i

Waste-to-plastics: process alternatives

SELIM NOURI a
KRISTIN KAGGERUDb

a
Department of Energy and Environment, Environmental Systems Analysis Division
(ESA)
CHALMERS UNIVERSITY OF TECHNOLOGY

b
Energy and Process Engineering department, Faculty of Engineering Science and
Technology
NORWEGIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY

Göteborg, Sweden 2006

ii
Waste-to-plastics: process alternatives

SELIM NOURI
KRISTIN KAGGERUD

ESA-report 2006:17
ISSN 1404-8167

Department of Energy and Environment, Environmental Systems Analysis Division

(ESA)
CHALMERS UNIVERSITY OF TECHNOLOGY

SE-412 96 GÖTEBORG
Sweden 2006

http://www.chalmers.se/ee/SV/forskning/forskargrupper/miljosystemanalys

CPM-report 2006:10
ISSN 1403-2694

CPM – Centre for Environmental Assessment of Product and Material Systems

CHALMERS UNIVERSITY OF TECHNOLOGY

SE-412 96 GÖTEBORG
Sweden 2006

www.cpm.chalmers.se

Frontpage photos: Biomass Gasification Methanol Synthesis. Photo: AIST; Methanol to

Olefins demo plant. Photo: ExxonMobil.

Chalmers reproservice
Göteborg, Sweden 2006

iii
Abstract

In this report, processes for converting woody biomass to plastics (BTP) and
waste plastics into plastics (PTP) are examined. The technologies evaluated
are thermochemical conversion of the raw material into polyethylene (PE)
and polypropylene (PP). The core strategy is to take the biomass or plastic
waste through gasification, water gas shift (WGS), methanol production,
methanol to olefins (MTO) and finally plastic production. The
environmental attractiveness of these emerging technologies is evaluated
using a combination of process modelling and life cycle assessment (LCA)
methodology. Several tools and simulation softwares have been combined
to carry out the study, including Aspen’s HYSYS, LCAiT and Excel.

Important factors have been identified and evaluated, like climate change
mitigation, feedstock availability, recycling loops and technological
improvements. Various improvements of the processes are evaluated with
respect to green house gases emissions potential for the system. The most
important outcomes of the study include:

1. Production of plastic from biomass and plastic waste seems possible

using the BTP and PTP processes, respectively.

2. As a plastic production system, the BTP seems more advantageous

than PTP regarding green house gases emissions.

3. The gasification unit, with the air separation unit to produce oxygen,
is the main contributors to CO2 emissions. A case with an improved
gasifier for plastic waste shows significant improvements.

4. To use hydrogen surplus from a chemical plant as a hydrogen fuel

cells feedstock is not the only option available. Hydrogen surplus
could be use to greatly improve the BTP and PTP routes - or similar
processes - as shown in this report.

5. The method, which combines LCA and process modelling, enables

an effective early-design phase evaluation.

iii
 The main numerical findings are summarised in the table A below.

Table A: Summary of kg CO2-equivalent (CO2-eqv) and waste per functional unit for the various scenarios.

Scenario Renewable CO2- Non-renewable CO2- Waste per functional unit

eqv eqv
Dry As received

Base case BTP 5.8 1.4 4.7 9.4

PTP 5.8 2.2 3.6 3.6

Improved gasifier PTP 4.4 1.4 2.8 2.8 (1.4)1

H2 added BTP 3.5 1.1 3.4 6.7

PTP 3.5 1.7 2.7 2.7

1
50 % oil slurry in the treated material; 1.4 kg of waste plastics and 1.4 kg of oil per functional unit. Functional
unit: 1 kg of plastic produced

Keywords: Methanol-to-Olefins (MTO); synthesis gas; gasification; Life

Cycle Assessment; process modelling; renewable plastics.

iv
Preface
We would like to express our warmest gratitude to all people that in one
way or another have contributed to the completion of this report.

We highly appreciated the participation and collaboration from all

correspondents in the CPM network, as well as all engineers – especially
from Norsk Hydro and Borealis - who helped us. Their supportive and kind
efforts to enhance the content of our report with real industrial expertise are
priceless and exclusive of their time, knowledge, experience and input, this
report could not have been concluded. Finally, we would like to thank our
Norwegian colleague, Kristin Kaggerud, for her participation, insightful
comments, constructive criticism and encouraging words throughout the
entire process of creating this report.

Göteborg, June 2006

Selim Nouri

v
Nomenclature

ASU: Air separation unit. Process that separate the air into its main
compounds: oxygen, nitrogen, argon and rare gases if necessary.

Biomass: material that are biological in origin, such as grasses, trees,

municipal solid waste, etc.

BDP: barrel per day.

BTP: biomass to polymer.

CH4: methane.

CO: carbon monoxide.

CO2: carbon dioxide.

CO2eq: carbon dioxide equivalent; the amount of carbon dioxide by

weight emitted into the atmosphere that would produce the equivalent
radiative forcing as a given weight of another greenhouse gas. Carbon
dioxide equivalents are the product of the weight of gas being
considered and its global warming potential.

DME: dimethyl ether (CH3-O-CH3) is the simplest of all ether; DME is

currently manufactured from methanol by dehydration.

GHG: green house gases.

GTL: gas to liquid, process that transform natural gas into a more
transportable liquid fuel.

HDPE: high density polyethylene

HHV: high heating value

vi
LCA: life cycle assessment

LCI: Life Cycle Inventory

LDPE: Low density polyethylene

LNG: liquefied natural gas. LNG process liquefies natural gas for easier
transportation using cryogenic process

MeOH: methanol

MeOH/DME: methanol/dimethyl-ether. Since DME is the “dehydrated

version” of MeOH (2MeOH => DME +H2O) and that it is not still clear
(studies are performed and industries are working on it) to assess
whether it is better or not to produce directly one or the other. We will
not judge this issue and will consider MeOH and DME as almost the
same product at first. It is not that important for our first study of the
BTP route since the MTO can be fed either with MeOH or DME.

MJ: megajoule [106 J]

MM: million [106]

MMBtu: million British thermal units

MTBE: methyl tertiary butyl ether

MTD: metric ton per day

MTO: methanol to olefins

MTP: methanol to propylene

NREL: US national renewable energy laboratory

PE: polyethylene

PLA: Polylactic acid, degradable polyester commercially available

PP: polypropylene

PTP: plastics to plastics

vii
WTT study: well-to-tank study

viii
Table of contents

Abstract........................................................................................................iii

Preface...........................................................................................................v

Nomenclature................................................................................................vi

Table of contents..........................................................................................ix

1 INTRODUCTION....................................................................................xiii

2 METHODOLOGY...................................................................................xiii

3 GOAL AND SCOPE................................................................................xiv

3.1 Options to model...............................................................................xiv

3.2 Initial flowchart.................................................................................xiv

3.3 Functional unit...................................................................................xv

3.4 Environmental impact categories ......................................................xv

3.5 Type of LCA approach.......................................................................xv

3.6 System boundaries.............................................................................xvi

3.7 Geographical boundaries...................................................................xvi

3.8 Time horizon.....................................................................................xvi

3.9 Cut-off criteria...................................................................................xvi

3.10 Boundaries in relation to other process/product life cycles and

allocation................................................................................................xvii

3.11 System subdivisions......................................................................xvii

ix
 3.12 Data quality requirements.............................................................xvii

3.13 Assumptions and limitations.........................................................xvii

4 PROCESS DESCRIPTIONS.................................................................xviii

4.1 Gasification........................................................................................xix

4.2 Water gas shift (WGS)......................................................................xxi

4.3 Sulferox – removal of sulphur..........................................................xxii

4.4 CO2 removal unit.............................................................................xxii

4.5 Methanol production.......................................................................xxiii

4.6 Air separation unit (ASU)...............................................................xxiv

4.7 Methanol to olefins (MTO).............................................................xxiv

4.8 Borealis Borstar process for production of HDPE and PP..............xxvi

5 SCENARIOS.........................................................................................xxvii

5.1 Base case scenario.........................................................................xxviii

5.1.1 Gasification to clean syngas...................................................xxviii

5.1.2 Methanol to plastics................................................................xxxii

5.1.3 Transportation........................................................................xxxiii

5.2 Technological improvement of the gasifier...................................xxxiv

5.3 Addition of hydrogen......................................................................xxxv

5.4 Change in electricity and transport systems..................................xxxvi

5.5 Models..........................................................................................xxxvii

6 RESULTS.............................................................................................xxxix

6.1 Base case scenario ..............................................................................xl

x
 6.1.1 methanol island as one unit..........................................................xl

6.1.2 methanol island shown as separate units....................................xlii

6.2 Technological improvement..............................................................xlv

6.2.1 THEORETICAL maximum.......................................................xlv

6.2.2 wood waste and technology improvement.................................xlv

6.2.3 plastic waste and technology improvement...............................xlvi

6.3 Addition of hydrogen.....................................................................xlviii

6.4 Transport system...................................................................................l

6.5 Electricity mix......................................................................................li

7 DISCUSSION...........................................................................................liii

8 CONCLUSION........................................................................................lxii

9 REFERENCES........................................................................................lxiv

Appendix 1: waste recovery potential.....................................................lxviii

Appendix 2 : Waste availability, ethylene network in EU, etc.................lxix

....................................................................................................................lxx

Map.1 EU oil and gas transportation system

http://www.inogate.org/inogate/en/resources/maps ...................................lxx

...................................................................................................................lxxi

Map.2 Refineries, Pipelines and Crackers in Europe, Appe – Association of

petrochemicals producers in Europe, 2004
http://www.petrochemistry.net/ftp/pressroom/map_europe2004.pdf .......lxxi

10 Appendix 3: Detailled process unit flowsheets:...................................lxxii

Appendix 4: EU El-mix.........................................................................lxxviii

xi
Appendix 5: waste feedstock composition..............................................lxxix

Appendix 6: models.................................................................................lxxxi

Appendix 7: assignment of CO2 emission............................................lxxxiv

Appendix 8: impact categories..............................................................lxxxvi

Appendix 9: oil and emissions....................................................................xci

Appendix 11 : Hydrogen production environmental impact....................xciv

Appendix 12: Lock-hopper feeding system ...............................................civ

Appendix 13: Theoretical maximum..................................................cvi

Appendix 14: HDPE and PP Borstar processes commercial analysis and technology
review (Nexant 2002)..................................................................................cix

Appendix 15: Different Methanol to Olefin concepts ..............................cxii

xii
1 INTRODUCTION
In these times of high energy demand, waste monetization strategies are highly
appreciated. Wood wastes from forest and pulp-and-paper industries, as well as plastic
wastes represent interesting feedstocks for syngas based processes that can lead to
numerous products, including plastics production. Those processes could help to
monetize waste thus reducing the amount of waste while saving fossil fuels (cf. appendix
1) and mitigating climate change. However, the concept of waste-to-plastics and more
particularly the plastics-to-plastics (PTP) route needs to be modelled in terms of
environmental impact and chemical engineering. Indeed, previous studies (Nouri, Tillman
2005, Kaggerud et al 2003) have shown the potential for syngas based process to olefins
and plastics as an alternative to oil and gas feedstocks. The purpose of the research
presented here is to evaluate the environmental impact of the different process
configurations that may suit plastics production from wood or plastic wastes.

2 METHODOLOGY
To evaluate the environmental performance of the plastic production process from
alternative feedstocks (wood waste and waste plastics), we have combined several
technical and environmental methodologies and simulation softwares. Among them are
process modeling softwares and LCA softwares, the combination of which gave the
results presented and discussed in this paper.

Process modelling softwares are tools for managers and engineers to find the optimum
process design and link business objectives with process design. They allow simulation of
different process designs, specification of process equipment, evaluation of the effects of
changes (feed, equipment etc) on the process and the assessment of process deficiencies.
They also offer modules where the financial outcome of the process may be projected.
Environmental issues, however, are assessed by these softwares only in a very limited
way. Energy use and other resource consumption such as feed-stock are modelled, but
they do not allow for modelling of emissions to the natural environment, and hence not
environmental impact. They do thus not support modelling of what-if-scenarios with
respect to environmental aspects. This is rather surprising, given the strong development
of life cycle assessment (LCA) approaches during the last decade and the chemical
engineering roots of life cycle assessment.

xiii
In this project LCA and process modelling were linked. Aspen HYSYS was used to
simulate a waste to plastics process. The results from the Aspen HYSYS model were then
exported and integrated in an LCA model to calculate the environmental impacts of the
process. Variations of the base cases were then simulated – changes of energy systems,
logistics, plant configurations…etc... – in a series of sensitivity analyses.

3 GOAL AND SCOPE

The goal of the study is to model the production of plastics from waste and to see the pros
and cons of different process configurations. The reason for carrying out the study is to
evaluate different design alternatives at an early design phase for production of plastics
from waste. And more generally; does it even make sense, from an environmental point
of view, to produce plastics from waste plastics or wood waste?

3.1 Options to model

Different ways to produce polyolefins from waste using syngas technologies will be
modelled and evaluated with respect to environmental performance. The results will be
used to identify the best option for production of polyolefins from waste plastics and
wood waste by modifying process options like technology, plant configuration and
location. In addition to identifying the best options for each of the waste sources, it is
interesting to look at the differences and similarities of the two options, a comparative
study. The different composition and nature of the two feedstocks require different
configurations and to a certain extent different technology. One example is the chlorine
content in the plastic waste, which is not present in biomass at all. Special attention will
also be given to the distinction between CO2 which originate from the waste and CO2
from other sources, like electricity production and fuel for transport.

3.2 Initial flowchart

The initial flowchart includes 6 main steps (cf. figure 1): the gasifier, the gas cleaning
section, the water gas shift, the methanol synthesis, the methanol-to-olefins unit and the
polyolefin unit.

xiv
Figure 1: Block diagram for production of plastic from biomass (wood waste) and plastic waste, the system
boundary is shown as the dotted line.

3.3 Functional unit

The functional unit (FU) is production of 1 kg polymer, of which 0.68 kg is HDPE and
0.32 kg is PP. Please note that the data used for both mass and energy balances are valid
only for the given capacity of the process as the performance of chemical processes is
dependent on scale. The assumed capacity of each process is given in Section 4.

3.4 Environmental impact categories

Different configurations for production of polyolefins from waste are evaluated with
respect to Global warming potential (GWP), energy use and acidification. Global
warming potential and energy will be used as main indicators to select the best way to
process waste to polymer.

