Leather
Leather
Leather
Pol. J. Chem.
23, 4,
Tech.,
17—25,
Vol. 10.2478/pjct-2021-0033
23, No. 4, 2021 17
Product diversification from pomelo peel. Essential oil, Pectin and semi-
dried pomelo peel
Le T. N. Huyen1, On T. N. H.1, Tran T. Y. Nhi2, 3, Dao T. Phat2, 3, *, Mai H. Cang1, *
1
Faculty of Chemical Engineering and Food Technology, Nong Lam University, Thu Duc District, Ho Chi Minh City,
Vietnam
2
Institute of Environmental Technology and Sustainable Development, Nguyen Tat Thanh University, Ho Chi Minh City,
Vietnam
3
Faculty of Environmental and Food Engineering, Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam
*
Corresponding author: e-mail: dtphat@ntt.edu.vn; maihuynhcang@hcmuaf.edu.vn
Currently, agriculture has shifted to green production, in which the recycling of post-production by-products
is a key issue. In the present work, by-products such as pomelos were studied to promote consumption
and enhance the value of pomelo. From pomelo material, essential oils extracted from pomelo peels,
pectin, and drying pomelo products have been diversified. In the extraction process of essential oils,
the hydrodistillation method was applied in conjunction with the response surface method to obtain the
optimal conditions of influence factors. These essential oils were quantified as well as determined for
components by GC-MS. The pectin recognition process was done by immersion method in HCl acid
(pH 2) and the drying process was made with a heat pump dryer under the effects of drying temperature,
drying time and wind rate. The results of the essential oil products reached the highest (0.88 ±0.006 g)
at the material size of 3 mm, the distillation time of 27 min, and the ratio of raw materials/solvents of
1/12 g/mL. The main components found in pomelo peeling essential oils included limonene (71.768%),
γ-terponene (12,847%), α-Phellandrene (2.979%), β-myrcene (2.668%), 1R-α-pinene (2,656%), and
β-pinene (1,191%). The pectin content was the highest under the temperature of 90 oC, extraction time
of 60 min and ratio/solvent ratio of 1:32 g/mL. Under these extraction conditions, 48% of concentrated
pectin content was obtained. Surveying conditions for drying white pomelo peels are capable of reversing:
refunded drying pomelos are drying heat pumps in the following conditions: 50 oC drying temperature,
the drying time of 90 min, and wind rate of 12 m/s. Product with hardness 309.862 N.
Keywords: Citrus grandis, Pomelo peel essential oil, Extract pectin, Pomelo peels products.
Extraction of essential oil separate the pectin extract from precipitates. After the
Pomelo peels were washed, drained, and had the filtration process, the pectin extract was concentrated at
white peel removed prior to the extraction process. a temperature of 60 oC until the concentration has 18.4%
100 g of pomelo peels were placed into a blender with Brix. In this study, the concentrated pectin extracts are
a surveyed water to raw materials ratio. The raw mate- used to determine the pectin content in the solution and
rial after grinding was transferred to a small 2000 mL the quality indicators of the pectin16.
container to conduct essential oil distillation during dif- Estimation for pectin content (%) was completely
ferent periods until the amount of essential oil tended random with single-type factors: material size D (D ≤
to increase (Fig. 1). 1, 1 ≤ d ≤ 5, 5 ≤ d ≤ 20, 20 ≤ D ≤ 25), a ratio of
The experiments were completely arranged randomly raw materials/solvents (1/24, 1/28, 1/32, 1/36 g/mL) and
with the rotating single-type factors: raw material size a completely randomly with variable is hydrolysis time
(5, 3, 2 mm), distillation time (10, 20, 30 min), and raw (60, 90, 120 min) and hydrolysis temperature (50, 70,
material/solvent ratio (1/8, 1/9, 1/10, 1/11, 1/12, 1/13 g/ 90 oC). The initial condition is pH 2, 1 h and the ratio
mL). Fixed conditions were as follows: 100 g of green of raw materials/solvents is 1/24 (g/mL).
pomelo peels material, distillation time of 30 min, the
ratio of raw materials/solvents of 1/10 g/mL, and water Pomelo peel drying process
as the solvent. Three factors of material size, distillation After washing with water several times, the white peel
time, the best ratio/solvent ratio were arranged in the was separated from the green and cut into the size of
rotating axis (Rotatable Central Composite Design) to 30 x 10 x 5 mm. 5 g materials were soaked in 60 mL of
determine the effects of these factors and optimizations alcohol at different concentrations for 1-5 h. After soaking
of the essential oil distillation process by response surface
with alcohol, pomelo white peel was rinsed with water
methodology (RSM).
many times at 40–60 oC to get rid of the alcohol smell
The crude oils were poured into a 100 mL glass beaker
and remove the residual naringin. Then, the pomelo peel
and then the appropriate amount of Na2SO4 is added to
was blanched at 90 oC in 30 s and then cooled quickly
anhydrous to obtain essential oils. Samples were stored
at 40–50 oC for 15–90 min. The dried materials were
at 4 oC in dark glass bottles until analysis.
stored in zipped bags to avoid environmental damage.
