The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 1-6

doi: 10.4028/p-aYNBt6

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-10-23

Revised:
2023-03-19

Accepted:
2023-03-19

Online:
2023-08-11

Studying the Factors Affecting De-Emulsification of Crude Oil

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

Zolfa. Q. Atshan and Muhanned A. Mohammed

Department of Chemical Engineering, University of Al-Nahrain, Iraq

Department of Chemical Engineering, University of Al-Nahrain, Iraq

zolfaqahtan123@gmail.com, dr.m.alhashimii@gmail.com

Keywords: De-emulsification, Crude oil, Centrifuge, Emulsion, Chemical method.

Abstract

The paper deals with highly stable emulsions. It is concentrated on de-emulsification of crude oil. In the petroleum industry, de-emulsification is an important and urgent task that is typically required for the treatment of crude oil. This work, suggests method using coupling device integrated centrifuge with chemical to strengthen the de-emulsification efficiency. A number of deemulsification runs were conducted to determine how centrifuge and chemical components affected the effectiveness of de-emulsifying crude oil and the separation of water, Different types of deemulsifiers the (ethylene glycol, choline chloride and ethyl cellulose), were used with different concentration of de-emulsifiers, de-emulsification time in centrifuge and centrifugal speed. Also studied at the same time. Studies on the de-emulsification of crude oil were conducted at room temperature. As the concentration of de-emulsifiers was increased, crude oil's de-emulsification efficiency rose, centrifuge time and centrifugal speed ,with de-emulsifier type effect on deemulsification, which reached maximum ( and ) at rate of ethylene glycol, choline chloride and ethyl cellulose respectively ,at 60 min and 4000 rpm . This method provides higher water separation from crude oil emulsion and quicker method.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

The petroleum business encounters several obstacles throughout manufacturing and delivery. The biggest problem with using saline water is producing highly stable emulsions (1). In an emulsion, one immiscible liquid phase (the dispersed phase) disperses as globules into another immiscible liquid phase (the continuous phase) in an emulsion. (2) . Emulsions must be avoided because the water in them consumes unnecessary space, accelerates corrosion in pipes and processing equipment, and increases costs (3).

There are many methods of de-emulsifying, including physical (thermal, mechanical, and electrical), chemical, and microbiological, but the chemical method remains the most widely used and commons method (4). The water-oil separation process of an emulsion can be greatly accelerated by combining two or more processes or operational units (5). Therefore, a coupling device integrated centrifugal and chemical are proposed (6).

Filipe X. Feitosa ...at el of, (2019), worked to create all-natural de-emulsifiers based on cardanol as an alternative to the more widely used petroleum-based ones. There are two sections to this study. First, the creation and evaluation of cardanol-based surfactant additives that were produced through several chemical methods, Cardanol formaldehyde resin (CFR), hydrogenated cardanol (HC), ethoxylated cardanol (EC), and cardanol formaldehyde resin (ECFR) are just a few examples

Second, the effectiveness of these additives in terms of emulsion separation capability has been assessed (7).
Study Zhongwei L, ...at el ,2019 (10). practical modification of tannic acid polyether de-emulsifier, the pilot-scale tannic acid de-emulsifier was changed to include polyaryl polymethylene isocyanate (PAPI), a highly active isocyanate, in order to more efficiently break the aged crude oil emulsion of the offshore platform. Its molecular weight and viscosity significantly rose with the addition of PAPI, but its relative solubility, hydroxyl number, and cloud point showed a different pattern, indicating an
increase in hydrophobicity. After applying the aforementioned modified de-emulsifier, noticeably better water removal of water-in-aged crude oil emulsion and considerable decrease in the water content in the oil phase were observed (8).

Murtada Mohammed Abdulredha, at el, (2020), they looked into how different surfactant doses, temperatures, toluene concentrations, pressure drops, and sitting times affected the de- emulsification of water in synthetic oil. They focused on propargyl alcohol and triethylene glycol. The effectiveness of surfactants in dissolving the emulsion was evaluated using the bottle test method. Additionally, a Pareto chart using a factorial design (2k1) to characterize the variables. The mathematical model was then established using CCD based on RSM, and the study's parameters were optimized using statistical analysis based on ANOVA (9).

This study proposed combining chemical and centrifugal water-oil separation with de- emulsification. The droplets are simultaneously subjected to extreme shearing and electrostatic coalescence, which may change the droplet size distribution. To our knowledge, no research on the water-oil separation model has been published that takes into account droplet dynamic properties with the coupling effect of chemical and centrifugal. It investigated how three distinct de-emulsifier series, including ethylene glycol, choline chloride, and ethyl cellulose, affected breaking the emulsion of crude oils. Deemulsification is impacted by centrifugation time, centrifuge speed, and concentration of the deemulsifier type

2. Materials and Experimental Techniques

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

2.1. Materials

A sample of crude oil was received from the Basra Oil Company, show table (2.1). Three deemulsifiers were used: ethylene glycol , Origin India), choline chloride , Origin India) and ethyl cellulose , Origin India).

Table (2.1): Physical properties of crude oil

2.2. De-emulsification

To determine whether these de-emulsifiers can successfully remove the water from crude oil emulsions, different concentrations( ,and ) of three different de-emulsifiers (ethylene glycol, choline chloride and ethyl cellulose) were added to the prepared water in the temperature room emulsion of crude oil. By using a magnetic stirrer to mix the water ( ) and crude oil ( ) for 120 minutes, a batch of each emulsion of crude oil was created. At were conducted series tests at various dosages using (ethylene glycol,choline chloride and ethyl cellulose). After adding the de-emulsifier and mixing the emulsion by hand for three minutes, homogenization was carried out. After that, a centrifuge was used to spin the tube at ( 1000,3000 , and 4000 ) rpm. The samples were examined periodically in( 15,30,45, and 60 )min to record the amount of separated water , which is calculated from the measured water contents by minus water content after centrifuge water removal where:- Ct 0 stands for the initial water content prior to settling, After centrifugation, water content isrepresented by Ct (10).
Subsequently, a crude oil sample was taken from the tube. show [figure.1]

Fig (1): (a) Centrifuge and (b) Sample of water separation.

Figure 2. Fig (1): (a) Centrifuge and (b) Sample of water separation.

3. Measurements

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

3.1. Effect of De-emulsifiers Types

Investigate the effects of several types of de-emulsifiers (ethylene glycol, choline chloride, ethyl cellulose) on emulsified crude oil.

3.2. Effect of Different Concentration of Emulsifiers on Water Separation Efficiency

The influence of varying amounts of different types of de-emulsifiers on water separation efficiency for emulsified crude oil is investigated in these tests.

3.3 Effect of Time of centrifuge on Water Separation

To determine the best feasible separation time, the amount of water separation is measured at various times in centrifuge.

3.4 Effect of Different Rotational Speed of Centrifuge on Water Separation

The spinning speed of a centrifuge at which the best water separation is obtained is being investigated.

4. Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

4.1 Effect of the Type of De-emulsifiers on Water Separation

Three types of de-emulsifiers were used (ethylene glycol ,choline chloride , and ethyl cellulose). The highest water separation rate for the ethylene glycol emulsifier was observed, reaching , as well as choline chloride, reaching , compared with ethyl cellulose, where the highest separation rate reached . The rotation speed of the centrifuge reaches 4000 rpm . Showfigures ( ), in fig(2) the concentration of ethylene glycol giving a high separation rate , The centrifuge speed of ethylene glycol produces a high separation rate in[ Fig .4] and the time of choline chloride in fig (3) respectively.

4.2 Effect of Different Concentration of De-emulsifiers on Water Separation Efficiency

Four different concentrations ( , and ) were used for each type of de-emulsifier (ethylene glycol, choline chloride, and ethyl cellulose) is given in [Fig .2]. The presence of deemulsifiers was obviously necessary in order to demulsify the stable water-in-crude oil emulsions. When de-emulsifiers are added to the emulsions, it is noticed that the stabilized water-in-oil
emulsions demulsify. However, this is very dependent on the de-emulsifier type and concentration (8). +At vol de-emulsifiers in 4000 rpm and 60 min , the dehydration ratios for the stabilized emulsions of ethylene glycol, choline chloride, and ethylene cellulose are , and , respectively. It is discovered that increasing the de-emulsifier concentration helps in deemulsification up until the critical micelle concentration is reached. Maximum level of dehydration efficiency of ethylene glycol, choline chloride and ethylene cellulose, are found to be and , respectively, at vol de-emulsifiers in 4000 rpm and 60 min .

Fig (2): Effect rate de-emulsifier on water separation from crude oil at 4000 rpm and 60 min

Figure 3. Fig (2): Effect rate de-emulsifier on water separation from crude oil at 4000 rpm and 60 min

4.3 Effect of Centrifuge Time on Water Separation

The centrifugation process was repeated four times, namely ( ) min at room temperature for different centrifuge speed ,and different concentrations , and 4%) of three de-emulsifiers( ethylene glycol, choline chloride, ethyl cellulose). Figure (3) displays a plot of water removal yield across various centrifugation times. The best rateof water removal is found in ethylene glycol, which removes water at a rate of about in 60 minutes at 4000 rpm and de-emulsifier; ethyl cellulose, which removes water at a rate of about in 60 minutes at 4000 rpm and de-emulsifier; and choline chloride, which removes water at a rate of about in 60 minutes at 4000 rpm and de-emulsifier . The longer of centrifugation time, it gives higher yield of water removal. This is because the oil droplets will have more time to separate from the emulsion during the separation process. The figure shows that longercentrifugation times produce superior separation results (water removal yield)(5).

Fig (3): Effect time on water separation from crude oil at 1000 rpm and de-emulsifier

Figure 4. Fig (3): Effect time on water separation from crude oil at 1000 rpm and de-emulsifier

4.4 Effect of Different Rotational Speed of Centrifuge on Water Separation

In this study, the effectiveness of de-emulsifying crude oil was examined at various centrifugal speeds ( 1000,3000 , and 4,000 ) rpm and centrifugal times ( , and 60 ) min, with the crude oil maintained at room temperature. Results are displayed in [Fig .4]. As can be seen, a higher centrifugal speed results in a higher de-emulsification efficiency since the smaller droplets migrate due to the improved centrifugal force at a higher speed. The improvement of the de-emulsification efficiency is widely known to be constrained by the centrifugal speed. Additionally, it should be noted that the deemulsification efficiency steadily increased at first while maintaining a nearly constant level as centrifugal time increased. This is due to the fact that the centrifugal forcegenerated by a particular speed can only move droplets of the same size and is useless for smaller droplets (10). The highest yield of water removal is found in ethylene glycol about in 4000 rpm at ( 30,45 and 60 )min and vol de-emulsifier, ethyl cellulose vol in 4000 rpm at and vol deemulsifier ,and choline chloride in 4000 rpm at de-emulsifier . A longer centrifugation speed results in a higher yield of water removal.

Fig (4): Effect centrifuge speed on de-emulsification at 60 min and de-emulsifier

Figure 5. Fig (4): Effect centrifuge speed on de-emulsification at 60 min and de-emulsifier

5. Conclusions

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

According to the current study, de-emulsifiers and centrifuges are both required for the deemulsification of crude oil. The amount of the de-emulsifier in the mixture greatly influences how well the water and crude oil separate. According to the experiment's findings, the separation rate will increase as the de-emulsifier concentration is raised. The longer the centrifuge time, the greater the percentage of water separation, and this is what was observed from the results. The speed of rotation of the centrifuge has a significant effect on increasing the separation rate. The higher the rotation speed, the higher the separation rate. In addition to that, the de-emulsifier type has a great effect on de-emulsification process, ethylene glycol has maximum separation, second choline chloride and third ethyl cellulose.

References

The original version of this paper is available on https://www.scientific.net/EC.4.1.pdf

Abdulraheim, A.M. (2018). Green polymeric surface active agents for crude oil demulsification. Journal of Molecular Liquids, 271, 329-341.

Wong, S.F., Lim, J. S., & Dol, S. S. (2015). Crude oil emulsion: A review on formation, classification and stability of water-in-oil emulsions. Journal of Petroleum Science and Engineering, 135, 498-504.

Al-Sabagh, A. M., Elsharaky, E. A., & El-Tabey, A. E. (2017). Demulsification performance and the relative solubility number (RSN) of modified poly(maleic anhydride-alt-1-dodecene) on naturally asphaltenic crude oil emulsion. Journal of Dispersion Science and Technology, 38(2), 288-295.

Vallejo-Cardona, A. A., Martínez-Palou, R., Chávez-Gómez, B., García-Caloca, G., GuerraCamacho, J., Cerón-Camacho, R., Reyes-Ávila, J., Karamath, J. R., & Aburto, J. (2017). Demulsification of crude oil-in-water emulsions by means of fungal spores. PLoS ONE, 12(2), 1-17.

Gong, H., Li, W., Zhang, X., Peng, Y., Yu, B., & Mou, Y. (2021). Effects of droplet dynamic characteristics on the separation performance of a demulsification and dewatering device coupling electric and centrifugal fields. Separation and Purification Technology, 257(October 2020), 117905.

Gong, H., Yu, B., Dai, F., Peng, Y., & Shao, J. (2018). Simulation on performance of a demulsification and dewatering device with coupling double fields: Swirl centrifugal field and high-voltage electric field. Separation and Purification Technology, 207, 124-132.

Feitosa, F. X., Alves, R. S., & de Sant'Ana, H. B. (2019). Synthesis and application of additives based on cardanol as demulsifier for water-in-oil emulsions. Fuel, 245(September 2018), 2128.

Li, Z., An, S., Liu, Y., Hua, Z., Li, F., Wang, X., Jing, B., & Tan, Y. (2019). Practical Modification of Tannic Acid Polyether Demulsifier and Its Highly Efficient Demulsification for Water-in-Aging Crude Oil Emulsions. ACS Omega, 4(24), 20697-20707.

Abdulredha, M. M., Hussain, S. A., & Abdullah, L. C. (2020). Optimization of the demulsification of water in oil emulsion via non-ionic surfactant by the response surface methods. Journal of Petroleum Science and Engineering, 184(May 2019), 106463.

Wu, J., Xu, Y., Dabros, T., & Hamza, H. (2003). Effect of Demulsifier Properties on Destabilization of Water-in-Oil Emulsion. Energy and Fuels, 17(6), 1554-1559.

Ma, J., Li, X., Zhang, X., Sui, H., He, L., & Wang, S. (2020). A novel oxygen-containing demulsifier for efficient breaking of water-in-oil emulsions. Chemical Engineering Journal, 385, 123826.

Abdurahman H. Nour, F.S. Mohammed. (2009), Demulsification of Virgin Coconut Oil by Centrifugation Method: A Feasibility Study,

Lv, X., Song, Z., Yu, J., Su, Y., Zhao, X., Sun, J., Mao, Y., & Wang, W. (2020). Study on the demulsification of refinery oily sludge enhanced by microwave irradiation. Fuel, 279 (February).

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

Table of Contents

Studying the Factors Affecting De-Emulsification of Crude Oil

Zolfa Q. Atshan, Muhanned A. Mohammed

Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Samer G. Abdulridha, Ali J. Radhi, Marwa N. Abbas, Amal K. Shehab, Wisam M. Aluaibi

A Review: Membrane Reactor for Hydrogen Production: Modeling and Simulation

Alaa Hasan Kassi, Tahseen A. Al-Hattab

Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

Marwa F. Abdul Jabbar, Abdulkareem Dahash Affat, Luay Badr Hamad

Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

S. Susi, Makhmudun Ainuri, Wagiman Wagiman, Muhammad Affan Fajar Falah

Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

Tran Quoc Toan, Thi Thu Thuy Dinh, Thi Tuyen Tran, Thi Bich Hoang, Quoc Long Pham, Quyet Chien Nguyen, Nguyen Ngoc Quy, Thanh Viet Nguyen

Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Ignatius Sudaryadi, Fiola Oktaweni, Intan Endri Pramono, Khaliza Wima Fatikasary, Hana Widiawati, Sutikno Sutikno

Keywords Index

Authors Index

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 7-16

doi: 10.4028/p-kL6QSL

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-12-05

Revised:
2023-04-11

Accepted:
2023-04-11

Online:
2023-08-11

Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Samer G. Abdulridha , Ali J. Radhi , Marwa N. Abbas , Amal K. Shehab , Wisam M. Aluaibi

¹Petroleum Research and Development Center, Ministry of Oil, Baghdad, Iraq

Technical Directorate, Ministry of Oil, Baghdad, Iraq

dr.samer.abdulridha@gmail.com, alialjabari70@gmail.com, amal.k.shehab@gmail.com, wesamalmusawi1@gmail.com

*Corresponding author

These authors contributed equally to this work

Keywords: Catalytic cracking, VGO, Y zeolite, Mesoporosity

Abstract

Prototype of FCC catalyst were formulated by mixing the stabilised Y zeolites ( ) with polyvinal alcohol (PVA) (7%) as a solution binder and bentonite (25%). The Y zeolite including the original HY with of 2.6 (cat.-2.6) and dealuminated HY with of 30 (cat.-30) were used and tested for catalytic cracking of Iraqi vacuum gas oil (VGO) obtained from Al-Dura refinery using a pilot plant. The cracking process was carried out at a temperature of and atmospheric pressure, The weight ratio of catalyst / oil ratio was 3 and 5 . The results show that higher conversion of and better product distribution (gasoline, kerosene and gas oil) could be obtained over cat. 30 resulting to a good liquid product yield. The catalytic activity, in terms of VGO conversion was not affected over cat.-30 in spite of its lower acidity, suggesting the determinate of mesoporosity in the Y zeolite (cat.-30) catalysed cracking reactions. A higher yield of to mid-distillates (i.e.Naphtha and kerosene) was as a result of the improvements in the diffusion to and from catalyst structure.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

