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Potential in Processing Indonesia Natural Resources into Renewable Phenolic

Compounds

Petrochemical industry is an important industry sector which process raw

hydrocarbons from petroleum refineries into beneficial chemical products to fulfill
human needs. The products are polymer, solvent, surfactant, adhesive,
pharmaceutical, and many others. They are grouped into three different groups
called feedstock, intermediate, and finished product. Feedstock is a raw
hydrocarbon that is a product of petroleum refineries, such as benzene, toluene, and
xylene. Feedstock is processed in a thermal or catalytic cracking to produce more
complex compounds like phenol, propylene, methanol, and ethyl alcohol and they
are grouped as intermediates. These intermediates are processed with
dehalogenation, hydrogenation, addition, or polymerization reaction to produce
final products such as plastic, rubber, synthetic fiber, detergent, alcohol, paint,
pharmaceutical, etc.
Lately, almost 95% of monomer hydrocarbons or intermediates are
produced from coal and petroleum which are fossilized carbon.1 Fossilized carbon-
dependant in intermediate production, has lead to several problems. Depleting oil
reserves, greenhouse gas emissions and accumulations of non-degradable waste
have motivated the scientist to do researches and find alternative sources of
renewable hydrocarbons.
Indonesia as a tropical country has abundant natural resources which have
great potential to find renewable hydrocarbon resources. Plants and agro-based
industry wastes are a source of renewable hydrocarbon and they are eco-friendly
because of their biodegradability and low toxicity during preparation, usage, and
disposal. One of intermediate hydrocarbons that possesses great potential to be
produced in Indonesia is phenol compounds.
Phenolic compounds are widely used as a raw material in plastic,
explosives, drugs, pharmaceuticals, dye and dye intermediate industry. Until now,
the primary source of phenol production is from processing cumene peroxide which

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is a petroleum product. Phenolic compound demand in Indonesia tends to increase

annually, as shown in Table 1. Dean of pharmacy school Institut Teknologi
Bandung Hadi Tjahjono claim that 90 percent of total raw materials in
pharmaceutical including phenol as the building block of medicines are imported,
while in 2014, Indonesia needs to provide medicines for 240 million people. In
2012, Indonesia spend 21 million USD in importing phenol and the import value is
predicted to reach 31 million USD or 425 billion Rupiah in 2014.2

Table I. Imported Phenol Data in Indonesia

Year Capacity (ton/year)

2010 13,935
2011 19,290
2012 14,593
2013 16,630
2014 20,337
2015 21,134

(Source: Indonesia Bureau of Statistic, 2010 – 2015)

Unfortunately, with this high phenol demand, there is no available plant that
can produces phenol in Indonesia, therefore, Indonesia needs in phenolic
compounds are fulfilled by importing phenol from Japan and United States. With
phenolic compounds high demand and the absence of phenol plant, making it
promising to build a new phenol plant with natural resources as the raw material.
Natural phenolic compounds can be found in cashew nut shell liquid (CNSL),
tannin, palm oil shell, and coconut shell tar (CST).3 Because of the limitation in raw
material availability and complexity in processing
lignin, tannin and coconut shell tar (CST) compared to
CNSL and palm oil shell, therefore promising
renewable phenol resources in Indonesia are cashew
nut shell liquid (CNSL), and palm oil.
CNSL is a reddish brown viscous liquid
obtained as a product of cashew nut shell extraction.
Fig 1. Phenol in CNSL The main phenolic compounds in CNSL are

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[a] anarcadic acid (71,7%), [b] cardanol (4,7%), [c] cardol (18,7%), and [d] 2-
methyl-cardol (2,7%), as shown in Figure 1, and the remaining 2,2% unidentified
polymeric material.4 Based on data from Indonesia Tree Crop Estate Statistics, raw
cashew nut production in 2016 has reached 130.072 tons with 30.726 tons or 23,6%
of total production is imported and the remaining 99.346 tons or 76,4% are used to
fulfill domestic needs.5 Cashew nut shell percentage in raw cashew nut is about
45% which contain 30 – 35% CNSL,6 therefore Indonesia potential in the
production of CNSL is 13,411 tons/year. The number of CNSL production will be
increased if the exported raw cashew nuts are first processed to collect their shells
and then exported in form of cashew nut only. CNSL is commercially produced in
two ways and available in two grades. The first is natural grade: the cold-processed
CNSL, obtained by solvent extraction of cashew nut shells, has anacardic acids (60–
70%) and cardols (20–25%) as major components. 7 The second is technical grade:
the hot-processed/heat-extracted CNSL, which oozes out of the shells during
roasting of the nuts for separation of the kernels.

