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

5, 631637

631

Rainer Diercks1
Jan-Dirk Arndt1

Review

Stefan Freyer1
Reiner Geier2
Otto Machhammer1
Jrg Schwartze2

Raw Material Changes in the Chemical

Industry

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 increased sharply and coal quickly developed into a key raw material in the chemical industry, mainly in the production of dyes. In the past century, there has been
a consistent changeover in fossil fuel sources from coal to crude oil and natural
gas due to lower prices, simpler logistics and the versatility in usage of oil and
gas. In view of the limited availability and increasing price of crude oil and natural gas, the question now arises as to how the raw material base will develop in the
future?

BASF SE, Chemicals Research

and Engineering,
Ludwigshafen, Germany.
BASF SE, Strategic Controlling,
Ludwigshafen, Germany.
BASF Catalysts LLC, Iselin,
USA.

Keywords: Chemical industry, Process development, Raw materials

Received: January 31, 2008; accepted: February 27, 2008
DOI: 10.1002/ceat.200800061

Introduction

The availability and prices of natural resources for material

and energy purposes have always played a major role in shaping the structure of the chemical industry. Reliable and economical 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.

Nowadays, carbon-based products in the chemical industry

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 distribution and their static range, which results from the proportion of the reserve that can be explored using modern technologies 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 predominantly 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.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 2. Use of raw materials in the German chemical industry.

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Table 1. Static range of raw material reserves.

Main Producers

Static Rage
Years

Oil

Saudi Arabia, Russia

42

Gas

Russia, Iran

63

Hard Coal

China, USA

159

Brown Coal

Germany, USA

227

Cereal

America, EU

00

Plant Oil

America, Malaysia

00

Wood/Lignin

America, EU

00

Source: Bundesanstalt fr Geowissenschaften und Rohstoffe 2004; BP

Statistical Review of World Energy June 2005

i.e., synthesis gas (CO/H2), olefins, acetylene and the aromatics, all derived using existing conversion technologies,
Tab. 2, is illustrated in a simplified form in Fig. 5. The following characteristics are particularly noteworthy from Fig. 5:
At present, all basic chemicals, in particular BTX (benzene,
toluene, xylene), can only be produced in sufficient quantities from crude oil.
Synthesis gas can be produced as the general-purpose building block from all carboniferous compounds.
Renewable raw materials offer the possibility of exploiting
the synthetic efficiency of nature, i.e., by preserving some of
the existing chemical functionalities.
Table 2. Conversion technologies: From raw materials to basic
chemicals.
Raw Material

Technology

Basic Chemicals

Oil

Cracking

Olefins, Aromatics

Catalytic Reforming

Aromatics

Steam Reforming

Syngas

Cracking

Ethylene

Dehydrogenation

Olefins

Gasification

Syngas

Coking

Aromatics

Gas (C1C4)

Coal

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 consumption in the areas of energy and nutrition. The supply/demand balance is equally influential in the price of raw materials. 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.

Figure 4. Price development of fossil fuels.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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
crude oil in refineries.

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2.2

Process development

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 hydrocarbons. However, the growth rates for propylene are higher than
for ethylene, which means that technologies leading to decoupling are very attractive. The higher alkanes of natural gas can
be used for this purpose.

Figure 6. Typical product composition of a naphtha cracker.

Natural Gas

Natural gas consists basically of methane, but depending on

the source can also contain higher alkanes, Tab. 3. LPG (liquefied 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.
Table 3. Typical composition of natural gas at the drilling hole.
Component

Minimum

Maximum

Methane

79 %

98 %

Ethane

1%

12 %

Propane

0%

6%

Butane

0%

3%

C5+

0%

3%

w/o acidic components and water

3.1

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Alkane Dehydrogenation

One technology suitable for the selective production of propylene is propane dehydrogenation (PDH), Fig. 7. The reaction
occurs via an extremely endothermic catalytic process. There

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 7. Propane dehydrogenation technologies.

are currently two main technical concepts for feeding the heat
of reaction into the system: (a) In adiabatic processes, the propane 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 processes licensed by UOP, ABB, Uhde and Linde/BASF, Tab. 4.
With the exception of the chromium/aluminum oxide-catalyzed Catofin process of ABB, each process utilizes a platinum
catalyst. In UOPs Oleflex process, moving bed reactors are
operated adiabatically with external catalyst regeneration. The
Catofin process employs adiabatic fixed bed reactors that, unlike the reactors in the Oleflex process, are operated discontinuously. Both Uhdes 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

Licence

UOP

ABB

Uhde

Linde/BASF

Catalyst

Pt/Support

Cr/Al-Oxide Pt/Support

Reactor Type Moving bed Packed bed

adiabatic

3.2

adiabatic

Pt/Support

Packed bed

Packed bed

isothermal

isothermal

C1 Chemistry from Natural Gas

Methane is the principal component of natural gas and can be

converted to various C1 building blocks, Fig. 8. Hydrogen cyanide 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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4.1

Calcium Carbide Process

Coke can be converted into calcium carbide in the conventional 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 produce slaked lime and slag as coupling products.

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-Bartholom 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).

