
millimeters. New catalysts are available with at a pressure of ca. 800 kPa. Overhead gases of
different geometrical structures such as rings or the column, consisting of on-spec ethylene, are
other shapes that result in lower pressure drop. routed to a compressor after heating to ambient
This contributes in overall energy saving, be- temperature in a feed–effluent exchanger and are
cause the front-end hydrogenation is located in compressed to ca. 2000 kPa. Part of the com-
the main cracked gas stream where this pressure pressed ethylene vapor is cooled and routed to the
drop directly affects the cracked gas compressor reboiler where it is condensed, providing heat
outlet pressure. duty for reboiling. The condensed ethylene is
recycled as reflux to the top of the column.
Ethylene Fractionation. Ethylene fraction- Ethylene product is discharged to battery limits
ation separates ethylene as a high-purity over- from the discharge side of the compressor. Heat-
head product (> 99.9 wt %) from ethane, which pumped ethylene fractionation can use a dedi-
is combined with propane and recycled for crack- cated compressor. More common is the integra-
ing. For this difficult fractionation, the net work tion of the heat-pumped ethylene splitter in the
done by the refrigeration system is high because ethylene compressor, using the 3rd stage of this
of the high reflux and low temperature required compressor as a heat pump.
(Fig. 37) [56, 69]. Fractionation requires a high This process has some advantages over the
reflux ratio (ca. 4) and as many as 90–125 high-pressure fractionation process with respect
separation stages [59, 60, 65, 66, 69]. The ethyl- to investment and energy consumption. Less
ene purity desired is typically > 99.9 wt %. The equipment is involved, and because of the better
feed stream comes from the acetylene-removal relative volatility of ethylene and ethane at lower
step that follows chilling, or from the demetha- pressure, a lower reflux ratio and less column
nizer or deethanizer. trays are required,altogether resulting in lower
There are basically two processes in commer- power consumption, smaller column size, and
cial use: high-pressure fractionation and heat- generally less equipment. However it is not
pumped C2 fractionation. feasible to use the heat-pumped process in com-
bination with tail-end hydrogenation because of
High-Pressure Fractionation. High-pres- the light ends present in the feed stream.
sure fractionation, operating in the pressure Ethylene is generally discharged to battery
range of 1700–2800 kPa, is typically used in limits as a gas. However, production of up to
tail-end hydrogenation systems. Heating and 50 % of production as the liquid phase and the use
cooling of the column is integrated into the of storage facilities is also practiced.The ethylene
propene refrigeration cycle. Low-pressure pro- plant is typically equipped with ethylene product
pene refrigerant is vaporized in the top condens- storage capacity in order to balance production
er, providing chilling duty. Vaporized propene is and consumption of downstream plants. Two
typically compressed in two stages of the refrig- storage types are commercial practice:
Vol. 13 Ethylene 511
Semirefrigerated storage at about 1500 kPa however it is practically not used because of
and 40 C, using spherical containers of a lacking demand for this product.
size of up to 3000 m3 (for smaller storage
inventories). C4 Hydrogenation. The C4 cut from the top
Atmospheric storage tanks, operated at atmo- of the debutanizer typically contains small
spheric pressure and 103 C. The size of these amounts of vinylacetylene and ethylacetylene,
tanks is not limited, typically in the range of ca. 50 % 1,3-butadiene, and a few percent of
10 000–20 000 m3. Tank systems are usually butanes; the balance consists of various types of
equipped with liquefaction facilities in order to butenes, of which isobutene is the most impor-
handle boil-off gases and incoming flash gases. tant. Depending on the nature of the downstream
Product vaporization facilities for the full capac- processes it may be necessary to hydrogenate
ity of the plant are provided in order to continue some of the unsaturated components. The fol-
ethylene supply to downstream users in the case lowing hydrogenation steps are in commercial
of a plant upset. use:
Pyrolysis Gasoline Hydrogenation. Pyroly- This separation to polymer grade propene re-
sis gasoline — the C5 to C10 hydrocarbon product quires typically 150–230 stages and a reflux ratio
fraction — consists mainly of aromatics. The of 20 because of the close boiling points of
nonaromatics are mainly unsaturated hydrocar- propene and propane. Two basic processes are
bons with a high portion of acetylenes and dienes. applied for this difficult separation task: poly-
This stream is unstable and cannot be stored, as mer-grade fractionators operate at ca 1800 kPa,
the unsaturated components react further, form- with cooling water in the overhead condenser and
ing polymers and gum. Depending on the down- hot quench water in the reboiler. In the case of
stream processes pyrolysis gasoline is hydroge- naphtha cracking and where sufficient waste heat
nated and fractionated in different steps. The is available from the hot quench water cycle this
most common process route is as follows: is the most economic process. If no waste heat for
reboiling is available, or where upstream cooling
1. Selective hydrogenation of the total gasoline water temperature is higher than 35 C a heat-
to hydrogenate acetylenes, dienes, and sty- pumped propene fractionator is applied. In this
rene to olefinic compounds. After stabiliza- case the fractionator operates at ca. 800–
tion and removal of oil this stream is suitable 1100 kPa, and the overhead gases are com-
for use as motor fuel. The reaction is typically pressed and condensed in the reboiler. By means
controlled in a way that the residual styrene of this process the condenser heat is raised to a
value is ca 0.5 %. higher temperature level, and further use is made
2. Fractionation of the effluent of the 1st stage of it in the reboiler. The advantage of this system
hydrogenation into a C5 cut, a C6–C8 heart cut, is that no external heat for reboiling and only
and a C9þ cut. small quantities of cooling water are required.
