Resources, Conservation and Recycling 25 (1999) 85–109

Review
A review of plastics waste recycling and the
flotation of plastics

Huiting Shent a, R.J. Pugh b,*, E. Forssberg c

a
Changsha Research Institute of Mining and Metallurgy, Changsha, 410012, China
b
Institute for Surface Chemistry, Box 5607, SE-11486 Stockholm, Sweden
c
Department of Chemical and Metallurgical Engineering, Di6ision of Mineral Processing,
Luleå Uni6ersity of Technology, S-97187 Luleå, Sweden

Accepted 28 April 1998

Abstract

This paper summarizes the importance of plastic waste recycling and plastic waste
separation. Based on an analysis of the physical and chemical characteristics of plastics and
plastic waste, the potentials and limitations of several technological processes are discussed.
In addition, a review of the surface chemical aspects of plastic flotation is presented. It can
be concluded that the flotation of plastics is a fairly flexible technique and could prove to be
a useful process for the separation of mixtures of several different types of plastics. However,
more research and development effort is required before this technology can be introduced
to industry. © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Flotation of plastics; Waste recycling; Waste separation

1. Introduction

More and more plastics wastes are generated by industry and householders.
Statistics shows that plastics waste in municipal solid waste (MSW) in the USA

* Corresponding author. Tel.: + 46 8 7909900; fax: + 46 8 208998; e-mail: bob.pugh@surfchem.kth.se

0921-3449/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII S0921-3449(98)00017-2
 86

Table 1
Composition of total solid waste stream by individual country (percentage by weight) (from [3])

Substances Netherlandsa Swedenb Switzerlandc UKd West Germanye USSRf Chinag Japanh Indiai Egyptj USAk

Glass 7 7 8 15 12 7 1 — 1 2 8
Nonferrous metals 3 — 1 — 4 — — — — — —

Metals — 3 5 7 — 4 1 5 — — 9
Ferrous and nonferrous metals — — — — — — — — 1 4

Organics 53 30 29 23 42 38 45 16 36 70 26
Paper, cardboard 24 40 32 34 20 22 5 37 3 10 41
Plastics 6 9 13 4 4 6 1 15 — 1 6
Textiles 2 — 3 4 4 3 — 4 4 2
Wood 1 1 — — — 2 — — — — —

Wood leather, rubber linoleum, textiles 1 3 3 — 2 2 1 3 — — 8

Fine waste and minerals — — l 7 11 — — 6

Miscellaneous inorganics (e.g. ash, dirt) — — — — — — 46 — 50 10 2

Others 3 7 5 6 1 16 — 14 5 1
Total 100 100 100 100 100 100 100 100 100 100 100

a
Luca Bonomo and A.E. Higginson, International Overview on Solid Waste Management, 1988. p. 161.
b
Solid Waste Management in Sweden, The Swedish Association of Public Cleansing and Solid Waste Management, February 1988, p. 6.
c
1983; Personal communication with Mr. Oggier, BUS (Federal EPA), Bern, Switzerland, 8/13/87.
d
1980, Luca Bonomo and A.E. Higginson, International Overview on Solid Waste Management, 1988, p. 232.
e
1979/1980; Luca Bonomo and A.E. Higginson, International Overview on Solid Waste Management, 1988, p. 67.
f
Minsk, USSR, 1986, Robert E. Blattert, To Russia, with sludge: Americans see Soviet waste, World Wastes, September 1980, p. 58.
g
Beijing: Susan Hillenbrand, One billion people can’t be wrong, Waste Age, October 1986, p. 97.
H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

h
Osaka, Japan, 1980; Luca Bonomo and A.E. Higginson, International Overview on Solid Waste Management, 1988, p. 138.
i
Calcutta, India; D.B. Cook and J.M. Kalbermatten, Prospects for resource recovery from urban solid wastes in developing countries, World Bank, Washington, DC, 1982.
j
Cairo, Egypt; D.B. Cook and J.M. Kalbermatten, Prospects for resource recovery from urban solid wastes in developing countries, World Bank, Washington, DC, 1982.
k
Franklin and Associates, Characteristics of MSW in the USA, 1960-2000, 3/30/88. Source: From Ref. 37, p. 80. Reproduced courtesy of Waste Age Magazine.
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 87

