CHAPTER ONE

INTRODUCTION

1.1 GENERAL BACKGROUND

Worldwide plastic production has surged over the past 50 years. In 2016, it reached 335
million tonnes per annum, with Europe alone producing 60 million tonnes. Over the next 20
years, it is expected to double. Plastic packaging is the most important product (26% of the
total volume of all plastics used), although it has a short life compared to plastics used in, for
example, the construction and car industries. Plastic producers and transformers are keen to
highlight the benefits derived from plastic packaging; not only does it deliver direct economic
profits, but it also helps prevent food waste and contamination. Further, by lessening the
weight of packaging, it can reduce the fuel used in the transport of goods. This is certainly
important, but even if these plastics are re-used, they inevitably become waste at some point.
If we are to close the loop of the circular economy, this waste needs to be seen as a resource
to be plugged back into the life cycle of plastics (PlasticsEurope, 2018). Unfortunately, a very
large quantity of plastic waste leaks into the environment causing significant economic and
ecological damage. For example, some 5–13 million tonnes of plastic (1.5–4% of global
plastic production) end up in the ocean every year (Geyer et al., 2017). Educational
campaigns are now focusing on the idea of citizens understanding themselves as members of
a global community that can reduce the demand for plastic. However, according to all current
expert reports, if the advantages of plastics are to be enjoyed in full, we also need to promote
the most sustainable waste management alternatives, encourage recycling, use energy
recovery as a complementary option and restrict the dumping in landfills of all recoverable
plastic waste.

Economic growth and changing consumption and production patterns are resulting into rapid
increase in generation of waste plastics in the world. Due to the increase in generation, waste
plastics are becoming a major stream in solid waste. After food waste and paper waste,
plastic waste is the major constitute of municipal and industrial waste in cities. Even the cities
with low economic growth have started producing more plastic waste due to plastic
packaging, plastic shopping bags, Polyethylene bottles and other goods/appliances which
uses plastic as the major component. This increase has turned into a major challenge for local
authorities, responsible for solid waste management and sanitation. Due to lack of integrated

1
solid waste management, most of the plastic waste is neither collected properly nor disposed
of in appropriate manner to avoid its negative impacts on environment and public health and
waste plastics are causing littering and chocking of sewerage system.

1.2 PROBLEM STATEMENT

2 Plastics are man-made

organic materials that are
produced from oil and natural
gas as raw
3 materials. They are
relatively cheap, durable and
versatile material. Products
made from plastics
4 have brought benefits to
society in terms of economic
activity, jobs and quality of
life. Plastics

2
5 can even help reduce energy
consumption and greenhouse
gas emissions in many
circumstances,
6 even in some packaging
applications when compared
to the alternatives (European
commission
7 DG ENV, 2011). The
benefits driven from plastics
compel manufacturers to
increase production.
8 FOEN (2003) indicates that,
plastics form around 15% of
household refuse and
according to a
3
9 report published in
December 2010, the U.S.
Environmental Protection
Agency (USEPA)
10 determined that, the
United States alone generated
30 million tonnes of plastic
waste in 2009.
11 It is believed after their
entry into the environment,
plastics can persist up to 100
years without
12 being decomposed by
sunlight and/or
microorganisms (Stevens,
2001 and UNEP, 2005a).
4
13 The issue of plastic waste
management is therefore a
major global phenomenon
that has
14 crept up over the decades,
and really requires a global
and comprehensive solution
that includes
15 systemic rethinks about
usage, production and
recycle. It is a crucial
problem not only for
16 developing countries but
for the developed countries as
well.
17
1845
5
19 The message is made
in such a way and always
interesting attention. The
message is
20 formulated through
symbols which is easy to
understand or understand
communicant.
21 Campaign on plastic
problems has been launch
massively around the world,
but in fact the plastic
22 problem hasn’t get the
clear of point. The
campaign itself has been
supported by the
6
23 Government. In some
area in Indonesia, Regional
Regulations has been
applied to control the
24 plastic use. The Bali
Provincial Government
prohibits various components
and communities in
25 the area from using
disposable plastic, along with
the issuance of the Bali
Governor Regulation
26 Number 97 of 2018. In
the Bali’s Governor
Regulation Number 97 Year
2018 concerning the
7
27 Limitation of Disposable
Plastic Waste that has been
issued on December 21 ,
there are three
28 ingredients that are
made of or contain
prohibited plastic
ingredients, namely plastic
bags,
29 polystyrene, and plastic
straws.
30 There is a decisive
condition the success or
failure of a campaign,
according to Wilbur

8
31 Schramm is quoted in
Rosady Ruslan's book
Public Relations Research
Methods, the coalition
32 supporting the success or
failure of delivering messages
inside campaigning is as
follows:
3 3 Many
municipalities, cities and
towns the world over
continue to grapple with the
problem
34 because it imposes
negative environmental

9
 externalities. It is usually
non-biodegradable and
35 therefore can remain as
waste in the environment for
a very long time, it may pose
risks to human
36 health as well as the
environment; and it can be
difficult to reuse and/or
recycle in practice. The
37 campaign on plastic
shouldn’t only focusing to
“not to use” plastic, instead
build awareness on
38 the plastic waste
management, plastic used
10
 plastic through a recycle
process could be made into
39 higher-value products.
40 Plastics are man-made
organic materials that are
produced from oil and natural
gas as raw
41 materials. They are
relatively cheap, durable and
versatile material. Products
made from plastics
42 have brought benefits to
society in terms of economic
activity, jobs and quality of
life. Plastics

11
43 can even help reduce
energy consumption and
greenhouse gas emissions in
many circumstances,
44 even in some packaging
applications when compared
to the alternatives (European
commission
45 DG ENV, 2011). The
benefits driven from plastics
compel manufacturers to
increase production.
46 FOEN (2003) indicates
that, plastics form around
15% of household refuse
and according to a
12
47 report published in
December 2010, the U.S.
Environmental Protection
Agency (USEPA)
48 determined that, the
United States alone generated
30 million tonnes of plastic
waste in 2009.
49 It is believed after their
entry into the environment,
plastics can persist up to 100
years without
50 being decomposed by
sunlight and/or
microorganisms (Stevens,
2001 and UNEP, 2005a).
13
51 The issue of plastic waste
management is therefore a
major global phenomenon
that has
52 crept up over the decades,
and really requires a global
and comprehensive solution
that includes
53 systemic rethinks about
usage, production and
recycle. It is a crucial
problem not only for
54 developing countries but
for the developed countries as
well.
55
5645
14
57 The message is made
in such a way and always
interesting attention. The
message is
58 formulated through
symbols which is easy to
understand or understand
communicant.
59 Campaign on plastic
problems has been launch
massively around the world,
but in fact the plastic
60 problem hasn’t get the
clear of point. The
campaign itself has been
supported by the
15
61 Government. In some
area in Indonesia, Regional
Regulations has been
applied to control the
62 plastic use. The Bali
Provincial Government
prohibits various components
and communities in
63 the area from using
disposable plastic, along with
the issuance of the Bali
Governor Regulation
64 Number 97 of 2018. In
the Bali’s Governor
Regulation Number 97 Year
2018 concerning the
16
65 Limitation of Disposable
Plastic Waste that has been
issued on December 21 ,
there are three
66 ingredients that are
made of or contain
prohibited plastic
ingredients, namely plastic
bags,
67 polystyrene, and plastic
straws.
68 There is a decisive
condition the success or
failure of a campaign,
according to Wilbur

17
69 Schramm is quoted in
Rosady Ruslan's book
Public Relations Research
Methods, the coalition
70 supporting the success or
failure of delivering messages
inside campaigning is as
follows:
7 1 Many
municipalities, cities and
towns the world over
continue to grapple with the
problem
72 because it imposes
negative environmental

18
 externalities. It is usually
non-biodegradable and
73 therefore can remain as
waste in the environment for
a very long time, it may pose
risks to human
74 health as well as the
environment; and it can be
difficult to reuse and/or
recycle in practice. The
75 campaign on plastic
shouldn’t only focusing to
“not to use” plastic, instead
build awareness on
76 the plastic waste
management, plastic used
19
 plastic through a recycle
process could be made into
77 higher-value products
78 Plastics are man-made
organic materials that are
produced from oil and natural
gas as raw
79 materials. They are
relatively cheap, durable and
versatile material. Products
made from plastics
80 have brought benefits to
society in terms of economic
activity, jobs and quality of
life. Plastics

20
81 can even help reduce
energy consumption and
greenhouse gas emissions in
many circumstances,
82 even in some packaging
applications when compared
to the alternatives (European
commission
83 DG ENV, 2011). The
benefits driven from plastics
compel manufacturers to
increase production.
84 FOEN (2003) indicates
that, plastics form around
15% of household refuse
and according to a
21
85 report published in
December 2010, the U.S.
Environmental Protection
Agency (USEPA)
86 determined that, the
United States alone generated
30 million tonnes of plastic
waste in 2009.
87 It is believed after their
entry into the environment,
plastics can persist up to 100
years without
88 being decomposed by
sunlight and/or
microorganisms (Stevens,
2001 and UNEP, 2005a).
22
89 The issue of plastic waste
management is therefore a
major global phenomenon
that has
90 crept up over the decades,
and really requires a global
and comprehensive solution
that includes
91 systemic rethinks about
usage, production and
recycle. It is a crucial
problem not only for
92 developing countries but
for the developed countries as
well.
93
9445
23
95 The message is made
in such a way and always
interesting attention. The
message is
96 formulated through
symbols which is easy to
understand or understand
communicant.
97 Campaign on plastic
problems has been launch
massively around the world,
but in fact the plastic
98 problem hasn’t get the
clear of point. The
campaign itself has been
supported by the
24
99 Government. In some
area in Indonesia, Regional
Regulations has been
applied to control the
100 plastic use. The Bali
Provincial Government
prohibits various components
and communities in
101 the area from using
disposable plastic, along with
the issuance of the Bali
Governor Regulation
102 Number 97 of 2018. In
the Bali’s Governor
Regulation Number 97 Year
2018 concerning the
25
103 Limitation of Disposable
Plastic Waste that has been
issued on December 21 ,
there are three
104 ingredients that are
made of or contain
prohibited plastic
ingredients, namely plastic
bags,
105 polystyrene, and plastic
straws.
106 There is a decisive
condition the success or
failure of a campaign,
according to Wilbur

