Waste and Biomass Valorization

https://doi.org/10.1007/s12649-022-01726-9

ORIGINAL PAPER

Valorization of Monoterpene Hydrocarbon Fraction of Essential Oil

to High‑Value Oxygenated Monoterpenoids by Solvent‑Free Catalytic
Modification Using 1%Pd‑β‑Zeolite
Madhuri Gupta1,3 · Prashant Kumar1,3 · Praveen Kumar Sharma1 · Shubham Srivastava1,3 · Priyabrat Mohapatra2 ·
Chandan Singh Chanotiya1,3 · Prasant Kumar Rout1,3 

Received: 16 October 2021 / Accepted: 6 February 2022

© The Author(s), under exclusive licence to Springer Nature B.V. 2022

Abstract
Monoterpene hydrocarbons are the unwanted, off-smelling fractions in most of the essential oils. Due to the absence of
functional groups in monoterpene hydrocarbons, it is difficult to solubilize in common solvents such as water, ethanol, etc.
Hence, this fraction is removed from the essential oil in deterpenation process before their application in formulations.
Pinene (α-,β-), the monoterpene hydrocarbons are found in most of the essential oils. In the present work, pinene isomers
are esterified to valuable compounds such as terpinyl acetate, bornyl acetate and fenchyl acetate. They are widely used as
fragrance ingredients in various food and cosmetic products with improved organoleptic profiles. Hence, a solvent-free pro-
cess has been developed for the selective conversion of pinene to terpinyl acetate and bornyl acetate using 1%Pd-β-Zeolite
(ZE) at room temperature (30 °C). The different percentage of Pd loading over β-ZE was studied on the transformation of
α-pinene. It was attained 98% of conversion with the selectivity to 54.2% of terpinyl acetate, and 34.8% of bornyl acetate
at 30 °C in 2 h using 1%Pd-β-ZE. Similarly, the synthesized catalyst (1%Pd-β-ZE) has been shown excellent activity for
α-pinene esterification under the 50 psi N
­ 2 at 50 °C to produce 83% selectivity towards bornyl acetate. The esterification of
monoterpene hydrocarbons-rich essential oils (salaiguggul, guggul, black pepper, rosemary, and nutmeg) were carried out at
30 °C with 1%Pd-β-ZE for selective transformation to bornyl acetate, terpinyl acetate, and fenchyl acetate. Since the reactions
are carried out without any additional use of organic solvents, hence, makes the overall process quite attractive. This study
will help to develop an eco-friendly strategy for the valorization of bicyclic monoterpene hydrocarbons-rich essential oils.

Madhuri Gupta and Prashant Kumar contributed equally to this

work.

* Prasant Kumar Rout

pk.rout@cimap.res.in; prasantrout@gmail.com
1
Phytochemistry Division, CSIR-Central Institute
of Medicinal and Aromatic Plants, Lucknow,
Uttar Pradesh 226015, India
2
Chemistry Department, C.V. Raman Global University,
Bhubaneswar, Odisha 752054, India
3
Academy of Scientific and Innovative Research (AcSIR),
Ghaziabad 201002, India

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 Waste and Biomass Valorization

Graphical Abstract

Keywords  α-Pinene. Terpinyl acetate · Bornyl acetate · 1%Pd-β-Zeolite · Essential oil · Monoterpenoids

Statement of Novelty composition at 30 °C in 2 h under atmospheric conditions.

These modifications of essential oils are carried out using the
The monoterpene hydrocarbon fraction (26–78%) is gener- 1%Pd-β-ZE re-usable catalyst in presence of food-additive
ated as waste in the essential oil processing industries. For acetic acid to act as a reagent as well as reaction medium.
complete utilization of essential oils, a novel 1%Pd-β-ZE
catalyst was synthesized for the selective transformation of
monoterpene hydrocarbons to oxygenated monoterpenoids
Introduction
without fractionation. The process has been demonstrated
using α-pinene as a model compound in atmospheric condi-
The natural fragrance and refreshing ingredients are wit-
tions as well as an inert environment using 50 psi ­N2 pressure.
nessing high demand due to the enhanced usage of plant-
Interestingly, it was converted to terpinyl acetate (54.2%) and
based essential oils over synthetic chemicals. It is associ-
bornyl acetate (83.0%) as major products in atmospheric as
ated with plentiful wellbeing such as aromatherapy, flavors,
well as N
­ 2 environments, respectively. Therefore, the product
food-preservatives, etc. For illustration, the comprehensive
can be manipulated with varying reaction conditions as per
essential oils trading exceeds 7.5 billion USD in 2018 and is
requirement. First time noticed that the essential oils rich in
expected to rise more than 9% compound annual growth rate
bicyclic monoterpene hydrocarbons such as α-thujene, sabi-
(CAGR) in between 2021 and 2026 [1]. Essential oils and
nene, α-pinene, β-pinene, camphene, myrcene, δ-3-carene,
their terpenoids are among the most important ingredients
etc. are catalytically-transformed to terpinyl acetate, bornyl
used by the cosmetic and perfumery industries. There is a
acetate, and fenchyl acetate without much alternation of

