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MATERIALE PLASTICE

https://revmaterialeplastice.ro
https://doi.org/10.37358/Mat.Plast.1964

Deodorizing Methods for Recycled High-density Polyethylene


Plastic Wastes
HO DANY1, WONG WHUI DHONG1, KOH WENG JIAT1, TAN KIANT LEONG1,
NOR YULIANA YUHANA1*, GILBERT TAN2
1
Program of Chemical Engineering, Department of Chemical and Process Engineering, Faculty of Engineering & Built
Environment, Universiti Kebangsaan Malaysia, Bangi, Malaysia
2
Green Concept Technology Sdn. Bhd., Lot P.T 14277, Jalan Perusahaan 26, Kaw.11, Jalan Banting, Pandamaran, 42000
Pelabuhan Klang, Selangor Darul Ehsan, Malaysia

Abstracts.The recycling of high-density polyethylene plastic (HDPE) plays a crucial role in sustainable
development. However, obstacles to the use of recycled HDPE remain because of the material and
processing properties and odors of recycled HDPE. The odor of recycled detergent bottle plastic leads
to rejection by most detergent manufacturers. Recently, some recycling enterprises have adapted
recycling with odor reduction processes involving the use of solvents, antimicrobial additives, and odor
extraction units in feeders and extruders. However, these processes may affect the quality and cost of
recycled plastic. Most small and medium businesses (SMBs) may not favor these effects due to their
limited models and resources. In addition, most SMBs are unwilling to replace their current recycling
operation units. Hence, this study aimed to find alternative and economical ways for odor reduction in
the recycling process. A modification of the recycling process was introduced in the pretreatment of
plastic flakes before entry into the feeder of an extrusion unit. The effect of selected washing
temperatures, i.e., 65℃, 75℃, 85℃, and 95℃, on the removal of odor from recycled HDPE was further
studied. The addition of sodium bicarbonate, calcium carbonate, and citric acid into a heated water
bath enhanced the deodorizing effect. The relationship of these three chemicals with the deodorization
of HDPE plastics was investigated through sensory evaluation. Lastly, the potential of the deodorized
recycled HDPE for resin pellet production and commercialization were investigated.

Keywords: High-density polyethylene (HDPE), recycling process, economical, deodorizing, sustainable

1.Introduction
Over the last 11 years, the plastics industry has become one of Malaysia's most varied and vibrantly
growing industries, showing an average growth rate of 15% [1]. Malaysia began purchasing recycled
plastic from China in 2017 after China banned plastic imports. Discarded plastic contains 24 recyclable
and solid waste forms [2]. The growth of imported plastic waste has increased the recycling industry's
production. Recycled high-density polyethylene (HDPE) can be categorized into HDPE natural and
HDPE mix. HDPE recycling processes are commonly used in manufacturing domestic goods, such as
bottles, cans, toys, helmets, piping, and recycling bins. For detergent manufacturers, the cost of recycled
HDPE is considerably lower than that of virgin HDPE. However, we face the problem of eliminating
the bad odor of HDPE during recycling. Odor-control recycling technologies are complicated and costly
and thus cannot be afforded by SMEs. Moreover, they may affect the consistency of the plastic being
recycled. New technologies are required to improve HDPE recovery. This study aimed to examine the
deodorization of recycled HDPE through treatment with sodium bicarbonate, calcium carbonate, and
citric acid in a water bath at various temperatures.
Sodium bicarbonate, also known as baking soda, is used as an effective adsorbent in the odor
treatment of recycled HDPE to remove various undesirable substances, such as volatile and toxic
compounds [3]. Sodium citrate, which is obtained from the reaction between sodium bicarbonate and
citric acid, is another odor neutralizer that is useful for eliminating bad smells by balancing pH [4].

*email: [email protected]

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MATERIALE PLASTICE
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Calcium carbonate, also known as limestone, has the capability to mask odor and pungency [5].

2.Materials and methods


2.1. Preparation of samples
HDPE materials were supplied by KA Plastic Enterprise. HDPE natural plastics originate from milk
and sauce bottles and are primarily used to contain food. HDPE mix is derived from detergent and
shampoo bottles. KA Plastic Enterprise is a company whose task is to collect, sort, and crush recycled
plastics. A total of 25 g each of HDPE mix and HDPE natural flakes was weighed out and then cold
washed with regular stirring in 500 mL of water to remove soil. The plastics were then rinsed off and
filtered out.