Extraction of pectin Bitterness removal experiment
Pomelo peels were used as the raw materials for The experiment of removing bitterness indicated by
extracting pectin. Freshly collected pomelos were selec- naringin concentration (mg/mL) in pomelo peel was
ted and blanched at 90 oC in 5 seconds14. The material performed completely randomly with single-type factors:
after being blanched was dried on a tray at 58.5 oC for soaking time (1, 2, 3, 4, 5 h), alcohol concentration (50,
4 h. The materials were flipped after the first 2 h to 60, 70, 80, 96%), the temperature of the discharge (40,
ensure that both sides of the materials were completely 45, 50, 60 oC), and the number of discharge (1, 2, 3, 4, 5
dried and achieved 13.8% of moisture. The dried peels times). The initial conditions included 500 mL of water
are sieved into different sizes. At the temperature of for each discharge and the 3 s of mixing time.
50–90 oC (based on previous work by Homa et al.15 and
Salma et al. 201216), different volumes of 0.01 N HCl Moisture content measurement
acid solution were added to 10 g of crushed materials The moisture content of drying materials (%) was
for 60–120 min to extract. A vacuum filter was used to investigated completely randomly with single-type fac-
Pol. J. Chem. Tech., Vol. 23, No. 4, 2021 19
tors: drying time (15, 30, 45, 60, 75, 90 min) and drying In which: M is the mass of precipitate Calcium Pectat
temperature (40, 45, 50 oC). (g); mp is the original sample volume (g); P is pectin
content (%); 0.92 is the conversion factor from Calcium
Survey after drying Pectat to Pectin.
The post-drying process was surveyed completely ran- Determination of naringin content: The white pomelo
domly with single-type factors: soak water temperature peel soaked in alcohol was added with 0.2 mL of NaOH
(room temperature, 50 oC, 100 oC), and soaking time and 0.2 mL of NaOH 4 N. Absorbance was measured at
(1, 2, 3, 4, 5 h). 420 nm of wavelength. Naringin’s standard line equation
was applied to estimate the amount of Naringin level
Analysis method that has been removed16.
Moisture index of pomelo peels is determined by drying
method to constant mass, ash defined according to TCVN Data processing
5253: 1990; The pH index of the material is measured Each experiment was repeated 3 times, calculated, and
by adding 50 mL of distilled water to 10 g of pomelo graphed with Microsoft® Office Excel 2013 software.
peels that was grounded and filtered. Quantification of ANOVA statistical analysis and Least Significant Dif-
glucose sugar, saccharose in pomelo shells by Bertrand ference tests are used to compare the effects of factors,
method and acid hydrolysis method (17; the volume of handled with Statgraphics Centurion XV 9 (Statgraphics
pomelo essential oil after distillation was determined Technologies, Inc., USA), and support of JMP statistics
according to TCVN 189: 1993 and components analysis software 10 with 95% reliability is applied to all statistics.
was according to the GC/MS method18–19.
RESULTS AND DISCUSSION
Operating conditions of GC-MS:
Pomelos have an average volume of about 968 g/L
The chemical composition of the pomelo fruit oil was
of fruits, yet the peel accounts for 36.4% of the fruit
determined by GC–MS analysis using GC Agilent 6890
(about 352 g). For each pomelo peel, the green ones
N instrument coupled with HP5-MS capillary column
contain 71.5% of the total essential oil content and the
(30 mm × 0.25 mm × 0.25 mm) and MS 5973 inert.
remaining is contained by white ones, along with high
The carrier gas was He. The split rate was set at 1:50.
pectin content. The physicochemical properties of pomelo
The pressure of the head column was 9.3 psi. 25 mL
peels are presented in Table 1.
of essential oil was added with 1.0 mL n-hexane and
dehydrated with Na2SO4. The flow rate was constant Surveying the distillation of pomelo essential oils
at 1 mL/min. Injector temperature is 250 oC and the Three main factors that affect the extraction process
rate of division is 30. Oven program for samples: 50 oC have been identified as raw material size, distillation
kept for 2 min, then increased by 2 oC/min to 80 oC, time, and raw material/solvent ratio. Figure 2 shows the
continued to increase by 5 oC/min to 150 oC, continued
to increase by 10 oC/min to 200 oC, increase 20 oC/min
to 300 oC hold for 5 min. Spectra compared with the
library of NIST database.
