Chem. Eng. Technol. 2008, 31, No.

5, 631–637 631

Rainer Diercks1 Review

Jan-Dirk Arndt1
Stefan Freyer1 Raw Material Changes in the Chemical
Reiner Geier2
Otto Machhammer1 Industry
Jörg Schwartze2
Martin Volland3 Until the 19th century, renewable raw materials were the major source of energy
generation and material use. With the Industrial Revolution, the use of coal in-
1
BASF SE, Chemicals Research creased sharply and coal quickly developed into a key raw material in the chemi-
and Engineering, cal industry, mainly in the production of dyes. In the past century, there has been
Ludwigshafen, Germany. a consistent changeover in fossil fuel sources from coal to crude oil and natural
2 gas due to lower prices, simpler logistics and the versatility in usage of oil and
BASF SE, Strategic Controlling,
gas. In view of the limited availability and increasing price of crude oil and natur-
Ludwigshafen, Germany.
al gas, the question now arises as to how the raw material base will develop in the
3
BASF Catalysts LLC, Iselin, future?
USA.
Keywords: Chemical industry, Process development, Raw materials
Received: January 31, 2008; accepted: February 27, 2008
DOI: 10.1002/ceat.200800061

1 Introduction Nowadays, carbon-based products in the chemical industry

The availability and prices of natural resources for material
and energy purposes have always played a major role in shap-
ing the structure of the chemical industry. Reliable and eco-
nomical access to carbon sources is a major success factor in
the manufacture of basic organic products. The importance of
the individual sources of carbon has changed dramatically over
the past 200 years, and the qualitative situation is presented in
Fig. 1.
in Germany are largely produced on the basis of crude oil,
Fig. 2. In terms of material use in Germany, gas and renewable
raw materials are evenly balanced, whereas coal is currently of
low importance. The change in raw materials in the chemical
industry signifies not only a conversion from oil to renewable
raw materials but also to gas and coal. The important factors
in the selection of raw materials are based upon availability,
comparative price and efficient conversion technologies. The
availability of raw materials depends upon their regional distri-
bution and their static range, which results from the propor-
tion of the reserve that can be explored using modern technol-
ogies and current consumption, Tab. 1.
The scale of the material use of fossil fuels is clearly behind
that of energy use. Agricultural products are used predomi-
nantly for nutrition, Fig. 3. Therefore, the price of carbon con-

Figure 1. Raw materials change (qualitative).

–
Correspondence: Prof. R. Diercks (rainer.diercks@basf.com), Head of
Chemicals Research and Engineering, BASF SE, D-67056 Ludwigshafen,
Germany. Figure 2. Use of raw materials in the German chemical industry.

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632 R. Diercks et al. Chem. Eng. Technol. 2008, 31, No. 5, 631–637

Table 1. Static range of raw material reserves. i.e., synthesis gas (CO/H2), olefins, acetylene and the aro-
matics, all derived using existing conversion technologies,
Main Producers Static Rage Tab. 2, is illustrated in a simplified form in Fig. 5. The follow-
Years
ing characteristics are particularly noteworthy from Fig. 5:
Oil Saudi Arabia, Russia 42 ● At present, all basic chemicals, in particular BTX (benzene,
toluene, xylene), can only be produced in sufficient quanti-
Gas Russia, Iran 63
ties from crude oil.
Hard Coal China, USA 159 ● Synthesis gas can be produced as the general-purpose build-

Brown Coal Germany, USA 227

ing block from all carboniferous compounds.
● Renewable raw materials offer the possibility of exploiting
Cereal America, EU 00 the synthetic efficiency of nature, i.e., by preserving some of
Plant Oil America, Malaysia 00 the existing chemical functionalities.

Wood/Lignin America, EU 00
Table 2. Conversion technologies: From raw materials to basic
chemicals.
Source: Bundesanstalt für Geowissenschaften und Rohstoffe 2004; BP
Statistical Review of World Energy June 2005 Raw Material Technology Basic Chemicals

Oil Cracking Olefins, Aromatics

Catalytic Reforming Aromatics

Gas (C1–C4) Steam Reforming Syngas

Cracking Ethylene
Dehydrogenation Olefins

Coal Gasification Syngas

Coking Aromatics
Calcium-Carbide-Process Acetylene

Renewable Resources Fermentation Ethanols

Chemical Transformation Glycerine, ...

Figure 3. Use of carbon-containing raw materials.

taining raw materials will be determined in the future by con-

sumption in the areas of energy and nutrition. The supply/de-
mand balance is equally influential in the price of raw materi-
als. In recent years, political instability in supplier countries
where oil and gas reserves are concentrated has led to a sharp
increase in oil and gas prices, Fig. 4. The price of coal, on the
other hand, has increased to a comparatively lower extent.
The correlation between raw materials and the first elements
of chemical value-added chains or the core basic chemicals,

Figure 5. Raw materials for chemical value added chains.

