Contents

Cover

Title page

Copyright page

Preface

Chapter 1: General Aspects

1.1 History of the Literature
1.2 Amount of Wastes
1.3 Metal Content in Wastes
1.4 Analysis Procedures
1.5 Standards
1.6 Special Problems with Plastics
References

Chapter 2: Environmental Aspects

2.1 Pollution of the Marine Environment
2.2 Pollution of the Terrestrial Environment
References

Chapter 3: Recycling Methods

3.1 Alternative Plastic Materials
3.2 Mechanical Recycling
3.3 Primary Recycling
3.4 Renewable Polymer Synthesis
3.5 Preparation and Regeneration of Catalysts
3.6 Pyrolysis Methods
3.7 Metallized Plastics Waste
3.8 Mixed Plastics
3.9 Separation Processes
3.10 Triboelectrostatic Separation
3.11 Wet Gravity Separation
3.12 Supercritical Water
3.13 Solvent Treatment
References

Chapter 4: Recovery of Monomers

4.1 Process for Obtaining a Polymerizable Monomer
4.2 Pyrolysis in Carrier Gas
4.3 Fluidized Bed Method
4.4 Recovery of Monomers from Waste Gas Streams
4.5 Polyolefins
4.6 Poly(styrene)
4.7 Phenolic Resins
4.8 Poly(carbonate)
4.9 Poly(ethylene terephthalate)
4.10 Nylon
4.11 Poly(urethane)
4.12 Sequential Processes for Mixed Plastics
4.13 Waste Fiber Reinforced Plastics
References

Chapter 5: Recovery into Fuels

5.1 Poly(ethylene)
5.2 Thermal and Catalytic Processes
5.3 Mixed Waste Plastics
5.4 Hydrocarbon Fuels
5.5 High-Value Hydrocarbon Products
5.6 Purified Crude Oil
5.7 Lubricating Oil
5.8 Waxes and Grease Base Stocks
5.9 Co-pyrolysis of Landfill Recovered Plastic Wastes and Used Lubrication Oils
5.10 PVC Wastes
5.11 Iron Oxide Catalyst
5.12 Landfill
References

Chapter 6: Specific Materials

6.1 Catalysts for Recycling
6.2 Polyolefins
6.3 Poly(styrene)
6.4 Poly(carbonate)
6.5 Poly(ethylene terephthalate)
6.6 Poly(vinyl chloride)
6.7 Pyrolysis of Mixed Plastics
6.8 Technical Biopolymers
6.9 Co-processing of Waste Plastics and Petroleum Residue
6.10 Automotive Waste Plastics
6.11 Phthalates
6.12 Enzymatic Degradation
6.13 Electronic Waste
6.14 Fiberglass Reinforced Plastics
6.15 Usage in Concrete
6.16 Recycling of Floor Coverings
References

Index

Acronyms
Chemicals
General Index

End User License Agreement

List of Illustrations

Chapter 1

Figure 1.1 Reflectance spectra of a black Poly(propylene) and a non-black Poly(propylene), reproduced from an open access article (21).
Figure 1.2 Flow diagram of a stock-based model (54).
Figure 1.3 Dichlorodiphenyltrichloroethane.

Chapter 2

Figure 2.1 Pathways of plastics into the marine environment (20).
Figure 2.2 Styrene oligomers.
Figure 2.3 Plastic additives.
Figure 2.4 Northern fulmars. Reprinted from Wikipedia, licence: GFDL/C-C-by-2.5 (64).

Chapter 3

Figure 3.1 Stages of mechanical recycling (12).
Figure 3.2 Change in density of waste EPS at different oven temperatures (26).
Figure 3.3 Solvents.
Figure 3.4 Electrospinning process.
Figure 3.5 Limonene concentration in the carbon dioxide exit stream (35).
Figure 3.6 Terpenes.
Figure 3.7 Transverse section of rotary reactors (61).
Figure 3.8 Materials separation process (74).
Figure 3.9 Strategies for the separation of plastics by froth flotation (78).
Figure 3.10 Activation for the Fenton reaction (92).
Figure 3.11 Device for using supercritical water (119).
Figure 3.12 Solvents for recovering a polyester polymer.
Figure 3.13 Turpentine liquid compounds.

Chapter 4

Figure 4.1 Dibenzoyl hexamethylene diamine.
Figure 4.2 N,N-Dimethylaminopyridine.

Chapter 5

Figure 5.1 Schematic diagram of a device to obtain raw oil (21).
Figure 5.2 Apparatus for conducting the thermolysis of plastic waste with continuous waste plastics feeding (33).
Figure 5.3 System for recycling waste plastic (34).
Figure 5.4 Systems for conditioning synthetic crude oils (36).