26
107 Schramm is quoted in
Rosady Ruslan's book
Public Relations Research
Methods, the coalition
108 supporting the success or
failure of delivering messages
inside campaigning is as
follows:
1 0 9 Man
y municipalities, cities and
towns the world over
continue to grapple with the
problem
110 because it imposes
negative environmental

27
 externalities. It is usually
non-biodegradable and
111 therefore can remain as
waste in the environment for
a very long time, it may pose
risks to human
112 health as well as the
environment; and it can be
difficult to reuse and/or
recycle in practice. The
113 campaign on plastic
shouldn’t only focusing to
“not to use” plastic, instead
build awareness on
114 the plastic waste
management, plastic used
28
 plastic through a recycle
process could be made into
115 higher-value products
116 Plastics are man-made
organic materials that are
produced from oil and natural
gas as raw
117 materials. They are
relatively cheap, durable and
versatile material. Products
made from plastics
118 have brought benefits to
society in terms of economic
activity, jobs and quality of
life. Plastics

29
119 can even help reduce
energy consumption and
greenhouse gas emissions in
many circumstances,
120 even in some packaging
applications when compared
to the alternatives (European
commission
121 DG ENV, 2011). The
benefits driven from plastics
compel manufacturers to
increase production.
122 FOEN (2003) indicates
that, plastics form around
15% of household refuse
and according to a
30
123 report published in
December 2010, the U.S.
Environmental Protection
Agency (USEPA)
124 determined that, the
United States alone generated
30 million tonnes of plastic
waste in 2009.
125 It is believed after their
entry into the environment,
plastics can persist up to 100
years without
126 being decomposed by
sunlight and/or
microorganisms (Stevens,
2001 and UNEP, 2005a).
31
127 The issue of plastic waste
management is therefore a
major global phenomenon
that has
128 crept up over the decades,
and really requires a global
and comprehensive solution
that includes
129 systemic rethinks about
usage, production and
recycle. It is a crucial
problem not only for
130 developing countries but
for the developed countries as
well.
131
132 45
32
133 The message is made
in such a way and always
interesting attention. The
message is
134 formulated through
symbols which is easy to
understand or understand
communicant.
135 Campaign on plastic
problems has been launch
massively around the world,
but in fact the plastic
136 problem hasn’t get the
clear of point. The
campaign itself has been
supported by the
33
137 Government. In some
area in Indonesia, Regional
Regulations has been
applied to control the
138 plastic use. The Bali
Provincial Government
prohibits various components
and communities in
139 the area from using
disposable plastic, along with
the issuance of the Bali
Governor Regulation
140 Number 97 of 2018. In
the Bali’s Governor
Regulation Number 97 Year
2018 concerning the
34
141 Limitation of Disposable
Plastic Waste that has been
issued on December 21 ,
there are three
142 ingredients that are
made of or contain
prohibited plastic
ingredients, namely plastic
bags,
143 polystyrene, and plastic
straws.
144 There is a decisive
condition the success or
failure of a campaign,
according to Wilbur

35
145 Schramm is quoted in
Rosady Ruslan's book
Public Relations Research
Methods, the coalition
146 supporting the success or
failure of delivering messages
inside campaigning is as
follows:
1 4 7 Man
y municipalities, cities and
towns the world over
continue to grapple with the
problem
148 because it imposes
negative environmental

36
 externalities. It is usually
non-biodegradable and
149 therefore can remain as
waste in the environment for
a very long time, it may pose
risks to human
150 health as well as the
environment; and it can be
difficult to reuse and/or
recycle in practice. The
151 campaign on plastic
shouldn’t only focusing to
“not to use” plastic, instead
build awareness on
152 the plastic waste
management, plastic used
37
 plastic through a recycle
process could be made into
153 higher-value products
Poor management of plastic and wood wastes - ranging from non-existing collection systems

to ineffective disposal - cause air pollution, water and soil contamination. Open and

unsanitary landfills contribute to contamination of drinking water and can cause infection and

transmit diseases. The dispersal of debris pollutes ecosystems and dangerous substances from

electronic waste or industrial garbage puts a strain on the health of urban dwellers and the

environment.

The harmful effect of conventional fuel such as crude oil to the environment; when fossil

fuels are burned, they release carbon dioxide and other greenhouse gases, which in turn trap

heat in our atmosphere, making them the primary contributors to global warming and climate

change.

Plastics are man-made organic

materials that are produced
from oil and natural gas as raw
materials. They are relatively
cheap, durable and versatile

38
material. Products made from
plastics
have brought benefits to
society in terms of economic
activity, jobs and quality of
life. Plastics
can even help reduce energy
consumption and greenhouse
gas emissions in many
circumstances,
even in some packaging
applications when compared to
the alternatives (European
commission
DG ENV, 2011). The benefits
driven from plastics compel
39
manufacturers to increase
production.
FOEN (2003) indicates that,
plastics form around 15% of
household refuse and
according to a
report published in
December 2010, the U.S.
Environmental Protection
Agency (USEPA)
determined that, the United
States alone generated 30
million tonnes of plastic waste
in 2009.
It is believed after their entry
into the environment, plastics
40
can persist up to 100 years
without
being decomposed by sunlight
and/or microorganisms
(Stevens, 2001 and UNEP,
2005a).
The issue of plastic waste
management is therefore a
major global phenomenon that
has
crept up over the decades, and
really requires a global and
comprehensive solution that
includes
systemic rethinks about
usage, production and
41
recycle. It is a crucial
problem not only for
developing countries but for
the developed countries as
well.
45
The message is made in
such a way and always
interesting attention. The
message is
formulated through symbols
which is easy to understand or
understand communicant.
Campaign on plastic problems
has been launch massively

42
around the world, but in fact
the plastic
problem hasn’t get the clear
of point. The campaign
itself has been supported by
the
Government. In some area in
Indonesia, Regional
Regulations has been applied
to control the
plastic use. The Bali Provincial
Government prohibits various
components and communities
in
the area from using disposable
plastic, along with the issuance
43
of the Bali Governor
Regulation
Number 97 of 2018. In the
Bali’s Governor Regulation
Number 97 Year 2018
concerning the
Limitation of Disposable
Plastic Waste that has been
issued on December 21 ,
there are three
ingredients that are made of
or contain prohibited plastic
ingredients, namely plastic
bags,
polystyrene, and plastic straws.

44
 There is a decisive
condition the success or
failure of a campaign,
according to Wilbur
Schramm is quoted in
Rosady Ruslan's book Public
Relations Research Methods,
the coalition
supporting the success or
failure of delivering messages
inside campaigning is as
follows:
Many municipalities,
cities and towns the world over
continue to grapple with the
problem
45
because it imposes negative
environmental externalities. It
is usually non-biodegradable
and
therefore can remain as waste
in the environment for a very
long time, it may pose risks to
human
health as well as the
environment; and it can be
difficult to reuse and/or
recycle in practice. The
campaign on plastic shouldn’t
only focusing to “not to use”
plastic, instead build
awareness on
46
the plastic waste management,
plastic used plastic through a
recycle process could be made
into
higher-value products.
1.3 AIM AND OBJECTIVES

The aim of this project is to study the photocatalytic conversion of plastic waste

(polyethylene) to Formic Acid which can serve as alternative source of energy for hydrogen

cell machines.

The overall objectives of the project include;

a) identify suitable plastic waste material(s) type that can decompose via photo-catalysis
to yield a solution that can be analysed for presence of formic acid,

b) design of a cylindrical steel vessel wherein birch wood (betula pubescens) can
undergo hydrothermal process, and,

c) create a carbon-neutral energy source that is; Formic acid, using the results obtained
from (a) and (b) respectively.

1.4 JUSTIFICATION OF STUDY

A critical review of the literature revealed that, during the last decade, but a fewer number of

studies on the management, use and misuse of plastic and wood waste, have been carried out

in South-west Nigeria. The little studies have revealed that the plastic and wood wastes can

47
 be converted into fuel or other materials which would be useful for the society using Acetic

or Formic Acids at certain conditions. The results obtained from this study indicates that

there is a need to encourage and also device means to focus on the management of waste in

our community and by so doing, providing an alternative or pocket friendly fuel production.