In the petrochemical industry, the demand for useful light fuels such as gasoline, kerosene and gas oil has increased with time due to the formidable growth of world population, industry and economy across the globe.[1,2] Approximately half of the primitive petroleum deposits have been consumed.[3] The production of conventional oils, including both light and medium oils with high market value, has reached the maximum capacity in the early 1960s then followed a constant decrease due to the depletion of resources.[3,4]
Unconventional oil resources, including the heavy oil, extra heavy oil and bitumen, represent about of the world's oil fields.[5] With the current technologies such as enhanced oil recovery (EOR), thermal methods, miscible displacement and chemical flooding, the technically recoverable amounts of heavy oil have been estimated at 430 billion barrels which means that large deposits of heavy oil has to be available for further exploitation.[5,6]
In order to obtain useful light hydrocarbons from the residual oil, common refinery techniques such as hydrocracking, thermal cracking and catalytic cracking have been used.[7] Catalytic cracking is a class of conversion processes which can process a wide range of feed stocks. This process is used to break down the high boiling, high molecular weight of hydrocarbons into lighter valuable products in the presence of catalyst.[7,8,9] The catalyst used by the catalytic cracking is usually the solid acid catalyst such as zeolites, amorphous silica-alumina combinations and natural aluminosilicates.[10] Zeolite is a very important class of microporous catalysts used in the catalytic cracking process. The function of zeolites is to improve the process efficiency and product selectivity through breaking the long chain molecules into shorter valuable products molecules (i.e. gasoline range organics). Thus, high activity in terms of conversion (recovery of more useful gasoline products from the feedstock),
less residuum and insignificant amount of coke formation can be obtained by employing the zeolites as catalyst.[9,10,11,12]
Catalytic cracking has a number of advantages. By catalytic cracking, high yields of gasoline with the high octane number are produced. Furthermore, catalytic cracking yields substantial quantities of gaseous light olefins, which are important platform chemicals for the polymer industry. Finally, the catalytic cracking process owns large flexibility and improved selectivity, being able to (i) produce both aviation turbine kerosene (ATK) and motor gasoline and (ii) accommodate the variation in the market demand for the production of gas oil.[9]
Sonthisawate et al.,[13] investigated the catalytic cracking of vacuum gas (VGO) oil and atmospheric residue (AR) using of composite catalysts of silica-alumina and zeolites containing microporous and mesoporous to form catalyst with hierarchical structure. The reaction temperature was under a stream of He. They concluded that selectivity of cracking for gas product in AR was higher than that in VGO, which indicated that dealkylation of aromatic components, proceeded. Their result also showed that improved in conversion due to increase diffusion rate of raw materials with increasing pore size for both Y and zeolite containing catalysts. In the concerning on type of zeolite included more than of gasoline selectivity from both VGO and AR was obtained by using Y zeolite containing catalysts.
Catalytic cracking of VGO over zeolite type Y, mordenite, zeolite Y / alumina and mordenite / alumina have been performed by Hwan Lee et al.[14] with a different pore size distribution for cracking activity of VGO and the selectivity of the products such as kerosene, gasoline and diesel. The cracking temperature was for 75 sec . The result indicated that the conversion of VGO over zeolite Y/alumina catalysts with a wide pore size distribution is about the same as that over pure zeolites Y butless coke was formed over zeolite / alumina compared to those over pure zeolites, also the catalysts containing zeolite Y show higher conversion of VGO than these on the catalysts containing mordenite. The selectivity of olefin is smaller on the catalyst containing Y zeolite compared to the catalyst containing mordenites because of low-bimolecular hydrogen-transfer reaction rates.[14]
Scherzer and McArthur [15] studied a series of fluid catalytic cracking (FCC) catalysts with a particular composition and physical properties for cracking high nitrogen feedstock. A higher content of zeolite together with the presence of high surface, area acid sites and a high pore size distribution in the catalyst matrix was suitable for cracking high nitrogen feedstock.
This research project is suggested by the Technical directorate, Ministry of Oil due to the incessant high demand for gasoline range products. Particularly, this research project will perform catalytic cracking of VGO which is produced by Iraqi refineries using commercial catalysts (i.e. zeolites or FCC catalysts). The present work has two main novel points including, firstly, the formulation of the catalyst using Y zeolite and polyvinal alcohol (PVA) and bentonite, which was done in the petroleum research and development centre labs after several attempts to find out the suitable percentage of each component, secondly, tested the catalytic performance of the prepared catalyst for catalytic cracking of VGO fraction obtained from local refinery. Catalytic cracking of VGO was carried out over the prepared catalysts formulated with Y zeolites having different degree of ratio and mesoporosity in order to process the heavy feedstocks in FCC and increase the mid - distillates yield. A comprehensive analysis regarding characterisations for the two commercial Y zeolites ( of 2.6 and 30 ) was also accomplished. Catalytic products will be then distilled to assess their boiling point ranges. Additionally, the products yield will be discussed. Therefore, the research project is expected to play a pivotal role in enabling the exploitation/conversion of heavy hydrocarbons into useful light hydrocarbons products.

Experimental

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Chemicals and materials

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Commercial Y zeolites (CBV600 and CVB760) were obtained from Zeolyst International. CBV600 (H form) has a silicon to aluminium ratio of 2.6 . CVB760 (H form) has the of 30. Polyvinyl Alcohol (PVA) solution and Bentonite were used as binder.

For the catalytic cracking reaction, vacuum gas oil (VGO) as a feedstock with density of was obtained from Dura refinery.

Preparation of catalysts

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

To prepare the catalysts, of zeolites Y (CBV -600 or CBV -760 types) were mixed with of Polyvinyl Alcohol (PVA) as a solution binder and of Bentonite.
The PVA was dissolved in deionized water using heater magnetic stirrer with continuous heating up to and stirring for about 2 h . The Y zeolite powder was mixed with bentonite and PVA in order prepare the catalyst paste. The obtained paste was then added inside the Mini Screw Extruder to obtain the extruded shape of the catalyst. Average size of the prepared catalysts is in length and their diameter is around 2 mm . The extruded catalysts were finally dried at for 5 h followed by calcination at for 4 h . The final extruded catalyst after drying and calcination. The catalysts were named cat.-2.6 and cat.-30 according to the ratio of the parent samples (Y zeolites).

Characterisation of materials

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Powder X-ray diffraction (PXRD) patterns of the both Y zeolites were recorded in the range of on a shimadzu-6000, Japan X-ray diffractometer -6000 with the conditions of radiation operating, .
Fourier transform infrared spectroscopy (FTIR) (type Shimadzu, Japan) was used to characterise the obtained Y zeolites using KBr tablets. The spectra were obtained at ambient temperature by 56 scans at resolution in the wavelength range of .
The textural properties were assessed after nitrogen ( ) adsorption - desorption at using a Micromeritics ASAP 2020 instrument. Prior to the physisorption measurement, sample was degassed at under vacuum for 5 h . The specific surface area of the zeolites was measured according to Brunauer-Emmett-Teller (BET) method. Mesopore size distribution analysis was determined with the Barrett-Joyner-Halenda (BJH) model on the adsorption branch of the isotherm. The grain crushing strength of formed Y zeolite was carried out using (Crush SP - 50 ) from MA.TEC materials technologies, USA. The crushing device is in compliant with ASTM D4197 and ASTM D6175. Calcination of formed catalysts was performed using Muffle furnace "Carbolite" , UK, While drying were carried out using "memmert" dryer , Germany.

Catalytic experiments

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

The catalytic cracking of VGO was performed in a Multi-Purpose Unit (MPU) (as shown in Fig. 1 a and b) fixed- bed reactor at , with a feed time of 60 sec , and the weight ratio of catalyst to oil was changed in a range of 3 and 5 keeping the amount of catalyst constant ( 62 g ), and changing the amount of oil fed, in order to vary the conversion. The relevant calculation of weight hourly space velocity (WHSV) was and , corresponding to catalyst /oil weight ratio ( ) 3 and 5, respectively. Table 1 shows the properties of the VGO.
Prior to each experiment, the system was purged with flow for 15 min at the reaction temperature. After reaction, stripping of the catalyst was carried out for 15 min using a flow .During the reaction and stripping steps, the liquid products were collected in the corresponding glass receivers located at the exit of low pressure separator.

Table 1: VGO feedstock properties

Properties | Value
Density @15 °C (gm/ml) | 0.91
Viscosity @ 40 °C (cSt) | 48
Sulfur Content wt.% | 1.4
Initial Boiling Point °C | 307
Final Boiling Point °C | 532

Fig. 1: (a) Schematic diagram and (b) photo of a technical pilot scale catalytic cracking apparatus (Multi-purpose unit) fixed bed reactor.

Fig. 1. (a) Schematic diagram and (b) photo of a technical pilot scale catalytic cracking apparatus (Multi-purpose unit) fixed bed reactor.

Product analysis

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Collected liquid products were weighted and then analyzed by a distillation method using petroleum fraction distillation apparatus. The amounts of gasoline, kerosene and gas oil were also weighted and quantified considering boiling point temperature ranges from initial boiling point (IBP) to 175, 176 -250 , and , respectively.

Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Properties comparison of thezeolite catalysts.

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Both XRD patterns and FTIR spectra of the two catalysts as shown in Fig. 2 displayed the characteristic features of FAU type zeolite. XRD analysis of the Y zeolite catalysts (Fig. 2 a) exhibits the identical characteristic diffraction peaks of FAU zeolite in the wide angle range of . FTIR was performed to measure the characteristic vibration bands of Y zeolites catalysts (Fig. 2b). The band at around can be attributed the structure-insensitive and/or bending vibration of the internal tetrahedral aluminosilicate framework.[16] The band at is assigned to the double six membered ring external linkage peak of Y zeolites (FAU structure). The bands between 693-785 are associated with the internal symmetrical stretching vibrations of Y zeolites. The other two distinct peaks at and are assigned to internal tetrahedral asymmetrical stretching and external linkage asymmetrical stretching, respectively.[16,17]

Fig. 2: a) XRD patterns and b) FT-IR spectra of Y zeolite catalysts.

Fig. 2. a) XRD patterns and b) FT-IR spectra of Y zeolite catalysts.

Table 2: Crushing strength of the Y zeolite catalysts

Sample | Crush Strength (N/mm)
Cat.-2.6 | 3.22
Cat.-30 | 5.61

The adsorption-desorption isotherms of the Y zeolite catalysts are showed in Fig. 3. The cat.-2.6 displays a type I isotherm corresponding to the microporous nature of the cat.2,6.[18] On the other hand, the cat.- 30 zeolite catalyst shows the typical IV behaviours with the H 2 hysteresis loop, suggesting the presence of mesopores in the catalyst. The textural properties of the catalyst prepared by this work is summarised in

Table 3 The cat.-2.6 displays insignificant mesoporous features concerning the specific external surface area ( ) of and specific mesopore volume ( ).

Sample | SBET (m²/g) | Sext (m²/g) | Smicro (m²/g) | Vtotal (cm³/g) | Vmeso (cm³/g) | Vmicro (cm³/g)
cat.-2.6 | 15.6 | 15.6 | 0 | 0.016 | 0.016 | 0
cat.-30 | 18.5 | 15.9 | 2.6 | 0.026 | 0.025 | 0.001

Fig. 3. adsorption-desorption isotherms of Y zeolite catalysts.

In comparison with cat.-2.6, the cat.-30 has more mesoporous features. For example, regarding the external surface area, cat- 30 possess values of at which is higher than that recorded for cat. -2.6 at . Cat. -30 exhibits a comparable BET surface areas ( ), indicating the well preservation of intrinsic zeolite structure and presence of mesoporous structures.

Micropore and mesopore size distributions (PSDs) of the prepared materials are shown in Fig. 4. Micropore PSDs of both catalysts (Fig. 4a) exhibit the mean distribution centred at around 0.74 nm which is the intrinsic micropore size of zeolite Y. Mesopore PSDs (Fig. 4b) display the distribution of well-developed mesopores in a range of for cat. -30 while cat 2.6 did not show any mesopores.

Table 3: Textural properties of the Y zeolite catalysts.

Sample
Vtotala
[cm³ g⁻¹]
Vmicrob
[cm³ g⁻¹]
Vmesoc
[cm³ g⁻¹]
SBET
[m² g⁻¹]
Smicrob
[m² g⁻¹]
Sexternalb
[m² g⁻¹]

Cat.-2.6
0.35
0.35
0
858
848
10

Cat.-30
0.54
0.28
0.26
798
516
282

total volume adsorbed at ; based on the -plot method; .

Fig. 4: (a) Micropore PSDs by the Horváth-Kawazoe (HK) method and (b) mesopores PSDs by the Barrett-Joyner-Halenda method for the Y zeolite catalysts.

Fig. 4. (a) Micropore PSDs by the Horváth-Kawazoe (HK) method and (b) mesopores PSDs by the Barrett-Joyner-Halenda method for the Y zeolite catalysts.

Catalytic cracking of vacuum gas oil (VGO)

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Fluid catalytic cracking process which is used in petrochemical industry, is one of the largest acidbased catalytic reactions. The FCC process is used to transform the heavy oil into valuable products such as gasoline, kerosene and other products in the presence of zeolite composed catalyst.
In related catalysts, zeolites have been used in many industrial catalysis, particularly petrochemical conversion processes such as fluid catalytic cracking (FCC), alkylation and isomerisation, because zeolites have a good hydrothermal stability, high surface area, strong acidity and well shape selectivity. In particular, the faujasite (FAU) Y has a three dimensional pore structure with a window aperture of and a spherical supercage with a diameter of and it is considered as the most important active additives in FCC catalysts for gasoline range organics.

Fig. 5: Conversion of VGO feedstock over Y zeolite catalysts at different catalyst/VGO ratios.

Fig. 5. Conversion of VGO feedstock over Y zeolite catalysts at different catalyst/VGO ratios.

Catalytic cracking of VGO (obtained from Daura refinery) was carried out at a range of conversion achieved by changing the catalyst to VGO ratio (cat/oil) 3 and 5, corresponding to WHSV of and , respectively. Zeolites Y and USY with of 2.6 and 30 respectively were used. As shown in Fig. 5, the conversion profile of VGO over both cat-2.6 and cat-30 are increased when increasing the cat/oil ratio (i.e. decreasing space velocities). This finding proves that the conversion is a function of reaction time for all catalyst. This is in agreement with previous studies.[20] They observed that the total conversion increased when space velocities decreased. Increasing the contact time (i.e. reducing WHSV) of the feed molecules is boosting the VGO conversion. Similar finding for the effect of WHSV on the VGO conversion is obtained by previous work. [20]

As the utmost important additive in FCC catalyst, Y zeolites with mesoporosity have been proved to be extremely beneficial for refineries.[24] The catalytic cracking activity of cat-30 was evaluated in reference to the cat-2.6 (parent Y ). In general terms, acidity and porosity of zeolites are equally important for cracking reactions. However, with huge molecules such as VGO, the cracking of VGO requires a catalyst with the accessible acidic sites.[22] The accessibility of the bulky molecules to the acidic sites depends on the porous framework of the zeolitic catalyst. Cat-2.6 has the lower VGO conversion over the course of reaction (i.e. about and for both cat/oil of 3 and 5 , respectively); while cat-30 exhibits higher cracking activity (i.e. about and ) for cat/oil of 3 and 5, respectively. The superior cracking performance of cat-30 over the course of the catalytic cracking tests can be assigned to presence of abundant intracrystalline mesoporosity, enhancing an excellent molecular diffusion to the acidic sites.

The yields of various hydrocarbons fractions in FCC are shown in Fig. 6. The hydrocarbons fractions were noticed in the VGO conversions over both catalysts. Generally, gasoline and kerosene are the products with the highest yields. Cat-30 promoted the yield to gasoline at , which is higher than cat-2.6 ( ), suggesting that cat-30 has a good cracking activity than cat-2.6. The well activity of cat-30 could be assigned to its intracrystalline mesoporosity. The hierarchical feature of cat-30 improves the accessibility to and diffusion through zeolite framework. In all cases, the yield of kerosene displayed utmost as a function of the conversion. This is identification to its well-known intermediate role in the conversion mechanism of FCC process.[23]
It can be observed in Fig. 6 a, that gasoline fraction yields are steadily rising as a function of conversion. Interestingly, cracking of VGO over cat-30 produced a lower yield of gas oil than kerosene and gasoline. It can be concluded that cat-30 favours a lighter petroleum fraction with a high
market value (i.e. gasoline and kerosene). It is worth mentioning that gas oil which is contributed significantly to diesel pool is also demanded by the market.

Fig. 6: Hydrocarbon yields as a function of the conversion of VGO feedstock over Y zeolite catalysts (a) gasoline, (b) kerosene, (c) gas oil.

Fig. 6. Hydrocarbon yields as a function of the conversion of VGO feedstock over Y zeolite catalysts (a) gasoline, (b) kerosene, (c) gas oil.

Table 4: Properties of hydrocarbon yields

Test Name | Ref. [21] | catalytic cracking
|  | cat/oil=3 | cat/oil=5
Density @ 15.6 °C | 0.7 | 0.75 | 0.75
Distillation (Boiling Point °C) | (30 - 180) | (30 - 180) | (30 - 180)

Table 4: Properties of hydrocarbon yields

Test Name | Ref. [21] | catalytic cracking
|  | cat/oil= 3 | cat/oil=5
Density @ 15.6 °C | 0.7 | 0.75 | 0.75
Distillation (Boiling Point °C) | (30 - 180) | (30 - 180) | (30 - 180)

Cat.2.6 Kerosene
Test Name | Ref. [21] | catalytic cracking
| cat/oil=3 | cat/oil=5
Density @ | 0.8 | 0.81 | 0.81
Distillation (Boiling Point |  |  |

Cat.30|Kerosene |
Test Name | Ref. [21] | catalytic cracking
cat/oil | cat/oil=5
Density @ | 0.8 | 0.81 | 0.8
Distillation (Boiling Point |  |  |

Cat.2.6 \Gas Oil
Test Name | Ref. [21] | catalytic cracking
cat/oil=3 | cat/oil=5
Density @ | 0.85 | 0.86 | 0.84
Distillation (Boiling Point |  |  |

Table 4 lists the density values and relevant boiling points ranges of the hydrocarbon yields obtained over the two comparative catalysts (i.e. cat.-2.6 and cat.-30) for both cat/oil ratios of 3 and 5. The density of the cracking fractions have been measured and compared with the marketing specifications guide of Iraqi petroleum products as the reference. By comparing the measured densities of obtained fraction for both catalysts with the reference, it can be seen that the petroleum fractions density is comparable to the reference within the similar boiling points ranges, indicating that the obtained cracking fractions were successfully produced. In details, the naphtha produced from vgo cracking was with a density of which is comparable to the referenced one (i.e. ). VGO cracking over both cat.-2.6 and cat.-30 produced kerosene and gas oil with a density of and , respectively. Both recorded densities of kerosene and gas oil are similar to the one recorded in the reference.

Conclusions

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Two commercials FAU Y zeolite were formulated as FCC catalyst and analysed comprehensively for their porous and acidic properties, aiming at exploring their catalytic performance in the catalytic cracking of VGO. The obtained results by sorption displayed the hierarchical feature of mesoporosity in zeolite. For example, in comparison to cat.-2.6, cat.-30 has a higher intercrystal mesopososity with relatively high moesopore volume of and external surface area of . The hierarchical mesoposrosity in cat.- 30 showed significantly improved catalytic performance compared to cat.-2.6 in the cracking reactions. Independently of the catalyst, the conversion of VGO over cat.-30 at the same condition was higher than that over cat.-2.6. The catalyst with higher mesoporosity exhibited a higher observed activity that the microporous catalyst (i.e. 2.6). As a result, a better diffusion transport of bulky molecules in the feedstock (VGO) could be obtained leading to improve the accessibility to the active sites, and the higher density of acid sites catalysing the cracking reactions. The catalytic results show that higher conversion of and better product distribution (gasoline, kerosene and gas oil) could be obtained resulting to a good liquid product yield.The yield of gasoline ( ) and kerosene ( ) obtained over cat.- 30 was considerably higher than the cat.-2.6. The cat.-30 with intracrystalline mesoporosity promoted a good yield to gasoline and kerosene, which is higher than the reference catalyst cat.-2.6 (i.e. gasoline at and kerosene ). Despite the lower acidity of cat.-30, the catalytic activity, in terms of vgo conversion were not affected, suggesting the determinate of mesoporosity in the Y zeolite (cat.-30) catalysed cracking reactions. A higher yield to mid-distillates was as a result of the improvements in the diffusion to and from catalyst structure.