reached 13.2 million metric tons in 1988 and it comprised 8% of MSW by weight
(21% by volume) [1,2]. In fact, plastics waste has become one of the larger
categories in MSW, particularly in industrialized countries, as shown in Table 1 [3].
The growth of plastics waste has a great impact on the management of MSW by
landfilling and incineration, because available capacity for landfill of MSW is
declining and plastics incineration may cause emission and toxic fly and bottom ash
which contain lead and cadmium [4].
One alternative way to plastics waste disposal is recycling. Plastics waste recy-
cling is a method of reducing the quantity of net discards of MSW. Although the
benefits have not been quantified, plastics recycling also offers the potential to
generate demonstrable savings in fossil fuel consumption, both because the recycled
plastics can supplement and even compete with ‘virgin’ resins produced from
refined fossil fuel and because the energy required to yield recycled plastics may be
less than that consumed in the production of the same resins from virgin feedstocks
[4]. Therefore plastics waste recycling conserves both material and energy and
provides a comparatively simple way to make a substantial reduction in the overall
volume of MSW.
Although plastics recycling is important, the estimates made in the late 90’s, as
shown in Table 2 [3], indicate that only a small percentage of postconsumer plastics
waste is recycled around the world. For this reason, attention is being focused on
the development of recycling technologies, for example, in the USA, Germany and
Japan.
Recycling plastics encompasses four phases of activity, namely collection, separa-
tion, processing/manufacturing and marketing. Because only using clean, homoge-
neous resins can produce the highest-quality recycled plastic products in the existing
secondary process (material recycling) and high-value chemical products in the
existing tertiary process (feedstock recycling) [4], an effective separation of mixed
plastics waste is necessary. Although several separation technologies, including
automatic sorting, gravity separation and electrostatic separation, can be applied to
separate mixed plastics waste, they have their limitations (see Sections 2 and 3).
Froth flotation is a major and efficient separation method in mineral processing
engineering and could prove useful for mixed plastics separation [5].

Table 2
Percentage of plastics waste recycled (from [3])

USA 2% (1989)
France B1% (1988)
Germany 1–2% (1988)
Italy B0.5% (1990)
UK 1–2% (1988)
Canada 1% (1990)
88 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

Table 3
The US sales of plastics by resin (from [4]) (Million pounds, 1988)

Resin Sales As % of total

sales

Thermoplastic resins
Low-density polyethylene (LDPE) 9865 17.3
Polyvinyl chloride and copolymers (PVC) 8323 14.6
High-density polyethylene (HOPE) 8244 14.5
Polypropylene (PP) 7304 12.B
Polystyrene (PS) 5131 9.0
Thermoplastic polyester (incl. Polyethylene terephthalate (PET) and 2007 3.5
polybutylene terephthalate (PBT))
Acrylonitrile/butadiene/styrene (ABS) 1238 2.2
Other styrenics (a) 1220 2.1
Other vinyl’s (b) 958 1.7
Nylon 558 1.0
Acrylics 697 1.2
Thermoplastic elastomers 495 0.9
Polycarbonate 430 0.8
Polyphenylene-based alloys (c) 180 0.3
Styrene/acrylonilrile (SAN) 137 0.2
Polyacetal 128 0.2
Cellulosics 90 0.2
Total-thermoplastic 47 005 82.6
Thermosetting resins
Phenolic 3032 5.3
Polyurethane 2905 5. t
Urea and melamine 1515 2.7
Polyester, unsaturated 1373 2.4
Epoxy 470 0.8
Alkyd 320 0.6
Total-thermosetting 9615 16.9
Others (d) 288 0.5
Total 56 908 100.0

2. Plastics waste

In order to evaluate the potential of plastics flotation in mixed plastics separation

and develop more practical technologies, it is necessary to examine the characteris-
tics of mixed plastics waste and the physical and chemical properties of plastics.
These include the consumption of plastics, the origin and composition of plastics
waste stream, the physical and chemical properties of plastics and plastic composi-
tion and polymer composition.
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 89

2.1. The consumption of plastics

Table 3 [4] shows the trend in consumption of plastics in spite of the difference
in the consumption of plastics in different countries. Polymers are categorized as
thermoplastics or thermoses plastics. Of these two categories, the former can be
melted and reformed — a characteristic that is important in recycling plastic prod-
ucts [4,6]. As shown in Table 3 (a) industry and householders consume many types
of plastics. This means plastics waste is made up of many different types of plastics
because it is difficult and frequently impossible to collect plastics waste by resin
respectively (b) thermoplastics compose 82.6% of total plastics. This major fraction
of total plastics is significant for material recycling and (c) in material recycling, an
average 16.9% of thermoses plastics has to be removed from thermoplastics.
2.2. The origin and composition of plastics waste stream