3. The C6–C8 cut is further processed in a 2nd The fractionation design depends on the concen-
stage hydrogenation step to convert olefins to tration of propene in the feed, which varies from
paraffins and naphthenes and to convert all 70 % for propane cracking to 95 % for naphtha
sulfur to H2S, which is removed from the cracking [66, 67, 69].
product in a downstream stripper. this process The heat pump is typically driven by a dedi-
is necessary to prepare the heart cut for aro- cated compressor, in particular cases the heat
matics recovery. The specification is con- pump is integrated into the propene refrigeration
trolled via the bromine number, which is cycle combining heat pump and 3rd stage of this
typically 0.5. machine.
The feed stream to the propene fractionator
C2, C3, and C4 hydrogenation as well as 1st usually comes from the methylacetylene and
stage, selective gasoline hydrogenation use pal- propadiene hydrogenation step. Excess hydrogen
ladium-based catalyst. Palladium catalyst, how- and methane are purged in an upstream stripper
ever, are sensitive with respect to metallic poi- or as light ends in the column overhead or from
sons such arsenic or mercury, that may be present the overhead condensate [59, 60, 65–67, 69].
in the cracked gas in small traces, originating
from feedstock contaminants. If such contami- Hydrogen Purification. Hydrogen is pro-
nants are to be expected, the Pd catalyst must be duced in the cryogenic section of the plant at a
protected by guard beds, consisting of various purity of typically 80–95 vol%. However, the
metallic oxides like CuO, ZnO, PbO, impregnat- product stream contains some 1000 ppm of car-
ed activated carbon, and other materials. The 1st bon monoxide. Hydrogen product is required in
stage gasoline hydrogenation catalyst, however, the ethylene plant as make-up stream for the
should preferably be based on nickel metal if hydrogenation units. Excess hydrogen is typical-
these contaminants are present, because nickel ly a desired product. However, hydrogen must be
catalysts are much less sensitive to them. free of carbon monoxide as CO is a poison for all
hydrogenation processes. Today two processes
Propene fractionation separates propene are in commercial use in ethylene plants to purify
as a chemical-grade overhead product (typically hydrogen: (1) methanation of CO in a catalytic
93–95 wt % min.) or more frequently as poly- process, converting CO to methane and water,
mer-grade propene (> 99.5 wt %) from propane. after which the effluent must be dried in adsorber
Vol. 13 Ethylene 513
beds; (2) hydrogen purification by adsorption in a Figure 37 shows the net heat and work re-
pressure-swing adsorption unit, producing CO- quired in a typical front-end demethanization
free high-purity hydrogen. plant with liquid feedstock. The less expensive
refrigerant, propene, is used from þ 25 to
40 C and the more expensive ethylene, from
5.3.3. Utilities ca. 40 to 100 C. The latter requires higher
work input per unit of refrigeration;for example,
Refrigeration. Refrigeration in ethylene Figure 37 shows that 41 % of the heat absorbed
plants is important and costly. Refrigeration by the ethylene refrigeration system requires
optimization is vital in plant design. Typically, 58 % of the net work [69]. Refrigerants are
two different refrigeration systems are em- usually generated by compression to 1600–
ployed, namely, ethylene and propene (or pro- 2000 kPa in multistage units, followed by expan-
pene–propane), each of which generates chilling sion to generate the lowest refrigeration temper-
duty at two to five different temperature levels. ature. Superheated ethylene is cooled and con-
Propene refrigeration is designed as a closed- densed with propene refrigerant. Propene, after
loop system in which the heat removed by cool- compression, is cooled with process cooling
ing water or by air cooling by condensing the water [59, 66, 69]. With open-loop systems,
refrigerant after the final compression stage. which are used less frequently, products are
Ethylene refrigeration systems are designed as circulated in the refrigeration loops rather than
closed- and open-loop systems. Open-loop cy- isolated. Careful operation and reliable design of
cles integrate the ethylene-fractionation tower in compressors (gas seals) reduces contami-
the refrigeration system. Propene and ethylene nation [66].