3.5 Type of LCA approach

Since the configuration changes have direct impact on green house gases emissions, it is
important to account for carbon that come from the feedstock (wood or waste plastics)
separately from that of green house gases emanating from energy systems or logistics.

xv
For practical , but not entirely so, reasons, we have in this study used the term renewable
carbon emissions for all carbon originating from the feedstock, irrespective of whether it
is plastic wastes or wood waste. Of course carbon dioxide emanating from recycled
plastics today is really fossil in origin, but the terminology chosen allows for making
what-if scenarios in a change-oriented LCA perspective: what if the plastics are originally
renewable?...

3.6 System boundaries

For the methodology used (process modelling and LCA) a cradle to gate perspective was
used. The technical system takes into account the consequences of the different process
configuration to produce polyolefins, from the waste collection to the output of the
polyolefin unit. Production and use of plastics are not included. Neither are the forestry
that produces wood waste as a by-product nor the use phase of PE and PP plastics. Some
waste management systems literature data were used in this report to compare processes
with existing systems.

3.7 Geographical boundaries

Many process and market parameters are closely linked to choice of location (electricity
production, product demand, waste availability, transport, etc.). The modelled process
train will be located in Western Europe using an E.U electricity mix. It is an advantage
for the process to be located close to a hydrogen source; hence it will be located near a
chlorine plant, a refinery, a methanol or ammonia plant (Lasher et al 2005). In addition to
the Western European location a localisation in Poland will also be studied in the
sensitivity analysis also be carried out. Appendix 2 maps outline the waste availability,
transport, H2 availability…etc…of potential sites in Poland and Western Europe.

3.8 Time horizon

The technologies included in this study are processes that can be built within 5 years. The
study is based on a technology screening that identified syngas based processes able to
produce polymers using existing technology (pilot plant scale or demo plant scale
minimum). As a consequence of choosing only available technologies, or close to
available, future developments - like electricity generation via fuel cells - are not
considered. However, an advantage is that data availability is better and more consistent.

3.9 Cut-off criteria

Production of capital goods, transport means and buildings are not considered in this
study.

xvi
 3.10 Boundaries in relation to other process/product life cycles
and allocation
We try to avoid allocation when possible (cf. FU). H2 from Cl2-production and refineries
is seen as excess by-product production; hence the production is not allocated to plastic
production.

3.11 System subdivisions

Since we are using a change oriented LCA approach subdivision of the systems into a
foreground and a background could be appropriate. The foreground system will be the
main 6 steps described in 3.2 and the background system will be the other units (H2
production, steam island…), electricity production and transports. The difference between
background and foreground systems is mainly due to which part of the system is under
direct influence of the decision maker (here the future manager of the plant for instance).
The foreground system is directly influence by measures taken and the background
indirectly.

3.12 Data quality requirements

As mentioned in Section 3.8, processes which can be commercialised within 5 years have
been chosen for this study. Data are taken from technical reports and published papers.

3.13 Assumptions and limitations

It is assumed, in accordance with most of the studies performed in this field, that syngas
processes have a great potential regarding variation in waste feedstock and that
pressurized oxygen blown gasification is the most robust way to make syngas from waste
(Drift, A. van der (Bram) 2005). One of the main limitations is the data availability.

xvii
4 PROCESS DESCRIPTIONS

In this section the processes for production of plastic from biomass (wood waste) and
plastic waste are presented and described. The only technological difference between the
two scenarios is the gasification unit, where different gasifiers are used to produce syngas
suitable for methanol production. The remaining units in the process train are similar,
however, with some adjustment for the different composition of the syngas biomass and
waste plastic, respectively.

The Plastic waste to plastic (PTP) concept is developed by Norsk Hydro and offers a
closed-loop system for a large scale recycling of mixed plastic waste back to plastic. The
concept envisages combining existing technologies for waste treatment and production of
valuable chemicals. The concept is outlined in Figure 1. The core strategy is taking plastic
waste back to plastic. The mixed plastic waste is collected and pre-treated making it
usable in a gasification process. The plastic waste is broken down to the chemical
components, CO and H2, in the gasifier. In order to produce new plastic material, the CO
and H2 are converted to methanol which is further reacted over a catalyst to produce
olefins by use of the patented UOP/Hydro Methanol to Olefins process (MTO). Olefins
are the feedstock in the production of plastic; e.g. PVC, PE, PP and PET. The mixed
plastic waste also contains metals and other inorganics, which will be separated from the
synthesis gas in the gasifier and recovered. The metals can replace virgin metals and the
other inorganics are recovered as a glazed slag, known as frit and usable e.g. in roadbeds
or in cement production. All carbonaceous material is a potential feedstock in the
concept; here we look at biomass and waste plastic material.

Two operating processes worldwide have produced chemicals from plastics waste, one in
Germany and one in Japan. SVZ in Germany has produced methanol from mixed waste
(Malkow, 2004) and Ebara in Japan produces ammonia from plastic waste (Parkinson,
2002), they are both gasifying the plastics waste. About biomass as a feedstock, there are
many on-going projects to produce fuels and chemicals from biomass (Kwant, 2004), and
for the promising pressurized oxygen blown technology, 2 pilots plant have been
identified as leading projects: the Choren GmbH owned BtL plant in Freiburg, Germany
which produces FT-diesel from biomass, and the MHI ltd Biomass Gasification Methanol

xviii
Synthesis System constructed in the Kawagoe Power Station of Chubu EPCO (Japan)
which produces methanol from biomass.

Based on a previous technology screening (Nouri & Tillman 2005), process information
for the different process units has been collected. The main sources for the process
descriptions are Ekbom et al (BioMeeT and BioMeeT II reports), Future Energy (2003),
Hamelinck and Faaij (2001) and Nirula (1994). The block diagram given in Figure 1 is
the basis for the process description given here. All technologies are at a technological
status where they are either commercially available or close to marketing. All process
units are explained with a block diagram, for more detailed flowsheets see Appendix 3.

4.1 Gasification
In the gasification unit carbonaceous waste reacts with oxygen in a partial oxidation
producing synthesis gas. Synthesis gas consists mainly of CO, H2, CO2 and H2O, where
CO and H2 are the most desirable components when the syngas is to be used in
production of methanol. Pure O2 is chosen as the oxygen source in this concept to assure a
high calorific syngas; hence the following overall, strongly exothermic, reaction will take
place in the gasifier. In the equation (4-0) the subscript p is used to indicate that this is a
reaction with various polymers, which consists of different monomers (CxHy).

x⋅ p  y⋅ p
(C H )
x y p + O2 → ( x ⋅ p ) CO +  H 2 (4-0)
2  2 

Two different gasification technologies have been chosen for gasification of biomass and
plastic waste, respectively, they are shown in Figure 2 and 3.

xix
Figure 2: Block diagram of the gasification unit for biomass (Ekbom et al, 2003)

Figure 3: Block diagram of the gasification unit for plastic waste (Future Energy, 2003)

Both gasification technologies operate at temperatures of ~1200ºC and medium pressure.

They are both fed with oxygen in order to obtain a high quality syngas. The gasifier used
for biomass is an oxygen blown reactor bubbling fluidised bed (with a dolomite bed). Part
of the CO2 removed from the syngas is recycled to the process and used in the lock
hopper feeding system (cf. Appendix 12). Excess heat from the high temperature process
is used to produce high pressure steam for downstream processes.

The gasifier used for plastic waste is an entrained flow gasifier (cf. figure 4), where water
or oil is used as the slurry material. Chlorine from the waste material is removed from the
syngas and recovered as NaCl. In order to avoid dioxin formation, the product gas is led
to a direct quench. The use of a direct quench, results in less high temperature heat
available for steam generation. Consequently large amounts of low pressure steam are
produced in the plastic gasifier.

xx
Figure 4: Different types of gasifiers (Bain, 2004)

4.2 Water gas shift (WGS)

The syngas leaving the gasifiers does not contain enough hydrogen for a high yield in the
methanol production unit; hence the gas is led to the shift reactor where the hydrogen
content is adjusted. In the water gas shift unit CO and H2O are shifted towards CO2 and
H2 over a catalyst. The reaction is slightly exothermic and is given in Equation 4-1.

CO + H 2 O ↔ CO 2 + H 2 4-1

The reaction is used to adjust the H2/CO-ratio to better suit the requirements in the
methanol production unit. As the reaction is exothermic, a high yield of hydrogen is
favoured by a low temperature. The WGS unit is modelled as two Gibbs reactors in
Aspen HYSYS, the first at high temperature (350ºC) to utilise the kinetics for a fast
reaction at high temperatures, the second at low temperature (260ºC) to shift the
exothermic reaction 4-1 to the right at the more preferable low temperature.
Temperatures were taken from Hamelinck et al. (2001). The block diagram is shown in
Figure 5.

xxi
Figure 5: Block diagram of the water gas shift reactor system

4.3 Sulferox – removal of sulphur

The Sulferox process treats the syngas and removes the sulphur from the stream. The
treated gas is sent to the CO2-removal unit, whereas the stream that contains sulphur is
treated further in the Sulferox unit to produce solid sulphur. The process is shown in
Figure 6.

Figure 6: Block diagram for Sulferox, removal of sulphur from the syngas (Ekbom et al, 2000).

4.4 CO2 removal unit

CO2 is removed from the syngas before it enters the methanol production unit. The block
diagram showing the CO2 removal unit is given in Figure 7. CO 2 is removed by use of
amine absorption, where CO2 reacts with the amine in the absorber, the treated gas is then
released with a low CO2 content. The amine is then regenerated by adding steam in the
stripper, which release CO2 to vent.

xxii
Figure 7: Block diagram for the process of CO2 removal from the syngas (BioMeeT, 2000).

4.5 Methanol production

The next step in the concept is the production of methanol from syngas, which is achieved
by a conventional methanol process (Liquid Phase methanol reactor). The main reactions
are given below, both are exothermic reactions. In order to obtain maximum catalyst
activity, 5% of the feed should be CO2 (Moulijn, 2003).

CO + 2 H 2 → CH 3 OH (3)

CO 2 + 3H 2 → CH 3 OH + H 2 O (4)

The conversion in the methanol reactor is low; hence a high recycling rate of the
unreacted syngas is necessary. Part of the recycle gas is taken out as a purge gas in order
to avoid build up of inert in the system. The purge gas is used as an energy source for
steam generation. The methanol process given in Figure 8 differs from plants converting
natural gas into methanol, since the MTO plant tolerates crude methanol as input. This
means that the separation of methanol and water in distillation columns is avoided.

xxiii
Figure 8: Block diagram for methanol production from the gasifier (BioMeeT, 2000).

4.6 Air separation unit (ASU)

Both gasification technologies are operated with 95% purity oxygen as the oxidation
agent. Production of O2 is done in an air separation unit. Air is compressed and cooled,
and then separated in a cryogenic distillation column. The block diagram is given in
Figure 9.

Figure 9: Block diagram showing production of oxygen from air by use of cryogenic distillation

4.7 Methanol to olefins (MTO)

In the MTO process methanol is converted to olefins (mainly ethylene and propylene)
over a catalyst. The principal reaction is given as Equation 4-2 (Kvisle et al., 2002).

5CH 3OH → CH 2 CH 2 + CH 2 C HCH 3 + 5H 2 O 4-2

The block diagram of the MTO unit is given in Figure 10. The process consists of two
parts; the circulating fluidised bed reactor and the separation sequence. The MTO plant is
flexible wit regard to the C2/C3-ratio, and typically the ratio can be modified within a

xxiv
range of 0.75-1.5 by adjusting the operating severity, with higher temperature leading to
higher C2/C3-ratio (Kvisle et al., 2002).

Part of the reactant forms coke on the surface of the catalyst, which is beneficial as it
increases the catalyst activity. Around 5% coking is suitable (Kvisle 2005), however large
build-up of coke will hinder the products to be formed, and consequently the catalyst has
to be regenerated. The catalyst is regenerated by burning off the coke by air in the second
of the two reactors in the fluidised reactor system. The regeneration process emits CO2 to
air as shown in figure 10.

Figure 10: Block diagram for the MTO unit (Kvisle et al., 2002).

Based on extensive tests in the demonstration plant, the MTO process is to be scaled up to
a single train unit with capacity of up to one million tonnes of light olefins per year
(Kvisle et al., 2002). Basic engineering of the first planned commercial MTO plant based
on stranded natural gas, has been carried out. The plant will be part of a petrochemical
complex in Nigeria, and is scheduled to come on stream in 2009, putting ahead of the
projected 2007 date for a rival Egyptian MTO project. The plant will convert 2.5 million
tonnes methanol into 400,000 tonnes of ethylene and 400,000 tonnes of propylene
(Chementator, 2003). There are actually around the world 5 different MTO concept units
on-going pilot projects: the MTO process demonstration unit (PDU) from UOP/HYDRO
in Porsgrunn (Norway), the Lurgi Methanol To Propylene (MTP) PDU in Tjelbergodden
(Norway), the ExxonMobil MTO PDU in Baytown, Texas (USA), the Total

xxv
Petrochemicals Olefin Cracking Process integrated with UOP/Hydro MTO (starting
expected in 2007) in Feluy (Belgium) and the JGC Corp dimethyl ether to propylene
(DTP) pilot (expected for 2007) in Japan. More details about the different MTO concepts
are available in Appendix 15. No MTO plants is planned before 2009.

4.8 Borealis Borstar process for production of HDPE and PP

The block diagrams for production of HDPE and PP by use of the Borealis’s Borstar
technology are shown in Figure 11 and 12, respectively. More details are given in
Appendix 14.

Figure 11: Block diagram of Borealis’s Borstar technology for production of HDPE from ethylene

Figure 12: Block diagram of Borealis’s Borstar technology for production of PP from propylene

xxvi
5 SCENARIOS
In this section the different scenarios are outlined with assumptions, mass and energy
balances. The base case scenario is discussed in detail, whereas for the other scenarios
(Table 1) only the differences from the base case scenario are discussed. Each change is
compared to the base case scenario in order to identify the most important factors for
change in the system.

Table 1: Different scenarios modelled.

