Department of Process and Environmental Engineering Mass and Heat Transfer Process Laboratory Jenni Yl-Mella

28.4.2005

480360S Environmental Catalysis (3 cr.)

RECYCLING OF POLYMERS
Plastics have become common materials of our everyday lives, and many of their properties, such as durability, versatility and light-weight, can be a significant factor in achieving sustainable development. However, plastic applications also contribute to the growing amounts of solid waste generated, as plastic products are often used only once before disposal. The disposal problem is not simply technical, but it also has social, economic and even political aspects. This is the reason why several different methods have been explored and applied for solving the problems associated with polymer waste handling and disposal. (Strong 2000) The alternatives of practical techniques for solid waste management are shown in Figure 1.
WASTE MANAGEMENT TECHNIQUES

Clean technology redesign

Waste source elimination or reduction

Reprocessing

External recycling

Disposal methods

Reworking Material recovery Process redesign Alternative input material Incineration Product redesign Treatment Landfill etc.

Awareness training monitoring

Process modelling and optimization

Customer co-operation By-product

Recycling / Recovery Incineration

Good operating practices, maintenance and good housekeeping

Input material changes

Most profitable

Least profitable

Figure 1 Practical techniques for waste management (Phillips 2000). Even though external recycling is not the most profitable technique for the treatment of plastic waste, it will have a significant role in the future. In spite of the application of clean technologies and waste elimination, it is not expected that the amounts of plastic wastes will decline, thus, new recycling methods will have to be developed. From the perspective of catalysis, chemical recycling of plastic wastes is the most noteworthy of plastic waste recovery techniques.

Energy recovery
Waste incineration, or controlled burning, is typically considered as a disposal method, because it is usually applied as a method of reducing the volume of miscellaneous municipal waste. However, incineration of plastics can also be seen as recovery method, as plastics could replace the application of other oil based fuels. It can be viewed that the plastic application is the first purpose of oil, and energy production is the secondary task. Indeed incineration with energy reclamation is considered as a recovery method and, due to their high energy content, plastic waste is a valuable fuel. The heat capacity of plastics and some other materials are shown in the table 1. Table 1 Heat capacity of plastics and some other materials (Yl-Mella 2002).
Material Heat capacity [MJ/kg] 18 27 46 41 35
Unit MJ/m3 (0 C)

Material

Heat capacity [MJ/kg] 41 26 36 * 10 17

PVC PE PET PS ABS

*

Heavy fuel oil Coal Natural gas Milled peat Paper

Mechanical recycling
Plastics can also be recovered from waste via mechanical recycling. The mechanical recycling process involves a number of operational steps: separation of plastics by resin type, washing to remove dirt and contaminants, grinding and crushing to reduce the plastics particle size, extrusion by heat and reprocessing into new plastic goods. This type of recycling is mainly restricted to thermoplastics because thermosets cannot be remoulded by the effect of heat. (Aguado and Serrano 1999) Mechanical recycling of plastics is limited by the compatibility between the different types of polymers. Presence of a polymer dispersed in a matrix of a second polymer may dramatically change the properties and hinder the possibilities to use it in the conventional applications. A good example of this is the impacts of polyvinyl chloride (PVC) during polyethylene terephthalate (PET) processing. Only a small amount of PVC in the recycled PET strongly reduces the commercial value of the latter. (Aguado and Serrano 1999) Another problem with mechanical recycling is the presence in plastic waste of products made of the same resin but with different colour, which usually impart an undesirable grey colour to the recycled plastic. (Aguado and Serrano 1999) In addition, most polymers suffer certain degradation during their use due to effects of temperature, ultraviolet radiation oxygen and ozone. Therefore, recycled polymers exhibit lower properties and performance than the virgin polymers, and are useful only for undemanding and lesser value applications. Recycling of plastics without prior separation by resin produces a material with mechanical properties similar to timber. Hence, it is often used for the replacement of timber in certain applications. A higher quality of recycled plastics is achieved when separation by resin is carried out prior to the remoulding step. (Aguado and Serrano 1999) Stages and their relations in the mechanical recycling of plastics are shown in Figure 2.

3
B Reclamation - Grinding - Washing - Separating - Classification - Quality control

Shredded material

Specified regrind

A Logistics - Transportation - Collection - Disassembly - Sorting - Shredding - Quality control

C Homogenizing - Storage - Mixing - Conveying - Pelletizing - Quality control

Used Product
F Use - Processor - System manufacturers - Sales - First user - Maintenance/repair - Last user

Base recyclable

D Compounding - Blending - Reinforcing - Filling - Modifying - Stabilizing - Quality control

Application

E Marketing - Application development - Specification - Design - Availability - Quality constancy - Price

Recyclable/ Virgin material

Figure 2 Stages in the mechanical recycling of plastics (Burgdorf et al. 1997).

