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INTERNATIONAL JOURNAL OF CHEMICAL REACTOR ENGINEERING

Volume 5

2007

Article A85

A Comparison of Gasification with Pyrolysis for the Recycling of Plastic Containing Wastes

Ruby Ray

RB Thorpe

Fluids

&

Systems,

School

of

Engineering,

FEPS

(J2),

University

of

Surrey,

ruby che@yahoo.com

 

Fluids

&

Systems,

School

of

Engineering,

FEPS

(J2),

University

of

Surrey,

rex.thorpe@surrey.ac.uk ISSN 1542-6580 Copyright c 2007 The Berkeley Electronic Press. All rights reserved.

A Comparison of Gasification with Pyrolysis for the Recycling of Plastic Containing Wastes

Ruby Ray and RB Thorpe

Abstract

In the present investigation, pyrolysis and gasification, two widely used ther- mochemical processes, are compared as potential chemical recycling methods for MWP and plastic rich MSW in terms of products of high value and their end uses. High temperature pyrolysis results in a wide spectrum of products which also con- tain monomers of C2-C4 range such as ethylene and 1,3-butadiene. Recovery of monomers from their isomers and other products is difficult and energy-intensive. Gasification breaks solid wastes into simple molecules (mainly CO & H 2 ) which subsequently can be converted to value added liquid chemicals (namely alcohols) by a catalytic synthesis processes. Synthetic alcohol then can be converted to the desired petrochemical precursors. After reviewing different aspects of both pyrolysis and gasification, recycling through gasification is chosen as the pre- ferred route for project SPORT as syngas product can be converted into several key petrochemical products in high yield.

KEYWORDS: MPW, recycling, pyrolysis, gasification

Ray and Thorpe: A Comparison of Gasification with Pyrolysis

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1. INTRODUCTION

The amounts of mixed plastic wastes (MPW) (including separated auto-shredder waste (ASW) and waste agricultural plastics (WAP)) and plastic-containing municipal solid waste (MSW) have been increasing steadily in recent years and disposal of these wastes has become a global issue that has attracted the attention of researchers, businessmen, politicians, regulators and environmental activists. The world's annual consumption of plastic materials has increased from around 5 million tonnes in the 1950s to nearly 100 million tonnes today (Waste online, 2007). The amount of plastic waste generated annually in the UK is estimated to be nearly 3 million tonnes (Waste online, 2007). It is estimated that more than 50% of all plastics that end up in this waste is packaging, three-quarters of which is from households. Only 7% by weight of total plastic waste is currently being recycled in the UK (Waste online, 2007). Due to their typically low density, the polymeric wastes occupy a large volume of the waste stream leading to the problem of disposal.

The disposal options for plastic wastes are either landfilling or incineration. The current recovery options are energy recovery or recycling. Recycling includes mechanical processes as well as chemical and various emerging technologies. As almost all plastics are not biodegradable, composting is not an option. The recovery options for plastics are discussed below.

Mechanical recycling is often regarded as the ideal recovery option for plastics, and this is certainly true for items such as blow moulded containers and pallet wrap film, which are easily identified by polymer type and separated from the waste stream. However, this is not the case for the majority of mixed plastic waste. Mixed waste plastics encompass a wide range of materials with wide ranging properties, developed specifically to suit each individual application. Mixed Plastic Wastes are mainly composed of low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). Due to the complex nature and the ever increasing use of composite materials and flexible plastic films, separating individual plastic components, that are suitable for mechanical recycling, is becoming more difficult, costly and energy intensive. As a consequence, mechanical recycling is not the most sustainable recovery option for the majority of mixed plastic waste.

Energy recovery, i.e. combustion of mixed waste plastics with the recovery of the energy content is another proven option, which is widely used for plastic recycling in many parts of the world. As all polymers have high chemical heat content, energy recovery offers a way of winning back some value from polymer wastes. Carefully controlled energy recovery processes are above landfilling in the Waste Hierarchy (DEFRA, UK), but there is persistent public perception issues associated with energy recovery, and there continues to be opponents to this form of recovery. The concerns appear to be centred on the potential loss of resource and the potential formation of dioxins and furans from energy recovery processes. There is a clear need for a more sustainable recycling technology (in terms of economics, environmental performance, and social acceptance) for MWP and plastics-rich MSW to produce fuels or valuable monomer molecules.

Chemical recycling implies a change of the chemical structure of the material, but in such a way that some of the resulting chemicals can be used to produce the original polymer(s) again or other valuable chemicals. Chemical recycling is often used to refer to the various processes for recycling pure waste PET. These include glycolysis, methanolysis, hydrolysis, saponification and pyrolysis. Costs are often high with chemical recycling processes and large scale operations are required for them to be economic.

Pyrolysis can also be considered to be chemical recycling process as it cracks the polymeric chains into smaller molecules without changing their basic chemical structure. Gasification is also a chemically based process and showing increasing potential as a sustainable recycling option for plastics and other waste materials because it enables a broader range of carbon materials to be broken down into basic molecules, to be used as building blocks for a range of new products.

The absolute value of recycling mixed waste plastics through pyrolysis or gasification depends on the particular products targeted. Different products ranging from monomers to synthetic transport fuel can be obtained by chemical recycling of MPW and plastic rich MSW. The market prices of these products can vary greatly.