References

The original version of this paper is available on https://www.scientific.net/EC.4.7.pdf

Wei, Y.; Parmentier, T. E.; de Jong, K. P.; Zecevic, J., Tailoring and visualizing the pore architecture of hierarchical zeolites. Chem Soc Rev 2015, 44 (20), 7234-61.

Usman, Abdulhafiz, et al. "Catalytic cracking of crude oil to light olefins and naphtha: Experimental and kinetic modeling." Chemical engineering research and design 120 (2017): 121-137

Hashemi R, Nassar NN, Pereira Almao P. Nanoparticle technology for heavy oil in-situ upgrading and recovery enhancement: Opportunities and challenges. Appl Energy 2014; 133: 374-87.

Fumoto E, Tago T, Masuda T. Production of lighter fuels by cracking petroleum residual oils with steam over zirconia-supporting iron oxide catalysts. Energy and Fuels 2006; 20: 1-6.

Box D, Wakeman T, Smith J. The end of cheap oil the consequences. Ecologist 2005; 35: 046.

Santos RG, Loh W, Bannwart AC, Trevisan O V. An overview of heavy oil properties and its recovery and transportation methods. Brazilian J Chem Eng 2014; 31: 571-90.

Meyer RF, Attanasi ED. Heavy oil and natural bitumen-strategic petroleum resources. United States Geol Surv 2003; 70-03: 1-6.

Ibarra, Álvaro, et al. "A hybrid FCC/HZSM-5 catalyst for the catalytic cracking of a VGO/Biooil blend in FCC conditions." Catalysts 10.10 (2020): 1157.

Speight J. The Refinery of the Future. Burlington: Elsevier Science: Burlington, 2010.

Vermeiren W, Gilson J-P. Impact of Zeolites on the Petroleum and Petrochemical Industry. Top Catal 2009; 52: 1131-61.

Robert A. Meyers. Handbook of Petroleum Refining Processes. New York: McGraw- Hill, 2004.

García, J.R., Fals, J., Dietta, L.E., & Sedran, U. (2022). VGO from shale oil. FCC processability and co-processing with conventional VGO. Fuel, 328, 125327.

Sonthisawate, T., et al., Catalytic cracking reaction of vacuum gas oil and atmospheric residue by zeolite-containing microporous and mesoporous composites using Curie point pyrolyzer. Fuel Processing Technology, 2016. 142: p. 337-344.

Lee, K.-H., B.-H. Ha, and Y.-W. Lee, Catalytic Cracking of Vacuum Gas Oil over the Modified Mordenites and Y-Type Zeolites Mixed with Alumina. Industrial & Engineering Chemistry Research, 1998. 37(5): p. 1761-1768.

Scherzer, J. and D.P. McArthur, Catalytic cracking of high-nitrogen petroleum feedstocks: effect of catalyst composition and properties. Industrial & Engineering Chemistry Research, 1988. 27(9): p. 1571-1576.

Zhao J, Yin Y, Li Y, Chen W, Liu B. Synthesis and characterization of mesoporous zeolite Y by using block copolymers as templates. Chem Eng J 2016; 284: 405-11.

FLANIGEN EM, KHATAMI H, SZYMANSKI HA. Infrared Structural Studies of Zeolite Frameworks. 1974: 201-29.

Sing KSW. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl Chem 1985; 57: 603-19.

Husein MM, Alkhaldi SJ. In Situ Preparation of Alumina Nanoparticles in Heavy Oil and Their Thermal Cracking Performance. Energy & Fuels 2014; 28: 6563-9.

Corma A, Martínez C, Sauvanaud L. New materials as FCC active matrix components for maximizing diesel (light cycle oil, LCO) and minimizing its aromatic content. Catal Today 2007; 127: 3-16.

Li, Kunhao and Valla, Julia and Garcia-Martinez J. Realizing the commercial potential of hierarchical zeolites: new opportunities in catalytic cracking. ChemCatChem 2014; 6: 46-66.

Zhai S, Zhang Y, Wu D, Sun Y, Wang S. Comparative study on the structural, acidic and catalytic properties of nano-sized and large-particulate mesoporous aluminosilicates. Top Catal 2006; 39: 227-35.

Harding R., Peters A., Nee JR. New developments in FCC catalyst technology. Appl Catal

Marketing specifications guide of Iraqi petroleum products 2013

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 17-31

doi: 10.4028/p-XakNe1

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-11-11

Revised:
2023-04-03

Accepted:
2023-04-03

Online:
2023-08-11

A Review: Membrane Reactor for Hydrogen Production: Modeling and Simulation

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Alaa Hasan Kassi , Tahseen A. Al-Hattab

Chemical Engineering Department, Babylon University, Babylon, Iraq.

alaa90eng@gmail.com, alhattab.t@gmail.com

Abstract

A membrane reactor is a multifactional vessel used for production. Hydrogen's three spectrum colors are dependent on carbon present. Two types of membrane with high permeability to hydrogen (polymeric and metallic). Hydrogen is produced in two systems: conventional reactors and membrane reactors (which separate and purify hydrogen in a single vessel). There are many types of membrane reactors according to design (catalytic membrane reactor (CMR), fixed bed reactor (FBMR), fluidized bed reactor (FBMR), etc. The transport mechanism of through the membrane by a "sorption-diffusion mechanism" and the government equations that are used for membrane reactor modeling and simulation, such as continuity, momentum, mass, and heat transfer equations of the CMR, and the thickness of the membrane. These equations are solved by MATLAB, COMSOL, and the Finite Element Method to simulate the MR at different parameters: rate of conversion, rate of sweep gas, temperature, pressure, rate of permeation through a membrane, and activity of the catalyst. We summarized theoretical studies for membrane reactors, including the operation conditions, type of hydrocarbon feed, type of production method, kind of catalyst, and heat effect.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Growing interest in using hydrogen as an energy source is a result of the likelihood of climate change brought on by global warming. The majority of the world's energy demands are currently met by fossil fuels, but they regretfully emit a lot of greenhouse gases, particularly carbon dioxide. As a clean fuel that produces no or other pollutants, hydrogen is viewed as a potential future energy source. All that is left when it burns away is water. Fuel cell technology is designed to use hydrogen to convert chemical energy directly into electrical energy [1].
Hydrogen, the most common element in the world, has only recently (within the last 300 years) been recognized as a pure, non-toxic material. Despite being an energy vector rather than a major energy source, hydrogen has some qualities that make it a good candidate for the transition to renewable energy [2].
The three hydrogen isotopes protium, deuterium, and tritium are distinct from one another. One proton and one electron make up protium, the main component of hydrogen, the simplest element. Despite being the lightest element, hydrogen has the highest energy content per unit mass among all fuels [3].

Hydrogen Method Production

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Since gas cannot be found in nature as readily available molecules, it must be created from substances that already contain it. In particular, hydrocarbons and fossil fuels, or even renewable sources, can be used to make hydrogen [4]. Table 1 shows each method's benefits, drawbacks, efficiency, and cost [5].

Table gas production methods from petrolume fuels with their benefits, drawbacks, performance and cost [5].

Green hydrogen is the only hydrogen fuel that is carbon-neutral because it doesn't produce any carbon during manufacturing or consumption. Grey hydrogen produces carbon during the extraction and production processes. Grey hydrogen has been developed to blue hydrogen, which seizes and stores the carbon produced during synthesis. Renewable energy sources are used to produce green hydrogen. Table 2 shows the three hues of the hydrogen spectrum, grey, blue, and green, according to their carbon output [6].

Table 2 The colour of [6].

| Grey | Blue | Green
Process | "Steam methane reforming (SMR)" "Auto-thermal reforming (ATR)" | "Carbon Capture and Storage (CCS)" | "Electrolysis"
"Source" | CH₄, gasifier coal, heavy oil | CO₂-rich stream | H₂O
Carbon leave | 8.5–10 kg | 0.8–4.4 kg | No emissions carbon

The hydro-treating methods used in refineries to turn raw materials into higher-value compounds (like ammonia and methanol) or feedstock for hydrogen [7]. To meet commercial demands, hydrogen separation and purification are now necessary. Membrane separation, cryogenic distillation, pressure swing adsorption, and wet and dry scrubbing are a few of the procedures used to separate hydrogen from other gases and purify it [8].

Phase change, sorbents, and their regeneration are frequently not used in membrane-based separation technologies for mixtures of gas and vapor. As a result, membrane technologies are appealing due to their advantages such as energy efficiency, operational continuity and simplicity, small footprint, simplicity in scaling up, module compactness and modularity, and environmental cost and friendliness. The energy required by membrane-based distillation procedures could be lower than that of conventional techniques [9].

Types of Membrane

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

According to the substance used to make the membrane, which has a high permeability to hydrogen, there are two different varieties, and they are divided into two categories.

a. Polymeric Membrane

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

The use of polymeric membranes in commercial gas separation processes is common[10]. Polymeric glass and rubber membranes are two different types of polymer membranes. Because of their better mechanical properties and high gas selectivity, glassy polymer membranes were more practical for commercial applications than rubber polymeric membranes.

b. Metallic Membrane

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Dense membranes made of palladium, platinum, nickel, and the metallic elements in bands IIIV of the chemical elements have theoretically unlimited selectivity since they can transport hydrogen in a dissociated form [11].

b. 1 Non-Palladium Membranes

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Palladium is a particularly desirable material for metal-based membranes because it is highly selective towards hydrogen and allows for the synthesis of pure . Nevertheless, palladium is expensive, and its price is erratic [12]. Thus, it was necessary to create membranes using less expensive metals. Due to their lower cost and strong hydrogen permeability, Group 5 metals with a body-centric cubic structure like tantalum, vanadium (V) and niobium (Nb) present a viable alternative to platinum. The palladium layer still required hydrogen penetration, though. When exposed to an interdiffusion between Pd and V at temperatures above , the membranes begin to deteriorate .

b. 2 Palladium (Pd) Membranes

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Palladium (Pd)-based membranes for the purification of hydrogen provide the greatest selectivity and penetration due to their special permeation mechanism [13]. A dense palladium-based membrane can be employed to separate pure hydrogen [14]. Palladium membranes can function at temperatures that are substantially higher than those of polymer membranes, which makes them perfect for use in membrane reactors or for removing hydrogen from gas streams at high temperatures [15].

Combining a Catalytic Reaction with the Membrane Separation Process

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

The membrane reactor and traditional methods for creating hydrogen are contrasted in Figure 1. Because of the separation and reaction, this is referred to as a "membrane reactor."

Fig. 1 (a) "A conventional reactor system" (b) "Catalytic membrane reactor system"

Fig. 1. (a) "A conventional reactor system" (b) "Catalytic membrane reactor system"

In Table 3. "the most common membrane reactor configurations" that have been reviewed in this[16]

Table 3 "Classification of Membrane Reactors"[16].

Acronym | Definition
"CMR | Catalytic membrane reactor"
"CNMR | Catalytic non-permselective membrane reactor"
"PBMR | Packed-bed membrane reactor"
"PBCMR | Packed-bed catalytic membrane reactor"
"FBMR | Fluidized-bed membrane reactor"
"FBCMR | Fluidized-bed catalytic membrane reactor"

Mechanisum ofTransport Through the Membrane

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

The sorption-diffusion mechanism allows to diffuse through substantial metal obstacles. Permeation of a high partial pressure gas zone into a low partial pressure gas region happens in stages: (1) Atomic hydrogen sorption into the bulk metal (2) dissociative adsorption of at the gas-metal interface atomic hydrogen recombination to create hydrogen molecules at the metal/gas permeate interface is followed by (3) atomic hydrogen diffusion through the bulk metal membrane and (4) molecular hydrogen desorption.

The efficiency of any reactor is assessed using a variety of operational factors and design considerations, such as the ratio of reactant in the feed, temperature, pressure, membrane properties, the kind of catalyst, the rate of sweep gas, etc. Under these conditions, it seems that mathematical models are an effective tool for all kinds of reactor research and simulation [17].

Governing Equations for Membrane Reactor

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

The government equations that are used for membrane reactor modeling and simulation can be shown below and are used via many articles.

When developing the CFD model, consideration was given to the continuity equation (Eq.1), momentum equation (Eq.2), and mass transfer equation (Eq.3) [18].
f. ɛ. u

f. ui. f. Di, e.

The CFD model also needed to apply additional equations to calculate some of the parameters found in Eqs. (1 to 3), as explained in the next section. based on the Ergun equation (Eq. (4)) was found to be:

is the permeation the flux of the permeation ( Ji ) of the component i , can calculate by
, retentate -Pi , permeate)

Where Pei is i -species permeate
Use the Arrhenius equation to calculate Pei
Pei Po,

The recovery of flare gas is shown in Figure 2 below for the "catalytic membrane reactor". In this study, the membrane reactor model is solved under the straightforward conditions of negligible axial diffusion, steady-state conditions, negligible radial convective mass transfer, and substantial heat conduction of the membrane material [19].

Fig. 2 CMR for gas flare recovery [19].

Fig. 2. CMR for gas flare recovery [19].

The implicit finite element method is used to solve the model equations numerically, and the governing equations have been introduced to the MATLAB programming for the purpose of model development.

The Tube Side the Governing Equations

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

In order to account for the mass transfer convective in the axial and radial direction, chemical reactions, diffusion direction, and the mass balance for each component in (tube side: 0 to ) is given:

The equation of overall heat transfer

The flux of permeation flux through the membrane

The Shell Side the Governing Equations

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Bian, Z., et al;[20], utilized simulations of the enclosed equations mentioned in table 4 and their solution using the COMSOL software to explore the behavior of a catalytic membrane reactor for the dry reforming of methane.

Table 4 Equations of Two-dimensional CFD model [20].

Permeate side | Retentate side
Continuity equation
∇(ρv⃗) = 0 | ∇(ερv) = 0
ρ = P/(RT Σiwi/Mi) | ρ = P/(RT Σi wi/Mi)
Momentum equation
ρv⃗·∇v⃗ = −∇[P + μ(∇v⃗ + (∇v⃗)T − (2μ/3)(∇v⃗)] | v⃗ = −(κ/μ)∇P
Mass equation
∇.ji⃗ + ρ(v⃗·∇)wi = 0 | ∇.ji⃗ + ρ(v⃗·∇)wi = Ri
ji⃗ = −ρwi Σj Dij[∇xi + (xj − wj)(∇Pi/P)] | ji⃗ = −ρwi Σj Dieff[∇xi + (xj − wj)(∇Pi/P)]
xi = (wk/Mk)·(Σi wk/Mk)⁻¹ | xi = (wk/Mk)·(Σi wk/Mk)⁻¹

The primary goal of this paper is to review theoretical research on methods of producing hydrogen using membrane reactor modeling and simulation. This review will focus on the best membrane to use depending on the amount of hydrogen permeability, which is influenced by a number of different factors, including temperature, pressure, catalyst type, feed rate, sweep gas flow rate, feed purity, and reactor type depending on how the catalyst is arranged in the membrane.

Grace, J., et al;[21], used SMR equilibrium modeling with oxygen and hydrogen withdrawals. Water is a necessary reactant in this process because it is a byproduct of the oxidation reactions needed to create autothermal conditions. The operation at lower temperatures, lower and greater pressures are made possible by the permeable membranes and O 2 to steam methane reforming reactors.

Iulianelli, A., et al;[22], produced greater methane and hydrogen yield conversion than traditional FBR rates under the same conditions when simulating steam methane reforming in a dense Pd-Ag MR packed with a nickel-based catalyst at low pressure (1.0-3.0 bar) and temperatures ranging from 400 to of pure hydrogen may be produced in the packed bed membrane reactor without the addition of CO or CO 2 using sweep gas on the permeate side.

Coronel, L., et al;[23], investigates this FBCMR using numerical simulations and a 2-dimensional model with mass, momentum, and energy balances. The fixed bed is believed to be formed using catalyst particles that are specifically made for steam reformation at low and temperature ratios. A composite Pd membrane was proposed for H 2 permeation. After the model was verified by experimental data, a comparison of a straightforward 1-dimentional model to a more intricate 2-dimentional model was made to determine how well it represented the membrane reactor. The effectiveness of a simplified 1-dinentional model to simulate the membrane reactor was assessed and discussed in contrast. Pressure, inlet temperature, steam excess, space velocity, and the rate of sweep gas in the permeate are the primary operational parameters.

Chein, R., et al;[24], Utilizing a 3-dimensional mathematical model, a water gas shift reaction in MR was employed to mimic the synthesis of H 2 from coal-derived syngas. The working temperature at the gasifier exit is , which is the typical syngas temperature. The productivity of the reactor was investigated in relation to the ( ) ratio, reactant residence time, reactant composition, sweep gas flow rate, and membrane permeance. H 2 recovery and CO conversion were utilized to evaluate the reactor's performance. Increases in the ratio, membrane permeance, and sweep gas flow rate were noted. Limiting values for H 2 recovery and CO conversion were found when these parameters were raised further, which improved the reactor's performance. Additionally, the mathematical results demonstrated that the reactor's efficiency decreased as the content climbed.

Chompupun, K., et al; [25], used a 3-dimensional model for the catalytic membrane reactor in the COMSOL Multiphysics program that takes into account energy, momentum, and the effects of multicomponent diffusion. We examine the best geometrical arrangement for the suggested design. There are ideas offered for the reactor's design. It has been proven that the surface area-to-reactor volume ratio of the design with the best membrane, , is correlated with a Peclet numberDamkohler product that is near to 1 .

Lee, B., et al;[26], utilized a CFD model for the dry reforming of methane (CO2 reforming) in conventional packed bed reactors (PBR) and membrane reactors (MR), with the heating tube serving as both types of reactors' main heat source. An unusual packed bed reactor and a membrane reactor have both been explored to see how reactor geometry affects temperature and profiles of hydrogen and methane concentrations. The membrane centre distances in an MR were , and 0.045 m from the reactor centre. Using COMSOL Multiphysics modelling.

Cifuentes, A., et al;[27], used a 3-dimensional CFD non-isothermal model with mass transfer constraints. Under different pressure feed load and temperature circumstances, it was projected that reverse water-gas shift, methanation, and steam methan reforming would occur. The model evaluated and simulated the catalytic membrane reactor under various operating conditions. catalyst pellets are packed during the steam reforming of methanol with a steam to carbon ratio of .

Table 5 Summarized of Membrane Reactor Modeling and Simulation Studies.

