INTRODUCTION

27

5 SOME FEASIBLE PROCESSES

A brief survey is given of a number of processes that have been used in Europe for
plastics pyrolysis. At present, all of these projects have been mothballed. The most relevant
initiatives are according to [15] :
1. Hamburg University Pyrolysis Process, high-temperature pyrolysis of mixed plastics,
using a uid bed reactor. Demonstration plant at Ebenhausen has not survived shakedown, due to various operating problems.
2. BASF low-temperature pyrolysis of mixed plastics, using a battery of stirred tank
reactors for liquefaction.
3. BP low-temperature pyrolysis of mixed plastics, using a uid bed reactor.
4. Veba Oil hydrogenation technologies.
5.1 PILOT AND INDUSTRIAL PLANT OPERATION
5.1.1 Hamburg University, Ebenhausen

A plant operating according to the Hamburg University pyrolysis process was built at
Ebenhausen, with a capacity of 5000 tonnes per year. The feasibility of converting polyolens by pyrolysis was successfully demonstrated, with yields from PE/PP mixtures of
typically 51% (m/m) gas, 42% (m/m) liquids and the balance unaccounted for. However,
the gas to liquids ratio is very sensitive to pyrolysis temperature. Since gas and oil are the
major pyrolysis products, economic viability crucially depends on the price of crude oil.
Under present conditions, protability and economic viability are unsatisfactory at this
small scale of operation.
5.1.2 BASF, Ludwigshafen

The BASF feedstock recycling process was designed to handle mixed plastic waste, as
supplied by the DSD (Duales System Deutschland) green dot packaging collection system.
A large pilot plant, with a substantial capacity of 15 000 tonne/yr, was started up in
Ludwigshafen in 1994. At that time DSD estimated the total volume of mixed packaging
plastics available for feedstock recycling at around 750 000 ton/yr. BASF offered to erect
a full-scale industrial plant with a capacity of 300 000 ton/yr, but decided in 1996 to shut
down the pilot plant, since no agreement could be reached on a guaranteed long-term
waste supply and a gate fee sufcient to cover the costs.
In the BASF process, plastic waste is converted into petrochemical products in a threestage process. Before feeding, the plastics are shredded, freed from other materials and
agglomerated, to improve handling and enhance the density. In the rst stage, the plastics
are melted and liqueed in an agitated tank. The gaseous hydrochloric acid, evolving from
PVC at temperatures up to 300 C, is absorbed in a water washer, and further processed
to aqueous hydrochloric acid, to be reused in other BASF production plants.
In a second stage, the plastic oil was fed into a tubular cracker reactor, heated at over
400 C and thus cracked into compounds of different chain lengths, forming petrochemical
raw materials. The oils and gases thus obtained are separated in a third stage, resulting
in the production of naphtha, aromatic fractions, and high-boiling oils. About 2030%
of gases and 6070% of oils are produced and subsequently separated in a distillation
column.

28

A. BUEKENS
HCI

Gases
Plastic

Pre-treatment

Liquefaction
and cracking

Separation

Oils
High boilers,
residues

Figure 1.1 Schematic representation of the BASF pyrolysis process. (Reproduced by

permission of TNO)

The naphtha produced by the feedstock process is treated in a steam cracker, and the
monomers (e.g. ethylene, propylene, butadiene) are recovered. These raw materials are
then used for the production of virgin plastic materials. High-boiling oils can be processed
into synthesis gas or conversion coke and then be transferred for further use. All these
products have outlets in the local BASF production plants.
During two years of trial operation, the pilot plant demonstrated its suitability. Although
the process can be considered proven, it is at present neither used by BASF, nor elsewhere
in Germany, because the quantities of plastic waste and dump fee needed for the plant to
be economically viable are not available in Germany (Figure 1.1).
The process products are:

HCl, which is either neutralized, or processed in a hydrochloric acid production plant;

naphtha to be converted into monomers in a steam cracker;
various monomers, which can be used for the production of virgin plastic materials;
high-boiling oils, to be processed into synthesis gas or conversion coke;
process residues, consisting typically of 5% minerals and metals, e.g. pigments or
aluminium can lids.

Processing plastic waste by the BASF process would have required a gate fee of
160/tonne for a plant with a capacity of 300 000 tonne/yr and a fee of 250/tonne for a
plant capacity of 150 000 tonne/yr [15].

5.1.3 BP, Grangemouth

In the early 1990s BP Chemicals rst tested technology for feedstock recycling, using
a uid bed cracking process. Research on a laboratory scale was followed (1994) by
demonstration at a continuous pilot plant scale (nominal 50 kg/hr) at BPs Grangemouth
site, using mixed waste packaging plastics. The technology was further developed with
some support from a Consortium of European companies (Elf Atochem, EniChem, DSM,
CREED) and from APME. In 1998, BP Chemicals, VALPAK and Shanks & McEwan, set
up a joint project (POLSCO), to study the feasibility of a 25 000 tonne/yr plant, including
logistics infrastructure for supplying mixed plastics from Scotland. The project was seen
as a remedy to the expected UK shortage in recycling capability, required to comply with
EU and UK Packaging and Packaging Waste Directive.