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Vol. 5 [2007], Article A85

However, the value relative to energy recovery is more consistent and can be expressed relative to oil price. Representative prices at $40 oil are given in Table 1 below.

Table 1. Margin of chemical recycling over thermal recycling

Product

Representative Price @ $40 oil

Spot prices, 2005 (Brown, 2005)

Diesel

$340/t

$447/t

Gasoline

$365/t

$598/t

Fuel Oil

$240/t

$356/t

Ethylene

$840/t

$816/t

Propylene

$630/t

$760/t

1, 3 Butadiene

$530/t

$1014/t

Benzene, Toluene, Xylene

$540/t

$861/t

Styrene

$1020/t

$1432/t

Pyrolysis and gasification are related technologies as both processes decompose organic waste by exposing it to high temperatures and limit the amount of oxygen present during decomposition; gasification allows a small amount of oxygen whereas pyrolysis allows none. With pyrolysis processes, a substantial amount of the intrinsic chemical energy of plastic waste can be recovered through products for instance monomers and transport fuel. But pyrolysis, which is an endothermic process, requires significant energy input to drive the process. The heat transfer issue often restricts pyrolysis to small scale plants. Gasification breaks solid wastes into simple molecules (mainly carbon monoxide & hydrogen) which subsequently can be converted to value-added petrochemical building blocks such as monomers. But during gasification, a fraction of the intrinsic chemical energy of the feed plastic is lost due to CO 2 formation. In both processes, the product distribution and consequently the economics of the process are strongly influenced by the operating conditions used.

The present study is under project SPORT (‘Sustainable Plastics to Olefins Recycling Technology’) which is funded by the UK DTI. The aim of Project SPORT is to identify and adapt a sustainable recycling process for mixed plastic wastes that crack the waste plastics back to basic valuable monomer molecules mainly C2-C4 monomers for petrochemical recycling and to established its economical viability. It is estimated that 4% of the world's annual oil production is used as a feedstock for plastics production and an additional 3-4% during manufacture of those plastics (Waste online, 2007). The majority of this plastic is not recycled after use but landfilled. Therefore, efficient waste plastic recycling technology to produce valuable monomer molecules for petrochemical recycling can play a key role to reduce fossil fuel consumption. The main objective of this paper is a comparison of pyrolysis and gasification of MWP and plastic rich MSW in terms of products of high value and their end uses and to suggest the preferred route of chemical recycling of plastic wastes for project SPORT. The review of this suggestion using more modern decision making tools such as LCA (Life Cycle Analysis) is beyond the scope of this paper.

2. CHEMICAL RECYCLING PROCESSES

2.1 Pyrolysis

Pyrolysis refers to the thermal decomposition of organic material at elevated temperatures in the absence of oxygen. Pyrolysis differs from other thermal conversion processes, i.e. gasification and combustion, in that it is an endothermic process. Yang and Roy (1996) reported that the overall endothermic heat of pyrolysis of NR (natural rubber) and SBR (styrene-butadiene rubber) are 870 and 550 kJ/kg respectively at 510 °C. Pyrolysis process produces a mixture of combustible gases (primarily methane, other hydrocarbons, hydrogen and carbon monoxide), hydrocarbon liquids (contain several constituents over a wide range of molecular weight) and carbon rich solid residues. The relative quantities of gas, liquid and solid depend on the mode of pyrolysis and operating conditions like temperature, rate of heating, pressure and residence time. More liquid is produced at lower temperatures whereas higher temperatures and longer residence times produce more gas. Lower process temperature and longer vapour residence time favour the production of charcoal (Bridgwater, 2003).

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Ray and Thorpe: A Comparison of Gasification with Pyrolysis

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Pyrolysis offers an attractive technique of chemical recycling of mixed plastics waste. It can decompose long polymeric chains of the plastic to reusable monomers, hydrocarbon fuels having carbon number distribution in the range of C1 – C50 and valuable aromatic solvents like benzene, toluene etc. The product distribution of pyrolytic reaction of polymeric material highly depends on the nature of the feed plastic waste and operating conditions mainly temperature. Changing these variables, it is possible to obtain a predominantly liquid hydrocarbon product with potential for use as a fuel or a mixture of gaseous and liquid products that can be used as a petrochemical building block (Mader and Mennicken, 1995).

Thermal degradation of plastic materials follows both consecutive and competing reaction paths to give a wide array of products and intermediates. The sequences of reactions are complex in nature and involve both endothermic and exothermic processes. Several investigators (Bockhorn et al., 1999; Zhou et al., 2006; Saha et al., 2007) have reported the overall kinetic parameters for the thermal decomposition of individual plastics namely waste low-density polyethylene (LDPE), polypropylene (PP), waste polyethylene terephthalate (PET), polyvinyl chloride (PVC) etc, but work on pyrolysis kinetics of mixed plastic waste has yet to be done. The mechanism of thermal decomposition of plastics has been expressed by the investigators (Bockhorn et al., 1999; Zhou et al., 2006; Saha et al., 2007) using formal degressive rate expressions

d α =

dt

( )(

k T

. 1

α

)

a

(1)

with m 0 being the initial

m α the final mass; k is the reaction rate constant and a the apparent order of the overall

decomposition reaction. Introducing the Arrhenius type temperature dependency for the rate constant,

mass, m the actual mass and

Where α is the degree of conversion which is defined as

(

α= m m

0

) (

/

m

0

m

α

)

k

=

k

0

e /

E

RT

and the heating rate, β = dT / dt , Equation (1) is transformed into

d

α

dt

=   k   .e

0

β

(

E / RT

)

(

. 1

α

)

a

(2)

The overall kinetic parameters k 0 , E and a have been evaluated using Equation (2). Though most of the researchers reported the kinetic parameters for the decomposition of plastics, Bockhorn et al. (1999) also studied kinetics of formation of products like HCl, benzene from the isothermal degradation of PVC.