No. | Reactor - type | Condition | Feed | Catalyst | Production Method | Softewaer | Configuration | Ref .
1 | MR (Pd-Ag) | T=513k, P=10ban, Isothermal | methanol | Ni/Al₂O₃ | Steam Reforming | COMSOL multiphy-sics | Configuration diagram | [18]
2 | FBMR (Pd) | T=580C, P=2.9MPa Isothermal, | Methane | Ni/Al₂O₃ | Steam Reforming | RAND algorithm | - | [21]
3 | CMR (dense Pd–Ag) | T=400 and 500 °C, P=(1.0– 3.0 bar), Isothermal | Methane | Ni/Al₂O₃ | Steam Reforming | fourth-order Rungee Kutta method | Configuration diagram | [22]
4 | Tubular MR (dense Pd–Ag ) | T=823 K, P=101, 325 Pa, Isothermal | Methane | Rh/La₂O₃, Rh/La₂ O₃ – SiO₂ | Dry Reforming | MathCad ™ Profes-sional software | Configuration diagram | [23]
4 | MR (Pd) | T=900C, P= 1.013×10⁵Pa, Isothermal | Methane | Ni/Al₂O₃ | Steam Reforming | COMSOL multi-physics | Configuration diagram | [24]

Summary

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

The evaluation of the aforementioned study led us to the following conclusions:

Traditional catalytic reactors cannot produce as efficiently as catalytic membrane reactors (CMR) can (TCR).

The steam reforming process (SR) is a further method for producing that uses sweep gas to obtain from the permit side and natural gas as the feed to the reactor.

The best membrane material with a high rate of permeability across the membrane is a palladium-based alloy; silica is often employed as a backup option to palladium metal.

Simulated the experimental data using the COMSOL software, MATLAB, and Finite Element Method in order to compare the modeling and simulation findings with the actual results and to investigate the mass, momentum, and energy aspects of the process.

Nomenclature

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

Subscripts

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

CMR Catalytic Membrane Reactor.
MSR Methane Steam reforming.
S Shell side.
T Tube side.
f Fluid.
CFD Computational fluid dynamics
Pd palladium
MR Membrane reactor
SCR Steam to carbon ratio

References

The original version of this paper is available on https://www.scientific.net/EC.4.17.pdf

S. P. Katikaneni et al., "Catalytic Membrane Reactor for Hydrogen Production from Liquid Petroleum Fuels: Bench Scale Studies," Saudi Aramco Journal of Technology, p. 35, 2008.

M. Martino, C. Ruocco, E. Meloni, P. Pullumbi, and V. Palma, "Main hydrogen production processes: An overview," Catalysts, vol. 11, no. 5, p. 547, 2021.

S. Z. Baykara, "Hydrogen: A brief overview on its sources, production and environmental impact," International Journal of Hydrogen Energy, vol. 43, no. 23, pp. 10605-10614, 2018.

G. Cipriani et al., "Perspective on hydrogen energy carrier and its automotive applications," International Journal of Hydrogen Energy, vol. 39, no. 16, pp. 8482-8494, 2014.

S. S. Kumar and V. Himabindu, "Hydrogen production by PEM water electrolysis-A review," Materials Science for Energy Technologies, vol. 2, no. 3, pp. 442-454, 2019.

T. Yusaf et al., "Sustainable Aviation-Hydrogen Is the Future. Sustainability 2022, 14, 548," ed: s Note: MDPI stays neutral with regard to jurisdictional claims in published ..., 2022.

V. Spallina et al., "Direct route from ethanol to pure hydrogen through autothermal reforming in a membrane reactor: Experimental demonstration, reactor modelling and design," Energy, vol. 143, pp. 666-681, 2018.

N. Pal, M. Agarwal, K. Maheshwari, and Y. S. Solanki, "A review on types, fabrication and support material of hydrogen separation membrane," Materials Today: Proceedings, vol. 28, pp. 1386-1391, 2020.

C. Z. Liang, T.-S. Chung, and J.-Y. Lai, "A review of polymeric composite membranes for gas separation and energy production," Progress in Polymer Science, vol. 97, p. 101141, 2019.

Y. Vijay, S. Wate, N. Acharya, and J. Garg, "The titanium-coated polymeric membranes for hydrogen recovery," International journal of hydrogen energy, vol. 27, no. 9, pp. 905-908, 2002.

S. K. Gade, P. M. Thoen, and J. D. Way, "Unsupported palladium alloy foil membranes fabricated by electroless plating," Journal of Membrane Science, vol. 316, no. 1-2, pp. 112118, 2008.

M. Weber et al., "Hydrogen selective palladium-alumina composite membranes prepared by Atomic Layer Deposition," Journal of membrane Science, vol. 596, p. 117701, 2020.

D. P. Tanaka, J. Medrano, J. V. Sole, and F. Gallucci, "Metallic membranes for hydrogen separation," in Current trends and future developments on (bio-) membranes: Elsevier, 2020, pp. 1-29.

L. Roses, G. Manzolini, S. Campanari, E. De Wit, and M. Walter, "Techno-economic assessment of membrane reactor technologies for pure hydrogen production for fuel cell vehicle fleets," Energy & fuels, vol. 27, no. 8, pp. 4423-4431, 2013.

S. Paglieri and J. Way, "Innovations in palladium membrane research," Separation and Purification Methods, vol. 31, no. 1, pp. 1-169, 2002.

J. Sanchez and T. T. Tsotsis, "Current developments and future research in catalytic membrane reactors," in Membrane Science and Technology, vol. 4: Elsevier, 1996, pp. 529568.

F. Gallucci, L. Paturzo, and A. Basile, "A simulation study of the steam reforming of methane in a dense tubular membrane reactor," International Journal of Hydrogen Energy, vol. 29, no. 6, pp. 611-617, 2004.

K. Ghasemzadeh, J. Harasi, T. Amiri, A. Basile, and A. Iulianelli, "Methanol steam reforming for hydrogen generation: A comparative modeling study between silica and Pd-based membrane reactors by CFD method," Fuel Processing Technology, vol. 199, p. 106273, 2020.

M. Saidi, "Application of catalytic membrane reactor for pure hydrogen production by flare gas recovery as a novel approach," International Journal of Hydrogen Energy, vol. 43, no. 31, pp. 14834-14847, 2018.

Z. Bian et al., "CFD simulation of a hydrogen-permeable membrane reactor for CO2 reforming of CH4: the interplay of the reaction and hydrogen permeation," Energy & Fuels, vol. 34, no. 10, pp. 12366-12378, 2020.

J. R. Grace, X. Li, and C. J. Lim, "Equilibrium modelling of catalytic steam reforming of methane in membrane reactors with oxygen addition," Catalysis today, vol. 64, no. 3-4, pp. 141-149, 2001.

A. Iulianelli et al., "H2 production by low pressure methane steam reforming in a membrane reactor over a Ni-based catalyst: experimental and modeling," International journal of hydrogen energy, vol. 35, no. 20, pp. 11514-11524, 2010.

L. Coronel, J. Múnera, E. A. Lombardo, and L. M. Cornaglia, "Pd based membrane reactor for ultra pure hydrogen production through the dry reforming of methane. Experimental and modeling studies," Applied Catalysis A: General, vol. 400, no. 1-2, pp. 185-194, 2011.

R. Chein, Y. Chen, Y. Chyou, and J. Chung, "Three-dimensional numerical modeling on high pressure membrane reactors for high temperature water-gas shift reaction," International journal of hydrogen energy, vol. 39, no. 28, pp. 15517-15529, 2014.

T. Chompupun, S. Limtrakul, T. Vatanatham, C. Kanhari, and P. A. Ramachandran, "Experiments, modeling and scaling-up of membrane reactors for hydrogen production via steam methane reforming," Chemical Engineering and Processing-Process Intensification, vol. 134, pp. 124-140, 2018.

B. Lee et al., "CO2 reforming of methane for H 2 production in a membrane reactor as CO 2 utilization: computational fluid dynamics studies with a reactor geometry," International Journal of Hydrogen Energy, vol. 44, no. 4, pp. 2298-2311, 2019.

A. Cifuentes, L. Soler, R. Torres, and J. Llorca, "Methanol steam reforming over in a catalytic membrane reactor: An experimental and modelling study," International Journal of Hydrogen Energy, vol. 47, no. 22, pp. 11574-11588, 2022.

C. A. Cornaglia, M. E. Adrover, J. F. Múnera, M. N. Pedernera, D. O. Borio, and E. A. Lombardo, "Production of ultrapure hydrogen in a Pd-Ag membrane reactor using noble metals supported on La-Si oxides. Heterogeneous modeling for the water gas shift reaction," International journal of hydrogen energy, vol. 38, no. 25, pp. 10485-10493, 2013.

M. De Falco, L. Di Paola, and L. Marrelli, "Heat transfer and hydrogen permeability in modelling industrial membrane reactors for methane steam reforming," International Journal of Hydrogen Energy, vol. 32, no. 14, pp. 2902-2913, 2007.

H.-S. Yang and C.-T. Chou, "Non-isothermal simulation of cyclohexane dehydrogenation in an inert membrane reactor with catalytic pellets in the feed-side chamber," Journal of the Chinese Institute of Chemical Engineers, vol. 39, no. 3, pp. 227-235, 2008.

M. Rahimpour and M. Bayat, "Production of ultrapure hydrogen via utilizing fluidization concept from coupling of methanol and benzene synthesis in a hydrogen-permselective membrane reactor," International journal of hydrogen energy, vol. 36, no. 11, pp. 6616-6627, 2011.

H. Choi et al., "CFD analysis and scale up of a baffled membrane reactor for hydrogen production by steam methane reforming," Computers & Chemical Engineering, vol. 165, p. 107912, 2022.

R. Ben-Mansour et al., "Comprehensive parametric investigation of methane reforming and hydrogen separation using a CFD model," Energy Conversion and Management, vol. 249, p. 114838, 2021.

M. Upadhyay, H. Lee, A. Kim, S.-h. Lee, and H. Lim, "CFD simulation of methane steam reforming in a membrane reactor: Performance characteristics over range of operating window," International Journal of Hydrogen Energy, vol. 46, no. 59, pp. 30402-30411, 2021.

G. Ji, M. Zhao, and G. Wang, "Computational fluid dynamic simulation of a sorptionenhanced palladium membrane reactor for enhancing hydrogen production from methane steam reforming," Energy, vol. 147, pp. 884-895, 2018.

H. W. A. El Hawa, S. N. Paglieri, C. C. Morris, A. Harale, and J. D. Way, "Application of a composite membrane to hydrogen production in a high temperature membrane reactor," Separation and Purification Technology, vol. 147, pp. 388-397, 2015.

K. S. Patel and A. K. Sunol, "Modeling and simulation of methane steam reforming in a thermally coupled membrane reactor," International Journal of Hydrogen Energy, vol. 32, no. 13, pp. 2344-2358, 2007.

P. Marín, Y. Patiño, F. V. Díez, and S. Ordóñez, "Modelling of hydrogen perm-selective membrane reactors for catalytic methane steam reforming," International journal of hydrogen energy, vol. 37, no. 23, pp. 18433-18445, 2012.

R. Ma, B. Castro-Dominguez, I. P. Mardilovich, A. G. Dixon, and Y. H. Ma, "Experimental and simulation studies of the production of renewable hydrogen through ethanol steam reforming in a large-scale catalytic membrane reactor," Chemical engineering journal, vol. 303, pp. 302-313, 2016.

A. Shafiee, M. Arab, Z. Lai, Z. Liu, and A. Abbas, "Modelling and sequential simulation of multi-tubular metallic membrane and techno-economics of a hydrogen production process employing thin-layer membrane reactor," international journal of hydrogen energy, vol. 41, no. 42, pp. 19081-19097, 2016.

Y.-R. Chen, T. Tsuru, and D.-Y. Kang, "Simulation and design of catalytic membrane reactor for hydrogen production via methylcyclohexane dehydrogenation," International Journal of Hydrogen Energy, vol. 42, no. 42, pp. 26296-26307, 2017.

B.M. Cruz and J. D. da Silva, "A two-dimensional mathematical model for the catalytic steam reforming of methane in both conventional fixed-bed and fixed-bed membrane reactors for the Production of hydrogen," International Journal of Hydrogen Energy, vol. 42, no. 37, pp. 23670-23690, 2017.

P. Ribeirinha, M. Abdollahzadeh, M. Boaventura, and A. Mendes, "H2 production with low carbon content via MSR in packed bed membrane reactors for high-temperature polymeric electrolyte membrane fuel cell," Applied Energy, vol. 188, pp. 409-419, 2017.

W. Yu et al., "Simulation of a porous ceramic membrane reactor for hydrogen production," International journal of hydrogen energy, vol. 30, no. 10, pp. 1071-1079, 2005.

Y. Benguerba, M. Virginie, C. Dumas, and B. Ernst, "Computational fluid dynamics study of the dry reforming of methane over catalyst in a membrane reactor. Coke deposition," Kinetics and Catalysis, vol. 58, pp. 328-338, 2017.

M. S. Macedo, M. Soria, and L. M. Madeira, "Glycerol steam reforming for hydrogen production: Traditional versus membrane reactor," International Journal of Hydrogen Energy, vol. 44, no. 45, pp. 24719-24732, 2019.

X. Yang, S. Wang, B. Li, Y. He, and H. Liu, "Performance of ethanol steam reforming in a membrane-assisted packed bed reactor using multiscale modelling," Fuel, vol. 274, p. 117829, 2020.

N. Ghasem, "Modeling and simulation of CO2 absorption enhancement in hollow-fiber membrane contactors using CNT-water-based nanofluids," Journal of Membrane Science and Research, vol. 5, no. 4, pp. 295-302, 2019.

M. Patrascu and M. Sheintuch, "On-site pure hydrogen production by methane steam reforming in high flux membrane reactor: Experimental validation, model predictions and membrane inhibition," Chemical Engineering Journal, vol. 262, pp. 862-874, 2015.

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 33-39

doi: 10.4028/p-EnBm0E

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-11-16

Revised:
2023-03-09

Accepted:
2023-03-15

Online:
2023-08-11

Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

Marwa F. Abdul Jabbar , Abdulkareem Dahash Affat , Luay Badr Hamad

¹Department of Chemical Engineering, Al-Nahrain University, Iraq.

Department of Mechanical Engineering, College of Engineering, Al-Mustansiriyah Univ., Baghdad, Iraq

marwa.f.abduljabbar@nahrainuniv.edu.iq, abdulkareem.d.affat@nahrainuniv.edu.iq, luaybadr75@uomustansiriyah.edu.

Keywords: Transesterification, sawdust, heterogeneous catalyst, biodiesel, waste cooking oil

Abstract

Due to the greenhouse effect of increased fossil fuel use, resulting in an increase in the period during which fossil fuels will remain available. Because of its advantages for the environment and its production from renewable resources, biodiesel has grown more appealing. As there is a supply of used cooking oil, interest in producing biodiesel is rising. This research examines how CaO and sawdust function as heterogeneous catalysts in transesterification regarding ethanol to produce bio-diesel from the used cooking oil. The impacts of the subsequent variables on the yield of the created biodiesel were investigated. Those parameters include the catalyst concentration ( ), reaction period ( ), the molar ratio of ethanol to oil ( ), and temperature ( 45 to ). This led to the discovery that CaO catalyst is more efficient compared to the sawdust catalyst, with the maximum percentage yield being for the sawdust catalyst and for the CaO catalyst under catalyst conditions ( ), ethanol oil molar ratio of , and 65 Celsius temperature for 3 hours. It was evident from the results that the biodiesel fuel produced by the catalyst developed in this study fell within the acceptable range of biodiesel fuel.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

With growing environmental concerns and global oil reserves depleted, there is a strong demand for other sources of petroleum-based fuel, such as gasoline and diesel [1].Currently, transportation is virtually totally reliant on petroleum-derived fuels globally. Petroleum is one of the limited sources of fuel that has become increasingly expensive and scarce [2] and is one of the primary sources of the emissions of the anthropogenic carbon dioxide (CO2) into the atmosphere. In addition, the presence of sulphur in diesel has severely limited its use as a result of pollution and corrosion. Scientists have had to look at alternative forms of renewable energy [3].

Biofuels are an alternative to petroleum-based transport fuels that can be useful for improving energy security while reducing greenhouse gas (GHG) emissions and urban air pollution. Biodiesel is a modern alternative diesel fuel explored as a potential alternative to the conventional diesel [4].

Biodiesel can be defined as a blend of fatty acid methyl esters (FAME) that is made of oil feedstocks like the non-edible oils, vegetable oils, waste cooking oils, animal oil/fats, and tallow that may be utilized in diesel engines with no changes [5]. Blending and direct use of microemulsions, vegetable oils, transesterification, and thermal cracking are the most common processes for producing biodiesel [6]. Transesterification is considered as the most popular process for synthesizing biodiesel among all of the approaches described above. With the existence of catalyst, transesterification represents the reaction of oil or fat with alcohol that leads to producing glycerol or esters. Due to its high costs and low production, refined edible oils such as rapeseed oil, soybean oil and palm oil are not referred to as raw materials in developed countries[7]. As a result, animal fats, non-edible plant oil, and waste cooking oil have been utilized. Transesterification might be catalyzed in a variety of ways, including with homogeneous acids, heterogeneous bases, homogeneous bases, enzymes, heterogeneous acids, carbon-based catalysts, ionic liquids, etc. [8]. The quick
reaction rates of homogeneous base catalysts account for their general acceptance. This procedure has many disadvantages since it takes a lot of energy to purify the product and separate the catalysts that are not reusable, resulting in large chemical waste and energy waste [9].

At the end of the reaction, heterogeneous catalysts can be readily isolated from the products and reused in the subsequent reaction cycle.Alkaline and alkali earth oxides [10], mixed metal oxides [11], and supported alkali metal catalysts are all examples of heterogeneous base catalysts [12].

This study intends to create biodiesel from waste cooking oil utiizing a heterogeneous catalyst made from waste (saw dust). In addition, it focuses on investigating the effects of different variables on the catalysis process, such as ethanol: oil molar ratio, reaction duration, catalyst percentage, and temperature for the purpose of establishing the best conditions for biodiesel generation.

Materials and Method

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

In this study, waste cooking oil (WCO) has been utilized as the base oil for transesterification, while ethanol was utilized as alcohol, which was obtained from Hayman Ltd, East Ways Park, UK. Saw dust was employed as a heterogeneous catalyst and calcium oxide was made through calcining calcium carbonate at a temperature of for 90 min to be utilized as a catalyst as well. In a 3 necked glass reactor (i.e. batch reactor), the transesterification reaction has been carried out as shown in Fig. 1. A condenser was installed in the middle of the reactor's necks for condensing ethanol vapors, a thermometer in one of the necks, and a withdrawn sample in the third neck. The reaction flask has been filled with waste cooking oil and heated till reaching the desired level by the reaction temperature. Also, the heat controller was a magnetic stirrer which changed the heating power to achieve the desired reaction temperature. The catalyst and alcohol are added after reaching the required temperature. Then, agitation began at 600 rpm to ensure proper mixing of the compounds and to avoid any potential mass transfer issues.This was the starting point of reaction. Furthermore, the reaction mix has been transferred into a separating funnel and was left to settle for a period of 24 hours after it was done. According to the density difference, the biodiesel has been separated from residue's top layer and the yield was determined using Eq. (1).