2.2. Early Stage of investigation


The best temperature and time for hot washing to remove the odor retained in HDPE plastics were
observed. The cold-washed plastics were subjected to hot washing in 500 mL of water at 65°C for 10
min. After 10min, the plastics were rinsed and then transferred into a tank equipped with a blower for
20min of drying. The temperature of the tank was approximately 40°C-50°C. The experiments were
repeated by varying the temperatures of the hot-washing section to 75°C, 85°C, and 95°C. Then, the
whole experiments were repeated on both types of plastics with 15min of hot washing at each
temperature. The dried plastic samples were collected and analyzed through sensory evaluation. The
best results for the temperature and duration for hot washing were chosen after inspection.

2.3. Chemical treatment


Three chemicals, namely, sodium bicarbonate, calcium carbonate, and citric acid, were chosen to
remove odors from recycled HDPE. A total of 20 g of sodium bicarbonate was weighed out and poured
into 500 mL of water before the plastics were subjected to hot washing. The plastics were immersed in
the solution and then hot washed. After the selected duration, the plastics were rinsed and dried. The
dried samples were collected and examined. The experiments were repeated by using calcium carbonate
and a combination of sodium bicarbonate and citric acid.

2.4. Parameter measurements


2.4.1. Sensory evaluation
The panel members who participated in the experiment were well educated on the sensory properties
of HDPE plastics. A trained panel of 15 members, including researchers from this investigation,
examined the plastic HDPE samples before and after treatment. A scale of 1-5 was used in this
investigation, with 1 indicating undesirability and 5 indicating outstanding odor reduction. The rating
score for each sample was finalized by obtaining an average score for each sample from the panel
members.

2.4.2. Scanning electron microscopy and energy dispersive X-ray analysis


Scanning electron microscopy (SEM) was used to analyze the surface morphology of HDPE plastic
samples before and after treatment. Energy dispersive X-ray (EDX) analysis coupled with SEM was
performed on the selected HDPE plastic samples to characterize the composition of the samples. The
data generated by EDX analysis consisted of spectra showing peaks that corresponded to the elements.
The true composition of the sample could be analyzed on the basis of the data.

2.4.3. Fourier-transform infrared spectroscopy analysis


Fourier transform infrared spectroscopy (FTIR) analysis was performed to obtain an infrared
spectrum of the absorption or emission of organic and polymeric materials. It was used to characterize
the chemical composition on the surface of the selected HDPE samples. The presented spectrum, which

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MATERIALE PLASTICE
https://revmaterialeplastice.ro
https://doi.org/10.37358/Mat.Plast.1964

encompassed the wavelength range of 4000 cm−1 to 500 cm−1, was used to represent the molecular
fingerprint of the samples.

3. Results and discussions


The odor reduction level was determined by using a rating system with scores of 1 to 5 provided by
each team member. Next, the rating score for each sample was finalized by obtaining an average score
from each of the 15 panel members. The highest score indicated the best odor reduction level for the
HDPE plastic samples.

Table 1. Average scores of odor reduction level based on different temperatures and
washing time using water only in hot washing section
(1= Strong Odors, 5=Weak Odors after treatment)
Time Average scores of an odor reduction level
(minutes)/ Temperature (˚C)
HDPE Natural HDPE Mix
10 min 15min 10 min 15min
65 1.00 1.00 1.00 1.00
75 2.30 2.00 1.00 1.70
85 1.30 1.70 1.00 1.30
95 2.70 2.30 1.30 2.00

Table 2. Average odor reduction scores based on different chemicals used in 95℃ hot water
for HDPE Natural and HDPE Mix in 10 and 15 min, respectively.
(1= Strong Odors, 5=Weak Odors after treatment)
Type of Chemicals/ Type of plastic Average odor reduction scores
HDPE Natural HDPE Mix
Sodium bicarbonate 3.00 2.70
Calcium carbonate 4.00 2.30
Sodium bicarbonate with added citric acid 3.80 4.00

Figure 1. SEM images of surface morphology of HDPE Natural Plastic flake under 50X
magnifying power: A) Unwashed, B) cold wash only C) cold wash 10 min and hot
wash 10 min at 95˚C with added 40g/L calcium carbonate

Figure 2. SEM images of surface morphology of HDPE Mix Plastic


flake under 50X magnifying power: D) Unwashed, E) Cold wash only F) cold
wash 10 min and hot wash 15 min at 95oC with added 40g/L sodium bicarbonate

