An Overview of Industrial Processes for the Production

of Olefins C4 Hydrocarbons
Michael Bender[1]

Abstract
The survey describes industrial processes for the
production of light olefins emphasizing on C4 hydrocarbons. Value chains in the petrochemical and
the oil refining industry are strongly interrelated
with regards to olefin production. An account is

given on the production and the consumption

volumes of the various C4 hydrocarbons on a global
basis, including an outlook for alternative, petrochemical and bio-based processes for the production of C4 olefins.

Keywords: Butadiene, Butylene, Hydrocarbons, Industrial processes, Olefins

Received: June 25, 2014; accepted: June 30, 2014
DOI: 10.1002/cben.201400016

Production and Consumption

of Butenes

Today, light olefins are produced by a number of processes in

the petrochemical and oil refining industry. Worldwide, a volume of 1 billion t of various hydrocarbon feedstock is used to
generate approx. 400 million t of light olefins per year. The
residual product volume (ca. 600 million t) is composed of
higher hydrocarbons, mainly of gasoline fractions (Fig. 1).
Approx. 60 % of the global feedstock volume is processed in
fluid-catalytic cracking (FCC) units in oil refineries. The remainder of 40 % is used in steam cracking in ethylene plants.
Ethylene is almost exclusively generated in these plants, in similar amounts from steam cracking of naphtha and gas oil and
of ethane and liquefied petroleum gas (LPG), respectively.
At present, increasing volumes of ethylene are also produced
by modified FCC processes, such as deep catalytic cracking
(DCC). In difference to ethylene, only half of the global propylene volume is generated by steam cracking, mostly of naphtha
and gas oil. The other half of the global propylene production
rests on conventional FCC units in oil refineries. About a tenth
of the global propylene is generated in dedicated processes, in
particular by olefin metathesis of 2-butene and ethylene, as well
as by propane dehydrogenation (PDH).
In difference to the former two light olefins, C4 hydrocarbons are mainly generated in FCC units as a by-product of gasoline production. Only a quarter of the global C4 hydrocarbon
volume stems from steam cracking of naphtha and gas oil.
Marginal volumes of C4 olefins are currently produced by butane dehydrogenation (BDH).
While volume growth rates of the light olefins are close to
the growth of the gross domestic product (GDP) at 4 to 5 % a1,
the world gasoline demand is expected to grow by only 1 % a1.

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Thus, growth in global feedstock for olefin production can be

expected to be slower by 1 to 2 % than olefin growth rates, i.e.,
at approx. 3 % a1.
Four different C4 olefins are industrially relevant, namely
1-butene, 2-butene, isobutene, and butadiene. These olefins are
generated and further processed jointly with n- and isobutane
in a complex network of industrial processes. In some cases the
C4 olefins are purified and used in substance, but in the majority of all cases C4 olefins are further processed when contained
in C4 fractions, the so-called raffinates (Fig. 2).
Steam cracking of naphtha and gas oil yields a butadienerich C4 fraction, the so-called crude C4. Butadiene is produced
in substance from this product stream by extraction, yielding a
by-product stream of the remaining C4 components, the socalled raffinate 1. Raffinate 1 is rich in isobutene, but also contains significant amounts of the n-butene isomers. In some
cases the valuable butadiene is not recovered, but crude C4 is
processed by selective hydrogenation of the butadiene, yielding
additional volumes of n-butenes in the raffinate 1 product
stream.
Steam cracking of ethane or LPG yields only small amounts
of C4 olefins that cannot be recovered economically. These
volumes are often hydrogenated fully to butanes, which are recycled back into the cracker furnaces as so-called co-crack. Instead, 1-butene that is required, e.g., as a co-monomer for the
manufacturing of linear low density polyethylene (lldPE), can
be produced from ethylene by dimerization.

[1]

Dr. Michael Bender

BASF SE, Ludwigshafen, Germany.
E-Mail: michael.bender@basf.com

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a)
Dehydrogenation
2%

Steam cracking,
Ethane & LPG
11%

Steam cracking,
liquid feed
28%
Fluid-catalytic
cracking
59%

Total HCx feed to Olefins

1,015 Mmto / +3 % p.a.

b)
Fluid / Deep
Catalytic Cracking
5%

Steam cracking,
Ethane & LPG
38%

Steam cracking,
Naphtha / GO
57%

Ethylene
156 Mmto / +4.5% p.a.

c)
Propane
Dehydrogenation
5%
Metathesis
5%
Fluid / Deep
Catalytic Cracking
39%

Other (XTP, etc.)

