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Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews


journal homepage: www.elsevier.com/locate/rser

Development circumstances of four recycling industries (used motor oil, MARK


acidic sludge, plastic wastes and blown bitumen) in the world

Syeda Azeem Unnisaa, Malek Hassanpourb,
a
Department of Environmental Sciences, Osmania University, Telangana, Hyderabad, 500007 A.P, India
b
Researcher of Regional Center for Environment Studies, Osmania University, Telangana, Hyderabad, 500007 A.P, India

A R T I C L E I N F O A BS T RAC T

Keywords: The conspicuous global challenges that we are departing towards them today comprise to be addressed in the
Used motor oil multifaceted frameworks of economy, society, environment and technology. In recent years, the consensus of
Acidic sludge demanding for sustainable development and its implementation has been unanimously posed. Along with this
Plastic wastes affirm, high added value, knowledge-based, competitive sustainable manufacturing and business excellence
Blown bitumen
have been widely scrutinized as a prominent enabler and handler especially in recycling industries sector.
Current review survey encompasses the development circumstances of four major recycling industries in Iran
and over the world. Thus, evaluation of the individual techniques exploited in the four recycling industries
indicated that employed processes had the lowest economic outlay and the highest revenue in comparison to
other technologies. Additives can be utilized as raw materials for production of economically valuable
bituminous products. The recycling and converting processes are not only cost-effective, but they also descent
the environmental risk to a large level, using new techniques to zero. Economic indices, business excellence
score and the quality of the obtained products represented that these processes support sustainable
development of industries.

1. Introduction the SD aspects of these industries [2]. Jonidi and Hassanpour [3]
reported that in the Europe, about 25 industries deal with used oils
Recycling of waste materials in developing and civilizing countries recovery. Typical recovery processes are maturing in many countries
is growing and it is driven by economic necessity associated to poverty like Germany (7 units), Italy (5 units), France, Spain, Denmark, Iran,
and environmental protection. Recent surveys revealed that successive Poland, Slovakia and Greece. Modern industries are constructing and
PSW and used motor oil recoveries dominate all other kinds of wastes implementing in many of countries (France, Germany, Italy, and
recycling started since 1960. While only a fraction of the total plastic Spain). It has been estimated about 200 recycling industries (small
wastes are being recycled in many western countries, around 95% and industries) of used motor oil in Iran and about 400 recovering
75% of the PSW appear to be recycled in developing countries. industries in the USA, Canada, Tunisia and Saudi Arabia. These
However, the quality of the successively recycled products in terms of statistics are also extendable for other aforementioned industries [4].
their physical appearance, products properties, health hazards are in On the other hand, with regard to existing massive quantities of wastes
serious argues [1,2]. Numerous small recycling industries of plastic and residuals of oil and AS generated by processes implemented in
wastes, blown bitumen and used motor oil have been currently above-named industries, miscellaneous organic components especially
implemented heedless to economic assessments, modern technologies VOCs, it is indispensable identifying the modern technologies and
and facilities are developing and maturing day by day in Iran and over practices so that remove, recovery and remediation from the pollutants
the world. On the other hand, the aforementioned industries have and by-products, fortifying and promoting the performance and BE in
properly employed commensurate and sumptuary technologies for order to achieve the SD for recycling industries of used motor oil, AS,
recovering, treating, and recycling of wastes from disposed products blown bitumen and plastic wastes. For instance, Poli et al. [5] reported
and pay attention to the number of existing industries in developing that high quantities of plastics refused to the environment are ingested
countries and the world, quality of obtained products and quantity of by lots of sea turtles that made a serious problem to them and
usages, it is indispensable focusing on the performance, economic, and environment in Paraíba, Northeast Brazil. Jonidi and Hassanpour [3]


Corresponding author.
E-mail address: Malek.hassanpour@yahoo.com (M. Hassanpour).

http://dx.doi.org/10.1016/j.rser.2017.01.109
Received 10 February 2016; Received in revised form 10 December 2016; Accepted 15 January 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Nomenclature PCDFs Polychlorinated dibenzofurans


PVC Polyvinylchloride
AS Acidic sludge PP Polypropylene
ASTM American Society for Testing Materials PS Polystyrene
ABS Acrylonitrile Butadiene Styrene PB Poly-butylene
BE Business excellence PBT Polybutylene theraphalate
BES Business excellence score PEBA Polyether Block Amide
Cst Centistokes PET Poly-ethylene terephthalate
CSFs Critical success factors PI Polyisoprene
CFCs Chlorofluorocarbons PMP Polymethyl Pentene
CVD Chemical Vapor Deposition PU (ether) Polyurethane
D mm Deci millimetre PA Polyamides
DBD Dielectric-Barrier Discharge PC Polycarbonates
EMAC Ethylene-Methyl Acrylate Copolymer PVDC Poly-vinylidene chloride
EPR Ethylene Propylene Rubber PVDF Polyvinylidene fluoride
EEA Ethylene Ethyl Acrylate PEST Polyester textiles
EVA Ethylene Vinyl Acetate PMMA Polymethyl methacrylate
EPS Expanded polystyrene PVD Physical Vapor Deposition
EFQM European Federation for Quality Management SD Sustainable Development
GIS Geographic Information System SBS Styrene - Butadiene – Styrene
HDPE High Density Polyethylene SP Softening point
HIPS High Impact Polystyrene SHRP Strategic Highway Research Program
KBEM Kanji's Business Excellence Model SBR Styrene–Butadiene–Rubber
LDPE Low Density Polyethylene SAN Styrene Acrylo Nitrile
NBR Nitrile Butadiene Rubber TDA Thermal de-asphalting
OE Organizational excellence TFE Thin Film Evaporation
PSW Plastic solid wastes TVOCs Total Volatile Organic Compounds
PI Penetration Index USA United States America
PG Performance grade VOCs Volatile organic compounds
PE Polyethylene wt% Weight percentage
PAHs Polycyclic Aromatic Hydrocarbons WL Weight loss

estimated that AS is a by-product from used motor oil reprocessing vironmental impacts of processes in a certain industry. Bradley and
industries, which thousands tons of this sludge are disposed into the Thompson [10] surveyed on the relationship among oil revenue and
environment as a hazardous waste material in Iran and all over the many of key macro-economic variables, crude oil revenues with output,
world daily. expenditures of consumer, unemployment, and stock.
SD as a concept is a description to many different interpretations. It It is indispensable to realize BE, because potentially causes to
can be as a simple, complex description or as we like to establish that, success of an industry via development and implement a practice for
but the indispensable thing is that it besets individuals, industries, and performance measurement criteria beyond the presentation of financial
governments to embed indisputable decisions, which safeguard a views. By the way, Hassanpour [11] has reported the trend of SD using
common future. It is an all-encompassing approach that engulfs and KBEM in used motor oil industries. According to the development and
underpins the future of the planet. The intense stream of wastes establishment numerous aforementioned industries and its priority to
concerning loss and dissociation of natural resources, pollution, society, planet, environment and economic it is indispensable figuring
resource inequality, and climate change enables arisen focus on the out to the connection and relation among four recycling industries and
demand to protect the environment. Against the background of a main factors of SD. On the other hand, we all live on the same planet
restricted sources of raw material supply, and an understanding of the and share a common fate. Fig. 1 represents the dependence and
true impact and long-term effects of the polluting of our environment, coherence among the multifaceted frameworks so that identify the
science has revealed to the world that significant aspects enquires to be concepts in SD. The main objective of present study was survey of
taken to discuss with the consequences of industrial performances in development circumstances of four recycling industries (used motor
terms of economy cycle, society satisfaction, environment protection oil, AS, blown bitumen and plastic wastes). To achieve to this purpose,
and technology development [6]. Economic assessment comprises the requirements of the industries were surveyed upon available and
variety of deals about the investments and outlays for recycling environmental and new technologies.
industries and underpins closely the employed capital. The major
outlays can be divided into organization and control costs incurred by
2. Technology
the offices, wastes collecting expenditures and operational investments
associated to final storage facilities prior to recycling investments. Cost
The recycling industries of used motor oil are utilized to retrieve of
computations are based on detailed estimates that reflect typical
used motor oil generated in light and heavy vehicles. The acid/clay
investment costs, interest rates, transportation costs, materials, equip-
practice is so popular process in lots of developing countries because of
ment and fixed, working costs and etc to set up and start operation
so many economic advantages and other benefits. Plastic wastes and
[2,7,8]. In present research was used of economic indices such as
blown bitumen recycling industries actually have main role to decrease
value-added percent, profit, annual revenue, breakeven point, time of
the plastic wastes quantity through of the wastes flow as a pioneer
return on investment, value-added, output value. By the way, Marchetti
industries in consumption of plastic wastes, used motor oil and AS
and Errazu [9] have also studied the economic indices such as
[2,12,13]. According to the announcement of Iranian industry organi-
productivity, raw material usage, economic competitiveness and en-
zation, about 200 reprocessing plants (acid/clay process) of used motor

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S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Business
Excellence

Environment and Sustainable Economic


pollutants Development and society

Industries and
technologies
Fig. 2. Four recycling industries cycles [source: this study].

Fig. 1. Represents the multifaceted frameworks of sustainable development [source: this recovery rate of used lubricants and post consumer plastic wastes by
study]. country in some recent studies. These values are not clear in Iran. Fig. 2
presents the four recycling industries cycles and existing relations
oil and lots of plastic and blown bitumen recycling industries are among them.
commonly active in Iran and over the world. This process (acid/clay)
yields around 15 barrels of AS per 100 barrels of used oil as hazardous 2.1. Used motor oil and AS recycling industries
waste material, which can be effectively retrieved. AS recycling industry
is generally within or next to the recycling plants of used motor oil that Some of the major options which may be used for disposal of used
is posing to establishment and utilization [14]. Lubricating oils motor oil are reuse, thermal cracking and incineration, ground treat-
constitute additives which are used in the plastics, blown bitumen ment and mulching procedures. However, each of these practices has
and AS industries for reducing the adhesion, to lower the friction and/ particular limitations. Combustion and all other practices of disposal
or to improve the elastic properties [15,16]. Table 1 represents the for used motor oils are uneconomical and led to the wastage of

Table 1
Recovery rate of used lubricants and post-consumer plastic wastes by country [4,17].

Used lubricants Plastic wastes

Region Consumption (ton) Predicted recoverable rate Recoverable rate (%) Recycling rate Energy recovery rate Disposal rate

* * *
Switzerland 24% 76% –
* * *
Syprus 16% – 84%
* * *
Norway 37% 55% 8%
* * *
Stonia 32% 26% 42%
* * *
Slovakia 28% 26% 46%
* * *
Slovenia 28% 24% 48%
* * *
Czech republic 32% 18% 50%
* * *
Hungary 21% 21% 58%
* * *
Poland 25% 17% 58%
* * *
Romania 27% 15% 58%
* * *
Bulgaria 17% 9% 74%
* * *
Latvia 22% 6% 72%
* * *
Lithuania 24% – 76%
Austria 102400 44 74 24% 72% 4%
Belgium 173608 44 79 32% 62% 6%
Denmark 71416 65 75 28% 66% 6%
Finland 89194 54 80 18% 44% 38%
France 888771 49 56 19% 43% 38%
Germany 1076149 50 85 33% 63% 4%
Greece 88000 68 37 17% 8% 75%
Ireland 38900 51 86 31% 25% 44%
Italy 681100 40 74 26% 16% 48%
Luxemburg 10150 50 39 24% 70% 6%
Netherlands 154685 54 72 33% 59% 8%
Purtugal 113200 55 64 34% 13% 53%
Spain 496141 55 47 28% 16% 56%
Sweden 146847 54 80 34% 61% 5%
Great Britain 803667 51 86 22% 9% 69%
* * *
Malta 13% – 87%
* * *
Europe 4934228 49 49

*
No data.