13
Waste and Biomass Valorization
prevalence application of essential oils; especially oxygen-
ated terpenoids are used as active ingredients in cosmet-
ics, perfumery, therapeutics, etc. [2, 3]. On the other hand,
terpene-hydrocarbons gave off smell, hardly displayed the
bioactivity, and were also insoluble in the ethanol–water
solvent. Hence, in the process of deterpenation, these ter-
pene-hydrocarbons are removed. This process is facilitated
to increase the percentage of organoleptically superior oxy-
genated terpenoids in the essential oil fraction. Hence, the
left-out terpene hydrocarbons were treated as waste prod-
ucts [4]. In the present study, monoterpene hydrocarbons
(26–78%) rich high-value essential oils such as Boswellia
serrata (Salaiguggal), Commiphora mukul (Guggul), Myris-
tica fragrans (Nutmeg), Piper nigrum (Black pepper), Salvia
rosmarinus (Rosemary) were taken for suitable modification
to enhance the olfactometry value.
Alternatively, esterification of α-pinene gave value-added
products such as terpinyl acetate, bornyl acetate, and fenchyl
acetate. These esters were widely used as fragrance ingredi-
ents in various food and cosmetic products. Terpinyl acetate
and bornyl acetate were synthesized directly by the esterifi-
cation of α-pinene with an acid catalyst [5]. It was prepared
in two stages, (i) first, the pinene was treated with mineral
acids to produce monoterpene alcohols, (ii) esterification
of monoterpene alcohols using acetic anhydride to produce
the corresponding acetates. The major drawbacks of these
processes are the use of a large amount of acids and corro-
sive chemicals. The strong Bronsted acidity has facilitated
this reaction, so heteropoly acids are a class of compounds
known for their strong acidic character to follow the order
of ­H3PW12O40 > ­H4SiW12O40 > ­H3PM12O40 > ­H4SiMO12O40
[5]. Due to the strong acidic character, some pinene con-
versions were reported taking H ­ 3PW12O40 as the catalyst.
These heteropoly acids are miscible in most of the solvents,
hence creating a problem for their isolation from the reac-
tion medium. Alternatively, the heterogeneous catalysts are
preferred due to their high selectivity towards the desired
products, and also reuse in subsequent batches. Liu et al. [6]
were reported the formation of terpinyl acetate with 27.8%
of selectivity using ionic liquid as the catalyst. Wijayati et al.
[7] were reported the esterification of α-pinene (isolated
from turpentine oil) using natural zeolite (ZE) to result in
21.4% of yield with the selectivity of 28.87%. Further, ter-
pinyl acetate yield has been enhanced (52.83%) with higher
selectivity of 61.38% using H/ZY at 40 °C [8, 9].
The present work aimed with the following objectives,
(a) development of a solvent-free catalytic process for selec-
tive transformation of pinene to terpinyl acetate and bornyl
acetate using prepared Pd/β-ZE catalysts, (b) optimization of
process conditions to obtain the maximum yield, (c) to study
the shift in selectivity of α-pinene under nitrogen environ-
ment towards bornyl acetate transformation, and (d) applica-
tion of the developed process to valorize some monoterpene
hydrocarbons rich essential oils such as salaiguggul, guggul,
nutmug, black pepper, and rosemary to terpinyl acetate and
bornyl acetate. A suitable greener process has been devel-
oped for the transformation of these monoterpene hydrocar-
bon-rich essential oils for better commercial applications.
Materials and Methods
Chemical and Reagents
α-Pinene, β-pinene standards and Pd(NO3)2 were procured
from Sigma-Aldrich, India. β-ZE was purchased from
Alfa-Aesar, Hyderabad. Other chemicals and solvents like
aqueous ­HNO3, ­NH4NO3, ­NaHCO3, anhydrous ­Na2SO4,
dichloromethane (DCM), and glacial acetic acid, etc. were
procured from Merck India.
Plant Material
Authentic materials of Salaiguggul (Boswellia serrata) and
Guggul (Commiphora mukul) were gifted by Jawaharlal
Krushi Vishwavidyalaya, Jabalpur. Black pepper, Nutmeg,
and Rosemary were purchased from the local market of Luc-
know, and a voucher specimen has been submitted in the
Herbarium of CSIR-CIMAP Lucknow.
Essential Oil Extraction
The powdered materials of salaiguggul (BS), guggul (CM),
black pepper seed (PN), nutmeg fruits (MF), rosemary leaves
(SR) were subjected to hydrodistillation in a Clevenger-type
apparatus for 6 h to get colorless volatile oil. These oils were
dried over anhydrous ­Na2SO4 to remove traces of moisture,
filled in glass bottle, and stored in a refrigerator at 4 °C until
use.
Catalyst Preparation
Pd(NO3)2 was dissolved in an aqueous H ­ NO3 (0.01  M)
solution. Then, 1 g of β-ZE was dispersed into 25 mL of
water solution by stirring for 30 min, followed by adding
aqueous Pd(NO3)2 solution with varying Pd (0.1, 0.5, 1, and
2%) load. Then 20 mg of N ­ H4NO3 was added, followed by
stirring for another 2 h. The mixture was then centrifuged
and thoroughly washed with distilled water. The precipitate
was dried and calcined at 300 °C to obtain 0.1%Pd-β-ZE,
0.5%Pd-β-ZE, 1%Pd-β-ZE, 2%Pd-β-ZE.
Characterization of Catalysts
The XRD spectra of the composites were recorded through
Rigaku diffractometer (Rigaku, Japan) by using Cu Kα
13