1%
Steam cracking,
Ethane & LPG
8%
Steam cracking,
naphtha & GO
42%
Propylene
100 Mmto / +5 % p.a.

d)
Steam cracking,
Ethane & LPG
4%
Delayed
Coking
1%
Fluid-catalytic
cracking*
69%

Steam cracking,
liquid feed
22%

Butane
Dehydrogenation
4%
Crude C4 yield, total
132 Mmto / +4 % p.a.

Figure 1. Global volumes by process type: Total hydrocarbon

feedstock supply to light olefins production (a); ethylene, propylene, and butenes (b, c, and d). Own estimates were based on
sources [16].

C4 olefin recovery in oil refineries, mainly from FCC units,

and in small volumes in delayed coking units, directly yields
raffinate 1. These product streams can be further processed
jointly with similar streams from ethylene plants. The usual

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processes for olefin production yield C4 hydrocarbons in different ratios. Steam cracking almost exclusively yields C4 olefins,
while FCC units are operated such that the total C4 olefin content and the isobutane content of the raffinate 1 stream are in a
stoichiometric one-to-one balance. This ratio is required to further process these components into alkylate gasoline. n-Butane
does not react under the alkylation process conditions. Other
ratios of C4 hydrocarbons are obtained, e.g., in the upcoming
dehydrogenation processes (Tab. 1).
Beyond butadiene production, raffinates are further processed to a number of different products. Raffinate 1 is used to
manufacture methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE) by acid-catalyzed, selective etherification of
isobutene with methanol and ethanol, respectively. Both MTBE
and ETBE are large-scale products used as important additives
to the gasoline pool.
Alternatively, C4 olefins can be catalytically converted with
isobutane in raffinates yielding alkylate gasoline, another important additive to the gasoline pool. Additional isobutene
volumes can be generated from n-butenes by acid-catalyzed
skeletal isomerization. As an example for this process type
CDTechs ISOMPlus process can be named. ISOMPlus operates
a ferrierite catalyst at 340 to 440 C to generate isobutene from
n-butenes by rearranging the molecular carbon skeleton [13].
Isobutene can be recovered in substance by acid-catalyzed
cleavage of MTBE or iso- and tert-butanol, respectively. Isobutene is consumed in substance, e.g., for the production of polyisobutene (PIB).
1-Butene can be isomerized by acid catalysis or by hydroisomerization to 2-butene. N-olefins can be produced in substance
by catalytic distillation. They are used for some specific, mostly
chemical production processes.

The Growing Market for Butenes

Worldwide, approx. 30 million t of isobutylene are generated

per year, mainly in oil refineries, where it is directly processed
into MTBE, ETBE, and alkylate gasoline. Much smaller volumes are chemically processed into elastomers such as PIB or
into chemical intermediates such as methacrylic acid and its
derivatives (Fig. 3).
The growth rate of global isobutylene volumes is largely driven by growth of its two main products. Historically, alkylate
gasoline and MTBE volumes have grown rapidly by approx.
4 % a1. MTBE volumes but were stagnant in the recent past
due to the MTBE ban in the U.S. and other regions. Meanwhile, ETBE has started to substitute these volumes and growth
of the two ethers combined is expected to continue at historic
pace, supporting an expected growth rate of approx. 4 % a1 for
global isobutylene volumes in future. Similar to isobutylene,
1-butene is generated by three quarters in FCC units. Only a
quarter of the global 1-butene volume is generated in ethylene
plants, mostly from naphtha and gas oil. Small volumes are
produced on purpose by dimerization of ethylene, e.g., by the
Alphabutol process of the Institute Francais du Petrol (IFP).
These volumes are often used as co-monomer for the polyethylene (lldPE) production (Fig. 4).

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primary generation

Bio mass

Syn
Gas

MeOH

BD
Extract

Butanediol
Methanol-toOlefins

Catalytic
Distillation

N-butene Isom.

Skeletal
Isomer.

Butene-1

Alkylate
gasoline

Full C4 Hydro
Ethanol

Isobutene

Butanes

n-BDH

Iso-BDH

EthanoltoButadiene

(Hydro)Isom.
Butene-2

MTBE / TBA
cleavage

Coal

Acetylene

Delayed Coking

Raff III [butene-2-rich]

Vacuum
Residue

FCC Cracking

Raff II [butene-1-rich]

Crude Oil

Gas Oil

PIB

Higher Olefin
Cracking

Naphtha

Alkylation

Methane

BD
SHU

XTBE /
TAME

Condensate

products

Oxidative DeHydrogenation
Crude C4
[Butadienerich]

Raff I [iso-butene-rich]