2 Crude Oil
2.1 Distillation in Refineries

The key starting materials in the chemical industry, i.e.,

naphtha and aromatics, are produced during the processing of
Figure 4. Price development of fossil fuels. crude oil in refineries.

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Chem. Eng. Technol. 2008, 31, No. 5, 631–637 Process development 633

2.2 Steam Cracking

Naphtha is the major raw material in the chemical industry for

the production of basic chemicals by steam cracking, which
predominantly produces the olefins ethylene and propylene,
Fig. 6. Aromatics are another important product of naphtha
cracking. However, if gases such as ethane and propane are
cracked, virtually no aromatics are produced, with ethylene
and propylene being produced instead. Ethylene is inevitably
produced as the coupling product in the cracking of hydrocar-
bons. However, the growth rates for propylene are higher than
for ethylene, which means that technologies leading to decou-
pling are very attractive. The higher alkanes of natural gas can
Figure 7. Propane dehydrogenation technologies.
be used for this purpose.

Figure 6. Typical product composition of a naphtha cracker.
3 Natural Gas
Natural gas consists basically of methane, but depending on
the source can also contain higher alkanes, Tab. 3. LPG (lique-
fied petroleum gas, C3-C4) is also produced in refineries. The
higher alkanes can be used in the chemical industry without
C-C coupling reactions. Technologies using propane as a raw
material are a particular focus of recent development.
are currently two main technical concepts for feeding the heat
of reaction into the system: (a) In adiabatic processes, the pro-
pane is heated prior to entering the reaction zone and cools
along the reaction route, and (b) in isothermal processes, the
required heat is fed into the system via the reactor wall. This
means that lower inlet temperatures are possible in isothermal
processes with the consequence that fewer by-products are
generated in undesirable thermal cracking reactions.
There are currently four commercially available PDH pro-
cesses licensed by UOP, ABB, Uhde and Linde/BASF, Tab. 4.
With the exception of the chromium/aluminum oxide-cata-
lyzed Catofin® process of ABB, each process utilizes a platinum
catalyst. In UOP’s Oleflex® process, moving bed reactors are
operated adiabatically with external catalyst regeneration. The
Catofin® process employs adiabatic fixed bed reactors that, un-
like the reactors in the Oleflex® process, are operated discon-
tinuously. Both Uhde’s STAR process®, as well as the Linde/
BASF process, are based on isothermal fixed-bed reactors. In
addition to the temperature controlled high selectivities, the
Linde/BASF process is characterized by low specific investment
and low production costs.
Table 4. Comparison of PDH technologies.

Process Oleflex Catofin STAR Linde/BASF

Table 3. Typical composition of natural gas at the drilling hole.
Licence UOP ABB Uhde Linde/BASF
Component Minimum Maximum
Catalyst Pt/Support Cr/Al-Oxide Pt/Support Pt/Support
Methane 79 % 98 %
Reactor Type Moving bed Packed bed Packed bed Packed bed
Ethane 1% 12 %
adiabatic adiabatic isothermal isothermal
Propane 0% 6%
Butane 0% 3%
C5+ 0% 3% 3.2 C1 Chemistry from Natural Gas

w/o acidic components and water
3.1 Alkane Dehydrogenation
One technology suitable for the selective production of propyl-
ene is propane dehydrogenation (PDH), Fig. 7. The reaction
occurs via an extremely endothermic catalytic process. There
Methane is the principal component of natural gas and can be
converted to various C1 building blocks, Fig. 8. Hydrogen cya-
nide can be obtained by ammoxidation of methane and radical
chlorination enables access to methyl chlorides. Methanol and
formaldehyde can be produced using synthesis gas, which is
obtained, for example, by the steam reforming of methane.
Furthermore, carbon monoxide from synthesis gas can be used
in the production of phosgene.