refrigerant systems act as a chilling cascade. Heat
removed from the process by the ethylene cycle Energy. Utility consumption, expressed in
at temperatures below 50 C is shifted to the joules per kilogram, is the energy required to
propene cycle by condensing high-pressure eth- produce 1 kg of ethylene product. Feedstock,
ylene refrigerant by means of vaporizing low- coproducts, and process design should be de-
pressure ethylene refrigerant. Refrigerant tem- scribed fully for comparative purposes. Process
peratures are chosen to accommodate diverse optimization has to consider the cost of energy
plant needs most efficiently. Methane refrigera- relative to capital costs, ease of process opera-
tion by simple expansion (not employed as a tion, product and byproduct quality control re-
refrigeration loop) generates additional cooling quirements, safety, and many other issues. The
and especially the lower temperatures needed to specific solution is always a compromise be-
purify hydrogen for special purposes. tween the above mentioned parameters. Since
Some processes add a third refrigeration cycle the early 1970s until today, increased energy
to the cascade, using methane as refrigerant for costs led to a reduction of energy consumption
the generation of low-temperature chilling duty by nearly 50 %. This was accomplished by
below 100 C. applying sophisticated process steps and design-
Ethylene, propene, propane and methane are ing the plants with a high degree of heat integra-
used because of their physical properties and tion. Waste heat from cracked-gas cooling is
availability in the ethylene plant [67]. utilized wherever possible, heat pumps, side
One licensor recommends the application of reboilers, low-pressure distillation are applied.
a mixed refrigerant system, covering the full Modern design tools such as advanced process
temperature range from 150 C to þ10 C by simulators or pinch analysis programs help the
one compressor only. Advantage of this system designer to find the optimum solution for an
is the saving of one or even two compressor- individual case. Efficiencies of major energy
turbine sets. This process applies a mixture of consuming equipment such as cracking furnaces
ethylene and propene or even ethylene, propene, and compressor-turbines have continuously been
and methane as refrigerant. Consequently the improved.
QT curve of the vaporizing coolant is not Approximate energy consumption to produce
isothermal but follows on increasing line. 1 kg of ethylene from various feedstocks is in the
[76]. range of 15 000 kJ/kg to 27 000 kJ/kg (see below)
514 Ethylene Vol. 13
A reduction of ca. 2000 J/ per kilogram eth- process the heat must be discharged to the ambi-
ylene product is possible by using hot exhaust ent. Cooling is most commonly performed via a
from gas turbines in the pyrolysis area as com- cooling-water cycle, discharging heat to the am-
bustion air to preheat combustion fuel, or in a bient via a cooling tower. In areas where cooling
heat-recovery boiler. The turbines may also op- water is not available (e.g., new large petrochem-
timize energy use to produce electricity or can ical complexes in the Persian gulf area) heat is
drive fractionation compressors and heat pumps discharged to the sea via the primary/secondary
[56, 58, 63, 64, 66, 67, 69]. The application of cooling-water cycle, or to the air via air-fin cool-
such a combined-cycle system, however, is cost- ers. Both options require higher process tempera-
ly and pays off only under special circumstances. tures leading to a slight reduction in energy
Such installations are installed mainly in Japan efficiency and higher installation costs.
and Korea, few of them in the rest of the world. In The ethylene process requires a number of
none of the new large-scale crackers built in the utilities, some of them like fuel gas and steam
early 2000s such installations are applied. being produced in the plant itself. Depending on
Most of the energy consumed is introduced feedstock and plant specifics fuel and steam must
into the ethylene process via firing the cracking be supported by import or may be in excess.
furnaces. The recovery process is driven by waste Typical consumption figures for various feed-
heat, recovered from the cracking furnaces via stocks for a standard-size 1000 t/a ethylene plant
steam production in the TLEs or by recovering are summarized in Table 11.
heat from the furnace effluent stream. The main Because feedstock composition, flow
energy consumers in the recovery section are the schemes, and product distribution are undefined,
cracked-gas compressor and the refrigerant com- these values are approximate but they are
pressors, in which a total power of ca.0.6– representative.