Butanes

conversion processes

Ethylene Dimerisation

Ethane /
Propane

Steam cracking

Natural Gas

crudes

Butadiene

Figure 2. Network of petrochemical and refinery processes for the generation and conversion of C4 hydrocarbons; Starting from raw materials a number of crudes are produced first that are used as feedstock for the primary generation of olefins. C4 olefins are further processed from their raffinates and in some cases are recovered in substance before being used as a chemical feedstock.
Table 1. Composition of raw C4 hydrocarbon streams generated in different petrochemical and refinery processes; the red boxes indicate the difference in butane to butene ratios between steam cracking and fluid catalytic cracking.
C4

Boiling
point [C]

Yield [wt %]
SC, low
severity

SC, high
severity

FCC
cracker

n-Butane
BDH

Ethanol
ETB

n-Butene
ODH

MTO
[ZSM-5]

1,3-Butadiene

4.4

28

49

0.2

913

90

58

Isobutene

6.9

32

22

24

~ 30*

cis-Butene-2

+3.7

11

3741

10

~ 60

trans-Butene-2

+0.9

Butene-1

6.3

20

14

15

Isobutane

11.7

37

n-Butane

0.5

[7]

[7]

Source

Most of the 1-butene is consumed in the production of alkylate gasoline, while only one quarter is used in the production
of chemicals and polymers. After isomerization to 2-butene
1-butene volumes are also consumed to produce propylene by
metathesis with ethylene. Similar to isobutylene volumes of
1-butene will grow mainly along with alkylate gasoline.The
supply and demand situation for 2-butene is very similar to
1-butene. 2-Butene is also produced mainly in refineries and is
converted by approx. three quarters into alkylate gasoline. The
FCC process yields a 2-butene to 1-butene ratio much closer to

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15

1.3

12

~ 50

[8]

[9]

[10]

< 10**

[11, 12]

thermodynamic equilibrium than that of the steam cracking

process. Thus, FCC units have a larger share in global 2-butene
production than in 1-butene production (Fig. 5).
Since most of the global C4 hydrocarbon volumes are produced in oil refineries this raises the question of why such a
small part of these volumes become available to the petrochemical industry. As already explained above, C4 hydrocarbons in
refineries are mainly used as a feedstock for the gasoline pool,
either directly as a C4 additive in cooler periods of the year or
in warmer periods as alkylate gasoline or as tert-butyl ether

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a)

a)
Isobutane
Dehydrogenation
14%

Propylene
via metathesis
24%

b)
Fluid-catalytic
cracking, total
62%

Steam cracking,
liquid feed
24%

Methyl Ethyl
Ketone,
6%

Alkylate
gasoline
70%

Isobutylene by source
30 Mmto / +4 % p.a.

2-Butene by use
14 Mmto / +4 % p.a.

b)

b)
Synthetic
Rubber
9%

Chemicals,
other
3%

Fluid-catalytic
cracking, total
86%

Steam cracking,
14%

MTBE / ETBE
41%
Alkylate
gasoline
47%

Figure 3. Global isobutylene volumes and growth; a) volumes

by production process, estimated from global capacities and
typical C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, estimated from [1417].

a)

Figure 5. Global butene-2 volumes and growth; a) volumes by

production process, estimated from global capacities and typical C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, estimated
from [20, 21].

Alkylate
gasoline
7%

Ethylene
dimerisation
4%

Butane
7%

XTBE
2%

Fluid-catalytic
cracking, total
73%
Steam
cracking
23%

2-Butene by source
14 Mmto / +4 % p.a.

Isobutylene by use
30 Mmto / +4 % p.a.

Bioethanol
10%

Gasoline
fractions
75%
Gasoline, total
1,000 Mmto / 1 % p.a.

Butene-1 by source
18 Mmto / +4 % p.a.

Figure 6. The global gasoline pool, volumes by component. Individual components and their physical properties relevant to
gasoline blending are summarized in Tab. 2 [22, 23].

b)
Chemicals
6%

Polybutene-1,
3%

Polyethylene
(hdPE / lldPE)
9%
Alkylate
gasoline
73%
Propylene
via metathesis
10%

Butene-1 by use
18 Mmto / +4 % p.a.

Figure 4. Global butene-1 volumes and growth; a) volumes by

production process, estimated from global capacities and typical C4 yields (see Fig. 1 and Tab. 1); b) volumes by use, estimated
from [18, 19].