The volume of pomelo peels obtained after the drying
process was divided by the material volume after soaking;
The drying pomelo is stiffened by holding onto the hollow
pillar, then a needle head 15 mm was forced until the
head pinched through the sample. The measurement
was performed in triplicates and data were recorded.
Determination of pectin content by Calci Pectate me-
thod: Pectin extracted from the green peel of pomelo, Figure 2. Effect of materials size on essential oil mass
was quantified by using the calcium pectate method.
The method is based on the Calcium Pectat salt in the
form of a precipitate. A total of 10 g of concentrated
pectin was mixed with 100 mL NaOH for 7 hours. Then,
CaCl2 2 N and CH3COOH 1N were added and the re-
action was allowed for 5 min and 1 h, respectively. The
mixture was then heated for 5 min, cooled down, and
filtered through filter paper to obtain constant mass.
The precipitate was dissolved with hot distilled water to
remove chlorine ions. Finally, the mixture was allowed
to dry at 105 oC to constant mass.
The composition of the remaining four compounds content dropped sharply if D exceeds 5 mm. During
fluctuated 0.501% to 0.767%. A similar result was also the extraction process, small size particles have more
reported by Kenya, SM Njoroge et al.20, where pomelo advantages than large ones when combined with solvents,
(Citrus grandis Osbeck) grown in Kenya was found to as it is easier for them to contact, dissolve into solvents,
contain 98.8% of essential oils compounds and 94.8% and facilitate protopectin conversion Pectin24. For large-
of which was limonene, followed by α-terpinene (1.8%) -sized raw materials, the solvent is limited to grain cells,
and α-pinene (0.5%). In China, pomelo essential oil the time of penetration is longer, so the pectin content
(Citrus maxima) obtained by the steam distillation me- is obtained less. Statistical results ANOVA shows that
thod contained Limonene (46.83%) and β-caryophyllene the size of the material affects the pectin content. The
epoxide (20.17%) as the main components21. The richness LSD table shows that the size 1 <= D <= 5 is diffe-
of volatile compounds in essential oils may be due to rent from the remaining dimensions. So 1 <= D <= 5
the use of different extracts techniques. In addition, the was selected as the parameter for the next experiments.
compound of the essential oil also belongs to the growth Figure 7 shows that when increasing the rate of so-
conditions and harvesting time22. lvents in raw materials, the pectin content increases
and reaches the highest value of 54.802%. However,
the pectin content decreases when the ratio of raw
materials/solvents is 1/36. The proportion of solvents
is an important factor for pectin content as the rate of
increased solvents would increase (1) the surface area
between the raw materials and solvents25, and (2) the
dissolution of solids and solvents as it penetrates deeply
into the material cells, hence enhancing pectin extraction
efficiency. On the other hand, when the solvent reduces
a high amount of the pectin content, causing the extract
to dilute, the pectin content obtained is low. The results
Figure 6. Effect of raw material size on pectin content from ANOVA show that the ratio of material/solvent
significantly affected the pectin content up to 95%.
According to the LSD classification test table, the ratio
1/32 g/mL is significantly different, as compared to the
remaining rates. Therefore, the ratio of materials and
solvents 1/32 g/mL was selected for the next experiments.
The above results are consistent with the research of
Bahare et al.26, the authors have chosen the ratio of
1/30 g/mL when surveying the influence of raw material/
solvent on pectin-extraction performance lemon peels.
the plant tissues, increasing the pectin extraction pro- extraction efficiency. ANOVA statistical results show that
ductivity27. At a temperature of 50 oC and the time of alcohol concentration and soaking time have an impact
extracting 60 min, the pectin content obtained is 10.715 on Naringin levels at a 95% confidence level. These two
±0.004%. When increasing the time to 120 min at the factors interact with each other. Implementing the LSD
same temperature, the pectin content increased to 31.263 classification test on the concentration shows a distinct
±0.039%, yet the efficiency has not been significantly difference at 50% concentration, as compared to 60, 70,
improved. If the temperature increases to 90 oC and the 80 and 96% concentration. LSD results of time show
extraction time is 60 min, the pectin content is 66.464 that 5 h was significantly different from 1, 2, 3, and 4 h.