Feedstock recycling
Feedstock recycling of plastics, also referred to as chemical or tertiary recycling is based on the decomposition of polymers by means of heat, chemical, or catalytic agent, to yield a variety of products ranging from the chemical monomers to a mixtures of compounds with possible applications as a source of chemicals or fuels. (Aguado and Serrano 1999) The chemical recycling processes can be classified into three main areas (Janssen and van Santen 1999): 1. Recycling to fuels (gasoline, liquefied petroleum gas (LPG) and diesel oils) 2. Recycling to monomers 3. Recycling to industrial chemicals. Depending on recyclable plastic types, desired composition and molecule weight of products, many different methods of feedstock recycling can be implemented within above areas. (Yl-Mella 2002, Janssen and van Santen 1999). For example, Figure 3 illustrates the methods for the feedstock recycling of plastics and rubber.

Plastics and rubber wastes

Hydrogenation

Gasification

Chemical depolymerization

Thermal treatments

Catalytic cracking and reforming

Figure 3 Alternatives for the feedstock recycling of plastics and rubber wastes (Aguado and Serrano 1999) Up till now. only a small number of chemical recycling methods have been commercially realized but the interest in more efficient processes is still growing due to the emerging need of polymer waste recycling in the future. At the present, feedstock recycling is more limited by process economy than by technical reasons. The factors which determine the profitability of alternative feedstock recycling methods are the degree of separation required in raw wastes, the value of the products obtained, and the capital investments in the processing facilities. (Aguado and Serrano 1999) According to the separation steps required, the methods can be ordered as follows: gasification < thermal treatments hydrogenation < catalytic cracking < chemical depolymerization. However, the feedstock methods can be ordered also according to the commercial value of the products. In that case, the order of methods will be as follows: thermal oils synthesis gas < hydrogenation oils catalytic oils < monomers. It is interesting to note that the required pre-treatments and product value follow almost reverse orders. (Aguado and Serrano 1999) However, comparison of required pre-treatments and product value is not enough. Many other factors should be included for an adequate comparison of these methods. For instance the possibility of carrying out the treatment in existing or new facilities, minimum size of the industrial plants needed to be profitable, required investments and plants location are such factors. (Aguado and Serrano 1999)

Hydrogenation Hydrogenation of plastics is a potential alternative for breaking down the polymer chain. Compared to treatments in the absence of hydrogen, hydrogenation leads to the formation of highly saturated products, avoiding the presence of olefins in the liquid fractions, which favours their use as fuels without further treatments. Moreover, hydrogenation promotes the removal of hetero atoms, such as chlorine (Cl), nitrogen (N) and sulphur (S), in the form of volatile compounds. However, hydrogenation suffers several drawbacks, mainly due to the cost of hydrogen and the need to operate under high pressure. (Aguado and Serrano 1999) Even though some non-catalytic hydrogenation processes have been developed, most of the hydrogenation processes require the presence of bi-functional catalysts to promote hydrogen addition reactions. A typical catalyst in the hydrogenation includes transition metals, such as palladium (Pt), nickel (Ni), molybdenum (Mo) and iron (Fe), supported on acid solids such as alumina, zeolites or amorphous silica-alumina. (Aguado and Serrano 1999)

Gasification Gasification can be considered to be a partial oxidation process of carbonaceous material leading predominantly to a mixture of carbon monoxide (CO) and hydrogen (H2). It is also called synthesis gas or syngas because of its application in a variety of chemical synthesis. Gasification has been initially developed for coal conversion, but it has been further applied also to the processing of heavy petroleum fractions and natural gas. (Aguado and Serrano 1999) Gasification is an efficient treatment for polymeric waste because of its several advantages: it is not necessary to separate the different polymer types, and it is possible to mix plastic wastes with other, non-plastic solid waste before gasification. However, the profitability of a gasification process largely depends on the value and applications of the synthesis gas. Syngas can be used for the synthesis of various chemicals, such as methanol, ammonia or acetic acid, but it can also be burned in combustors. However, incineration of synthesis gas cannot be really considered as a feedstock recycling of plastics, rather it is considered as a means of energy recovery. (Aguado and Serrano 1999) When oxygen or air is used as a gasification agent, the content of agent in the reaction must be kept low, in order to avoid complete oxidation into carbon dioxide and water. Gasification can be promoted by metal catalyst, which is typically added in aqueous solutions. (Aguado and Serrano 1999) The basic reactions during gasification of carbonaceous material are shown in scheme 1.

Scheme 1 Basic reactions during the gasification of a carbonaceous material (Aguado and Serrano 1999).

