Engineering Chemistry Volume 2

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Volume 2 of Engineering Chemistry

ISSN print 2813-6527
ISSN web 2813-6535

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Table of Contents

Chapter 1: Synthesis and Optical Properties of Metal-Organic Frameworks

Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

G. Nagalakshmi, I.M. Nandeesh, Basappa C. Yallur, Vinayak Adimule, Sheetal Batakurki

Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Vinuta Kamat, Vinayak Adimule, Basappa C. Yallur, D.H. Manjunath, Sheetal Batakurki

Chapter 2: Waste Recycling

Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

Sinar Perbawani Abrina Anggraini, Mahfud Mahfud, Sri Rachmania Juliastuti, Suprapto Suprapto

Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

Rafli Eghbal Haraki, Arenst Andreas Arie, Ratna Frida Susanti, Haryo Satriya Oktaviano, Agung Nugroho

Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Meta Fitri Rizkiana, Boy Arief Fachri, Syahrul Gunawan, Mohammad Nor, Iswahyono Iswahyono, Bekti Palupi, Istiqomah Rahmawati, Helda Wika Amini

LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Jenny Novianti Muliarahayu Soetedjo, Michael Osborn, Lucas Adriel Setiawan, Farhan Azka Fadillah, Felicia Tjandra, Kevin Frendy Mulya, Evan Rariel Nehemia, Tedi Hudaya

Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Fatma Darkbira, Oussama Kheireddine Nehar, Fatima Zohra Chiboub Fellah, Thierry Roisnel, Abdelghani Chiboub Fellah

Keywords Index

Authors Index

Chapter 1

Synthesis and Optical Properties of Metal-Organic Frameworks

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 3-11

doi: 10.4028/p-fdqs03

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

Submitted:
2022-12-25

Revised:
2023-02-14

Accepted:
2023-02-16

Online:
2023-05-16

Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

The original version of this paper is available on https://www.scientific.net/EC.2.3.pdf

Nagalakshmi G. , Nandeesha I.M. , Basappa C. Yallur , Vinayak Adimule , Sheetal Batakurki

Soundarya Institute of Management and Science, Soundarya Nagar Sidedahalli Nagasandra Post, Bengaluru-560073, India.

Department of Chemistry, M.S. Ramaiah Institute of Technology (Affiliated to VTU), Bangalore560054, Karnataka, India.

Angadi Institute of Technology and Management (AITM), Savagaon Road, Belagavi 591108. Karnataka, India.

Department of Chemistry M S Ramaiah University of Applied Sciences, Bangalore-560058, Karnataka, India.

nagalaxmig@soundaryainstituions.in, Nandeeshim@gmail.com, yallurbc@msrit.edu, chemistry@aitmbgm.ac.in, sheetalbatakurki.cy.mp@msruas.ac.in

Keywords: Metal organic frameworks, Copper metal, Bandgap energy, photoluminescence.

Abstract

Two new copper-based metal organic frame work (Cu-MOF21 and CU-MOF-22) was synthesized using bromo malonaldehyde and terephthalic an amino terephthalic acid. They synthesized CU-MOFs were characterized by FT-IR, UV-Visible spectroscopy. The XRD diffraction pattern indicated at and . The Tauc's method was employed to calculate the band gap of Cu-MOFs and was found that Cu-MOFS-21 exhibited 3.14 eV and Cu-MOF-22 with average bandgap energy at 3.61 eV attributed to the ligand-metal charge transfer. The results indicate that both Cu -MOFs can be further modified by suitable dopants to enhance the conductivity and reduce the band gap energy.