The major end-use markets for plastics may become the origin of plastics waste
stream. Fig. 1 shows the end-use markets and the resins consumed [4]. From Fig.
1, we can see (a) the largest market for plastics is packaging at 33.5%. In this sector,
a major source of plastic waste is the ‘curbside mix’ generated by residential
households. PET constitutes a significant fraction of the curbside mix and repre-
sents an important recycling opportunity. PVC often composes a small fraction
(about 3% by weight) of the curbside mix but it has to be removed from PET. The
separation of PVC bottles from PET bottles is often conducted by automatic
sorting [7], but typically plastic household wastes are chopped or ground to
facilitate handling, processing, or transportation so that contaminants to be sepa-
rated exist as flakes within the recoverable bulk plastic [8]. Separating this mix by
automatic sorting is difficult (b) plastic wastes generated by the other sectors may
be in the form of shredded scraps, e.g. plastic scraps from scrapped automobiles,
waste electric and electronic equipment, cable and plastic processing plants. These
plastic wastes are also difficult to separate by automatic sorting and (c) even from
a single sector, plastic wastes are made up of many types of resins.

3. The physical and chemical properties of plastics

3.1. Physical properties

The physical separation of mixed plastics depends closely on the physical

properties of the plastics being separated. There are two categories of physical
properties, namely fixed physical properties, such as bulk density and physical
properties which can be modified, such as surface energy, particle size, shape,
surface roughness etc. Fig. 2 [9] lists the density of some plastics. It is shown in the
list that some plastics, e.g. PVC and PP, can be separated by applying gravity
separation (including heavy medium separation) [10,11], but it is difficult or even
impossible to separate plastics (e.g. PVC and PET)with too slight density difference
by this method.
90 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

Fig. 3 [9,32] shows the triboelectric charging series of the plastics. In principle all
listed plastics can be separated from each other by electrostatic separation. How-
ever, in practice, the technique has its limitations because (a) different additives in
the same type of plastic cause the position in the charging series to shift. This may
decrease the difference in charging property and therefore the separation efficiency
(b) contamination can work out adversely, but it is inevitable that plastic wastes are
frequently polluted in practice (c) the binary mixture may be suitable to electro-
static separation, but mixed plastics containing more than two types of plastics may
cause a decrease in separation efficiency [9] and (d) like in gravity separation it is
difficult to separate the plastics with too slight difference in triboelectric charging
property by electrostatic separation.
The wettability of plastics can be characterized by the measurement of contact
angles with water. In addition to the difference in the intrinsic wettability of
plastics, as shown in Table 4 [12], it is possible to change the wettability of different

Fig. 1. Plastic resins in the market categories (redrawn from [4]).

 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 91

Fig. 2. Density of plastics (from [9]).

plastics by various conditioning methods (see Section 4) and hence to achieve

selective flotation. Therefore plastics potation separation is fairly flexible and could
prove useful for separating mixtures of plastics.

3.2. The chemical properties of plastics

The most notable difference between minerals and plastics which is relevant to
flotation is in that mineral surfaces consist of high surface energy inorganic
compounds, whereas plastics surfaces are made up of low energy organic com-
pounds. Table 5 [13,14] lists the formula of some large consumpable plastics (see
Table 3). From this list, it can be seen that (a) some polymers contain no polar
groups, e.g. PE, PP and PS, whereas others contain some polar lateral groups which
contain electronegative atoms such as oxygen, nitrogen or chlorine (b) apolar
groups in the polymers are different. Some are aliphatic and others are aromatic
and (c) some plastics contains mixtures of polymers.

Fig. 3. Triboelectric charging sequence (from [9]).

92 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

Table 4
Surface tension (gS/G) and contact angle with water (redrawn from [12])

Polymer gS/G (mN/m) Contact angle with water (°)

GRPP 32.7 96.3

PS 43.0 86.3
ABS 42.7 83.7
PC 44.5 80.3
PA6 43.8 61.4
PMMA 43.8 72.9
PVC 42.3 84.6
POM 44.9 71.2

The composition of plastics largely results from the plastic processing or manu-
facturing procedures. Plastics are not pure polymers. They consist of polymers and
additives. Selective surface modification of plastics by conditioning (see Section 4)
is intrinsically related to the composition of plastics and the chemical and physical
properties of their polymers. However, this relation has not yet been understood
completely.

4. Plastics flotation

Flotation is undoubtedly the most important and versatile mineral-processing

technique and both use and application are being expanded to treat greater tonages
and to cover new areas [15]. Compared with mineral flotation originally patented in
1877 [31], plastics flotation is just in its infancy. Plastic flotation research began in
the 1970s but there are few full scale applications of this technique in industry at
present. However, more and more attention is now being focused on this subject
[13]. This section provides a technological review of the principles and the develop-
ment of plastics flotation.

4.1. The principles of plastics flotation

Plastics flotation utilizes the difference in surface properties of different plastics.