Figure 1: Diagram of equipment

Figure 1. Figure 1: Diagram of equipment

Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

Scanning electron microscopy

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

Using SEM, researchers could examine the catalyst's particle size and surface morphology (Fig. 2). The SEM image clearly demonstrates that the catalyst particles have fibrous morphology, where CaO has an agglomerate of rod-like regular structure and the sawdust has fibrous morphology with lengths ranging from a few hundred nanometers to a few micrometers.

Figure 2: SEM for (a) Sawdust (b) CaO

Figure 2. Figure 2: SEM for (a) Sawdust (b) CaO

BET surface area

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

The Surface Area (SA) of the catalyst considered to be significant parameters influencing catalytic activity. SA for sawdust was while for Cao .

Effect of oil to alcohol molar ratio

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

The percentage yield of alcohol biodiesel had been studied as a function of alcohol/oil molar ratio (moles of alcohol/moles of oil; , and ). At a temperature of 65 Celsius, catalyst concentration, and 3 hrs of reaction time. In Fig. 3 , it has been shown that as the molar ratio was increased, the yield of biodiesel produced increased from 22 to for CaO catalyst and 10.5 to for the sawdust catalyst. As would be expected, this can be explained by the fact that increasing the alcohol content leads the reaction to spread to additional products. This behavior is consistent with the findings of Marwa and Ruqaya [13], who discovered that lauric acid conversion increased as the ethanol to acid molar ratio increased.

Figure 3: Effects of oil to alcohol molar ratio on yield of biodiesel at , catalyst concentration 0.5% and time 3 h

Figure 3. Figure 3: Effects of oil to alcohol molar ratio on yield of biodiesel at , catalyst concentration 0.5% and time 3 h

Effects of catalyst amount

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

Transesterfication may involve the use of different catalyst concentrations. The effect of catalyst levels (at , alcohol/oil molar ratio (12:1) for 3 hrs ) on percentage yield of the bio-diesel is shown in Fig. 4. Yield increased as the amount of the catalyst had been increased from ( , rising from and for sawdust and calcium oxide, respectively. Figure 3 illustrates that an optimum amount of catalyst of could achieve a maximum percent yield of biodiesel of using calcium oxide catalyst and using sawdust catalyst. The adsorption process on the catalyst surface growing may be the cause of the increase in yield as the catalyst quantity increases. Kamisah et al.[14] show the same behavior in their study. Norshahidatul and Fatin [15] also noticed the yield increases as catalyst amount increased.

Figure 4: Effects of the concentration of the catalyst on yield of bio-diesel at temperature , oil to alcohol molar ratiol:12 and time 3 h

Figure 4. Figure 4: Effects of the concentration of the catalyst on yield of bio-diesel at temperature , oil to alcohol molar ratiol:12 and time 3 h

Effect of temperature

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

Using CaO and sawdust catalysts, biodiesel is produced by combining ethanol and used cooking oil in a 1:12 mole ratio for 3 hours at different temperature degrees ( , and ). The impact of the temperature operation on biodiesel production is shown in fig. 5 . The yield will rise to a specific point before starting to fall. The higher the temperature, the lower the viscosity of the oil and the faster the reaction. If the temperature rises above the ideal temperature, biodiesel production
will decrease because the alcohol concentration will decrease as the alcohol evaporates. The ideal temperature is around 55 degrees Celsius. At , sawdust and CaO catalyst yields were identified to be and , respectively, with yields increasing to and at a temperature of . The yield dropped to and for two catalysts at a temperature of 65 degrees Celsius. This behavior agrees with Sisca V. et.al [16] who used CaO catalyst.

Figure 5: Effects of the temperature on yield of bio-diesel at catalyst concentration , oil to alcohol molar ratiol:12 and time 3 h

Figure 5. Figure 5: Effects of the temperature on yield of bio-diesel at catalyst concentration , oil to alcohol molar ratiol:12 and time 3 h

Effect of time

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

One of the most crucial factors influencing the conversion of biodiesel is thought to be the time of the reaction. The impact of time on production of biodiesel is shown in Fig. 6. With catalyst concentration of and ethanol to oil molar ratio of 12:1, the reaction has been carried out at . Following catalyst concentration, 4 hrs of reaction time at , and molar ratio of oil to alcohol, the highest conversion obtained using the catalyst CaO is , while the maximum conversion that has been obtained using sawdust catalyst is . This is brought on by a rise in the relative solubility of the produced glycerol in the reaction medium. The same behavior was also shwon by Sisca V. et.al [16].

Figure 6: Effect of time on yield of biodiesel at catalyst concentration 0.5%, oil to alcohol molar ratio1:12 and temperature

Figure 6. Figure 6: Effect of time on yield of biodiesel at catalyst concentration 0.5%, oil to alcohol molar ratio1:12 and temperature

Characteristics of produced biodiesel

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

The ASTM method was used to analyze the fuel characteristics of the acquired biodiesel generated by sawdust and CaO catalysts. As shown in Table 1, biodiesel made from ethanol demonstrated excellent fuel qualities that fell within parameters of the bio-diesel standard and were in good agreement with earlier findings [17] as well.

Table 1: Properties of biodiesel

Fuel properties | Biodiesel | ASTM limits for B 100
Flash point °C | 155 | 100-170
Pour point °C | -9 | -15-10
Cloud point °C | - 4 | -3-12
Viscosity @40°C c.st | 5.763 | 4-6
Density g/ml | 0.878 | 0.86-0.9

Conclusions

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

This research showed that waste cooking oil could be utilized to make biodiesel, which may be utilized as alternative fuel in traditional diesel engines. The findings revealed that catalyst concentrations, ethanol to oil molar ratio, temperature of reaction, and reaction time all have an impact on bio-diesel production by transesterification with ethanol in the presence of two types of heterogeneous catalysts ( CaO and sawdust). The best yield percentages of and have been obtained utilizing an ethanol: oil molar ratio of as catalyst ( ) and for 3 hours with the using sawdust and CaO catalyst, respectively.

References

The original version of this paper is available on https://www.scientific.net/EC.4.33.pdf

W. G. Ying, The investigation of blending properties of biodiesel and diesel fuel, J Jiangsu Polytech. Univ. 15(2003).

A. Subrata, S.Karmakar and M.Souti, Properties of various plants and animals feedstocks for biodiesel production, Biores. Tec. (2010) 7201-7210.

A.M. Namasivayam, T. Korakianitis and R.J. Crookes, Biodiesel, emulsified biodiesel and dimethyl ether as pilot fuels for natural gas fuelled engines, Appl. Ener. 87(2010) 769-78.

L.C. Meher, D.V. Sagar and S.N. Naik, Technical aspects of biodiesel production by transesterification-a review, Rene. and Sustain. Ener. Rev. 10(2006) 248-268.

K. Noiroj, P. Intarapong, A. Luengnaruemitchai and S. J In, A comparative study of and catalysts for biodiesel production via transesterification from palm oil, Renew. Ener. 34(2009) 1145-1150.

F. Ma and M.A. Hanna, Biodiesel production: a review, Bioresour. Technol. 70(1999) 1-15.

F.A. Dawodu, O. Ayodele, J. Xin, S. Zhang and D. Yan, Effective conversion of non-edible oil with high free fatty acid into biodiesel by sulphonated carbon catalyst, Appl. Energy 114(2014)819-826.

L.J. Konwar, J. Boro and D. Deka, Review on latest developments in biodiesel production using carbon-based catalysts, Renew. Sustain. Ener. Rev. 29(2014)546-564.

Q. Shu, Z. Nawaz, J. Gao, Y. Liao, Q. Zhang, D. Wang and J.Wang, Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: Reaction and separation, Bioresour. Technol. 101(2010) 5374-5384.

M.L. Savaliya, M.S. Bhakhar, and B.Z. Dholakiya, Cutting Cost Technology for the Preparation of Biodiesel Using Environmentally Benign and Cheaper Catalyst, Catal. Lett. 146 (2016) 2313-2323.

A.K. Singh and S.D. Fernando, Transesterification of Soybean Oil Using Heterogeneous Catalysts, Energy & Fuels 22(2008) 2067-2069.

W. Xie, X. Huang and H. Li, Soybean oil methyl esters preparation using NaX zeolites loaded with KOH as a heterogeneous catalyst, Bioresour. Technol. 98(2007) 936-939.

R. Q. Sabah and M. F. Abdul Jabbar, Esterification of Lauric Acid with Ethanol Using Zirconium Oxide as Heterogeneous Catalyst, Petrol. and Coal J. 62(3)(2020) 799-803.

K. D. Pandiangan, W. Si. Ilim, H. Satria and N. Jamarun, Catalytic Performance of CaO/SiO2 Prepared from Local Limestone Industry and Rice Husk Silica, Journal of Pure and Applied. Chemistry Research 8(2) (2019) 170-178.

N.A. M. Shohaimi and F. N. S. Marodzi, Transesterification of Waste Cooking Oil in Biodiesel Production Utilizing Heterogeneous Catalyst, Malaysian Journal of Analytical Sciences 22 (1)(2018) 157-165.

V. Sisca, S. Zilfa and N. Jamarun, Biodiesel Production from Waste Cooking Oil Using Catalyst Calcium Oxide Derived of Limestone Lintau Buo, Archives of Pharmacy Practice 11(3)(2020) 8-14.

F. Yasar, Biodiesel production via waste eggshell as a low-cost heterogeneous catalyst: its effects on some critical fuel properties and comparison with CaO, Fuel 255(2019) 115828.

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 41-49

doi: 10.4028/p-ugJQs1

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-08-02

Revised:
2022-10-30

Accepted:
2023-04-12

Online:
2023-08-11

Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

Susi Susi , Makhmudun Ainuri , Wagiman Wagiman and Muhammad Affan Fajar Falah

Doctoral Programme of Agroindustrial Technology, Faculty of Agricultural Technology, Universitas Gadjah Mada, JI. Flora No 1 Bulaksumur Yogyakarta, Indonesia, 55281

Department of Agroindustrial Technology, Faculty of Agriculture, University of Lambung Mangkurat, Banjarbaru, JI A Yani KM 36 Banjarbaru Kalimantan Selatan 70714

Department of Agroindustrial Technology, Faculty of Agricultural Technology, Universitas Gadjah Mada, JI. Flora No 1 Bulaksumur Yogyakarta, Indonesia, 55281

susi0577@mail.ugm.ac.id, dun@ugm.ac.id, ayuafif@ugm.ac.id,

Keywords: OPEFB, cellulose, bleaching, delignification

Abstract

Oil palm empty fruit bunches (OPEFB) are oil palm industry waste which is indeed abundant. OPEFB waste has been explored to make fiber, cellulose, and its derivatives. Extracting cellulose can depolymerize several components, including hemicellulose, lignin, and color elements. The combination of bleaching under acidic conditions and alkaline delignification gave different changes, one of which depends on the type of bleacher, concentration, reaction time, and the number of stages carried out. This study aimed to examine the effect of concentration and bleaching time on the physical and chemical characteristics that indicate the depolymerization process of OPEFB fiber. Depolymerization was shown by cellulose color, purity, and crystallinity changes. The bleacher concentration and bleaching time affected the shift in cellulose mass. High concentrations of bleachers will reduce the cellulose mass significantly. The chromophore elements OPEFB was depolymerized. The change was shown in color from brown to gray-white with different brightness intensities. The XRD test indicated that there was a correlation between low crystallinity with the use of high bleacher concentrations.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

Chang [1] stated that empty fruit bunches are solid residues from the palm oil processing industry estimated to reach 20 percent of the weight of fresh fruit of Elaeis guineensis. Oil palm Empty Fruit Bunches (OPEFB) weigh approximately 3.5 kg , have a thickness of up to 130 mm , a width of 300 mm , and a length of 300 mm . OPEFB is composed of several essential substances that can be utilized and processed into other materials with more economic value. The cellulose content in OPEFB ranges from . Although classified as agricultural waste, OPEFB can produce a high-quality final product.

Cellulose is a linear homopolymer composed of D-anhydroglucopyranose units consisting of (1-4)-glycosidic bonds. Natural cellulose, also known as cellulose I, is a semi-crystalline polymer arranged in parallel structures and is not the most stable crystalline form [2]. The regenerated cellulose product, commonly known as cellulose II, has the same molecular formula as cellulose I but is more stable and can be molded into certain products such as membranes, hydrogels, aerogels, and fibers .

Getting cellulose from OPEFB, delignification, and bleaching processes were undertaken. In the extraction process, a delignification process is first carried out and followed by bleaching to get the whiteness of cellulose. Based on previous studies, the bleaching process under acidic conditions can be carried out early before alkaline delignification. The bleaching condition will degrade the OPEFB color components. It will also help open the cell wall structure of OPEFB. The release of lignin inside
the cell wall in the alkaline delignification process will be more accessible. The acidic bleaching process can depolymerize the structure by reducing hemicellulose, lignin, and extractive impurities.

The cellulose extracted from the fiber was affected by the pretreatment conditions, such as the chemical type, concentration, duration, and temperature of the hydrolysis treatment. Alkaline treatment only partially removed hemicellulose and lignin. Further chemical treatment through a bleaching process can obtain a higher cellulose content. The research applied acidic bleaching before delignification to degrade the brown chromophore element of OPEFB and produce high-purity cellulose. Depolymerization was indicated by changes in color, cellulose content, and crystallinity, which will later become a reference for the derivate product. This study aimed to examine the effect of concentration and bleaching time on the physical and chemical characteristics that indicate the depolymerization process in OPEFB fiber.

Experimental Methods

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

Materials and Equipment. OPEFB was obtained from PT Nurciptasari Moeda Sentosa, South Kalimantan, NaOH (Merck), (Clover Chemicals Ltd), glacial acetic acid (Merck), (Merck), and distilled water. The equipment, such as a beaker glass, hotplate stirrer, spatula, filter paper, filter cloth, X-Ray Diffraction (XRD) (Rigaku MiniFlex HyPix-400 MF (2D HPAD)-USA), and colorimeter CIELAB lab tool apps, were used.

Preparation of OPEFB. OPEFB was collected after the threshing process from the Palm Oil Mill. OPEFB was washed using hot water, manually separated into stalks and grains, then rinsed up to 4 times using clean water. Furthermore, the fibers were soaked with a soap solution ( ) to remove residual oil and dust for 5 h and rinsed with clean water. They were drained and dried in an oven at for 48 h . Dried OPEFB , cut into 5 cm , ground, and sifted on a 30 mesh sieve.

Cellulose Extraction Process (Bleaching and Delignification). Ten grams of OPEFB fiber were bleached using according to concentrations (1.5, 3, and 4.5%) with a ratio of 1:25(w/v) at a temperature of for variations of 1, 2, and 3 h under acidic conditions of using acetic acid. The bleached fibers were dried and weighed. The bleached fibers were delignified using a solution with a ratio of 1:20 at room temperature. Delignified cellulose was washed with distilled water and dried. The cellulose is refluxed for 30 minutes with distilled water for washing and continued by drying at for 24 h .

Parameter of Analysis. The cellulose was measured by its yield after the bleaching and delignification process. The cellulose was analyzed, including moisture content, ash content, water extractive material, hemicellulose, cellulose, and lignin content. Color cellulose was analyzed using CIE L*, CIE , and CIE parameters and crystallinity test using X-Ray Diffraction (XRD).

Test Method for Cellulose. Analysis of fiber components was carried out using the Chesson method [5]. A one-gram powder sample was added with 150 mL of distilled water and refluxed for 2 h. The solution was filtered and washed until the pH was neutral and then dried at , weighed, and calculated using Eq. 1. The residue 1 obtained was added with 150 mL of and refluxed for 2 h . The sample was then filtered and washed until the pH was neutral, dried at until dry, then weighed and calculated using Eq. 2. The residue 2 obtained was added with 10 mL of and macerated for 4 h in room temperature. The sample was added with 150 mL of 0.5 , refluxed for 2 h , filtered, and washed until the pH was neutral. The residue was dried at until dry, then weighed and calculated using Eq. 3. The calculation of lignin content using Eq. 4. is as follows:
water - soluble extractive value
hemicellulose content
cellulose content
lignin content

X-Ray Diffraction. X-ray diffraction (XRD) was carried out to study sample crystallinity. The sample patterns of all cellulose samples were pressed to form pellets and recorded on an X'Pert Xray diffractometer using Ni-filtered radiation ( 30 kV and 30 mA ). The diffraction intensity was measured between the Bragg angle (2θ) of . Scan speed of , step width of . The crystallinity index (CrI) was calculated by the Segal formula [6] using intensity measurements at and (amorphous) :

indicates the maximum intensity at is the lowest intensity corresponding to the value of near .

CIE-Lab color. CIE-Lab color measurement using colorimeter lab tools apps (modification from Kristanoko et al. [7]) The smartphone camera used is Android Vivo Y 20 SV2029 with a triple macro camera specification of . Lighting uses 15 Watt LED lamps. The sample is placed on the cup evenly, the distance between the camera and the sample is 12 cm without flash, and the color scan is carried out in live mode, which is carried out at 25 random points on the sample. The colorimeter will convert the recorded color into CIE *L, CIE *a CIE *b, and export data via email.

Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

Yield, Moisture Content, and Ash Content. The bleaching process using is generally intended to remove a material's color components. Acidic bleaching at pH 4-4.5 will depolymerize chromophores, lignin, cellulose, hemicellulose, and crystallinity cellulose. The reaction can be observed by decreasing fiber mass or yield after the bleaching and delignification process on the cellulose from OPEFB. The changes in cellulose extracted with variations in bleaching conditions are presented in Fig. 1.

Figure 1. a) Yield profile bleached and delignified cellulose; b) moisture and ash content profile of cellulose ( concentration (%); bleaching time (hours))

Figure 1. Figure 1. a) Yield profile bleached and delignified cellulose; b) moisture and ash content profile of cellulose ( concentration (%); bleaching time (hours))

The bleaching process was carried out in the first stage, and Fig. 1a shows that the concentration of will significantly affect the depolymerization. The bleaching process with a higher concentration caused decreasing the fiber mass after bleaching. According to Kim [8], acid hydrolysis of lignocellulosic can depolymerize cellulose and hemicellulose into monomers without pretreatment.

Implementation bleaching at for 1 and 3 h in resulted in yields of and , which were greater than those of and . A high yield does not
indicate a high purity of cellulose. There was still a lot of lignin content left in the fiber. After the alkaline delignification process, the cellulose yield decreased. Yield reduction from bleaching to delignification varied at and concentrations in the range of , while at concentrations, the yield reduction reached concentration significantly causes depolymerization of color, lignin, hemicellulose, and other impurity components. Fig. 1b shows that the bleaching and delignification processes significantly reduced the ash content of cellulose, while the water content of cellulose was not significantly different. Fiber contains minerals such as silica; the bleaching and delignification process can reduce the mineral content in cellulose.