Wood waste feedstock Waste plastics feedstock

Base case*

Base case with coal electricity

Base case with hydropower

electricity

Transport of feedstock from

another country

Transport of methanol to the

MTO

Gasifier improvement

H2 addition

* In establishing the base case scenario the main data sources – apart from plastics gasification process - were the BioMeeT and
BioMeeT II reports (Ekbom et al 2000, 2003).The BioMeeT II is based on the BioMeeT report. In this study we have used the process

xxvii
descriptions in BioMeeT, and the new mass and energy flows given in BioMeeT II. It was not possible to use one single source for
data input to the study, as each of them have a specific context; the BioMeeT report contains data about a possible methanol
production combined with energy production, the BioMeeT II is focusing on maximizing the methanol production and its feasibility in
term of cost and market situation. In order to maximize the production of plastic material a high methanol production is desirable,
hence the mass and energy balances in the BioMeeT II report suits our requirements the best. The process descriptions are however not
included in the second report, hence the BioMeeT report was used for the process descriptions. We adapted the different process
information given in the reports, and based on the detailed information given in the BioMeeT report, a simple model for Water Gas
Shift (WGS), gas cleaning and methanol production was built in Aspen HYSYS.

5.1 Base case scenario

5.1.1 GASIFICATION TO CLEAN SYNGAS

As mentioned in Section 4.1, gasification requires different technological solutions for

treatment of biomass and plastic waste. The gasifier used for biomass feedstock is based
on the BioMeeT and BioMeeT II reports. The gasification is done in a 1-step reactor,
technology by Carbona Oy engineers in 1999 (Ekbom et al, 2000). Gasification
technologies using a two steps reactor, where the biomass is first pyrolysed with
subsequent gasification has also been proposed (Van der Drift, 2005). The BioMeeT II
report which aim to maximise the methanol output, has added a catalytic reformer at the
output of the gasifier to decrease the higher hydrocarbons in the syngas (including tars)
and increase the yield of H2 and CO. A high H2 content is suitable for methanol
production.

For gasification of waste plastic, data were taken from a feasibility study made by Future
Energy for Hydro Polymers in 2003 (Future Energy, 2003). The feasibility study
evaluates the possibility of gasifying plastic waste in an entrained flow gasifier based on
Noell technology. The aim of the study is to produce synthesis gas with high calorific
value, which can be further processes to methanol. The feasibility study looked at
gasification of 1 million tons of plastic waste per year, which was broken down to 3
process trains for practical reasons. In the base case scenario the option with water slurry
is chosen, a higher quality syngas is, however, obtained by use of oil slurry in the gasifier.
This is discussed later.

The composition of the raw syngas from the gasifier, for both biomass and plastic waste
is given in Table 2. Without tar cracking, the syngas quality of biomass is close to the
syngas from plastic waste. The composition of the waste material is given in Appendix 5.

xxviii
Table 2: Composition of synthesis gas out of the gasifier

Biomass Plastic waste

(Ekbom, 2003) (Future Energy, 2003)

Component
Raw gas Dry basis Raw gas Dry basis

[vol%] [vol%] [vol%] [vol%]

CO 25.83 32.68 20.61 37.19

CO2 15.81 20.0 12.2 22.01

H2 33.53 42.42 21.3 38.43

H2O 20.97 0 44.58 0

CH4 0.17 0.22 0 0

N2 3.65 4.62 0.75 1.35

HCl 0 0 0.54 0.97

H2S 0.0147 0.0186 0.02 0.04

COS 0.001 0.0013 0 0

NH3+HCN 0.0279 0.0353 0 0

H2/(CO+CO2) 0.81 0.81 0.65 0.65

Data for energy consumption in the Air Separation Unit (ASU) are taken from the
BioMeeT II report for both biomass and plastic waste gasification, and adjusted for the
higher oxygen use in the plastic waste gasifier.

The raw product gas from the gasifier reacts with steam in the WGS to increase the H2
content in the syngas. The data taken from the BioMeeT II report is used for both plastic
waste and biomass. All numbers, mass and energy balance, are adjusted to the new mass
flow and composition by use of the Aspen HYSYS model. The H2/CO-ratio at the outlet

xxix
of the gasifier is the same for the syngas based on plastic and biomass, the mass flow,
however, differs.

After the WGS reactor, sulphur and CO2 is removed before the syngas can be transformed
to methanol. The gas cleaning section (sulphur and CO2 removal) is also modelled in
HYSYS by using a component splitter to establish the mass flows. The component split
fraction is taken from BioMeeT and used for both plastic waste and biomass.

The energy use in production of methanol from biomass is taken from the BioMeeT II
report. For plastic waste, the energy use for the gasifier is taken from the Future Energy
study (2003), whereas the energy use in WGS, gas cleaning and methanol production is
scaled by use of a linear correlation between mass and energy balances in the BioMeeT II
report.

The methanol process is given in Figure 8. The off gas from the methanol plant is
combusted to generate steam. The methanol production given in Figure 8 differs from
plants converting natural gas into methanol, since it does not include steam reforming of
natural gas and in addition the MTO plant tolerate crude methanol as input, which means
that the separation of methanol and water in distillation columns is avoided. The energy
consumption given in the BioMeeT II (Table 3) report includes separation of methanol
and water. Since pure methanol is not needed in the MTO process, crude methanol with
about 20-30% water will be used (Kvisle 2004). The energy consumed is reduced to 2/3
of the total energy consumption given in the BioMeeT II report. The energy reduction is
calculated by using a HYSYS model for methanol production, which shows that
approximately 1/3 of the energy (steam and electricity) is used in separation (Rahul et al.,
2004).

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Table 3: Biomass to Liquid (BtL) energy and mass balance (Ekbom 2003)

Energy (MJ) Material flows (MJ)

Process Unit
Electricity Steam Input Output

Gasification 3.3 32.68 229 176.2

island

SulFerox + 15.81 11.1 176.2 174.2

Shift Island

CO2 Removal 1.3 8.9 174.2 173.3

Island

Methanol 5.1 7.6 173.3 142.6

Island

The energy consumption in the waste to methanol is based on the Sankey diagram given
in the BioMeeT II report. The energy need for each unit is then calculated based on the
given energy flows. The BioMeeT II report assumes that the processes involved in waste
to methanol are integrated through a steam island. The gasifier has excess energy used to
produce steam directly, whereas the off gases in the methanol reactor are burned in a heat
recovery steam generator (HRSG) to produce steam. It is not clear whether this
integration is the optimum, but the recovery of off gases and high temperature processes
show at least some process integration.

The electricity consumed in the production is assumed to be E.U average including 9 %

grid loss. Life Cycle Inventory (LCI) data come from the LCAiT “Energy & transport
database” (2004). The composition of the E.U mix is given in Appendix 4. Changes in the
electricity mix are discussed in Section 6.5.

xxxi
5.1.2 METHANOL TO PLASTICS

The MTO unit, converting methanol to olefins, is the UOP/Hydro patented MTO process.
Mass and energy balances are based on information provided by Norsk Hydro and a SRI
report (Nirula, 1994). Crude methanol is used in the MTO reactor, giving a product
distribution as shown in Table 4. Ethylene and propylene are products used as feedstock
in production of PP and HDPE, whereas butene is sold as a by-product. The remaining
products, Fuel gas, are burned to provide energy for the process. This is in accordance
with the MATTER report (Joosten 2003).

Table 4: Product distribution from the MTO process (Nirula, 1994)

Component Product gas [wt%]

Products Ethylene 55.2

Propylene 27.0

Butene 7.8

Flue gas CO 0.32

H2 0.26

CH4 1.7

C2H6 1.7

C2H4 0.28

C3H8 1.5

C4H10 1.4

C5+ 3.0

Using the product distribution from Table 4, per kg of ethylene produced the following
are required: 3.74 kg methanol, 3.08 kg steam at 100 bars and 0.034 kWh electricity
(Nirula, 1994).

xxxii
Plastic production is done by use of the Borstar technology and the data are taken from
Nexant and its study on Borealis Borstar processes for PP and HDPE (Paulik 2005). The
production of polyolefins is very clean, where emissions originate in the electricity
production mainly. The efficiency of ethylene to HDPE and propylene to PP is 100 % and
98.7 %, respectively.

The MTO and plastic production is not integrated with the waste-to-methanol island. It is
assumed that there is enough steam for all process steps when the off gases from
methanol and MTO are burned.

5.1.3 TRANSPORTATION

Transport of waste and intermediate products are included in the assessment.

Figure 13: Base case transport system with collection of waste by trucks

For our base case, only feedstock logistics have been modelled with transport of woody
biomass and waste plastics by trucks to the plant (cf. figure 13). LCI data for transport of
biomass - collection by heavy truck, 123 km distance, and new truck engines emissions -
are taken from the BioMeeT II report and relevant sources (c.f. LCAiT paper bag case
study for the 123 km distance to the plant). For plastic waste, transport by truck for 200
km with empty return is used. This transport distance is chosen based on previous work
published by Björklund et al. (2005). The LCI data for the transport of plastics are taken
from Baumann and Tillman (2004). The fuel used in transportation is based on fossil
resources.

xxxiii
 5.2 Technological improvement of the gasifier
The gasification technology applied in the base case for plastic wastes uses water slurry.
The quality of the syngas from gasification of plastic waste can be improved by using oil
slurry instead. The disadvantage is that oil has to be bought for the slurry. In some cases
the slurry can be based on used oil. Used oil is not allowed on landfill and one treatment
method is to gasify it for energy or material purposes. When oil slurry is used, the
calorific value of the feed to the gasifier increases, resulting in a higher quality syngas.
Higher quality means less CO2 and more CO and H2 compared to the base case with water
slurry.

The assumptions used in the calculations are:

1. Production and transport of the used oil is not included as the overall impact of the
transport is very low
2. The energy use for each process step is scaled with respect to the change in mass
flows

For biomass gasification an improved technology is already used in the base case scenario
when the tar cracker is included. Katofsky (1993) and Williams et al. (1995) have
evaluated technologies for production of methanol from biomass that are likely to be
commercial on the short term. They have shown that methanol can be produced from
biomass with a net high heating value (HHV) energy efficiency between 54 and 58 %.
The scale of production was fixed at 400 MWth. Hamelinck and Faaij (2001) have
modelled various process routes from biomass to methanol by use of the Aspen+
software. The objective of their study was to identify concepts for biomass to methanol
and hydrogen that may lead to higher overall energy efficiencies and lower costs on
longer term. They have found that methanol can be produced from biomass with a HHV
efficiency of 52-59%.

The corresponding HHV efficiency for the base case system described in Section 5.1, is
53.8%. This implies that the technology improvement potential is limited with the
technologies that exist today.

xxxiv
Addition of coal: the addition of coal in a biomass based feedstock has not been
mentioned – as far as we know – however co-gasification of coal and biomass is a classic
option for making greener coal based power or fuels (by adding biomass into a coal
feedstock stream). Efficiencies have been simulated for biomass-coal co-gasification
systems up to a coal-biomass ratio of one (Chmielnak et al 2002).

5.3 Addition of hydrogen

Another way to improve the system is to avoid the shift reactor by addition of hydrogen
to the system. Hydrogen is added to the syngas prior to the methanol reactor in order to
adjust the H2/CO-ratio in favour of the methanol production unit.

Hydrogen is produced as a main product and a valuable by-product in industrial processes

(Steinberg and Cheng, 1989). The most widely used production route for hydrogen
production is catalytic steam reforming of natural gas. When this technology is used, 50%
of the hydrogen produced comes from water (steam) and 50% from the methane used as
feed (Steinberg and Cheng, 1989). Another production route for hydrogen is gasification
of coal with downstream water gas shift of the carbon-rich synthesis gas. Hydrogen is
also produced by electrolysis of water. This process requires large amounts of electricity,
whereas all the hydrogen produced comes from the renewable resource water.

Hydrogen is also an important by-product in a number of chemical processes. These

processes include production of chlorine from the electrolytic chlor-alkali process,
hydrogen produced from crude oil refinery processes, in the production of coke from coal
in the coke oven gases and in chemical dehydrogenation processes, e.g. ethylene plant
purge gases, ammonia dissociation and hydrodealkylation (Steinberg and Cheng, 1989).
In this study we concentrate on by-product hydrogen from chlor-alkali and refinery
processes even if other sources of potential cheap available hydrogen are available
(Lasher et al 2005). Again, none of the emissions from chlor-alkali or refinery processes
are allocated to the hydrogen added, as it is seen as a by-product which is regardless of
the need for hydrogen elsewhere. More details are given in Appendix 10.

Compared to the base case scenario, the WGS reactor is removed. Hydrogen is added to
the syngas until the same H2/CO-ratio as in the base case is obtained. All downstream
units are adjusted linearly to the new mass flow.

xxxv
 5.4 Change in electricity and transport systems
The electricity mix used in the base case scenario is the E.U electricity mix, which is an
average for electricity production in E.U. Other electricity mixes can however be found,
for example hydropower in Norway and coal based in some Eastern European countries.
The change in overall CO2 emissions with change in electricity mix is shown in Section
6.5.

Transport of feedstock, intermediates and products influence the overall global warming
potential of the system. In the base case scenario only transport of the waste material is
included in the results as the processes are assumed to be located in the same place. In
order to look at the influence transport distances have on the overall impact, increased
transport distance for the waste material and transport of the intermediate product
methanol is introduced (cf. figure 14). The transport distance for feedstock is increased
from 200 km by truck for plastic waste (123 km for wood wastes) to transport from
Norway to Poland. The following transport is modelled; 123 km for wood wastes and 200
km for plastics, by truck in Norway, followed by 780 km by boat from Norway to Poland
and finally 300 km by truck in Poland, empty return. The intermediate product, methanol
is liquid at room temperature with a boiling point at 65ºC, hence transport of methanol
can be done by boat. The transport distance is set to 10000 km, which is a relevant
number for methanol shipping. Indeed it represents the distance between a methanol plant
based on natural gas (in Chile for instance) and the end market (California, for instance,
with MTBE production, even if MTBE will be phased out in this state in 2007 due to
water contamination). Santiago-San Francisco is about 9548 km, if one wants a today’s
situation example. For our model those 10000 km represent the distance between the
waste-to-methanol plant and the methanol-to-plastic plant. It is the distance between the
region where the feedstock is available and where the waste handling facilities and
infrastructures are not that developed and/or greatly needed (for instance south-east Asia
or India), and Europe where the olefins conversion and high quality plastic facilities exist
near the market (the distance between Singapore and Oslo is about 17000 km).

xxxvi
Figure 14: Changes in transport system

5.5 Models
Gasifiers have been modelled using process modelling software in numerous reports. For
simplicity and practical reason, the gasification step is not included in our HYSYS model.
HYSYS was used to simulate a waste-to-plastics route via syngas and methanol, which is
then converted into light olefins. Two different cases were investigated, using wood waste
and plastic waste, respectively, as feed-stock. Based on literature/industrial data (cf. 1
Figure 15), we built a HYSYS model. The model takes the raw syngas from the gasifier
as an input and treats it all the way to methanol. The steps in the HYSYS model are the
following:
- Water removal from the syngas, done by component splitter (Figure 15).
- Water gas shift (WGS) as a two stage process with addition of water to obtain a
H2/CO-ratio of 2 after the WGS (Figure 15).
- Removal of sulphur done by a component splitter using the same split fraction for
all scenarios (Figure 15).
- Removal of CO2 done by two component splitters, where the first one is “recycle
gas” to the biomass gasifier, and the second is flue gas. For plastic waste the
output from the first and second splitter are classified as flues gas as no recycle
gas is needed in the gasifier (Figure 15).

xxxvii
 - Reaction of cleaned syngas to methanol, at conversion of 92% (Ekbom, 2003).
The reactor is followed by a component split of methanol, water and non-reacted
syngas. The unreacted syngas is used as fuel gas in the steam island.
- The CO2 emissions from the steam island are calculated by combustion of the flue
gas from the methanol reactor.