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S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Table 2
Regenerative technologies comparison in terms of environmental-friendly and economic costs [3,17].

Regenerative Technologies Energy requirement Industrial scale Economic costs AS Residual oil sludge Hazardous wastes

Distillation High Large industries Low Little Much VOCs


Solvent de-asphalting High Large industries High Little Much VOCs
TFE with hydro-finishing High Large industries High None Little VOCs
TFE with clay-finishing High Large industries High None Little VOCs
TFE with solvent finishing High Large industries High None Little VOCs
Solvent extraction hydro-finishing High Large industries High None Little VOCs
TDA High Large industries High None Little VOCs
Acid/clay Low Small industries Low Much Much VOCs

resources [3,18]. The recycling of used motor oils can be an appropriate used for absorption but solvent to segregate oil and foreign compounds
and economical alternative instead of combustion [3,19]. Table 2 [24]. Solvent extraction hydro-finishing technique incorporates solvent
represents available regenerative technologies comparison in terms of extraction and hydro-finishing via eliminating the foreign compounds
environmental-friendly and economic costs over the world. by solvent and then reinforcing oil quality by hydro-finishing. Using
According to Table 2 each of the functional regeneration technol- TDA with clay finishing and TDA with hydro-finishing techniques the
ogies can be utilized as a treatment practice for used motor oil. The oil is divided to 3 kinds at high temperature encompasses vacuum gas
layout of functional regeneration technologies is carried out depending oil, base oil (as lubricant) and asphalt residues. Next, the extra
on the quality of applied oil and concentration of existing pollutants in purification is completed upon base oil by hydro-finishing or clay-
used motor oils [20,21]. The operational procedure of all technologies finishing under high-pressure for continuous utilization [25].
comprise the following four stages, (1) Dewater/defuel, (2) De-asphalt, The acid/clay technique (Fig. 3) is experiencing serious quirks for
(3) Fractionation, (4) Finishing. During two first stages, the foreign environmental safety. The main by-product of this technique is the
components, moisture, fundamental compounds of light fuel like fuel huge quantity of AS which is classified as hazardous waste material
and naphtha, solid foreign components such as metal powder derived [26]. This technique yields about 15 barrels of AS per 100 barrels of
from mechanical wear and additive added to crude oil are segregated used oil which its composition besets unsaturated compounds which
from used motor oil respectively. The third stage is applied to choose or are non-polar and asphaltene analogous to bitumen [14,27].
eliminate a specific kind of components based on boiling points and Hassanpur et al. [28], used from some additives such as SBS,
then final treatment is performed to eliminate some specific foreign bentonite, lime and sodium hydroxide so that physical modification
components which cannot be eliminate through of the former stages of AS. SBS is bitumen modifier as one of the elastomer – thermoplastic
[17,20]. with wt% 2–4), bentonite due to the chemical structure as a filler,
The distillation technique pertains on the pollutants concentration stabilizer and agent concentration with wt% (1, 2, 4, 6, 8, 10) and lime
of used motor oil and product quality applied as vacuum distillation, and sodium hydroxide were used to decreasing acidity value of AS and
heating or preliminary distillation and TFE, is utilized and accommo- promoting the role of bentonite stability in bitumen via ratios equal (1–
dated prior to the acid-clay process and the rest of operation stream 5 g), were mixed with AS of industry (samples 50 g). Results indicated
looks like to the acid-clay technique (Fig. 3 presents a diagrammatic that because of rising SP from 25 to 48 °C, falling WL% from 3 to 1.25,
layout of AS recycling plants and used motor oil industry) [17,22]. promoting the penetration degree to 230 mm, Frass breaking point to
Solvent de-asphalting technique is similar to the two former −7 and PI to the degree standard enacted (+1), the AS properties and
techniques (distillation and acid/clay) except its solvent extraction its performance were modified using both SBS and bentonite. These
and stripping [23]. The latest outlined technology is TFE; and TDA is in parameters were not measureable for the initial AS except SP and WL
addition to the latter procedure. TFE is generally exploited in USA and about 25°C and 3% respectively. Using all of additives with aforemen-
Europe, while the other techniques, especially the acid/clay technology tioned percentages AS converted to a useless product. In other study by
are run usually in the less-developed nations. TFE with hydro-finish- Hassanpour et al. [29] both of the SBS and bentonite were utilized to
ing, clay finishing and solvent finishing are exploited to segregate oil modify AS properties as well as a concentrator mixer so that separating
and foreign compounds via a TFE, and purify it through of the hydro- spilled oil into AS. The results revealed that performance parameters
finishing to prevent the secondary pollution. The particular compounds such as SP, WL, penetration degree, PI, Frass breaking point and
such as chlorine, nitrogen, oxygen, and sulfur are removed by hydro- thermal sensitivity increased from 37°C, 1.3%, 230 dmm, −0.07854,
finishing. There is a difference among these techniques, that clay is −5°C and 0.0451 to 54°C, 1%, 130 dmm, 2.7094, −11°C, 0.02721

Fig. 3. Diagram of layout acidic sludge recycling plants and used motor oil industry [14].

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S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Table 3
Performance parameters of AS recycling [30].

The properties of The optimal properties of Jonidi et al. [14]


bitumen bitumen for climatic
conditions of Iran

SP (°C) 20 to 85 54
WL % 1 1
Penetration degree 30 to130 130
(dmm)
PI −2 to +2 0.5774
Frass breaking point −12 −11
PG Different Different; (70, −16), (58,
−16), (64, −10), (76, −16)

respectively. Both of bentonite and SBS in wt% of 2 and 4 were the


suitable additives in retrieval of AS to the polymer bitumen respec-
tively. It has a worth to mention that study has been confirmed as a
patent by the registration number 75360 in Iran. Table 3 represents the
performance parameters of AS recycling (obtained products) after final
Fig. 4. GIS map of the different regions of Iran based on the PG [31].
modification.
Table 4 presents the bitumen produced and PG from all provinces
is the quality appearance for products, so Table 6 shows the properties
of through Iran that has been calculated based on the both minimum
of base oils for all recycling and refining technologies of used motor oil
temperature and seven-day consecutive maximum air temperature
and crude oil.
values from numerous weather stations located in different locations
Hamidi et al. [33] confirmed that with addition of 1.5–6 wt%
of Iran and based on SHRP tests (Frass breaking point, Rutting,
bentonite, the value of SP increased from 63 to 67 °C in rubber
Fatigue and climatic conditions) [31].
bitumen. The least penetration degree was obtained in the 3 wt%
The results of PG have some utilities such as deciding about the use
bentonite (25 dmm). Ziari et al. [34], found that with addition of 10,
of bitumen in a given climatic situation, obtaining the engineering
15, 20, 25 and 30 wt% bentonite on the bitumen blends 47/67, the
properties and as well as grading of bitumen. The performance of
values of penetration degree, SP and PI were changed from 67 to 14
modified bitumen at high, intermediate, and low temperatures is
dmm, 47–59.5°C and 0.92 to 0.85 respectively. Saleh and Muslim [35],
estimated based on SHRP. In the grading system, the physical proper-
determined that by addition of 3, 6, 9, 12 and 15 wt% bentonite in
ties are constant for all of performance grades, but the temperature at
polymeric blends, the mechanical properties such as hardness, mod-
which physical properties were obtained could be altered, depending
ulus of elasticity and thermal stability of polymeric blends had
on the atmospheric situation of usage. Traffic load has also critical role
increased considerably. Chen et al. [36], offered that with addition
in the selection of the applied bitumen. If the traffic load at the
1–6 wt% SBS in the bitumen blends of 31/93 and 43/62, the value of
equivalent standard axles (80 kN) be more than 107, the designer has
SP was increased. Casey et al. [37], reported that with addition 2–4 wt
to select the bitumen with one grade more than available PG. Based on
% SBS, the value of SP in the mastic asphalt was promoted from 39.8 to
the available PG from bitumen utilized in provinces of Iran and
46.5 °C. Rasoulzadeh et al. [38], utilized the recycled PE to improve the
obtained results suggest that this kind of bitumen would be used in
properties of vacuum distillation residuals and have found that SP was
different regions of Iran. Fig. 4 and Table 5 represent PG for different
promoted from 41 to 117 °C. Penetration degree value was also
regions of Iran [14,31,32].
reduced from 202 to 47 dmm. It is indispensable to point out that in
The another important aspect in studies related to SD of industries
the current study the used SBS was contained 20–30% PE. Sengoz and
Isikyakar [39], revealed that with addition 2–6 wt% SBS on the
Table 4 bitumen blends of 50/70, the values of both SP and PI were increased
PG values for all provinces of Iran [31]. from 49 to 69 °C and from −0.92 to 2.46 while, the penetration degree
was decreased from 63 dmm to 48. Behbahani et al. [40], reported that
Province PG Province PG with addition of 2,3,4,5 and 6 wt% SBR, the SP, PI and penetration
Zahedan 70–10, 64–16 Bandar Abass 70–10 degree were increased for the blends of bitumen 60/70, Tehran
Kerman 64–22, 64–16, 70–10 Abadan 64–16, 70–10 Refinery. Kok and Akpolat [41], found 3% SBS as a more effective
Khoram Abad 64–22, 64–16, 58–22 Kordestan 58–28, 64–22, 64– modifier percentage to promote the bitumen performance properties.
16 Abtahi and Dibaji [42], determined PG using the minimum and
Mashhad 64–22, 58–22, 64–16 Sanandaj 68–34, 68–22, 54–
28, 58–28
maximum daily temperatures of 20 stations, the maximum and
Gorgan 64–10, 64–22 Tehran 64–22, 64–16, 68– minimum pavement temperatures values for different regions of
16, 64–22 Isfahan Province, Iran. With regard to PG of zones, the suitable
Semnan 64–16, 64–10, 70–10 Rasht 58–28, 68–16, 64– bitumen was determined for each region. Asi [43], depicted a PG
10, 58–34
map using data of 20 years of continuous temperature of the eleven
Yazd 64–16, 64–10, 70–10 Hamedan 64–16, 64–22
Shiraz 64–16, 64–10, 70–10, Ghazvin 64–10, 64–16, 64– weather stations based on the highest and lowest temperature intervals
64–22 22 of asphalt in Hashemite Kingdom of Jordan and the country was
Isfahan 64–16, 64–10, 70–10, Zanjan 58–28, 58–22, 64– divided to several zones. Shen et al. [44], used SHRP for achieving to
64–22, 58–22 22 an appropriate PG of reclaimed asphalt pavement. Stelea [45],
Shahr kord 58–22, 70–22 East Azarbaijan 64–22, 58–16, 58–
presented that using SHRP (based on PG and 7 consecutive days
22, 58–28
Yasooj 70–10, 64–22 West Azarbaijan 58–22, 62–28, 58– maximal temperature) to test on the highway bitumen results in high
16 performance in asphalt mix design.
Ahvaz 76–10, 70–10 Mazandaran 64–22
Arak 64–16, 64–28 Sari 58–16

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S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Table 5
PG for all provinces of throughout Iran [31].