There are four main methods available in the literature, namely (a) carrying out
flotation in a liquid medium (may be aqueous mixture or non aqueous) with a
specific value of surface tension (b) selective wetting of the plastics surface by
chemical conditioning such as adsorption of chemicals (i.e. wetting agents or
polymers) (c) selective wetting by physical conditioning and (d) selective hydropho-
bic modification to the plastics surface by chemical conditioning.

4.1.1. Utilizing a liquid medium with a specific 6alue of gL/G

As shown in Table 4, the surface tensions of plastics are lower than that of water.
Plastics are hydrophobic by nature and exhibit differences in surface energy.
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 93

Gamma flotation permits the flotation separation of solids to be achieved providing

the critical-surface-tension-of-wetting values for different solids are different. The
critical surface tension of wetting for a solid (gc) is defined as the surface tension of
the liquid at which the solid surface exhibits a hydrophobic to hydrophilic transi-
tion. Values given by Shibata et al. [16] are for PVC =40.2 mN/m, PC =33 mN/m,
PPE = 30 mN/m and POM= 26 mN/m. If a sufficient difference exists between the
critical surface tensions of two plastics, selective wetting can be achieved by
reducing the liquid surface tension gL/G. At appropriate values of gL/G, air bubbles

Table 5
Structural formula of some plastics
94 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

Fig. 4. A comparison of critical surface tension of wetting for two inherently hydrophobic solids (from
[17]).

will adhere onto particles with the lower gc value, promoting flotation, whereas
particles having the higher gc value will be wetted sufficiently as to suppress bubble
attachment during this process.
This is demonstrated in Fig. 4 and Fig. 5 [17] which show a comparison of gc for
two different plastics and the theoretical flotation recovery versus surface tension

Fig. 5. A theoretical plot conceptualizing separation by Gamma flotation (from [17]).

 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 95

regions. Buchan and Yarar [2,17] applied Gamma flotation to separating PET and
PVC. PVC is maintained hydrophobic, while PET becomes wetted after reducing
the liquid surface tension to appropriate values.

4.1.2. Selecti6e wetting by chemical conditioning (adsorption of wetting agents)

Most often plastic mixtures show insufficient differences in their interfacial
energies to enable separation by gamma flotation [5,12]. In such cases, selective
modification of the hydrophobic surface is necessary. One method of selective
wetting is by chemical conditioning. It is a process in which the adsorption of the
reagents on the plastic surfaces leads to a decrease in hydrophobicity of the
solid-liquid interface In the selective wetting process, the wettability of different
types of plastics is enhanced selectively.
Although numerous research projects have been initiated on plastics flotation
during the past two decades, fundamental studies published on this subject are
scarce [12]. Recently, there have been several papers published discussing the
mechanisms of selective wetting by chemical conditioning. Based on the analysis of
the composition and structure of polymers, Stuckrad et al. [5] discussed the
interaction between the molecules of the plastic surface and the depressant
molecules and suggested the following mechanisms:
1. The predominant number of the lateral groups of the polymer chains of the
plastics consists of non-polar carbon hydrogens. That is the reason for the
mainly physical interactions between the molecules of the plastic surface and the
depressant molecules. The interaction force include the dispersive van-der-Waals
force as well as hydrogen bondings.
2. Some polymers contain polar lateral groups with oxygen, nitrogen, chlorine or
other atoms. Such lateral groups enable dipole–dipole van-der-Waals interac-
tion as well as Lewis-acid-base interactions with the dipoles of the depressant
molecules.
3. Chemical bonding between the polymers of the plastic surface and the depres-
sant molecules are very rare, because plastics have low surface energies and are
nearly chemically inert under the environment of a flotation process.
4. Electrostatic interactions occur seldom because of the absence of a minimum
amount of free charge carriers.
The suggested adsorption model is shown in Fig. 6.
Fraunholcz et al. [18] studied the mechanisms of the adsorption of depressants on
plastics and suggested the following mechanisms:
1. The adsorption of depressants on plastics is mainly driven by physisorption.
2. The interaction forces include hydrophobic interactions and electrostatic forces.
Hydrogen bonding is not involved in the adsorption on plastics.
3. Zeta-potential measurements indicate a non-selective adsorption of surfactants
on most types of plastics, although selective bubble attachment to different
plastics occurs during flotation.
4. The intrinsic surface polarity of plastics appears to play an important role for
the resulting overall effect of depressants.
 96

Table 6
Results of batch separation test (%) (redrawn from [24])

Batch test Sample Floated material Residual matter

Plastics Content (%) Plastics Content (%) Recovery (%) Plastics Content (%) Recovery (%)