Syngas from
gasifier

Water
Figure 15: LCA-process modelling integration for the waste-to-plastics case study

removal
The results from the HYSYS model were then exported (cf. 2 Figure 15) to an Excel LCA
model which includes input, output and emissions for each process step, normalised to the
functional unit (1 kg of plastics). The process units Methanol To Olefin (MTO), Air
Separation Unit (ASU), transport and plastic production were not modelled in HYSYS
and these process data were taken directly into the Excel model. The Excel model was
used to calculate the CO2 emissions from the system, both renewable and non-renewable.
The mass flows were then exported to the LCAiT software (cf. 3 Figure 15) to calculate
the environmental impacts of the process and what-if scenarios using LCAiT databases.

Water gas
Finally the impact assessments graphs together with the Life Cycle Inventories were
exported to Excel files for LCA results presentation (cf. 4 Figure 15).

Following are some indications about the models:

shift
xxxviii
Data for the ASU is taken from the BioMeeT report, adjusting the energy use linearly
with mass flow for the different scenarios.

MTO is based on the SRI report, with mass flows and energy use as given in Section
5.1.2. The CO2 emissions from combustion of the flue gases are calculated by complete
combustion in HYSYS, whereas the CO2 emissions from regeneration of the catalyst are
adjusted linearly by the amount of methanol treated.

Transport of the waste material is modelled as given in Section 5.1.3.

Production of plastic material is modelled by use of material and energy balances given in
the Borealis Borstar technology.

References to the models are given in Appendix 6.

6 RESULTS
The results given in this section (cf. table 5) are based on the combined Hysys, Excel and
LCAiT models described in Section 5.5. The base case scenario for wood and plastic
waste is presented first, followed by closer look at the most important factors influencing
the total performance of the system. The factors that are tested for the sensitivity in the
system are technological improvement of the gasifier, additional H2 to the system, change
in transport system and variation of electricity mix. The focus in this section is on global
warming potential, given in CO2-equivalents, and energy use.

Table 5: Results summary of CO2-eqv and waste per functional unit for the various scenarios.

Scenario Renewable Non-renewable Waste per functional unit

CO2 CO2
Dry As received

Base case Wood 5.8 1.4 4.7 9.4

Plastic 5.8 2.2 3.6 3.6

Improved gasifier Plastic 4.4 1.4 2.8 2.8 (1.4)1

H2 added Wood 3.5 1.1 3.4 6.7

xxxix
 Plastic 3.5 1.7 2.7 2.7
1
50 % oil slurry in the treated material; 1.4 kg of waste plastics per functional unit and 1.4 kg of oil per
functional unit.

6.1 Base case scenario

The results for the base case scenario are presented in two steps. First the methanol
island, which consists of gasification, ASU, sulphur removal, CO2 removal, steam
generation and methanol production, is treated as one unit, and then the methanol island is
broken down into its separate units. This is explained in more detail in Section 6.1.2.

6.1.1 METHANOL ISLAND AS ONE UNIT

The results presented here include the entire system producing new plastic from wood
waste and plastic waste, respectively. All numbers are given per functional unit, 0.68 kg
HDPE and 0.32 kg PP. The CO2-equivalents are divided into renewable and non-
renewable. Non-renewable comes from combustion of fossil fuels, e.g. electricity
production and fuels, whereas CO2 formed by carbon in the waste material is formed
renewable. It can be argued that CO2 from oxidation of plastic waste is not renewable,
and should have been given a different name. The discussion will not be outlined here,
but it is chosen to represent the CO2 emitted from the waste as renewable. The reason for
keeping renewable and non-renewable CO2 separate is the added knowledge that can be
achieved by this method.

xl
 9

8
Non-renewable CO2
Renewable CO2
7

6
CO2 eqv [kg]

0
Plastic

Plastic

Plastic

Plastic

Plastic

Plastic
Plastic
Wood

Wood
Wood

Wood

Wood

Wood

Wood
MeOH MTO HDPE PP Transport Preparation Total

Figure 16: Global warming potential for each process step per f.u., kg polymer. The clear columns
represent “renewable” CO2, whereas the dark columns represent non-renewable CO2.

From Figure 16 it can be seen that production of methanol from waste is dominating the
CO2 emissions for both wood and plastic waste. The columns named MeOH in the figure
include gasification, WGS, gas cleaning, ASU and methanol production. Further the CO2
emitted from the waste material (here: Renewable CO2) dominate over CO2 emitted from
other sources. Other sources include production of electricity and emissions during
transport. The main difference between wood and plastic waste is the higher non-
renewable CO2 emissions in gasification of plastic waste. The reason is the higher oxygen
consumption in the gasifier, resulting in a higher electricity consumption in the energy
intensive ASU. The last two columns in Figure 16 show the total contribution from wood
and plastic waste, respectively, and it can bee seen that production from plastic waste has
a higher global warming potential than wood. The main difference is the electricity
consumption.

xli
The renewable CO2 emitted in the MTO comes from combustion of the flue gases as
given in Table 4. The energy released in the combustion is used in steam production for
the MTO process. Transport of waste material has a minor impact on the total emissions.

A closer look at the non-renewable CO2 emissions are given in Figure 17a and b, showing
that the waste to methanol still dominates the picture, but production of HDPE is also
contributing. The reason that HDPE contribute more than PP is the higher production of
HDPE defined in the functional unit and the higher power demand for HDPE unit (Paulik
2005). For wood waste, see Figure 17a, the contribution is more diverse than for plastic
waste; this is due to the higher contribution from methanol in the plastic waste case,
which consequently dominates the other categories. In addition, preparation of the waste
is included in MeOH for plastic waste, which is given as a separate category or wood
waste. Emissions from transport of the waste are negligible compared to the total CO2
emission from the system.

Preparation
PP Transport
Transport HDPE
PP
MTO

HDPE

MTO MeOH
MeOH

Figure 17a: Contribution to non- Figure 17b: Contribution to non-

renewable CO2 by unit in production of renewable CO2 by unit in production of
plastic from wood waste. plastic from plastic waste

6.1.2 METHANOL ISLAND SHOWN AS SEPARATE UNITS

Since the main contributor is production of methanol from waste, it interesting to take a
closer look at the units included; gasification, WGS, gas cleaning and methanol

xlii
production. There are several reasons for treating the methanol island as one unit; the
most important is that allocation problems are avoided. Problems with allocation arise
when the emissions are to be allocated to the various units in the methanol island.
However, in order to look at specific improvement factors for the methanol island, it is
necessary to look into the details. Various ways of allocating the CO2 emissions are
outlined in Appendix 7.

The results can be represented in two ways; based on where CO2 is emitted or where it is
formed. The first approach allocates most of the environmental burden on the CO 2
removal unit; whereas the second approach allocate the emissions to the gasifier and the
shift reactor. The latter of the two approaches is chosen here, as it seems to represent the
impact in such a way that it can be used in system evaluation and improvement.

7 Non-renewable CO2
Renewable CO2
6

5
CO2 eqv [kg]

0
Plastic

Plastic

Plastic

Plastic

Plastic
Plastic

Plastic

Plastic
Wood

Wood

Wood

Wood
Wood

Wood

Wood

Wood

Gasifier ASU Shift Sulferox CO2 Methanol Steam Total

removal

Figure 18: Global warming potential for each process step in production of methanol from waste per f.u, kg
polymer. The clear columns represent “renewable” CO2, whereas the dark columns represent non-
renewable CO2.

xliii
In Figure 18 the global warming potential are given for each unit in the methanol island.
The picture is similar for both plastic and wood waste, with the gasifier and shift units as
the main contributors.

The CO2 emissions from this system can be divided into three categories:

• CO2 as a result of the technology chosen

• CO2 from “system restrictions”
• Renewable and non-renewable CO2

An example of technology restrictions is the CO2 emitted from the gasifier. This can be
decreased by better performance of the gasifier [Technology]. Second, the CO2 formed in
the shift reactor is due to the need for a higher H2/CO-ratio in the methanol production.
These emissions can not be decreased by improved technology in each unit, only by
improving the system [System restrictions]. The third entry is the difference between
renewable and non-renewable CO2. Part of the CO2 released comes from the treated
material, part from transport and energy use [renewable/non-renewable].

The potential for technology improvement is primarily in the gasifier, where large
amounts of renewable CO2 are emitted. Technology improvement of the gasifier is
discussed in Section 6.2. In addition to the gasifier itself, the production of oxygen is
energy intensive, which contributes to a large part of the non-renewable CO 2 emissions.
Any decrease in oxygen use per functional unit is beneficial in addition to improved
technology for production of oxygen. Use of alternatives O2-production technologies –
separation membranes, electrolysis, etc… - are not studied here, but the use of
membranes is probably one of the most interesting alternatives. The cryogenic process
route is the preferred one today, whereas advanced concepts for heat integration can
favour the use of membranes or chemical separation in the future (Smith and Klosek,
2001).

The CO2 allocated to the shift reactor shows the potential for improvement of the system.
In the WGS, CO is shifted to H2 to increase the methanol yield, resulting in formation of

xliv
CO2. The system can be improved by increasing the H 2/CO-ratio in the syngas to avoid
shifting of CO. One way to increase the ratio, is to add hydrogen to the stream, this is
shown in Section 6.3.

6.2 Technological improvement

Technological improvement of the units is one way of improving the performance of the
system. In this section focus is on improvement of the gasifier, as it is identified as one
potential improvement factor. The section starts with a look at the theoretical maximum
yield in the gasifier, followed by an approach to increase the syngas quality for wood
waste and plastic waste.

6.2.1 THEORETICAL MAXIMUM

In order to identify the theoretical maximum yield for the gasifier, the method of
minimisation of Gibbs energy is used by modelling a Gibbs reactor in Hysys. The details
are given in Appendix 13. The energy released in the exothermic reaction with oxygen is
used to break down the plastic waste in the pyrolysis zone. If the energy required for the
endothermic pyrolysis reaction is higher than the energy released in gasification zone,
more oxygen has to be used in order to support the more exothermic reaction to complete
combustion. The results from the Hysys model shows that there is a surplus of energy
released in the gasification zone compared to the heat required in the pyrolysis zone,
which means that theoretically it is possible to reduce the CO2 emissions close to 0. The
excess heat results in a rise in temperature.

6.2.2 WOOD WASTE AND TECHNOLOGY IMPROVEMENT

As mentioned in section 5.2, Katofsky (1993) and Williams et al. (1995) have found that
methanol can be produced from biomass with a HHV efficiency of 52-59%. The
corresponding HHV efficiency for the base case system shown in Section 5.1, is 53.8%.
This implies that the technology improvement potential is limited with the technologies
that exist today.

The addition* of coal in a biomass based feedstock is not commonly used - as far as we
know - but improving coal based gasifiers by adding some biomass in the input is a
classic strategy.

* By addition, we mean that the main stream is biomass and that some coal is added but do not represent an important part of the
energy flowrate.

xlv
6.2.3 PLASTIC WASTE AND TECHNOLOGY IMPROVEMENT

The results from gasification technology using oil slurry are presented in this section. We
remind the reader some of the assumptions made for this derivation:

1. The slurry is based on used oil.

2. Production and transport of the used oil is not included as the overall impact of the
transport is very low
3. The energy use for each process step is scaled with respect to the change in mass
flows

In Figure 20 and 21 the total CO2 emissions from the system are given. The total CO2-
eqvivalents are reduced from 8 kg in the base case to 5.8 kg in this improved case.

6
Non-renew able CO2
5 Renew able CO2

4
CO2 eqv [kg]

0
Figure 20: GlobalMeOH
warming potential for each process
MTO step per f.u., kg PP
HDPE polymer fromTransport
waste plastics. The
clear columns represent “renewable” CO2, whereas the dark columns represent non-renewable CO2

As in Section 6.1.2 the methanol island represents waste treatment, gasification and
production of methanol. In Figure 21 the methanol island is broken down to show where
the CO2 equivalents are produced, again in accordance with the representation in Section
6.1.2.

xlvi
 2,5
Non-renewable CO2
Renewable CO2
2

1,5
CO2 eqv [kg]

0,5

0
Gasifier ASU Shift Sulferox CO2 Methanol Steam
Figure 21: Global warming potential for each process step in theremoval
methanol island - MeOH figure 20 - per
f.u., kg polymer from waste plastics. The clear columns represent “renewable” CO2, whereas the dark
columns represent non-renewable CO2

Table 6: Summary of renewable and non-renewable CO2-eqv for plastic waste in base case and the case
with technology improvements improved case.

Base case [kg CO2 eqv] Technology improvement [kg CO2 eqv]
Unit
Renewable CO2 Non-renewable CO2 Renewable CO2 Non-renewable CO2

Gasifier 3.23 0.50 1.11 0.19

ASU 0 1.15 0 0.73

Shift 1.58 0 2.34 0

Sulferox 0 0 0 0

CO2 removal 0 0.065 0 0.045

Methanol 0 0.17 0 0.16

Steam 0.50 0 0.47 0

xlvii
MTO 0.52 0.012 0.52 0.013

HDPE 0 0.19 0 0.19

PP 0 0.063 0 0.063

Transport 0 0.034 0 0.013

Total 5.83 2.18 4.44 1.40

The summary of renewable and non-renewable CO2 equivalents in the improved case
compared to the base case is given in Table 6. The change in non-renewable CO 2 is larger
than the corresponding change in renewable CO2. The reason for the large reduction in
non-renewable CO2 is mainly lower need for oxygen per unit of syngas produced in the
gasifier and less natural gas used in the improved gasifier. These two reductions refer to
the entry “ASU” and “Gasifier” respectively.