PG
Green 58–16* 58–34* 58–22* 68–16 64–22 64–28
Yellow 70–10 58–28*
Brown 1 70–10 64–16 64–22 58–16* 68–22 68–28 58–28* 70–28 64–10
Orange 70–28 64–28 70–10 58–16* 58–34* 76–10 64–22 64–16 64–10 52–22* 58–28* 58–22*

*
Cold regions (North and West North). 1- Warm regions.

2.2. Blown bitumen production industry Table 7


Blown bitumen production technologies comparison in terms of environmental-friendly
and economic costs [12,46].
This procedure is also carried out in many practices such as
catalytic, non-catalytic and reactor. The main practice of road bitumen Technology Economic costs Industrial Hazardous Residuals
properties improvement contains the catalytic oxidation. In catalytic scale wastes
practice is added some chemicals additives during process so that
Catalytic Economical Small VOCs Oil sludge
reduce the aeration period [12]. Table 7 offers blown bitumen produc-
technique industry
tion technologies comparison in terms of environmental-friendly and Air blowing Economical Small VOCs Oil sludge
economic costs. technique industry
Catalytic systems utilized in oxidation technique encompass some Reactor Economical Large VOCs Oil sludge
catalysts such as iron nano-particle, iron carboxylate and aluminum technique industry

chloride, P2O5, FeCl3 and etc. Catalytic air blowing practice of bitumen
most extensively employed today has been described by Hoiberg
other words, the blown bitumen generation operation mainly encom-
[47,48], via P2O5 and FeCl3 as catalysts for accelerating the oxidation
passes various stages of bitumen aeration, loading, cooling and
rate. Later, Shearon and Hoiberg [49] explained the details for utilizing
packaging. It should be noticed that gases and vapors escaped and
of P2O5 as a modifier in the air blowing technique. Illman and sommer
stripped during operation pass through of the aeration pipes installed
[50] confirmed the use of hexafluoro phosphoric acid as an aid to
in top of the tower and then they are traversed into contact condenser.
generate blown bitumen. Fink et el. [51] offered heating of 80–90%
In this section, by spraying water, smelly gasses, oily and non-volatile
asphaltic residuum with 2–20% by weight ferric chloride. Catalyst of
components of the gas phase are separated and transferred by water
type iron nano-particles shows a higher efficiency than the type of iron
into the sewage. Other non-separated components escaped from
carboxylate (as such or in the presence of aluminum chloride) in the
condenser are conducted and burned in the furnace [12]. Fig. 5
oxidation process.
represents layout units of the small blown bitumen production industry
The conventional blowing operation has some particular limitations
in Iran.
with regard to efficient oxygen management, cooking and etc. Some
Blown bitumen 90/15 is the main product of industry by using raw
precautions are urgent to cope with high temperature. Therefore,
oil to generate. Hassanpour [12] reported using AS, as a new additive
temperature of reaction is fixed via water stream. Incorporation of
(as an initial, concentrated or recovered product to 54/130 bitumen) to
feed air and quantity of air introduced to bitumen in aeration process
generate blown bitumen has been promoted the SP from 90 to 110 by
are two prominent variables to produce the bitumen 60/70. In this
ratio of about 11.4 for the bitumen 60/70 to AS (Table 18). AS is free in
case, to generate bitumen 90/15 or 85/25, volume ratio about 20–25%
Iran now because it is refused into environment. Therefore, it can be a
either, oil distilled or crude oil is injected to feed bitumen in order to
strength point to beckon the stakeholders and industries owners. In
promote and elevate the flexibility of product. Due to a rise in
general, air blown bitumen is superior to bitumen processed by other
temperature, quantity of air introduced, retention time and pressure
methods in terms of high temperature susceptibility and performance
of tower, the reaction rate increases. In order to achieve the appro-
characteristics [46].
priate product and impede coming into view explosive states, tempera-
As a result, conventional blowing process has a disadvantage of
ture must be actually hindered at 265–270 °C. After curing in the
non-uniform reaction with air and water pollution, off gases etc. The
tower, bitumen should be immediately discharged to an empty tank or
two most notable developments of the immediate past are the Biturox
barrels to be delivered. Long retention time of the bitumen is so
and petro canada processes. In first process the reactor is key
dangerous to the devices and facilities. This point has a worth to
component of aforementioned process as it provides the reaction
mention that extra aeration rate added, will accumulate at the empty
control to achieve the chemical modification via promoting PI. In the
space of towel and causes beginning of fire or more likely to internal
second process bitumen is produced by blending and a catalytic
explosion. Aerated tower contains 70% bitumen and air injection is
polimerization/air oxidation process is also employed in order to
fulfilled at 232–190 °C. In the end, the temperature of product should
ascend the chemical composition and rheology of bitumen [46].
be kept between 150–165 °C so that loading and packaging. On the

Table 6
Properties of base motor oils (International Standard DEF STAN 91-43/8).

Motor oil grade SAE50 SAE40 SAE30 SAE10 SAE5 Regenerated oil Reprocessing oilb

Specific gravity 0.89 0.89 0.89 – – – 0.88


Viscosity in 100 °C (Cst) 21.9–16.3 16.3–12.5 12.5–9.3 9.6–7.3 7.3–5.5 9.63 9.5–12.5
Minimum Viscosity index 95 95 95 – – 92 90
Minimum flash point 204 204 200 190 185 234 200
Pour point −9 −9 −18 −25 −30 −3 –
Color 3–4.5 3–4 3–3.5 1 2.5–3.5
Maximum rate of acidic number – – – – – – 5%
Copper corrosion (100 °C) – – – – – – 0

b
Base oil quality (Acid/clay process).

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S.A. Unnisa, M. Hassanpour Renewable and Sustainable Energy Reviews 72 (2017) 605–624

Table 8
Existing technologies for recycling PSW [2,53,54].

Classification Practice Residuals Economic


costs

Primary (Re- Injection moulding VOCs, etc Middle-cost


extrusion)
Secondary Cutting/shredding, Dust, airborn Middle-cost
Fig. 5. Layout units of the blown bitumen production industry [12]. (Mechanical) Milling, Grinding particles

Tertiary Pyrolysis Char, waxes, CO2, Usually


Another aspect that has a worth to mention is using additives
(Chemical) Gasification NOx, Sox, VOCs, high-cost
(especially nano-products) to develop technologies as well as create Hydrogenation PAHs, PCDFs,
new techniques and practices. Assari [52] used recycled plastic Catalytic cracking Airborne particles
materials as a modifier with various gravity grades (2%, 4%, 6%) Condensation polymers and etc.
mixed to 60/70 bitumen of Tehran refinery and it's affects upon the Smelting by blast
furnace
penetration grade, SP, ductility, and PI indicated that adding these
Degradation
materials lead to improve physical properties of bitumen. Incineration
Hydrolysis
2.3. Plastic wastes recycling industry Glycolysis
Fractionation
Hydroglycolysis
PSW recycling procedures could be classified into four major Aminolysis
categories such as re-extrusion (primary), mechanical (secondary), Methanolysis
chemical (tertiary) and energy recovery (quaternary). Table 8 repre- Acid cleavage
Quaternary Burning PSW to produce Usually low-
sents available technologies to recovery PSW over the world.
(Energy energy in the form of heat, cost
By the Table 8 each practice procures a unique set of privileges that recovery) steam and electricity
makes it particularly beneficial for certain locations, applications or
demands. Although primary and secondary recycling techniques are
well implemented and extensively applied. But, mechanical recycling as must be dried in the heating furnace or passed through of the
a kind of physical treatment of PSW can only be accomplished on evaporation in the evaporator of the winding machine granulator.
single-polymer plastic, e.g. PE, PP, PS, etc. Therefore, separation,
washing and preparation of PSW are all urgent to make up high quality, 2.3.4. Granules (fourth step)
clear, clean and homogenous end-products. It has surveyed that many To prepare the milled particles for use in downstream apparatuses
practices can be employed for separation operation such as manual, or to incorporate with raw materials the grinding particles washed
selective dissolution, hydro-cyclone, melt filtration, selective flotation must be converted as cubes or granules. Then, extrusions are utilized
process, liquid-fluidized bed classification, X-ray fluorescence, laser- for pelletizing are three kinds for PET or PVC (ABC, PC, HIPS, PP, AS,
induced plasma spectroscopy method, Tribo-electrostatic separation PE, etc). The bulk of dyes and pigments can be added to plastics in
and etc [2,54]. Re-extrusion recycling is the re-introduction of scrap, present step.
industrial or single-polymer plastic parts to the extrusion cycle so that
generate products of analogous materials. Currently, the most common 2.3.4.1. Extrusion moulding. PSW flakes or particles are molten and
procedure to retrieve of the PSW is via primary recycling techniques extruded through of a mould by single or twin screws to make a new
[55]. The steps utilized to retrieve the PSW encompass major four framework. Products from this process encompass pipes, sheets, film
steps. The operational processes of all steps contain the following has and wire covering.
been explained.

2.3.1. Sorting Wastes (first step) 2.3.4.2. Injection moulding. The heated and molten PSW are injected
The plastic wastes are classified after collecting based on kinds of into a mould to solidify and make the product up expected. Products
materials such as PE, PP, soft and hard degrees. Tables 9 and 10 show made this procedure encompass washbowls, buckets and plastic
polymer type classification based on photochemical behavior, compar- models to larger products such as bumpers and pallets.
ison of some initiators of photo-degradation and products of photo-
chemical reactions for common polymers respectively.
2.3.4.3. Blow moulding. A hollow plastic melt, produced by extrusion
2.3.2. Crushing and grinding (second step) or injection is joined and swelled in a mould, using air to form bottles
The soft and hard compounds should be crushed individually by for all types of uses, such as shampoo bottles.
different mills. The obtained particles are often altered based on their
usages and usually applied as they have a size of less than one inch.
2.3.4.4. Vacuum moulding. A heat-softened sheet is accommodated in
2.3.2.1. Washing. The ingredients produced from crushing and a mould, and the hollow space between the sheet and mould is
grinding should be washed. Soda or conventional detergent powders insulated and discharged to make products up such as cups and trays.
can be applied so that washing that consumption quantity pertains on
the circumstances of wastes. Tables 11–13 present common
contaminants, general effect of non-polymeric contaminants on 2.3.4.5. Inflation moulding. Extrusion moulding is used where molten
plastic recycling practices. PSW are swelled into a cylinder to make a film up. This procedure is
used to make products such as shopping bags. Fig. 6 represents the
layout of recycling unit of plastic wastes in industries of Iran [2].
2.3.3. Dewatering and drying (third step)
These particles are cleaned by water and moisture, that is why, they

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Table 9
Polymer type classification based on photochemical behavior [55].