radiation at 40 kV and 130 mA in the scanning angle of
5–50o at 0.05 ­min−1of scanning speed. The spectra are pre-
sented with the 2θ Vs intensity. FT-IR spectra of samples
were carried out by the KBR pellet method in the region
4000–500 ­cm−1 using Nicolet 400D-Impact FT-IR spectro-
photometer. Dry KBR 200 mg with 5 mg sample are well
mixed to create pellets by applying 10,000 hydraulic pres-
sure for 2–3 min. Each sample is scan 200 times, and spectra
recorded are plotted the wave number against transmittance
(%).
Tristar 3000 surface area (SA) analyzer of Micromeritics,
USA make was utilized to determine the SA of the com-
posites/catalysts (10 mg) using adsorbate (liquid nitrogen).
Before analysis, the samples were degassed for 3 h at 150 °C
before recording the SA. Isotherms have been recorded in
the range of 0.05 to 0.3 of relative pressure and isotherms are
found as straight curves. SEM evaluations of catalysts were
carried out using QUANTA-250, FEI (Netherland) SEM
machine. Samples (50 mg) have been coated with gold by
Sputter Coater for 50 s (Model No: Q150 TES frocoram
Technology, U.K). The catalysts were layered with silver
sputtering. The instrument was kept at 20 kV for determin-
ing the particle size and shape of the catalysts.
TGA evaluations of composites were analyzed using
TGA/DSC 1 Star system of Mettler-Toledo make. About
5 mg of samples were taken in a silica crucible and put in the
weighing panel. The weight loss was recorded in the tem-
perature program of 50–500 °C (5 °C ­min−1), 500–1000 °C
(10 °C  ­min−1) under nitrogen as a purge gas with a flow
rate of 40 mL ­min−1. The TGA data were further evaluated
by taking the first derivative to obtain differential thermo-
gravimetry (DTG).
Reaction Procedures
Esterification of α‑Pinene at Room Temperature
The reaction was conducted in a stopper conical flask. First,
10 mg of α-pinene, 100 mg glacial acetic acid, and 1 mg
catalyst were introduced into a conical flask. Then the reac-
tion mixture was allowed to stir 600 rpm at room tempera-
ture up to 2 h. After the completion of reactions, reaction
mixtures were diluted with DCM separately and filtered with
Whatman filter paper. These filtrates were neutralized with
­NaHCO3, and partitioned with distilled water in a separat-
ing funnel. DCM fractions were collected and combined,
then removed DCM in a rota vapor at 30 °C under 380 mbar
pressure. Product samples were stored at 4 °C until analysis.
Esterification of α‑Pinene under the Presence of Nitrogen
A similar reaction mixture ratio was also carried in a 25 mL
pressurized reactor (Amar Instrumentation make, Mumbai,
13
Waste and Biomass Valorization
India) for performing a reaction under ­N2 pressure of 50 psi.
After the completion of the reactions, the reaction mixture
was cooled and depressurized. Then, the reaction mixture
was diluted with DCM and filtered with Whatman filter
paper. These filtrates were neutralized with N ­ aHCO3, and
partitioned with distilled water in a separating funnel. DCM
fractions were collected and combined, then removed DCM
in a rota vapor at 30 °C under 380 mbar pressure. Product
samples were stored at 4 °C until analysis.
Volarization of Essential Oil by Optimized Esterification
Reaction
Similarly, each 100 mg of essential oil was used for the
esterification reaction and proceeded with this transforma-
tion at optimized conditions. The optimized parameters were
considered based on the monoterpene hydrocarbon frac-
tion in the essential oils. After completion of the reaction,
the modified oil samples were stored at 4 °C until further
analysis.
GC‑FID and GC/MS Analysis
Each essential oil, such as BS, CM, PN, MF, and SR were
analyzed before the reaction. The α-pinene, as well as its
modified compounds, essential oils, and semi-synthesis reac-
tion mixtures, were analyzed using a fused silica capillary
column (Elite-5MS) through a Varian-CP 3800 GC equipped
with a flame ionization detector (FID). The column length
was 30 m and id of 0.25 mm, which inner side film coating
thickness was 0.25 μm. Hydrogen was used as a carrier gas
with a flow rate of 1 mL ­min−1. Injector and detector tem-