Introduction

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Metal based materials play very important role in various fields to achieve biologically active materials [1-10], energy storage materials [11-14], optical properties [15-20], photoluminescence [21-24], photocatalytic activity to study the dye degradation of hazardous dyes [25-27], sensors for various applications [28-30], high conducting electrical materials [31, 32], solar energy devices an efficient light source [33-36].
Metal organic frame works (MOFs) are molecules with small organic compounds that act as linkers and are connected to the various metal clusters through co-ordination bondage leading a diversified hybrid crystalline structure with varied physical and chemical properties [37]. In recent years, MOFs have been attracted research across the multidisciplinary subjects [38, 39], due to their diversified physical properties such as optical [40,41], large surface area, high porosity, geometrically welldesigned structures and versatility in chemical properties attained due to numerous functional groups of organic linkers [42, 43]. Various heteroatoms such as oxygen, nitrogen, sulfur have been used as organic ligands []. Carbonyl based fused compounds such as terephthalic acid, aminoterephthalic acid, benzenetricarboxylic acid, isonicotinic acid, diphenyl dicarboxylic acid, dihydroxy-1,4benezenedicarboxylic acid, naphthalenedicarboxylic acid, 1,3,5- benzenetriphosphoric acid, 1,5naphthalenedisulfonic acid, tetrakis (4-cyanophenyl)methane, adenine, histidine, tartaric acid, azciaic acid, glutaric acid, oxalic acid, fumaric acid, lactic acid, formic acid, gallic acid, 4, 4', 4'' - (S)-trazine-2,4,6-triyl-tribenzoic acid, 4,4'4'' benzene-1,3,5-triyl-tribenzoic acid, benzene-1,2,4,5 tetracarboxylic acid, meso-terakis(4-carboxylicphenyl)porphyrin acid, nitrogen containing such as bipyridine, hexamethylene tetramine, imidazole, 2-methylimidazole, pyridine-4-carboxylic acid, meso-tetrakis(4-carboxylicphenyl)porphyrin acid etc. [44, 45]. To enhance their porosity property, tunable surface area, many metals are incorporated into the organic linkers through coordination
bonds [46]. The metals interact with the linker (organic molecules containing more of conjugated system or lone pair of electrons) either through interactions or through weak Van der walls force or through charge transfer mechanism [47]. These mechanisms help to increase the conductivity properties of MOFs by potentially enhancing the applications of MOFS as energy storage materials, electrochemical system and electrocatalyst. Metals such as copper, nickel, silver, cobalt, zinc, scandium, cadmium, aluminum, strontium, chromium, vanadium, cerium, titanium, zirconium, etc. were widely used metals in enhancing the conductivity and porosity of the many composite and metal organic frame works. Among which copper-based MOFs as an efficient hybrid porous substance that can be used for various applications [48, 49], and among many p-type semiconductors, Cupric oxide is the most prominent metal oxide having high conductivity with a narrow band gap of 1.2 eV resulting in a to a grate choice of material for solar dye sensitized applications, supercapacitors, electrochemical catalysis applications etc. The copper-based MOFs have been synthesized by various methods to obtain varied morphology and electrocatalytic properties. Few of the methods that are used are precipitation method, hydro/solvothermal methods [50]. The optimal molar ration of ligand to metal is one of the essential factors to obtain the highly purified Cu-MOFs. Temperature also plays a crucial role during the synthesis to obtain maximum porosity, highly geometrically structured MOFs. Copper metal organic frame works doped with melamine are reported to have antibacterial property [51]. Thus, copper-based metal organic frame works are synthesized by numerous methods having wide applications in various fields of science. In the present work, two copper-based metal organic frame work were synthesized by chemical methods using bromo monoaldehyde as organic linker by solvothermal method. The synthesized Cu-MOFs are characterized by FT-IR, UV- Visible absorption spectra and XRD. The bandgap energy was calculated using Tauc plots and photoluminescence properties were carried out for both MOFs.

Experimental

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Materials: All the chemicals and reagents have been purchased from Avra Synthesis Private Ltd, Sigma Aldrich, India and utilized without further modifications. 1,1,3,3-tetramethoxy propane (Sigma Aldrich), Terephthalic acid 98%, 2-Amino-terephthalic acid 98% (Avra Synthesis Private Ltd), Cu (NO3)2.3H2O 98% (Sigma-Aldrich Ltd).

Preparation of 2-bromomalonaldehyde: Starting material 2-bromomalonaldehyde was prepared using the procedure given in literature. To a 100 ml of aqueous solution of tetramethoxypropane , concentrated was added and stirred until it forms homogeneous solution, wherein temperature of the reaction mixture was maintained below and later bromine solution was added drop wise slowly and stirring was continued for another 30 minutes. Then, reaction mixture was concentrated under vacuum maintaining temperature below until thick slurry was obtained, and further washed using 200 mL cold water, 100 ml of cold dichloromethane and dried in vacuum. Yield: , MP: (Lit: ).

Preparation of Cu-MOF, compound 1: Followed the solvothermal method to synthesis these compounds. An equimolar amount of terephthalic acid ( ) and Cu (NO3) were taken in 50 ml DMF and kept at 1200 C in hot air oven for 48 hours. Nano polymer MOFs was kept for stirring by adding one equivalent of 2bromomalonaldehyde and continued for stirring for another two hours. Then centrifuged the reaction mixture ( 7000 rpm for 5 min ) by repeatedly washing the compound formed with DMF, then with ethanol and dried the composite in vacuum oven at .