1.5 SCOPE OF WORK

The scope of this research work involved the following;

a) Waste management overview

b) Management of plastic waste

c) Recycling of plastic waste

d) Environmental pollution

e) Public awareness

CHAPTER TWO

LITERATURE REVIEW

2.1 GENERAL OVERVIEW

48
In modern life, plastics are ubiquitous. Its early usage dated back to 1600 B.C., at the time
when human hands shaped natural rubber and polymerized into different useful objects in
prehistoric Mesoamerica (Serrano et al., 2012). Diverse usage and manufacturing of plastics
and plastic products began in 1839 when polystyrene (PS) and vulcanized rubber were
discovered. Production of bakelite which is the first truly synthetic polymer was in 1907 in
Belgium (Alexandra, 2012), however, by 1930, bakelite was everywhere, especially in
fashion, communication and electrical and automotive industries (Rehan et al., 2017). It
took a decade after this for mass production of plastics to begin and it has constantly
expanded ever since.

As at 2008, the annual plastic production was estimated to be 245 million tons globally. At
present, single-use packaging is the largest sector, accounting for almost 40% of the overall
plastic usage in Europe (Jung et al., 2010), this is followed by consumer goods, materials
for construction, automotive, electrical and agriculture applications at 22%, 20%, 9%, 6%
and 3%, respectively (Nizami et al., 2016). It was estimated in 2015, that the highest rate of
production is in Asia (with 49% of total global output, with China as the largest world
producer (28%), followed by North America and Europe at 19% each. In terms of
production, the rest regions are of lesser importance although not necessarily in terms of
plastic consumption (Alexandra, 2012).

Globally, plastic production was estimated to be 380 million tonnes in 2018. Since 1950 to
2018, plastics of about 6.3 billion tonnes have been produced worldwide, 9% and 12% of
which have been recycled and incinerated, respectively. Plastics of about 5 million tonnes
are yearly consumed in UK alone, with only about one-quarter recycled, and the rest
landfilled. It has been suggested by researchers that by 2050, oceans might contain more
plastics than fish in terms of weight (Nizami et al., 2016). Yearly, approximately 500 billion
plastic bags are used out of which an estimated 13 million tonnes ends up in the ocean,
killing approximately 100,000 marine lives (Alexandra, 2012).

Plastic productions has increased in twenty-fold since 1964. Globally, approximately 311
million tonnes of plastics were produced in 2014, expected to double in about 20 year time
and possibly quadruple by 2050. International Energy Agency World Energy Outlook in
2015 estimated that, the largest application, plastic packaging (26% of the overall volume),
is envisaged to have continuous strong growth, which might double within 15 years, with a

49
 possibility of fourfold increase by 2050, to about 318 million tonnes yearly, which is higher
than the whole plastic industry today

There are different types of plastics based on their constituents and type of materials used
in their production. Table 1 shows the different types of plastics, their properties and
common uses.

Table 2.1: Types of plastics, their properties and common uses.

Symbols Types of Common uses Properties Recycled into
plastics
Polyethylene Soft drinks, water bottles, Clear, tough, solvent Pillow and
terephthalates containers, salad dressing, biscuit resistant, barrier to gas and sleeping bag
trays and salad domes. moisture, softens at 80 ℃. filling,
clothing, soft
drink bottles,
carpeting,
building
insulation
High density Shopping bags, freezer bags, Hard to semi-flexible, Recycling bins,
polyethylene buckets, shampoo, milk bottles, resistant to chemicals and compost bins,
(HDPE) ice cream containers, juice moisture, waxy surface,
bottles, chemical and detergent opaque, softens at 75 ℃,
bottles, rigid agricultural pipe, easily coloured, processed
crates. and formed
Polyvinyl Cosmetic container, plumbing Strong, tough, softens at Compost bin
Chloride (PVC) pipes and fittings, electrical 80 ℃, can be clear, can be
conduct, blister packs, wall solvent welded.
cladding, roof sheeting, bottles,
garden hose, Shoe soles, cable
sheathing, blood bags and tubing.
Plasticized Flexible, clear, elastic, can
Polyvinyl

50
 chloride PVC-P. be solvent welded.
Low density Refuse bags, Irrigation tubings, Soft flexible, waxy Bin liners,
polyethylene mulch film, cling wrap, garbage surface, translucent, pallet sheets
(LDPE) bags, squeeze bottles. softens at 70 ℃, scratches
easily.
Polypropylene Microwave dishes, lunch boxes, Hard and translucent, Pegs, bins,
(PP) packaging tape, garden furniture, soften at 140 ℃, pipes, pallet
kettles, bottles and ice cream translucent, withstands sheets.
tubs, potato chip bags, straws solvents, versatile.

Polystyrene CD cases, plastic cutlery, Clear, glassy rigid, opaque, Recycle bin
(PS) imitation glassware, low cost semi-tough, soften at 95
brittle toys, video cases/foamed ℃, Affected by fat, acids
polystyrene cups, protective and solvents, but resistant
packaging, building and food to alkalis, salt solutions,
insulation Low water absorption,
Expanded when not pigmented is
polystyrene (PS- clear, is odour and taste
E) free.

Special types of
Polystyrene (PS) are
available for special
applications.
Other Automotive and appliance Includes all resins and Recycle bins
components, computers, multi-materials (e.g.
electronics, cooler bottles, laminates) properties
packaging dependent on plastic or
combination of plastics
Source: 99precycling

51
2.2 MANAGEMENT OF PLASTIC WASTE

2.2.1 LANDFILLING

Approximately 10% of household waste is plastics and mostly end up on the landfill
(Dimitrov et al., 2013). Even though landfilling is the commonest waste management
conventional approach in many countries, however, scarcity of space for landfills is
becoming a major problem. For example, historically, landfilling was attractive in the UK
because it is relatively cheap and simple without necessarily requiring treatment, cleaning
or separation. In 1999, 65% (8.4 million tonnes per annum) of the overall household waste
recoverable plastics were sent to landfill in Western Europe (Lopez et al., 2009),but at
present in the UK, plastic waste landfilling is the least favored waste management option.
There is a growing environmental and public health concern about the potential effects of
landfills because of the types and quantities of toxic chemicals and their potential for
leaching at landfill sites. It is now a government policy in the UK to reduce the amount of
wastes landfilled (e.g. Landfill Directive European Commission 1999/31/EC) which has
been difficult to materialize as an estimated 60% of England's municipal wastes is still sent
to the landfills compared to an estimated of 20% and 37% in Germany and France,
respectively (Inman, 2012).

Environmental pollution and risks to public health can be reduced if the landfills are well-
managed, although there are possibilities of soil and groundwater contamination by
disintegrated plastic byproducts and additives that can persist in the environment on long-
term basis (Dimitrov et al., 2013).

2.2.2 PLASTIC INCINERATION

An alternative to landfilling of plastic waste is incineration, but growing concerns exist

about the potential atmospheric release of hazardous chemicals during the process. For
instance, plastic waste fumes release halogenated additives and polyvinyl chloride, while
furans, dioxins, and polychlorinated biphenyls (PCBs) are released from incineration of
plastics into the environment. The disadvantage of combustion of plastics is the air
pollution caused by the noxious fumes released into the atmospheres. The combustion
heater of the flue systems is permanently damaged by plastics during plastic incineration
and the products of this plastic combustion are detrimental to both humans and the

52
environment. Compounds of low molecular weight can vaporize directly into the air
thereby polluting the air and based on their varieties, some may form a combustible
mixture, while others may oxidize in solid form.

Incineration of plastics is usually accompanied with the formation of chark, and the coking
extent is dependent on the conditions of incineration (Marcilla et al., 2004). Gaseous release
in the process of plastic and plastic composite products incineration are very dangerous. For
example, Table 2 shows the compounds release during the incineration of PVC and the
health effects of these compounds. In the process of incineration of plastics, soot, ashes and
different powders are produced, which eventually settles on plants and soil, with the
potential to migrate to the aquatic environment. Rainfall can make some of these toxic
compounds to sink into the soil, contaminate the ground water or absorbed by plants
growing on this soil, thus, becoming incorporated into the food chain. Some of these plastic
incineration products can chemically react with water and the resulting compounds can
alter the pH thereby change the functioning of aquatic ecosystems.

Due to the potential pollution impact on the environment, plastic incineration is less
employed for waste management in comparison to recycling and landfilling. Notable
exceptions to this are European countries like Sweden and Denmark, as well as Japan, with
massive incinerator facilities for managing municipal solid waste including plastics.
However, countries like Hungary has enacted regulations, 29/2014. (XI. 28.) Regulation of
the Ministry of Agriculture on waste incineration, which allow for only licensed plastic
waste incineration plants to incinerate plastics, while all other forms of burning plastic
waste are banned. An advantage of plastic incineration is the recovery of energy from the
plastic wastes (Lopez et al., 2009).

2.2.3 RECYCLING OF PLASTICS

Reprocessing of recovered plastic scraps or wastes into usable products is called plastic
recycling. Most plastics are non-biodegradable in nature, hence, the fundamental work is
reduction of waste emissions, effective management and recycling of resulting wastes
(Frigo et al., 2014; Mukherjee and Thamotharan, 2014). Recycling of plastics is a major
aspect of the worldwide efforts in minimizing the yearly 8 million tonnes of plastics in the
waste stream entering the Earth's ocean (Lopez et al., 2009; Heras et al., 2014). According
to Hopewell, et al. (2014), plastic recycling terminology is complex due to varieties of

53
recovery activities and recycling. There are four main categories of recycling which are:
primary (which involves the mechanical reprocessing of plastics into a new product with
equivalent properties), secondary (which involves the mechanical reprocessing of plastics
into a product with lower properties), tertiary (which involves the recovery of the chemical
constituents of the plastics) and quaternary (which involves energy recovery from the
plastics).