peratures were maintained at 280 °C. The oven temperature
was programmed as follows: 60–240 °C with the rate of
3 °C/min, 240 °C (20 min). The concentrated samples were
injected with a split ratio of 1:30, and an injection volume
of 0.02 μL was drawn through a micro-syringe. The gas
chromatography-mass spectrometry (GC/MS) analyses were
performed on a PerkinElmer Clarus 680 gas chromatograph
coupled to a Clarus SQ 8C mass spectrometer. The peaks
were recorded after 3 min to avoid the detection of solvent;
the mass range from 40 to 500 amu with electron ioniza-
tion (EI) 70 eV. The column and temperature program was
similar, as mentioned in the GC analysis. The temperature of
the interface was 220 °C. The carrier gas was Helium with a
flow rate of 1 mL ­min−1. The sample (0.3 μL) was inserted
through the injector port set at 250 °C. The compounds were
identified by mass spectra library search (NIST/EPA/NIH
and Wiley registry of mass spectral data, 7th edition) and by
matching with the reported Kovats indices (KI) [10]. Finally,
the compounds were confirmed by considering retention
Waste and Biomass Valorization
time, the elution order of terpenoids, calculated value of
relative retention indices (RRI) of a homologous series of
n-alkanes ­(C8-C18 hydrocarbons).
Catalyst Reusability
After the reaction, the catalyst was filtered and washed prop-
erly with ethanol to follow acetone. Then the dried catalyst
was washed in water, and calcined for 4 h for use in the
subsequent batch of reaction. Then the catalyst reusability
was tested for the next three batch processes.
Results and Discussion
Characteristics of the Catalysts
The XRD signals of (0.1, 0.5, and 1%) Pd-β-ZE have resem-
bled the microporous β-ZE (Fig. 1A), which indicated that
Pd incorporation does not transform the physical structure
of β-ZE. In the present spectra, the diffraction signals were
clearly identified. However, no extra peaks of Pd species
have been observed in the Pd-β-ZE diffraction spectra. It
might be due to the low concentration and proper distri-
bution of Pd species over the ZE surface or by overlap-
ping ZE diffraction signals with the metal oxide species.
The decrease in intensity of some diffraction signals was
observed, which attributes to the successful incorporation
of Pd. FT-IR spectra are given the comparative intensity of
different groups in the β-ZE, as well as (0.1, 0.5, and 1%) in
Pd-β-ZE (Fig. 1B). Signal corresponding to the Si–O bend-
ing vibration is observed at ∼460 ­cm−1 [11], the symmetric
Fig. 1  A XRD spectra of 0.1%Pd-β-ZE, 0.5%-Pd-β-ZE and 1% Pd-β-ZE catalyst. B FT-IR analysis of 0.1%Pd-β-ZE, 0.5%-Pd-β-ZE and 1%
Pd-β-ZE catalyst
Table 1  Surface area analysis of catalyst
Catalyst BET Langmuir Total pore Average pore
surface area surface area volume diameter ­(Ao)
­(m2 ­g−1) ­(m2 ­g−1) ­(cm3 ­g−1)
β-ZE 650.4 794.5 0.35 34.6
1%Pd-β-ZE 400.2 594.5 0.33 33.4
and asymmetric stretching vibrations of Si–O-Pd are present
at ∼790 and 920–1220 ­cm−1.
BET and Langmuir surface area of β-ZE and synthesized
1%Pd-β-ZE is calculated using ­N 2 adsorption–desorp-
tion isotherm, and the data are presented in Table 1. The
total surface area, micropore volume, and pore diameter of
1%Pd-β-ZE are slightly lower than β-ZE. The decrease in
surface area is attributed to the impregnation of low surface
area metal oxides over β-ZE or the formation of small metal
oxide species in the porous channel of β-ZE to partially
blocking its micropore [12, 13]. SEM images of synthesized
catalyst are presented in Fig. 2A–C. It indicated that all the
particles possessed a uniform spherical shape. The effect of
metal loading as the highly aggregated form is noticed in
1%Pd loading on the ZE surface is compared to the lower
stacking of Pd (0.1, and 0.5%). Also, the SEM-EDAX of
1%Pd-β-ZE was conducted to authenticate the incorporation
of Pd. From Fig. 2D, it is confirmed that the incorporation
of Pd over β-ZE surface. The TGA graph has shown the
thermostability of Pd-β-ZE catalysts in comparison to the
base material (β-ZE) (Fig. 2E). All Pd impregnated β-ZE
catalysts have been displayed higher stability up to 1000 °C.
13