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MATERIALE PLASTICE
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Figure 3. EDX analysis showed the atomic percentage of each element in HDPE Natural
plastic flake: 1) Unwashed, 2) cold wash only, 3) cold wash 10 min, and hot wash
10 min at 95 ˚C with added 40g/L calcium carbonate

Figure 4. EDX analysis showed the atomic percentage of each element in HDPE Mix flake:
4) Unwashed, 5) cold wash only, 6) cold wash 10 min and hot wash 15 min at 95oC
with added 40g/L sodium bicarbonate

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MATERIALE PLASTICE
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https://doi.org/10.37358/Mat.Plast.1964

HDPE Mix without wash HDPE Natural without wash

HDPE Mix sodium bicarbonate HDPE Natural Calcium Carbonate

HDPE Mix sodium bicarbonate + citric acid HDPE Natural citric acid + sodium Bicarbonate
Figure 5. FTIR analysis of selected HDPE plastic samples at conditions

Table 1 reveals that the highest odor control score for HDPE natural was obtained by using the hot
washing technique at 95°C for 10 min, whereas the highest score for HDPE mix was obtained through
hot washing at 95°C for 15 min. As inferred from the result, increasing the washing temperature further
should have a substantial effect. However, HDPE has melting points that usually range from 120°C to
150°C [6], and its crystallization temperature is 100°C. In addition, the most appropriate crystallization
temperature for HDPE crystals that are moderately grown on fibers is 100°C, which is the temperature
at which lamellae with the maximum size and uniformity form [7]. Thus, the temperature for washing
was regulated to be below the melting point of HDPE.
A longer hot washing time (15 min) was needed to obtain better odor elimination results for HDPE
mix plastic than for HDPE natural (10 min). The surface of the HDPE plastic was scattered with various
chemicals, mainly volatile organic compounds (VOCs), which are responsible for most odors in
synthetic polymers [8]. The removal of VOCs will thus result in odor elimination. Extending the washing
time increased the efficiency of the process because adhesives were effectively eliminated. However,
after prolonged washing, VOC removal became negligible as emissions decreased [9]. Therefore,
washing at 95°C for 10–15 min intervals was sufficient. HDPE mix plastics were more odorous than
HDPE natural plastics because they come from various sources that primarily contained detergents,
cosmetics, and other materials. Hence, a long hot-washing duration was needed for HDPE mix plastics.

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MATERIALE PLASTICE
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The hot water temperature of 95℃ was chosen for the chemical treatment of HDPE natural and
HDPE mix for 10 and 15 min. As shown in Table 2, the best results for HDPE mix were achieved through
washing with sodium bicarbonate and citric acid; however, calcium carbonate was more effective in
washing out the odor of HDPE natural. The FTIR results showed that the peak of HDPE natural after
washing with sodium bicarbonate and citric acid was higher than that after washing with calcium
carbonate. The HDPE mix exhibited the opposite effects.
As shown in Figure 1 and 2, the surfaces of HDPE natural (A) and HDPE mix (D) without any
treatment were rough and coated with dirt and impurities. However, the surface of HDPE Natural (B)
became clean and smooth after cold washing. A white residue became evenly distributed on the surface
of HDPE natural (C) after hot washing with calcium carbonate. As shown in (E) and (F), the surface of
HDPE mix was still rougher compared with that of HDPE natural but showed less dirt after cold and hot
washing.
EDX analysis showed that the percentage of each element in both types of recycled HDPE had
decreased. EDX analysis revealed that the surfaces of HDPE samples 1 and 4 comprised numerous
elements that originated from various chemicals that were retained. Although further cold and hot
washing with calcium carbonate at the optimal temperature (2 & 3) would wash off some chemical
compounds that were scattered on the surfaces of HDPE natural, calcium carbonate precipitates would
remain (3). Moreover, fewer elements were scattered on (6) than on (5) due to the effectiveness of
sodium bicarbonate treatment. The use of chemical material in a hot wash left some compounds with
calcium and sodium elements scattered on (3) and (6).
FT‐IR was carried out to determine the chemical changes in HDPE samples before and after
treatment. The FT-IR result in Figure 5 showed that the characteristic peaks corresponding to the
structure of the chemicals reduced significantly when HDPE underwent a series of washes. The peak
value of unwashed HDPE natural is shown in Table 3. After chemical treatment, the peaks of the
carbonyl compound, hetero-oxy compounds, and ether and oxy compounds reduced. The functional
groups of organic components on the surface of HDPE natural are tabulated in Table 3. The peak values
of the unwashed HDPE mix are shown in Table 4. The peaks of aliphatic alkane, aryl group, aliphatic
organo-halogen compound, hetero-oxy compounds, inorganic ions, ether, and oxy compound group,
aromatic amino, alcohol and hydroxy compound, methyne, aryl group, amine, and amino reduced after
chemical treatment.