Type Description Typical examples

A Polymer non-absorbing; photo-oxidation depends on normal structure alone ABS, EMAc, EPR, NBR, PB, PBT, PEBA, PET, PI (Isoperene),
PMP, PU (ether), SBR
B Polymer non-absorbing; photo-oxidation depends on normal structure and no-absorbing chromophores EEA, EVA, LDPE, PP
C Polymer absorbing; direct photochemical reaction of absorbing groups and photo-oxidation controlled PA−6, PA−11, PA−12, PC, PS, PU (ester), SAN
by chemical defects which are not chromophores
D Polymer non-absorbing; photochemistry controlled by chemical defects and chromophore impurities PVC, PVDC, PVDF

Tables 14–16 represent comparison of virgin and regenerated PVC, Table 11


municipal properties of model and waste plastic products before and Common contaminants in recycled polymers [55].
after recycling technique respectively.
Polymer Recycle source Contamination
Many of the PSW tertiary and quaternary treatment techniques
appear to be robust and worthy of further attentions. The major PET Beverage bottles PVC, green PET, AL, water, glue, oligomers
advantage of chemical recycling is the feasibility of treating hetero- HDPE Milk/water bottles PP, milk residue, pigments, paper, EPS, cork
geneous and contaminated polymers with restricted usage of pre- LDPE Greenhouse films Insecticide, soil, Ni, oxidation products
LDPE Shopping bags Paper receipts, printing ink, food scraps
treatment. Products of chemical recycling have confirmed to be useful
PP Battery cases Pb, Cu, acid, grease, dirt
as either fuels or petrochemical feedstock. Some operational processes HDPE Detergent bottles Paper, glue, surfactant, bleach, white spirit
of chemical recycling like catalytic cracking is operated via solid PET Photographic film Silver halids, gelatin, caustic residues
catalysts such as silica-alumina, ZSM-5, zeolites, meso-porous materi- Phenolic Circuit boards Cu, Tetrabromobisphenol A
als and re-making up in following facilitate and accelerate the selective LDPE Multilayer film Ethylene vinyl alcohol, polyamide, ionomer
PVC Beverage bottles PET, PE, paper, AL foil, PP
breakdown of PSW. Thermal degradation techniques allow achieving to
ABS Appliance housings Poly-brominated flame retardants
a number of constituting molecules, combustible gases and/or energy SBR Automobile tires Steel wire, fiber, oil extender
using high operating temperatures for dissociation and its procedure is LDPE Mulch film Soil (up to 30%), iron (up to 3% in soil)
completed via mechanical and chemical energy. The main degradative
extrusion and catalytic cracking technologies employed for PSW
chemical recycling operations comprise the IKV, Leuna degradative gasification operation of PSW include the WGT, OSC, Texaco, SVZ,
extrusion, Stahlwerkke Bremen and Fuji, Kentucky, Leuna degradative Akzo Nobel processes. Plastics, when burnt in the absence of sufficient
extrusion + steam cracking, Amoco, Mazda, Nikon, Molten Metal oxygen, produce CO apart from generating the heat energy. This
processes which are running in so many nations [53,58]. property of plastics has been utilized in blast furnace to reduce the
Pyrolysis means thermal cracking in an inert atmosphere, but cost of raw material [53,58].
gasification in the sub-stoichiometric presence of air usually causing Glycolysis and some similar techniques are a polymer's reaction
to CO and CO2 production. One of the important technologies posed by with diols at temperatures above 200 °C [59]. Hydrogenation means
a number of industries in Austria, Germany, Korea, Italy and the addition of H2 by chemical reaction through of the unit operation.
Switzerland, is the PYROPLEQ process. Aforementioned process is The main technology applied in PSW recycling via hydrogenation is the
based on pyrolysis at 450–500 °C in an externally heated rotary drum Veba Oel AG process. No longer in operation technologies for this
and gas combustion at 1200 °C. ConTherm, TECHNIP, NRC, Pyro- practice are called RWE, Hiedrierwerke, Freiber processes [53].
Melt, BP polymer cracking process, BASF, NKT, Noell, KEU, Akzo, Finally, energy recovery was found to be a suitable solution to PSW.
Wayene, Toshiba, Berliner are unique processes which have confirmed The quantity of energy generated in kilns and reactors utilized in this
to be successful for PSW, enrich in PVC. The main processes posed in procedure is sufficiently evaluated up to the point of operation. In

Table 10
Comparison of some initiators of photo-degradation and products of photochemical reactions for common polymers [56].

Initiators and accelerators Products of

Photolysis Photo-oxidation

PA Conjugated carbonyl unsaturations, products of photo-oxidation, Tio2, Amines, CO, hydrogen, hydrocarbons, Amines, CO, CO2, acids, ammonia, water,
derivatives of anthraquinone, copper compounds carboxylic acids, pyroles, crosslinks aldehydes, peroxides
PC Bisphenol A, Stilbenes, water, some organic pigments Chain scissions, crosslinks, free radicals, Chain scissions, hydroperoxides, free radicals,
hydroxyl groups, ethers, unsaturations carbonyl groups
PE Unsaturations, aromatic carbonyl compounds, hydrogen at tertiary Crosslinks, free radicals Free radicals, hydroperoxides, carbonyl groups,
carbon, aromatic amines, groups formed during oxidation chain scissions
(hydroperoxides, carbonyl and carboxyl), benzophenones, quinines,
transition metal compounds, Tio2, polynuclear aromatics
PEST Ferrocene, Co octoate, water, naphthalene, keto-ester Free radicals, acids, aromatics, chain Free radicals, hydroperoxides, carbonyls, chain
scissions, crosslinks scissions
PMMA Residual initiators and monomers Crosslinks, formaldehyde, H, CO, Crosslinks, hydroperoxides, hydroxyl,
methanol, methyl formate, CO2 carbonyls, aldehydes
PS Acetophenone, benzophenone, enones, diketones, phenylacetaldehyde, Hydrogen, benzene, conjugated double CO2, water ketones, unsaturations,
succinimides, benzoyl peroxide, in-chain peroxide linkages, bounds, methane, ethylene, crosslinks, hydroperoxides, radicals, chain scissions,
hydroperoxides, polycyclic aromatics hydrocarbons, Fe (III), derivatives, radicals quinomethane structures
Co salts of fatty acids, AlCl3, silicat-alomina catalyst
PVC Unsaturations, carbonyl groups, solvents, impurities, (e.g., Free radicals, unsaturations, crosslinks Free radicals, unsaturations, carbonyl groups,
benzophenone), anti-oxidants, metalo-organics, (e.g., Cd scetate, chain scissions, hydroperoxides
Ferrocene), metal chlorides (eg., CdCl2, ZnCl2), metal salts (e.g., iron and
copper salts), metal oxides (ZnO, Al2O3, Tio2), pigments

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Table 12 3. Economic aspect of development


General effect of non-polymeric contamination on polymer recycling [55].
3.1. Economic estimation and BE procedure
Contamination Effect on recycling

Melts Plugs injection nozzle; catalyzes polymer oxidation In order to economic estimation of four recycling industries the
Paper, fibers Blow-outs in molded bottles; bubble collapse in film working hours of the personnel were obtained to be about 270 working
extrusion
days per year with a shift of 8 h. The required electrical energy (Kwh)
Soil, dirt Lowers aesthetic quality of recycle; causes gels and stress
concentrations and water were calculated for about 300 working days per year. The
Pigment, dyes Unwanted color variation; catalysis of polymer oxidation required water was calculated to be about 3 L/m2 – green space, 100 L
Water Hydrolytic degradation in PET; surface defects in PE / person – day and for the firefighting and safety targets by a factor of
Lubricating oil Undesirable odors; processing fumes 1.5. The staff salaries were assumed for a period of 14 months, with
Milk Recycle plasticization, lowering impact strength; rancid
23% of total salaries for insurance expenditures and pensions and an
odor of butyric acid
Terephthalic esters Discoloration of PET expense of $ 100 per month for transportation. Due to the low cost of
Hydro-peroxides Initiates thermal and photo-oxidative reactions working capital was avoided from taking a loan out for industries.
Herbicides Toxic fumes present hazard to operators Finally, economic evaluation was performed using empirical Eqs. (1–
Flame retardants May produce super-toxic compounds
11) [62,63].
Caustic residues Fogging of photographic film emulsion on PET
Q = MC′T (1)

Table 13 W = 0.75( ∑ e) × A (2)


Effect of PVC contamination on various practices of recycling [55].
C = 0.005 × P (3)
Classification Practice Effect of contamination
V = p − (( ∑ ) e + A′ + F + Cf ) (4)
Primary In-house scrap Polymer discoloration due to conjugated
recovery sequences %V = V × 100/ p (5)
Secondary Melt reprocessing Evolution of HCL at 170 °C; machinery
corrosion; discoloration and black specs in
PET
Qp = V − (( ∑ ) I + L + D + S ) (6)
Tertiary Pyrolysis Formation of CaCl2 which blocks reactor
liquefaction tubes poisoning of cracking catalyst Cv = Cvd /Cp (7)
Quaternary Incineration HCL and possibly chlorinated dioxins
Ph = Tf /Cv − Cs (8)

Cpi = Cvp + Cfp (9)


recent studies the Wierckx et al. [60] revealed that creating novel
enzymatic degradation modules employing plastic hydrolases with high Ai = Ts − Cpi (10)
quantities of plastic de-polymerization is feasible. While Pseudomonas
microbes are able to degrade plastics such as PE, the rates of Vt = If / Ai (11)
degradation are slow. Although Pseudomonas cannot degrade PET, In Eqs. (1–11), Q, M, Cʹ, T, W, e, A, C, P, V, Aʹ, F, Cf, Qp, I, L, D, S,
but in a biotechnological process PET is converted to Poly Hydroxy Cv, Cvd, Cp, Ph, Tf, Cs, Cpi, Cvp, Cfp, Ai, Ts, Vt and If, are the required
Alkanoate. Also, using ethylene glycol as a product of PET de- heating amount (Kj), flow rate (m3/h), thermal capacity, temperature
polymerization was reported for Pseudomonas species. On the other (K°), required electrical energy, summation of electrical energy con-
hand, Nano-sized particles plastics are produced via combination of sumption (facilities, manufacturing line apparatus, building and cam-
photo-degradation, oxidation and mechanical abrasion in the environ- pus), area (m2), selling expenses, selling price, value-added, initial
ment, the successful enzymatic dissociation is only feasible for biode- materials (Additives and barrels), maintenance, unforeseen costs,
gradable plastics and most conventional and bulk plastic wastes are profit, insurance, costs of interest and fees, depreciation, salary,
non-biodegradable, therefore this technique does not has a significant variable expense of commodity unit, variable project expenses, produc-
role in decline the quantity of plastics [61]. However, all techniques tion capacity, breakeven point, total fixed expenses, selling expense of
above-named persuade the stakeholders for economic evaluation commodity unit, manufacturing outlay, variable manufacturing outlay,
depend on their applications. fixed manufacturing outlay, annual revenue, total selling price, time of
return on investment and fixed capital respectively [64,65]. The
requirements of industries capital cost have been calculated from the
data of DACE price book (DACE (Dutch Association of Cost
Engineers)), edition November 2012 and according to change rate in
case study location [66].

Fig. 6. Layout of recycling units of plastic wastes [2].

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Table 14
Comparison of virgin and regenerated PVC [57].

Test Method Unit Requirement Virgin PVC Regenerated PVC

Impact strength DIN-EN 53753 (Double-V notch) KJ/M2 40 65 62


Impact strength by falling weight DIN-EN 477 (T=20 °C, M= 1 kg) No break No break No break
Thermal shrinkage DIN-EN 479 % 2 1.6–1.7 1.4–1.6
Appearance after heating at 150 °C DIN-EN 478 OK OK
Strength of welder corners DIN-EN 514 N 5300 8000 7700

Table 15 Table 17
Municipal properties of model polymers before and after recycling technique [57]. Requirements of used oil and acidic sludge industries [69,70].