1 PS 50 PS — 98.4 — — —
PVC 50 — — — PVC 96.5 98.4
2 PP 50 PP — 98.8 — — —
PVC 50 — — — PVC 97.8 98.8
3 PMMA 50 PMMA — 98.8 — — —
PVC 50 — — — PVC 97.3 98.9
4 PE 50 PE — 98.8 — — —
PVC 50 — — — PVC 97.3 98.9
5 Nylon 50 Nylon — 98.5 — — —
PVC 50 — — — PVC 98.5 98.5
6 PS+PP 34+33 PS+PP — 98.7 — — —
PVC 33 — — — PVC 97.4 97.4
7 PS+PP+PE 20+20+20+20 PS+PP+PE — 98.9 — — —
+ Nylon +Nylon
PVC 20 — — — PVC 95.9 95.9
8 PP 47 PP 97.0 98.9 — — —
PS 53 — — — PS 99.0 97.4
9 PP 50 PP 98.8 97.3 — — —
H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

PE 50 — — — PE 97.3 98.9
10 PET 50 PET 100.0 97.0 — — —
Cellulose triac- 50 — — — Cellulose triac- 99.8 93.8
etate etate
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 97

Fig. 6. Adsorption mechanism of surface-active reagents at the surface of non-polar polymers (from [5]).

5. The cations have a profound influence on the adsorption of polyelectrolytes,

mainly because they reduce the repulsion between the charged segments of
polyelectrolytes (the so-called screening effect), which facilitates adsorption.
They also modify the segment-surface electrostatic interactions.
Le Guern etc. [19] examined the adsorption of lignosulfonate (LG) on PET and
PVC. The XPS analysis results show that co-adsorption of LG and calcium on PET
and PVC occurred and a larger quantity of LG seemed to adsorb on PET
producing a coverage of 16%. For PVC the cover ratio was about half this value.
The author attributed the mechanism of adsorption mainly to electrostatic interac-
tion since LG is an anionic reagent. Both PVC and PET are also negatively
charged, even in a solution containing calcium. Calcium, with its two positive
charges, might act as a bridge between the reagent and surface of the plastics.
As mentioned above, different authors suggested different or even inconsistent
mechanisms for the adsorption of reagents on plastics. Furthermore, the relation-
ship of selective wetting of plastics by chemical conditioning to the composition of
plastics and the chemical and physical properties of their polymers has not yet been
understood completely.

4.1.3. Selecti6e wetting by physical conditioning

An alternative way to increase the wettability of the plastic surface is physical
conditioning by which hydrophilic functionality’s, such as O, –OH, –COOH, etc.,
are grafted into the polymer chains located on the surface. This can be achieved, for
example, by means of a plasma treatment. Other surface treatments utilize corona
discharge, wet oxidative chemical reactions and photografting methods.
Stuckrad et al. [5] described a plasma treatment technique. In the plasma
treatment process, the very high energy density of the plasma components allows
the generation of true chemical bonds between plasma components and the plastic
surface. In order to increase the wettability of plastic surface, a suitable processing
gas must be present to produce high energetic polar atoms or groups into the
polymeric structure of the plastic surface. One example of such a processing gas is
oxygen. The reaction is complicated but can be simplified and described as follows:
98 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

This modification due to a plasma-activation usually does not directly cause

selective wetting. However, this surface modification causes an excited energetic
state of the surface which is only temporary. The surface changes or aging effects
may occur over a longer period of time. This process is not the reverse transforma-
tion of the surface into its original state, but a statistically determined removing of
the high energetic functional lateral group to energetically more favored positions
below the plastic surface. The extent and the kinetics of this process depend largely
on the steric mobility of the polymeric chains, its lateral groups and the availability
of energetically suitable positions. Therefore selective wetting of surface can be
obtained if there is a sufficient difference in their molecular mobility, as shown in
Fig. 7.
Physical conditioning is still a relatively new and little investigated process with
a high potential for innovation because it is free from pollution. It may have
expected advantages over the long term.

4.1.4. Selecti6e hydrophobic modification by chemical conditioning

Contrary to selective wetting by chemical conditioning, selective hydrophobic
modification by chemical conditioning is a process in which a surface conditioning
agent is selectively solubilized in the plastics and is capable of penetrating into the
surfaces for a relatively small distance or depth. This produces relatively hydropho-
bic plastics which can be floated in an aerated aqueous medium. The plastics which
are unaffected by the reagent are recovered from the bottom of the aqueous
medium [8].
Kobler [8] developed this technique to separate PVC from PET recently. It is also
a new and little investigated process, especially for the separation of other plastics.

Fig. 7. Flotation of a mixture of ABS and PC after plasma-activation as a function of aging time (from
[5]).
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 99

Fig. 8. Influence of non-ionic surfactants on the recovery of different plastics. Dosage: 60 mg/l, pH 6,
T =20°C. Corresponding gS/G and gL/G values are given in parentheses and expressed in mN/m (from
[12]).