During the present study, we have examined a number of commercially available polymeric pyrolysis process options which could produce valuable monomer molecules mainly C2-C4 range for project SPORT. It is observed that most of the commercial organisations like Cynar Plc, Alphakat Technologies, Gossler Envitec, offering pyrolysis technology to the investor, predominantly target low temperature pyrolysis of waste plastic to produce high quality synthetic fuels namely gasoline, diesel and fuel oil. A pyrolysis temperature within the range of 350-450 o C is the best operating temperature for plastic cracking to valuable liquid petroleum fuels. It is understood (Ballice, 2002; Lee and Shin, 2007) that at low temperature, polymeric feedstock primarily devolatilize to produce high molecular weight hydrocarbons with carbon number ranging from C5–C50. The plastic cracking process of Cynar Plc, known as the ThermoFuel process, is a process whereby scrap and waste plastics are gently 'cracked' at relatively low temperatures (370-420 ºC) to give synthetic fuel with an average carbon range similar to diesel oil. The Alphakat Technologies claims to produce synthetic diesel in one step by catalytic depolymerisation of hydrocarbon containing waste material such as mixed waste plastic with a reactor temperature of 350 ºC (Krzesinski, 2006). Gossler Envitec has developed thermal-catalytic cracking processes with temperature range of 350-400 o C for the recycling of polyolefin’s like polypropylene and polyethylene. Their polyolefin recycling technology mainly produces synthetic fuel (gasoline, diesel and fuel oil). Noting the product range, low temperature pyrolysis is not a desirable option for project SPORT but because of the high current value of transport fuel, it does seem commercially interesting.

In high temperature pyrolysis, where the temperature varies within the range of 650-850 o C, secondary gas phase cracking occurs and the primary devolatilization products are cracked to result a wide spectrum of smaller hydrocarbons (ranging from C1–C9) like alkenes, alkanes, aromatics and gaseous by-products. Several investigators

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Vol. 5 [2007], Article A85

(Arena and Mastellone, 2000; Herna´ndez et al., 2005; Mastral et al., 2002; Sodero et al., 1996) have studied various aspects of high temperature pyrolysis of polymers mainly polyolefin’s which is the major fraction of mixed plastic waste. High temperature pyrolysis of plastic rich in polyolefin’s typically produces 65-85% gases, 18-22% liquid and the rest soot (Sodero et al., 1996). A typical composition of the gas is 4-10% methane, 22-31 wt% ethylene, 1.5- 2.7 wt% ethane, 10-14 wt% propylene, 0.5-1 wt% propane, 4.5–5 wt% n/iso-butene, 0.3-0.6 wt% cis/trans-2-butene, 6-7 wt% butadiene (mostly 1,3-butadiene) (Sodero et al., 1996). The temperature and residence time have a great influence on the product distribution in high temperature pyrolysis. Mastral et al. (2002) obtained their highest gas yield of 86.4 wt% by pyrolysing HDPE at 780°C. Above 850°C, the gas yield decreased due to cyclation reactions that formed aromatic hydrocarbons. They also reported that yield of methane increases with increasing residence time at higher temperature whereas fractions of C3 and C4 compounds decrease with increasing residence time. However, C 2 H 2 and C 2 H 6 yields were not affected by the residence time. So, the gaseous products contain valuable monomers of C2-C4 range like ethylene, propylene and 1,3-butadiene for petrochemical recycling, but the recovery of the valuable monomers from their isomers and other products is difficult, costly and energy-intensive. For instance, recovery of propylene from propane and 1,3-butadiene from n/iso butane would be very difficult by distillation due to their close boiling point (Table 2). In fact this problem is well understood which is why olefin units have dedicated distillation and solvent extraction units for separating these monomers from the streams of close boiling compounds. These separations are expensive and need to be performed at scale to be economic. Where it is possible to integrate a pyrolysis plant with a refinery or olefins unit, the additional capital cost of the light gas separations could be minimised. However, transporting plastic waste over long distances to refineries is not an ideal option because it implies high transport costs and environmental impact. Due to high calorific value, gaseous products can be used as fuel, but this is also not the most desired end use for project SPORT. Liquid product mainly contains 32-35% aliphatics (mainly C5-C9 hydrocarbons) and 65-68% aromatics namely benzene, toluene, styrene, naphthalene etc (Day et al., 1999; Kaminsky and Kim, 1999). Day et al. (1999) reported that the yield of the aliphatic compounds falls off rapidly as the pyrolysis temperature increases while that of the aromatic compounds remain relatively constant. As C5-C9 hydrocarbons are gasoline range products, they can be mixed after treatment into the gasoline pool. Some valuable chemicals can be recovered from this mixture if their percentage is high enough. As the actual product distribution of C5-C9 range liquid obtained form pyrolysis of mixed plastic is not available in literature or from any commercial organisation, it is very difficult to identify the quantity of any valuable compounds for petrochemical recycling.