0.7 kWh per kilogram ethylene is typically con-
sumed. This power is usually provided by steam
turbines, driven by steam generated and super- 5.3.4. Process Advances
heated in the cracking furnaces.Steam produced
in the cracking furnaces and steam consumed in Major advances have been made in feedstock
the ISBL ethylene plant is typically balanced. availability and process design [56, 69],:
Depending on feed and byproducts some steam
export or import is experienced. . Feedstock cost and availability, new cracking
technology, and concerns for the environment
Cooling. Ethylene production is a very en- and health have influenced changes in process
ergy-intensive process. Only some 20 % of the technology.
heat input is absorbed by the chemical reactions . Rapid development has occurred in process
of the olefin production. The balance drives the control, data management, and optimization
process by driving turbines and pumps, heating systems. Control of individual units, as well as
columns, and process streams. At the end of the of the overall process, has had a significant
impact on operations. Improved analysis and current technology. However, it seems that tech-
cracking-simulation models are required to nical constraints may not be the ultimate limiting
more fully apply state-of-the-art process factor. The industry will face the challenge of
control. building larger plants if demanded by the market.
. Major improvements have been made in the Nontechnical issues such as logistic, feed avail-
selectivity and efficiency of cracking by oper- ability, product offtake, and risk analysis will
ating at higher temperature. Coils with shorter dominate this decision.
residence time and faster quenching systems
have been developed. Energy requirements
have been reduced by heat recovery from 5.4. Ethanol based Production of
furnace flue gas, economizer gas, and cracked Ethylene
gas; refrigeration energy requirements have
been lowered by increased application and Ethanol (! Ethanol, Section 5.1.1.) (space-
improved design of heat-exchange and distil- filling model in Fig. 38) can be produced com-
lation systems. Use of gas turbines has in- mercially by hydration of ethylene, a reaction
creased, with the sale of electricity generated. known for more than 100 years, or by fermentation
At the same time, control, reliability, and of starches, sugar crops, or lignocellulose [77].
efficiency of operation have improved [66, 67]. The synthetic production of ethanol from
. The reliability,plant availability service life, ethylene is currently not economical because of
have considerably improved.Plants are de- high raw-material costs and accounts only for
signed today for uninterrupted operation be- less than 5 % of world’s ethanol production.
tween turnarounds of five years. More than 95 % of world’s ethanol production
. Improved fractionation process designs pro- stems from agricultural crops with increasing
vide additional flexibility and further reduce share. A proportion of 35 % of the ethanol is
process energy consumption while meeting used in beverages or food applications whereas
plant-reliability and product-quality demands 65 % is utilized as fuel.
[67]. As can be seen from Table 12, the biomass
. Improved hydrogenation catalysts allow more used for production of ethanol can vary in a wide
selective and more stable removal of impuri- range in composition.
ties and better quality control. Independent of the biomass utilized for fer-
mentation, four main steps are always involved in
5.3.5. Plant Size the production of bioethanol:
At the beginning of industrial ethylene produc- 1. Feedstock treatment to get a sugar solution
tion, in the 1950s, first commercial ethylene 2. Addition of yeasts or bacteria to convert sugar
plants had a standard size of some 20 103 t/ into ethanol and CO2
a. In the next generation of plants, built in the 3. Distillation to separate ethanol from fermen-
1960s, plant capacity was already expanded to 60 tation broth
80 103 t/a. The era of large-scale plants 4. If required dehydrating (water removal)
started in the 1970s when the standard size
reached some 300 400–103 t/a. Since then
until today typical plant capacity has continu-
ously been increased to more than 106 t/a.
Most of the large crackers, contracted during the
boom period 2004–2006, most of them in the
Middle East, have an ethylene capacity of 1 Color
1.5 106 t/a. Fig
Table 12. Typical composition of the main feedstocks used for ethanol production [78]
Sugars, wt% Fiber, % Protein, wt% Oil/fat, wt% Ash, wt% Water, wt%
Color
Fig
Figure 39. Bioethanol production in Brazil, the EU, and the United States (1975 – 2006) [79]
Vol. 13 Ethylene 517
Table 14. Productivity of first-generation biomass for ethanol pro- 420 US$/t, and in the case of US and Canada corn
duction [83, 84]
860 US$/t. European cereals and sugar beet result
Sugar cane Sugar beet Corn in raw material costs of 600 – 1000 US$/t.
A typical process scheme of the typical plants
Ethanol, L/ha 5500 5000 3000
Nitrogen fertilizer, kg/ha 64 101 164
for ethanol from sugar cane in Brazil with inte-
grated sugar and energy (electricity) production
is shown in Figure 41.