4.2. The de6elopment of plastics flotation

As mentioned before, the research on plastics flotation began in the 1970s [32].
Some of the patents obtained on the separation of plastics aimed mainly at flotation
separation of PVC from other plastics [8,20,21]. More extensive work focusing on
the fundamental research on plastics flotation was done by several authors recently.
A pilot plant for plastics flotation was recently established in Germany [5].

4.2.1. Utilizing a liquid medium with a specific 6alue of surface tension

An earlier report describing the separation of plastics by Gamma flotation was
published by Yarar [22] in 1982. Using methyl isobutyl carbinol as a frother and
exploiting the inherent hydrophobicity of plastic labels, the process was shown to
separate cellulose from bottle labels as well as record-sleeve laminates.
Later, Buchan and Yarar [2,17] presented two papers describing the application
of Gamma flotation to separating PVC and PET. In a 20%CH3OH/80%H2O
flotation medium containing 190 ppm MIBC at pH 11 with surface tension 40.8
dynes/cm, the PET recovery was 0%, while the PVC recovery reached 92%.
More test results of plastics separation by Gamma flotation were achieved
recently by Norbert Fraunholcz et al. [12] in their study on the influence of
non-ionic surfactants (frothers) on plastics flotation. The results are shown in Fig.
8 and Fig. 9. The authors attributed the differences in flotation behavior to the
depressing effect of the frothers and the result of the reduced liquid surface tension.
100 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

4.2.2. Selecti6e wetting by chemical conditioning by adsorption of wetting agents

4.2.2.1. Using lignin sulfonate or organic colloids as wetting agents. One of the
earliest US patents on plastics flotation was granted to Izumi et al. [23] in 1976.
Using an alkali metal or alkaline earth metal salt of lignin sulfonic acid as a wetting
agent, the method can separate PVC from PS, PP, PE, or PA.
At the same time, a more detailed paper describing the addition of a wetting
agent (sodium lignin sulfonate, or organic colloids such as quebracho, gelatine, glue
or tannic acid) to selectively change the surface properties of specific plastics from
hydrophobic to hydrophilic was presented by Saito et al. [24], as shown in Table 6.
A specific plastic (residual matter) with grades 96–100% and recoveries between
96– 100% was successfully be achieved by flotation utilizing fine bubbles (0.2–0.5
mm in diameter).
In 1992, Jordan [25] reported the flotation separation of PET and PVC. The
clean PET and PVC mixture was conditioned in a solution of 45 g/t gelatine and
floated in a short column flotation cell in an upward flow of water. In a single
flotation step, over 75% of the PET was recovered as a high purity product
containing 99.8% PET. The report also described the important influence of particle
size on the floatability of the plastic particles.

4.2.2.2. The influence of particle size and roughness and bubble size on plastics
flotation. In 1983, Vogt et al. [26] published a paper discussing the flotation
separation of a mixture of PE, PS and PVC and examined the effects of the size of
bubble and particle and the reagents used. High-speed cinematography indicated
the importance of bubble and particle size control and the need to minimize
turbulence of flotation pulp.

Fig. 9. Influence of the liquid surface tension on the recovery of different plastics with C11EO8 as a
surfactant, pH 6, T= 20°C, pine oil 30 mg/l. Corresponding gS/G and gL/G values are given in
parentheses and expressed in mN/m (from [12]).
Table 7
Some other wetting agents used (redrawn from [28 – 30])

Authors Date Wetting agents Other conditions Plastics systems

Float Residual

E.G. Valdez et al. 1979.9 Sodium silicate fatty amine (Aeromine 3037) pH 9.0–9.3. Stage one PS duPont Nylon. Zytel
nylon
pH 4.5–5.0, Stage two duPont Nylon Zytel nylon
Sodium silicate fatty amine (Aeromine 3037) pH 9.0–9.3. Stage one PS Zytel nylon, ABS
pH 4.5–5.0, Stage two ABS Zytel nylon
Sodium silicate fatty amine (Aeromine 3037) pH 9.0–9.3. Stage one PS Zytel nylon. Acrylics
pH 4.5–5.0, Stage two Acylics Zytel nylon

E.A. Sisson et al. 1993.10 NEODOL@91-6 HLB = 12.5 NaOH: 5% PVC PET
TRITON X-114 NaOH: 5–10% PVC PET