Fig. 2  SEM images of catalyst Pd-β-ZE A 0.1% Pd loading, B 0.5% Pd loading, C 1%Pd loading, D SEM-EDAX of 1% Pd-β-ZE catalyst, E
TGA spectra of 0.1%Pd-β-ZE, 0.5%-Pd-β-ZE and 1% Pd-β-ZE catalyst
Esterification of α‑Pinene at Room Temperature
α-Pinene was esterified in the presence of glacial acetic
using 1%Pd-β-ZE to produce terpinyl acetate and bornyl
acetate with a high conversion percentage. For that differ-
ent parameter has been optimized such as metal loading,
the effect of temperature, and reaction time. The general
mechanism of α-pinene esterification is given in Scheme 1a.
Effect of Metal Loading and Catalyst Ratio
To study the influence of metal loading on α-pinene esterifi-
cation, the reaction is carried out with Pd-β-ZE with varying
the Pd loading (0.1, 0.5, 1, and 2 wt%). The β-ZE has been
shown a 45% conversion of α-pinene with 22% selectivity
towards terpinyl acetate, while the Pd loaded β-ZE is dis-
played maximum conversion with good selectivity (Fig. 3A).
Among them, 1%Pd-β-ZE was given the highest conversion
(98%) with a selectivity of terpinyl acetate (54%) and bor-
nyl acetate (34%). On further increasing the Pd loading the
pinene was fully consumed, but selectivity to acetates was
poor. Hence, the lower amount of Pd over β-ZE was assisted
in partial delocalization of double bond to form the desired
cyclized product (terpinyl acetate, and bornyl acetate). But
at higher Pd loading, it might be changed the attacking site
13
Waste and Biomass Valorization
to produce undesired Products. Also, 1%Pd-β-ZE is associ-
ated with low surface area as compared to the base material
(β-ZE), but it has shown higher conversion of α-pinene with
maximum selectivity to bornyl acetate and terpinyl acetate.
It might be due to the high dispersion of metal oxide species
over β-ZE to increase the overall catalytic activity. Further,
different ratios of catalyst to α-pinene were taken for the
optimization study. It is found that the proportion (1:10)
of 1%Pd-β-ZE to α-pinene is most suitable for providing a
higher conversion percentage with better selectivity towards
the monoterpene acetates (Fig. 3B).
Effect of Temperature
The effect of reaction temperature on the above transfor-
mation is given in Fig. 4A. The results indicated that the
increase of temperature was enhanced the consumption of
α-pinene, but decreased the yield of terpinyl acetate and bor-
nyl acetate. The highest selectivity was obtained at room
temperature (30 °C), and only a few percentages of α-pinene
were unreacted after 2 h of reaction time.
Waste and Biomass Valorization
Scheme 1  Possible transforma-
tion of A pinene to acetates, B
bicyclic monoterpene hydrocar-
bons to monoterpene acetates /
alcohols
Effect of Reaction Time
The reaction is carried out at various time ranges from
30–240 min, as shown in Fig. 4B. It indicated that with
the increase of reaction time, the yield of terpinyl ace-
tate and bornyl acetate was increased. After 120 min, the
percentage of terpinyl acetate and bornyl acetate were
declined; thus, 120 min was the optimum reaction time.
Hence, the optimum parameters were used for esterifica-
tion of α-pinene to terpinyl acetate and bornyl acetate to
give maximum conversion with the highest selectivity
under the following conditions; 1%Pd-β-ZE, in 120 min
with a catalyst-reactant ratio of 1:10 at room temperature
(30 °C). Further, β-pinene was followed a similar trend
for the above transformation to terpinyl acetate and bornyl
acetate.
Catalyst Reusability
The characterization parameters of re-used catalyst
(1%Pd-β-ZE) were very similar to the original prepared cata-
lyst. The catalytic active sites are retained for the subsequent
three batches with similar conversion percentage (Fig. 4C).
Hence, the catalyst is truly heterogeneous in nature.
Esterification of α‑Pinene under an Inert
and Pressurized Atmosphere
α-Pinene esterification was performed in the presence of
­N2 by using 1%Pd-β-ZE to produce a significant percentage
of bornyl acetate (83%) in a 1:10 ratio of reactant to cata-
lyst. The different parameter has been optimized such as the
effect of temperature (30 to 60 ºC), ­N2 pressure (30 to 60
psi), and reaction time (30 to 120 min) (Fig. 5). The reaction
temperature under the 50 psi N ­ 2 pressure was only trans-
formed 47% α-pinene to 42% of bornyl acetate and terpinyl
acetate at room temperature (30 °C). When the temperature
was increased, the α-pinene was almost consumed (97%)
with enhanced selectivity towards bornyl acetate (83%) and
terpinyl acetate (8%) at 50 ºC. The further increase of tem-