Figure 41. Scheme of a sugar-cane-based bioethanol refinery with integrated electricity and sugar production
Figure 42. Net naphtha costs (naphtha minus byproduct revenue) per ton ethylene and costs of wheat (Canada, US) and sugar
cane (Brazil) [10, 85, 86] (average wheat and sugar cane costs 2000–2007)
nonreacted ethanol is separated from gaseous much smaller. Due to the high selectivity (99 %),
products. In the caustic wash system, oxygenate the amount of unwanted byproducts is small. The
byproducts are removed and a crude ethylene energy consumption for the dehydration varies
stream leaves to a final purification unit in order according to the required purification grade. In
to obtain the purity required in the downstream total, the ethanol-based ethylene production re-
application. quires less than half of the energy consumption of
In the patent literature, several schemes with a modern steam cracker.
fixed- or fluidized-bed reactors are described CO2 emission per ton of ethylene is lower as a
[81]. consequence of the selectivity (99% vs. 40 % in a
For polymerization to polyethylene, the final naphtha cracker) by almost 60 %.
purification has to bring the coproducts, such as As an energy source, bioethanol in principle is
oxygenates, hydrocarbons, etc to the typical carbon-neutral. The amount of CO2 released
polymer specification by distillation, adsorption, during ethanol production and combustion has
etc. already been absorbed from atmosphere during
Other applications such as ethylene for EDC the growth of the crops due to photosynthesis.
requires less stringent specification and will have However, application of fertilizers during growth
a simpler purification unit. of crops has a negative impact on the greenhouse
Due to the economics and the availability of gas balance.
low-cost ethanol in sufficient quantities in Brazil, An overall CO2 balance for ethanol as biofuel
several projects have been announced recently. (including transportation and the process itself)
Solvay announced a 60 000 t/a bioethylene plant shows 70 % lower CO2 emissions compared to
based on sugar-cane-derived ethanol for produc- the balance for fossil fuel [91, 84, 87, 92]. For
tion of 360 000 t/a of PVC in Santo Andre ethylene production, CO2 emissions must be
(Brazil). Braskem plans a 450 000 t/a biopo- even less because this is a more selective process.
lyethylene plant in Brazil based on sugar-cane Data for CO2 balances are not published, but a
ethanol, to be started up in 2009. DOW has a joint significant reduction of more than 80 % of CO2
venture with Crystalserv in Brazil and plans a emissions and significantly less NOx production,
350 000 t/a Dowlex plant for linear low-density due to lower temperatures, can be assumed.
polyethylene to start up in 2011 [88–90]. In summary, from environmental point of
These three projects together represent view a bioethanol-based ethylene production is
860 000 t/a of ethylene, equivalent to 1.365 much better than the conventional steam crack-
106 t/a or 1.72 109 L of ethanol. ing process because less CO2, CO, NOx,
and particulates are produced due to the use of
renewable raw materials and because of lower
5.4.4. Environmental Issues temperatures and a more selective process.
stream processing in the near future. Second- then converts the methanol to olefins. Economics
generation processes based on lignocellulose of this new process seem to be competitive with
biomass will be fully integrated into petrochem- conventional processes [94]. The process is
ical complexes and are the future of bio- based on a fluidized-bed reactor for conversion
refining. of methanol. 80 % of the carbon content of
methanol is converted into ethylene and propene.
The process has been tested in a 0.5 t/d unit
5.5. Other Processes and Feedstocks in Norway. Methanol obtained from syngas
can be converted in high selectivity (but at a low
Ethylene has also been produced by other pro- rate) to ethanol with the help of catalysts and
cesses and from other feedstocks [93]. Options promoters.
for long-range feedstock availability and price, In order to be competitive to the mega-scale
as well as in-place refining and chemical pro- ethane crackers in the Middle East with lowest
cesses, influence process design and feedstock feedstock costs worldwide, methanol has to be
selection because of their high economic impact produced in huge quantities of approximately
on manufacturing cost. Other drivers for new 5 106 t/a leading to an olefins output of ap-
developments are the utilization of associated proximately 2 106 t/a of ethylene and propene.
gas and natural gas as petrochemical feedstock, The ratio of propene to ethylene can be adjusted
as the value of these fractions offers advantages over a wide range and propene - ethylene ratios as
with respect to costs compared to crude oil based required by the market (0.8 to 0.9) can be pro-
feedstock. In addition as flaring of associated gas duced via this route.
is no option anymore, other utlization is required Another development by Lurgi is the MTP
for those streams. process, similar to MTO, however, with a maxi-
mized propene output.
Recovery from FCC Offgas. Recovery of
ethylene and propene from FCC off-gas has Syngas. Fischer–Tropsch and modified
gained importance, but due to the NOx content, Fischer–Tropsch processes are used to produce
some steps have to be integrated to reduce the risk (1) olefins directly as a byproduct of gasoline and
of formation of explosive resins from butadiene diesel fuel production; (2) LPG and paraffin
and N2O3. intermediates, which are cracked to produce
olefins; and (3) intermediate oxygenated liquids,
Crude Oil or Residual Oil. A number of which are dehydrated and separated to produce
nontubular reactors, developed to crack unpro- olefins (! Coal Liquefaction). Syngas is pro-
cessed hydrocarbon feedstocks, exist in various duced by gasification of coal and other materials
stages of development and commercial ope- (! Gas Production, Section 8.2.2.3.).
ration [93].