Jian-Yang Hwang 1995.1 (C2H4O)40C15H24O HLB= 17.8 — ABS Phenoxy

et al.
(C2H4O)40C15H24O HLB= 17.8 — ABS PVC
(C2H4O)40C15H24O HLB= 17.8 — ABS PET
(C2H4O)40C15H24O HLB= 17.8 Dosage: 0.04 g/l, stage one PC+ABS PVC
Dosage: 0.15 g/l, stage ABS PC
H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

two
101
102 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

A similar conclusion was made by Biddulph et al. [27] in their study on flotation
separation of mixed plastics by using high-speed camera. The results indicate that
small bubble(0.5 – 0.8 mm) with low impact velocity (5–8 cm/s) will cause immedi-
ate adherence at first contact of the bubble with the surface. Using tannic acid as
a wetting agent and a-terpineol as a frother, the authors obtained a wetting order
for different plastics, i.e. nylon 6.6\ PET\ PVC/U \ PS\ PVC/S.
A study on flotation separation of PVC and PET was also reported recently [19].
In this study, the FTIR analysis of PET before and after grinding, indicated that no
significant change in surface chemistry occurred in either case, but the displacement
of certain bands suggested slight amorphization of very fine particles (B 50 mm)
after laboratory impact grinding. SEM analysis of PVC and PET showed that they
exhibit differences in surface roughness which provides anchor points for air-bub-
bles during flotation. Selective wetting of PVC can be achieved by using LG at
concentration below 0.02 g/l (1 kg/tonne of plastics), ammonium or soda at a high
concentration (5% by weight). The author also discussed the mechanisms of
adsorption from XPS analysis (see Section 4.1.2).

4.2.2.3. Using other wetting agents. Several US patents [28–30] reported plastics
flotation by using other wetting agents, as summarized in Table 7. In this study, the
wetting agent (C2H4O)40C15H24O, was shown to have a better selectivity (see Fig.
10).

4.2.2.4. Comprehensi6e research. Shibata et al. [16] explored the flotation separation
of four engineering plastics namely PC, PVC, POM and PPE. The results show that
(a) no significant effect of pH was observed in the range of 5 to 12 during flotation
(b) Amongst a wide variety of depressants tested (including sodium lignin sulfonate,
saponin, polyvinyl alcohol, Aerosol OT, sorbitan monolaurate, polyoxyethylene
lauryl ether and tannic acid), lignin sulfonate was found to be a good depressant for
PVC. Saponin/Aerosol OT combination was most effective in depressing PC. A
flowsheet was thus developed for separating the plastics, as shown in Fig. 11.
Extensive fundamental research on plastics flotation was made by Fraunholcz et
al. recently [12,18]. The tests were focused on examining the influence of a variety
of reagents on the floatability of different plastics (including GRPP, HIPS, ABS,
PC, PA6, PMMA, PVC and POM), including non-ionic surfactants (frothers
commonly used in mineral processing), electrolytes and inorganic depressants
(inorganic depressants commonly used in mineral processing), low-molecular-
weight complex compounds (organic depressants commonly used in mineral pro-
cessing) and macromolecular organic depressants (commonly used as depressants or
flocculants in mineral processing). These are shown in Table 8.
From the flotation test results it was suggested that: (a) the effects of the
non-ionic surfactants on the wettability of the plastics appear to be governed,
mainly by Gamma flotation; (b) cations (including Na + , Ca2 + , Mg2 + , Fe2 + , Fe3 +
and H + ) have a significant influence on the adsorption of polyelectrolytes (anionic
macromolecular depressants) and weak acidic non-ionic macromolecular depres-
sants on the plastics investigated; (c) none of the inorganic depressants affects the
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 103

Table 8
The reagents investigated

Name Abbreviation

1 Non-ionic surfactants (frothers)

Diacetone alcohol DAL
Methyl isobutyl carbinol MIBC
Tripolypropylene glycol methyl ether PPG3
Iso-octanol IOL
Pine oil (a-Terpineol) POIL
Polyethylene glycol dodecyl C11EO8
Nonylphenol polyglycol ether.10EO C9+6EO10
2 Electrolytes
Na2CO3
NaCl
NaNO3
MgCl2
CaCl2
FeCl2
FeCl3
HCl
3 Inorganic depressants
Sodium disulphite NaDS
Sodium hexa meta phosphate NaPh
Sodium silicate NaSi
4 Low-molecular-weight complex compounds
Malic acid MAC
Tartaric acid TAC
Citric acid CAC
1,2,3-trihydroxy benzene THB
2,4,6-trihydroxy benzoic acid THBA
5 Macromolecular wetting agents
Arabicum gum, composition: ARG
m:n:p:q = 1:1:3:3
Na-carboxymethyl cellulose NaCMC
Na-lignin sulfonate NaLS
Potato starch PST
Quebracho QUE
Tannic acid TNA
Polyvinyl alcohol PVA
Na-polyacrylic acid NaPAA
Polyacrylamide PAM
Polyethylene oxide PEO

flotability of the plastics to any measurable degree; (d) the complex compounds do
not adsorb on the plastics in sufficient amount to depress them during flotation; (e)
when the macromolecular depressants are used, selective wetting can be achieved
between the apolar plastics, e.g. PP and PS and the polar plastics, e.g. PVC,
 104
H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

Fig. 10. The depressing effect of some wetting agents on plastics (redrawn from [30]).
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 105

Fig. 11. Proposed flowsheet for separation of plastics from mixtures: the mass balance as well as the
recovery and grade of concentrated products at each stage (from [16]).