In comparison to the lucrative metal recycling but similar to the low value of glass
recycling, recycling of plastics is often more challenging because of low density and low
value. Also, there are several technical issues to deal with when recycling plastic. Melting
together of different plastic types often cause phase-separation similar to oil and water, and
they set in these layers. The resulting phase boundaries is responsible for structural
weakness in the final product(s), which has limited the application of this polymer blends.
This is the case with polyethylene and polypropylene, which are the two plastics commonly
manufactured, and therefore has limited their use for recycling. Of recent, block
copolymers has been proposed as a form of macromolecular welding flux or molecular
stitches in other to overcome this challenge of phase-separation during plastic recycling.

There can be increase in the percentage of plastics with the possibility of full recycling
instead of the large quantity generated as wastes if package good manufacturers reduce
their mixing of packaging materials and eliminate contaminants. In view of this, a design
guide has been issued by the Association of Plastics Recyclers for recyclability of plastics
(Inman, 2012).There has been an increase in the volume of post-consumer plastics recycled
since 1990, although it is still incomparable to other items like corrugated fiberboard
(approximately 70%) and newspaper (approximately 80%). For example, in US, the post-
consumer plastic wastes generated in 2008 was approximately 33.6 million tons, out of
which 6.5% (2.2 million tons) were recycled, while 8% (2.6 million tons) and 86% (28.9
million tons) were burned and landfilled, respectively (Lopez et al., 2009).

Some governments use policy to encourage postconsumer recycling, such as the EU

Directive on packaging and packaging waste (94/62/EC). This subsequently led Germany to
set-up legislation for extended producer responsibility that resulted in the die Gru¨nePunkt
(Green Dot) scheme to implement recovery and recycling of packaging. In the UK,
producer responsibility was enacted through a scheme for generating and trading packaging
recovery notes, plus more recently a landfill levy to fund a range of waste reduction

54
activities. As a consequence of all the above trends, the market value of recycled polymer
and hence the viability of recycling have increased markedly over the last few years,
Globally in 2015, about 9% of the 6.3 billion tons plastic wastes generated had been
recycled, while 12% and 79% were incinerated and landfilled, respectively (Marcilla et al.,
2004). However, in 2016, the global rate of recycling grew to about 14% of the total
generated plastic waste. Major contributors to this increment include countries like Japan,
where plastic waste recycling rose from 39% (1996) to 83% (2014) according to their
Plastic Waste Management Institute.

2.3 ENVIRONMENTAL POLLUTION BY PLASTIC WASTES

Distribution of plastic waste is associated with human populations. Increase in human

population has led to increase demands for plastics and plastic products. Indiscriminate
disposal of wastes from plastics and plastic products can lead to environmental pollution
which is evident in several ways including environmental natural beauty deterioration,
entanglement and death of aquatic organisms (Inman, 2012), sewage system blockage in
towns and cities especially in developing countries, resulting in creating conducive
environment for breeding mosquitoes and other disease causing vectors and production of
foul smells, reduction in water percolation and normal agricultural soils aeration thus
causing reduced productivity in such lands.

In human occupational and residential environment, plastic products are present in large
volume. Pollution by plastics and plastic products can damage and contaminate the
terrestrial environment and can be subsequently transferred to the aquatic environment.
There is a shortage of data on the volume of plastic wastes on land in comparison to the
voluminous data which exist on plastic debris in marine habitat, despite the fact that about
80% of plastic waste present at sea originates from land-related sources (Rehan et al.,
2017). Dumping of plastics on land or landfilling plastics leads to abiotic and biotic
degradation of the plastics, where plastic additives (e.g. stabilizers, harmful colorant
moieties, plasticizers and heavy metals) can leach and eventually percolate into various
aspects of the environment, thereby causing soil and water contamination. Reports have
shown that microplastics as well as synthetic polymer fibres are still detectable five years
after they have been applied to sewage sludge and soils (Inman, 2012). Chlorinated plastics
are capable of leaching out toxic chemicals into the soil and subsequently seep into the

55
underground water or surrounding aquatic system thereby polluting the ecosystem.
Methane, a dangerous greenhouse gas, which significantly contributes to global warming is
released during microbial biodegradation of plastics.

Plate. 2.3: Picture showing the plastic waste in the ocean Source: Thenewyorker

Approximately 165 million tonnes of plastic wastes were estimated to be present in the
oceans of the world in 2012, while an average of 8 million tonnes of plastics are annually
released into the ocean, with about 5 trillion plastic pieces floating on the ocean (Jung et al.,
2010). Typically, plastics in the oceans can degrade within a year but not completely.
During this plastic degradation process, toxic chemicals like polystyrene and BPA can be
released into the water causing water pollution. Wastes found in the oceans are made up of
approximately 80% plastics. Plastic debris which are floating on the ocean can be rapidly
colonized by sea organisms and due to persistence on the ocean surface for a long period of
time, this mayaid the movement of 'alien' or non-native species. Contaminants from
microplastics are bioavailable for many marine lives because of their presence in benthic
and pelagic ecosystems and their small sizes (Rehan et al., 2017). Within the marine
ecosystem, plastics have been reported to concentrate and sorb contaminants present in the

56
seawater from different other sources. Examples of such contaminants are persistent
organic pollutants like nonylphenol, PCBs, dichlorodiphenyldichloroethylene (DDE) and
phenanthrene, with potential to accumulate in several fold on the plastic debris compared to
the surrounding seawater. More than 260 species of marine organisms such as turtles,
invertebrates, seabirds, fish and mammals ingested or are entangled in or with plastic
debris, leading to reduced movement, feeding, reproductive output, ulcers, lacerations and
eventual death.

Plate. 2.4: Remains of whale washed out of sea due to plastic waste Source:
Ecowatch

Carbon dioxide and methane are released into the air when plastic wastes which were
landfilled finally decompose. During the decomposition of solid waste in landfills in 2008,
an estimated CO2 equivalent (eqCO2) volume released into the atmosphere was 20 million
tonnes. CO2 is also released into the atmosphere during the burning of plastics and plastic
products, and this CO 2 is capable of trapping radiant heat and hinder it from escaping from
the earth causing global warming [(Gandidi et al., 2018). Air pollution is one of the major
environmental threats to public health, and it is responsible for more than 6 million deaths
57
associated with environmental pollution. Open burning of plastics and plastic products
releases pollutants such as heavy metals, dioxins, PCBs and furans which when inhaled can
cause health risks especially respiratory disorders. The role of plastics in air pollution in the
developing and poor countries of the world cannot be overemphasized, and the impact on
the future generations may be massive.

Food supplies for human consumption can be adversely affected if animals are poisoned by
toxic constituents from wastes of plastics and plastic products (Jung et al., 2010). Indeed,
report of threat to survival of large marine mammals have been documented due to large
amount of plastic wastes entering the world oceans.

Animals are exposed to plastic wastes majorly through ingestion and entanglement,
however, ingestion is more frequent than entanglement. Most animals in the oceans
mistaking plastic wastes dumped in the ocean for food, thereby ingesting them.
Furthermore, entanglement in plastic products like nets can cause harm, damage and even
death in marine animals. Reports have shown that more than 260 different species of
vertebrate and invertebrate animals ingest plastics or are entangled by plastic or plastic
products, with more than 400,000 deaths of marine mammals. Marine pollution by plastic
wastes majorly affects sea turtles and other species whose main food are jelly fishes
because they often confuse discarded plastic bags for jelly fish. A similar situation is
common in sea birds which can confuse microplastics for cuttlefish or with fishes, which
can mistake plastic wastes for their natural prey (Gandidi et al., 2018). Ingestion of plastic
wastes is capable of causing obstruction and physical damage to bird's digestive system,
reduce the digestive ability of the system leading to starvation, malnutrition and eventually,
death.

58
Plate 2.5: Plastic waste found in the guts of a dead duck Source: Plasticwastes

Many birds, turtles, fishes, seals and other marine animals have died by drowning or
suffocation as a result of entanglement in plastic debris. Entanglement has been observed to
cause health risks in estimated 243 species of marine lives, often ending in fatalities.
Animal entanglement by plastic debris also contributes to death from predators, as the
animals are unable to untangle themselves and escape. Coral reefs have been damaged by
dragging nets and other plastic products along sea beds (Lee, 2012). Often times, discarded
fishing nets also called "ghost nets" trap marine animals, leading to starvation and death.
Table 3 shows the effects of different types of plastics on animals and the mechanism(s) of
action.

59
2.4 PUBLIC HEALTH EFFECTS OF PLASTIC WASTES

It is generally believed that plastic polymers are lethargic and of little concern to public
health, however, different types of additives and the residual monomers possibly retained
from these polymers are responsible for the suspected health risks. Most of the additives
present in plastics are potential carcinogens and endocrine disruptors (Xue et al., 2017).
Ingestion, skin contact and inhalation are the main routes of exposure of humans to these
additives. Dermatitis have been reported from skin contact with some of the additives
present in plastics. Microplastics are major contaminants that can bioaccumulate in the food
chain after ingestion by a wide range of freshwater and marine lives leading to a public
health risk (Rehan et al., 2017). Human consumption of animals exposed to microplastics
and plastic additives can be detrimental. Biomonitoring studies on human tissues have
shown that plastic constituents persist in human population through the measurement of
environmental contaminants (Rizzarelli et al., 2016).

2.5 PLASTIC WASTE MANAGEMENT AND RECYCLING

In reducing toxic effects of plastic wastes on the environment and public health, waste
management plays a major role. For global reduction of plastic litters and ocean pollution,
there is need for improvement in proper plastic waste collection, treatment and disposal
(Gaca et al,. 2008). Inadequate management of landfills will make way for harmful
chemicals in plastic wastes to leach into the environment, polluting the soil, air and
underground water.