±0.003% produced high-efficiency product quality. Therefore, alcohol content of 50% and the soaking time
This result is consistent with the study of Xue et al.28, of 5 h were selected to perform the next experiments.
wherein the process of extracting pectin, acid addition The above results are both similar to the studies of
was kept as short as possible to prevent breaking gly- Zhou et al.31, where 50% and 90 min have been selected
coside and ester bonding. This can negatively affect the when surveying the influence of alcohol content and
molecular weight and glue properties of pectin, reducing extraction time Naringin levels from pomelos. On the
the pectin content obtained. At a temperature of 90 oC other hand, Nguyen Cam Van et al.32 showed that 70%
with an extraction period of 90 min and 120 min, the alcohol concentration in 1 h is suitable for extraction of
pectin content tends to decrease by 33.157 ±0.049% naringin from pomelo by ultrasonic extraction method.
and 18.765 ±0.023%, respectively. Extracting pectin Figure 10 shows the effect of the flush temperature
with high temperatures with extended time can cause on Naringin concentration. High temperature encourages
pectin hydrolysis into short-chain sugar which is unable Naringin to dissolve easily into water, thereby reducing
to precipitate by using normal acids, thus reducing pectin the bitterness of pomelos. When the water is discharged
content22. Statistical results ANOVA shows that P-value at a temperature of 50 oC, the concentration of Naringin
<0.05, indicating that the temperature and time affected 0.0005 mg/mL, which is higher than the 45 oC discharges
the pectin content with a reliable level of 95%. These two temperature with a concentration of 0.0011 mg/mL. When
factors interact with each other. LSD results indicate 60 the soaked water temperature increases to 60 oC, the
min and 90 oC significantly different from the remaining naringin concentration decreases to 0.0006 mg/mL. By
time and temperature. Therefore, 60 min and 90 oC feeling, the sample of pomelo at this temperature has
were selected for the next experiments. Similar results been corrupted, the structure of pomelo is destroyed.
have been reported with Nurul and colleagues29, Foo The appropriate discharge temperature not only increases
et al.30 selected 60 min and 90 oC when surveying the the efficiency of bitter separation but also contributes to
influence of time and temperature on pectin extraction holding the structure of pomelos, ensuring sensory and
performance from sweet potato peels. quality. ANOVA statistics show that P-value = 0.0000
<0.05, indicating that the flush temperature affects the
Surveying the process of drying pomelo Naringin concentration at a 95% confidence level. LSD
table shows that the 50 oC temperature is significantly
Survey removes bitter matter in pomelo different from 45 oC and not different from 60 oC. The-
Figure 9 shows the influence of alcohol concentrations refore, 50 oC is the right temperature to perform the
and soaking time on naringin concentration. Alcohol next experiment. The results are different compared to
is a common solvent that is capable of dissolving fla- the research of Zhou et al.31, who also selected 60 oC
vonoids, especially naringin. In general, when alcohol when studying the effect of extraction temperature on
concentrations increased from 50% to 96%, causing naringin levels from pomelos. By using the ultrasonic
Naringin concentration decreased. This can be explained extraction method, Nguyen Cam Van et al.32 chose 55 oC
because the amount of alcohol is too much-diluted solu- as the optimal temperature for an experiment.
tion, Naringin concentration decreases. When increasing Figure 11 shows the influence of the amount of dis-
soaking time from 1 h to 5 h, Naringin concentration charge on naringin concentration. To increase the bit-
increase and reach the highest value of 0.0178 mg/ml terness effect, the number of discharges is an important
at 5 h and 50%. However, at the same concentration parameter that helps to reduce the smell of alcohol and
of 50% alcohol, 5 h and 4 h soaking time has an insi- to limit microorganisms while eliminating the residual
gnificant difference. Long soaking time causes naringin
to dissolve completely into the solvent, increasing the
30. Foo, J.X., Abang, Z.D.N. & Ismail, N.H. 2016. Effect of 32. Nguyễn Cẩm Vân, Nguyễn Minh Chính, Đào Văn Đôn,
Extraction Parameters on the Yield of Sweet Potato Pectin. Nguyễn Tuấn Quang, Nguyễn Quỳnh Ngọc và Nguyễn Văn
Proceedings of the 6th International Graduate Conference on Thuận, 2015. Nghiên Cứu Chiết Xuất Naringin Bằng Dung
Engineering. Science and Humanities. Universiti Teknologi Môi Ethanol Từ Cùi Bưởi (Citrus Maxima), Tạp Chí Y - Dược
Malaysia. 146–148. Học Quân Sự Số 1.
31. Zhou, S., Wang, H. & Du, J. 2006. Ethanol extraction
technology of naringin from grapefruit peel. Transac. Chinese
Soc. Agric. Engin. 22,184–187.