One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst
Corresponding email: ifnata@ulm.ac.id
Published at : 24 May 2019
Volume : IJtech
Vol 10, No 3 (2019)
DOI : https://doi.org/10.14716/ijtech.v10i3.2924
Ma’rifah, Y.N., Nata, I., Wijayanti, H., Mirwan, A., Irawan, C., Putra, M.D., Hidetaka, K., 2019. One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst. International Journal of Technology. Volume 10(3), pp. 512-520
| Yulia Nurul Ma’rifah | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Iryanti Nata | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Hesti Wijayanti | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Agus Mirwan | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Chairul Irawan | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Meilana Dharma Putra | Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia |
| Kawakita Hidetaka | Department of Chemistry and Applied Chemistry, Saga University, Saga 840-8502, Japan |
The main purpose of this study is to
produce and generate a solid acid catalyst from biomass with high reactivity
that can be used in catalytical reactions such as hydrolysis, and is
environmentally friendly and reusable. A biocarbon-based sulfonated catalyst was prepared by
the carbonization of palm empty fruit bunches (PEFB), followed by sulfonation.
In order to enhance the acidity of the biocarbon, different concentrations of
hydroxyethylsulfonic acid were added to the solution during sulfonation at 180o
C for 4 h in a Teflon stainless steel autoclave. The H+ ion
capacity of the biocarbon-sulfonated acid catalyst (BSC) was increased twofold
(3.57 mmol/g) in the presence of 10% of hydroxyethylsulfonic acid and 10% of
acrylic acid. X-Ray Fluorescence (XRF) analysis showed that the BC-SO3H
contained 38% of S. The original structure of the PEFB after carbonization
disintegrated from the fibrous materials onto porous carbon. The crystalline
index (CrI) of the PEFB significantly decreased to about 32% and a wide broad
peak of a X-Ray Diffraction (XRD) pattern of around 20-30o were observed, which shows that an amorphous biocarbon
structure had been identified. Fourier Transform Infra-Red (FT-IR) analysis
confirmed that the -SO3H, COOH and -OH functional groups were
deposited on the carbon due to specific peaks at around 1180 cm-1,
1724 cm-1 and 3431 cm-1, respectively. Decomposition of the
sulfonic groups on the biocarbon-sulfonated solid catalyst was observed from
227.9o C, as it shown by thermal gravimetric analysis (TGA).
Acid catalyst; Biocarbon; Palm empty fruit bunch; Sulfonated; Sulfonation
Palm is one of the most important commodities in Indonesia due
to its rapid development. The major product from the palm industry is Crude
Palm Oil (CPO), but with its increasing production, the waste, that takes the
form of empty fruit bunches, has increased. Nowadays, biomass and industrial
waste have become very interesting issues as aspects of catalyst development,
both in research and from the technical point of view, due to their valuable
merit of industrial waste (Guerrero-Pérez et al., 2006; Kusrini et al., 2018).
Biomass energy is an ideal clean and renewable energy source, characterized by
its wide range of sources, low prices, strong reproducibility and less
pollution creation (Wenjing et al., 2018).
In the
using of solid acid catalysts, they are easy and efficient when separated from their products, are reusable and it is possible
to apply them in wide of applications, but most such catalysts developed are
expensive and quite difficult to prepare (Okuhara, 2002).
Theoretically, at low carbonization (400–600oC), biomass
generates a highly cross-linked, multi-ringed, aromatic structure anchored to
lignin that can be easily functionalized with catalytically active acidic
groups by slow pyrolysis (Kastner et al., 2012). Generally, a two-step process is involved in the
production of sulfonated carbonaceous materials. Saccharide is incompletely
carbonized at a temperature of > 400°C for >15 h under an inert atmosphere. A large
amount of sulphuric acid use in the sulfonation process at a high temperature
for the inactive surface of carbonaceous material (Zong et al., 2007). This process uses hazardous material and a large
amount of harmful waste is produced; moreover, the carbon in the concentrate
sulphuric also needs special attention for its separation and treatment.
Hydrothermal
carbonization (HTC) is a thermochemical process capable of converting wet
biomass into a carbon-enriched solid as hydrochar. The HTC process consists of
several reactions conducted both in series and in parallel, including
hydrolysis, dehydration, decarboxylation, condensation and aromatization (Merzari et al., 2018). HTC is process which
involves the decomposition of several carbohydrates in aqueous solution at
180°C. This method is cheap, mild and environmental friendly, as no organic
solvents, catalysts or surfactants are used (Titirici et al., 2007). In a previous study, Xiao et
al. (2010) performed hydrothermal treatment with hydroxyethylsulfonic acid as a
sulfonate agent to produce carbon from glucose and used it for an
esterification process in order to examine its catalytic ability. However, this
procedure only achieved 1.7 mmol/g of acidity and still owned little of
functional groups. Therefore, to generate carbonaceous material loaded with
carboxylic groups, known as an active group that participates in the reaction,
acrylic acid was added (Bautista-Toledo et al., 2005). In order to produce a high content of functional
groups on the
carbon material, it is possible
to modify the surface by a one-step HTC process for sulfonation and thus
improve the acidity of the carbon.
This work focuses on the effect of
hydroxyethylsulfonic acid
concentration and the addition of acrylic acid during the hydrothermal process.
Therefore, the characterization of aspects such as acidity, morphological
structure, crystalline structure, functional groups and thermal gravimetric
analysis was investigated.
The strong acid content, rich of sulfonic and carboxylic groups of
materials could be easily synthesized by a one-step hydrothermal process using biocarbon
from incomplete carbonization of PEFB, and in the presence of hydroxyethylsulfonic,
acrylic and citric acid in mild conditions. The simplicity of operation, high
activity and stability, low cost of raw materials and reusability are the main
features of this original biocarbon-based sulfonated solid acid catalyst, which
demonstrates that biocarbon has great potential for green processes in various
catalytic applications.
The authors are grateful for the financial support from International
Research Collaboration and Scientific Publication (contract No.
040/UN8.2/PL/2018), Ministry of Research, Technology and Higher Education,
Republic of Indonesia.
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