Aromatic fraction of liquid product from plastic pyrolysis is of much interest from recycling point of view. Day et al. (1999) reported that the mono-aromatics are the most dominant organic compounds identified in the pyrolysis liquid at high temperature, with benzene, toluene, naphthalene, indene and styrene being the major components. Other aromatics such as ethylbenzene, indene, p-xylene are also detected in the aromatic mixture. Among all these mono-aromatics, styrene is the most valuable monomer. But the close boiling point of styrene to ethylbenzene, and other components preclude the use of classical distillation as a separation method. A solvent- based extractive distillation system, which is complicated and costly, can extract and purify styrene. Benzene and toluene are also valuable products. But from boiling point table (Table2), it is clear that benzene, when recovered by distillation, would be associated with other C6 compounds e.g. cyclohexene, cyclohexane. Toluene would also be associated with other close boiling compounds e.g. 2,5-dimethylhexane, 2,4-dimethylhexane, cyclopentane etc if they present in the liquid mixture. To avoid such contamination, general practices of recovering BTX aromatics are by either liquid-liquid extraction or solvent-based extractive distillation.

Moreover, in project SPORT we are interested in recycling ASR as well. Automobile shredder residue (ASR), highly heterogeneous polymeric waste stream produced by shredding operations during the recycling of automobiles, contains not only different plastics but rubber, foam, textiles and metals. Product distribution of pyrolysis of ASR is more complicated. Pyrolysis of ASR produces more solid residue than other polymeric waste. Day et al. (1996) reported that solid residue is the major product of ASR pyrolysis process, ranging from 80% at 500°C to 70% at 750 °C whereas gas and liquid product in pyrolysate are of 20% and 10% respectively. The solid residues can be considered to be composed of three components. An organic fraction composed of organic material (not fully degraded polymeric species and high molecular weight products), a carbonaceous char and inorganic ash (including metals residues). Therefore, a major part of the intrinsic chemical energy in ASR is lost in solid residue. Disposal of this solid residue is a major environmental concern. Another major concern with ASR pyrolysis processes is the possible formation of carcinogenic compounds of environmental concern such as polycyclic aromatic hydrocarbons (PAH’s), polychlorinated biphenyls, dioxins and furans. Rausa and Pollesel (1997) pyrolyzed ASR at 650, 800 and 850 °C and detected several PAH’s as well as phenol, benzaldehyde, and

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Ray and Thorpe: A Comparison of Gasification with Pyrolysis

5

chlorobenzene as pyrolysis products. At 650°C, the PAH’s accounted for 1.3% of the pyrolyzate while at 800 and 850 °C they increased to 32.3 and 55.1%, respectively. Hence, pyrolysis of ASR does not appear to be an attractive option.

Table 2. Boiling points of monomers, BTX and close boiling compounds thereto

Components

Normal boiling point,

Components

Normal boiling point,

 

(

o C)

 

(

o C)

Ethylene Ethane Propylene Propane n/iso Butene

-103

2,4-dimethylpentane

80.5

-88

Cyclohexane

80.7

-47.8

Cyclohexene

82.9

-42.1

Ethylcyclopentane

103.4

-6.3

2,5-dimethylhexane

109.1

1,3-Butadiene

-4.5

2,4-dimethylhexane

109.4

Trans-2-butene

0.8

Toluene

110.6

Cis-2-butene

3.7

3,3-dimethylhexane

111.9

1,2-Butadiene

10.8

cyclopentane

118.7

Methyl-cyclopentane

71.8

Ethylbenzene

136.1

2,3-dimethyl-2-butene

73.2

p-Xylene

138.3

Benzene

80.1

Styrene

145.1

2.2 Gasification

In thermal gasification, combustible material is partially oxidized into a gaseous energy carrier in a high-temperature reducing atmosphere, using air, steam or oxygen as the gasification agent. Gasification occurs in a number of sequential steps:

Drying to evaporate moisture

Pyrolysis to produce volatiles, vaporised tars or oils and a solid char residue

Gasification or partial oxidation of the solid char, pyrolysis tars and pyrolysis gases

Typically, the exothermic reaction between carbon and oxygen provides the heat energy required to drive the pyrolysis and endothermic char gasification reactions. The main prevailing reactions along with their kinetic information occurring in the gasifier are given in the Table 3. This kinetic information could be useful in the sizing of a gasifier. The key components of product gas, which is commonly known as synthesis gas, include H 2 , CO, CO 2 , CH 4 and N 2 (if air is used as the gasification agent).