perature (60 ºC) adversely impacts the acetate’s selectivity,
as shown in Fig. 5A. The effect of N ­ 2 pressure at 50 ºC was
optimized from 30 to 60 psi and obtained the maximum
conversion of 97% at 50 psi N ­ 2 pressure with high selectiv-
ity towards bornyl acetate (83%). While further increasing
pressure to 60 psi, the selectivity percentage is decreased,
as shown in Fig. 5B. The reaction time of 60 min was rea-
sonably sufficient to obtain 83% of bornyl acetate. Hence,
further additional time (1 h) only consumed 2–3% of extra
α-pinene, but it is achieved by lowering the percentage of
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Fig. 3  α-Pinene transformation, A Effect of Pd loading, B Effect of Catalyst and α-pinene ratio (TA: Terpinyl acetate, BA: Bornyl acetate)
monoterpene acetates (Fig. 5C). Finally, 97% transformation
of α-pinene to bornyl acetate (83%) and terpinyl acetate (8%)
was attained under 50 psi ­N2 pressure at 50 ºC in an hour.
Valorization of Monoterpene Hydrocarbons Rich
Essential Oil
The yields of essential oils were 5.2, 1.1, 1.4, 4.0, and
1.3% for BS, CM, PN, MF, SR, respectively. The esteri-
fications of cyclic-monoterpenes rich above essential oils
including pinenes were esterified at 30 °C for valorization
(Scheme 1b). Due to the ease of operation, the optimized
atmospheric conditions were selected for this transformation
reaction. These essential oils were used for valorization to
bornyl acetate, fenchyl acetate, and terpinyl acetate using
glacial acetic acid with 1%Pd-β-ZE at 30 °C for 2 h.
The composition of fresh essential oils and their modi-
fied compositions are presented in Table 2. The fresh essen-
tial oils compositions were revealed that the monoterpene
hydrocarbon ranged from 26.2–78.9%, and these essential
oils were contained mostly monoterpenoids. These essential
oils were comprised of lesser oxygenated monoterpenoids,
which diminished their commercial importance in the aroma
industries [4]. The oxygenated compounds are generally pre-
ferred due to their characteristic flavors and hence catego-
rized as superior quality. Due to the numerous advantages,
the percentage of oxygenated terpenoids in the essential
oils has become an important criterion to attract higher
prices [14, 15]. Guggul, salaiguggul, nutmeg, rosemary,
and black pepper essential oils have reasonable amounts
of bicyclic monoterpene hydrocarbons such as α-thujene,
α-pinene, camphene, sabinene, β-pinene, δ-3-carene, etc.
These bicyclic monoterpenes are comparatively unstable
due to the bond angle stress; hence these are transformed
13
Waste and Biomass Valorization
to the corresponding structural related acetates such as
terpinyl acetate, bornyl acetate, and fenchyl acetate using
glacial acetic acid with 1%Pd-β-ZE at 30 °C in 2 h. Interest-
ingly, it is noticed that a few percentages of these acetates
may be hydrolyzed to the alcohols (Scheme 1b). Hence, the
percentage of camphor, terpinen-4-ol, and α-terpineol were
increased in the modified oils. The monocyclic monoter-
pene hydrocarbons such as α-terpinene, limonene, and
acyclic myrcene are partially transformed into oxygenated
terpenoids (Scheme 2a). On the other hand, isomers of p-/o-
cymene are stable aromatic monoterpene hydrocarbons
(Scheme 2b).
The BS, MF, and CM were contained 74.1, 78.9, and
73.7% of monoterpene hydrocarbons. These essential oils
were enriched with α-thujene, α-pinene, sabinene, and
β-pinene. As expected, these are transformed into terpinyl
acetate, bornyl acetate, and fenchyl acetate. On the other
hand, limonene, γ-terpinene and α-terpinolene were par-
tially transformed into oxygenated terpenoids. In addition,
PN and SR were contained limonene and 1,8-cineole as a
major percentage, and these compounds are partially con-
verted to other oxygenated terpenoids. Only the organo-
leptically important 1,8-cineole is present 48.0% in the
SR essential oil, but it most likely partially transformed to
α-terpineol and terpinyl acetate (Scheme 3). 1,8-Cineole is
a bicyclic[2 + 2] monoterpenoid, which is partially trans-
formed to terpinyl acetate in acetic acid in the presence of
1%Pd-β-ZE. Hence, the esterification time of PN and SR
should be shortened to prevent 1,8-cineole transformation.
From the above modification of monoterpene hydrocar-
bons to organoleptically superior acetates was attained under
very mild reaction conditions. The valorizations of monoter-
pene hydrocarbons enrich essential oil into oxygenated
monoterpenoids such as fenchyl acetate, bornyl acetate, and
Waste and Biomass Valorization