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(XTBE, Fig. 6).When blending C4-based components in the

gasoline pool, two main aspects are important: on the one
hand, blending alkylate gasoline and XTBE leads to an increase
of the octane number and, thus, of the gasoline quality; on the
other hand, alkylate gasoline limits the so-called Reid vapor
pressure of gasoline more effectively than XTBE components.
In difference, blending bioethanol into the gasoline pool leads
to a significant increase of the Reid vapor pressure. This increase can be compensated for by co-blending alkylate gasoline
better than by blending with XTBE components.
Consequently, the strong growth of bioethanol volumes in
gasoline is, hence, coupled to an equally strong growth of the
global alkylate gasoline demand. At the same time total gasoline production is almost stagnant, whereby available C4 hydro-

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Table 2. Individual components and their physical properties relevant to gasoline blending [22, 23]
Component

Blend octane number

(RON + MON)/2

Reid vapor pressure

[psi]

Net energy
[%]

Crude gasoline

88

611

100

Ethanol

112

1822

65

Isobutanol

102

45

82

Alkylate gasoline

95

45

95

C4 raffinate

86104

5070

~ 105

MTBE

110

80

ETBE

111

83

ponent for the gasoline pool, a trend still in its infancy. Biobutanol boosts the octane number of gasoline, but unlike bioethanol, without increasing its
Reid vapor pressure. This would relieve the demand for alkylate gasoline as a low-vapor pressure
blending component and, thus, could make C4 olefins from refineries available for the petrochemical
industry.
Since all three butenes are expected to grow by
about 4 % a1, it will be interesting to see how the
corresponding volumes will be produced. With
much lower growth rates in gasoline volumes FCC
units will not be able to satisfy this growing demand
alone. Also, with ethylene plants being converted
from liquid to gas feedstock butene availability from
steam cracking will also decrease, potentially leaving
behind a supply gap in C4 olefins.

a)

b)
Alkylate gasoline, total
65 Mmto / 4 % p.a.

Figure 7. Volumes and growth rates of the two main blend

components for the gasoline pool; a) bioethanol [24]; b) alkylate
gasoline [14].

carbon volumes, mostly from FCC units do not grow as

strongly as their two main gasoline products (Fig. 7).
No significant change of this situation can be expected midterm. Refinery operators will have only little incentives to ship
their C4 hydrocarbons to consumers in the petrochemical industry. Long term, the demand situation for alkylate gasoline
could ease, if bioethanol is substituted by biobutanol as a com-

Alternative Sources for Butenes

When turning our view to alternative processes for manufacturing C4 olefins dehydrogenation of the corresponding butane
is the first process that must be mentioned. Iso- and n-butane
can be dehydrogenated to raffinate-2 and raffinate-1-compatible product streams, respectively (Fig. 8). Butadiene-rich crude
C4 streams can be generated from n-butenes by oxidative dehydrogenation and can be further processed conventionally by
butadiene extraction. Butanes are available as feedstock in large
amounts from natural gas, from crude oil distillation, or as a
residual stream from raffinate processing in oil refineries and
petrochemical plants.
Industrial processes for dehydrogenation of light paraffins
are available from various licensors (Tab. 3). Due to thermodynamics of the dehydrogenation reaction operating temperatures are high at around 600 C and the processes are operated
at relatively low pressure. Most of the processes use a combination of platinum and tin as the active ingredient of the dehydrogenation catalyst while support materials are different for
different licensors. As an exemption the Catofin process uses
an alumina-supported chromium oxide catalyst.
Dehydrogenation processes typically operate at partial conversion of the paraffin feedstock between 50 and 60 %. Under
these conditions the processes reach C4 olefin selectivities of
about 90 %. The remainder of the converted feedstock (~10 %)
forms coke deposits on the catalyst surface. These deposits are
used in some process types like in the Catofin and in the Oleflex process to generate internal process heat by combustion
during catalyst regeneration. In contrast, the STAR process uses
steam injection into the reactant stream to minimize coke deposits by internal steam reforming. Depending on the coke
management concept cycle times between two catalyst regeneration steps vary between a few minutes and several hours per
cycle for the various process types.

Figure 8. Dehydrogenation reaction of n-butane (left) and isobutane (right).

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Table 3. Industrial processes for the dehydrogenation of butanes to butenes [2527].

Process parameters

UOP oleflex

Uhde STAR process

Clariant Catofin

Linde-BASF process

Reactor

Moving bed, radial flow,

adiabatic

Fixed-bed, isothermal plus adiabatic

reactor

Fixed-bed, adiabatic

Fixed-bed, isothermal

T [C]

580650

570590

560650

550650

p [bar]

0.30.5

>1

Cycle time

510 d

7h

620 min

~9h

X(C4 ) per pass [%]