Attractive features of gasification include: the ability to produce a consistent synthesis gas product and the ability to accommodate a wide variety of feedstock. Gasification of waste has many potential benefits when compared with conventional options such as incineration. One of them is that highly toxic dioxin and furan compounds are not expected to be present in the synthesis gas (Orr and Maxwell, 2000). This is for the two following reasons. First, the reducing gas environment precludes the formation of the free chlorine from HCl, thus preventing chlorination of any dioxin precursor in the syngas. Secondly, the high temperature in the gasification process effectively destroys any dioxin/furan compounds or their precursors in the feed. The reducing atmosphere in gasification system also prevents the oxidation of sulphur and nitrogen compounds to SOx and NOx (Orr and Maxwell, 2000).

The gasification process has also few downsides. It produces CO 2 which is a detrimental greenhouse gas and a fraction of the intrinsic chemical energy of the feed waste is also lost through this CO 2 . Moreover, synthesis gas from a waste gasifier contains several impurities like particulates (entrained ash, char, fluid bed material etc.), tars (refractory aromatics), hydrogen halides, volatile heavy metals and heavy metal compounds (e.g. Hg, Pb, Cd) and alkaline compounds, depending on the fuel composition, mode of gasification and the type of gasifier used. Many of these are toxic substances that pose ecological and human health risks if released into the environment. Because of these impurities, the syngas needs to pass through extensive gas cleaning systems before being used by subsequent downstream processes.

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Vol. 5 [2007], Article A85

Table 3. Kinetic data of main prevailing reactions occurring in the gasifier

 

Reactions

   

Rate constant

Heat of reactions (kJ/mol)

Oxidation

   

3

407.4

C

+ O

2

CO

2

k

=

5.67

×

10

(Di Blasi, 2000)

9

×

exp

160x10

RT

s

-1

(Levenspiel, 1982)

Gasification Boudouard reaction:

   

12

22409.64

-1

-173.8

   

k

=

1.6

×

10

 

×

exp

s

C

+

CO

2

2CO

Steam carbon reaction:

 

(Freund, 1986)

3

T

17500

-1

(Caram and

Amundson, 1977)

-131.0

 

k

=

1.33

×

10

T

×

exp

s

C

+ H O CO + H

2

2

 

T

(Arai and Hasatani, 1987)

 

(Arai and Hasatani,

1987)

Water gas shift reaction:

CO

+ H O CO

2

2

+ H

2

k

=

5.14

×

10

4

×

exp 3.995

×

10

4 T  

 

43.47

(Arai and Hasatani,

 

(kmol/m 3 ) -1 s

-1

(Arai and Hasatani, 1987)

 

1987)

CO

2

+

H

2

CO

+

H

2

O

k

=

2.63

×

10

6

×

exp 3.995

×

10

4

T

2762

T

-43.47

(Arai and Hasatani,

 

(kmol/m 3 ) -1 s -1 (Arai and Hasatani, 1987)

 

1987)

Air gasification produces a poor-quality gas in terms of calorific value (4-7 MJ/m 3 higher heating value) which is suitable as a fuel for boilers, engines and turbines, but is not suitable for use as synthesis gas for conversion to liquid products due to its high N 2 content. Gasification with pure oxygen results in a medium heating value gas with a higher quality mixture of carbon monoxide and hydrogen and virtually no nitrogen but has drawbacks; high production cost of oxygen and hazards associated with handling of oxygen during gasification. Gasification with steam is more commonly called “reforming” and results in a hydrogen and carbon dioxide rich synthesis gas. The main disadvantage of steam gasification is the quantity of heat that needs to be supplied to the reaction and consequently, the complexity of the reactor (Bridgwater, 1995).

The syngas gas from oxygen or steam gasification, which is rich of CO and H 2 can be used as a chemical building block from which a wide assortment of commercial chemicals may be manufactured. A major use of syngas is for methanol manufacture. Syngas conversion to methanol is an well known process where the conversion takes place in a high pressure (80 – 100 barg) fixed bed reactor using a copper based catalyst at around 240 o C. Methanol is a commodity chemical used as a feed to many manufacturing processes including Methanol to Olefins and Methanol to Propylene. Syngas can also be converted to mixed alcohols by gas-to-liquid catalytic conversion processes e.g. processes using ultrafine Mo–Co–K catalysts (Zhang et al., 2001) or molybdenum sulphide (K/Co/MoS 2 ) as catalyst (Nirula, 1996). The general stoichiometry for alcohol formation may be represented as follows:

nCO + 2nH 2 C n H 2n+l OH + (n-l)H 2 O

(3)

Alcohol synthesis reactions are highly exothermic (H = -101.74 kJ/mol CO converted). The exothermic heat of reaction can be used for steam generation which steam can subsequently be utilized to produce electricity. Alcohol synthesis reactions are always associated with the equilibrium water gas shift reaction:

CO + H 2 O CO 2 + H 2

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Ray and Thorpe: A Comparison of Gasification with Pyrolysis

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By choosing an appropriate catalyst, greater flexibility in terms of methanol/higher alcohols ratios, lower water content in the reaction product and higher selectivities to the desired liquid alcohol products in the C2-C4 range can be achieved.

Dow/Union Carbide (Nirula, 1996) developed a modified Fischer-Tropsch catalyst system based on molybdenum sulphide for their process of mixed alcohols from syngas. The following table (Table 4) reveals the product distribution based on 40% CO conversion obtained in Dow/Union Carbide patent.