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634 R. Diercks et al.
Figure 8. Methane-based value added chains and conversion
technologies.
However, there are few methane-based basic products where
production involves a C-C coupling (build-up reaction). One
of the few examples is an acetylene synthesis based upon the
Sachsse-Bartholomé process developed by BASF, in which the
C-C link is achieved by partial oxidation.
Higher alkanes for use as fuel can be produced by the
Fischer-Tropsch synthesis (FT) and olefins can be obtained
from methanol using the MTO (methanol-to-olefins) process.
Acetic acid is produced on a large scale using the Monsanto
process via methanol carbonylation. FT and MTO conversion
technologies based upon synthesis gas/methanol are discussed
in the “Comprehensive Technologies” section (Sec. 6).
4 Coal
As a result of its relatively constant low price, coal is once again
becoming increasingly more attractive for energy generation
and for material use. Coke can be produced from coal by cok-
ing and converted subsequently into acetylene. Synthesis gas
can be produced by coal gasification and can be converted into
chemical products via a similar route to synthesis gas from
methane. Coal can also be hydrogenated directly to fuels,
Fig. 9.
Figure 9. Conversion technologies for coal.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eng. Technol. 2008, 31, No. 5, 631–637
4.1 Calcium Carbide Process
Coke can be converted into calcium carbide in the conven-
tional electric arc process, Fig. 10. In the first step, lime is
burned and then reacted with coke in the arc at temperatures
over 2000 °C to form calcium carbide, during which carbon
disproportionates to carbide and carbon monoxide. Acetylene
is released by treating the calcium carbide with water to pro-
duce slaked lime and slag as coupling products.
Figure 10. Acetylene from coke by the electric arc process.
The advantages of this process are the very simple produc-
tion of acetylene as well as the facile transport of the carbide,
providing a high degree of flexibility in the use of acetylene.
The disadvantages of this process lie in the high temperatures
needed, the high electrical energy requirement of 4 kWh per
1 kg calcium carbide and the link required to consumer indus-
tries for the reuse of the slaked lime and slag.
4.2 Coal Liquefaction
The term ‘coal liquefaction’ nowadays refers to the Fischer-
Tropsch synthesis from synthesis gas, but coal liquefaction tra-
ditionally means the direct conversion of coal to liquid hydro-
carbons by hydrogenation, Fig. 11.
As a result of the high technological requirements, direct
coal liquefaction using the Bergius method for producing fuels
(instead of production from oil) was only feasible during Ger-
many’s drive for self-sufficiency. By 1945, capacity for the pro-
duction of an annual 4 million tons of fuel had been generated
in Germany.
5 Renewable Raw Materials
Conversion from oil to renewable raw materials is motivated
by current price issues, the finite nature of raw materials gener-
ated from fossil fuels, CO2 problems as well as the dependence
on raw material producing countries. In addition to fossil
fuels, biomass can also be converted into synthesis gas and
used as elements in chemical value-added chains (see below).
Here, it becomes possible to exploit the synthetic efficiency of
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Chem. Eng. Technol. 2008, 31, No. 5, 631–637
Figure 11. Coal liquefaction according to Bergius.
nature, i.e., by preserving some of the existing chemical func-
tionalities. In addition to plant oils for surfactants, bioethanol
has recently attracted increasing interest, particularly on the
basis of production from sugar and glycerol found in the waste
streams of biodiesel production.
5.1 Bioethanol
The volume of bioethanol has grown tremendously in the past
few years, particularly as a result of state subsidies, to over 30
million tons/year worldwide. Bioethanol is used predominant-
ly as a fuel in flex-fuel cars, which can be run both on petrol
and on ethanol, and in the manufacture of the fuel additive
ETBE (ethyl-tert-butyl-ether). The price of bioethanol has ri-
sen sharply in recent years as a result of linking to the fuel
pool. The most important applications for bioethanol are
shown in Fig. 12.
Figure 12. Uses of bioethanol.
The dehydration of ethanol produces ethylene, an important
building block in petrochemicals. However, at present, no eco-
nomic process to produce ethylene from bioethanol is avail-
able. Selective dehydrogenation of ethanol can be used to gen-
erate the reactive building block acetaldehyde, which can be
further used in condensation reactions. Oxidation of ethanol
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Process development 635
can produce acetic acid, which is currently formed mainly
via the methanol carbonylation of synthesis gas. Bioetha-
nol can also be used in the manufacturing of ethylamines.
Depending on availability, it is foreseen that ethanol could
become increasingly important for the chemical industry.
5.2 Glycerol
The state-sponsored growth in the production of biodiesel
(ca. 3 million tons/year in Europe) is leading to an in-
creased side-production of glycerol (10 % by weight). This
has led to a significant price decrease and a subsequent
sharpening of focus on glycerol as a potential chemical raw
material. For example, processes for the production of al-
cohols or epichlorohydrin based on glycerol are currently
being discussed.
There is no prospect of a complete conversion of chemi-
cal raw materials to renewable raw materials in the medium
term due to availability, price structure and the lower level of
development of suitable technologies. The wider use of renew-
able raw materials requires further developments in suitable
chemical and mechanical process technology for the digestion
of biomass, new biotechnological processes, new catalysts and
efficient concepts for product recovery.
6 Comprehensive Technologies
The following sections discuss technologies with synthesis gas
as a feed. There are two major technologies for the petrochem-
ical production of basic chemicals: Fischer-Tropsch (FT) as
well as methanol-to-olefins (MTO) and methanol-to-propyl-
ene (MTP®, Lurgi AG).
6.1 CO2 Issues
Each of the carbon sources mentioned can principally be con-
verted into synthesis gas. However, in view of the recent dis-
cussions regarding climate change, the raw material source
must be considered in the context of its corresponding CO2
emission, Tab. 5. For example, a molar ratio H2 to CO of 2 is
required for methanol production by the Fischer-Tropsch syn-
thesis. Using coal as raw material, the production of synthesis
Table 5. CO2 issues for syngas production.
H:C CO2:Syngas*
[mol/mol] [t/t]
Hard Coal 0.6 2.2
Vacuum Residue 1.4 1.3
Gas 4 0.25
Biomass 2 CO2-neutral
* Syngas = H2:CO = 2 mol:1 mol → required ratio for methanol or FT
synthesis
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636 R. Diercks et al. Chem. Eng. Technol. 2008, 31, No. 5, 631–637