Color of Cellulose. The color of the oil palm empty fruit bunches was originally brown. After the bleaching process will fade to a whitish yellow, and if continued by the delignification, the color will be grayish white. The brightness of the cellulose color after the bleaching and delignification stages can be described by the CIE *L, CIE *a, and CIE *b values. OPEFB has the lightness value of CIE shown on a scale of 61.25, and after the bleaching comes to 80.15-84.97. The treatment of with a bleaching time of 1 h resulted in a lower CIE score than the others, especially when compared to the concentration at the same bleaching time. A low concentration of needed a longer bleaching process to get a high lightness level. However, it will provide intensive depolymerization at high concentrations and treated at a long bleaching period. However, the higher concentration positively correlated with the reduction of cellulose produced.

Figure 2. a) Pattern of CIE L, CIE a*, and CIE b*; b) Chroma and Hue pattern of cellulose from OPEFB ( concentration (%); bleaching time (hours))

Figure 2. Figure 2. a) Pattern of CIE L, CIE a*, and CIE b*; b) Chroma and Hue pattern of cellulose from OPEFB ( concentration (%); bleaching time (hours))

The CIE value (Fig. 2a) indicated the color intensity in the red-green range, and the CIE value indicated the yellow-blue range. Different bleaching treatments showed that the CIE and CIE b* values were relatively not significantly different. However, when compared with OPEFB, it showed a significant color reduction. The value of CIE a* of OPEFB is greater than cellulose and indicated the red tendency in OPEFB is more visible. Similarly, the value of CIE on OPEFB was 23.38, it was higher than that of cellulose in the range of 5-6. a higher positive CIE value leads to a stronger yellowish color.

The chroma and hue values among bleaching treatments did not significantly differ (Fig. 2b). The chroma value of cellulose averages 6.00 , it's different from the chroma's OPEFB is 24.88 . and the hue value of OPEFB and its cellulose were 27.14-35.95. In the context of color, hue refers to purity, hue is the main identity of color so that it can be easily distinguished from other colors. chroma is the degree of color strength or intensity of the color. The strongest colors are those with high chroma while the less intense ones are those with low chroma.

Brightening effect that can be caused by the presence of hexanuronic acid groups in the bleaching process. Hexenuronic acid is sensitive to acidic conditions, the hydrolytic stage can be carried out
either as part of the long-term chlorine stage at high temperatures to produce high brightness. This step aims to achieve selective hydrolytic degradation of hexenuronic acid groups into 5-formylfuroic acid and furoic acid [9].

The color change in OPEFB fiber (Fig. 3) shows a chromophores gradation after the bleaching process, which was naturally from brown to white in a color range of light brown to yellowish white. This degradation is strongly affected by the concentration of bleach and the duration of bleaching. In the bleaching process, some lignin removal occurs, and decreasing lignin will be continued in the alkaline delignification process (Fig. 3) so that the color changes in the cellulose are more visible than the OPEFB color. The success of the bleaching process determines the rate of color change from brown to white under acidic conditions before delignification. The main purpose of chemical pulp bleaching is to remove residual lignin and chromophore in the pulp without affecting the strength of the pulp. It's achieved through a multistage process by delignifying and further brightening the pulp [10].

Figure 3. Color of a) OPEFB fiber; after the bleaching process b) C1.5T3, c) C3T2, d) C4.5T3; after the delignification process e) C1.5T1, f) C1.5T3, g) C3T2 and h) C4.5 T3 ( concentration (%); bleaching time (hours))

Figure 3. Figure 3. Color of a) OPEFB fiber; after the bleaching process b) C1.5T3, c) C3T2, d) C4.5T3; after the delignification process e) C1.5T1, f) C1.5T3, g) C3T2 and h) C4.5 T3 ( concentration (%); bleaching time (hours))

The leaching of color components in OPEFB can be seen in the bleaching process, where the liquid changes from yellowish white to brownish yellow to dark brown (Fig. 4). The oxidation of the pulp with chlorine dioxide takes place at a temperature of about and with reaction time minutes. The initial consumption of chlorine dioxide by the pulp is very fast and within seconds, subsequently, the chlorine dioxide concentration will decrease to a considerable extent [11]. Changes in the color intensity of the bleach solution correlated with the duration of bleaching. The change to dark brown will begin after 45 minutes of the bleaching process at a temperature of . The color change is a cumulative element of chromophore and lignin from OPEFB fiber.

Figure 4. Changes in the color of the bleaching liquid at ) the beginning; ) the middle and ) the end of the bleaching process

Figure 4. Figure 4. Changes in the color of the bleaching liquid at ) the beginning; ) the middle and ) the end of the bleaching process

Cellulose and Lignin. The alkaline delignification process was less optimal in reducing the lignin content in cellulose, so it must be combined with a bleaching process under acidic conditions in the early stages of extraction. In the cellulose extraction process, reducing lignin content required reactivity to open the cell wall. Lignin is covalently bonded to cellulose, so it requires high reactivity to break the bond, making it easier to reduce the lignin content.

Figure 5. Content of water extractive, hemicellulose, cellulose, and lignin of OPEFB cellulose ( concentration (%); bleaching time (hours))

Figure 5. Figure 5. Content of water extractive, hemicellulose, cellulose, and lignin of OPEFB cellulose ( concentration (%); bleaching time (hours))

The cellulose content of OPEFB is . Fig. 6 describes that the concentration of in the bleaching process affects the increase in cellulose. Treatment of bleaching in for 2 h at resulted in cellulose being . At concentrations of and tended to produce a significant reduction in lignin in the range of , while the hemicellulose relatively decreased from to a range of Hemicellulose had an irregular structure, it is more amorphous than cellulose, so more readily hydrolyzed by acids to monomers. On the other hand, under acid conditions, it can be easily degraded to decomposition products, including furfural.

The extraction process with acid will cause hemicellulose to degrade, which is indicated by a decrease in the chain length. Acidic conditions will boost the autohydrolysis of hemicellulose glycosidic bonds, producing hemicellulose with low molecular weight and water-soluble [12]. Acidic conditions using acetic acid will contribute to hydronium ions that enhance the extraction kinetics. Chio et al. [13] stated that lignin is a complex structure and has low reactivity. The separation of lignin from the cellulose structure can be carried out by mechanical, thermochemical, chemical, and
biological catalysis. It is known that acid hydrolysis is widely used for depolymerization. The use of acetic acid to lower the pH can increase the depolymerization of lignin at the bond.

This research carried out the bleaching process under acidic conditions, followed by alkaline delignification. Lignin depolymerization can also occur in alkaline hydrolysis using NaOH or KOH . Using NaOH was proven to be able to depolymerize four times compared to without alkaline. The research was conducted treatment of as a base catalyst in the delignification process and carried out at room temperature. Evans et al. [14] stated that strong bases such as NaOH and KOH were able to convert and produce depolymerization products compared to weak bases. Alkaline delignification at low concentrations could not catalyze the depolymerization of lignin in water [15]. At the same concentration of with a bleaching time of 1 h and 3 h , cellulose still has lignin content ranging from , while at a concentration of for 2 h , there remains lignin residue.

Bleaching at for 3 h tends to give higher cellulose and lower hemicellulose than bleaching for 1 h . This phenomenon is not in line with bleaching at , where the cellulose content of 1 h of bleaching time is higher, and hemicellulose is lower than 3 h of bleaching time at the same concentration. According to Karagöz et al. [16], the formation of carboxylic acids during depolymerization can lower pH and enhance repolymerization.

X-ray diffraction. OPEFB is a type of wood fiber that is quite sturdy. Intensive bleaching and delignification treatment must be carried out to depolymerize it so high-purity cellulose can be obtained. Impurities in OPEFB are not only components of hemicellulose and lignin but also a waxy layer or wax on the outer wall. The grinding process in the initial treatment will help facilitate the depolymerization reaction by chemical components, both acids, and bases.

Figure 6. Correlation of and intensity on OPEFB cellulose

Figure 6. Figure 6. Correlation of and intensity on OPEFB cellulose

Based on Fig. 6, the peaks resulted in the range of , while the amorphous was in the range of . The low crystallinity indicates that the amorphous structure is high. The effect of concentration as a bleacher on crystallinity has not been fully explained. Based on Table 1, bleaching at of for 2 h resulted in crystallinity of , which is higher than at a concentration of . Bleaching at and concentration for 3 h gave lower crystallinity. Bleaching at of in excess time ( 3 h ) will not only reduce amorphous lignin and hemicellulose but will be able to erode the crystalline structure. On the other hand, the crystallinity index can be related to the phenomenon of crystalline polymorphism of cellulose. According to Nam et al. [17], irreversible polymorphic can changes in the crystalline structure of cellulose but the mechanism has not been fully explained. The bleaching process under acidic conditions and alkaline delignification will affect the rearrangement of the cellulose chain, which will later change cellulose I to cellulose II and have specific thermodynamic properties [18].

The crystallinity of cellulose can be increased by acid hydrolysis treatment. In this study, the crystallinity of cellulose becomes important to support the quality of microcrystalline cellulose (MCC). The crystallinity of cellulose is important in determining thermal stability, elasticity, absorption efficiency, and increasing stiffness [14]. Furthermore, high crystallinity MCC will also be able to support the mechanical strength of the hydrogel formulation.

Table 1. Crystallinity Index of cellulose from oil palm empty fruit bunches

Treatments
2θ I₀₀₂
[°]
2θ Iam
[°]
Intensity [cps °]
FWHM
[°]
Crystallinity
Index [%]

I₀₀₂
Iam

C4.5T1
23.58
17.1
9699
1999
3.67
79.39

C1.5T1
23.09
16.16
11520
2282
2.94
80.19

C3T2
23.01
17.47
4942
875
2.19
82.29

C4.5T3
22.55
18.19
6789
3006
3.69
55.72

C1.5T3
23.18
16.25
7229
2828
3.10
60.88

Note: concentration bleaching time; FWHM : Full Width at Half Maximum
Table 1 explains that the FWHM of cellulose resulting from has a higher value than the others, followed by and the lowest at . The FWHM value also shows a non-linear relationship with the crystallinity index. Adjacent peaks at positions (110) and (200) even overlap to a greater extent, increasing the intensity between them and resulting in smaller crystallinity values. The data showed that a smaller FWHM value indicates a higher CI. FWHM effect on CI was more significant for cellulose I than cellulose II [17].

Summary

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

Extracting cellulose by applying bleaching under acidic conditions and delignification provides OPEFB'cellulose purity by reducing some components were hemicellulose, lignin, and other impurities. Depolymerization occurs in the color element (chromophores), where the color of the fiber fades from brown to grayish white with the intensity of brightness depending on the bleacher concentration and the bleaching time. It will be positively correlated with the recovery of cellulose in it. From the results of the XRD test, the effect of bleacher concentration in acidic conditions and the duration of bleaching did not show a completely linear relationship, the bleaching period of 3 h gave a lower degree of cellulose crystallinity effect than the 1 and 2 h bleaching time.

Acknowledgments

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

The authors would like to thank Gadjah Mada University for its financial support for this research. This research was conducted using the Research Grant Fund in 2022 based on the Letter of Assignment No. 3550/UN1.P.III/Dit-Lit/PT.01.05/2022.

References

The original version of this paper is available on https://www.scientific.net/EC.4.41.pdf

S.H. Chang, An overview of empty fruit bunch from oil palm as feedstock for bio-oil production, Biomass and Bioenergy 62 (2014) 174-181.

A.D. French, Glucose, not cellobiose, is the repeating unit of cellulose and why that is important, Cellulose 24 (2017), 4605-4609, 2017.

B. Fei, R.A. Wach, H. Mitomo, F. Yoshii, T. Kume, Hydrogel of biodegradable cellulose derivatives. I. Radiation-induced crosslinking of CMC, J. Appl. Polym. Sci. 78 (2000) 278283.

F.N. Mohammad Padzil, S. H. Lee, Z. M. A. ari Ainun, C. H. Lee, L. C. Abdullah, Potential of oil palm empty fruit bunch resources in nanocellulose hydrogel production for versatile applications: A review, Materials 13 (2020).

R. Datta, Acidogenic fermentation of lignocellulose-acid yield and conversion of components, Biotechnol. Bioeng. 23 (1981) 2167-2170.

L. Segal, J.J. Creely, A.E. Martin, C. M. Conrad, An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer, Text. Res. J. 29 (1959) 786-794.

H. Kristanoko, F. Kusnandar, D. Herawati, Analisis warna berbasis smartphone android dan aplikasinya dalam pendugaan umur simpan konsentrat apel, agriTECH 41 (2021) 211.

T. H. Kim, Pretreatment of Lignocellulosic Biomass, Bioprocess. Technol. Biorefinery Sustain. Prod. Fuels, Chem. Polym. (2013) 91-110.

O. Sevastyanova, J. Li, G. Geilerstedt, On the reaction mechanism of the thermal yellowing of bleached chemical pulps, Nord. Pulp Pap. Res. J 21 (2006), 188-192.

A. Castellan S. Grelier, Color reversion of cellulosic and lignocellulosic fibers, Lignocellul. Fibers Wood Handb. Renew. Mater. Today's Environ. (2016) 531-551.

G. Gellerstedt, M. Pettersson, E. L. Lindfors, D. Robert, Reactions of lignin in chlorine dioxide bleaching of kraft pulps, Res. Chem. Intermed. 21 (1995) 441-456.

W. Farhat, R. A. Venditti, M. Hubbe, M. Taha, F. Becquart, and A. Ayoub, A review of waterresistant hemicellulose-based materials: processing and applications, ChemSusChem. 10 (2017), 305-323.

C. Chio, M. Sain, and W. Qin, Lignin utilization: A review of lignin depolymerization from various aspects, Renew. Sustain. Energy Rev. 107 (2019), 232-249.

S. K. Evans, O. N. Wesley, O. Nathan, and M. J. Moloto, Chemically purified cellulose and its nanocrystals from sugarcane baggase: isolation and characterization, Heliyon 10 (2019), p. e02635.

C. J. Knill and J. F. Kennedy, Degradation of cellulose under alkaline conditions, Carbohydr. Polym. 51 (2002) 281-300.

S. Karagöz, T. Bhaskar, A. Muto, and Y. Sakata, Hydrothermal upgrading of biomass: Effect of K 2 CO 3 concentration and biomass/water ratio on products distribution, Bioresour. Technol. 97 (2006) 90-98.

S. Nam, A. D. French, B. D. Condon, and M. Concha, Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose I and cellulose II, Carbohydr. Polym. 135 (2016) 1-9.

P. Langan, Y. Nishiyama, and H. Chanzy, X-ray structure of mercerized cellulose II at 1 Å resolution, Biomacromolecules 2 (2001) 410-416.

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 51-57

doi: 10.4028/p-oHM1mQ

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-07-12

Revised:
2022-09-19

Accepted:
2023-04-13

Online:
2023-08-11

Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

Quoc Toan , Thi Thu Thuy Dinh , Thi Tuyen Tran , Thi Bich Hoang , Quoc Long Pham , Quyet Chien Nguyen , Ngoc Quy Nguyen and Thanh Viet Nguyen

Institute of Natural Products Chemistry, Vietnam Academy of Science and Technology (VAST), Hanoi City, Vietnam

Graduate University of Science and Technology, Vietnam Academy of Science and Technology (VAST), Hanoi City, Vietnam

Faculty of Pharmacy, Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam

Faculty of Environmental and Food Engineering, Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam

Institute of Applied Technology and Sustainable Development, Nguyen Tat Thanh University, Ho Chi Minh City 700000, Vietnam

bichhoang.inpc@gmail.com; mar.biochem@fpt.vn; chientc48@yahoo.com; nnquy@ntt.edu.vn; n*ntviet@ntt.edu.vn

Keywords: agarwood, Aquilaria crassna, essential oil, GC-MS.

Abstract

The importance of natural products derived from agarwood species is increasingly emphasized in producing perfumery or cosmetic products made from agarwood species. On the other hand, due to the predominant amount of aromatic compounds in essential oils, frankincense essential oil is increasingly popular with high economic value. Therefore, in this study, we focused on the extraction process of essential oils and evaluated the chemical composition of the essential oils by the GC-MS method. Differences in the composition of essential oils between natural and artificial agarwood may be due to species, habitat conditions, climate, geographical conditions, and extraction methods in different regions. Specifically, volatile components in essential oils were identified as neopetasone ( ); dihydroagarofuran-15-al ( ); jinkho-eremol ( ); valerianol -agarofuran ( ); dihydrokaranone ( ), valenca-1(10), 8-dien-11-ol ( ) and selina-4,11-dien-14-ol ( ), contribute to determining the main aroma in agarwood essential oil.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

Currently, with consumers tending to use natural compounds, the world's demand for essential oils is increasing, especially those used in the aromatherapy and cosmetic industry [1-9]. Vietnam is in the tropical monsoon region, with high temperatures, rainfall, and relative humidity. Therefore, creating a rich and diverse flora, especially plants for essential oils; in which agarwood essential oil is often known as fragrant oil, the high-grade fragrance is an important product popular. Agarwood belongs to the family Thymelaeaceae; there are 19 species of Aquilaria found in the Asian region [10]. As a species of tree endemic to the hot and humid equatorial climate, it is commonly found in Southeast Asia and New Guinea islands in Oceania. In Vietnam, agarwood is distributed in provinces such as Ha Giang and Phu Quoc. A number of studies have confirmed that agarwood is a wood containing many aromatic resins produced from the trunk of the Aquilaria crassna tree. When the tree is injured, the oil in the tree gathers to resist the infection from the outside, the oil that remains gradually denatures and becomes agar, depending on the time of formation and the degree of infection that will give out large and small bass blocks and different shapes [11]. However, only about of trees in natural forests contain agarwood [10]. Besides, if there is human intervention in creating the wound of the tree, it is artificial agarwood. On the other hand, chemical studies on agarwood wood have
shown that aromatic compounds characterize the main chemical constituents of essential oils, such as sesquiterpenes, sesquiterpene paranoids, chromone derivatives, pentadecanoic acid, and tetradecanoic acid [12-15].

Some extraction methods for essential agarwood oil may include hydrogen distillation, steam distillation, carbon dioxide extraction, solvent extraction, florasol/phytol extraction, etc. [12,16,17]. Each extraction method has its advantages and disadvantages. However, hydrodistillation is a popular process used in essential oil extraction because of its environmental friendliness, low operating costs, and the ability almost completely to extract the essential oil contained in the material. The objective of this study was to extract Agarwood essential oil by hydrodistillation method and chemical compound analysis based on Gas Chromatography - Mass Spectrometry (GC-MS). The recovery efficiency of essential oils was calculated and compared with previously published parameters.