Proper wastewater management will prevent microplastics from entering the environment
from the landfills. Most treated wastewaters are discharged into rivers or oceans, therefore,
there is need for a ban such as Annex V to the International Convention for Prevention of
Pollution from Ship (MARPOL) agreement, which will prevent plastic waste disposal into
the sea (Gandidi et al,. 2018).

2.6 EDUCATION AND PUBLIC AWARENESS

Efforts must be made to educate the general populace on the potential environmental and
public health effect of pollution by plastic wastes. This will go a long way to reduce the

60
pollution rate and preserve the quality of the environment. There is need for people to be
aware of the chemical constituents of plastic products and their health effects. Educational
curriculums at different levels must include ways of plastic pollution reduction and waste
management systems as information resources.

2.7 BIOPLASTICS AS ALTERNATIVE

Bioplastics is a plastic produced from cellulose that is made of wood pulp by a British
chemist in the 1850s. Now, bioplastics can be produced from different biodegradable and
non-biodegradable materials including weeds, hemp, plant oil, potato starch, cellulose, corn
starch, etc. (Serrano et al., 2012; Ratnasari et al., 2017). Sugar-based bioplastics can
biodegrade under normal conditions for composting (Ma et al., 2017). Bioplastics are
environmentally friendly since they require less fossil fuels during production in
comparison to other types of plastic (Serrano et al., 2012; Ratnasari et al., 2017).

Although bioplastics have been used commercially in just few applications, they are widely
used in consumer goods for items that are disposable like cutlery, bowls, pots, crockery,
straws and packaging (Rehan et al., 2017). In principle, bioplastics can replace petroleum-
derived plastics in many applications, however, the problem lies with the cost and
performance of bioplastics. If there are no specific regulations globally to limit the use of
conventional plastics, there may be no favorable usage of bioplastics. For example, Italy
has since 2011 enacted law that made it compulsory for biodegradable plastic bags to be
used for shopping (Gandidi et al., 2018).In the production of bioplastics, substitute for
fossil fuel resources like wood, cellulose, sugar and starch are used. This has made
bioplastic production more sustainable and environmentally friendly in comparison to
conventional plastic production (Rehan et al., 2017). The production of bioplastics
decreases consumption of non-renewable energy and reduces the emission of greenhouse
gases (Serrano et al., 2012; Ratnasari et al., 2017).

We believed that the problem of plastic waste generation and the accompanied
environmental and public health effects can be handled if globally, manufacturers can
embrace the use of bioplastics. The biodegradability with little or no toxic products left
behind will go a long way to protect our natural environment from the menace of
conventional plastic wastes, protect our world's organisms and make the world safer for
humans.

61
2.8 HYDROTHERMAL CONVERSION OF WOOD WASTE (BIRCH WOOD) TO

FORMIC ACID

Thermally treated wood has been investigated since the middle of the last century and is

nowadays produced industrially in many European countries. This has been reviewed in a

number of papers (Millitz and Tjeerdsma 2000; Syrja’nen et al. 2000; Vernois 2000; Rapp

and Sailer 2001; Sundqvist 2003). Various types of treatments have been tested and generally

performed in an oxygen-free environment and at temperatures between 150 and 250 oC. Heat

treatment of wood causes a reduction of hygroscopicity, which gives less swelling, shrinkage

and enhanced fungal resistance compared with untreated wood, thus making it a more durable

material and an alternative for wood with added preservatives in exterior applications

(Tjeerdsma et al. 1998a; Kamden et al. 1999).

2.8 FORMIC ACID

Formic acid (HCO2H), also called methanoic acid, the simplest of the carboxylic acids, used
in processing textiles and leather. Formic acid was first isolated from certain ants and was
named after the Latin formica, meaning “ant.” It is made by the action of sulfuric acid upon
sodium formate, which is produced from carbon monoxide and sodium hydroxide.
Formic acid is also prepared in the form of its esters by treatment of carbon monoxide with
an alcohol such as methanol (methyl alcohol) in the presence of a catalyst.

Formic acid is not a typical carboxylic acid; it is distinguished by its acid strength, its failure
to form an anhydride, and its reactivity as a reducing agent—a property due to the ―CHO

62
group, which imparts some of the character of an aldehyde. The methyl and ethyl esters of
formic acid are commercially produced. Concentrated sulfuric acid dehydrates formic acid to
carbon monoxide.

Pure formic acid is a colorless, fuming liquid with a pungent odor; it irritates the mucous
membranes and blisters the skin. It freezes at 8.4 °C (47.1 °F) and boils at 100.7 °C (213.3
°F).

Fig 2.6: Structure and properties of formic acid Source: Chemistrypage

2.8.1 USES OF FORMIC ACID

1) When mixed with lead(Pd) and heated, emits hydrogen gas, this hydrogen gas is used to
power hydrogen fuel cell batteries
2) Used as a mixture with citric acid or HCl because alone it is unable to remove iron
oxide deposits.
3) Used in major industrial chemicals in the group of saturated monocarboxylic acids.
4) Used as a reducing agent to reduce sodium and potassium dichromate.

63
5) Useful material in the dyeing and tanning industries, but other competing acids have, as a
rule, been cheaper and the use of formic acid has therefore been restricted to a few cases
for which it has peculiar advantages

2.8.2 Formic Acid (Safety)

The principal danger from formic acid is from skin or eye contact with liquid formic acid or
with the concentrated vapours. Any of these exposure routes can cause severe chemical
burns, and eye exposure can result in permanent eye damage. Inhaled vapours may similarly
cause irritation or burns in the respiratory tract. Since carbon-monoxide may also be present
in formic acid vapours, care should be taken wherever large quantities of formic acid fumes
are present. The US OSHA Permissible Exposure Level (PEL) of formic acid vapour in the
work environment is 5 parts per million parts of air (ppm).

Formic acid is readily metabolized and eliminated by the body. Nonetheless, some chronic
effects have been documented. Some animal experiments have demonstrated it to be
a mutagen, and chronic exposure may cause liver or kidney damage. Another possibility with
chronic exposure is development of a skin allergy that manifests upon re-exposure to the
chemical.

The hazards of solutions of formic acid depend on the concentration. The following Table 2.2
lists the EU classification of formic acid solutions:

Table 2.2: EU classification of formic acid solutions

Concentration Classification R-Phrases

by weight

2%–10% Irritant (Xi) R36/38

10%–90% Corrosive (C) R34

>90% Corrosive (C) R35

SOURCE: Wikipedia

64
 CHAPTER THREE

MATERIALS AND METHODOLOGY

3.1 POLYCATALYTIC CONVERSION OF LOW DENSITY POLYETHYLENE

Materials include; LDPE (pure water sachet), vanadium based catalyst, benzene used as
solvent, and UV light (sunshine).

Photo-catalysis is a type of catalysis that results in the modification of the rate of a

photoreaction (a chemical reaction that involves the absorption of light by one or more
reacting species) by adding substances (catalysts) that participate in the chemical reaction

without being consumed. It typically involves three distinct steps;

i. light absorption of photocatalysts to excite charge carriers,

ii. separation and transportation of the photogenerated charge carriers, and

iii. redox reaction on the surface of the catalyst.

3.1.1 PROCESS ENGAGED IN THE PHOTOCATALYTIC VALORIZATION OF

PLASTIC WASTE

1) 2.5grams of pure-water sachet is cut and shredded into bits

2) 100ml of Benzene is used as solvent and heated to a temperature of 80 degrees Celsius.

Almost hitting boiling point

65
3) The shredded pure water sachet is poured into the boiling benzene and allowed to

completely dissolve

4) After dissolving and whilst still hot the solution is filtered to separate the blue colour

pigments from it and allowed to cool

Plate 3.1:Shredding of Low Density Polyethylene

5) 1g of Vanadium Oxide catalyst is then added to the solution and mixed

6) The solution is incubated for 14days in the presence of sunlight.

7) After 14 days, the solution is then taken to the laboratory to be analyzed for presence of

Formic Acid.

3.2 HYDROTHERMAL TREATMENT OF BIOMASS

66
Hydrothermal treatment refers to a thermochemical process for decomposing carbonaceous

materials such as coal and biomass with water in a high temperature and high pressure

condition. The use of such method for processing biomass was firstly developed by Bobleter

and his co-workers in 1976 and had attracted much attention for hydrolysis of lignocellulosic

materials since then

Betula Pubescens Wood, locally known as Meligner is used as sample. Birch (Betula

pubescens) in Nigeria, which had never been dried, was cut into specimens of nine (9)

different sizes, 11 - 31·4 mm3 and stored in a freezer.

3.2.1 WOOD SAMPLES

Birch Wood (Betula Pubescens), locally known as Meligner is used as sample. Birch (Betula
pubescens) in Nigeria, which had never been dried, was cut into specimens of nine (9)
different sizes.

3.2.2 DESIGN AND FABRICATION

Fabrication of metal refers to the building of metal structures. This is done via a variety of
processes such as cutting, bending, profiling, welding and assembling. Metals such as steel,
aluminum and other ferrous and non-ferrous metals are used in the fabrication process. A No
flange metal cylinders.

Fig. 3.2: Steel Cylinder with lid

67
Cylinder Configurator design, a cylinder with stock tooling. Standard engineering “rules of
thumb” are used in computations. Calculations are based on the information provided below
in table 3.2 to ensure the most practical solution for the cylinder needs.