Test LDPE HDPE PP Main annual material and equipment Total annual Total cost $
rates
Virgin Recycled Virgin Recycled Virgin Recycled
AS 891 m3 –
Tensile stress at max 8.6 8.6 32.5 33.1 23.7 28.5 Bentonite soil 330.32 t 103.225
load (MPa) SBS polymer 35.64 t 66825
Elongation at break 83 146 550 553 620 682 Barrels (220 L) 4050 no. 36450
(%) Used motor oil 5770 m3 1154000
Tensile stress at yield 8.6 8.6 14.4 14.9 18.5 21.3 Acid sulfuric 411.3 t 154237.5
(Mpa) Cao 22.5 t 1406.25
Elastic modulus 303 360 104 128 297 354 Additives as polymer for base oil 66 t 144375
(Mpa) Fat acid 112.5 t 249600.5
Drums 4.5 l for motor oil 700000 no. 284375
Drums 1 kg for grease 787500 no. 123046.8
Table 16 Boxes with 24 empty spaces for grease 34453 no. 10766.6
Municipal properties of waste plastic products before and after recycling technique [57]. Boxes with 6 empty spaces for motor 122500 no. 15312.5
oil
Test LDPE HDPE PP Bitumen 54/130 891 t 417656.25
Motor oil 3000 t 4687500
Virgin Recycled Virgin Recycled Virgin Recycled Grease 750 t 703125
Required energy for heating of mixing 60324098 KJ Supply by by-
Tensile stress at max 17.0 17.6 14.8 22.0 25.3 28.5 tanks to 180 °C and distillation products
load (Mpa) tanks
Elongation at break 711 722 721 732 602 652 Required electrical energy 287820 (kwh) 3598
(%) Required water 16980 m3 1171.6
Tensile stress at yield 8.8 8.9 14.8 17.2 23.3 25.0 Water supply facilities 15625
(Mpa) Split AC (Internal wiring, transformers 13125
Elastic modulus 175 182 189 250 626 674 and emergency power generators)
(Mpa) Fire extinguishers (Total) 54 no. 3402
Stoves (Total) 9 no. 270
Cooler (Total) 8 no. 240
Ventilation system (Total) 14 no. 280
In order to figure out BE was used from KBEM and EFQM. KBEM
Office equipment, furniture and etc – 2500
body is pertain on CSFS. CSFs encompass the required activities to Lab equipment (for the oil and bitumen – 5000
arrive the industrial objectives. Therefore, CSFS are associated to key quality control)
motors of performance. BES is the final outcome of overall OE in Transportation (a vehicle weighing 4 t, 7 no. 85000
car and fork)
uniting all CSFS. The role of KBEM and Kanji business score are infer
Staff salary (33 persons) 33 Persons 110000
to the assessment of industrial performance of the internal and Required fuel (stoves) 2360 L 332
external stakeholders respectively. Thus, it was used Eq. (14) so. Petroleum expenses (Transportation 44400 L 9712.5
KBEM score is equal with performance excellence A plus B [11]. vehicle and cars)
Required land 20000 m2 100000
A+B Construction of infrastructure 2284 m2 228400
BES = × 10
2 (12) (buildings)
Pavement and asphalt 5542 m2 53688
KBEM = A + B (13) Landscaping 2000 m2 2000
Ground tank 2*15*12 1 no. 28000a
∑ BI Mixing tanks equipped with heating to 2 no. 3150a
B=
N (14) 180 °C
Propeller mixers with power 3.5 Hp 5 no. 945a
In order to study different factors together were used multiple Sewage pumps with power 10 Hp 2 no. 840a
weighting systems. Each of KBEM items has a worth equal with 50 Stainless steel vacuum pumps with 4 no. 1260a
scores in EFQM. Therefore, in the aforementioned system were power 7.5 Hp
assumed 900 scores for items in EFQM until KBEM be enable to Gear pumps with power 5.5 Hp 13 no. 2730a
Condenser 4 no. 840a
survey OE values in a diagram. In present study each of the EFQM Sedimentation tank 20 m3 7 no. 26250a
items was matched with two items of KBEM [67,68]. Distillation tanks 4 no. 104864.55a
Jonidi and Hassanpour [69] discerned economic indices of the used Mixing tanks 5 no. 12796.87a
motor oil industry equipped to AS recycling plant (The breakeven point Grease cooking chamber 1 no. 3062.5a
Filter presses with 20 blades (62*62) 1 no. 17187.5a
about 6% and the time of return on investment about 0.26 (3.2
months)). The economical point of view, the indices values such as a
With 5% cost of installation.
value-added percent, annual revenue, breakeven point, value-added
were computed for the AS recycling process by Hassanpour [70]. The

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Table 18 Table 19
Requirements of blown bitumen production industry [12]. Requirements of plastic wastes recycling industry [2].

Main annual material and equipment Total annual Total cost $ Main annual material and equipment Total annual Total cost $
rates rates

Bitumen conveyor pump (17 atm) 2 no. 20000a Conveyor system 2.5 m 1 no. 1272.6a
Compressor or centrifuge (Capacity 2 no. 15150a Stainless steel washing chamber (2 m3) 1 no. 1908.9a
22 m3/min) Automatic dewatering machine (2 m3 Stainless 1 no. 3817.8a
Aeration tower (45 t, CS, thickness 1 no. 33000a steel)
5 mm) Drying machine equipped to flame and fan 1 no. 2757.3a
Kiln (2*2*3 m) 1 no. 3030a (1 m3 Stainless steel)
Flame (3 Hp) 7 no. 900a Device to produce the pellets (Twine, 100 kg/h) 1 no. 1230.6a
Storage tank (70 t) 4 no. 28000a Storage cone (Length= 2 m) 1 no. 222.6a
Condenser with capacity 85 m3/min 1 no. 210a Packaging machine (50 kg packs) 1 no. 2545.2a
(V=3 m3) Screening 1 no. 2227a
Bitumen 60/70 61600 t 6160000 Condenser 4 no. 882a
Raw oil or acidic sludge 5400 t Acidic sludge is Grinding machine equipped to washing 1 no. 5408.5a
free machine (500 kg/h-automatic 40 Hp)
Energy required for heating and 3240 GJ Burning by- PP or LDPE 1000 t 90909
melting of bitumen products NaCo3 (0.5g per kg wastes) 0.5 t 150
Boxes 35 kg 34300 no. 34300 50 kg packages 12600 no. 126000
Barrels 60000 no. 480000 Grinded pellets 400 t 400000
Blown bitumen 90/15 48000 t 12150000 Pellets (Very low density) 230 t 278787
Required electrical energy 642982.3 (KWH) 8037.83 Required electrical energy 538200 (KWH) 6727.96
Required water (12 m3/day) 3600 m3 248.2 Required water (6 m3 / day) 1800 m3 124.1
Water supply facilities 15625 Water supply facilities 15625
Split AC (Internal wiring, emergency 13125 Split AC (Internal wiring, transformers and 13125
power generators) emergency power generators)
Fire extinguishers (Total) 24 no. 1512 Fire extinguishers (Total) 54 no. 3402
Stoves (Total) 4 no. 170 Stoves (Total) 4 no. 120
Cooler (Total) 2 no. 1000 Cooler (Total) 2 no. 60
Ventilation system (Total) 7 no. 140 Ventilation system (Total) 7 no. 140
Office equipment, furniture and etc – 2500 Office equipment, furniture and etc – 2500
Lab equipment (for quality control) – 5000 Lab equipment, (for quality control) – 5000
Transportation (A vehicle weighing 4 t, 3 no. 40000 Transportation (A vehicle weighing 4 t, car and 3 no. 40000
car and fork) fork)
Staff salary 19 Persons 63333.33 Staff salary 9 Persons 30000
Required fuel (Stoves) 1080 L 162 Required fuel (Stoves) 1080 L 162
Petroleum expenses (Transportation 16200 L 3544 Petroleum expenses (Transportation vehicle 16200 L 3544
vehicle and cars) and cars)
Required land 2800 m2 35000 Required land 7600 m2 38000
Construction of infrastructure 805 m2 80500 Construction of infrastructure (Buildings) 2175 m2 217500
(Buildings) Pavement and asphalt 2771 m2 26844
Pavement and asphalt 1400 m2 13562.4 Landscaping 1000 m2 1000
Landscaping 1000 m2 1000
a
With 5% cost of installation.
a
With 5% cost of installation.
retained ownership or sale of products. Moosavi and Rajabi [71]
low breakeven point of about 14.7% and the time of return on reported that value-added will rise approximately equal to the average
investment around 1.05 (about 13 months) determined the fiscal annual growth rate of 18% for industries sector since 2009–2025 in
success of project. Further validation comes into view from the Iran.
Iranian industrial organization survey that presents low breakeven Van Kasteren and Nisworo [72] affirmed that biodiesel can be sold
point of about 22.5% and the time of return on investment around 0.9 at US$ 0.17/L (125000 t/year), US$ 0.24/L (80,000 t/year) and US$
(about 11 months) confirmed economic success of project for used 0.52/L for the smallest unit capacities (8000 t/year) with the existing
motor oil industries without AS recycling unit. Hassanpour [2,12] alkali, acid catalyzed and a supercritical trans-esterification technique.
reported the breakeven point about 2.46% and 15.93%, the time of Zhang et al. [73] declared that for three biodiesel plants with capacities
return on investment about 0.07 and 1.12 for blown bitumen and 100000 (1994), 7800 (1996) and 10560 (1999) tons/year the break-
plastic wastes recycling industry respectively. Tables 17–21 represent even prices in $/ton were 340,763, 420 respectively which utilized both
the results of studies. alkali- and acid-catalyzed techniques with waste cooking oil as the raw
The obtained values of value- added, value- added percent, profit, material. Cutler [65] revealed that decrease in oil quantities and energy
annual revenue, breakeven point, time of return on investment and return on investment has been raised the energy outlays of extraction
investment rate are putative and main economic indices. The time of of petroleum in the US. Energy return on investment comprises the
return on investment is the least time that will pursue the high profit as ratio of energy delivered to energy outlays. Greene et al. [74]
well as environment protection, business and SD involvements. The represented that a feebate rate of $ 500 per 0.01 gallon per mile
analysis of breakeven point identifies the relationship between outlays produces a 16% increase in fuel economy and 29% around $ 1000 so.
and revenues. Using this practice in current study thoroughly repre- Saving fuel for 3 years declines unit sales about 0.5%. But sales will
sents the time of return on investment. The breakeven point is shown follow increase, because the added value of implementation fuel
fixed and variable outlays of project at contrast with the running economy technologies outweighs the decrease in sales. Gonzalez et al.
revenues and prosecutes the lowest level of production which at this [75] disclosed the outlay of $ 0.49 L−1 of ethanol, cash cost of $
level profitability comes into view and the revenue of industries ample 0.46 L−1 and CAPEX of $ 1.03 L−1 of ethanol on the technical and
besets the fixed and variable outlays. In an industry is indispensable financial performance of high yield Eucalyptus biomass. The main
figuring the breakeven budget out to identify an expected market price outlays encompass the biomass, enzyme, tax, fuel, depreciation and
for products at some points in the future or to evaluate the choice of labors. Profitability of the process is very depend on biomass, carbohy-

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Table 20 Table 21
Economic indices [69,70]. Economic indices [2,12].