Preparation of Cu-MOF, compound 2: Synthesized via the solvothermal method where in same molar concentration of 2-amino terephthalic acid ( ) and in 50 mL of DMF and placed in hot air oven at for 48 hrs . Nano polymer MOFs was kept for stirring by adding one equivalent of 2-bromomalonaldehyde and continued for stirring for another two hours. Further, it was centrifuged ( 7000 rpm for 5 min ) with repeated washing in DMF, then with ethanol and the composite was dried. Figure 1. depicts the synthesis of Cu-MOFs.

Figure 1. Preparation of

Figure 1. Figure 1. Preparation of

Result and Discussion

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UV-Visible Spectral studies:

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Figure 2. UV-Visible spectrum of (a) Cu-MOF-21 and (b) Cu- MOF-22

Figure 2. Figure 2. UV-Visible spectrum of (a) Cu-MOF-21 and (b) Cu- MOF-22

The UV-visible spectra of the synthesized Cu-MOFs are shown in the fig No.2. The Cu-MOF-21 showed two absorption bands at 237 nm and 709 nm whereas Cu-MOF-22 showed absorption bands at 351 nm and 725 nm . Both the absorption bands recorded may corresponds to the and excitation attributing the interaction between the oxygen of the organic framework and apparently due to the optical transition of organic ligands to that of copper metal charge transfer [52].

FT-IR Spectral Analysis: The FT-IR spectrum of both CUMOFs were indicated in the Fig No 3. The presence of the O-H stretching band at were observed in the CU-MOF-1. Also, the band at corresponds to str, at stretching due to fermi resonance and band at corresponding to stretching.

Figure 3. FT-IR spectrum of (a) Cu-MOF-21 and (b) Cu-MOF-22.

Figure 3. Figure 3. FT-IR spectrum of (a) Cu-MOF-21 and (b) Cu-MOF-22.

A sharp peak at indicating the alkene like stretching due to the enolic form of aldehyde upon condensation of bromonaldehyde to the pterphthalic acid. In the FT-IR of Cu-MOF-22 band at and corresponding to stretching and N-H stretching due to the presence of hydroxyl groups of carboxylic acid and amine group and both the bands have lower frequency which might be due to the coordination bond between the organic ligand and the metal. Similarly, the alkene str was observed at bending at and corresponding to stretching frequencies.

XRD diffraction studies: The phase purity and crystallinity of synthesized Cu-MOFs were identified with the XRD diffraction studies as indicated in Figure 4. The A sharp arrow headed tripods with amorphous type of nature of peaks were observed due to the presence of pure copper with a cubic face centered structure. In both the Cu-MOFs the peaks values i, e at , attributed to planes at (020), (040)respectively.. Many other peaks were observed between at to . Most of the peaks match with the literature reported as JCPDS card no. 89-2838 and 04-0836 for copper [53]. The particle size calculation was done with respect to FESEM as less intense peaks were obtained in the XRD pattern. The crystallite size of Cu-MOFs were calculated using Scherrer equation.

where K is crystallite shape constant ( 0.94 ), is full width at half maximum, is wavelength of X ray radiation ( ) and is glancing angle. The crystalline particle sizes were observed between .

Figure 4. XRD patterns of (a) Cu-MOF-21 and (b) Cu- MOF-22

Figure 4. Figure 4. XRD patterns of (a) Cu-MOF-21 and (b) Cu- MOF-22

Photoluminescence features of Cu-MOFs

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The PL emission characteristic of Cu-MOFs were shown in Fig. No. 5 strong intense peak was observed at 505 nm was observed for both Cu -MOF-21 and Cu -MOF-22 attributing to the excitation of copper metals ions along with the ligands. A small peak was observed at 756 nm and 757 nm for Cu-MOF-21 and Cu-MOF-22 respectively. However, the presence of amine group didn't have any significant effect on the luminescent intensity of the Cu-MOF-22 with that of Cu-MOF-21.

Figure 5. Photoluminescence of (a) Cu-MOF-21 and (b) Cu- MOF-22.

Figure 5. Figure 5. Photoluminescence of (a) Cu-MOF-21 and (b) Cu- MOF-22.

Optical properties.

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Band gap analysis: The UV-Visible absorption spectra was carried out using 210 plus UV-Visible absorption Spectrometer. Bandgap energy was calculated by using Tauc's method and equation 2. Graphically the bandgap energy was obtained by extrapolating the tangential line intersecting x axis at as shown in Fig. From the graph, the bandgap energy for 3.14ev.
The three-bandgap energy for was at and 2.85 eV . The average of the three bandgap energies will be 3.61 eV . The increase in bandgap energy in Cu-MOF-2 which may be due to the lattice distortion hybridization. Fig No. 6 indicates the bandgap energy of Cu -MOFs.