A process offered by Shaw (Deep Catalytic Oxidative Coupling of Methane to Ethyl-
Cracking, DCC) employs catalysts particles, for ene. Many researchers worldwide have been
cracking and heat transfer functions. The DCC active in this field, using metal oxide catalysts
process is suitable for cracking VGO and similar at 700–900 C for the oxidative coupling of
heavy feedstocks. Main target light product of the methane. However, the yields obtained so far
DCC process is propene, similar to FCC process- (20–25 %) are not competitive with conventional
es in which propene output can be increased routes, since the ethylene concentration in the
significantly by catalyst modification. product gas is only ca. 10 vol % [95, 96]. Appli-
cation of special separative reactors has led to
Methanol can be catalytically dehydrated improved yields up to 50–60 % [97, 98].
and partially converted to ethylene over alumina
and zeolite catalysts. The process based on novel Dehydrogenation. Dehydrogenation of
zeolite catalysts (ZSM-5) was developed by ethane over Cr or Pt catalyst is limited by equi-
Mobil (MTO, Methanol to Olefins). A new de- librium and allows only very poor yield of ethyl-
velopment introduced by UOP/Norsk Hydro, ene. This route is not competitive with conven-
converts methane to methanol in a first stage and tional routes.
522 Ethylene Vol. 13
Metathesis. Metathesis of propene leads to populated areas. New procedures have been de-
ethylene and 1-butene: veloped that allow for flareless start up of
plant [99].
2 C3 H6 ÀC2 H4 þC4 H8
Since this reaction is reversible the ethylene/ Noise Protection. Ethylene plants contain
propene production of a plant can be adjusted to equipment that produces noise emission in the
market conditions. So far this technology has range above 85 dBA. These are the burners at
been applied in a plant in Canada and at the U.S. the furnaces and the large compressors.
Gulf Coast. Noise abatement measures are essential (silen-
As the demand for propene is increasing faster cers for burners, hoods for compressors) to
than the ethylene demand and due to the lack of bring the overall emissions into the range
propene production in new ethane crackers in the below 85 dBA. Other sources of noise emission
Middle East, metathesis has gained importance can be high velocities in piping or vibrations.
for the production of propene based on ethylene The detection of the source in this case is
and 2-butene feedstock. Several commercial sometimes very difficult and requires much
units applying metathesis for propene production expertise.
via this route are in operation. Contents of iso-
butene and butadiene in the feed create problems, Water Protection. The water emissions of
as coking rates of the applied catalysts are the plant result from quench water, dilution
increasing. steam, decoking water, and flare water dis-
charges. These streams have to be treated prop-
erly before being fed to the wastewater plant.
6. Environmental Protection Streams from the caustic-scrubbing section re-
quire chemical treatment (oxidation) before dis-
Ethylene plants with a production of up to charge to the wastewater unit.
1.5 106 t/a ethylene and a fired duty of up to
1000 mW require special measures for protec- Solid and Hazardous Wastes. Examples of
tion of the environment. Though national stan- process wastes are cleaning acids; filter car-
dards vary widely, the following general mea- tridges; catalysts; tars; polymers; waste oils;
sures are required for every new plant: coke; sodium nitrite used in column passivation;
N,N-dimethylformamide, acetone, or N-methyl-
Flue-Gas Emissions. NOx emissions are 2-pyrrolidone used in acetylene removal; sulfu-
limited by use of UltraLowNox burners or inte- ric acid from cooling towers; amine tars; and
grated SCR technology for catalytic reduction of antifoaming agents. These wastes have to be
NOx. In some regions limits for NOx emissions treated according to the relevant regulations for
are already < 50 ppm. Particulate emissions disposal.
during decoking can be reduced by incineration
or separation in cyclones. Incinerators can
achieve a reduction of 90 %, and high-perfor- 7. Quality Specifications
mance separators, up to 96 %.