Table 4. Product selectivities (mole%) based on 40% CO conversion (Nirula, 1996)

Product

Mole%

Methane

9.45

Ethane

0.75

Methanol

13.46

Ethanol

28.08

Propanols

9.32

Butanols

3.13

C5 alcohols

1.63

Methyl acetate

1.16

Ethyl acetate

1.02

Carbon dioxide

32.00

The above selectivity corresponds to 85% liquid product (alcohols and esters) and 15% gas product on a CO 2 -free basis. The liquid product contains 41.3 % ethanol and 13.7 % propanol. Methanol, ethanol and propanol are of particular interest as routes are available to convert these alcohols into important petrochemical monomers such as ethylene and propylene.

Plastics are good feedstock candidate for gasification process because many plastics have high calorific values and simple chemical structure composed primarily of carbon and hydrogen. But because of the size and the shape of the plastic products, the size reduction is necessary to produce a feed of high bulk density to facilitate ease of feeding.

In the present study, we have reviewed a number of commercially available gasification processes that can handle mixed plastic waste and plastic rich municipal solid waste. Different methods (Thermoselect process, Texaco gasification process, BASF conversion process, the Akzo Nobel steam gasification process, the Linde gasification process etc) have been developed in this field which claim to process mixed plastic waste and plastic rich municipal solid waste. For instance, the Themoselect process (Drost et al., 2004) claims to be an innovative high temperature waste recycling technology that can efficiently gasify mixed waste plastics mainly automotive shredder residues (ASR) mixed with MSW. Solid wastes (45%ASR and 55%MSW) can be continuously processed in fixed bed oxygen blown gasifier and residue melting reactor to achieve a maximum recovery of recyclable raw materials, with simultaneous utilization of the chemical energy contained within the waste material.

3. COMPARISON

After reviewing thoroughly both pyrolysis and gasification process for chemical recycling of mixed waste plastic, it appears that both have positive and negative aspects.

Low temperature pyrolysis of mixed plastic waste mainly produces synthetic transport fuel, which is not the desired product for project SPORT, but does currently have a reasonably high value. High temperature pyrolysis of polyolefin rich mixed plastic produces valuable monomers like ethylene, propylene, butadiene and styrene. By choosing proper operating conditions, namely temperature and residence time, it may be possible to produce reasonable fractions of valuable monomers for petrochemical recycling. However, the main problem associated with pyrolysis is its complex product distribution and product purification requirements. The gaseous products are well identified, but separation of valuable monomers like propylene and butadiene from their isomers and other

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International Journal of Chemical Reactor Engineering

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compounds is cost and energy intensive. An additional material issue is the need to remove acidic gases eg. HCl from the product stream. The liquid product (C5+) consists of a heterogeneous mixture of large number of

compounds and proper analysis of this steam to identify all compounds has not been published by any organisation.

A few of the aromatic compounds are named in literature, like styrene, benzene, toluene, but separation processes,

which would involve solvent extraction and extractive distillation due to the presence of close boiling compounds in the mixture, is costly and complicated and cannot be designed without a proper product analysis.

As the maximum practical size for a plastic processing plant is determined by the volume of suitable wastes that can be economically collected and transported to the plant and since the bulk density of plastic wastes is low and the transport costs high, even wastes generated comparatively close to the plant may be uneconomic to recover. That is why project SPORT is not limited to polyolefin rich mixed plastics feed. We are considering ASR and plastic rich MSW as well. But, ASR pyrolysis produces mainly solid residue which contains substantial amount of carbonaceous compounds. Efficiency of ASR pyrolysis process decreases as substantial amount intrinsic chemical energy of ASR is lost as solid residue. Moreover, it produces carcinogenic compounds of environmental concern such as polycyclic aromatic hydrocarbons (PAH’s), polychlorinated biphenyls, dioxins and furans etc.

Another difficulty with pyrolysis is that it is a less proven technology for mixed waste plastic on large scale. We reviewed several commercially-available pyrolysis process during this study but none of them are proven

at anywhere near the desired scale (>100 kt p.a.) of neither project SPORT nor do they have a track record of

reliable near continuous operation. For instance, ThermoFuel process of Cynar Plc can process only 10-20 tonnes of waste plastic per day i.e. 3.65-7.30 kt p.a.

On the other hand, gasification is a well defined technology and is already commercially available on the large scale. Information on the analysis of the gas product stream is available in the literature and in more and

sufficient detail on a commercially confidential basis. Gasification can handle different types of feedstock whether

it is mixed waste plastic including ASR or plastic rich MSW. Gasification converts the carbonaceous part of the

solid wastes into synthesis gas which consists of simple molecules (mainly CO & H 2 ). It also produces solid residue,

which contains mainly the inorganic part of the feedstock (a slag) and can be used as building material. CO & H 2 can be converted to value added liquid chemicals (namely alcohols) by a catalytic synthesis processes as explained above. The product obtained by this catalytic synthesis process is not complicated, it is well defined. By choosing appropriate catalyst, higher selectivities to alcohol products in the C1-C4 range can be achieved which then can be utilised in a number of petrochemical processes.