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 coking 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 10. Acetylene from coke by the electric arc process.

The advantages of this process are the very simple production 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 industries for the reuse of the slaked lime and slag.

4.2

The term coal liquefaction nowadays refers to the FischerTropsch synthesis from synthesis gas, but coal liquefaction traditionally means the direct conversion of coal to liquid hydrocarbons 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 Germanys drive for self-sufficiency. By 1945, capacity for the production of an annual 4 million tons of fuel had been generated
in Germany.

Figure 9. Conversion technologies for coal.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Coal Liquefaction

Renewable Raw Materials

Conversion from oil to renewable raw materials is motivated

by current price issues, the finite nature of raw materials generated 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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Process development

635

can produce acetic acid, which is currently formed mainly

via the methanol carbonylation of synthesis gas. Bioethanol 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

Figure 11. Coal liquefaction according to Bergius.

nature, i.e., by preserving some of the existing chemical functionalities. 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

Glycerol

The state-sponsored growth in the production of biodiesel

(ca. 3 million tons/year in Europe) is leading to an increased 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 alcohols or epichlorohydrin based on glycerol are currently
being discussed.
There is no prospect of a complete conversion of chemical 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 renewable 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.

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 predominantly 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 risen sharply in recent years as a result of linking to the fuel
pool. The most important applications for bioethanol are
shown in Fig. 12.

Comprehensive Technologies

The following sections discuss technologies with synthesis gas

as a feed. There are two major technologies for the petrochemical production of basic chemicals: Fischer-Tropsch (FT) as
well as methanol-to-olefins (MTO) and methanol-to-propylene (MTP, Lurgi AG).

6.1

CO2 Issues

Each of the carbon sources mentioned can principally be converted into synthesis gas. However, in view of the recent discussions 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 synthesis. Using coal as raw material, the production of synthesis

Table 5. CO2 issues for syngas production.

Figure 12. Uses of bioethanol.

The dehydration of ethanol produces ethylene, an important

building block in petrochemicals. However, at present, no economic process to produce ethylene from bioethanol is available. Selective dehydrogenation of ethanol can be used to generate the reactive building block acetaldehyde, which can be
further used in condensation reactions. Oxidation of ethanol

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

H:C
[mol/mol]

CO2:Syngas*
[t/t]

Hard Coal

0.6

2.2

Vacuum Residue

1.4

1.3

Gas

0.25

Biomass

CO2-neutral

* Syngas = H2:CO = 2 mol:1 mol required ratio for methanol or FT

synthesis

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gas with this molar ratio produces 2.2 tons of CO2 per ton of
synthesis gas. When natural gas is used, CO2 production is reduced by ca. a factor of 10. In biomass conversion, the CO2
balance is neutral, provided that no fossil fuels are used in the
processing steps.

6.2

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R. Diercks et al.

Fischer-Tropsch Technology

Synthesis gas, irrespective of the source, can be used to produce Fischer-Tropsch (FT) hydrocarbons, Fig. 13. This synthetic method was first discovered in 1925 by Franz Fischer
and Hans Tropsch and was developed to technical maturity in
Germany. The capacity generated was ca. 600 kton/year, and
therefore, much lower than that of coal liquefaction. The post1945 Fischer-Tropsch technology was further developed predominantly in South Africa due to the large quantities of available coal and the lack of access to crude oil during the apartheid regime.

6.3

MTO and MTP Technology

The MTO (methanol-to-olefins) and MTP (methanol-topropylene) processes were developed for the production of the
major short-chain C2C4 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
been realized on a large scale. The disadvantages of these processes include the high level of investment required for the
production of synthesis gas, methanol and olefins compared
with the established technologies (cracking and PDH).
Table 6. Comparison of technologies for the production of C2
C4 olefins from syngas.
MTO

MTP

Licence

UOP/Hydro

LURGI

Reactor

Fluidized Bed

Packed Bed

Temperature; Pressure

350 C; 2 bar

450 C; 1.5 bar

Light Gases

2%

1%

Ethylene

39 %

Propylene

42 %

72 %

Butenes

12 %

C5+ Hydrocarbons/Fuels

5%

27 %

Yield [Mass %]

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
0.81.0, whereby the products are predominantly waxes and
fuels such as petrol and diesel. The short-chain C2C4 olefins
important in petrochemicals cannot be obtained in current
FT process technologies or only by cracking the higher hydrocarbons.

Figure 14. Reaction mechanism and product composition for

the FT synthesis.

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However, the FT synthesis and both MTO and MTP processes would be very attractive if natural gas or coal become
available at competitive prices. The FT technology also produces high-quality fuels with a low aromatics and sulfur content. In the MTP technology, high-quality fuels are produced
as by-products to propylene.

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 industry in the foreseeable future due to its versatility; an assumption 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 particular, will become increasingly more important both for the energy and heat markets as well as for use as a chemical raw material. 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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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 ratio of fossil fuels to renewable sources, an increase in the importance 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.
Figure 15. Future trends from the point of view of the chemical
industry.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper was also published in German in Chem. Ing. Tech.

2007, 79 (5), 521. DOI: 10.1002/cite.200700025

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