50

~35

6065

C3 :30

S(C4 ) [%]

n-C4 : 81;
i-C4: 91

> 9193

90

C3 :90

Catalyst

Pt-Sn on Al2O3

Pt-SN Zn/Ca aluminate

Cr2O3 : Al2O3

Pt-Sn support

Endothermal dehydrogenation allows only partial conversion of ethane, propane, and of butane feedstock in the technically relevant range of operating temperatures up to 800 C
(Fig. 9). Heat of reaction can be introduced into the reaction
volume in three different ways (Fig. 10): the reaction volume
can be heated externally, e.g., by gas burners. Alternatively, the
reactant gas flow can be preheated to temperatures high
enough above the kinetic onset temperature to carry heat into
the reaction volume by its heat capacity. The heat capacity of
the reactant gas stream may be further increased by steam dilution to increase the amount of heat introduced. Thirdly, heat of
reaction can be generated internally by selective combustion of
the hydrogen that is released by the dehydrogenation reaction.
Oxygen that is mixed into the reactant gas stream reacts with
the hydrogen on the dehydrogenation catalyst.
100
Butane
Propane

Conversion [%]

75

Ethane

50

25

0
400

500
600
Temperature [C]

700

Figure 9. Thermodynamically limited conversion of light paraffins in endothermal dehydrogenation. The gray area indicates
the catalytically relevant range of operating temperatures;
from: [27].

Variable economics of olefin-producing processes also depend on by-product yields. As can be seen in Tab. 4 (yellow
boxes), when steam cracking propane and butanes, about one
quarter of the feedstock is converted into light gas, mainly synthesis gas and methane. However, when dehydrogenating these
paraffins, the resulting light-gas yield is much lower. Hence, C3

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Adiabatic

Isothermal

high Tin

Low Tin

Autothermal
Low Tin

z, t
RH = CP,gas T

RH = RHcomb.

RH = RHcomb.

preheated
reactant gas

external gas
firing

H2 combustion
in-situ

Figure 10. Heat management concepts for endothermal dehydrogenation processes; from [27].

and C4 dehydrogenation offer an incentive when compared to

steam-cracking of these two paraffins.
In contrast, steam cracking of ethane generates only small
volumes of low-valued light gas more comparable to light-gas
yields in C3 and C4 dehydrogenation. Thus, the potential dehydrogenation of ethane would not offer the same incentive over
ethane cracking as the dehydrogenation of higher paraffins
does over their respective steam cracking.
For the on-purpose production of butenes the dehydrogenation of butanes is advantageous over all the other processes described above, because it does not generate by-products in large
amounts.
Catalytic cracking of methanol is an interesting way to produce
light olefins in so-called methanol-to (MT) processes (Fig. 11).
2 CH3OH CH3OCH3 + H2O HCx + 2 H2O

Figure 11. Two-step reaction of methanol to hydrocarbons in

methanol-to processes.

The multitude of possibilities to produce methanol from carbon-containing raw materials via synthesis gas grants a flexible
access to light olefins from all four raw material sources natural gas, crude oil, coal, and biomass.
While ExxonMobils original methanol-to-gasoline (MTG)
process was dedicated primarily to gasoline production from
methanol, later developments like UOPs methanol-to-olefin

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Table 4. Industrial processes for the generation of light olefins and liquid hydrocarbons: product yields in percent of feedstock and
global volumes in Mmto [16, 28].
SC, C2

SC, C3

SC, C5

SC, naphtha

SC, GOs

Fuel-FCC

Load [Mmto feed]

80

28

19

~ 250

35

570

30

10

10

Share of C2 capacity [%]

28

7.5

4.1

53

5.7

1.3

4.0

C2 [Mmto]

42

11

~ 80

~2

~6

C2 yield [%]

53

40

32

~ 32

25

~ 0.4

20

C3 [Mmto]

3.7

40

36

C3 yield [%]

1.2

13.3

20

~ 16

~ 14

~6

1520

45

C4 yield [%]

2.2

13

10

10

15

19

45

~ 22

~ 36

~ 55

~ 35

Co-crack

35

12

45

50

50

Light gas

~8

25

23

~ 16

~ 11

Liquids

(MTO) and Lurgi-Air Liquides methanol-to-propylene (MTP)

processes were aimed at producing light olefins (Tab. 5). However, the main purpose of these processes is not the production
of C4 olefins but mainly of propylene and ethylene. Rather,
some modifications of these processes are available that further
upgrade the primary yield of the latter two olefins by catalytic
cracking of the small C4 olefins volumes that are co-generated
in the MT process. Industrial operating conditions allow for a
primary C4 hydrocarbon yield of ca. 1012 %, most of it as C4
paraffins. Hence, an industrial MT process for producing C4
olefins is not readily available yet.

Olefin-FCC n-Propane
PDH

n-Butane

er as can be seen from Fig. 12. Generating synthesis gas from

coal requires more equipment than from natural gas due to extensive processing of solids.
Depending on costs related to specific investment cheap coal
may not always be so cheap. The investment for a worldscale

Economics of Olefin-producing
Processes

The cost structure of all MT processes depends indirectly on

the raw material that is used to produce the methanol feedstock. Coal is relatively cheap per gram of carbon that ends in
methanol compared to natural gas. However, its specific invested capital per ton of methanol product is significantly high-

Figure 12. Economy of scale of petrochemical processes for the

production of light olefins based on alcohols as feedstock [33].