Table 3. Peaks value of untreated HDPE Natural and corresponded to its characteristics [10]
Wavelength (cm-1) Functional group Description
2919.36 / 2849.94 Aliphatic alkane Methylene C-H asym. / sym. stretch
1745.59 Carbonyl compound Alkyl carbonate and Ester
1539.79 Hetero-oxy compound Aromatic nitro compound
1463.17 Aliphatic alkane Methyl C-H asym. Bend
Inorganic ions Carbonate ion
Aryl group C=C-C stretch
875.91 Inorganic ions Carbonate ion
Hetero-oxy compound Aromatic phosphates
Ether and oxy compound Peroxides, C-O-O- stretch
718.66 Organo-halogen compound Aliphatic chloro-compound, C-Cl stretch
Alcohol and hydroxy compound Alcohol, OH out-of-plane bend

Table 4. Peaks value of untreated HDPE Mix and corresponded to its characteristics [10]
Wavelength (cm-1) Functional group Description
725.32 Organo-halogen compound Aliphatic chloro-compound, C-Cl stretch
Aliphatic alkane Methylene (CH2)n rocking
872.92 Ether and oxy compound group Peroxides, C-O-O-stretch
Hetero-oxy compound Aromatic phosphates
Inorganic ions Carbonate ion
1017.79 Aliphatic alkane Cyclohexane ring vibration, Skeletal C-C vibrations
Aryl group Aromatic C-H in-plane bend

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Aliphatic organohalogen compound Aliphatic fluoro compounds, C-F stretches


Hetero-oxy compound Aliphatic phosphates (P-O-C stretch)
Inorganic ions Phosphate ion
1120.16 Aliphatic alkane Skeletal C-C vibrations
Ether and oxy compound Alkyl-substituted ether, C-O stretch
Cyclic ethers, large rings, C-O stretch
Inorganic ions Sulfate ion
1261.27 Ether and oxy compound Aromatic ethers, aryl O stretch Epoxy
Amino group Aromatic primary amine, CN stretch
Alcohol and hydroxy compound Primary or secondary, OH in-plane bend
Amino group Aromatic primary amine, CN stretch
Alcohol and hydroxy compound Primary or secondary, OH in-plane bend
Methyne (>CH−) Skeletal C-C vibrations
1340.54 Aliphatic alkane Methyne Bend
Hetero-oxy compound Sulfonates, Aromatic nitro compounds, Organic
phosphate (P=O stretch)
Alcohol and hydroxy compound Phenol or tertiary alcohol
Carbonyl compound Carboxylate, carboxylic acid salt
-1409.27 Alcohol and hydroxy compound Phenol or tertiary alcohol, OH bend
Simple hetero-oxy compound: Sulfur-oxy compounds-Organic sulfates
Sulfur-oxy compounds
Common inorganic ions Ammonium ion
1505.53 Aryl group C=C-C stretch
Hetero-oxy compound Aromatic nitro compounds
1716.49 Carbonyl compound Carboxylic acid and ketone
2924.26 Aliphatic alkane Methyl/methylene asym. stretch
3434.94 Alcohol and hydroxy compound Hydroxy group, H-bonded OH stretch
Amine and amino compound Secondary heterocyclic amine stretches

The effective chemical compounds in the HDPE mix were the mixture of sodium bicarbonate and
citric acid. Baking soda is a weak alkali that can easily dissolve dirt and grease when utilized as a gentle
scouring powder in water. It also has unique buffering capabilities. It deodorizes by neutralizing acidic
and basic odor molecules, thus creating an odor-free state [11]. Citrate salt is produced through the
combination of two chemicals. Alkali metal citrate salts are readily soluble in water. The odors have at
least one functional group that could react with citrate salts. This reaction changed the compound
structure, resulting in a reduction or loss of the odorous characteristics of HDPE mix [12]. For HDPE
natural, calcium carbonate was highly efficient in minimizing offensive odors that contained alcohol
because it has high adsorption energy for alcohol groups. It has an affinity for delocalizing charges by
ordering the –OH group end of organic molecules such that molecular O associates with atomic Ca,
whereas H associates with CO3 [13].