The principles of gasification of pure polymeric wastes are similar to the gasification of carbonaceous material. However, certain details have to be taken into account when plastic and rubber wastes are processed. For instance, the heterogeneity of the starting materials, the problem of feeding the highly viscous melted plastics, and the possible formation of corrosive compounds such as hydrochloric acid (HCl) and polyvinyl chloride (PVC), are some examples of details that have to be taken into consideration. (Aguado and Serrano 1999)

Chemical depolymerization During the chemical depolymerization process, the polymer is cracked to the original monomer in the presence of different reagents. Recycled monomers are identical to those used in the preparation of virgin polymers, consequently, plastics prepared from both fresh monomers and depolymerization end products have similar characteristics and quality. (Aguado and Serrano 1999) Chemical depolymerization is the most established method of plastic feedstock recycling, even though it is restricted to the recycling of condensation polymers and there are no applications of decomposition of other polymers. The total volume of condensation polymers accounts for less than 15 % of all plastic wastes. As examples of common condensation polymers, polyesters, polyamides and polyacetals can be mentioned. Condensation polymers are obtained by the random reaction of two molecules, which proceeds with the liberation of a small molecule as the chain bonds are formed. In the chemical depolymerization, the reverse reaction of polymer formation takes place through the reaction of those small molecules with the polymeric chains. Depending on the chemical agent used to break down the polymer, different depolymerization routes are envisaged: for instance glycolysis, methanolysis, hydrolysis and ammonolysis. (Aguado and Serrano 1999) An example of depolymerization of polyethyleneteraphtalate (PET) is shown in Figure 4.

Figure 4 Depolymerization of PET into monomers by different solvolysis methods. (Janssen and van Santen (1999) Some promising alternatives of chemolysis have been also found through a combination of different treatments. The Ford hydroglycolysis process is a good example of these combined alternatives, as it couples hydrolytic and glycolytic reactions to degrade the polyurethane chains. Other combinations of chemolysis have also been studied. (Aguado and Serrano 1999)

Thermal treatment Thermal treatment is a collective term to describe different methods and processes developed for breaking down polymeric materials simply by treatment at high temperature in an inert atmosphere. They are mainly used for the feedstock recycling of addition polymers, whereas condensation polymers are preferably depolymerised by reaction with certain agents. (Aguado and Serrano 1999) Thermal decomposition of polymers can be considered as a depolymerization process in only a few cases, given that thermal decomposition of most polymers leads to a complex mixture of products, containing low monomer concentrations. The types and distribution of products derived form the thermal degradation of each polymer depend on a number of factors: the polymer itself, the reaction conditions and the type and operation mode of the reactor, for instance. (Aguado and Serrano 1999) There is some confusion regarding a thermal treatment of polymers is to be described as depolymerization, cracking, thermolysis or pyrolysis. For example, the term pyrolysis refers to the thermal decomposition of polymeric material at high temperatures (above 600 C), whereas thermal cracking refers to degradation at lower temperatures. However, in some cases, the process is not confined to any of the above process characteristics, for instance in the case when the temperature is continuously varied. In this situation it is difficult to assign one term to be used to describe the process. (Aguado and Serrano 1999) Thermal degradation of plastics and rubber proceeds through a radical mechanism, which may involve three different decomposition pathways (Aguado and Serrano 1999): 1. Random scission at any point in the thermal backbone leading to the formation of smaller polymeric fragments as primary products, which in turn may be subjected to additional random cracking reactions. 2. End-chain scission, where a small molecule and a long-chain polymeric fragment are formed. If the small molecule released is the starting monomer, the thermal degradation process can be considered as an actual depolymerization or unzipping process. 3. Abstraction of functional substituents to form small molecules. In this case, the polymer chain may retain its length or the release of the small molecule may be accompanied by cleavage of the polymeric chain. In many cases, several of these pathways occur simultaneously. During the thermal degradation of many polymers, other reactions may also occur at the same time. For instance during the cracking reactions isomerization, cyclization, aromatization and recombination can also take place. Thus, an increase in the degree of branching of the polymeric chains is usually observed, as they are reduced in length by thermal decomposition. (Aguado and Serrano 1999)

Catalytic cracking and reforming Catalytic cracking and reforming of plastic wastes are based on contact of the polymer with a catalyst that promotes its cleavage. In fact, plastic degradation proceeds in most cases by a combination of catalytic and thermal effects, which cannot be isolated. Beside catalytic cracking, the use of catalysts is usual also in other earlier mentioned processes, such as gasification and partial oxidation of plastics. However, there is no chemical agent incorporated to react directly with the polymer during the catalytic cracking process and the products derived from the polymer decomposition are not usually the starting monomers. (Aguado and Serrano 1999)