Fig. 4  α-Pinene esterification, A Temperature, B Time, C Re-usabil-

ity (TA: Terpinyl acetate, BA: Bornyl acetate)
Fig. 5  Different effect on α-pinene esterification A ­N2 pressure, B
Temperature, C Time (TA: Terpinyl acetate, BA: Bornyl acetate)
terpinyl acetate through a green process. The monoterpene
hydrocarbons were selectively modified to terpene alco-
hols and enriched the percentage of monoterpene acetates
(Table 2). The modified essential oils are organoleptically Conclusion
superior, and these might be displayed better bioactivities;
hence this is an industrial application for the valorization of 1%Pd-β-ZE has been shown an excellent catalytic activity
terpene hydrocarbon-rich essential oils. for α-pinene esterification at very mild reaction conditions.
In atmospheric conditions, the pinene is predominantly
produced terpinyl acetate along with bornyl acetate. But,

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Table 2  Modification of monoterpene-hydrocarbons rich essential oils
Compounds Boswellia Nutmeg Commiphora Black pepper Rosemary KI
Fresh (BS) Modified Fresh (MF) Modified(MFM) Fresh (CM) Modified Fresh (PN) Modified Fresh (SR) Modified
(BSM) (CMM) (PNM) (SRM)

α-Thujene 45.0 0.8 2.0 – 40.6 0.8 1.8 – – – 931

α-Pinene 8.5 0.7 17.0 0.5 2.5 0.3 12.2 – 11.6 0.3 939
Camphene 1.4 0.1 0.8 0.5 3.0 0.3 0.3 0.1 3.2 0.2 953
Sabinene 5.0 0.3 25.0 1.5 2.0 0.5 12.9 0.1 – – 976
β-Pinene 0.8 – 13.0 0.4 3.5 0.3 10.8 – 2.1 0.3 980
Myrcene 5.6 1.0 2.0 0.2 1.5 1.0 1.9 1.3 – – 991
δ-3-Carene 1.1 0.3 2.0 0.5 1.0 – 6.8 0.3 – – 1011
α-Terpinene 0.2 – 3.0 1.0 – – 0.2 2.0 – – 1018
o-Cymene 0.5 0.4 – – – – 0.1 0.2 – – 1022
p-Cymene 4.5 4.6 1.7 2.0 0.1 0.1 0.4 1.9 3.0 2.0 1026
Limonene 1.0 0.2 7.4 5.0 13.0 8.0 16.0 12.9 3.1 2.0 1031
1,8-Cineole – – – – 2.0 1.0 0.1 0.1 48.0 31.6 1033
γ-Terpinene 0.3 0.2 5.0 4.5 4.0 3.5 0.3 0.6 – – 1062
α-Terpinolene 0.2 – – – 2.5 1.5 0.1 0.1 – – 1088
Camphene – – – – – – – – 1.2 1.5 1098
(E)-Thujone 1.3 1.0 – – – – 0.3 0.2 – – –
Camphor – – – – – – – – 11.0 13.8 1114
Borneol – 2.0 – 1.5 8.0 10.2 0.1 1.1 2.6 8.2 1165
Terpinen-4-ol 1.8 3.0 6.0 7.5 1.5 1.8 0.2 1.1 0.6 1.6 1177
α-Terpineol 8.0 9.0 0.6 2.0 3.0 3.5 0.1 2.1 2.0 7.9 1189