The gasification process is self sustained as no external heat is required to drive the process. As gasifier operates at high temperature, synthesis gas is generally available at 1100-1200 o C. The heat energy of synthesis gas can be utilized to produce hot water or steam for electricity generation. This energy exaction increases the overall efficiency of the gasification process. During the present study, a flowsheet has been developed of the conversion of syngas to mixed alcohol using the Aspen Plus simulation package (Aspen flowsheet and discussion are in Section 4). The syngas composition and temperature is based on a process suitable for the gasification of the mixed plastic waste, the Thermoselect process (Drost et al., 2004). From the flowsheet, we have estimated the electricity generated utilising heat energy of hot synthesis gas and other hot process stream. The estimated electricity generated by the process is 713 kWh/t of Thermoselect waste feed.

However, chemical recycling through gasification has several downsides as well. The best form of gasification with respect to downstream processes is oxygen blown gasification, but this requires oxygen, which is expensive and has to be separated from air with a fairly high energy cost reported as 250 kWh per tonne of oxygen produced.

Petrochemical monomers (ethylene & propylene) obtained via a gasification route involves several significant and separate processing steps, namely

MSW feed preparation

Gasification

Syngas cleanup

Alcohol synthesis reaction

Separation of desired alcohols

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Further conversion of alcohol to valuable monomers

An extensive gas cleanup system is necessary as impurities in synthesis gas may deactivate the catalyst used in alcohol synthesis process. The combined effect of all the necessary processes may increase the monomer production cost. Another issue is that gasification produces significant amount of CO 2 which has detrimental greenhouse effect. But if we consider the CO 2 produced in supplying endothermic heat of reaction associated with pyrolysis process, the value appears to be comparable or sometimes more than the CO 2 emitted from gasifier depending upon the feed composition. We have calculated the typical CO 2 emission from power plant to generate electricity required to supply the endothermic heat (~ 1390 kWh/t of waste) of pyrolysis of polyolefin (50% polyethylene and 50% polypropylene) feed pyrolysing at 690 0 C. Calculated CO 2 emission associated with polyolefin pyrolysis is ~1.25 kg/kg of polyolefin feed. Whereas, Thermoselect process reported that CO 2 emission from gasifier processing solid waste (45% ASR and 55% MSW) feed is ~0.5 kg/kg of feed (Drost et al., 2004).

Finally we present a comparison in terms of energy and product of pyrolysis and gasification. We have information for the pyrolysis of polyolefins, a very favourable but unrealistic feed for project SPORT. Whereas we do have information for the gasification of a more general, more plentiful, mixed waste stream that contains plastic which is one of the proposed feed for project SPORT. Based on all the information outlined in the paper, we have constructed Table 5. Though we have tried to present a reasonable comparison in terms of energy and product of pyrolysis and gasification process in Table 5, we have to keep in mind the different feed for the processes. We cannot perform a fair economic comparison of pyrolysis with gasification as detailed product analysis of pyrolysis of mixed plastic waste or plastic rich MSW is not available either in literature or from any commercial organisation. Unless we know the exact product distribution from pyrolysis process, it is also not possible to design proper downstream processes such as gas cleanup system, product separation processes etc.

Table 5. Comparison in terms of energy and product

 

Pyrolysis of polyolefins

Gasification of a mixed waste

Energy Comparison

   

Energy required to produce O 2

-

250 kWh/t O 2 produced or 114.75 kWh/t of waste (based on Thermoselect Process)

Heat energy required to drive the process

~1390 kWh/t of waste

-

Electricity generated utilizing heat energy of product

-

713 kWh/t of waste (based on Thermoselect process)

Product Comparison

High Temperature Pyrolysis Product (approximate wt%)

Alcohol Products (approximate wt%) based on 40% CO conversion

Ethylene (26 wt%) Propylene (12 wt%) Butadiene (6.5 wt%) Styrene (1.6 wt%) Benzene/Toluene/Xylene (9 wt%)

Methanol (14.3 wt%) Ethanol (43 wt%) Propanol (18.6 wt%) Butanol (7.7 wt%) C5-alcohols (4.8 wt%)

Low Temperature Pyrolysis Product

Gasoline

Diesel

Fuel Oil

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4. SIMULATION OF MIXED WASTE PLASTIC TO OLEFINS PROCESS BASED ON GASIFICATION

In the present study under project SPORT, recycling of mixed waste plastic via gasification is considered as the suitable route. The Thermoselect gasifier (Drost et al., 2004; Drost and Kaiser, 2004) which claims to be suitable for processing mixed waste plastic including ASR or plastic rich MSW, has been chosen for base case study. The Thermoselect process is a proven technology available in a large scale demonstration facility and commercialised. Commercial plants are in operation in Karlsruhe, Germany, in Tokyo-Chiba, Japan and in Mutsu, Japan.

The whole process is explained in great detail by Drost et al. (2004) and Drost and Kaiser (2004). The gasifier used in the process is fixed bed oxygen blown gasifier with a residue melting reactor at the bottom to achieve a maximum recovery of recyclable raw materials. Prior to its gasification, the waste is processed in a degassing channel into dense plugs or briquettes. Radiated heat from the gasification reactor initiates the waste drying and decomposition processes in the degassing channel. The dried and charred briquettes emerge from the degassing channel into the gasifier and are exposed to steam (from water in the waste) and controlled injection of pure oxygen as the gasification medium. All organic materials in the waste are transformed into a synthesis gas with a composition that reflects the thermodynamic equilibrium at the top of the reactor (approximately 1200 °C, 1.2 bar). The metals and minerals continue to move to the bottom of the reactor which is a residue melting reactor where they are melted at 2000 °C by further injection of natural gas and oxygen. The liquid metals in the effluent from the residue melting reactor are recovered as two separate phases.