Chapter 6

Figure 6.1 Device for catalytically cracking waste plastics (7).
Figure 6.2 SEM microgram of FCC, reprinted from (10) with permission from Elsevier.
Figure 6.3 SEM microgram of coked FCC, reprinted from (10) with permission from Elsevier.
Figure 6.4 TGA curve of poly(ethylene) (13).
Figure 6.5 Chain cracking in the case of thermal pyrolysis (13).
Figure 6.6 Chain cracking in the case of catalytic pyrolysis (13).
Figure 6.7 Reaction pathway of the lumping reaction (36).
Figure 6.8 TEM micrographs of calcined hierarchical ZSM-5 samples, reprinted from (37), with permission from Elsevier.
Figure 6.9 Scanning electron microscope images of (a) the Y-zeolite and (b) the 1 w% Co-Y-zeolite and (c) the 5% Co-Y-zeolite after pyrolysis-catalysis of the high density poly(ethylene); reprinted from (42) open access from Elsevier.
Figure 6.10 Bulk hydroprocessing process (55).
Figure 6.11 Schematic diagram of the method of recovering rare earth elements (56).
Figure 6.12 Schematic of a conical spouted bed reactor, reprinted from (57) with permission from Elsevier.
Figure 6.13 Apparatus for pyrolysis of hydrocarbonacetous materials (71).
Figure 6.14 Degradation conversion (75).
Figure 6.15 Correlation plot of iTOC-CRDS-measured C13 values versus AMS-measured renewable bio-source carbon content for PET films (103).
Figure 6.16 Grinding machine (142).
Figure 6.17 Samples of glass fibers as obtained after the pyrolysis treatment and after the further calcination treatment (143).

List of Tables

Chapter 1

Table 1.1 Plastics production in the world (6).
Table 1.2 The literature with plastics recycling in the title of the papers found in Google Scholar in March 2018.
Table 1.3 Quantities of recycled PVC in Europe (12).
Table 1.4 Plastics recycling in European countries (6).
Table 1.5 Metal content of poly(ethylene) samples (9).
Table 1.6 Plastics Industry (SPI) recycling codes (68).
Table 1.7 Studies of micro-plastics in seafood and food (88).
Table 1.8 Micro-plastics exported by rivers to seas (126).

Chapter 2

Table 2.1 Rankings of marine debris (18).
Table 2.2 Population density, concentrations of the styrene oligomers in seawater and in sea sand (37).
Table 2.3 Example of chemicals (39).
Table 2.4 Rate of ingestion (56).
Table 2.5 Percentages of fulmars with ingested plastics (69).
Table 2.6 Mean concentration values (71).

Chapter 3

Table 3.1 Solubility of EPS at 25°C in certain solvents (29).
Table 3.2 Solubility of PS at 50°C in cyclic monoterpenes (30).
Table 3.3 Time required for the dissolution (30).
Table 3.4 Terpene and terpenoid content (36).
Table 3.5 Main components of the pyrolysis liquids (% area in GC) (51).
Table 3.6 Results for end-of-life vehicle thermal and thermocatalytic pyrolysis (52).
Table 3.7 Plastic pyrolysis methods (53).
Table 3.8 Materials of municipal solid waste (67).
Table 3.9 Specific gravity and contact angles (80).
Table 3.10 Purity (86).
Table 3.11 Contact angle (94).
Table 3.12 Separation of PC/ABS mixtures at different temperatures (93).
Table 3.13 Changes of the contact angles of certain polymers due to ozonization (99).
Table 3.14 Polymer recovery by the dissolution/reprecipitation technique (104).
Table 3.15 Solvents for recovering a polyester polymer (122–124).
Table 3.16 Specific compounds in a turpentine liquid (125).

Chapter 4

Table 4.1 Properties of the used catalysts (11).
Table 4.2 Mass balance of the pyrolysis of PS in the temperature range of 450°C to 700°C (16).
Table 4.3 Product yields from the pyrolysis of PC (24).
Table 4.4 Yield of terepthalic acid with the variation of the amount of sodium hydroxide (29).
Table 4.5 Yield of terepthalic acid with the variation of the particle size of PET (29).
Table 4.6 Yield of terepthalic acid with the variation of the reaction temperature (29).

Chapter 5

Table 5.1 Properties of the catalysts (3).
Table 5.2 Effect of the catalyst on the product distribution (18).
Table 5.3 Yields from different processes (24).
Table 5.4 Properties of waxes (43).
Table 5.5 Properties of liquid fuel from plastic waste and petroleum diesel fuel (49).
Table 5.6 Plastic waste types in a landfill (51).