For renewable CO2 the reduction in emissions is also significant for the technological
improvement. The syngas from the gasifier has a lower CO2 content, but also a smaller
H2/CO-ratio than the base case, hence more H2 has to be produced in the shift reactor.
When more CO is shifted in the WGS it results in a higher CO2 emission from the shift
reactor. In total, however, the CO2 emissions from the gasifier and the shift reactor are
lower for the improved technology.

6.3 Addition of hydrogen

In Table 7 and 8 the results are summarised for plastic waste and wood, respectively.
Compared with the base case, additional hydrogen improves the overall performance of
both systems. Instead of shifting part of the CO to hydrogen, hydrogen is added to the
high CO-content stream resulting in a higher plastic production. Higher plastic production
means less electricity needed per functional unit, resulting in lower non-renewable CO2
emitted from the ASU. Renewable CO2 is also reduced with this approach; the avoided
shift reaction is the main reason for the improvement.

Table 7: Summary of CO2-eqv for plastic waste in base case and the case with added H2 per f.u., kg
polymer.

xlviii
 Base case [kg CO2 eqv] Hydrogen added [kg CO2 eqv]
Unit
Renewable CO2 Non-renewable CO2 Renewable CO2 Non-renewable CO2

Gasifier 3.23 0.50 2.43 0.37

ASU 0 1.15 0 0.86

Shift 1.58 0 0 0

Sulferox 0 0 0 0

CO2 removal 0 0.065 0 0.049

Methanol 0 0.17 0 0.13

Steam 0.50 0 0.48 0

MTO 0.52 0.012 0.52 0.013

HDPE 0 0.19 0 0.19

PP 0 0.063 0 0.063

Transport 0 0.034 0 0.026

Total 5.83 2.18 3.50 1.70

Table 8: Summary of CO2-eqv for wood waste in base case and the case with added H2 per f.u., kg
polymer.

Base case [kg CO2 eqv] Hydrogen added [kg CO2 eqv]
Unit
Renewable CO2 Non-renewable CO2 Renewable CO2 Non-renewable CO2

Gasifier 3.51 0.20 2.50 0.14

ASU 0 0.49 0 0.35

Shift 1.15 0 0 0

Sulferox 0 0 0 0

CO2 removal 0 0.079 0 0.056

Methanol 0 0.31 0 0.22

Steam 0.61 0 0.52 0

MTO 0.52 0.013 0.52 0.013

xlix
HDPE 0 0.19 0 0.19

PP 0 0.042 0 0.063

Transport 0 0.047 0 0.033

Total 5.79 1.37 3.54 1.07

6.4 Transport system

In this section, the impact of transport system changes described in section 5.4 will be
described. Transport of feedstock, intermediates and products contribute to the overall
environmental impact of the system. In Section 5.1 it is shown that in the base case,
where only the feedstock is transported by truck over a distance of 200 km, transport is a
negligible part of the overall GWP of the systems. In this Section the transport distance
for feedstock is increased and long-distance transport of methanol is introduced.

The transport distance for feedstock is increased to transport the feedstock from Norway
to Poland. We remind the reader that the following transport is modelled: 200 km and 123
km by truck for plastics and wood respectively in Norway, 600 km by boat from Norway
to Poland and finally 200 km by truck in Poland, empty return. We choose Norway since
plastic waste is already shipped from Norway to Germany and transformed to methanol
via gasification (SVZ 2004) and that transport distance from Norway could be
extrapolated to Sweden or Finland for wood waste feedstock.

For methanol transport, the transport distance is set to 10000 km, which represent the
distance between the methanol plant and the end market region.

Change in transport only change the non-renewable CO2 eqv, the renewable emissions are
kept constant. Consequently, only the non-renewable CO2 eqv are presented here. In
Figure 22 the results from the increase in transport distance for methanol and feedstock
are given, respectively. In the base case, transport is a small contributor of the total GWP,
whereas for increased transport distances the transport is naturally more important. The
transport distance for methanol is longer than for the feedstock, which explains the larger
impact for transport of methanol. It is important to note, however, that only the non-

l
renewable CO2 are shown in Figure 22. From the base case it is known that the non-
renewable CO2 accounts for only 20-30% of the total CO2 equivalents emitted from the
system. The relative increase in the total GWP is hence lower than shown in Figure 16.

2,5

2
CO2 eqv [kg]

CO2 total
1,5
Transport

0,5

0
Base case Transport of Transport of Base case Transport of Transport of
MeOH feedstock MeOH feedstock

Figure 22: Change in non-renewable Wood CO2-eqv with increasing transport distances
Plastic for methanol and
feedstock, respectively per f.u., kg polymer.

6.5 Electricity mix

The total global warming potential of the system is dependent on the electricity mix used
in the evaluation. In this section the choice of the electricity mix is evaluated, comparing
the total GWP of the system with use of E.U electricity mix, electricity based on coal and
on hydropower. E.U electricity mix is used in the base case scenario. Composition of the
various electricity mixes are given in Appendix 4. As for transport, only the non-
renewable emissions are given because the renewable CO2 eqv will stay unchanged when
the electricity mix is changed.

In Table 9, the changes in non-renewable CO2 emissions with electricity mix are
summarised. In the first two columns the electricity related CO2 equivalents is shown,
whereas the total non-renewable CO2 emissions are given in the last two columns. Coal
based electricity emits approximately 70 % more CO2 equivalents than the E.U mix. For

li
both coal and the E.U mix, electricity is the main contributor to the total non-renewable
emissions. Hydropower is produced form water, and the CO2 emissions related to
production are very low, as shown in the first two columns in Table 9. In addition to CO2
emissions from electricity, emissions from transport also contribute to the total non-
renewable CO2 emissions. With the low contribution from electricity production,
transport becomes more important for the case with hydropower, with the consequence
that wood comes out with a higher GWP than plastic. Transport of wood is more
intensive than transport of plastic, mainly because more wood has to be transported per
functional unit.

Table 9: Change in total and electricity related non-renewable CO2 equivalents with varying electricity mix,
per f.u., kg polymer.

Electricity CO2-eqv [kg] Total CO2-eqv [kg]

Electricity mix
Wood Plastic Wood Plastic

E.U mix (base case) 1.1 2.0 1.3 2.1

Coal based 2.1 3.6 2.3 3.7

Hydropower 0.002 0.003 0.13 0.07

It is evident that the choice of electricity mix influences the overall renewable house gas
emissions from the systems that are evaluated. The conclusions will, however, not be
changed as long as the same electricity mix is used in the comparison.

lii
7 DISCUSSION
This report focuses on the global warming potential and to a certain extent also on the
energy use in the system (like most of the polymers LCA studies cf. Patel 2001). The
other impact categories are, however, also calculated and the results are given in
Appendix 8.

The results of the scenarios that are presented in the previous section all have one thing in
common; the renewable CO2 equivalents are dominating. The renewable CO2 is defined
as CO2 from the waste material; plastic waste or wood waste. The non-renewable CO2
comes from production of electricity and use of fossil fuels for transport.

The main difference between the “wood waste to plastic” and “plastic waste to plastic”, is
the large oxygen use in the plastic gasifier compared to the one used for biomass. There
are two reasons for this, the first and most important is the higher oxygen content in the
biomass than in plastic waste (38.6 wt% compared with 7.1 wt%) which means that less
added oxygen is needed for biomass. The second reason is the higher quality of the
syngas from the biomass gasifier (lower CO2 content) which means that less oxygen is
needed to produce the unwanted CO2 and H2O. It is important to note, however, that in
the base case scenario the biomass gasifier has a tar cracking unit added to the gasifier
which increases the quality of the syngas, the plastic waste gasifier does not have this,
and it is possible that this unit would have been beneficial also for the plastic waste
gasifier. Moreover, to avoid dioxin formation, the product gas out of the plastics gasifier
is led to a direct quench, resulting in less high temperature heat available for steam
generation.

The need for more oxygen in the plastic waste gasifier means more oxygen has to be
produced in the energy intensive air separation unit, this results in larger non-renewable
CO2 emissions. The other general trends that can be seen from the base case scenario are
that electricity production dominates the non-renewable CO2 emissions, and the methanol

liii
island (waste to methanol) is the dominant source for both renewable and non-renewable
CO2 for both systems.

Within the methanol island the largest contributors are the gasifier, steam generation and
shift reactor; this is shown in Figure 18. The steam generation uses off-gases from the
methanol reactor, and the combustion of this gas results in CO2 which is assigned to the
steam unit. The steam is used for all processes within the methanol island. The shift
reactor shifts CO and H2O to H2 and CO2 which results in non-renewable CO2 emissions.
The CO2 emissions from the shift reactor can be reduced and even avoided by addition of
hydrogen or higher hydrogen content in the waste material. The renewable emissions
from the gasifier can be reduced by improving the technology to decrease the CO 2 content
in the syngas. The non-renewable CO2 from the gasifier can be decreased by decreased
use of oxygen or a more energy efficient production than with electricity driven ASU. All
these improvements are discussed later.

Electricity production and transport

In the base case scenarios the results show that transport is of minor importance, whereas
use of electricity dominates the non-renewable CO2 emissions. The choice of electricity
mix in the base case is the E.U electricity mix. The composition is given in Appendix 4.
To look at the influence of electricity production two extremes were tested, coal based
electricity and hydropower. Use of coal based electricity increased the non-renewable
CO2 emissions with almost 100%. The use of hydropower for all electricity production
decreases the electricity dependent non-renewable CO2 close to zero, leaving the total
non-renewable CO2 emissions to be dominated by the emissions from transport. As the
electricity dominates the non-renewable CO2 emissions, choosing a low impact electricity
production is of major importance. In addition to hydropower other low impact electricity
sources includes among others wind power, solar cells and combustion of biomass. These
alternatives are not investigated further in this report. An alternative is also production of
more steam in the system, which can then be used to power the compressors that now use
electricity. This will of course decrease the amount of waste going to the end-product,
plastic. Compared to other studies were all electricity are assumed to be based on
renewable resources (Edwards et al 2003), the base case scenario shows a higher global
warming potential.

liv
For transport of feedstock, intermediates and products only feedstock were included in
the base case. The base(s) case(s) with transport of the waste(s) by truck (123 km for
wood wastes and 200 km for plastics) shows that transport is negligible compared to the
overall non-renewable CO2 emissions. The transport distance used for the base case is
short - compared to oil logistics for instance - and two scenarios were undertaken to look
at the impact of increasing the transport distances. First the transport distance for
feedstock was increased to transport from Norway to Poland (Oslo-Gdansk 781 km). The
following transport was modelled; 123 km for wood waste and 200 km by truck in
Norway, 781 km by boat from Norway to Poland and finally 300 km by truck in Poland,
empty return. Second transport of the intermediate product methanol was introduced,
modelled as transport by boat at a transport distance of 10000 km. This is approximately
the distance from Europe to Asia by boat.

By increasing the transport distances, the impact transport have on the overall non-
renewable CO2 is of course increasing. The transport distance for methanol is longer than
for the feedstock, which explains the larger impact for transport of methanol. The
transport related non-renewable CO2 for the case with increased waste transport is
approximately 4 times larger than the base case. When transport of methanol is
introduced, the transport related non-renewable CO2 is 15 times higher than the base case.
However, since transport has a low contribution to the total non-renewable CO 2, the
increase in total non-renewable CO2 is 10 % and 30 % for transport of waste and
methanol, respectively. It is important to note that from the base case it is known that the
non-renewable CO2 accounts for only 20-30% of the total CO2 equivalents emitted from
the system. The relative increase in the total GWP is hence even lower than the increase
in non-renewable CO2 with 8 % and 7 %, respectively. The findings are in agreement
with other studies which conclude that transport is of minor importance in waste handling
compared to the overall system (Ross et al., 2003; Eriksson 2005; Björklund et al 2005).

Improvement of gasifier

The biomass gasifier has a tar cracker at the outlet of the reactor in order to increase the
yield. The plastic waste gasifier uses another technology, but a tar cracker could possibly
be useful for this configuration as well, this is not discussed here due to lack of
information. Another disadvantage with the plastic waste gasifier is the high oxygen use
compared to the biomass case. An improvement of the gasifier is shown in Section 6.2.3.
By use of oil slurry instead of the water slurry, the syngas quality is increased and the use
of oxygen decrease. The result is less feedstock needed for production of the functional

lv
unit, which gives lower non-renewable and renewable CO2 emissions from the system.
The decrease is 25 % and 35 % for renewable and non-renewable CO2, respectively. The
large decrease in the non-renewable CO2 equivalents is due to less oxygen needed,
whereas the decrease in the renewable CO2 equivalents is because of the higher quality of
the syngas out of the gasifier. The high O2 use in the gasifier increases the non-renewable
CO2 emissions, which means that any decrease in oxygen use is beneficial as it will
reduce the electricity use and the total oxidation of carbon in the gasifier (higher quality
of syngas).

Transport, production and use of the oil are not included in the calculations above. In
Appendix 9 the CO2 emissions from production of crude oil are given, showing that the
impact is much smaller than the emissions from the plastic waste system. For transport of
the oil, the numbers will be close to the ones given for transport of waste. It is shown that
the total GWP is not influenced largely by transport.

System restrictions

The CO2 assigned to the shift reactor results from the shifting of CO to H 2 in order to
increase the H2/CO-ratio to what is required in the methanol reactor. In one scenario
hydrogen was added to the system to avoid the shift reactor, and thereby reduce the CO2
emitted from the system. The added hydrogen was taken as a by-product from chlorine
production, refineries or similar and consequently no environmental burdens were
allocated to the hydrogen. When this approach was taken the reduction in renewable CO2
was 40 % and non-renewable 22 % for both plastic and wood waste.