Experimental Methods

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

Plant material. Raw materials used in this study were collected from agarwood trees on Phu Quoc Island, Kien Giang province, Vietnam. Professor Le Cong Kiet (University of Natural Sciences, Vietnam National University, Ho Chi Minh City) botanically identified Aquilaria crassna Pierre ex. Lecomte belongs to the family Thymelaeaceae. Agarwood is transported to the laboratory, where the specimens are kept. Agarwood was taken from a 15 -year-old tree that has been symbiotic with a specific fungus (a product licensed by Lam Vien Co., Ltd.). After transplanting mushrooms, the tree will be harvested after 3 years; agarwood is obtained after the manual process of removing the unaffected woody parts. To preserve and avoid damage, agarwood samples were air-dried, ground into powder, and stored in paper bags at room temperature.
The essential oil extraction process. The process of extracting essential agarwood oil is done through two stages: First, a mixture of 500 g of agarwood samples and water is stored in a glass jar and kept for 3 weeks. In the next stage, the above mixture was distilled in a Clevenger-type apparatus for 72 hours until the first drop of oil appeared, heated to . After the distillation is finished, a mixture of essential oils and water is obtained; the water is removed and anhydrous with , and the essential oils will be stored in dark bottles for analysis.
The GC-MS analysis of essential oils. Agarwood essential oil was analyzed GC-MS on an Agilent Technologies HP7890A GC instrument, combined with an Agilent Technologies HP5975C mass spectrometry detector and a DB-XLB column ( 60 mm 0.25 mm , film thickness , Agilent Technologies). The elution times of components are expressed by the retention time index (RI) and are related to the retention times of a series of n -alkanes with the same GC program. Based on peak area GC (MSD response) calculates relative amounts of individual components without correction.

Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

The essential oil obtained from agarwood powder after soaking in beams combined with the hydrodistillation method gave a yield. Agarwood essential oil is a dark yellow liquid with a characteristic woody odor. The hydrodistillation process depends on the diffusion of oil droplets from the wood mass and their loss in the condensate. Therefore, the soaking process increases the efficiency of recovering the essential oil content. When soaking, due to the difference in water content inside and outside the wood cells, water penetrates the wood cell membrane and swells the wood pulp, but it depends on the size and shape of the wood pulp. When the cell membrane expands wide enough, it is easier for essential oils to penetrate the cell membrane and go to the outside environment. However, if the soaking time is too long, it will decompose some compounds in the essential oil, and the essential oil is lost during the soaking process, and the essential oil's performance will be degraded. Some published documents show that recovery efficiency depends on the extraction process or the input material. Huaiqiong Chen et al. (2011) conducted hydrodistillation extraction with three different raw materials and obtained the following results: agarwood is stimulated by chemical method (S1-0.042%), wild agarwood (S2-0.32%), and healthy plants (S3-0.0128%) as a control [18]. Patcharee Pripdeevech et al. (2011) showed that the extraction efficiency of essential oil
was up to when using the solid-phase microextraction method (SPME) for Aquilaria crassna sample (Rayong - Thailand) [19].

Table 1. The chemical composition of Vietnamese agarwood essential oil

Chemical name | Molecular Weight | Molecular Formular | CAS Number | This study Vietnam
Benzylacetone | 148.20 | C₁₀H₁₂O | 2550-26-7 | 1.53
2,6-Di-tert-butyl-4-methylphenol | 220.30 | C₁₅H₂₄O | 128-37-0 | 0.35
4,5-di-epi-Aristolochene | 204.35 | C₁₅H₂₄ | 26620-71-3 | 0.31
β-Agarofuran | 206.32 | C₁₄H₂₂O | 6040-08-0 | 8.02
β-Dihydroagarofuran | 222.37 | C₁₅H₂₆O | 5956-09-2 | 0.40
Anisylacetone | 178.23 | C₁₁H₁₄O₂ | 104-20-1 | 0.21
Agarofuran <a-> | 220.36 | C₁₅H₂₄O | 5956-12-7 | 0.49
nor-Ketoagarofuran | 222.33 | C₁₄H₂₂O₂ | 5986-25-4 | 0.36
Epoxybulnesene | 204.35 | C₁₅H₂₄ | 36911-11-0 | 1.27
Eudesmol <10-epi-g-> | 222.37 | C₁₅H₂₆O | 15051-81-7 | 2.44
Agarospirol | 222.37 | C₁₅H₂₆O | 23811-08-7 | 5.64
Hinesol | 222.37 | C₁₅H₂₆O | 23811-08-7 | 0.54
Jinkho-eremol | 220.35 | C₁₅H₂₆O | 86747-08-2 | 5.02
Valerianol | 222.37 | C₁₅H₂₆O | 20489-45-6 | 4.94
Eudesmol <a-> | 222.37 | C₁₅H₂₆O | 473-16-5 | 2.17
Valenca-1(10),8-dien-11-ol | 220.35 | C₁₅H₂₄O | 168099-20-5 | 5.95
Dehydrojinkho-eremol | 220.35 | C₁₅H₂₄O | 150034-02-9 | 1.65
4,15-Epoxy-dihydroagarofuran | 222.37 | C₁₅H₂₆O | 15052-76-3 | 1.72
Cadina-1(10),4-dien-8a-ol | 220.35 | C₁₅H₂₄O | 147853-18-7 | 0.95
Dihydroagarofuran-15-al | 222.37 | C₁₅H₂₆O | 20053-66-1 | 9.20
Selina-3,11-dien-9-ol | 220.35 | C₁₅H₂₄O | 133593-96-1 | 1.97
Neopetasone | 218.33 | C₁₅H₂₂O | 13902-42-6 | 14.43
Selina-4,11-dien-14-al | 218.34 | C₁₅H₂₂O | 150034-05-2 | 2.73
Dihydrokaranone | 218.34 | C₁₅H₂₂O | 19598-45-9 | 3.25
Nootkatone | 218.34 | C₁₅H₂₂O | 91416-23-8 | 0.61
oxo-agarospirol | 236.35 | C₁₅H₂₄O₂ | 93133-69-8 | 2.59
Total |  |  |  | 78.74

Fig. 1. Chromatogram of volatile compounds present in Vietnamese agarwood essential oil (absis?)

Fig. 1. Chromatogram of volatile compounds present in Vietnamese agarwood essential oil (absis?)

The volatile components of Frankincense essential oil were subjected to GC-MS analysis; specifically, the qualitative and quantitative results of the components are shown in Table 1. At the same time, the elution times of the compounds are characterized by the retention time (RI) value as the chromatographic configuration shown in (Figure 1). Most essential oils are made up of complex compounds such as sesquiterpene hydrocarbons, monoterpene hydrocarbons, and oxygenated sesquiterpenes. Through the recorded results, 27 different retention time values corresponding to 28 components were identified in the essential oil. Some components dominate in essential oils such as -agarofuran (8.02%); agarospirol (5.64%); valeriano (4.94%); valenca-1(10),8-dien-11-ol (5.95%); dihydroagarofuran-15-al (9.20%); neopetasone (14.43%) and dihydrokaranone (3.25%), eluted in order of increasing retention time. Next is the component Benzylacetone ( ); Epoxybulnesene ( ); eudesmol <10-epi-g-> ( ); eudesmol <a-> ( ); dehydroJinkho-eremol ( ); 4,15-epoxy-dihydroagarofuran (1.72%); selina-3,11-dien-9-ol (1.97%); selina-4,11-dien-14-al ( ) and oxo-agarospirol ( ), and some components were detected at low concentrations (<1%). Similarly, Nor Atikah Mat Yusoff et al. (2015) study surveyed the optimal conditions for extracting agarwood essential oil. The highest essential oil yield ( ) was obtained when a combination of hydrodistillation and agitator was involved in the extraction process.

At the same time, the research team analyzed the chemical compounds in essential agarwood oil and identified some key compounds agarospirol, 4-phenyl 2-butanone, -elemol, -muurolene and selina-3,11-dien-9-ol [20]. In another publication, Saiful Nizam Tajuddin et al. (2010) compared the chemical composition of agarwood essential oil extracted directly by hydrodistillation method and commercial essential oils. The differences were evident in the content of the major compounds present in specific essential oils, such as the laboratory essential oil -guaiene ( ), jinkho-eremol (6.5%), and 4-phenyl-2-butanone (32.1%). ) and commercial essential oils are eudesmol (3.2%), caryophellene oxide ( ) and -guaiene ( ) [21]. Depending on geographical location, climate, and origin of raw materials or variations, ecological types exist within agarwood tree species; essential agarwood oil will have different qualities in terms of quality compounds as well as recovery efficiency. Typical in the study of Patcharee Pripdeevech et al. (2011) used the same species of Aquilaria crassna from Thailand for the experiment, but the main compounds in the essential oil were -agarofuran, isoamyl dodecanoate, dehydroJinkho-eremol, kusunol and 9,11-eremophiladien-8-one. The research team also showed that the main aroma activity of essential oils is characterized by compounds of terpenes, of which -agarofuran based on high aroma concentration and specificity, should be considered the most important aroma contribution [19]. In addition, in 2019, the Dinh Thi

Thu Thuy et al. research group conducted a survey and evaluated essential agarwood oil from three different raw materials Khanh Hoa, Bac Giang, and Phu Quoc Island (Kien Giang province). Recovery efficiency was , respectively, and based on the hydrodistillation method. Also, the volatile compounds were determined dihydrokaranone ( ), agarospirol (2.98-3.42%), -agarofuran ( ), and neopetasone ( ) were mainly responsible for the quality of all essential oil samples. It can be seen that in the same extraction process or analysis method, different input materials also lead to different yields and qualities of essential oils [22].

Fig. 2. Structure of important sesquiterpene compounds in essential agarwood oil in Phu Quoc island of Vietnam

Fig. 2. Structure of important sesquiterpene compounds in essential agarwood oil in Phu Quoc island of Vietnam

Antibacterial and anti-inflammatory activities have been found in the literature as two prominent properties of essential agarwood oil. On the other hand, Penpun Wetwayaklung et al. (2009) detected the characteristic compounds in agarwood essential oil such as selina-4,11-dien-14-al, -selinene, and selina-4,11-dien-14-al and tested the activities. Inhibitory antibacterial activity against some strains of Staphylococcus aureus, Escherichia coli, and Candida albicans [11]. Specifically, Chen et al. found that essential oils extracted from artificial and natural agarwood have significant inhibitory effects on Bacillus subtilis and Staphylococcus aureus [23]. Similarly, in vitro testing of essential agarwood oil against Staphylococcus epidermidis also revealed a strong disrupting effect of the oil on cell walls, contributing to cell biofilm inhibition [24]. Regarding the anti-inflammatory effects, it was found that Jinkho-eremol and agarospirol were the main compounds responsible for the potent inhibitory activity of agarwood essential oil. Saad Sabbar Dahham et al. (2015) discovered that essential agarwood oil strongly inhibits the metastasis and proliferation of pancreatic cancer cells (MIA PaCa-2) through an in vitro model. Inhibitory effect of cells at ( ) and MIA PaCa-2 cytotoxic activity with on agarwood essential oil [25]. In addition, the inhibitory properties of cancer cells from the essential oil extract from the frankincense tree were further reported by Saad Sabbar Dahham et al. (2016) conducted an in vivo model of rat subcutaneous tumors, demonstrating that essential oils are safe with an LD 50 above [26]. The research team has opened up a potential avenue for preclinical use in animals against pancreatic and colorectal cancer based on the chemotherapeutic effects of the essential oil extract [25,26].

Summary

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

The recovery efficiency of agarwood essential oil was through the experimental results of extraction by the soaking process combined with the hydrodistillation method. The GC-MS method was used to identify and quantify the chemical components present in essential oils, with some of the
main components including agarospirol, -agarofuran, jinkho-eremol, valeriano, etc. Research on the extraction and identification of highly active compounds will contribute to opening up many reliable and valuable applications of frankincense oil. Therefore, the plants that give precious essential oils, which are highly applicable in many fields of production and life, have been studied, exploited, and processed by scientists to improve their use-value.

Acknowledgment

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

This study was financed by project number VAST04.02/16-17 granted by the Vietnam Academy of Science and Technology.

References

The original version of this paper is available on https://www.scientific.net/EC.4.51.pdf

N.T.T. Quyen, N.T.N. Quyen, H.T.K. Linh, T.T. Le Ngoc, H.L.T. Anh, N.H.K. Nguyen, T.H. Tran, H.N.T. Tam, M.H. Cang, Essential oil from lemon (Citrus aurantifolia) grown in Ben Tre Province, Vietnam: Condition extraction, chemical composition and antibacterial properties, Asian J. Chem. 32 (2020) 965-969.

T.T.K. Ngan, T.T. Hien, P.H. Danh, L.T.H. Nhan, L.X. Tien, Formulation of the lemongrass (Cymbopogon citratus) essential oil-based eco-friendly diffuse solution, IOP Conference Series: Materials Science and Engineering. 959 (2020) 012024.

T.T. Kim Ngan, N.C. Huong, X.T. Le, P.Q. Long, T.Q. Toan, D.M. Hoang Vo, V.T. Danh, L.N. Yen Trung, T.A. Trieu, Physico-chemical characteristics of Rosmarinus officinalis L. essential oils grown in Lam Dong province, Vietnam, Asian Journal of Chemistry. 31 (2019) 2759-2762.

T.K.N. Tran, T.H. Tran, T.H.N. Le, T.L. Xuan, N.Q.A. Phan, T.I. Cam, G.B. Long, Development of an aromatic wax product containing natural lemongrass (Cymbopogon citratus) essential oil, IOP Conference Series: Materials Science and Engineering. 736 (2020) 022066.

T.H. Tran, L.K. Ha, D.C. Nguyen, T.P. Dao, L.T.H. Nhan, D.H. Nguyen, T.D. Nguyen, D.V.N. Vo, Q.T. Tran, L.G. Bach, The study on extraction process and analysis of components in essential oils of black pepper (Piper nigrum L.) seeds harvested in Gia Lai Province, Vietnam, Processes. 7 (2019) 56.

T.H. Tran, P.T.N. Nguyen, V.T.T. Ho, T.H.N. Le, L.G. Bach, T.D. Nguyen, Using soft computing approaches for orange (Citrus nobilis Lour. var. nobilis) oils extraction process, IOP Conference Series: Materials Science and Engineering. 479 (2019) 012015.

T.K.N. Tran, T.H. Tran, X.T. Le, T.Q. Toan, T.T. Le Ngoc, H.L.T. Anh, M.H. Cang, Effect of storage conditions on the chemical composition of Vietnamese clove (Syzygium aromaticum) essential oil, Journal of Global Pharma Technology. 12 (2020) 447-454.

B.L. GİANG, L. BACH, Evaporation compounds of Dysphania ambrosioides (L.) essential oil from Lao Cai, Vietnamese isolated by hydrodistillation, Natural Volatiles and Essential Oils. 7 (2020) 34-40.

B.L. GİANG, Extraction process optimization and compositional determination of the essential oil from pomelo (Citrus grandis L.) grown in Tien Giang Province, Vietnam, Natural Volatiles and Essential Oils. 7 (2020) 26-33.

R. Naef, The volatile and semi-volatile constituents of agarwood, the infected heartwood of Aquilaria species: A review, Flavour and Fragrance Journal. 26 (2011) 73-87.

P. Wetwitayaklung, N. Thavanapong, J. Charoenteeraboon, Chemical constituents and antimicrobial activity of essential oil and extracts of heartwood of aquilaria crassna obtained from water distillation and supercritical fluid carbon dioxide extraction, Silpakorn U Science & Technology Journal. 3 (2009) 25-33.

M. Ishihara, T. Tsuneya, K. Uneyama, Components of the volatile concentrate of agarwood, Journal of Essential Oil Research. 5 (1993) 283-289.

M. Ishihara, T. Tsuneya, M. Shiga, K. Uneyama, Three sesquiterpenes from agarwood, Phytochemistry. 30 (1991) 563-566.

T. Nakanishi, E. Yamagata, K. Yoneda, T. Nagashima, I. Kawasaki, T. Yoshida, H. Mori, I. Miura, Three fragrant sesquiterpenes of agarwood, Phytochemistry. 23 (1984) 2066-2067.

P. Tamuli, P. Boruah, S.C. Nath, P. Leclercq, Essential oil of eaglewood tree: A product of pathogenesis, Journal of Essential Oil Research. 17 (2005) 601-604.

N.I. Bhuiyan, J. Begum, N.H. Bhuiyan, Analysis of essential oil of eaglewood tree (Aquilaria agallocha Roxb.) by gas chromatography mass spectrometry, Bangladesh Journal of Pharmacology. 4 (2009) 24-28.

N. Ismail, M.A.N. Azah, M. Jamil, M.H.F. Rahiman, S.N. Tajuddin, M.N. Taib, Analysis of high quality agarwood oil chemical compounds by means of SPME/GC-MS and Z-score technique, Malaysian Journal of Analytical Sciences. 17 (2013) 403-413.

M.R. Wang, W. Li, S. Luo, X. Zhao, C.H. Ma, S.X. Liu, GC-MS study of the chemical components of different Aquilaria sinensis (lour.) gilgorgans and agarwood from different asian countries, Molecules. 23 (2018) 1-14.

P. Pripdeevech, W. Khummueng, S.K. Park, Identification of odor-active components of agarwood essential oils from Thailand by solid phase microextraction-GC/MS and GC-O, Journal of Essential Oil Research. 23 (2011) 46-53.

N. Atikah, M. Yusoff, S.N. Tajuddin, A. Hisyam, N. Adila, M. Omar, Agarwood essential oil: study on optimum parameter and chemical compounds of hydrodistillation extraction, Journal of Applied Science and Agriculture J. Appl. Sci. & Agric. 10 (2015) 1-5.

S.N. Tajuddin, M.M. Yusoff, Chemical composition of volatile oils of Aquilaria malaccensis (Thymelaeaceae) from Malaysia, Natural Product Communications. 5 (2010) 1965-1968.

D.T.T. Thuy, T.T. Tuyen, T.T.T. Thuy, P.T.H. Minh, Q.T. Tran, P.Q. Long, D.C. Nguyen, L.G. Bach, N.Q. Chien, Isolation process and compound identification of agarwood essential oils from Aquilaria crassna cultivated at three different locations in Vietnam, Processes. 7 (2019) 432.

H. Chen, Y. Yang, J. Xue, J. Wei, Z. Zhang, H. Chen, Comparison of compositions and antimicrobial activities of essential oils from chemically stimulated agarwood, wild agarwood and healthy Aquilaria sinensis (Lour.) Gilg trees, Molecules. 16 (2011) 4884-4896.

S. Kamonwannasit, N. Nantapong, P. Kumkrai, P. Luecha, S. Kupittayanant, N. Chudapongse, Antibacterial activity of Aquilaria crassna leaf extract against Staphylococcus epidermidis by disruption of cell wall, Annals of Clinical Microbiology and Antimicrobials. 12 (2013) 1-7.