4. Conclusions
This research was performed to investigate the usage of chemicals to deodorize HDPE plastics
naturally at 95°C over a fixed period. Numerous odorants were found to be involved in the odors of the
sample and were successfully detected by targeted odorant analysis. This study showed that the causative
odorants included a wide variety of complex chemical structures. A mixture of sodium bicarbonate
(baking soda) and citric acid exerted significant deodorizing effects on HDPE mix, whereas calcium
carbonate demonstrated promising deodorizing effects on HDPE natural. The various sources of HDPE
plastics contributed various odorants that affected the effectiveness of particular chemicals in odor
reduction. The modified washing method greatly reduced the overall strength of odors. Developing
viable concepts for postconsumer HDPE packaging is vital for a circular economy.

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MATERIALE PLASTICE
https://revmaterialeplastice.ro
https://doi.org/10.37358/Mat.Plast.1964

Acknowledgement. The authors would like to thank Ministry of Higher Education Malaysia and
Universiti Kebangsaan Malaysia for their financial support under the grant FRGS/1/2018/TK05/UKM/
02/4 and GUP-2017-041.

References
1.KEMENTERIAN PERUMAHAN DAN KERAJAAN TEMPATAN, (2011), A Study on Plastic
Management in Peninsular Malaysia.
2.WONG, E. K., & JASMIN, A. F., (2019), Plastic: An Undegradable Problem. Retrieved July 20, 2020,
from http://www.krinstitute.org/Views-@-Plastic-;_An_Undegradable_Problem.aspx
3.JEONG, S., & YOO, S., (2017), Preparation and properties of sodium bicarbonate-incorporated LDPE
films with deodorising function for kimchi packaging. Packaging Technology and Science, 30(12), 781–
790. https://doi.org/10.1002/pts.2333
4. ***Anon, (2019), The Science of Febreze . Retrieved July 20, 2020, from
https://www.febreze.com/en-us/safety/science-and-chemicals-in-febreze
5.ADAMS, C., (2013), Using Barn Lime. Retrieved July 20, 2020, from
https://info.mannapro.com/equine/Using-Barn-Lime-Think-Again-Our-Friend-Sweet-Pea-Explains-
Why
6.O PALENE, (2016), MSDS of High Density Polyethylene. Retrieved from
https://www.opalindia.in/PDF/HDPE/Material Safety Data Sheet_HDPE.pdf
7.MIAO, W., ZHU, H., DUAN, T., CHEN, H., WU, F., JIANG, L., & WANG, Z., (2018), High-density
poly-ethylene crystals with double melting peaks induced by ultra-high-molecular-weight polyethylene
fibre. Royal Society Open Science, 5(7), 180394. https://doi.org/10.1098/rsos.180394
8.HODGSON, S. C., CASEY, R. J., BIGGER, S. W., & SCHEIRS, J., (2000), Review of volatile organic
compounds derived from polyethylene. Polymer - Plastics Technology and Engineering, 39(5), 845–
874. https://doi.org/10.1081/PPT-100101409
9.KREHULA, L. K., SIROCIC, A. P., DUKIC, M., & HRNJAK-MURGIC, Z. (2012). Cleaning
efficiency of poly(ethylene terephthalate) washing procedure in recycling process. Journal of
Elastomers and Plastics, 45(5), 429-444. https://doi.org/10.1177/0095244312457798
10.COATES, J., (2006), Interpretation of Infrared Spectra, A Practical Approach. In Encyclopedia of
Analytical Chemistry. https://doi.org/10.1002/9780470027318.a5606
11.***Gonneville Inc., (2018), Baking Soda Abrasive. Retrieved July 30, 2020, from
https://gonneville.com/baking-soda-abrasive/
12.***Anon, (2013), Citrate Salts for Eliminating Odors. Retrieved July 14, 2020, from
https://patentimages.storage.googleapis.com/5b/cc/87/b98f7ffcb666a2/WO2014137350A1.pdf
13.DENIS V., OKHRIMENK O., JOANNA NISSENBAUM, MARTIN PETER ANDERSSON, MATS
M.H. OLSSON, S. L. S. S., (2013), Adsorption Energies of Functional Groups to Calcium Carbonate
Polymorphs: The Importance of -OH and -COOH groups. Langmuir 29(35): 11062-11073.
https://doi.org/10.1021/la402305x

Manuscript received: 15.07.2021

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