As shown in Section 6.3 hydrogen can be produced from fossil fuels, water or renewable
fuels like biomass. If a dedicated hydrogen production is used to produce the required
hydrogen to the system the environmental burden should be assigned to the system. In
Appendix 11 the global warming potential of various production routes are given,
showing that production of hydrogen from biomass gasification is the process route with
lowest non-renewable CO2 emissions. It is not a solution to have an additional gasifier for
production of hydrogen to the system to avoid the shift. It is possible to add a natural gas
steam reformer to produce hydrogen rich syngas, where both the CO and H2 in the syngas
are utilized, the details of this approach is not discussed here. Based on the results given
in Appendix 11, it is not a good solution to choose a dedicated hydrogen production unit

lvi
for the system. However, if hydrogen is available as a by-product from other processes,
the improvement of the system is evident. Moreover our simulation shows that the
hydrogen excess at Perstorp Oxo in Stenungsund perfectly match this BTP or PTP
hydrogen need, thus allowing a future mapping of similar hydrogen excess sources that
can be dedicated to those gasification based processes.

“Wood to plastics” and “plastics to plastics”

The most obvious difference between the system with wood and plastic waste is that the
PTP process is a recycling system, whereas the BTP is an alternative production route to
green plastics. This difference does not affect the technical performance of the system,
but external conditions like legislation, availability and marketing for the products. These
external conditions will in turn affect the technological choices for the system. An
example is the question about addition of hydrogen, which might not make sense for
biomass, unless hydrogen comes from a renewable resource. For plastic waste, addition
of hydrogen from a fossil resource is probably more interesting since plastic waste is also
based on fossil resources.

Assignment of the CO2 emissions

As discussed, the CO2 emissions from this system can be divided into three categories:

• CO2 as a result of the technology chosen

• CO2 from “system restrictions”
• Renewable and non-renewable CO2

(All renewable CO2 comes from one of the two previous categories)

lvii
To assure that the CO2 emissions are assigned to the unit where the emissions are
formed, the following assignment has been used for renewable CO2:

Gasifier = All CO2 out of gasification reactor

Shift = All CO2 out of WGS reactor – Gasifier

Steam = All CO2 from combustion of flue-gas from methanol reactor

MTO = All CO2 from reactor (regeneration of catalyst) +

Combustion of off-gases (C5+, H2 and CO)

The traditional LCA approach, with assignment to the unit where the emissions occur,
does not provide information of were the emissions originate. With the approach shown
above, the CO2 is assigned to the unit where it is formed and consequently the results
can be used to identify needs for improvement.

Uncertainties:

Like all results from process modelling, the results presented here present some inherent
uncertainties. These uncertainties can come from:

- The models themselves (cf. uncertainties in Hysys models)

- The use of energy streams from the BioMeeT report converted to the plastic waste
case.
- The choice of technology (possible improvements for the ASU, methanol unit…
etc…)
- Process integration (the optimum configuration of the mass and energy streams is
not studied here)

lviii
Waste monetization strategies and impact on the models

Raw woody biomass waste has high water content (~50%), so larger amounts of material
– compare to waste plastics, coal, etc… - are needed for the same amount of methanol.
Transport is of minor importance, but for long transport distances the large amounts of
water that is transported can be a disadvantage. Indeed, drying or even pirolysis before
transportation could be an option. A decentralised-centralised model (cf. figure 23) with a
biomass/waste refining step between the collection and handling and the fuel production
step could be interesting to study in the case of bigger feedstock amount use. This has not
been studied here but could be easily added to our models.

lix
 Figure 23. Refining step between collection and fuel production (Choren 2001)

Environmental impact, positioning

For the Biomass to Plastics (BTP) process, the GHGs emissions - cradle to factory gate -
are about 1.4 kg CO2-eqv/kg plastic produced. Compared to production of various other
polymers (Vink et al 2003), this leads to the positioning given in Figure 24.

Cradle to factory gate GHGs emissions

80

60

40

20

0
Nylon 66

Nylon 6

BtP plastics
Polycarbonate

polystyrene

Polylactide
High impact

Polyethylene

Polyethylene
polystyrene

Cellophane

Polypropylene
polyethylene

polyethylene
High density
Low density

terephtalate

terephtalate
amorphous
solid state
purpose
General

GHG emiss. X 10 [kgCO2eq./kg]

Figure 24: Comparison of plastic production from BTP with virgin production of various products.

The PTP process, from a waste management perspective is an alternative to mechanical

plastic recycling or plastics incineration (cf. Table 10). Indeed, it produces plastic from
plastics and does not require a too specific sorting out step.

lx
Table 10: PTP and plastic waste handling options

Incineration

Incineration
Thermal Recycling
Direction energy PTP
(thermal
”mechanical”
energy plant)*
and
electricity**

Input 1 kg PE 1 kg PE 1 kg plastics 1 kg PE

Input 3.8 MJe 2.98 MJe

0.15 kg PE
Output 3.14 kg CO2eq 2.44 kg CO2eq 2.2 kg CO2eq
residue

0.27 kg plastics
25.3 MJth
Output 43 MJth 68% HDPE 0.85 kg PE
11.5 MJe
32% PP

* spine@cpm database 2006 (MJe = MJ electricity and MJth = MJ thermic)

** Tillman, Baumann 2004

The discussion regarding the specific pros and cons of the PTP compared to other waste
management systems will be done in further reports.

The other impact categories that are investigated include eutrophication, aquatic
ecotoxicity, ozone depletion and acidification. The results are not discussed here, as the
greenhouse potential is the most important of the categories for the discussion in this
report. In order to give the total picture, the results are given in Appendix 8.

lxi
8 CONCLUSION

Production of plastic from biomass and plastic waste is possible by use of the BTP and
PTP processes, respectively. The base case scenarios show an advantage for the biomass
case, with respect to the non-renewable CO2-equivivalents. The main reason for the lower
CO2 emissions in the biomass process is the lower oxygen use in that case. The main
source for non-renewable CO2-equivivalents in both the base case scenario is the gasifier
with the oxygen production. Various improvements for both cases are investigated.
Improvement of the plastic waste gasifier by use of oil slurry instead of water slurry
reduces the total CO2 emissions for the system by almost 40 %.

NB: The comparison between BTP and PTP is a little bit awkward, since those processes
are more complementary that competitors. Indeed, the BTP process is a way to produce
plastics from biomass thus being an alternative to other plastics production process,
whether they are based on biomass or fossil fuels (cf. figure 24), whereas the PTP is an
alternative to waste management of plastic wastes and recycling systems - regardless of
bio-origin of those plastic wastes - and could therefore be used to handle the plastics
produced via the BTP at their end-of-life. The so called “renewable” CO 2 for the PTP is
in this perspective very meaningful.

If hydrogen is available as a by-product close to the PTP/BTP plant, addition of hydrogen

to avoid the need for a water gas shift reactor to increase the H2/CO-ratio prior to the
methanol production unit is beneficial for the CO2 emissions. Please note that the
emissions from production of hydrogen are not included in the calculations as hydrogen is
only looked at as an option when it is available as a by-product. When this approach was
taken the reduction in renewable CO2 was 40 % and non-renewable 22 % for both plastic
and wood waste. When hydrogen is produced on purpose to increase the H2/CO-ratio,
depending on the production system (cf. Appendix 10), this conclusion could vary a lot.

lxii
Sensitivity analyses are carried out with respect to transport systems and the electricity
mix. The electricity mix used in all calculations is the E.U electricity mix given in
Appendix 4. If coal based electricity is used in the calculations the total non-renewable
CO2 emissions increases with 75%, whereas calculations with hydropower results in a
decrease of 90%. For increased transport distances the total emissions are of course
increasing. However, since transport has a low contribution to the total non-renewable
CO2, the increase in total non-renewable CO2 is 10 % and 30 % for transport of waste
from Norway to Poland and methanol from Europe to Asia, respectively. The findings are
in agreement with other studies which conclude that transport is of minor importance in
waste handling compared to the overall system.

Both BTP and PTP show interesting possibilities compared to virgin production and to
other recovery options. The environmental positioning of the BTP, compared to existing
bioplastics and oil-based polymers which are both outperformed, is confirmed. Moreover
the use of hydrogen excess sources for other purposes than fuel-cell dedicated programs
leads to great improvement of biomass and waste based processes. The PTP process is
closing the loop of plastic materials by a flexible recycling concept with a minimum need
for pre-treatment like sorting and washing.

The method used for evaluation of the concepts combine process modelling and life cycle
assessment. This gives a good understanding of the hot spots in the process with regard to
both the environmental impact and process performance. The method enables an effective
early-design phase evaluation.

lxiii
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Kaggerud, K., Sandberg P., Musdalslien, I, U., Nilsen, R, H., Leadbitter, J. A new
concept for waste plastic recycling. NTNU 2003

Katofsky RE, 1993, The production of fluid fuels from biomass, Center for Energy and
Environmental Studies/Princeton University, Princeton.

Krinke, S., Comparative Life-Cycle Assessment of SunDiesel and Conventional Diesel

Life Cycle Thinking in Business & Industry, Volkswagen AG.

lxv
Kvisle, S., Nilsen, H.R., Fuglerud, T., Grønvold, A., Vora, B.V., Pujado, P.R., Barger,
P.T. and Andersen, J.M., Methanol to Olefins: State of the Art and Perspectives, Erdöl
Erdgas Kohle, 2002; 118 (7/8): 361-364

Kwant, W. K, Knoef, H., Satus of biomass gasification in countries participating in the

IEA bioenergy task 33 biomass gasification and EU gasnet, October 2004.

Lasher et al , DOE Hydrogen Program, FY 2005 Progress Report, III.7 Fuel Choice for
Fuel Cell Vehicles: Hydrogen Infrastructure Costs

Lurgi 2002. Lurgi Methanol-to-Propylene Lurgi Methanol-to-Propylene -MTP®. The

most economic solution to produce on-purpose propylene. www.lurgi.com

Moulijn, J.A., Makkee, M. and van Diepen, A., Chemical Process Technology. 2 Ed,
England: John Wiley & Sons, 2003.

Malkow, T., Novel and innovative pyrolysis and gasification technologies for energy
efficient and environmentally sound MSW disposal, Waste Management, 2004; 24 (1)
53-79

Nexant Inc. www.nexant.com

Nirula SC. Ethylene from methane. Menlo Park: SRI international, Report No. 208; 1994.

Nouri, S., Syngas Integration, Integration of an ASU with a syngas process. Airliquide
R&D Center/Group: Chemicals and Refining. 2003

Nouri, S., Tillman, A-M., Evaluating synthesis gas based biomass to plastics (BTP)
technologies. Chalmers 2005.

Parkinson, G., Plastic wastes will be the new raw material for ammonia production,
Chemical Engineering, 2002; 109 (13): 13

Patel, M., Lessons to be learnt from LCAs for biodegradable polymers Review of Life
Cycle Assessments for Bioplastics, Utrecht University, 2001.

Paulik, C., Borealisgroup personal communication, 2005.

Ross, S., Evans, D., The environmental effect of reusing and recycling a plastic-based
packaging system Journal of Cleaner Production 11 (2003) 561–571

Salo, K., Carbona OY, personal communication, 2005.

lxvi
Smith, A.R., Klosek, J., A review of air separation technologies and their integration with
energy conversion processes. Air Products and Chemicals, Inc., Allentown, PA 18195,
USA. Fuel Processing Technology 70 (2001).115–134

spine@cpm database http://cpmdb.imi.chalmers.se/SpineAtCPM/database/cover.htm

Steinberg, M. and H.C. Cheng. 1989. “Modern and Prospective Technologies for
Hydrogen Production from Fossil Fuels,” Int. J. Hydrogen Energy, 14, 797-820.

SVZ GmbH 2004 www.svz-gmbh.de

UOP www.uop.com and http://www.uop.com/objects/26%20MTO%20process.pdf

Vink, E.T.H, Rabago, R.K., Glassner, A.D., Gruber, R.P., Applications of life cycle
assessment to NatureWorks polylactide (PLA) production. Polymer degradation and
stability, 80 (2003) 403-419

Williams RH, Larson ED, Katofsky RE and Chen J, 1995, Methanol and hydrogen from
biomass for transportation, with comparisons to methanol and hydrogen from natural gas
and coal, PU/CEES Report 292, Center for Energy and Environmental Studies/Princeton
University, Princeton, 47 pp.

lxvii
 Appendix 1: waste recovery potential

A very short and approximate but illustrative calculation of the waste recovery potential
has been made:

The OECD consumption is about 18 barrels of oil per year and per capita (Ifp 2005). The
amount of house hold waste generated each year is about 500 kg per capita (in the UK,
Hurst 2002). The composition of waste – which greatly varies between winter and
summer (Hurst 2002) – is for about 66% composed of biomass waste (paper, green waste,
food…). This represents about 330 kg of biomass waste. A BtL process (with an
efficiency of about 50%) transforms this amount of waste into about 1.8 MMBtu or about
0.3 barrel of oil equivalent. Waste biomass monetization from household waste only,
represents thus a saving of about 1.66 % of our total consumption of oil. For comparison,
GTL production outlook will reach 1 million BPD by 2020 – less than 3% of the world
markets for diesel and naphtha (Culligan 2005).

lxviii
 Appendix 2 : Waste availability, ethylene network
in EU, etc.

Poland an Eastern Europe represent an attractive place for the implementation of a first
waste to plastic plant and this for many reasons. First the non existence of an effective
and largely apply recycling systems (around 20% of packaging waste is recycled in
Poland compared to 63% in Sweden, EEA Signals 2004) let the door open to new
recycling strategies like the waste to plastic route. Secondly the well establish gas
network Map.1 (which can lead to cheap hydrogen sources; hydrogen comes from natural
gas today) and the different refineries location as well as ethylene pipelines Map.2 show a
well integrated petrochemical industry. Moreover some big harbours (like Gdansk for
Poland) near Scandinavian wood resources reinforce its attractiveness for Biomass to
plastic process implementation.

lxix
Map.1 EU oil and gas transportation system

http://www.inogate.org/inogate/en/resources/ma
ps

lxx
Map.2 Refineries, Pipelines and Crackers in Europe, Appe – Association of
petrochemicals producers in Europe, 2004

http://www.petrochemistry.net/ftp/pressroom/ma
p_europe2004.pdf

lxxi
10 Appendix 3: Detailled process unit flowsheets:

The main mass flows within the BTP and PTP concepts flowsheets are depicted below:

1. the gasification island (Ekbom et al 2000)

lxxii
2. the gas cleaning section: sulferox for biomass (Ekbom et al 2000) and chlorine
removal for plastic waste.

3. the CO2 removal unit (Ekbom et al 2000)

lxxiii
4. the methanol island (Ekbom et al 2000)

5. the Air Separation Unit (Air Liquide’s Aspen HYSYS model, Nouri 2003)

lxxiv
 N2 Heat Distillation
exchangers columns
O2
AIR

lxxv
 6. The methanol to olefins unit

MTO flowsheet, Andersen et al 2003.