Cardanol and cardol are desired to be products in CNSL because anarcadic

acid is a highly corrosive and poisonous material and it is less commercially. To
make a better conversion in CNSL into cardanol and cardol, CNSL extraction will
be done in hot-processed/heat-extracted process. In this process, CNSL is extracted
from the shell at high temperature in the range 80 – 200oC. Once it reaches a
temperature of 180oC it is kept for 2-3 hours to ensure the occurrence of
decarboxylation process. During this process, the percentage of cardanol increased
to ~68% at the expense of thermal decarboxylation of anarcadic acid. 3 Technical
grade of CNSL can be obtained by distillation at reduced pressure. The composition
of technical grade CNSL, is about 78% cardanol, 8% cardol and 2% polymeric
material.3 Separation of cardanol especially from cardol can be done with a physical
process such as vacuum distillation.

Indonesia and Malaysia are the leading producers of palm oil in the world.
In 2016, Indonesia produced 33,229,381 tons of palm oil with 24.150.232 tons are
exported.5 There are 470 palm oil plants operating until now and a single plant that

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has a capacity of 60 tons/hour production will produce 100 tons/hour of palm oil
wastes annually. In a year, total palm oil wastes productions are 28,7 MMT liquid
waste and 15,2 MMT solid waste.8 Solid agro-waste generated from the oil palm
mill industry such as oil palm fronds (OPF), empty fruit bunches (EFB) and oil
palm shell has nearly 60 – 80 % cellulose and 20 – 30 % lignin-content,9 which
mean Indonesia has 4,560,000 tons per year of lignin potential from oil palm mill
waste. This lignin in the wastes is to be processed in pyrolysis process to obtain
phenolic compounds product. Pyrolyzed palm shell oil contains a high percentage
of phenol and its derivatives, such as substituted cresol, pyrocatechol, guaiacol,
syringol, and eugenol as shown in Figure 2.

Oil palm shell waste that is obtained from palm oil mills first treated with
grinding, sieving and drying until it matched the specification of the reactor feed.
The reactor used in the process
is fluidized-bed with nitrogen
as the fluidization medium and
silica sand as the fluidized-bed
material with 500oC operating
Fig.2. Structure of phenols extracted from palm oil
temperature and pressure slightly
above atmospheric pressure.

A fluidized bed is used in the process because it has several advantages as

chemical reactor over the other types of reactor, it is higher heat and mass transfer
rates between the gas and solid particles, easier to control of temperature, easier to
scale up and flexible with regards to its feed rate and composition. The products
obtained from the process were pyrolysis liquid oil, char, and gas. Conversion of
pyrolysis oil from reactor feed is 56 wt% of total feed and this pyrolysis oil product,
contain 28,30% phenol, 16,90% acetic acid, 2,16% pyrocatechol, 1,36% eugenol,
and many other traces.10 Based on previous data, with 4.560 MMT per year lignin
and 56% is converted to pyrolysis oil which contains 28,30% phenol, therefore, the
potential phenol from palm oil shell is 722,669 tons per year. To separate phenol
from other pyrolysis oil products, an extraction process must be carried with

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standard solvent. It is to note that the requirements for the standard solvent are that
it should have at least a moderate solubility parameter, a moderate degree of
polarity, and capable of extracting phenol and their compositions from fast-
pyrolysis oil. The standard solvent is separated by evaporation technique to obtain
solvent free phenol product.

From all the statements above, it can be concluded that Indonesia has two
sources of phenol and derivatives, they are CNSL and palm oil shell. CNSL has
potential as a source of cardanol and cardol with 10.460,58 tons/year production
rate of cardanol and 1072,88 ton s/year of cardol. The economic value of
cardanol is $3000/ton,11 that means the production value is US$ 31 million or IDR
423 Billion. The process used in cardanol production is called hot-processed/heat-
extracted process and the separation process will be done by vacuum distillation.
Cardanol finds use in the chemical industry in Oil and Alcohol soluble resins,
laminating resins, rubber compounding and coatings, paints, and enamels. Palm oil
shell has a remarkable potential as a phenol resource. Potential production of phenol
from palm oil shell with fluidized bed reactor is 722,669 tons/year and with this rate
of production, it will exceed annual domestic phenol demand which is only 21,314
tons/year in 2015. This excess phenol production can be a new promising export
commodity and it will bring remarkably high profit since phenol prize is €1220/ton.
If the excess 701.354,8 tons/year phenol is to be sold, its value is estimated to be
EUR 881 million or IDR 14 trillion annually.

Table 2. Analysis Summary

Raw Material Potential Estimated
Phenolic
Availability, Production, Economic Value, Applications
Compound
tons/year tons/year Rupiah
Resin, rubber,
Cardanol 13,411 10.460 423 Billion coating, paints,
enamels
Plastic, explosives,
Phenol 4,560,000 722,669 14 Trillion drugs,
pharmaceuticals

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