29

INTRODUCTION

Some preparation of the waste plastics feed is required before pyrolysis, including size
reduction and removal of most nonplastics. This feed is charged into the heated uidized
bed reactor, operating at 500 C, in the absence of air. The plastics thermally crack to
hydrocarbons, which leave the bed together with the uidizing gas. Solid impurities and
some coke either accumulate in the bed or are carried out as ne particles and captured
by cyclones.
The decomposition of PVC leads to HCl formation, which is eventually neutralized by
contacting the hot gas with solid lime, resulting in a CaCl2 fraction to be landlled. The
process shows very good results concerning the removal of chlorine. With an input of
1% Cl, the products contain 10 ppm Cl, somewhat higher than the 5 ppm typical of
renery use. Also, metals like Pb, Cd and Sb can be removed to very low levels in the
products. Tests have shown that all hydrocarbon products can be used for further treatment
in reneries. The puried gas is cooled, condensing to a distillate feedstock, tested against
agreed specications before transfer to the downstream user plant. The light hydrocarbon
pyrolysis gases are compressed, reheated and returned to the reactor as uidizing gas.
Part of this stream could be used as fuel gas for heating the cracking reactor, but as it
is olen-rich, recovery options were also considered. The ow scheme is illustrated in
Figure 1.2.
The process ow diagram shows hydrocarbon recovery in two stages, since the heavy
fraction becomes a wax at about 60 C. Once recovered, the light and heavy fractions
(about 85% by weight) could be combined together for shipment to downstream renery
processing if the plastic feed is passed on as hydrocarbon liquid to the downstream plants.
The balance is gaseous at ambient temperature and could be used to heat the process. In
this way nearly all of the plastic is used with just solids separated as a waste product.
The gas has a high content of monomers (ethylene and propylene) with only some 15%
being methane.
Conceptually, the process can run in self-sufcient heating mode. In this case, overall
gas caloric requirement may need a small net export or import as the product gas quality

Lime
absorber

Plastics
waste

Reactor

Filter
Hydrocarbon
Distillate feedstock

Fuel gas

Figure 1.2 Schematic representation of the BP process. (Reproduced by permission of

TNO)

30

A. BUEKENS

varies with plastic feed specication and operating conditions. The other main utilities
needed are:
electrical power 60 kWh/tonne feed plastic;
cooling water 40 m3 /tonne feed plastic;
steam 1.2 tonne/tonne feed.
All emissions are very low and should comply with local regulations.
The cost of treatment depends on many factors such as scale, location, scope, required
preparation stages, and economic parameters used. Hence, comparison of the processes is
difcult. The investment costs of a plant of 25 000 tpa, located in Western Europe in 1998,
were estimated as 1520 M. Under these conditions, a gate fee of some 250 /tonne is
necessary. For a 50 000-tpa plant this gate fee could be some 150 /tonne. These gures
exclude the cost of collection and of preparation.

5.1.4 Veba Oil, Bottrop, Germany

From 1981 Veba Oil AG operated a coal-to-oil hydrogenation plant at Kohleol Anlage
Bottrop (KAB) in Germany, using the Bergius Pier coal liquefaction technology to convert
coal into naphtha and gas oil. In 1987 the plant was modied, applying Veba Combi
Cracking (VCC) technology to convert crude oil vacuum distillation residues into synthetic
crude. Since 1988 a share of the petroleum residue feedstock was substituted by chlorinecontaining waste (containing, e.g. PCBs). In 1992/1993 a depolymerization unit was added
in front, to process exclusively mixed plastics waste from packaging, as collected by DSD.
In 1998 some 87 000 tonnes were treated. DSD and Veba both agreed to terminate their
contract in 1999, instead of in 2003: hydrogenation was unable to compete economically
with treatment in blast furnaces and with the SVZ process at Schwarze Pumpe.
The plant includes rst a depolymerization section and then the VCC section
(Figure 1.3). In the rst section, the agglomerated plastic waste is depolymerized and
dechlorinated at 350400 C. The overhead product is partly condensed. The main part
(80%) of the chlorine introduced evolves as gaseous HCl in the light gases and is
washed out, yielding technical HCl. The condensate, still containing some 18% of the
chlorine input, is fed to a hydrotreater where the chlorine is eliminated together with the
water formed. The resulting chlorine-free condensate and gas are again mixed with the
depolymerizate for further treatment in the VCC section.
There, the depolymerizate is hydrogenated under high pressure (about 10 MPa) at some
400450 C, using a liquid phase reactor without internals. Separation yields a synthetic
crude oil, which may be processed in any oil renery. Light cracking products end up in the
off-gas and are sent to a treatment section, for removal of ammonia and hydrogen sulphide.
A hydrogenated bituminous residue comprises heavy hydrocarbons, still contaminated
with ashes, metals and salts. It is blended with coal for coke production (2 wt%).
The input specications for the plastic waste are:

particle size <1.0 cm;

bulk density 300 kg/m3
water content <1.0 weight %;
PVC <4% (2 weight % chlorine);