Economic indices of the used motor oil industry equipped to Cost $ Economic indices of plastic wastes recycling industry [12] Cost $
AS recycling unit
Data value
Data value
Grinded pellets 400000
Grease 703125 Pellets (Very low density) 278787
Bitumen 54/130 417656.3 Total value of annual selling of products 678787
Motor oil 4125000
Total value of annual selling of products 5245781.3 Output value
Additives, packages and required materials 217059
Output value Maintenance 14781.33
Additives, barrels and required materials 2240498.4 Energy consumption 10558
Maintenance 1624.075 Unforeseen costs of fixed capital 12937.42
Energy consumption 14814.1 Total cost 255335.75
Unforeseen costs of fixed capital 33049.43 Value-added 423451.25
Total cost 2289986 Value-added percent 62%
Value- added 2955795.3 Profit 366558
Value- added percent 56.34% Variable cost of commodity unit 389.65
Profit 2795396.8 Breakeven point 15.93%
Variable cost of commodity unit 535 Production cost 314494.4
Breakeven point (6%) 260.83 Annual revenue 364292.6
Production cost 2470258.36 Time of return on investment 1.12
Annual revenue 2775522.94 Economic indices of blown bitumen production industry [2] Cost $
Time of return on investment 0.26 (3.2 months)
Data value
Economic indices of recycling AS project of reprocessing industries to bitumen Blown bitumen 90/15 (new product 110/15) 12150000

Data value Output value


Value of annual selling of the product: Bitumen 417656.25 Additives, packages and required materials 6674300
The total production price 163248.9$ Maintenance 16887.2
Energy consumption 11992.03
Output value Unforeseen costs of fixed capital 44885.3
Additives and barrels 108843.75 Total cost 6748064.5
Maintenance 8214.77 Value- added 5401935.47
Energy consumption 7407.125 Value- added percent 44%
Unforeseen costs of fixed capital 8055.85 Profit 5308605.14
Value- added 285134.75 Variable cost of commodity unit 140.93
Value- added percent 68.2% Breakeven point (2.46%) 1183.67
Profit 249552.5 Production cost 6897748.4
Variable cost of commodity unit 141.8 Annual revenue 5252251.65
Breakeven point (14.7%) 131.4 Time of return on investment 0.07
Production cost 169285.7
Annual revenue 248370.5
Time of return on investment 1.05 (13 months) resources and partnership the weakness points in performance assess-
ment of three companies (Road Construction) by BE models. Amiri
Economic indices of used motor oil industry (Iranian industries organization, 2000)
Value- added 73941.8 [79] reported the both parameters of focus on customer and social
Value- added percent 36.3% results were strength points but process management, resources and
Breakeven point (14.7%) 22. 5% partnership the weakness points in an Hospital. Arjomandi et al. [80]
Production costs -
showed that implementation of policies and practices will guarantee
Annual revenue -
Return time on investment 0.9 (11 months) the quality in all aspects of its progress in universities using EFQM.
Tambi [81] suggested using KBEM to describing the values of indices
promoted and corresponding performance indicators as a practice to
drate percentage in biomass and enzyme cost. Haas [76] revealed that elevate quality and survey of higher education departments. Tutuncu
generation cost of soap-stock biodiesel is US$ 0.41/L and about 25% and Kucukusta [82] found relationship significant between EFQM and
less and biodiesel generated from soy oil. Song and lee [77], repre- organizational commitment of Meyer & Allen organization.
sented that based on studies on the costs of raw materials and the Leadership, partnerships and resources, policy and strategy, affective
potential market, the petroleum-based succinic acid process will be commitment, processes, results, people development and involvement
replaced by the fermentative succinic acid production system in future. and continuance commitment were the determinants of the organiza-
On the other hand, Table 22 shows the results of case studies tional commitment and EFQM respectively. On the other hand,
published by Hassanpour [2,11,12] in used motor oil and AS, blown Hassanpour [70] revealed that management of projects cost in
bitumen, plastic wastes industries using BE models. These models engineering projects such as road construction, hospital, used motor
allow multi – dimensional views on miscellaneous aspects of the oil, AS recycling industries have been based on a standard project
organization's internal, external and CSFs that include the required management body of knowledge in Iran and obtained results of
activities to get the industry objectives and key motors of performance. parametric models and cost estimates indicated that employers also
EFQM has been described on the assumption that BE is obtained assigned a management view-point on implementation of projects
through leadership driving policy and strategy that delivered through instead of control as well as a systematic view on the projects
people, partnership, resources and techniques. The models criteria, ingredients.
factors and obtained results indicated that aforementioned industries
were in SD involvements.
Jonidi and hassanpour [78] noticed that both parameters of
customer and community results were the strength points while the

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Table 22
Comparison of scores system for industries (used motor oil and acidic sludge, blown bitumen, plastic wastes respectively) [2,11,12].

KBEM EFQM

Criteria Score Criteria Score

Leadership 90.33, 90.33, 90.33 Leadership 90.55, 90.55, 91


Satisfy the citizen and customers 77.5, 77.5, 70 Policy and strategy 87.7, 87.7, 88
Satisfy the external customers 60, 60, 55 Employees 85.83, 85.83, 86
Satisfy the internal customers 60, 60, 60 Resources and partnership 90, 90, 90
Fact-based management 74.16, 74.16, 75 Process 81.66, 81.66, 82
Process or total work 80,83, 83 Customer results 78.33, 78.33, 80
Measurement 60, 60, 61 Employees results 73.88, 73.88, 73
Management relies on employees 70.41,70, 73 Community results 70, 70, 70
Team work 98, 98, 98 Key performance results 49.42, 49.42, 50
Employees make quality 70, 73, 73
Continuous improvement 70.4, 71.4, 72
Continuous improvement cycle 70.8, 74.8, 74
Prevention 80, 81, 82
BES 768.2, 802, 800.4 BES 806.77, 806.77, 809

4. Environmental development aspects from four recycling 4.1.2.2. Evaporative coolers. Evaporative coolers are designed to
industries condition the particulates before capture in another device such as
thermal oxidizers, incinerators, furnaces, calciners and kilns and boiler
4.1. Typical technologies for management of by-products and applications [83].
residuals
4.1.2.3. Fabric filter collectors. There are three basic dust collector
4.1.1. VOCs elimination technologies applications. Nuisance venting of conveyors, transfer points, packing
Many VOCs elimination technologies have been developed in some stations and so on this dust is often sent to waste. Next is product
studies. Table 23 presents many of the techniques. collection venting of classifiers, crushers, storage bins, air (pneumatic)
Membrane separation has developed into an important technology conveying systems, mills, and flash dryers. Last is process gas filtration
for separating VOCs from gas streams. It is the best suited for relatively venting of spray dryers, kilns, powder boilers, reactors and so on [83].
low-flow streams containing moderate VOC concentration [83]. The
removal of airborne contaminants and VOCs are an area of prominent 4.1.2.4. Fiber bed filters. This classification is specialized filtration
applications for photo-catalysis. The struggles to be encountered devices that primarily designed to coalesce and capture liquid
involve the treatment of relatively massive gas streams in devices with contaminants such as acid mists and aerosols the viscosity of which
low pressure-drops, good photo-catalyst irradiation and efficient is low enough that they flow or can be made to flow through of fiber bed
reactant species-photo-catalyst contacting. These designs were checked surface [83].
considering as performance qualifiers the levels of photo-conversion of
miscellaneous classifications of pollutants at different concentrations, 4.1.2.5. Packed towers. Packed towers are employed for control of
temperatures, relative humidity, pressures, space-times and irradiation soluble gases such as halide acids (such as HF and HCl), and to remove
times using the fluidized photo catalyst bed, annular packed bed, soluble organic compounds such as alcohols and aldehydes. Packed
photo-catalytic coated honeycomb monoliths, fixed powder layer, fiber towers are also used as gas coolers and condensers [83].
optic based, Photo-CREC air unit with venturi, flat plate fluidized bed,
fluidized bed photo-catalytic, fixed layer photo-catalytic, annular 4.1.2.6. Wet electrostatic precipitator. They are frequently utilized to
photo-catalytic, packed bed photo-catalytic, TiO2 coated monolith collect submicron particulate that arises from combustion, drying
photo-catalytic, photo-catalytic reactors with fiber optic bundles and operations, process chemical production, polishing devices, inlet low
Photo-CREC air with venturi [84–86]. loading of particulates and flows contain corrosive gases and similar
sources [83].
4.1.2. Dust, airborne particles and some pollutants control practices
Wet scrubbing, bag house, mechanically aided scrubbers, wet
electrostatic precipitator and dry cyclone collectors are designed to 4.1.3. Oily sludge management practices and some by-products
capture particulate dust or to increase the size of aerosols effectively The oily sludge generated has hazardous nature (Carcinogen). Oily
remove fine particles in the range from 0.1 µm to 20, 1, 10, 10 µm sludge includes various petroleum hydrocarbons, water, heavy metals,
respectively. Mechanically aided scrubbers are low cost, compact size and solid particles as hazardous waste materials [87]. Hu et al. [88]
and reliable devices which applied at low loading such as loading and asserted that some recovery and disposal practices could be employed
unloading facilities, fugitive dusts from storage facilities, wet coating to management and treatment of oily sludge such as, biodegradation,
operations, and etc [83]. oxidation, stabilization/solidification, incineration, froth floatation,
ultrasonic irradiation, electro-kinetic method, microwave irradiation,
4.1.2.1. Bio filters. Bio filters are often employed to control emissions pyrolysis, freeze / thaw, surfactant enhanced oil recovery, centrifuga-
of water-soluble or condensable hydrocarbons (such as alcohols), tion, and solvent extraction. Also, in the procedures launched via clay
phenols, aldehydes such as formaldehyde, odorous mercaptans, filter come out high quantities of cake filter. The filter cake discharged
organic acids, and similar compounds from filling operations and from the filter press can be utilized in drilling mud. It can also be
packing processes [83]. buried in landfill or treated. Asphalt residues and button residuals of all
distillation facilities can be profoundly utilized to produce different
kinds of bituminous or raw products for some industries and etc. The
obtained fuels of regenerative used motor oil technologies are used so

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Table 23
VOCs control technologies [83].