Ethylene quality worldwide is matched to cus-
Fugitive Emissions and VOC. The equip- tomer requirements; no single chemical-grade
ment used in a modern olefin plant has to meet the ethylene exists. However, ethylene content nor-
standards for emission of critical components mally exceeds 99.9 wt %. The reason for varia-
such as benzene. All components with a potential tion in ethylene specifications is due to the use of
to emit critical components must have a certain ethylene in downstream processes that differ in
tightness classification and have to be monitored sensitivity to impurities in ethylene, due to dif-
(pump seals, valves, etc.). Storage tanks and ferent catalyst systems being used. In general, the
piping are other sources of fugitive emissions. trend is towards lower impurity contents as more
active catalyst systems are developed. The larg-
Flaring. Flaring during start up should be est application for ethylene is polymerization to
avoided as much as possible, especially in highly HDPE, LDPE, and LLDPE. For these processes
Vol. 13 Ethylene 523
Table 16. Typical ethylene specifications (in ppm vol unless otherwise noted) [100]
Polymer Process
Ethylene 99.9 % min. 99.95 % min. 99.9 % min. 99.9 % 99.9 % min.
b
Methane 500 500b e
300
b
Ethane 500 500b e
500
Propene 20 20 50 20 10–15
Acetylene 0.1 2 55 0.1 2
Hydrogen 5 5 10 5 10
Carbon monoxide 0.1 1c 2d 0.1 2
Carbon dioxide 0.1 1c 5d 0.1 2
Oxygen 0.1 1 5 0.1 5
Water 0.1 5c 5d 0.1 2
MeOH 1c 5d 0.1 5
Sulfur as H2S 1 (wt)c 2 (wt)d 0.1 2 (wt)
Other polar compounds 1 2 0.1
DMF 2 (wt)
a
Values for metallocene catalyst are expected values.
b
Total combined not to exceed 0.125 %.
c
Total not to exceed 1 ppm wt.
d
Total must be less than 6 ppm.
e
Total combined not to exceed 300 ppm wt.
new catalyst systems have been developed, vapor pressure analyzers, and photoionization
including the metallocene catalysts, which are analyzers. Various automated wet methods are
more sensitive than other catalysts. Table 16 also used [101].
lists typical ethylene specifications for various Process optimization is critical for ethylene
polymerization processes. production because cracking reactions change as
Sulfur, oxygen, acetylene, hydrogen, carbon the run proceeds. Operating costs for plants of
monoxide and carbon dioxide are the most trou- this size are high [57, 103, 104]. Advances in
blesome and carefully controlled impurities, es- computer control, data acquisition, and informa-
pecially when ethylene from multiple sources is tion analysis have given impetus to studies of
mixed in transportation. process control, modeling, and optimization,
especially in heavier liquid cracking operations.
8. Chemical Analysis Models for all kinds of feedstocks are applied,
simulating all sections of the plant in detail, based
Laboratory analysis of ethylene is primarily by on detailed chemical analysis of the various
ASTM or modified ASTM gas chromatographic streams in the plant. With these tools operating
techniques. strategies can be followed, e.g., production of a
Process control may use over 100 analyzers to certain amount of ethylene, propene and other
monitor plant safety, operation, and optimization products at maximum profit, even if the feedstock
[101]. Measurements include personnel expo- quality or the type of feed change within short
sure, corrosion, furnace flue gas, steam systems, time. Such a computer controlled operation in-
water systems, condensate systems, stack emis- cludes the individual control of cracking fur-
sions, water emissions, feedstock quality, naces, columns, pumps, compressors, etc.
cracked gas analysis, distillation train product
quality and moisture control, and, in some
cases, heavy liquids product evaluation and con- 9. Storage and Transportation
trol [102].
Process control instruments include gas chro- Much of world ethylene production is consumed
matographs, combustible-gas detectors, conduc- locally, requiring little storage and transporta-
tivity analyzers, pH meters, densitometers, cor- tion. Interconnected pipelines and pressurized
rosion analyzers, oxygen and water analyzers, underground caverns in the United States and
524 Ethylene Vol. 13
Europe have been developed because of the ture must be > 4 C to prevent liquid ethylene
complex petrochemical infrastructure. They pro- from forming. If water is present, hydrates can
vide flexibility and prevent interruption of form below 15 C at normal operating pressure
supply. The following pipeline systems have and can plug equipment. Special procedures and
been developed (Fig. 44): precautions are used during commissioning of
pipelines to pressure test and dry the line and to
provide appropriate draining and venting during
United States: Texas–Louisiana [106] operation [108].
Canada: Fort Saskatchewan–Sarnia [105] Ethylene decomposition and spontaneous ig-
Great Britain: Grangemouth–Carrington nition can occur under certain conditions and can
Sevenside–Fawley [59]
result in pressure and temperature increases ca-
Europe: Northwest Europe (Frankfurt–Gelsenkirchen
and Brussels–Rotterdam areas) and pable of producing explosions. Such decompo-
Spain [59, 107, 108] sition is a function of pressure, temperature,
Former Soviet Nizhnekamsk–Salavat and Angarsk–Zima impurities (e.g., acetylene and oxygen), and cat-
Union: [109, 110]
alysts (e.g., rust and carbon). Appropriate com-
pression procedures, especially when nitrogen,
oxygen, or other diatomic gases are present, help
In the U.S. Gulf Coast area the pipeline grid to prevent decomposition [111].
is composed of common carriers and privately Ethylene is also transported by ship, barge,
owned pipelines. Storage caverns are naturally railcar, and tank truck. In the United States, these
occurring or artificially excavated salt domes; methods are normally limited to consumers not
limestone caverns are less usual. In contrast served by pipeline. In Europe, pipelines move a
to U.S. pipelines, which normally transport lower proportion of ethylene than in the
only ethylene, the 3000 km pipeline between United States.