7. The Borealis Borstar process (HDPE and PP)

Borstar PE process, Borealis (2005)

lxxvi
Borstar PP process, Borealis (2005)

lxxvii
 Appendix 4: EU El-mix

In the EU electricity is produced via a great number of different routes like coal, gas,
nuclear, hydro, oil etc. The combination, which actually do not correspond to a single
pathway is called EU mix and is used in this report to represent a typical electricity
supply. The shares of the different primary energy sources for electricity production are
shown in table 11.

Table 11: EU electricity mix (Edward et al 2003)

Source Share %

Nuclear 37.5

Coal 22.4

Oil 9.6

Gas 15.5

Hydro 12.4

Wind 0.4

Waste 1.8

Other renewables 0.3

lxxviii
 Appendix 5: waste feedstock composition

Biomass composition, like oil and gas (one has to remember that oil and gas - when
referencing to biogenic theory for oil formation - are mainly the products of compression
and heating of ancient vegetation) greatly vary depending on the type of biomass we are
looking at. A representative biomass and coal property table is shown below (cf. table
12).

Table 12: Biomass and coal properties, Bain 2004

Plastic waste composition varies also depending on the different sorts of plastics used
(PE, PP, PET, PVC…etc). For the PTP process a low chlorine content feedstock is used
to minimise the risk of corrosion and the cost of chlorine separation. Many strategies exist
to achieve a low-chlorine content feedstock and one has been developed by Volkswagen
for plastic recycling in cars (Goldmann 2005). Their approach to generate a low chlorine
plastics fraction out of shredder-residues works as follows. In a first step, they are able to
separate a so called sand-fraction (fines), a fibre fraction (light) and granulate fraction as
well as some metal fractions. Due to the composition and shape of the Cl-carrying

lxxix
substances (basically PVC) they are able, to concentrate most of the PVC in the coarse
plastic-fraction. This granulate called plastic-fraction is then treated in a wet density
separation step, where polyolefines and most of ABS end up in the light fraction whereas
PVC is concentrated in a heavy fraction. The PVC-depleted fraction is limited in Cl-
content to max. of 1.2 % which is sufficiently low. Lower chlorine content level could
also be achieve but at a higher price.

lxxx
 Appendix 6: models

Models:

The Hysys models are available as .hsc files:

- syngas from biomass gasification to methanol

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/MEOH34.ZIP

- syngas from plastic waste gasification to methanol

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/MEOH_PLASTIC.ZIP

The Excel models are available (with their derivations) as .xls files:

- Biomass to plastics (base case model)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/LCA%20BTP_wood2.xls

- Biomass to plastics (hydrogen addition case model)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/LCA
%20BTP_wood_h2.xls

- Biomass to plastics (LCAiT base case)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20BTP%20base%20case.xls

- Biomass to plastics (LCAiT electricity from hydropower scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Invemtory%20results
%20BTP%20derivation%20Hydro%20El.xls

- Biomass to plastics (LCAiT electricity from coal scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20BTP%20derivation%20coal%20el.xls

lxxxi
- Biomass to plastics (LCAiT hydrogen addition scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20BTP%20base%20case%20derived%20H2%20imported.xls

- Biomass to liquid, liquid transport and liquid to plastics (LCAiT transport system
scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20BTP%20derivation%20BtL%20MtP%2010000km.xls

- Biomass to plastics with biomass logistics (transport by truck/boat)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Invetory%20result
%20BtP%20derivation%20Oslo%20gdansk%20biomass%20transport.xls

- Plastics to plastics (base case model)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/LCA%20BTP_plastic.xls

- Plastics to plastics (hydrogen addition case model)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/LCA
%20BTP_plastic_h2.xls

- Plastics to plastics (waste oil fed gasifier case model)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/LCA
%20BTP_plastic_oilsl.xls

- Plastics to plastics (LCAiT base case)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20PTP
%20base%20case.xls

- Plastics to plastics (LCAiT electricity from hydropower scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20PTP%20derived%20hydro%20el.xls

- Plastics to plastics (LCAiT waste oil import scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20PTP%20oil%20and%20plastic%20derivation.xls

- Plastics to plastics (LCAiT electricity from coal scenario)

lxxxii
http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20PTP%20derivation%20coal%20el.xls

- Plastics to plastics (LCAiT hydrogen addition scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20PTP
%20H2%20import.xls

- Plastics to liquid, liquid transport and liquid to plastics (LCAiT transport system
scenario)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20results
%20PTP%20derivation%20PtM%20MTP%2010000%20km.xls

- Plastics to plastics with waste plastics logistics (transport by truck/boat)

http://www.esa.chalmers.se/Staff/bottomn_files/selim_files/Inventory%20result
%20PtP%20derivation%20Oslo%20gdansk%20waste%20logistics.xls

lxxxiii
 Appendix 7: assignment of CO2 emission

Assignment of the CO2 emissions

Three categories:

1. CO2 as a result of the technology chosen

2. CO2 from “system restrictions”
3. Renewable and non-renewable CO2

(All renewable CO2 comes from one of the two previous categories)

1. Ex: can be decreased by better performance of the gasifier [Technology].

2. Ex: the CO2 formed in the shift reactor are due to the need for a higher H2/CO-
ratio in the methanol production. These emissions can not be decreased by
improved technology in each unit, only by improving the system [System
restrictions].
3. The third entry is the difference between renewable and non renewable CO2. Part
of the CO2 released comes from the treated material, part from transport and
energy use [Renewable/non renewable]

To assure that the CO2 emissions are assigned to the unit where the emissions are
formed, the following assignment has been used for renewable CO2:

Gasifier = All CO2 out of gasification reactor

Shift = All CO2 out of WGS reactor – Gasifier

Steam = All CO2 from combustion of flue-gas from methanol reactor

MTO = All CO2 from reactor (regeneration of catalyst) +

Combustion of off-gases (C5+, H2 and CO)

lxxxiv
The traditional LCA approach, with assignment to the unit where the emissions occur,
does not provide information of were the emissions originate. With the approach shown
above, the CO2 is assigned to the unit where it is formed and consequently the results
can be used to identify need for improvement.

lxxxv
 Appendix 8: impact categories

Other impact categories results are available as Excel documents with their corresponding
LCI

The environmental impact assessment categories of the BTP and PTP routes derivation
calculated from LCAiT (/per kg of polymer produced) are summarized in the following
table (table 13).

Table 13: BTP and PTP environmental impact characterisation indicators.

Fossil “renewable Non Eutrophication Acidification Ecotoxicity

Energy CO2” kg renewable kg Nox kg SO2 aquatic 1000
use (not CO2 eq CO2 kg equivalent equivalent m3 polluted
total CO2 water
primary equivalent
energy)

BTP route 0.33 kWh 4.724 1,39 4,39e-3 1,24e-2 5,64e-3

BTP H2 0,23 kWh 3,031 1,05 3,27e-3 9,35e-3 4,2e-3

enriched

BtMeOH + 4,724 1,94 1,55e-2 2,72e-2 1,43e-2

MtP

BTP 4,724 1,58 7,08e-3 1,58e-2 8,53e-3

biomass
tanker

BTP hydro 4,724 0,126 1,09e-3 8,37e-4 1,43e-3

El

BTP coal 4,724 2,42 6,49e-3 8,16e-3 1,65e-3

El

PTP route 0,465 MJ 4,86 2,07 5,51e-3 1,85e-2 7,19e-3

PTP & H2 0,35 MJ 2,72 1,64 4,36e-3 1,46e-2 5,68e-3

lxxxvi
PtMeOH + 4,86 2,62 1,67e-2 3,33e-2 1,58e-2
MtP

PTP plastic 4,86 2,2 7,57e-3 2,1e-2 9,41e-3

tanker

PTP hydro 4,86 6,94e-2 3,12e-4 2,51e-4 5,79e-4

El

PTP coal 4,86 3,68 8,81e-3 1,18e-2 9,23e-4

El

PTP oil 3,63 1,32 3,43e-3 1,17e-2 4,43e-3

mix

Examples for BTP base case are:

lxxxvii
Examples for the PTP base case:

lxxxviii
lxxxix
xc
 Appendix 9: oil and emissions

For oil use in the case of plastic waste feedstock feed-in improvement, the impact of
producing the oil could also be taken into account. From the WTT study we have some
estimation for GHGs emissions and energy consumption for crude oil production and
transportation to the market. The figures are about 0.025 MJ/MJ energy consumption and
3.3 g CO2eq/MJ GHG emission for crude production, and 10 MJ/MJ energy consumption
and 0.8 g CO2eq/MJ emissions for transportation to the market (WTT Report). With an
energy density of about 45 MJ/kg for crude oil (Brown, Lemay, Bursten. Chemistry: The
Central Science. 5th ed) it represents a total of 451.125 MJ/kg and 184.5 g CO2eq/kg oil,
or 631.6 MJ/kg plastic and 258.3 g CO2eq/kg plastic produced.

The GHG emissions for the PTP route with oil blend as feedstock are 1.4 kg CO2eq/kg of
plastic produce, thus the oil production share in the environmental burden of plastic
production via this option is quite negligible.

Crude oil emissions: the GHG emissions for extracting crude oil are about 55.92 g CO2/
kg oil equivalent (Baumann, Tillman 2004).

More details are given in the EUCAR’s wtt report (Edwards et al 2003):

Table 14. Crude Oil emissions (Edwards et al 2003)

xci
Appendix 10: Hydrogen sources.

Hydrogen available sources could be divided into 2 categories:

- Hydrogen as a by product of an actual process or revamped unit.

- Hydrogen as a main product or intermediate (like syngas).

Since we do not want to allocate the hydrogen production, we will focus on the first
category for our case study. Moreover, the hydrogen import we are looking at to improve
the efficiency of our process is not sufficient enough to legitimate a real hydrogen
production train.

The particular case of Perstorp Oxo in Stenungsund (Sweden), which have switched from
oil to natural gas for some units and thus have an available hydrogen excess of about 1
ton per hour, is the practical example we will use in our model.

However it could be interesting to have more information about the other potential
available hydrogen sources when looking at a bigger biomass based process with
hydrogen adding. A list of hydrogen excess facilities has been produced for the US DOE
hydrogen program:

xcii
Table 15. Excess hydrogen sources (Lasher et al 2005)

xciii
 Appendix 11 : Hydrogen production
environmental impact.

Numerous LCAs are available about the impact of hydrogen production on the
environment. Whereas we focused on hydrogen as a by-product, and thus having a
negligible environmental impact, when the mass flow of hydrogen become important, we
have to be able to assess the impact of such a stream.

Depending on the way to produce hydrogen, the environmental impact greatly varies. For
instance when looking at CO2 emissions, well to tank studies show a great variation
depending on the feedstocks and the process (cf. Table 16)

Table 16. Hydrogen production routes GHGs emissions and energy expended.

Net GHG emitted (kg CO2eq/kg

H2) Energy expended Mjex/kg H2

Compressed-H2, Natural gas EU-

mix, On-site reforming 12,54983 101,304

COMPRESSED-H2, NATURAL
GAS 7000 km, On-site reforming 14,81149 132,996

COMPRESSED-H2, NATURAL
GAS 4000 km, On-site reforming 13,4004 114,24

COMPRESSED-H2: 7000 km,

Central reforming, Pipe
13,31963 101,148

COMPRESSED-H2: NATURAL
GAS 4000 km, Central reforming,
Pipe 11,93195 82,704

xciv
 COMPRESSED-H2: NAT GAS
4000 km, Central reforming, Road
12,04319 83,004

COMPRESSED-H2: NATURAL
GAS 4000 km, Central reforming,
Liquifaction, Road, Vap/comp. 16,14597 155,172

COMPRESSED-H2: LNG, On-site

reforming 14,33297 134,304

COMPRESSED-H2: LNG, Central

reforming, Pipe 12,85226 102,432

COMPRESSED-H2: Remote
NATURAL GAS, methanol, On-
site reforming 14,22578 135,732

COMPRESSED-H2: Coal EU-mix,

central reforming, Pipe
23,01384 140,34

COMPRESSED-H2: Wood waste,

On-site gasification 1,279597 146,28

COMPRESSED-H2: Wood waste,

Central gasification. Pipe 1,430397 116,364

COMPRESSED-H2: Wood Farmed,

On-site gasification 1,81834 149,22

COMPRESSED-H2: Wood Farmed,

Central gasification, pipe

1,695153 116,28

COMPRESSED-H2: NATURAL
GAS 7000 km, CCGT, On-site
Electrolyser 27,35251 327,12

COMPRESSED-H2: NATURAL
GAS 4000 km, CCGT, On-site
Electrolyser 24,45679 288,624

COMPRESSED-H2: NATURAL
GAS 4000 km, CCGT, Central
Electrolyser, Pipe 24,4591 294,66

COMPRESSED-H2: LNG, On-site

Electrolyser 26,38938 329,736

xcv
COMP H2: Farmed Wood, 200 MW
gasif, CCGT, On-site Electrolyser 1,49725 312,096

COMPRESSED-H2: Farmed Wood,

Conv power, On-site Electrolyser 3,68862 530,844

COMPRESSED-H2: Electricity
EU-mix, On-site Electrolyser 24,97642 434,628

COMPRESSED-H2: Electricity
coal EU-mix, On-site Electrolyser
50,8118 380,544

COMPRESSED-H2: Wind, Central

Electrolyser, Pipe
1,091337 94,392

LIQUIFIED-H2:NATURAL GAS
7000 km, Central reforming,
Liquifaction, Road 17,17308 161,892

LIQUIFIED-H2: NATURAL GAS

4000 km, Central reforming,
Liquifaction, Road 15,36622 137,856

LIQUIFIED-H2: Remote Ref,

Liquifaction, Sea, Road
16,74774 172,416

LIQUIFIED-H2: LNG, Central

reforming, Liquifaction, Road
16,52778 162,36

LIQUIFIED-H2: Wood Farmed,

Central gasification, Liquifaction,
Road 0,961017 179,628

LIQUIFIED-H2: NATURAL GAS

4000 km, CCGT, Central
Electrolyser, Liquifaction, Road
27,83097 343,944

LIQUIFIED-H2: Electricity EU-

mix, Central Electrolyser,
Liquifaction, Road
28,30873 506,88

xcvi
Thus using those data one can have an idea of the impact of producing and using
hydrogen when the flowrate of hydrogen used is not anymore characteristic of a by-
product or waste stream.