Table 5. Industrial processes for the catalytic cracking of methanol to hydrocarbons (MT processes).
ExxonMobil MTG

UOP/HYDRO MTO

Lurgi MTP

Sinopec S-MTO

T [C]

400420

340540

425

350550

p [bar]

~4

13

1.5

~1

Catalyst

ZSM-5 zeolite (ExxonMobil)

SAPO-34 zeolite (UOP)

ZSM-5 zeolite (Clariant)

SAPO-34 zeolite (Chia Thai Energy Mat.)

S(C2) [%]

1.1

37

5035

S(C3) [%]

4.5

37

64

3045

S(C4) [%]

C4 : 1.1C4 : 11.9

~ 12 (lab:2025)

~8

~ 11

S(C5 ) [%]

82.3 (no C10+)

~7

~ 25

< 10

Source

[29]

[30]

[31]

[32]

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bution margin 1 (CM1). For the present paper CM1 was calculated based on published product yields for the various
processes and on U.S. market prices for feedstock and products, respectively. All other cash expenses were neglected for
now. CM1 represents a rough estimate for the operating cashflow and, thus, compares profitability between different processes.
At current US market prices steam cracking of ethane yields
by far the highest CM1 margin, followed by propane dehydrogenation and by the two olefin-generating MT processes. CM1
margins of all other processes are significantly lower. For most
of the processes CM1 margins are driven by the product mix,
while for ethane cracking it is driven mainly by low feedstock
costs.
Regional differences, in general, play a major role in the selection of suitable processes to produce light olefins and other
basic petrochemicals (Fig. 14). Differences in feedstock prices
result from geological differences in raw material abundance.
In contrast, regional differences in market prices and product
demand result from differences in population and economic
power. Regions rich in raw material like the Middle East, the
former GUS countries, Australia, or Latin America possess a
comparatively small population and generate a low absolute
GDP. Petrochemicals that are produced in these regions are
predominantly exported, while countries poor in raw materials,
but rich in population and with a strong GDP like Europe or
Asia are net importers of these goods.
As an exception, the U.S. currently enjoy significant raw material resources and at the same time a strong demand for these
products in a large population with a strong economy. In addition, U.S. petrochemical producers increasingly export their
products globally.

MT plant based on coal may be higher by about $ 1.5 billion

than for one based on natural gas. For the first ten years, this
investment penalty would result in higher costs of approx.
300 million $ a1 (depreciation and capital costs at typical rates)
or around 150 $ t1methanol. These added costs are higher than
the variable cost advantage of coal versus cheap natural gas,
i.e., at 4 $ MMBtu1. Hence, under these conditions a coalbased MT process will not be competitive versus one based on
natural gas. However, when coal is cheap, i.e., at 60 $ t1, and
natural gas is expensive, i.e., at 12 $ MMBtu1, coal-based MT
processes become cost competitive (Fig. 13).
Economics of different petrochemical processes for the production of light olefins can be compared based on their contri-

US$ / metric ton

1,000
800
600
400

C2 Dimer.

MTP

ETE

MTO

MTG

C4 Dehydro

Deep FCC

C3 Dehydro

FCC

GO SC

Naphtha SC

Butane SC

Ethane SC

Propane SC

200

Figure 13. Economics of different petrochemical processes for

the production of light olefins; the values represent estimates of
contribution margins 1, i.e., revenue minus variable costs. All estimates are based on U.S. market prices for raw materials, feedstocks and products.

frmr. GUS states

Europe
North America
Asia Pacic
Middle East

Africa
Populaon
GDP

South America

Coal reserves

Australia

Oil reserves
Natural Gas reserves

Figure 14. Regional differences in population, GDP and raw material abundances; the global figures have been composed from individual Wikipedia entries by country for population, GDP and for the raw material reserves, respectively. Full scale of each graph represents a
60 % share of the region in the respective global figure.