There are many advantages in catalytic cracking compared to thermal cracking. For example, polymer molecules start to break down at lower temperatures. In consequence of the lower temperature, the energy requirement is also lower. Further, if the rates of reactions between catalytic and thermal cracking are compared, the catalytic process is faster than the thermal process because of lower activation energy. Using of catalysts also improves the quality and selectivity of products because the product distribution can be varied and controlled by the selected catalysts. (Yl-Mella 2002) All these factors illustrate the great potential of catalytic cracking for the conversion of polymeric wastes into valuable components. However, this method also suffers from drawbacks and problems, which are still not completely solved. For instance with time, the catalysts are deactivated by the decomposition of carbonaceous residues, and by poisons present in the raw waste stream such as chlorine (Cl) and nitrogen (N) compounds. Moreover, the inorganic compounds contained in the plastic wastes tent to remain with the catalysts, hindering their later recovery and re-use. For these reasons, catalytic cracking is mainly applied to polyolefinic wastes of relatively high purity, requiring a number of pre-treatment steps to remove compounds that may negatively affect the catalysts. (Aguado and Serrano 1999) Other difficulties arise from the high viscosity of the molten plastic, which hinders its flow through conventional fixed bed reactors. These problems are largely avoided when the catalytic conversion is combined with a simple thermal treatment, aimed at reducing the viscosity of the mixture and enabling the separation of unwanted components. (Aguado and Serrano 1999) A wide variety of catalysts have been found effective in promoting the decomposition of plastics materials: Friedel-Crafts catalysts, acidic and basic solids, bi-functional solids, etc. The most common catalysts used in plastics cracking are acidic solids, mainly alumina, amorphous silica-alumina and zeolites. These catalysts are typically used in petroleum processing and by petrochemical industries. They have very different textural and acidic properties, which directly determine their catalytic activity and product selectivity. This is an important factor, because the initiation step of polymer catalytic degradation depends on the type of acid sites and leads to different to cracking pathways. (Aguado and Serrano 1999)

Conclusions
Plastics have become common materials of our everyday lives and many of their properties contribute to sustainable development. However, at the end of their useful life, plastics waste may cause a waste management challenge. This problem is aggravated by the fact that plastic applications are often used only once before disposal. Waste incineration, or controlled burning, is typically considered as a disposal method because of its application for a mere reduction of the volume of waste. However, incineration with energy recovery is considered as a recovery methods, as plastics can replace other oil based fuels. The polymers in plastics can be recovered via mechanical recycling. This process involves a number of operations including separation of plastics by resin-type, washing to remove dirt and contaminants, grinding and crushing to reduce the plastics particle size, extrusion by heat, and reprocessing into new plastic goods. This type of recovery is mainly restricted to thermoplastics, because thermosets cannot be remoulded by the application of heat. The chemical recycling processes can be classified into recycling to fuels, monomers or industrial chemicals. During chemical recycling processes, plastic wastes can be remanufactured into valuable chemical feedstock by a large variety of thermal or catalytic processes. Thermal processes are less

sensitive than catalytic processes to dirt and critical impurities, such as Cl, S, N and heavy metals, however, the end products are mostly of lower quality and of lesser value. In the future, catalysis may offer an important contributions to the efficiency of feedstock recycling, provided that the problems of catalyst deactivation by contaminants can be overcome in an economic viable way. The alternative methods for feedstock recycling of plastic and rubber wastes can be summed up into the following classes: 1. Hydrogenation The polymer is degraded by the combined actions of heat, hydrogen and many cases catalysts. 2. Gasification Plastic wastes react with oxygen and/or steam to produce synthesis gas (CO and H2). 3. Chemical depolymerization Plastic wastes react with certain agents to yield the starting monomers. 4. Thermal cracking Plastic wastes are decomposed by the effect of heat in an inert atmosphere. 5. Catalytic cracking and reforming The polymer chains are broken down by the effect of catalyst, which promotes cleavage reactions.

References:
Aguado J & Serrano D (1999) Feedstock Recycling of Plastic Wastes. Royal Society of Chemistry, Clean Technology Monographs. Cambridge, UK. Burgdorf P, Keller B & Orth P (1997) Computer housings in material recycling loop. < http://www.plastics.bayer.com/bayer/ > (28.9.2001) Janssen FJJG & van Santen RA (1999) Environmental Catalysis. Imperial College Press, Netherlands Institute for Catalysis Research. London, UK. Phillips PS (2000) Practical techniques for waste management. University of Oulu. Industrial Ecology course for the Graduate School in Chemical Engineering. 22nd - 26th May 2000. Strong AB (2000) Plastics Materials and Processing. Prentice-Hall, New Jersey, USA. Yl-Mella J (2002) Recycling of Plastics from the Waste Electrical and Electronic Equipment (WEEE). University of Oulu, Department of Process and Environmental Engineering, Finland.