Device Inlet concentration PPMV Efficiency Advantages Disadvantages

Absorption 250 90% Especially good for inorganic acid gasses Limited applicability
1000 95%
5000 98%

Adsorption 200 50% Low capital investment, good for solvent Selective applicability, moisture and temperature
1000 90–95% recovery constraints
5000 98%

Condensation 500 50% good for product or solvent recovery Limited applicability
10,000 95%

Thermal incineration 20% 95% High destruction No organic can be recovered, capital intensive
100% 99% Wide applicability can recover heat energy

Catalytic incineration 50% 90% High destruction No organic can be recovered


100% Upper 95% Can be less expensive than thermal incineration Technical limitations that can poison
Flares Upper 98% High destruction No organic can be recovered, large emission only

that burning. The organic solvents applied in some procedures are the energy levels of gaseous particles are significantly motivated
recovered in the following recycling processes [89]. The char can either consequently are released the high density particles of electrons by
be additional processed onsite to discharge the energy content of the electrical discharge and lead to transformation, depletion and deforma-
carbon, or applied offsite in other thermal techniques. The residual tion processes. At atmospheric pressure and temperatures around 5000
output of char is employed as a fuel or as a feedstock for other K° products only are in the gaseous phase. At higher temperatures
petrochemical processes. Char generated is burned via a rotary drum upper than 10,000 K° ions only emerge under plasma state and at
incinerator or microwave techniques and etc [90]. Many of the higher temperatures (108) lead to the formation of a mixture of
products yielded by pyrolysis and gasification processes for PSW are electrons and naked nucleus [91,92]. Based on studies of America
well sold. The residual solids can be employed as carbon black or Aeronautics and Space Administration this state is called the fourth
activated carbon [53]. state of matter. All components of the galaxy have been made up by a
spinning cloud, when the temperature at the center of bulk arrived to
106 °C fusion reactions started and its radiations given off into space.
5. New technologies for management of by-products, wastes;
The sun as a main hot plasma source causes the upper layers of
redesign and reproduction
atmosphere are constantly bombarded by solar radiations [85]. The
solar interactions (solar wind) hit to earth's magnetosphere are
5.1. Plasma technology
captured or given off from the route. This phenomenon leads to a
shock wave that is accommodated by plasma. Therefore, origin of
In the classical view, materials can exist in any of the three states of
earth's magnetic field also refers to plasma. Plasma forces (natural
matter such as solid, liquid and gas. But in modern physics, a fourth
plasma) play a major role in the formation and destruction of celestial
state called the plasma state has been recognized. The mixture of gases
bodies like planets and stars, black holes and around 99% of cosmos
that existing ions are discharged in opposite directions from each
[92]. By the definitions, plasma technology may be of two types, natural
other, resulting in a zero net electrical discharge is called plasma state.
and manmade. Manmade plasmas are being produced in laboratories
On the other words, very reactive and ionized gas, discharging of
by raising the energy content of a material, and the energy in question
glaring light are other definitions from plasma state. Ionization process
can be any one of the following kinds - mechanical, thermal, chemical,
occurs when molecules of a gas are exposed to rays (radiation) energy,
radiation, rays, electrical, nucleus, energies, combination of them,
electrical currents or excessive thermal energy, during these processes

Table 24
Plasma technology and its classification [85,92].

Technology Classification Industrial scale

Non-Equilibrium (Cold plasma) Atmospheric pressure, non-equilibrium plasmas *Plasma unit for processing the ash of asbestos in France
DBD *Plasma unit for destroying the toxic wastes in Madison
Corona discharges *Plasma unit for processing the scrap cars in Japan
High-frequency plasmas *Plasma unit for processing the used tires in Jackson
Low-pressure, non-equilibrium plasmas *Plasma unit for removing the hazardous wastes and producing energy in the USA
Radio frequency electrical discharge
Electron cyclotron resonance plasmas
Helicon Plasmas
Direct current electricity discharges
Magnetically-confined plasmas
Low-frequency alternating current discharge
Low-pressure high-density plasmas
Micro Wave

Near-Equilibrium (Hot plasmas) Electric arcs


Ultra-high temperature plasmas-nuclear reactions
Modulated plasmas (Pulsed plasmas)
Plasma jets

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Table 25 extensive diversity of electrodes types, reactor geometry and nature of


Special applications of plasma [93,94,97–99]. the dielectric designed, which separates electrodes and the wall of the
reactor. This kind of discharge is a complex phenomenon which
Plasma applications
approximately contains high electron energy content. Employing this
-Recycling and converting wastes to energy kind of plasma promulgated for high value added compositions and
-Sterilization, disinfection and pasteurization of products; Electro-coagulation efficient and novel chemical processes or whenever there is no
-Cancer, diseases and injuries treatment; restoring skin and tissue; bio-ceramics;
appropriate practice or benign processing ambient demanded. These
ophthalmic materials
-Providing dielectric layers of semiconductors; hard coating discharges are often identified as partial discharges comprising DBD,
-Carbonization and production of environmentally friendly products (green corona discharges, constricted glows and etc which require complex
chemistry) and expensive vacuum batch-type chambers with low productivity
- Immobilization of enzymes, synthesis of DNA and proteins [92,102].
-Modification of fiber properties, ion implantation
-Developing and manufacturing sensors and chips, lamps, TV flat panels, magnetic
thin films 5.1.1.2. DBD. A non-thermal discharge generated by the application
-Covering transparent conductors; decorative coating and spraying operations and of a high voltage between two electrodes separated by a dielectric
chemical processing material is typically called DBD. The simplest type of emerging plasma
-Welding, melting/vaporization, etching, sputtering, mineralization, joining and
is the application of direct current discharge by employing radio
cutting metals and polymerization
-ICP-atomic emission spectroscopy, ICP-mass spectrometry, Laser induced plasma frequency for ignition. Usually, direct current discharge cannot be
spectroscopy sustained therefore alternating current is used for DBD applications.
Typically, DBD plasma torch is composed of an insulator tube (quartz),
electrodes, and a radio frequency power source. Employing DBD
assigns complex power suppliers with matching boxes [103]. It was
energies of thermal, mechanical (explosives) [85,92]. manifested that in a plane-parallel gap with insulated electrodes the
Plasma technology relatively is a new technology and can be very discharge takes place in many individual filamentary dissociation
efficient employed for the removal and recovery of hazardous waste channels. BD facilities have variety of electrode configurations and
materials (in solid, liquid and gas states) and decreasing the levels of are identified by one or more solid dielectric installed between the
pollutants, toxicity of materials and by-products [85,91]. Production of electrodes. In many experiences continuous flow- system, roll to roll
various organic and inorganic chemical material and durable, biode- frameworks have been applied involving mono or versatile-blade/
gradable, non-toxic or with very low toxic materials may soon become a cylinder (drum) electrode scales up. These kinds of frameworks, are
possibility in green chemistry [93,94]. Economic evaluation indicates running under atmospheric pressure air ambient utilized in variety of
that this technology can rightfully compete with other technologies, polymer film generation, processing industrial facilities, modification
regardless to its environmental and technical limitations. The capital (cleaning) of the surfaces of materials (e.g. polymers, semiconductors
cost of torch plasma could be in the vicinity of a dollar per watt. This etc) germicidal processes, pollution control, water treatment (direct) in
could make it very competitive with traditional thermal plasmas such industries and etc [104,105].
as arc plasma torches and RF induction plasmas [93,95,96]. Tables 24
and 25 introduce the plasma technology, its classification and parti- 5.1.1.3. Corona discharges. Corona discharge is always non-uniform,
cular applications as a zero pollutants technology. as the geometry of electrodes limits the gas ionizing process around the
The use of low-pressure plasmas for materials processing, pio- electrode. Type of corona discharge pertains on the geometry of the
neered by the semiconductor industry since the 1960 is a commercial electrodes, the type of gas, polarity of the active electrode and the
reality in technologies which procure extensive application of plastics voltage used. In a strong electric field, particles can arrive to sufficient
(automotive, aerospace, packaging, pharmaceutical, and other indus- kinetic energy to ionize gas molecules in an avalanche process, which
tries). Using plasma centrifugal furnace for the stabilization and can become to corona discharges, sparks, or to continuous arcs. The
decomposition of toxic and radioactive wastes as well as above-named corona will be fall when the strong electric field periphery a conductor
applications appear to meet the definition of green chemistry [93]. In is high sufficient to compose a conductive region, but not able to lead
this case, Sakaia and Hiraoka [100] noticed to existing four plants that electrical disruption or arcing. Otherwise, an electric spark will take
were running by individual plasma in Handa, Matsuyama, Mima, place, which is an abrupt electrical discharge. If the generator
Kamo also to eight other plants in Tokyo Ota, Omiya, Eastern Saitama continuously runs up the current, the spark will get back into a
and Tamagawa by electric arc in Japan. Also, reported that three continuous discharge is called arc [106,107]. The electric field
facilities of thermal plasmas for volume reduction from low-level segregates charged particles and impedes them from frequent
radioactive wastes are running by Atomic Energy Research Institute bounding, accelerating them to the opposite charge electrode to
in Japan. One is twin torch transferred arc system with the capacity of induce more electron and ion make up by collisions, making electron
4 t/day, and another is induction thermal plasma with induction avalanches. In corona discharges, ionization and electron joining (to
melting furnace. Wang et al. [101] disclosed that average decomposi- form negative ions) are initiated by electrons. Corona discharges can be
tion efficiency of the samples surveyed by thermal plasma furnace is either positive or negative, pertaining on the polarity of the existing
about 100% in toxic equivalent calculations. electrode (wire, pin and needle) and also run via use of low pressure
direct, alternating or high-frequency periodic currents. Corona state
5.1.1. A brief definition of the plasma reactors within conductor region are characterized by high removal efficiency,
low energy yields and low investment and operational costs compared
5.1.1.1. Atmospheric pressure, non-equilibrium plasmas. In contrast to other technologies, despite some disadvantages such as audible
with equilibrium plasma, the energy content of non-equilibrium noise, power loss, electromagnetic interference, insulation damage of
plasma is equally divided between all particles so they get a very high devices, purple glow and static electricity discharge with so many
level energy about tens of megawatts to 100 kW consequently, its applications composing production of ozone, sanitization of water,
temperature raises to about 4000–7000 °C. Therefore, limited removal of VOCs, scrubbing particles from air flows, air ionizers,
discharges with non-fixed characteristics (transitions between surface treatment of materials to change properties (adhesiveness,
different plasma models is unpredictable) are emerged in a wide hardness etc) [105,108].
range of temperatures and pressures. This state would take place in
the presence or absence of a liquid or solid insulation so it pertains on

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5.1.1.7. Direct current electricity discharges. It is a low-pressure-


inflamed discharge between two electrodes connected to a high-voltage
power source containing resistance from hundreds to thousands of
voltages. Its reactor encompasses pipes containing disc-shaped glass
cylinder with two electrodes upon plates [92]. Direct current power
supplies are applied for retrofit devices and often these devices are
employed together with direct plasma treatment devices to enhance
pollution gas treatment-hybrid implications [109].