Figure 6. The energy band gaps of (a) Cu-MOF-21 and (b) Cu- MOF-22

Figure 6. Figure 6. The energy band gaps of (a) Cu-MOF-21 and (b) Cu- MOF-22

Conclusion

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This work reports the synthesis of two new Cu-MOFs using bromo monaldehyde as organic linker and copper metal as conducting material. The synthesized CU-MOFs were characterized by FT-IR, XRD and UV-Visible spectrometer. The photoluminescence spectrum inferred the maximum excitation of both the Cu-MOFS at 516 nm . The synthesized Cu-MOF -21 showed 3.14 eV band gap
energy whereas the band gap energy for Cu-MOF-22 was at 3.61 eV . Though the obtained band gap energy is more, the bandgap energy can be addressed by adding suitable dopants and this work is in progress by our team to enhance the optical property of the Cu-MOFs.

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The original version of this paper is available on https://www.scientific.net/EC.2.3.pdf

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Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 13-22

doi: 10.4028/p-91j5nn

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

Submitted:
2022-12-25

Revised:
2023-02-21

Accepted:
2023-02-21

Online:
2023-05-16

Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

The original version of this paper is available on https://www.scientific.net/EC.2.13.pdf

Vinuta Kamat , Vinayak Adimule , Basappa C Yallur , Manjunath D.H. , Sheetal Batakurki

Department of Chemistry, Mangalore University, Mangalore-574199, Karnataka.

Angadi Institute of Technology and Management (AITM), Savagaon Road, Belagavi 591108. Karnataka, India.

Department of Chemistry, M.S. Ramaiah Institute of Technology (Affiliated to VTU), Bangalore560054, Karnataka, India.

Department of studies in Chemistry, Shivagangothri, Davangere University, Davangere - 577 007, India.

Department of Chemistry M. S. Ramaiah University of Applied Sciences, Bangalore-560054, Karnataka, India.

vinutakamat24@gmail.com, adimulevinayak@yahoo.in, yallurbc@gmail.com, manjunathdh@davangereuniversity.ac.in, sheetalrb@gmail.com.

Keywords: MOFs, Copper composites, RIT-62 Cu-MOFs, Nano metal oxide, Optical properties.

Abstract

Metal organic frameworks are the materials of today's generation and are widely used for their various physicochemical properties. MOFs are synthesized by various methods such chemical precipitation method, sol-gel method, hydrothermal method etc. To attain the required optoelectronic properties of MOFs, synthetic methods play a important role. In the present work, the synthesis of Cu-MOFs was carried out at and . The synthesized Cu-MOFs were labeled as RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2. Both the Cu-MOFs were characterized by FTIR, UV-visible spectra. The FESEM of both Cu-MOFs indicated that spherical particles with 120 to 200 nms . of particle size. Tauc's method was employed to compute the band gap of both Cu-MOFs. RIT 62-Cu-MOF-1 imparted 2.67 eV while RIT 62-Cu-MOF-2 imparted average of 2.06 eV off bandgap. 2.35 eV due to ligand-metal charge transfer observed through UV- visible spectra. Further, optimization of synthetic procedures to enhance the optical properties of Cu -MOFs.