Fort Saskatchewan and Sarnia transports Ethylene is also stored in underground high-
ethane, propane, and condensate in batches pressure pipelines and tanks (e.g., at 10 MPa)
[57, 105]. and in surface refrigerated tanks. In the latter,
In pipelines, ethylene is normally under a compression and liquefaction of vapor from the
pressure of 4–100 MPa. The upper end of the refrigerated tank, followed by reinjection of the
pressure range is significantly above the critical liquid, allow operation of the tank at pressures of
pressure. Below critical conditions, the tempera- only 7–70 kPa [57, 112].
Color
Fig
Table 17. World consumption of ethylene in 2000 (in %) below for a new plant based on naphtha feedstock
Use World
in the Asia/Pacific region:
LDPE 18
LLDPE 14
HDPE 26 Basis of economic analysis
EO/EG 12 Capacity 1000 103 t/a
EDC 14 Location Asia/Pacific
EB/SM 7 Feedstock naphtha
Others 9 Capital 10 years linear depreciation for
ISBL plant
15 years linear depreciation
for storage
Investment cost estimate $ 720 106for ISBL plant
$ 144 106 for OSBL plant
10. Uses and Economic Aspects Cost breakdown, %/t ethylene produced
Feedstock costs 47.4
More than 80 % of the ethylene consumed in Catalysts and chemicals 0.5
1993 was used to produce ethylene oxide; ethyl- Utilities 0.3
Cash cost 48.6
ene dichloride; and low-density, linear low-den-
Operating costs 1.9
sity, and high-density polyethylene. Significant Overheads 1.9
amounts are also used to make ethylbenzene,
oligomer products (e.g., alcohols and olefins),
acetaldehyde, and vinyl acetate. LDPE and
LLDPE are the fastest growing outlets for
ethylene.
11. Toxicology and Occupational
Table 17 shows the uses of ethylene in 2000 Health [116]
[113].
Worldwide ethylene growth rate is projected Ethylene is not markedly toxic, but high con-
at 4 to 5 % for the period of 2004 to 2009 [114] centrations may cause drowsiness, uncon-
with the Asian market growing at 6 to 7 % sciousness, or asphyxia because of oxygen
per year. displacement [117, 118]. The gas possesses
The estimated 2005 world nameplate produc- useful anesthetic properties, with rapid onset,
tion capacity was over 112.9 106 t/a (Table 18). quick recovery, and minimal effects on the heart
The principal influences on ethylene product or lungs [119].
value from the manufacturer’s viewpoint are In animal studies, ethylene was not irritating
primarily the price of feedstock raw materials, to the skin or eyes [120]. It did not cause cardiac
chemical and byproduct credits, and expected sensitization in a dog [121]. Mice and rats
return on capital costs associated with the exposed repeatedly to ethylene showed minimal
facilities. The fixed cost component for ethylene effects [122, 123]. In a chronic inhalation study
production is relatively modest because of the with rats, no toxic effects were found by histo-
high-volume commodity operation that has pathology, hematology, clinical chemistry, uri-
become the industry standard (e.g., up to nalysis, eye examination, or mortality rate [123].
1500 103 single-train plants). The cost break- Ethylene improved wound healing following
down per tonne of ethylene produced is listed muscle injury to mice [124].
Studies with rodents have shown that ethylene
caused increased serum pyruvate and liver
Table 18. Ethylene nameplate capacities by region in 2005 [115] weights [125], hypotension [126], decreased
Region Capacity, 103 t/a % of World capacity
cholinesterase activity [123], hypoglycemia
[127], and decreased inorganic phosphates
Europe (incl. Russia) 31 494 27.9
North America 33 830 30.0
[120]. No mutagenic activity was observed in
South America 5669 5.0 Escheria coli B and E. coli Sd-4 exposed to
Asia 39 880 35.3 ethylene [128].
Africa 1528 1.4 Ethylene is a plant hormone and is useful for
Australia 504 0.4
ripening fruits and vegetables [129, 130]. At high
526 Ethylene Vol. 13
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and Chemicals, Academic Press, New York 1969, p. 316. Processing, CRC/Taylor & Francis, Boca Raton, FL 2006.
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ology 36 (1972) no. 6, 558. Resources, Wiley, Chichester 2010.
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