gas with this molar ratio produces 2.2 tons of CO2 per ton of 6.3 MTO and MTP® Technology
synthesis gas. When natural gas is used, CO2 production is re-
duced by ca. a factor of 10. In biomass conversion, the CO2 The MTO (methanol-to-olefins) and MTP® (methanol-to-
balance is neutral, provided that no fossil fuels are used in the propylene) processes were developed for the production of the
processing steps. major short-chain C2–C4 olefins, Tab. 6. These processes are
available from UOP/Hydro and Lurgi under license. However,
although some projects are being planned, they have not yet
6.2 Fischer-Tropsch Technology been realized on a large scale. The disadvantages of these pro-
cesses include the high level of investment required for the
Synthesis gas, irrespective of the source, can be used to pro- production of synthesis gas, methanol and olefins compared
duce Fischer-Tropsch (FT) hydrocarbons, Fig. 13. This syn- with the established technologies (cracking and PDH).
thetic method was first discovered in 1925 by Franz Fischer
and Hans Tropsch and was developed to technical maturity in
Table 6. Comparison of technologies for the production of C2–
Germany. The capacity generated was ca. 600 kton/year, and
C4 olefins from syngas.
therefore, much lower than that of coal liquefaction. The post-
1945 Fischer-Tropsch technology was further developed pre- MTO MTP
dominantly in South Africa due to the large quantities of avail-
able coal and the lack of access to crude oil during the apart- Licence UOP/Hydro LURGI
heid regime. Reactor Fluidized Bed Packed Bed
Temperature; Pressure 350 °C; 2 bar 450 °C; 1.5 bar

Yield [Mass %]

Light Gases 2% 1%
Ethylene 39 % –
Propylene 42 % 72 %
Butenes 12 % –
C5+ Hydrocarbons/Fuels 5% 27 %
Figure 13. Fischer-Tropsch technology.

In the FT synthesis, a product mixture is generated using the
chain growth mechanism shown in Fig. 14. The composition
of this product mixture is dependent on the chain growth
probability, a. Current processes are run at an a value between
0.8–1.0, whereby the products are predominantly waxes and
fuels such as petrol and diesel. The short-chain C2–C4 olefins
important in petrochemicals cannot be obtained in current
FT process technologies or only by cracking the higher hydro-
carbons.
Figure 14. Reaction mechanism and product composition for
the FT synthesis.
However, the FT synthesis and both MTO and MTP® pro-
cesses would be very attractive if natural gas or coal become
available at competitive prices. The FT technology also pro-
duces high-quality fuels with a low aromatics and sulfur con-
tent. In the MTP® technology, high-quality fuels are produced
as by-products to propylene.
7 Outlook
Shifts in the use of fossil fuels and renewable raw materials are
expected in the future chemical industry, Fig. 15. Crude oil
will remain the dominant raw material in the chemical indus-
try in the foreseeable future due to its versatility; an assump-
tion substantiated by the existing capital-investment plants,
e.g. naphtha crackers. However, the alternative raw material
sources discussed in this review can be used in establishing
new capacities if oil prices remain high. Natural gas, in partic-
ular, will become increasingly more important both for the en-
ergy and heat markets as well as for use as a chemical raw ma-
terial. The current limiting factors are the lack of economic
technological processes for producing aromatics from natural
gas using C-C coupling reactions.
Coal will also become more important. Developments in
this area need to be made in advancing technologies for CO2
sequestration as well as establishing a stable political basis on

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Chem. Eng. Technol. 2008, 31, No. 5, 631–637
Figure 15. Future trends from the point of view of the chemical
industry.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Process development 637
the topic of CO2 emissions. From the authors’ point of view,
the renewable raw materials are becoming more economically
attractive for selected compounds with improved conversion
technologies. In the event of a significant shift in the price ra-
tio of fossil fuels to renewable sources, an increase in the im-
portance of renewable raw materials in the production of basic
chemicals is foreseeable.
Acknowledgement
The authors thank Dr. A. Seeber for her valuable help with the
preparation of the manuscript for this review article.
This paper was also published in German in Chem. Ing. Tech.
2007, 79 (5), 521. DOI: 10.1002/cite.200700025
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