The composition of synthesis gas obtained from the Thermoselect gasifier at 1200 °C is 35 vol% H 2 , 35 vol% CO, 25 vol% CO 2 and rest nitrogen. Synthesis gas also contains several impurities such as K, P 2 O 5 , H 2 S, HCl, Hg, Zn etc. Because of these impurities, the syngas needs to pass through extensive gas cleaning systems before being used by subsequent downstream processes. Though Thermoselect process uses wet gas cleaning system, in project SPORT dry gas cleaning process involving intimately mixing the flue gas stream with a solid/liquid sorbent/reactant that fixes the pollutant gases in a solid particle which is then collected, along with any process particulates/fly ash, on a fabric/ceramic filter (bag house filter) has been proposed.

During the present investigation, a flowsheet of conversion of syngas to mixed alcohol using the Aspen Plus simulation software has been developed (Figure1). As alcohol synthesis reactor operates at high temperature and high pressure, clean syngas coming from gas cleaning system are compressed using multiple compressors with intercoolers. CO 2 is removed from the syngas which is nothing but a diluent and also increasing the volume of the alcohol synthesis reactor. Mixed alcohol products have been separated by means of distillation. During the development of the base case flowsheet of mixed alcohol process, purge gas from the reactor recycle has been evolved which has been utilized for power generation using a combination of gas turbine and steam turbines. Sensible heat energy of the hot synthesis gas coming out from the gasifier is also used to generate the saturated high pressure steam (62 bar) which is subsequently utilized in high pressure steam turbine for electricity generation. Saturated HP steam at 62 bar has also been raised using heat energy released by alcohol synthesis reactor. From the Aspen simulation, we have estimated the electricity generated (Table 6) using the combination of gas turbine and low pressure and high pressure steam turbines. The estimated electricity generated by the process is 713 kWh/t of Thermoselect waste feed with a feed rate of 45.66 t/hr. Due to the commercial confidentiality, we can not reveal all the process details in this paper.

Table 6. Electricity generated in the syngas conversion to mixed alcohol process

Equipments

Electricity generated

Gas turbine High pressure steam turbine Low pressure steam turbine

9.05

MW

7.64

MW

4.75

MW

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5. CONCLUSION

Comparing pyrolysis and gasification and reviewing different aspects of them, recycling through gasification is chosen as the preferred route for project SPORT. The main driving forces towards gasification are its simple and well defined product (syngas) and its availability in large scale in commercial operation. Syngas can be converted to mixed alcohol products by a catalytic synthesis processes. Mixed alcohol products obtained from alcohol synthesis reactor is also well defined and choosing proper catalyst, it is also possible to obtain higher selectivity towards C1- C4 alcohols which subsequently can be converted into several key petrochemical products in high yield. As detail product distribution is also available for mixed alcohol products, proper design of downstream separation processes is possible.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the financial support of the UK DTI (Department of Trade and Industry) for project SPORT.

NOTATION

E

activation energy, J/mol

k

reaction rate constant, s -1

R

universal gas constant, J mol -1 K -1

t

time, s

T

temperature, K

Subscripts

o initial

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Combusted gas to stack Heat recovery from hot syngas & HP Steam raising 44 Syngas
Combusted gas
to stack
Heat recovery from hot syngas & HP Steam raising
44
Syngas to gas cleaning system
Saturated steam at 3.6 bar
BFW at 3.6 bar
42
43
Superheated steam
Boiler1
at 3.6 bar
50
35
Mixer3
Splitter2
36
37
Boiler2
HE4
BFW at 62 bar
49
Gas Turbine
32
38
Air
28
Superheate d steam
30
at 62 bar
LP steam
34
turbine
29
33
Compressor
51
Turbine
Combustor
HE3
Syngas from
gasifier at 1200 oC
48
31
40
HP steam
27
turbine
Mixer2
41
Water
47
(BFW return)
Cooler2
Valve2
18
46
Off gas recycle
Splitter1
Steam raising in Alcohol Synthesis Reactor
17
19
BFW at 62 bar
45
Cooler1
HE5
Saturate d steam at 62 bar
14
15
Compressor1
Mixed alcohol products
39
HE2
20
Flash1
9
Multiple compressor
Multiple compressor
21
CO2 absorber
Water separator
with intercooler
with intercooler
8
10
4
6
11
1
3
16
Mixer1
Seperated
HE1
Clean Syngas
from Gas cleaning system
5
Alcohol Synthesis
Mixed alcohol products
alcohol products
2
Reactor
7
MULTIFRAC
13
water
Alcohol seperation
water
units
CO2
water
12
Mixed alcohol products
Saturated steam at 62 bar
Off gas
LP steam to alcohol
seperation units

Figure1: Aspen flowsheet of syngas conversion to mixed alcohol products along with heat integration

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