PMMA and POM, but it is difficult to achieve selective wetting among the apolar
plastics or among the polar plastics; and (f) the non-ionic macromolecular depres-
sants which do not dissociate appreciably even at high OH − concentration depress
the plastics, independent of pH. Potato starch has not any effect on the floatability
of the plastics.

Table 9
Separation results of waste plastic mixture (from [5])

Waste plastic mixture Recovery Grade (mass%)

(mass%)

Adhesive carbonfibre reinforced plastics (CFR-prepegs) 98 99

and their protection sheet (PE)
ABS from the plastic fraction of vacuum cleaners 95 99
PC-PBT and TPE from the processing of bumpers 97 99
PP-GFR and PP from the plastic fraction of instrument 80 99
boards of used cars
PP-GFR and PA/PPO blend from the processing of car 99 99
back-doors
 106

Table 10
Proven abilities pilot plant (from [5])

Ability/proven Recovery Grade (mass%)

(mass%)

Transferability of the laboratory scale results into the technical scale/flotation of a physically conditioned 98 99
synthetic mixture with standard particle dimensions (4.0–6.3 mm) ABS and PC
Minimal pulp turbulence/flotation of a physically conditioned synthetic mixture with very large particle 98 98
dimensions (2×25×50 mm) ABS and PC
Applicability of flotation to sort real waste plastic mixtures on a technical scale/flotation of a chemically 92 99
conditioned mixture out of automobile scrap (glass fiber reinforced polypropylen and polyamid/
polyphenylenoxid blends out of the waste plastic fraction of car rear doors)
H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109
 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109 107

The mechanisms of the influence of the reagents on the wettability of the plastics
were examined in detail by the authors (see Section 4.1.2).
Recently Stuckrad et al. [5] published a paper describing the principles of chemical
conditioning and physical conditioning and reporting the flotation separation results
of synthetic plastic mixtures and real waste plastic mixtures on laboratory scale and
pilot scale, as shown in Tables 9 and 10.
Product qualities with grades higher than 99% and recoveries between 80 and 97
mass% can be achieved by using chemical conditioning and dry-physical conditioning.
The results also indicate the transferability of the flotation separation process from
synthetic mixtures to real waste plastic mixtures and from laboratory scale to pilot
scale.
4.2.3. Selecti6e wetting by physical conditioning
There are few reported studies on physical conditioning. Only one paper touching
this field, was presented recently by Stuckrad et al. [5]. The results, as shown in Table
10, indicate that physical conditioning is also an effective process for plastics
separation.

4.2.4. Selecti6e hydrophobic modification by chemical conditioning

A US patent [8] described a new method to separate PVC from PET. A chip
admixture is contacted with a surface conditioning agent (e.g. diisodecyl phthalate),
which is selectively solubilized in PVC and is capable of penetrating into the chip
for a relatively small distance or depth, to produce relatively hydrophobic PVC chips
which can be floated in an aerated aqueous medium. The PET chips are unaffected
by the reagent and are recovered from the bottom of the aqueous medium. The
flotation can be conducted in pure water without frothing or densifying agents. A
PVC removal of about 98% from PET was achieved.
To summarize, it can be seen that more and more attention is being focused on
the development of plastics flotation. The results available show that plastics flotation
is more flexible and could be useful for separating plastic mixtures. However, more
research needs to be done in order to put this technique into application in industry.

5. Conclusions

1. Statistics shows that plastics waste has become one of the larger categories in
MSW. Plastics recycling is important to the plastic industry, energy savings and
the environment.
2. The analysis on the characteristics of plastics waste and the physical properties
of plastics demonstrates that although several separation technologies (including
automatic sorting, gravity separation and electrostatic separation) can be ap-
plied to separate mixed plastics, they generally have their limitations.
3. The principles of plastics flotation show that it is more flexible than other
techniques and could prove useful in separating mixtures of plastics.
4. More research needs to be carried out before plastics flotation can be success-
fully applied in industry.
108 H. Shent et al. / Resources, Conser6ation and Recycling 25 (1999) 85–109

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