5.1.1.8. Electric arcs, magnetically-confined plasmas and Low-


pressure high-density plasmas. Arcs are relatively realized through
of the small existing potential between the electrodes and high density
Fig. 7. Arc plasma for forming the high temperature plasma [109]. currents (The densities of charge in the natural plasmas exceed in an
interval from 106 cm−3 in the ionosphere of the earth to 1022 cm−3 in
5.1.1.4. High-frequency plasmas. If in reinforcement discharges lightning) in a space by high and low pressure, anode and cathode
(high-frequency plasma) insulation is applied to cover electrodes, low electrodes and insulating layers. The sparks are conducted via high
pressure – direct current (10−2 to 102 and electrode voltage 100– currents (1–100000 A) by discharge inflamed and usually low voltage
1000 V) is independently charged up to high potential or floating (20–30 V). Therefore, temperature rises upon the plates (cathode) to
charge (as a potential where the net stream of charge is zero) and fluxes thousands K° in the atmospheric pressure. The magnetic coil confines
of ions and electrodes, regardless to initial potential employed in the particles flux, increases the plasma density (Fig. 7 represents arc
electrodes become equivalent. As a result, at each reducer voltage the plasma) [93].
neutralization process for existing potential upon plates of dielectric
gets back to equilibrium amount. Radio frequency discharges are An arc reactor equipped to two electrodes procures a high current
characterized by the electrode-less reactors or superseded using density ( > 101 ° A/m−2 usually 1012 A/m) to initiate and sustain an
electromagnetic field expanded by the electrical induction coil and arc. A cathode spot emerges on the cathode electrode results the high
contain local power density lower than that of a direct current plasma current density (104–108Am−2) locally, the current is focused over a
comprising low plasma loss and better ion generation efficiency, location roughly 1–10 µm diameter. Very high degrees of ionization are
simplicity of the concept, no requirements for direct current emerged where more cathode spots are exhibited consequently dense
magnetic fields, higher sputter-contamination, UV-damage and plasma is procured and then proceeds away from the cathode via an
heating of neutrals at the substrate. Multipole magnets can be used explosive emission process and is beckoned to the negatively biased
to increase radial plasma uniformity. The planar coil can also be moved substrates; this maintains a self-sustaining discharge. Advantages of
close to the wafer surface, resulting in near-planar source geometry, using arc plasmas including, high processing rates, high fluxes of
having good uniformity properties, even in the absence of multipole radical species, the potential for smaller installations, wide choice of
confinement. Radio frequency discharges are usually run in slightly reactants, high chemical reactivity and high quench rates. Erosion of
high pressure ambient so they are called glow discharges. Gliding the electrodes, arc flash, consumes quite lot electricity and noise can be
discharges are useful in many industrial applications, coating, painting, some drawbacks. Plasma arc with temperatures up to 6000–10,000 °C
dying, etc, plasma based surface treatments. Main advantages of them is used for waste treatment to convert them to gases and vitrified gases
can be noticed to near atmospheric pressure, energy of the electrons is [110,111]. Thermal arc discharge plasma can be exploited for an
much higher than that of the heavy species, simplicity of the power extensive range of applications, regarding industrial scale applications
supply system, intermediate system between thermal and non-thermal such as welding and cutting in metallurgy industry, spraying for
discharges, environmentally much cleaner than mechanical and wet provision of hard coatings composing high resistance properties,
chemical processes, fast processing and low cost [92,102]. production of catalytic materials, breakdown of hazardous waste,
plasma pyrolysis of organic components, generating synthetic gas,
5.1.1.5. Low-pressure, non-equilibrium, Radio frequency electrical design of mineral fiber, sterilization, waste treatment. The best usage of
discharge and electron cyclotron resonance plasmas. The low- plasma arc and torch from environmental outlook is plasma gasifica-
pressure, non-equilibrium plasmas are conducted and sustained tion/pyrolysis procuring synthetic gas (syngas; CO+H2).
using radio frequency, microwave and direct current power in a gas
ambient with or without an electric or magnetic field. All discharges 5.1.1.9. Ultra-high temperature plasmas-nuclear reactions. Ultra-
traverse through of the electron collision processes, impressed by high temperature plasmas-nuclear reactions reactor is run through of
electromagnetic activities or pure electrical current. Also, in this case the fission and fusion reactions by joining and incorporating light
electron cyclotron resonance can be used for creating accelerated atoms into heavier atoms and vice versa [112]. Using quarts pipes,
electrons [98]. magnet coils and etc the temperature is thoroughly handled. Also, in
this case the electron cyclotron resonance can be used for creating
5.1.1.6. Helicon plasmas. Many low-pressure plasma sources, such as accelerated electrons to start and run reactor [113].
direct current, radio frequency glow discharge, and electron cyclotron
resonance plasma sources are run at low-pressure [98]. There are two 5.1.1.10. Modulated plasmas (Pulsed plasmas), low-frequency
main sources for high-density radio frequency plasmas such as alternating current discharge. Plasma pulse (modulated plasma) is
resonant helical and helicon sources. In the case of resonant reactors created using a radio frequency carrier in a long period with low
of helicon, plasma is motivated through short-wave structure while the frequency which is switched on or off. When the power is off the
source of helical comprises a magnetic field with a wave imposed by a electron energy falls and on the contrary, the electron energy can spike,
cyclic model (like collar) around plasma. Incorporation of both consequently rising dissociation and ionization. Also, it contains
magnetic fields and radio frequency limit the radial electrons various voltages or normal currents with a constant flux [108]. But,
movements [92]. low-frequency alternating current discharge is conducted from a high

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Table 26
Bond energies and enthalpies of formation of free radicals [92,125].

Bond energies Enthalpies of formation of free radicals

Species Energy (eV) Species Energy (KJ/ Energy (eV)


mol)

Diatomic molecules
C-H 3.3 °CH° 596.3 6.1
C-N 7.8 CH2: 430.1 4.4
C-Cl 4.0 CH3° 146.0 1.5
C-F 5.7 HC˭C° 566.1 5.8
C˭O 11.2 HC˭CH2° 300.0 3.1
C-C 6.3 NH: 350.0 3.6

Polyatomic molecules
C˭C 7.6 NH2° 185.4 1.9
C≡C 10.0 :Si: 456.6 4.7 Fig. 8. Schematic diagram of the Plasmatron [125].
CH3-H 4.5 °SiCl0 195.0 2.0
C2H5-H 4.3 SiCl2: −163.0 −1.7 and etc) of diamond, heating, melting metals, precipitation and coating
CH2-CH-H 4.8 SiCl30 −318.0 −3.3 [102,118]. Based on the results of the various tests carried out, plasma
CHC-H 5.7 C6H50 328.9 3.4
C6F50 −547.7 −5.0
jet has been reported to be successful in the disposal of glass and
ceramic, municipal wastes, agricultural residue, coal, heavy metals, fly
Steam reforming for producing fuel Thermal decomposition required energy ash, radioactive wastes, industrial wastes, kiln dust, organic wastes,
cell required energy (KJ/mol) (KJ/mol) used tires, plastics, medical and biomedical wastes, chemical wastes,
C 167 – –
asbestos fibers and products containing persistent organic pollutants
CH4 230 – –
CH4O 114 CH4 62 and poly chlorinated biphenyls [119,120]. Thermal plasma is being
C2H2 99 C2H2 −235 utilized in the reformation of natural gas, hydrogen production, fuel
C2H4 269 C2H4 −65 cells and hydrogen-rich gases using gasification of industrial synthetics
C2H6 400 C2H6 66 oils and blends of oils, used lubricants and other fuels [121]. Other
C3H4 303 C3H4 −198
C3H6 462 C3H6 −39
mentionable uses of plasma jets are the production of waste-derived
C3H8 581 C3H8 80 fuels and alterations in the state of matter. Many of hazardous wastes,
C6H6 932 C6H6 −70 hydrocarbon-rich sludge can be recycled by jet plasma to give
C7H16 1343 C7H16 179 expensive and valuable materials such as diamond and graphite and
C8H16 1250 C8H16 −86
similar materials. Diamond-like carbon is a hard film which is made
from carbon composites and has physical properties like diamond. It
voltage transformer at frequencies under 100 Hz continuously [112]. also reveals very high abrasion resistance and a low coefficient friction
as well as it is kind of products associated to plasma jet technology.
Diamond powder is employed as suspensions in organic liquids
[98,122,123].
5.1.1.11. Micro wave. Three types of micro wave plasma reactors have
been recognized such as closed, open and resonance structures with a
magnetic field. These plasmas are sustained by micro wave energy In CVD process, instead of using the high pressure, diamond are
introduced into the reactor by coaxial cables or waveguides in the case produced by allowing the atoms to join together to form diamond
of higher powers regarding to its frequency. This type of discharges are [124]. The transfer rate depends on the pressure inside the chamber of
more difficult to maintain under low-pressure ambient [92]. deposition. The required pressure and temperature of this process is
1.35 m and 700–720 °C respectively. Also, in this practice a variety of
techniques and materials are used, as a source of carbon, hydrogen and
Fridman et al. [114] utilized pulsed corona plasma for removal of
activator. The required energy is supplied from heating elements,
VOCs from gas emissions of paper industry. By the way, high removal
flame, and microwave radiation. In order to start the reaction, mixture
efficiencies were achieved for VOCs by average power up to 20 W and
from both of the gases methane and hydrogen to ratio of 1–2% and 98–
6.4 kW for pilot plant. It also utilized to improve indoor air quality, air
99% are continuously introduced into the reactor respectively. Using
cooling and de-odorising via production of free radicals, elimination of
plasma reactor equipped to anode and cathode plates (electrical
black smoke, fuel odor, dust and TVOCs in industries such as
current; the ionization energies of many atoms and molecules comprise
petrochemical, steel, textile and etc. Sterilization efficiency for indoor
in the range between 10 and 20 eV [93] according to Table 26) is
pollutants has been estimated about 99.9%, 180 and 200 times faster
produced radicals of hydrogen in order to create active radicals of
than ultraviolet sterilization and ozone, 157% more powerful than
methyl and also develop the C–C bonds in core surface as well as
peroxide via producing free radicals respectively. It is a prominent
prevention of forming graphite layers. Table 26 shows bond energies
technique to eliminate TVOCs, CFCs, dioxins, furans, PAHs, poly
and enthalpies of formation of free radicals.
chlorinated biphenyls and NO, H2S, NOx, NH3, other solvents and
Kado et al. [104] revealed that direct dehydrogenation of methane
gases [98, 115, 116]. Hartz et al. [117] declared that destruction and
to generate more suitable chemicals was conducted using low tem-
removal efficiency of up to 99.6% for C2F6 was achieved using
perature plasmas such as spark discharge, DBD and corona. Results
microwave powers applied from 500 to 2000 W in surface wave
had shown that energy efficiency in spark discharge was much upper
plasmas as an innovative technology.
than that in DBD and corona discharge, methane highly dissociated to
atomic carbon and hydrogen in spark discharge. To form a thin layer of
5.1.1.12. Plasma jet or torch and its industrial and commercial
diamond by radicals of methyl on surface of core the reactor tempera-
applications. One of the most important kinds of hot plasma is the
ture must be handled. The results of researches have been reported the
plasma jet. There are several industrial applications of plasma jet
growth rate from 0.1 to 10 µm per hour using a heating element and if
reactors, including synthesis (such as SiC, Si3N4, AlN, acetylene gas
the flame be used as the source of energy the growth rate will grow

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quickly up to 100 µm per hour, but will not be good quality. Using per day it would be a prominent achievement that a very high amounts
microwave source the required energy and temperatures can be (90–100%) of industrial hazardous waste had become to an extremely
supplied as well as appropriate speed of growth the diamond layer. valuable additive or products as well as economic benefits, creating job
The growth process is performed at high temperatures so the melting opportunities, business and promoting the business excellence. The
point of the core used should be higher than the temperature of reactor. used motor oil, plastic wastes, blown bitumen and AS recycling
Commonly silicon, molybdenum and tungsten used as the core. Source industries undoubtedly are a boost to the economy, in the prevailing
of atoms and molecules can be gaseous, liquid or solid like AS. We can financial times. Plasma technology has abundant potential in pursuing
point out to this type of process as alterations in the state of matter a green world via impede culminating greenhouse gases emission from
from one form to another by plasma technology [126]. Bromberg et al. large and small scale industries and wastes can be retrieved into syngas
[125] revealed that Plasmatron reactor is employed for reforming and which is potentially able to supersede natural gas for industrial and
altering heavier hydrocarbons including bio-fuels and used motor oils energy exploitation as well as producing valuable products. Although,
can comprise some advantages such as compactness and low weight there is so much difficulty to its implementation because of complexity
(due to high power density), high conversion efficiencies, minimal of sciences, scarcity of sufficient information and facilities in develop-
outlays (simple metallic or carbon electrodes and power supplies), ing nations. However, employing new technologies can lead us towards
quick response period and variations in operation with a wide range of SD in all levels of recycling industries.
fuels. Fig. 8 presents a diagram of the Plasmatron.
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