Table 3.3: Cylinder Fabrication Configuration

Custom Industrial Cylinder Metric Units

Cylinder Diameter 100 mm
Length 500 mm
Lid Diameter 101mm

3.2.3 Processes engaged in the Hydro-thermal treatment of Wood

a) Nine (9) pieces of Birch Wood with average mass of 350g is carefully arranged in

the Steel Cylindrical Vessel

68
Plate 3.2: The Birch Wood to be Used for the Experiment (9 pieces)

b) 600ml of Distilled water is carefully poured into the vessel as well and filled up to

the brim with the birch wood inside to reduce the amount of H 2 (hydrogen gas) in the

vessel

Plate 3.3: Addition of Distilled Water to the Birch Wood in the Steel Vessel

c) The electric oven is put on and set to a temperature of 180degree Celsius before

putting the vessel in it

d) The vessel is heated in the electric oven at a constant temperature of 180 degrees

Celsius for a period of 2.5hrs

e) After the time is completed, The vessel is brought out and allowed to cool to room

temperature

69
Plate 3.4: Removal of Birch Wood From the Oven After Heating

f) The solution in the vessel is then poured out into a container and taken to the lab to

be analyzed for the presence of Formic Acid

Plate 3.5: Removal of the Liquid Extracts After Experiment

70
3.3 ANALYSIS OF FORMIC ACID IN AQUEOUS SOLUTION (LABORATORY

ANALYSIS)

Based on the method described earlier (Bethge and Lindstro¨m 1974), the following
procedure was performed. A sample from the aqueous solution (5.00 ml) was titrated with
0.185 M quaternary-ammonium salt solution, n-tetra butyl ammonium hydroxide (Q-salt) to
reach neutral pH (7.00). For samples with low acid contents, a 0.046-M Q-salt solution was
used instead.

The amount of Q-salt in mole needed to neutralise the solution (pH=7.0) was recorded, which
by equivalency gives the total amount of organic acids in the sample. To further stabilise the
Q-salt/acid complex, the titration proceeded to approximately pH 8. Hexanoic acid (0.108 M,
pH 8 with Q-salt) was used as internal standard. A small amount (mole) of internal standard
equivalent to the acid was added to the titrated sample.

Water and some solvents from the hydrothermal treatment of birch were evaporated in a
rotary evaporator, and dry acetone (5 ml), dried with molecular sieves, was added as a
solvent. Finally, benzyl bromide (98%) was added to the sample. The amount of benzyl
bromide was calculated from the total amount of acids in the sample to give an excess
amount of 30 equimolar percentage. The sample was then kept in a closed vessel at 40 degree
centigrade for 1 h

71
 CHAPTER FOUR

RESULTS AND DISCUSSION

4.1 PHOTOCATALYTIC CONVERSATION OF PLASTIC WASTE

(POLYETHYLENE)

The graph below shows the chromatography result for photocatalytic treatment of LDPE in
relation to the table below as well, showing presence of different acids formed at different
retention time.

Fig 4.1: Result for Photo-catalysis of LDPE showing different acid formation at different
time

72
Laboratory result of photocatalytic treatment of LDPE (sachet water) showing presence of
different types of acids present in the sample.

Pk# RT Area% Library/ID Ref# CAS# Qual

___________________________________________________________________________
__
1 4.871 12.06 C:\EnvDemo\NIST11.L
4-Chlorobuten-3-yne 1640 040589-38-6 72
1-Buten-3-yne, 2-chloro- 1641 017712-36-6 64
1-Buten-3-yne, 1-chloro-, (Z)- 1645 020374-90-7 64

2 6.729 0.16 C:\EnvDemo\NIST11.L

4-Heptafluorobutyryloxyhexadecane 224101 1000282-97-2 64
E-15-Heptadecenal 104157 1000130-97-9 59
1-Octadecene 104184 000112-88-9 59

3 7.029 24.00 C:\EnvDemo\NIST11.L

Toluene 2449 000108-88-3 60
1,5-Hexadien-3-yne, 2-methyl- 2476 000820-54-2 53
1-Cyclohexene, 1-ethynyl- 5105 1000327-56-5 47

4 7.048 7.42 C:\EnvDemo\NIST11.L

Hydrazinecarbothioamide 2391 000079-19-6 3
2,5-Dibenzyloxynitrobenzene 173308 051792-85-9 2
6-Difluoromethyl-5-phenylmethanesu 157526 1000317-93-5 1
lfonyl-1H-pyrimidine-2,4-dione

5 7.092 35.65 C:\EnvDemo\NIST11.L

Thiourea 972 000062-56-6 7
Ethene, 1,1-difluoro- 350 000075-38-7 5
Aminomethanesulfonic acid 6178 013881-91-9 5

6 7.330 15.12 C:\EnvDemo\NIST11.L

1,3-Butadiyne 117 000460-12-8 4
Chloromethane 118 000074-87-3 4
Acetaldehyde, chloro- 992 000107-20-0 1

7 7.724 0.92 C:\EnvDemo\NIST11.L

Benzene, propyl- 9407 000103-65-1 80
N-Benzyl-2-phenethylamine 70358 003647-71-0 64
Ethanol, 2-[(phenylmethyl)amino]- 24997 000104-63-2 64

8 8.687 3.89 C:\EnvDemo\NIST11.L

Acetophenone 9364 000098-86-2 87
6-Benzoylhexanoic acid 77184 007472-43-7 72
7-Benzoylheptanoic acid 88981 066147-75-9 59

9 9.069 0.09 C:\EnvDemo\NIST11.L

.beta.-Citronellol, heptafluorobut 184831 1000352-29-5 64
yrate
1,5-Heptadiene, 3,3,5-trimethyl- 16933 074630-29-8 59
2,6-Dimethyl-2-trans-6-octadiene 16932 002609-23-6 59

10 9.287 0.38 C:\EnvDemo\NIST11.L

Benzenemethanol, 4-methyl- 9962 000589-18-4 70
Phenol, 3,5-dimethyl- 9928 000108-68-9 55
Hydrazine, (3-methylphenyl)- 9837 000536-89-0 55

73
 11 9.356 0.05 C:\EnvDemo\NIST11.L
3,Trans-(1,1-dimethylethyl)-4,cis- 50177 1000215-62-4 42
methoxycyclohexan-1-ol
Pyrrolo[3,4-c]pyridine-1,3-dione, 95540 1000310-60-5 37
2-(4-fluorophenyl)-
Noruron 79108 018530-56-8 36

12 9.388 0.02 C:\EnvDemo\NIST11.L

2,4-Dichlorobenzaldehyde 1-methyl- 216769 1000222-66-7 38
1-(2,4,6-trinitrophenyl)hydrazone
3,Trans-(1,1-dimethylethyl)-4,cis- 50177 1000215-62-4 25
methoxycyclohexan-1-ol
Propiomazine 176766 000362-29-8 10

13 9.575 0.16 C:\EnvDemo\NIST11.L

Cyclopentane, 2-(1-hydroxy-2-propy 28366 1000155-43-4 47
l)-1,3-dimethyl-
Cycloheptanol, pentafluoropropiona 110174 1000376-25-7 43
te
Cycloheptene 2839 000628-92-2 43

14 9.744 0.06 C:\EnvDemo\NIST11.L

16,28-Secosolanidane-3,16-diol, (3 218275 055902-91-5 47
.beta.,5.alpha.,16.beta.,22.xi.,25
.xi.)-
2-Butenal, 2-ethenyl- 2807 020521-42-0 25
D-Fenchone 25071 004695-62-9 25

15 9.944 0.03 C:\EnvDemo\NIST11.L

Cyclohexanecarboxamide, N-furfuryl 66823 006341-32-8 50
2H-Pyran-4-ethanamine, 2-ethyl-N-( 166882 1000362-25-2 43
2-furanylmethyl)tetrahydro-2-methy
l-4-phenyl-
(3-Chloro-phenyl)(furan-2-ylmethyl 66668 1000303-12-5 40
)amine

Formic acid was not discovered in the photocatalytic sample solution. However, other acids
were discovered in the samples with almost same uses as formic acid. The acids includes;

1) Thiourea
2) Chloromethane
3) Acetaldehyde
4) Hydrazinecarbothioamide
5) Aminomethanesulfonic acid e.t.c

74
4.2 HYDROTHERMAL TREATMENT OF BIOMASS REPORT

The graph below shows the chromatography result for hydrothermal process of birch wood
(betula pubescens) solution in relation to the table below as well, showing presence of
different acids formed at different affluence time.