S.S. Dahham, Y.M. Tabana, L.E. Ahmed Hassan, M.B. Khadeer Ahamed, A.S. Abdul Majid, A.M.S. Abdul Majid, In vitro antimetastatic activity of Agarwood (Aquilaria crassna) essential oils against pancreatic cancer cells , Alexandria Journal of Medicine. 52 (2016) 141-150.

S.S. Dahham, L.E.A. Hassan, M.B.K. Ahamed, A.S.A. Majid, A.M.S.A. Majid, N.N. Zulkepli, In vivo toxicity and antitumor activity of essential oils extract from agarwood (Aquilaria crassna), BMC Complementary and Alternative Medicine. 16 (2016) 1-11.

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-4/978-3-0364-1370-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 4, pp 59-63

doi: 10.4028/p-g9Eic6

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2022-07-30

Revised:
2023-02-07

Accepted:
2023-04-12

Online:
2023-08-11

Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

Ignatius Sudaryadi , Fiola Oktaweni , Intan Endri Pramono , Khaliza Wima Fatikasary , Hana Widiawati , Sutikno Sutikno

Laboratoy of Entomology, Faculty of Biology, Universitas Gadjah Mada, JI. Teknika Selatan, Sekip Utara Yogyakarta 55281, Indonesia

Departement of Tropical Biology, Faculty of Biology, Universitas Gadjah Mada, JI. Teknika Selatan, Sekip Utara Yogyakarta 55281, Indonesia

Laboratory of Plant Structure and Development, Faculty of Biology, Universitas Gadjah Mada, JI. Teknika Selatan, Sekip Utara Yogyakarta 55281, Indonesia

dsudaryadi@ugm.ac.id, fiolaoktaweni@mail.ugm.ac.id, cintanendri99@mail.ugm.ac.id, khaliza.wima@mail.ugm.ac.id, hanawidiawati@mail.ugm.ac.id, sutikno_bio@ugm.ac.id

Keywords: T. laeviceps, propolis, bioactive compounds, Mount Merapi Slope, Yogyakarta

Abstract

The emergence of many new diseases due to viruses and bacteria demands for an increase in the discovery of natural alternative medicines. One example of sources of natural medicine is the honey and the propolis of Tetragonula laeviceps bee. The efficacy, physical and chemical properties of honey are known to be influenced by the type of pollen and the environment whilst the composition of propolis is influenced by the geological factors. Therefore, the purpose of this research was to study the composition of propolis' bioactive compounds of T.laeviceps bee from Mount Merapi Slope, Sleman, Yogyakarta. The bioactive compound composition of the propolis sample were analysed by Gas Chromatograph-Mass Spectrometry (GC-MS). The analysis showed that the propolis has various type of compounds containing up to 20 bioactive compounds which can be classified in three different groups namely alkaloids ( ), phenolics ( ), and terpenoids ( ). Most of these compounds were found to be biologically important. However, further research is still required to confirm the potential antimicrobial properties of the propolis' bioactive compounds.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

Many new diseases caused by viruses and bacteria generally attack the human immune system. A solution to prevent this is to take an alternative medicine to strengthen the body immunity. Indonesia has many potential of natural resources for medicinal products, such as the beekeeping products. Tetragonula laeviceps is classified as a stingless bee that is suitable for tropical areas. T. laeviceps produces many products such as honey, bee pollen, propolis, royal jelly, and beeswax [1].

Propolis is a complex resin compound produced by bees using the plant exudates. Propolis has a function to strengthen the structural stability of the hive. The composition of the chemical compounds in propolis can be efficacious as antibacterial, antiviral, and antitumor. The different characteristics of propolis are due to the differences in the composition of chemical compounds. The geological factors such as the place and the type of the plant-producing resin are the main factors that cause these differences in the composition of chemical compounds in propolis [2].

The area of Mount Merapi Slope, Sleman, Yogyakarta has a distinctive topography, and its vegetation is dominated by Salacca plantations. Therefore, this research was aimed to explore the composition of bioactive compounds found in T. laeviceps bee propolis as a source of antimicrobial medicine from Mount Merapi Slope in Sleman, Yogyakarta.

Experimental Methods

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

Sample collection of raw propolis. The raw propolis of . laeviceps sample was collected from their beehives in the Meliponiculture practice conducted in Mount Merapi Slope, Sleman, Yogyakarta.
Analysis of the bioactive compounds of propolis. This research was conducted at the Integrated Research and Testing Laboratory (LPPT) UGM. The extraction steps were generally done using the maceration method followed by an analysis using the Gas Chromatograph-Mass Spectrometry (GCMS) method [3]. First, the sample was heated in distilled water to remove the remaining honey. Next, the sample was cut into small pieces and left to air-dry. The dried sample was further grounded into smaller pieces and weighed to about 0.5 g . Then, it was mixed with MeOH solution with a ratio of 1:1 followed by a centrifugation at 900 rpm at room temperature for 5 min . About of the solution was then injected into Gas Chromatography (Shimadzu GCMS-QP2010S) set with an initial temperature of with a final temperature of . The type of column used was the Agilent HP-5MS UI and the type of detector used was the FID set at temperature using helium gas as the carrier gas.
Data Analysis, the resulting spectra were then compared with databases in WILEY229.LIB and NIST62 Mass spectra to identify the possible compounds contained in the sample.

Results and Discussion

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

Stinggless Bee Species. T. laeviceps is one of many stingless bee species that is widely cultivated in most tropical regions including Mount Merapi Slope, Sleman, Yogyakarta. Through their foraging activities, T. laeviceps produces honey, bee pollen, and propolis which are high in nutritional values and beneficial for human health. One apparent morphological characterization of their worker bee is its generally glossy black body colour (Fig. 1).

Fig. 1. The Worker Stingless bee (T. laeviceps)

Fig. 1. The Worker Stingless bee (T. laeviceps)

The body of the worker bee of T. laeviceps is predominantly shiny black. The abdomen is blackish brown. Head (caput) is black, and is sparsely covered with white fine hairs. Compound eyes are reddish, ocelli are blackish and large. Clypeus is blackhead and fully covered with fine white hairs. Antennal has 11 flagellomeres, scape is yellowish-brown, socket is grey, pedicel brown, first flagellomere is brown, second to tenth flagellomeres are brown and slightly black. Mandible has two teeth, brown and slightly black at basal. Mesoscutum is black and is fully covered with yellowish setae, scutellum is black entirely, and is covered with yellowish setae at posterior. Tegula is brown and forewings coloration uniform. Hindwings are semi-transparent and wing venation is dark brown. Hind tibiae is short, corbicula is pear shape sparsely is covered with long setae at apical but short at basal, entirely black and basitarsi is wholly black. First to sixth gastral tergites are fully brown and dark brown at dorsal part [4].
Bioactive compounds of propolis. In this study, the chromatogram of the sample in the form of GCMS spectra were analyzed and compared with the databases in WILEY229.LIB and NIST62 to identify the possible compounds contained in the sample.

Fig. 2. Chromatogram Stingless bee's propolis from Mount Merapi Slope, Sleman

Fig. 2. Chromatogram Stingless bee's propolis from Mount Merapi Slope, Sleman

Fig. 2 showed that there are 60 peaks detected in the chromatogram profile of the propolis sample. The compounds that represent each peak were listed in Table 1.

Table 1. Bioactive compounds in Stingless bee's propolis from Mount Merapi Slope, Sleman

Number.
Compound
Chemical
Formula
Area
(%)
Description

Group:
Alkaloids (70%)

1
(R)-Oxiran-2-ylmethanol
C₃H₆O₂
0.19
Volatile compounds

2
Isobutane
C₄H₁₀
1.92
Cosmetic raw materials

3
(2R,3R)-2,3-dimethyloxirane
C₄H₈O
2.89
Anti inflammatory,
anticancer

4
Ethanimidic acid, ethyl ester
C₄H₉NO
5.92
Antioxidant, anticancer

5
α-Fluoro-β-alanine
(3-amino-2-fluoropropanoic acid)
C₃H₆FNO₂
33.55
Antifungi

6
Glycidol
C₃H₆O₂
1.20
In vivo induction,
genotoxicity, and
carcinogenicity

7
Carbamic acid, methylnitroso-,ethyl ester
C₄H₈N₂O₃
6.89
Aromatic compound

8
Methyl 3,6 anhydrohexopyranoside
C₇H₁₂O₅
0.25
Antioxidant

9
1,2,3-Butanetriol
C₄H₁₀O₃
6.27
Food substitute for oils
and fats

10
[(2S)-oxiran-2-yl]methanol
C₃H₆O₂
24.07
Volatile compounds

11
Tetrahydrofuran-3,4-diol
C₄H₈O₃
0.97
Antioxidant

12
Tetrahydrofuran-3,4-diol
C₄H₈O₃
3.28
Antioxidant

13
Ethanethioic S-acid
C₂H₄OS
8.79
Fine chemical raw
materials

14
2,3-Epoxyhexanol
C₆H₁₂O₂
0.44
Antibacterial,
Antioxidant

15
2,3-Epoxyhexanol
C₆H₁₂O₂
0.51
Antibacterial,
Antioxidant

Group:
Phenolics (20%)

16
Hydroperoxide, heptyl
C₇H₁₆O₂
0.22
Antioxidant

17
Hydroperoxide, heptyl
C₇H₁₆O₂
0.68
Antioxidant

18
Hydroperoxide, heptyl
C₇H₁₆O₂
0.68
Antioxidant

19
Cyclopenta[c]furo[3',2':4,5]furo[2,3-h][1]benzopyran-11(1H)-one
C₁₇H₁₄O₇
0.65
Antioxidant

Group:
Terpenoids (5%)

20
3-Trifluoroacetoxydodecane
C₁₄H₂₅F₃O₂
0.64
Antiviral

Based on the data in Table 1, there are 20 different bioactive compounds identified from the propolis sample. The profile of the propolis' bioactive compounds shows the highly active foraging activity of T. laeviceps which produces propolis dominated by a group of bioactive alkaloids compounds (70%) with alpha-Fluoro- -alanine (3-amino-2-fluoropropanoic acid) ( ) as the largest percentage within the group. This specific compound includes the organooxygen compounds and the organo-nitrogen compounds derived from -amino acids and belongs to an alkaloid group that functions as a substrate for bile acid conjugate enzymes in cancer patients and has antifungal activity. The largest percentage is the [(2S)-oxiran-2-yl] methanol ( ) . This compound belongs to an alkaloid group that functions as an ingredient in making cosmetics. The next specific important compound is ethanethioic -acid ( ) ( ). This compound is a combination of anhydride and with clear yellow coloured liquid, a strong odour, and toxicity effect if swallowed, inhaled, and absorbed by the skin. This compound includes organosulfur compounds which are generally used as chemical raw materials for synthetic drugs [5]. The reactivity of ethanethioic -acid is generally in selective amide or peptide bonds synthesized by the reaction between active carboxylic acids, such as hydrochloric acid, or esters with , or NaSH [6].

The GC-MS analysis (Table 1) showed that propolis' chromatogram has various types of compounds consisting of up to 20 bioactive compounds which can be classified in 3 (three) different groups namely alkaloids ( ), phenolics ( ), and terpenoids ( ). The high number of alkaloidproducing plants may indicate a need for chemical protection against herbivores under the harsh conditions of the mountain environment [7]. Meanwhile, the high portion of phenolic compounds could be due to the large constituent of chemicals found in plants that are natural antioxidants and the phenolic compounds are secondary metabolites produced and accumulated by plants during their defence mechanism due to stress [8]. The phenolic compounds with high bioactive properties have the ability to develop into functional foods, nutraceuticals and drugs due to the presence of bioactive compounds can possess anti-microbial, anti-cancer, antioxidant, chemoprotective, anti-cholesterol, and immunomodulatory properties. [9,10].

In general, propolis contains alkaloids, phenolics, terpenoids and their esters, sugars, alcohols, ketones, hydrocarbons, amino acids,vitamins and minerals [11]. Nearly 300 chemical compounds have been identified. These compounds are not necessarily present in all propolis, because their presence depends mainly on the botanical and geographical origin, the species of bee and the harvest season, as well as of various environmental factors [12,13].

Summary

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

The propolis' bioactive compounds of T. laeviceps bees from the meliponiculture practice in Mount Merapi Slope, Sleman, Yogyakarta consists of three groups which are alkaloids ( ), flavonoids (20%), and terpenoids (5%) with alpha-Fluoro-ß-alanine or 3-amino-2-fluoropropanoic acid as the most dominant compound in the alkaloid group. Further research is still required to explore the potential bioactivity in various medicinal treatments as well as its antimicrobial activity.

Acknowledgment

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

High gratitude was delivered to the Directorate of Research, UGM for the financial support under RTA Grant for 2022, the Laboratory of Entomology and the Laboratory of Plant Structure and Development, Faculty of Biology, UGM, for the research facilities.

References

The original version of this paper is available on https://www.scientific.net/EC.4.59.pdf

S.N.A.S. Salleh, W.L.W. Johari, N.A.M. Hanapiah, A comprehensive review on chemical compounds, biological actions and potential health benefits of stingless bee propolis, Sains Malays. 51 (2022) 733-745.

A. Sulaeman, A.M. Fikri, N. Kalsum, M. Mahani, Chapter 25 - Trigona propolis and its potency for health and healing process, in: R.B. Singh, R.R. Watson, T. Takahashi (Eds), The role of functional food security in global health, Academic Press, Cambridge, Massachusetts, United States, 2019, pp. 425-448.

J.A.I. Devi, A.K. Muthu, Gas chromatography mass spectrometry analysis of bioactive constituents in the ethanolic extract of Saccharum spontaneum Linn., Int. J. Pharm. Pharm. Sci. 6 (2014) 1-23.

M. Trianto, H. Purwanto, Morphological characteristics and morphometrics of Stingless Bees (Hymenoptera: Meliponini) in Yogyakarta Indonesia, Biodiversitas 21 (2020) 2619-2628.

C. Ignea, E. Ioannou, P. Georgantea, S. Loupassaki, F.A. Trikka, A.K. Kanelis, A.M. Makris, V. Roussi, S.C. Kamprani, Reconstructing the chemical diversity of labdane-type diterpene biosynthesis in yeast, Metab. Eng. 28 (2015) 91-103.

M.M. Sachitanand, N.G. Hosahudya, Thioacetic acid/NASH-mediated synthesis of -protected amino thioacids and their utility in peptide synthesis, J. Org. Chem. 79 (2014) 2377-2383.

K. Tayjanov, N.Z. Mamadalieva, M. Wink, Diversity of the mountain flora of central asia with emphasis on alkaloid-producing plants, Diversity 9 (2017) 11.

A.T. Getachew, C. Jacobsen, S.L. Holdt, Emerging technologies for the extraction of marine phenolics: opportunities and challenges, Mar. Drugs. 18(8) (2020) 389.

L. Paiva, E. Lima, A.I. Neto, M. Marcone,J. Baptista, Nutritional and functional bioactivity value of selected azorean macroalgae: Ulva Compressa, Ulva Rigida, Gelidium Microdon, and Pterocladiella Capillacea, J. Food Sci. 82 (2017) 1757-1764.

J. Cotas, D. Pacheco, A.M. Gonçalves, P. Silva, L.G. Carvalho, L. Pereira, Seaweeds' nutraceutical and biomedical potential in cancer therapy: a concise review, J. Cancer Metastasis Treat. 7 (2021) 13.

S.I. Anjum, A. Ullah, K.A. Khan, M. Attaullah, H. Khan, H. Ali, M.A. Bashir, M. Tahir, M.J. Ansari, H.A. Ghramh, Composition and functional properties of propolis (bee glue): A review, Saudi J. Biol. Sci. 7 (2018) 1695-1703.

T.G. do Nascimento, R.E. dos Santos Arruda, E.T. da Cruz Almeida, J.M. dos Santos Oliveira, I.D. Basílio-Júnior, I.C.C. de MoraesPorto, A.R. Rodriges Sabino, J. Tonholo, A. Gray, R.E. Edrada Ebel, Comprehensive multivariate correlations between climatic effect, metabolite-profile, antioxidant capacity and antibacterial activity of Brazilian red propolis metabolitesduring seasonal study, Sci. Rep. 9 (2019) 18293.

S. Gardini, D. Bertelli, L. Marchetti, R. Graziosi, D. Pinetti, M. Plessi, G.L. Marcazzan, Chemical composition of Italian propolisof different ecoregional origin, J. Apic. Res. 57 (2018) 639647.

This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

Keywords Index

A

Agarwood Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

Aquilaria Crassna Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

B

Bioactive Compounds Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Biodiesel Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

Bleaching Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

C

Catalytic Cracking Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Cellulose Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

Centrifuge Studying the Factors Affecting De-Emulsification of Crude Oil

Chemical Method Studying the Factors Affecting De-Emulsification of Crude Oil

Crude Oil Studying the Factors Affecting De-Emulsification of Crude Oil

D

De-emulsification Studying the Factors Affecting De-Emulsification of Crude Oil

Delignification Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

E

Emulsion Studying the Factors Affecting De-Emulsification of Crude Oil

Essential Oil Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

G

Gc-ms Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

H

Heterogeneous Catalyst Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

M

Mesoporosity Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Mount Merapi Slope Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

O

Opefb Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

P

Propolis Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

S

Sawdust Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

T

T. Laeviceps Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Transesterification Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

V

Vgo Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

W

Waste Cooking Oil Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

Y

Y Zeolite Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Yogyakarta Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Authors Index

A

Abbas, M. Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Abdulridha, S. Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Affat, A. Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

Ainuri, M. Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

Al-Hattab, T. A Review: Membrane Reactor for Hydrogen Production: Modeling and Simulation

Aluaibi, W. Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Atshan, Z. Studying the Factors Affecting De-Emulsification of Crude Oil

D

Dinh, T. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

F

Falah, M. Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

Fatikasary, K. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

H

Hamad, L. Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

Hoang, T. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

J

Jabbar, M. Transesterification of Waste Cooking Oil Using Natural and Chemical Materials as Catalyst

K

Kassi, A. A Review: Membrane Reactor for Hydrogen Production: Modeling and Simulation

M

Mohammed, M. Studying the Factors Affecting De-Emulsification of Crude Oil

N

Nguyen, Q. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

Nguyen, T. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

O

Oktaweni, F. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

P

Pham, Q. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

Pramono, I. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Q

Quy, N. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

R

Radhi, A. Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

S

Shehab, A. Maximizing High Value Light Products by Catalytic Cracking of VGO Produced by Iraqi Refinery over Formulated FCC Catalyst

Sudaryadi, I. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

Susi, S. Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

Sutikno, S. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta

T

Toan, T. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

Tran, T. Chemical Compositions of Essential Oil of Agarwood (Aquilaria crassna) Harvested in Phu Quoc Island, Vietnam

W

Wagiman, W. Depolymerization of Cellulose Components from Oil Palm Empty Fruit Bunches in Bleaching and Delignification Process

Widiawati, H. Propolis Bioactive Compounds of Stingless Bees (Tetragonula laeviceps) from Mount Merapi Slope, Sleman, Yogyakarta