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Due to these regional differences it is necessary to take transport costs for raw materials and for petrochemical products into account when deciding on investments into petrochemical
process equipment and on the location of the individual investment (Tab. 6).
High specific costs are related to the transport of hydrocarbon equivalents in particular for liquefied natural gas (LNG)
and for liquefied petroleum gas (LPG). However, methanol and
biomass, such as corn, also come with relatively high transport
costs when calculated by the ton of hydrocarbon equivalent.
For LNG and LPG, costs are high mainly due to an extensive
infrastructure transport of methanol, and biomass is expensive
because they contain large amounts of water that must be
transported alongside. Due to cheap infrastructure, crude oil
and gasoline but also coal can be transported relatively cheap.
The differences in specific transport costs require petrochemical processes that are based on natural gas, ethane, and
LPG to be operated in the region of raw material abundance,
e.g., in the Middle East, but also in the United States. Ethane
cracking is currently big in these two regions. In contrast, oilor coal-based processes are often operated in the region where
petrochemical products are to be marketed, e.g., in Europe or
in Asia. Olefin production in these two regions relies predominantly on naphtha cracking and in Asia industrial MT plants
that use coal-based methanol feedstock have been installed
worldwide for the first time.

a)
nitrile rubber
4%
SBD block
copolymers
6%
ABS polymers
12%

Other
4%
SB.
elastomers
28%
polybutadiene
26%
Butadiene
10 Mmto / 4.5% p.a.

SB latex
12%

b)
Other (ODH)
4%

Steam cracking,
Ethane & LPG
17%

FCC, total
1%

Steam cracking,
Naphtha & GO
78%

Butadiene
10 Mmto / 4.5% p.a.

Figure 15. Global butadiene volumes and growth; a) volumes

by production process; b) volumes by use; estimates based on
[39, 40].

Butadiene A very special case

directions. These amplitudes are much larger than for the other
olefins, making decision timing for new investments into butadiene production very difficult.
At present butadiene is only produced by steam cracking of
naphtha. Butadiene yields in FCC units are very low. Butadiene
interferes negatively in the acid-catalyzed alkylate gasoline production. Therefore, butadiene is removed from FCC raffinates
by selective hydrogenation. With increasing amounts of ethane
cracking, butadiene may be produced in future by ethylene dimerization followed by oxidative dehydrogenation.
In addition to steam cracking butadiene could be produced
from coal or biomass via butanediol as an intermediate. Start-

Butadiene represents a peculiar case in the world of C4 olefins.

It is mainly used as a monomer in the production of various
elastomers. Elastomers are predominantly used in the tire industry and, hence, its consumption pattern depends on the
global car industry. Its global volumes are somewhat smaller
than for the other three C4 olefins, mostly because it is exclusively used in petrochemical production, while the other C4
olefins are consumed mainly in gasoline products (Fig. 15).
Butadiene prices vary with large amplitudes over time
(Fig. 16). Changes in demand and supply occur in sync over
the economic cycle, leading to hefty price changes in both

Table 6. Overseas shipment costs for different raw materials and petrochemical products; cost figures have been collected from [3438].
Commodity

Shipment cost
[US $ t1]

Energy content
[MMBtu t1]

Shipment costs
[US $ MMBtu]

Shipment costs
[US $ t1H2C eq.]

Liquefied natural gas (LNG)

140

53.4

2.64

160

Liquefied petroleum gas (LPG)

100 (Panama)
150200 (Cape Horn)

47.3

2.114.22

100200

U.S. crude oil

1117

39.7

0.280.43

1020

U.S. gasoline

1012

41.2

0.410.49

1012

U.S. coal

1020

~ 27

0.370.74

2040 (via MTX)

U.S. methanol

3060

19

1.583.16

70140

U.S. ethanol

3060

25.6

1.172.34

5080

U.S. corn

3060

~ 15

2.004.00

109174 (via EtOH)

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At butene conversion between 75 and 90 %, the selectivities

to butadiene range at 90 % or higher. Different mixed-metal
oxide catalysts are operated, resulting in space time yields between 500 and 1000 kg m3h1. Feedstream compositions of the
different processes vary with regard to their content in oxygen,
steam, and butene.
CM1 margins for ODH processes are difficult to obtain due to
the large amplitudes in butadiene prices. For a representative
butadiene price of 2000 $ t1, the CM1 margin would amount to
approx. 400 $ t1, when assuming typical U.S. prices for raffinate
feedstock. These estimates show that ODH processes will play
an important role in the global butadiene supply in the future.

5000

US$ per ton

4000

Olefin prices
2010-2013

3000

2000

1000

Figure 16. Prices for butadiene (red curve) versus those for ethylene (blue), propylene (velvet), and naphtha (black) between
2010 and 2013; amplitudes in butadiene prices are much larger
than for the latter three materials [40].

ing with coal-based Reppe chemistry, butadiene could be obtained by catalytic dehydration of butanediol, originally a process that was operated in the 1940s to produce synthetic rubber. A somewhat more conventional way to butadiene would
be the dimerization of ethanol [41] after Lebedev or after Ostromislensky. Bioethanol can be produced routinely from biomass by fermentation. However, ethanol dimerization has not
been optimized for industrial yields. These processes were often
operated in war times or in isolated national economies. Hence,
their profitability is often not competitive in todays world market.
Beyond steam cracking of liquids, additional butadiene can
be generated by oxidative dehydrogenation (ODH) of n-butenes (Fig. 17).
,