Fig 4.2: Hydrothermal treatment showing different acid formation at different time

75
 Laboratory result of hydrothermal treatment of birch wood (betula pubescens) showing
presence of different acid formation at different retention time

Pk# RT Area% Library/ID Ref# CAS# Qual

_____________________________________________________________________________
1 3.921 12.21 C:\EnvDemo\NIST11.L
4-Chlorobuten-3-yne 1640 040589-38-6 64
1-Buten-3-yne, 2-chloro- 1641 017712-36-6 59
1,2,3-Butatriene, 1-chloro- 1642 020658-21-3 56

2 3.952 8.33 C:\EnvDemo\NIST11.L

3-Amino-s-triazole 1323 000061-82-5 2
2,3,4,5-Tetrahydropyridazine 1355 000694-06-4 2
Formamide, N-(cyanomethyl)- 1339 005018-27-9 2

3 3.983 7.23 C:\EnvDemo\NIST11.L

3-Amino-s-triazole 1323 000061-82-5 2
Thiophene 1350 000110-02-1 2
Benzene-D6 1448 001076-43-3 2

4 4.021 12.54 C:\EnvDemo\NIST11.L

Methylene chloride 1525 000075-09-2 4
Pyridine-D5- 1373 007291-22-7 2
Thiophene 1353 000110-02-1 2

5 4.077 9.67 C:\EnvDemo\NIST11.L

Chloromethane 119 000074-87-3 3
1,3-Butadiyne 116 000460-12-8 3
Acetaldehyde, chloro- 993 000107-20-0 1

6 4.102 38.44 C:\EnvDemo\NIST11.L

Ethanol, 2,2'-[1,2-ethanediylbis(o 88552 000111-21-7 3
xy)]bis-, diacetate
Cyclohexene, 3R-acetamido-4cis,6ci 142409 1000153-71-4 3
s-bis(acetoxy)-5trans-dimethylamin
o-
1,3-Dioxolane, 4-methyl-2-pentadec 143174 054950-56-0 3
yl-

7 6.323 1.42 C:\EnvDemo\NIST11.L

Benzo[b]naphtho[1,2-e][1,4]dioxin- 105625 055320-08-6 91
6a(6H)-ol, 5,12a-dihydro-
Ethylbenzene 5088 000100-41-4 87
o-Xylene 5083 000095-47-6 76

8 6.592 0.09 C:\EnvDemo\NIST11.L

Histamine, N-acetyl-2,5-dibromo- 152245 1000116-97-6 47
n-Hexadecanoic acid 107549 000057-10-3 45
Tetradecanoic acid 84455 000544-63-8 45

9 6.660 0.14 C:\EnvDemo\NIST11.L

12-Bromododecanoic acid 125405 073367-80-3 18
Piperidin-4-one, 1,2,5-trimethyl-, 73210 1000294-64-0 14
thiosemicarbazone
i-Propyl 14-methyl-\pentadecanoate 143170 1000336-62-4 14

10 6.710 0.03 C:\EnvDemo\NIST11.L

1-Phenyloxycarbonyl-7-pentyl-7-aza 128393 1000284-54-5 38
bicyclo[4.1.0]heptane

76
 4(1H)-Pyrimidinone, 2-(ethylthio)- 28670 006965-19-1 38
Propanoic acid, 2-[(3-chlorophenyl 207240 1000362-44-0 16
)amino]-3,3,3-trifluoro-2-[(2-fura
nylcarbonyl)amino]-, ethyl ester

11 7.223 -0.10 C:\EnvDemo\NIST11.L

1-Octadecene 104184 000112-88-9 91
cis-9-Hexadecenoic acid 105678 1000333-19-5 90
9-Octadecenoic acid, (E)- 129352 000112-79-8 86

12 7.323 0.05 C:\EnvDemo\NIST11.L

9-Octadecenoic acid, (E)- 129353 000112-79-8 41
n-Hexadecanoic acid 107549 000057-10-3 30
Hexadecenoic acid, Z-11- 105679 002416-20-8 30

13 7.505 0.15 C:\EnvDemo\NIST11.L

Oleic Acid 129336 000112-80-1 78
9-Octadecenoic acid (Z)-, tetradec 232371 022393-85-7 53
yl ester
cis-9-Hexadecenal 92517 056219-04-6 50

14 8.249 2.20 C:\EnvDemo\NIST11.L

cis-13-Octadecenoic acid 129347 013126-39-1 96
cis-Vaccenic acid 129339 000506-17-2 96
Oleic Acid 129338 000112-80-1 93

15 8.356 0.68 C:\EnvDemo\NIST11.L

Oxacyclotridecan-2-one 59521 000947-05-7 50
Oxacyclotetradecan-2-one, 13-methy 82801 057092-32-7 38
l-
Methyl 12-oxo-9-dodecenoate 82596 022418-58-2 25

16 8.543 1.52 C:\EnvDemo\NIST11.L

trans-9-Octadecenoic acid, trimeth 186757 096851-47-7 25
ylsilyl ester
4,5-Decanediol, 6-ethyl- 62636 022607-12-1 22
Nandrolone TMS Derivative 181423 1000379-14-1 15

17 8.712 2.44 C:\EnvDemo\NIST11.L

Tricyclo[4.2.1.1(2,5)]dec-7-en-9-o 23793 1000191-01-9 46
5,8-Methano-4H-3,1-benzoxazine-2-t 46756 1000142-76-5 43
hione, 1,2,4a-rel,5-trans,8-trans,
8a-cis-hexahydro-
2-Amino-2-butenedinitrile 2485 1000196-60-0 43

18 8.800 0.27 C:\EnvDemo\NIST11.L

1-(Cyclohexyl-hydroxy-amino)-propa 40814 160423-57-4 14
n-2-ol
1-(4-Iodo-phenyl)-4-(3-phenyl-ally 217720 331667-48-2 14
lidene)-pyrazolidine-3,5-dione
1,4-Dioxaspiro[4.5]decane, 7-(benz 214652 1000197-20-7 14
odioxol-5-yl)-8-nitro-9-(tetrahydr
opyran-2-yloxy)-

19 8.856 0.61 C:\EnvDemo\NIST11.L

Bicyclo[2.2.1]hept-5-ene-2-carboxy 26095 000769-85-7 59
lic acid, methyl ester, exo-
6-exo-Methyl-5-exo-norbornenol 10538 060362-83-6 59
1,2,4-Metheno-1H-cyclobuta[cd]pent 22759 013351-15-0 45
alen-3-ol, octahydro-, (1.alpha.,1
a.beta.,2.alpha.,3.alpha.,3a.beta.

77
 ,4.alpha.,4a.beta.,5b.beta.,6S*)-

20 8.912 0.47 C:\EnvDemo\NIST11.L

Isoquinolinium, 2-(m-nitroanilino) 114705 031383-03-6 10
-, hydroxide, inner salt
Ala-Thr, trimethylsilyl ether, tri 171880 1000333-68-0 9
methylsilyl ester
3, 4-Secocondyfolan-3-one, 12-[2-(a 229159 055283-38-0 9
cetyloxy)-1-methoxyethoxy]-16,19-e
poxy-2-hydroxy-4-methyl-, [12(S),1
4. beta., 16. beta., 19R]-

21 8.994 0.75 C:\EnvDemo\NIST11.L

Diethyl sulfone 9683 000597-35-3 50
5-exo-Methyl-5-norbornenol 10520 003212-13-3 50
Unfortunately, formic acid was not discovered in the samples. However, other acids were
discovered in the samples with almost same uses as formic acid. The acids includes;

1. Propanoic acid
2. Oleic acid
3. Fumaric acid
4. Pyridine
5. Tridecanoic acid e.t.c

4.3 Possible reasons for the outcome of both Photocatalytic of LDPE and
Hydrothermal treatment of birch wood not giving off Formic Acid

There are a couple of suspected reason for not obtaining the said outcome from this research
which could include

1) For each of the processes, a certain volume of solution needed were obtained for the
tests which was 100mL
2) As requested by the senior technologist in central research laboratory FUTA; 5mL of
each sample were extracted from the 100mL for the test
3) Of the 5mL, only about 2mL was extracted and used to conduct the test

78
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATION

5.1 CONCLUSION
This study successfully demonstrates the degradation of plastic waste, low-density
polyethylene film (LDPE) in benzene and its conversion to useful chemicals using visible
light excited heterogeneous vanadium photo-catalyst. Unfortunately, formic acid was not
discovered in the samples
Furthermore, during the hydrothermal treatment of birch wood, no considerable amount
of formic acid was released in the wood material. Very low or zero concentration of
formic acid despite the relation to high treatment temperatures and long treatment times.
The results indicate that acid formation can be a serious problem in industrial heat
treatment processes. Formic acid is volatile, and more experiments are needed to study
how the acid formation from wood is affected by different process conditions in industrial
plants

5.2 RECOMMENDATION

Having knowledge of this smaller proportion of the sample solution that participated in the
test, it can be suggested that;

1. There was not enough knowledge about the practical aspect of chemistry
2. Perhaps, during the extraction for the wood sample, the wood samples solution which
was prepared using distilled water (and water can’t be put in the gas chromatography
machine) hence, a need to separate the chemical solution from the water solution, so
the addition of dichloromethane to achieve the separation could have affected the
result
3. Perhaps, the quantity of the sample sent for test (2mL) was too little for formic acid to
be picked within the elusion time of the gas chromatograph

Therefore, it can be recommended these few ideas be put into consideration in further

research on this study;

79
a) Enough quantity of samples should be produced to increase chances of getting the

desired solution

b) Substantial proportion of sample volume of the sample should be used for the gas

chromatography test to achieve more accuracy

c) The design of an industrial process should control the acid formation that results from

hydrothermal treatment to avoid cellulose degradation in the wood. If possible, the

hydrothermal treatment should be performed in neutral to alkaline conditions.

80
 REFERENCE

Alexandra, L. C. (2012). Municipal Solid Waste: Turning a Problem into resource waste: The
Challenges Facing Developing Countries, Urban Specialist. World Bank. 2–4 p.

Al-Salem, S.M., P. Lettieri, and J. Baeyens, (2009). Recycling and recovery routes of plastic
solid waste (PSW): A review. Waste Management, 29(10): p. 2625-2643.

Al-Salem, S.M., P. Lettieri, and J. Baeyens, (2010). The valorization of plastic solid waste
(PSW) by primary to quaternary routes: From re-use to energy and chemicals. Progress in
Energy and Combustion Science, 36(1): p. 103-129.