Fenchyl acetate – 4.6 – 3.5 – 0.5 – 4.5 – 1.6 1234
Bornyl acetate – 13.2 1.2 16.0 – 18.0 – 14.0 – 5.3 1285
Terpinyl acetate – 45.5 0 36.0 – 36.0 0.1 22.2 – 11.4 1350
(E)-Caryophyllene – – – – – – 29.7 27.2 1.6 1.9 1418
Total 85.2 86.9 86.7 85.6 88.2 87.3 94.4 92.0 92.0 89.6
Monoterpene 74.1 8.6 78.9 19.1 73.7 16.3 63.8 19.5 26.2 6.3
hydrocarbons
Oxygenated monoterpenes 11.0 78.3 7.8 66.5 14.5 71.0 0.9 45.3 64.2 81.4
Other biomarkers 14.0 13.0 13.0 14.0 11.0 12.0 34.0 32.0 8.0 10.0
Waste and Biomass Valorization
Waste and Biomass Valorization
Scheme 2  Monoterpene hydro-
carbons, A Monocyclic/acyclic,
B Aromatic
Scheme 3  Catalytic modification of 1,8-cineole to terpiny lacetate
interestingly, the neutral environment (50 psi nitrogen) is
solely produced bornyl acetate with a very little percentage
of terpinyl acetate. These monoterpene acetates are widely
used as fragrance ingredients in various foods and cosmetic
products. Our work on the valorization of monoterpene
hydrocarbons in the essential oils of salaiguggul, guggul,
nutmeg, rosemary, black pepper to terpinyl acetate, bornyl
acetate, and fenchyl acetate, and modified oils are organo-
leptically superior. The monoterpene hydrocarbons such
as α-thujene, α-pinene, camphene, sabinene, β-pinene, and
δ-3-carene are fully transformed into monoterpene acetates/
alcohols. As the reaction is carried out without any organic
solvents makes the overall process eco-friendly. This is the
first report on the valorization of monoterpene hydrocarbon
enrich essential oil to high-value monoterpene acetates. A
solvent-free process has been developed for the selective
conversion of bicyclic monoterpene hydrocarbons to terpi-
nyl acetate and bornyl acetate using 1%Pd-β-ZE at room
temperature. This process may be practiced by the industry
to overcome the deterpenation process.
Acknowledgements  We are grateful to the Director, CSIR-CIMAP,
Lucknow for providing the necessary laboratory facilities under
the CSIR-Aroma mission (HCP0007, PE-II). The authors are
thankful to SERB, DST for fellowship to PKS, and financial grant
(CRG/2021/002525) for carrying out this work.
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