In case of the BTP base case, the hydrogen flowrate is 1612 kg/h or 0.1256 kg/kg plastic
produced thus, the environmental impact to take into account depending on the way to
produce the hydrogen could be calculated by adding the following numbers (cf. table 17)
to the already calculated GWP and energy use:

Table 17. BTP GHGs emissions and energy expended depending on hydrogen sources.

Net GHG emitted (kg CO2eq/kg Energy expended Mjex/kg Plastic

plastic) BTP with H2 BTP with H2

Compressed-H2, Natural gas EU- 1,58 12,72

mix, On-site reforming

COMPRESSED-H2, NATURAL 1,86 16,70

GAS 7000 km, On-site reforming

COMPRESSED-H2, NATURAL 1,68 14,35

GAS 4000 km, On-site reforming

COMPRESSED-H2: 7000 km, 1,67 12,70

Central reforming, Pipe

COMPRESSED-H2: NATURAL 1,50 10,39

GAS 4000 km, Central
reforming, Pipe

COMPRESSED-H2: NATURAL 1,51 10,43

GAS 4000 km, Central
reforming, Road

COMPRESSED-H2: NATURAL 2,03 19,49

GAS 4000 km, Central
reforming, Liquifaction, Road,
Vap/comp.

xcvii
COMPRESSED-H2: LNG, On- 1,80 16,87
site reforming

COMPRESSED-H2: LNG, 1,61 12,87

Central reforming, Pipe

COMPRESSED-H2: Remote 1,79 17,05

NATURAL GAS, methanol, On-
site reforming

COMPRESSED-H2: Coal EU- 2,89 17,63

mix, central reforming, Pipe

COMPRESSED-H2: Wood 0,16 18,37

waste, On-site gasification

COMPRESSED-H2: Wood 0,18 14,62

waste, Central gasification. Pipe

COMPRESSED-H2: Wood 0,23 18,74

Farmed, On-site gasification

COMPRESSED-H2: Wood 0,21 14,60

Farmed, Central gasification, pipe

COMPRESSED-H2: NATURAL 3,44 41,09

GAS 7000 km, CCGT, On-site
Electrolyser

COMPRESSED-H2: NATURAL 3,07 36,25

GAS 4000 km, CCGT, On-site
Electrolyser

COMPRESSED-H2: NATURAL 3,07 37,01

GAS 4000 km, CCGT, Central
Electrolyser, Pipe

COMPRESSED-H2: LNG, On- 3,31 41,41

site Electrolyser

COMPRESSED-H2: Farmed 0,19 39,20

Wood, 200 MW gasif, CCGT,
On-site Electrolyser

COMPRESSED-H2: Farmed 0,46 66,67

Wood, Conv power, On-site

xcviii
 Electrolyser

COMPRESSED-H2: Electricity 3,14 54,59

EU-mix, On-site Electrolyser

COMPRESSED-H2: Electricity 6,38 47,80

coal EU-mix, On-site Electrolyser

COMPRESSED-H2: Wind, 0,14 11,86

Central Electrolyser, Pipe

LIQUIFIED-H2:NATURAL 2,16 20,33

GAS 7000 km, Central
reforming, Liquifaction, Road

LIQUIFIED-H2: NATURAL 1,93 17,31

GAS 4000 km, Central
reforming, Liquifaction, Road

LIQUIFIED-H2: Remote Ref, 2,10 21,66

Liquifaction, Sea, Road

LIQUIFIED-H2: LNG, Central 2,08 20,39

reforming, Liquifaction, Road

LIQUIFIED-H2: Wood Farmed, 0,12 22,56

Central gasification, Liquifaction,
Road

LIQUIFIED-H2: NATURAL 3,50 43,20

GAS 4000 km, CCGT, Central
Electrolyser, Liquifaction, Road

LIQUIFIED-H2: Electricity EU- 3,56 63,66

mix, Central Electrolyser,
Liquifaction, Road

The results we found from our model for the BTP route with H2 import were, in terms of
GHGs emissions, about 1.09 kg of non renewable CO2eq emitted per kg of plastic
produced. The environmental impact, in terms of GHGs emissions is not that big if

xcix
hydrogen comes from wood gasification, but quite important regarding the total impact of
plastic production if from natural gas reforming for instance.

For the PTP case with hydrogen import, the flowrate is about 2016 kg/h or 0.14 kg/kg of
plastic produced, thus the additional environmental impact of producing H2 in terms of
GHGs and energy consumption depending on how is produced the hydrogen is
summarized in the following table (table 18):

Table 18. GHGs emissions and energy expended for the PTP process depending on the hydrogen source.

Net GHG emitted (kg CO2eq/kg Energy expended Mjex/kg Plastic

plastic) PTP with H2 PTP with H2

Compressed-H2, Natural gas EU-

1,76 14,18
mix, On-site reforming

COMPRESSED-H2, NATURAL
2,07 18,62
GAS 7000 km, On-site reforming

COMPRESSED-H2, NATURAL
1,88 15,99
GAS 4000 km, On-site reforming

COMPRESSED-H2: 7000 km,

1,86 14,16
Central reforming, Pipe

COMPRESSED-H2: NATURAL
GAS 4000 km, Central reforming, 1,67 11,58
Pipe

COMPRESSED-H2: NATURAL
GAS 4000 km, Central reforming, 1,69 11,62
Road

COMPRESSED-H2: NATURAL
GAS 4000 km, Central reforming, 2,26 21,72
Liquifaction, Road, Vap/comp.

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COMPRESSED-H2: LNG, On-site
2,01 18,80
reforming

COMPRESSED-H2: LNG, Central

1,80 14,34
reforming, Pipe

COMPRESSED-H2: Remote
NATURAL GAS, methanol, On- 1,99 19,00
site reforming

COMPRESSED-H2: Coal EU-mix,

3,22 19,65
central reforming, Pipe

COMPRESSED-H2: Wood waste,

0,18 20,48
On-site gasification

COMPRESSED-H2: Wood waste,

0,20 16,29
Central gasification. Pipe

COMPRESSED-H2: Wood
0,25 20,89
Farmed, On-site gasification

COMPRESSED-H2: Wood
0,24 16,28
Farmed, Central gasification, pipe

COMPRESSED-H2: NATURAL
GAS 7000 km, CCGT, On-site 3,83 45,80
Electrolyser

COMPRESSED-H2: NATURAL
GAS 4000 km, CCGT, On-site 3,42 40,41
Electrolyser

COMPRESSED-H2: NATURAL
GAS 4000 km, CCGT, Central 3,42 41,25
Electrolyser, Pipe

COMPRESSED-H2: LNG, On-site

3,69 46,16
Electrolyser

COMPRESSED-H2: Farmed
Wood, 200 MW gasif, CCGT, On- 0,21 43,69
site Electrolyser

COMP-H2: Farmed Wood, Conv

0,52 74,32
power, On-site Electrolyser

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 COMPRESSED-H2: Electricity
3,50 60,85
EU-mix, On-site Electrolyser

COMPRESSED-H2: Electricity
7,11 53,28
coal EU-mix, On-site Electrolyser

COMPRESSED-H2: Wind,
0,15 13,21
Central Electrolyser, Pipe

LIQUIFIED-H2:NATURAL GAS
7000 km, Central reforming, 2,40 22,66
Liquifaction, Road

LIQUIFIED-H2: NATURAL GAS

4000 km, Central reforming, 2,15 19,30
Liquifaction, Road

LIQUIFIED-H2: Remote Ref,

2,34 24,14
Liquifaction, Sea, Road

LIQUIFIED-H2: LNG, Central

2,31 22,73
reforming, Liquifaction, Road

LIQUIFIED-H2: Wood Farmed,

Central gasification, Liquifaction, 0,13 25,15
Road

LIQUIFIED-H2: NATURAL GAS

4000 km, CCGT, Central 3,90 48,15
Electrolyser, Liquifaction, Road

LIQUIFIED-H2: Electricity EU-

mix, Central Electrolyser, 3,96 70,96
Liquifaction, Road

Again with emissions of 1.7 kg of CO2eq per kg of plastic produced, the addition of
hydrogen has a low impact if the hydrogen comes from renewables like wind or wood
waste, but is not negligible if H2 comes from natural gas for instance.

This kind of discussion about the impact or importance of H2 addition is only “virtual”
and here to give an idea of the magnitude of hydrogen production compared to plastic
production from biomass, in terms of GHGs emissions. Indeed, we kindly remind the
reader that the option of adding hydrogen has been considered only to increase the H2/CO
ratio at the output of the gasifier and thus try to reduce the waste of renewable carbon

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released along the process. It would be completely absurd to dedicate a full H2
production unit - based on the same gasification technology – to fulfil this task, since the
same problem of renewable CO2 waste would arise in the aforementioned unit.

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Appendix 12: Lock-hopper feeding system

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This feeder is used in the 20 MWth biomass pressurised gasification - Carbona Oy
gasifier - pilot plant in Tampere (Finland).

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 APPENDIX 13: THEORETICAL MAXIMUM

In order to identify the theoretical maximum yield for the gasifier, the method of
minimisation of Gibbs energy is used.

The global gasification reaction can be written as follows:

CH y Oz + wH 2O + mO 2 + 3.76 mN 2 = x1 H 2 + x2CO + x3CO 2 + x4 H 2O + x5CH 4 + 3.76 mN 2

A Gibbs reactor was modelled in Hysys in order to look at the product gas composition
with varying reaction temperature and oxygen fed to the reactor. The results are shown in
the Figures below (figure 25, 26 and 27). The amount of oxygen is given as molar flow at
the x-axis, the amount of pyrolysis product fed to the reactor is held constant at 100
kmol/h.

Product composition, T=900C

0,5
0,45
0,4 CH4
0,35
O2
Molar fraction

0,3
H2
0,25
CO
0,2
0,15 CO2
0,1 H2O
0,05
0
20 30 40 50 60
Oxygen [k m ol/h]

Figure 25: Product composition with increasing amount of oxygen, at T=900°C

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 Product com position, T=1000C

0,5
0,45
0,4 CH4
0,35 O2
Molar fraction

0,3
H2
0,25
CO
0,2
0,15 CO2
0,1 H2O
0,05
0
20 30 40 50 60
Oxygen [km ol/h]

Figure 26: Product composition with increasing amount of oxygen, at T=1000°C

Product com position, T=1200C

0,5
0,45
0,4 CH4
0,35 O2
Molar fraction

0,3
H2
0,25
CO
0,2
0,15 CO2
0,1 H2O
0,05
0
20 30 40 50 60
Oxyge n [k m ol/h]

Figure 27: Product composition with increasing amount of oxygen, at T=1200°C

The CO and H2 yield compared to CH4, H2O and CO2 increases with increasing
temperature, hence a high operating temperature is desirable. For an operating
temperature at 1200°C, the highest yield is at 25 kmol/h of oxygen (1/4 of the pyrolysis
product), which is the stochiometric amount of oxygen in the net reaction:

C ( s ) + H 2 + O2 ↔ CO + H 2

However, as the less exothermic reaction to CO2 and H2O is less important at high
temperature, the available heat from the reaction system is less. This heat is used in the

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pyrolysis part of the process. For the given optimum point, the heat released is
3.96 ⋅10 6 kJ .

Menges et al (1992) gives the following energy of reaction

1
(−CH 2 −) + O2 ↔ CO + H 2 ∆ rx H = −92 kJ
2

With ∆ fH(H2) = 0, ∆ fH(O2) = 0, and ∆ fH(CO) = -111kJ, the corresponding value for
plastic, -CH2-, is -19kJ. The energy needed for the pyrolysis and heating of the substances
to the inlet temperature of the gasifier is then:

1. Pyrolysis:

k1 9 J⋅ 1 m 0 0o⋅ 1 k l0 mp 0 r o⋅ 0.5ok l dmp u r o co l t d = 9 u k5 c J 0t 0

m o kl m o l k mi n o l el t
2. Heating from 25°C to 480°C:

∆Q (T = 25 → 480 o C ) = 1.005 ⋅10 6 kJ

Total heat required = 1.1 ⋅10

6
kJ

This shows that there is a surplus of energy released in the gasification zone compared to
the heat required in the pyrolysis zone. The excess heat results in a rise in temperature.

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Appendix 14: HDPE and PP Borstar processes
commercial analysis and technology review
(Nexant 2002)

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cx
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 Appendix 15: Different Methanol to Olefin
concepts

ExxonMobil MTO Baytown (USA, TX)

 Status: PDU from methanol to olefins (80 times larger than competition)
optimized for commercialization. MTO linked with polyolefin unit. no
commercial project expected until 2014, cf.: “Exxon pursues only projects
that will turn a profit even in the leanest years” (Rex Tillerson, head of Exxon
Mobil)

 Propylene/ethylene ratio is 1

 ~ 40% high olefinic gasoline as co-product

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Figure 28: MTO PDU picture and environmental performance graph (ExxonMobil 2005)

Lurgi MTP Tjeldbergodden (Norway)

 Status: pilot plant and PDU (PDU > 5000 hours ) optimized for
commercialization, not expected untill 2008 (signed Iranian project at a
standstill)

 High propylene selectivity

 Süd-Chemie AG (Munich, Germany) commercial catalyst

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Figure 29: Lurgi MTP PDU picture in Norway (Lurgi 2002)

Figure 30: Lurgi MTP process flow chart (Lurgi 2002)

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UOP/Hydro MTO Porsgrunn (Norway) (technology data used in this report)

 Status: PDU (up to 1 ton/day methanol since 1995) optimized for

commercialization, not expected untill 2008 (Nigeria, Egypt)

 Propylene/ethylene ratio is flexible

 Only 0.2 tons C4+ co-products per ton of light olefins

Figure 31: UOP/Hydro MTO picture, in Norway and carbon yield graph (UOP/Hydro 2003)

JGC Corp DTO, Dimethyl ether To Olefins (Japan)

 Status: 1 ton/day pilot plant

 DME to propylene with higher yield than Lurgi MTP

Figure 32: JGC Corp DTP process flowchart (JGC Corp 2005)

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UOP/Total MTO/OC Feluy (Belgium)

 Status: PDU (2006) optimized for commercialization, MTO followed by

polyolefin unit.

 MTO/OC methanol to light olefins carbon yield is ~ 90%

Figure 33: MTO/OCP coupling flowchart (UOP 2002)

Figure 34: Co-products production of MTO/OCP coupling positioned within other olefin production
processes (UOP 2003)

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