Aznar, M.P, (2006). Plastic waste elimination by co-gasification with coal and biomass in
fluidized bed with air in pilot plant. Fuel Processing Technology, 87(5): p. 409-420.

Brill, T.B. and P.E. Savage, (2004). Chapter 16 - Kinetics and mechanisms of hydrothermal
organic reactions, in Aqueous Systems at Elevated Temperatures and Pressures, D.A.P.F.-
P.H. Harvey, Editor. Academic Press: London. p. 643-675.

Dimitrov, N., Krehula, L. K., Siročić, A. P., and Hrnjak-Murgić, Z. (2013). Analysis of
recycled PET bottles products by pyrolysis-gas chromatography. Polym. Degrad. Stab. 98,
972–979. doi: 10.1016/j.polymdegradstab.2013.02.013

Ederer, H.J., (1999). Modelling of the pyrolysis of tert-butylbenzene in supercritical water.

The Journal of Supercritical Fluids, 15(3): p. 191-204.

EN1534:2000 (2000) Wood and parquet flflooring—determination of resistance to

indentation (Brinell)

Feng Z, Ale´n R, Niemela¨ K (2002) Formation of aliphatic carboxylic acids during Soda-AQ
pulping of Kenaf bark. Holzforschung 56:388–394

Fengel D, Wegener G (1989) Wood: chemistry, ultrastructure, reactions. Walter de Gruyter,

New York, Berlin

Frigo, S., Seggiani, M., Puccini, M., and Vitolo, S. (2014). Liquid fuel production from waste
tyre pyrolysis and its utilisation in a Diesel engine. Fuel 116, 399–408. doi:
10.1016/j.fuel.2013.08.044

81
Gaca, P., Drzewiecka, M., Kaleta, W., Kozubek, H., and Nowinska, K. (2008). Catalytic
degradation of polyethylene over mesoporous molecular sieve MCM-41 modified with
heteropoly compounds. Polish J. Environ. Stud. 17, 25–35.

Gaca, P., Drzewiecka, M., Kaleta, W., Kozubek, H., and Nowinska, K. (2008). Catalytic
degradation of polyethylene over mesoporous molecular sieve MCM-41 modified with
heteropoly compounds. Polish J. Environ. Stud. 17, 25–35

Gandidi, I. M., Susila, M. D., Mustofa, A., and Pambudi, N. A. (2018). Thermal–Catalytic
cracking of real MSW into Bio-Crude Oil. J. Energy Inst. 91, 304–310. doi:
10.1016/j.joei.2016.11.005

Garrote G, Dominguez H, Parajo´ JC (2001) Study on the deacetylation of hemicelluloses

during the hydrothermal processing of Eucalyptus wood. Holz Roh Werkst 59:53–
59

Geyer, R., Jambeck, J.R., and Law, K.L. (2017) Production, use, and fate of all plastics ever
made. Sci Adv 3: e1700782

Henriksson G (1995) Course material in wood chemistry. Royal Institute of Technology,

Division of Forest Products Chemical Engineering, Stockholm, Sweden

Heras, F., Jimenez-Cordero, D., Gilarranz, M. A., Alonso-Morales, N., and Rodriguez, J. J.
(2014). Activation of waste tire char by cyclic liquid-phase oxidation. Fuel Process. Technol.
127, 157–162. doi: 10.1016/j.fuproc.2014.06.018

Hodgkinson JM (2000) Flexure. In: Hodgkinson JM (ed) Mechanical testing of advanced

fifibre composites. Woodhead Publishing Limited, Cambridge, England, pp 124–142

Hon DN-S, Minemura N (1991) Color and discoloration. In: Hon DN-S, Shiraishi N (eds)
Wood and cellulosic chemistry. Marcel Dekker, New York, pp 395–454

Houser, T.J., (2014). The reactivity of tetrahydroquinoline, benzylamine and bibenzyl with
supercritical water. Fuel, 1989. 68(3): p. 323-327.

Inman, M. (2012). Cooking up fuel. Nat. Clim. Change 2, 218–220. doi:

10.1038/nclimate1466

Jung B, Roffffael E (2002) U¨ber die Acidita¨t einheimischer Holzarten. Holz Roh Werkst
60:154

82
Jung, S. H., Cho, M. H., Kang, B. S., and Kim, J. S. (2010). Pyrolysis of a fraction of waste
polypropylene and polyethylene for the recovery of BTX aromatics using a fluidized bed
reactor. Fuel Process. Technol. 91, 277–284. doi: 10.1016/j.fuproc.2009.10.009

Kamden DP, Pizzi A, Guyonnet R, Jermannaud A (1999) Durability of heat-treated wood. In:
Proceedings: IRG WP: International research group on wood preservation 30,
Rosenheim, Germany, 6–11 June, pp 1–15

Katritzky, A.R., (1994). Aqueous High-Temperature Chemistry of Carbo- and Heterocycles.

20. Reactions of Some Benzenoid Hydrocarbons and Oxygen-Containing Derivatives in
Supercritical Water at 460 .degree.C. Energy & Fuels, 8(2): p. 487-497.

Lai Y-Z (1991) Chemical degradation. In: Hon DN-S, Shiraishi N (eds) Wood and cellulosic
chemistry. Marcel Dekker, New York, pp 455–524

Lopez, G., Olazar, M., Artetxe, M., Amutio, M., Elordi, G., and Bilbao, J. (2009). Steam
activation of pyrolytic tyre char at different temperatures. J. Anal. Appl. Pyrol. 85, 539–543.
doi: 10.1016/j.jaap.2008.11.002

Lundquist, L., (2014). Life Cycle Engineering of Plastics. Materials & Mechanical. 2000:
Elsevier Science Ltd. 1-220.

Ma, C., Yu, J., Wang, B., Song, Z., Xiang, J., Hu, S. (2017). Catalytic pyrolysis of flame
retarded high impact polystyrene over various solid acid catalysts. Fuel Process.
Technol. 155, 32–41. doi: 10.1016/j.fuproc.2016.01.018

Marcilla, A., Beltrán, M. I., Hernández, F., and Navarro, R. (2004). HZSM5 and HUSY
deactivation during the catalytic pyrolysis of polyethylene. Appl. Catal. A Gen. 278, 37–43.
doi: 10.1016/j.apcata.2004.09.023

McCollom, T.M., J.S. Seewald, and B.R.T. Simoneit, (2001). Reactivity of monocyclic
aromatic compounds under hydrothermal conditions. Geochimica et Cosmochimica Acta,
65(3): p. 455-468.

Motonobu, G., (2009). Chemical recycling of plastics using sub- and supercritical fluids. The
Journal of Supercritical Fluids. 47(3): p. 500-507.

83
Mukherjee, M. K., and Thamotharan, P. C. (2014). Performance and emission test of several
blends of waste plastic oil with diesel and ethanol on four stroke twin cylinder diesel
engine. IOSR J. Mech. Civil Eng. 11, 2278–1684. doi: 10.9790/1684-11214751

Nikles, D.E. and M.S. Farahat, (2005). New Motivation for the Depolymerization Products
Derived from Poly (Ethylene Terephthalate) (PET) Waste: a Review. Macromolecular
Materials and Engineering, 290(1): p. 13-30.

Nizami, A. S., Ouda, O. K. M., Rehan, M., El-Maghraby, A. M. O., Gardy, J., Hassanpour,
A., (2016). The potential of Saudi Arabian natural zeolites in energy recovery
technologies. Energy 108, 162–171. doi: 10.1016/j.energy.2015.07.030

Panda, A.K., R.K. Singh, and D.K. Mishra, (2010). Thermolysis of waste plastics to liquid
fuel: A suitable method for plastic waste management and manufacture of value added
products—A world prospective. Renewable and Sustainable Energy Reviews, 14(1): p. 233-
248.

PlasticsEurope (2018) Annual review 2017–2018. URL

https://www.plasticseurope.org/download_file/force/1830/ 181

Ratnasari, D. K., Nahil, M. A., and Williams, P. T. (2017). Catalytic pyrolysis of waste
plastics using staged catalysis for production of gasoline range hydrocarbon oils. J. Anal.
Appl. Pyrolysis 124, 631–637. doi: 10.1016/j.jaap.2016.12.027

Rehan, M., Miandad, R., Barakat, M. A., Ismail, I. M. I., Almeelbi, T., Gardy, J., (2017).
Effect of zeolite catalysts on pyrolysis liquid oil. Int. Biodeterior. Biodegrad. 119, 162–175.
doi: 10.1016/j.ibiod.2016.11.015

Rizzarelli, P., Rapisarda, M., Perna, S., Mirabella, E. F., La Carta, S., Puglisi, C., (2016).
Determination of polyethylene in biodegradable polymer blends and in compostable carrier
bags by Py-GC/MS and TGA. J. Anal. Appl. Pyrolysis 117,72–81. doi:
10.1016/j.jaap.2015.12.014

Serrano, D. P., Aguado, J., and Escola, J. M. (2012). Developing advanced catalysts for the
conversion of polyolefinic waste plastics into fuels and chemicals. ACS Catal. 2, 1924–1941.
doi: 10.1021/cs3003403

Watanabe, M., (1998). Polyethylene conversion in supercritical water. The Journal of

Supercritical Fluids, 13(1–3): p. 247-25

84
Xue, Y., Johnston, P., and Bai, X. (2017). Effect of catalyst contact mode and gas atmosphere
during catalytic pyrolysis of waste plastics. Energy Conv. Manag. 142, 441–451. doi:
10.1016/j.enconman.2017.03.071

85