O2, H2O

In the past, technical developments resulted in a number of fermentative processes for the production of industrial chemicals.
With a 10% share in the global gasoline pool, bioethanol has already arrived in the group of very large industrial chemical
products. In recent years, several start-up companies have begun to develop fermentation processes for the production of
higher industrial alcohols such as isobutanol and butanediol.
Typical yields of these processes range from 0.3 to 0.5 talcohol
per ton of sugar or corn starch [46] (Tab. 8).
Table 8. Fermentative yields of different industrial alcohols
(column 1 and 2, from: [46]) and CM1 margins of different olefins obtained from these alcohols by catalytic dehydration (column 3 and 4). It is assumed for simplification that the dehydration process yields 100% olefins. *Prices [$ t1]: 2000 (i-butylene)
and 2500 (butadiene).

+ H2O

Figure 17. Oxidative dehydrogenation (ODH) of n-butenes to

butadiene.

Product streams of these processes can be processed further

similar to crude C4, i.e., by extraction of the butadiene. ODH
processes were developed by several companies and some of
these processes are available on a license basis (Tab. 7).

Outlook Biochemical Processes

for C4 Olefin Production

Bio-alcohol

Yield

Olefin from
bio-alcohol

CM1 [$ t1]

Ethanol

0.45 t t1corn

Ethylene

~ 110

Isobutanol

0.35 t t1sugar

Isobutylene*

500 +500

1,4-Butanediol

0.5 t t1sugar

Butadiene*

~ 300

Catalytic dehydration of the corresponding industrial monoalcohols easily yields ethylene [47] and isobutylene [48], while
the same reaction on 1,4-butanediol does not easily produce
butadiene [49] (Fig. 18).

Table 7. Survey of four different ODH processes; additional ODH processes were developed by BP Chemicals, Mitsubishi Chemicals and
Nippon Zeon.
Phillips O/X/D

Petro/Tex Oxo/D

SK Energy ODH

BASF ODH

X (n-C4 ) [%]

7580

75

83

~ 95

S (BD) [%]

90

77.3

96

~ 95

512:1:1

24:2:1

15:1>0.75

015:1:2

STY (BD) [kg m h ]

24780

5501090

900

~ 450

Catalyst

Li-Sn-POx

Zn-, Mn-, Mg-ferrite

ZnFeFeO4

Bi-Mo-Fe-oxides

Source

[42]

[43]

[44]

[45]

Steam: n-C4 :O2

3 1

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145

Conclusion

Today, a number of processes for the generation, the conversion and the separation of C4 olefins in petrochemicals and
in oil refineries are already available on
industrial scale. At present the majority
of global C4 olefin volumes are generated
and further processed in oil refineries
making blend components for the gasoline pool. Their availability for petrochemical production purposes hinges on
Figure 18. Catalytic dehydration of various alcohols to the corresponding light olefins.
their valuation relative to their alternative
production by petrochemical processes.
In future, butane dehydrogenation will yield increasing vola)
umes of C4 olefins. Smaller volumes of butadiene will be generated by oxidative dehydrogenation of butenes obtained by dehydrogenation before. MT processes may also be tuned for C4
olefin production depending on further process development.
Bio-based routes to C4 olefins are still in their infancy. Their
success will largely depend on the development of market prices for biomass raw materials and on a potential solution of the
conflict of food versus fuel.
The author has declared no conflict of interests.

b)

Figure 19. Long-term market prices for sugar (a) [50] and for
maize (b) [51].

In any case, it can be concluded that the comparatively simple dehydration of bio-based industrial alcohols can generate
positive CM1 margins and, depending on market prices, may
become as profitable as conventional petrochemical processes.
However, prices of bio-based raw materials for the fermentative production of alcohols may undergo drastic changes that
could easily undermine process profitability on the long run.
After a long period of relatively stable prices soft commodities
have recently experienced price hikes that doubled or even
tripled market prices for certain carbohydrates (Fig. 19).
Despite of these uncertainties additional efforts will be spent
in future developments of production processes for petrochemicals on the basis of biomass can be expected. Hopefully, some
of these processes will also grant access to bio-based C4 olefins.

www.ChemBioEngRev.de

Michael Bender received his

Ph.D. in Physical Chemistry in
1997 from the Ruhr-Universitat Bochum, having worked in
the group of Prof. Freund. He
took his first position with
BASF as catalyst researcher in
the same year. From 2001 to
2009, he held business positions with BASF as product
manager and business manager for petrochemical catalysts. In 2009, Dr. Bender became a R&D group leader and
was promoted to Senior Expert in Catalyst Research with
BASF SE, Ludwigshafen, in 2013.

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