Chapter 6

Table 6.1 Gaseous products obtained from PE pyrolysis (3, 4).
Table 6.2 Product distributions from Zn-ZSM-11 catalyzed pyrolysis waste different ratios of plastic waste (15).
Table 6.3 Reaction rate constants (22).
Table 6.4 Product yields from different pyrolysis methods (24).
Table 6.5 Yields of the pyrolysis products (30).
Table 6.6 Calorific value data (31).
Table 6.7 Main products (C1–C8) obtained from HDPE pyrolysis (34).
Table 6.8 Catalysts used in the catalytic degradation of PE/PP polymer waste (36).
Table 6.9 Surface area and porosity of the catalysts (42).
Table 6.10 Product distribution (52).
Table 6.11 Overall product distributions of fresh, steamed and used FCC catalysts (52).
Table 6.12 Main products of post-consumer waste plastics (53).
Table 6.13 RON numbers (59).
Table 6.14 Products of pyrolysis (60).
Table 6.15 Performance of nickel- and iron-based catalysts (64).
Table 6.16 Pseudo first order degradation rate constants (70).
Table 6.17 Effect of degradation temperature (75).
Table 6.18 Effect of degradation temperature (75).
Table 6.19 Separation techniques for PVC waste plastics (84).
Table 6.20 Polyolefins (87).
Table 6.21 Product distribution as a function of temperature and hydrogen pressure using HDPE with 1% Pt/USY (89).
Table 6.22 Product distributions from an ECat-1 (93).
Table 6.23 Activation energy and coke content (94).
Table 6.24 Product distributions from FCC-R1 catalyzed pyrolysis waste at fluidizing nitrogen rates (99).
Table 6.25 Product distributions from FCC-R1 catalyzed pyrolysis waste at different ratios of plastic waste (99).
Table 6.26 Assemblies used in automotive parts (111).
Table 6.27 Major oxides in clay and automotive waste plastics ash (XRF analysis) (107).
Table 6.28 Elements in clay and automotive waste plastics ash (ICP analysis) (107).
Table 6.29 Phthalates (113).
Table 6.30 Categories of electrical and electronic waste (125).
Table 6.31 Compositions and typical densities of the main plastics in an electronic waste sample (131).
Table 6.32 Composition of metal elements extracted from FPCB and from conventionally recycled PCB (138).
Table 6.33 Properties of the Portland Pozzolona cement (155).
Table 6.34 Compressive strength test results (155).

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Library of Congress Cataloging-in-Publication Data
ISBN 978-1-119-53608-6

Preface

The scientific literature with respect to plastic recycling increased dramatically after the mid-1970s and remains a growing field, since the production of polymers, and thus the problems concerning the disposal of these materials after their life cycle, are continuously growing.

Recently, in several countries, official announcements and warnings concerning the pollution caused by plastic wastes have been published.

For these reasons, the problems of plastic waste management have been collected from several recent scientific publications in this monograph.

Plastic recycling refers to a method that can regain the original plastic material. However, there are still more sophisticated methods available for the treatment and management of waste plastics.

These methods include the following:

Basic primary recycling, where the materials are sorted as such and collected individually. In chemical recycling, the monomers and related compounds are sampled by special chemical treatments. Other methods, such as pyrolysis can produce fuels from waste plastics, etc. These methods and others are treated in one of the chapters.

The book starts with general aspects, such as amount of plastics production, types of waste plastics, analysis procedures for identification of waste plastic types, standards for waste treatment and contaminants in recycled plastics.

Then, in another chapter, environmental aspects, such as pollution in the marine environment, such as ingestion of plastics by marine animals, and pollution in landfills are dealt with.

Furthermore, the recycling methods for plastics and then the methods for the recovery of monomers are reported in detail. Also, the advantages of the use of bio-based plastics are discussed.

Another chapter deals with the recovery into fuels, since this has also become an important aspect.

Finally, specific materials are detailed, including recycling methods for individual plastic types, and special catalysts. Here, special uses are also reported, such as the use of plastic fibers in concrete and others.

This textmay be of importance for scientists engaged in the problems of plastics waste management and also for the education of students that are interested in the current problems of plastics recycling.

The text focuses on the basic issues and also the literature of the past decade. The book provides a broad overview of plastic recycling procedures and waste management.

How to Use This Book

Utmost care has been taken to present reliable data. Because of the vast variety of material presented here, however, the text cannot be complete in all aspects, and it is recommended that the reader study the original literature for more complete information.

Index

There are three indices: an index of acronyms, an index of chemicals, and a general index. In the index of chemicals, compounds that occur extensively are not included at every occurrence, but rather when they appear in an important context. When a compound is found in a figure, the entry is marked in boldface letters in the chemical index.

Acknowledgements

I am indebted to our university librarians, Dr. Christian Hasenhüttl, Dr. Johann Delanoy, Franz Jurek, Margit Keshmiri, Dolores Knabl Steinhäufl, Friedrich Scheer, Christian Slamenik, Renate Tschabuschnig, and Elisabeth Groß for their support in literature acquisition. In addition, many thanks to the head of my department, ProfessorWolfgang Kern, for his interest and permission to prepare this text.

I also want to express my gratitude to all the scientists who have carefully published their results concerning the topics dealt with herein. This book could not have been otherwise compiled.

Last, but not least, I want to thank the publisher, Martin Scrivener, for his abiding interest and help in the preparation of the text. In addition, my thanks go to Jean Markovic, who made the final copyedit with utmost care.

Johannes Fink
Leoben, 11th July 2018