Introduction

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The filed "optoelectronics" deals with the study of interaction of electromagnetic light with the materials of interest. Various metal-based materials are synthesized to achieve the high conducting nature for varied applications such as semiconductors, optical fibers in electronic field, biosensing and bio-imaging in medical filed, solar energy devices an efficient light source, both photocatalysis and electrocatalysis in bioremediation of dyes and drugs, as a non-invasive technique in determination of heavy metals, hazardous elements in agricultural crops, etc., [1]. Reflectivity, refractivity, transparency, translucent, opaque, thermal emission, photoconductivity, luminescence, absorptivity, optical activity, scattering, turbidity, fluorescence and phosphorescence, birefringence, etc., are all the properties of optical active material [2-7]. The optical properties of the materials are significantly dependent on various factors such as particle size, thickness, composition of substance, ratio of conducting substance, structure of the material, dielectric constant etc., accounting to internal properties and external properties such as humidity, light, temperature, and wavelength of light and angle of illumination [8]. In recent years more than one metal is added as dopants to enhance the conducting nature of the materials. Transition metals and their metal oxides are believed to enhance the optoelectronic properties of the materials and are widely used as dopants [9-18]. In fact, the size reduction of metals into nanometallic form have enormously increased the physico-chemical properties of the materials [19]. Metals such as cobalt, antimony, zirconium, gadolinium, strontium,
yttrium, palladium, molybdenum, titanium, cadmium etc., have enhanced the conducting, chemical, magnetic, thermal, electronic properties of the metals and used widely for their photovoltaic applications, photoluminescence, perovskite, photocatalytic degradation, semiconductors, organic reactions etc. [20-32]. Even the small heterocyclic compounds, polymers having greater number of conjugation and easily accessible free electrons present in the heteroatoms aids in enhancing the optical properties and biological activities off the materials [33-39]. In recent years, the application of hybrid materials such as organic metal frame works have also resulted in significant contribution towards increasing the optoelectronic properties of the material [40]. Various organic linkers containing functional groups such as carboxylic acid, amine functionality, sulfur are used along with the transition metals to fine tune the required optical energy for the requisite applications [41-42]. Similarly, various metals containing iron, copper, cobalt, chromium, cadmium, vanadium, zinc, nickel, manganese, scandium, etc., along with organic framework have been reported [44]. Copper based metal organic framework having band gap energy of , and 2.56 eV were obtained for the copper based with organic linkers as 1,4-benzene dicarboxylic acid, 2-amino-1,4benzene dicarboxylic acid, and benzene-1,3,5-tricarboxylic acid synthesized by ultrasonication method and were used to trap the gas at room temperature [45]. Similarly, 1,3,5benzenetricarboxylic acid with copper metal synthesized by the hydrothermal method reported to possess 3.86 eV band gap energy was used in photocatalytic degradation of rhodamine B dye present in the water sample [46]. Synthesis of the material plays a crucial role in attaining the required optical property of the material. Precipitations, Co-precipitation, hydrothermal method, sol-gel method, micro-emulsion, chemical- vapor deposition, electrochemical method of deposition etc., are all well reported methods in the literature for the synthesis of metal organic frame works to obtain the required optical properties. Apart from conventional heating, ultrasound and microwave heating are all employed in the synthesis of MOFs to obtain uniform crystal size, regular shape, thin films, membranes, and various other shapes are reported in the literature. Variation in temperature, stoichiometric ration of starting materials, solvent ratio, pressure, stirring time, speed, pH of the reaction etc., [47], are important parameters that aid in acquiring the requisite morphology of MOFs. In direct precipitation method, the synthesis of MOFs is carried at room temperature in presence of greener solvents [48]. The present work focuses on the investigation of temperature effect on the synthesis of copper-based MOF. The synthesized Cu MOFs are characterized by UV- Visible spectrum, FTIR and XRD. The optical properties of the MOFs are also studied.

Experimental

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Materials: All the chemicals and reagents procured from Avra Synthesis Private Ltd, Sd-Fine Chemical Ltd., Sigma Aldrich, India and used without any further purifications. 1,1,3,3-tetramethoxy propane (Sigma Aldrich), 4-Mercaptobenzoic acid (Sigma Aldrich), Cu (NO3)2.3H2O 98 % (Sigma-Aldrich Ltd).
Preparation of 2-bromomalonaldehyde: Starting material 2-bromomalonaldehyde was prepared using the procedure given in literature. To a 100 ml of aqueous solution of 1, 1, 3, 3tetramethoxypropane , concentrated was added and stirred until it forms homogeneous solution, wherein temperature of the reaction mixture was maintained below and later bromine solution was added drop wise slowly and stirring was continued for another 30 minutes. Then, reaction mixture was concentrated under vacuum maintaining temperature below until thick slurry was obtained, and further washed using 200 mL cold water, 100 ml of cold dichloromethane and dried in vacuum. Yield: , MP: (Lit: ).
General Procedure for Synthesis of 4-((1,3-dioxopropan-2-yl)thio)benzoic acid (RIT 62): Mixed both 4-mercaptobenzoic acid ( ) and 2-bromomalonaldehyde ( 0.245 g , 0.0016 mol ) in a 4 ml glass vail and did the microwave irradiation using domes- tic microwave own at high power for 2 min . Completion of the reaction was monitored by TLC and crude product was purified by column chromatography on silica gel using ethyl acetate/n-hexane ( ) and yield is .

Synthesis of Cu-MOF's: Cu-MOF synthesized through solvothermal method in which an equimolar amount of RIT-62 and were collected in DMF and kept at and in an oven for 48 hours. Centrifuged the reaction mixture ( 7000 rpm for 5 min ) by repeatedly washing the composite formed with DMF, then with ethanol and dried the composite in vacuum oven at 1500 C .

Figure 1. Preparation of Cu-MOF's: compound 1 and 2.

Figure 1. Figure 1. Preparation of Cu-MOF's: compound 1 and 2.

Result and Discussion

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Figure 2. UV-visible spectra of (a) RIT 62-Cu-MOF-1 and (b) RIT 62-Cu-MOF-2

Figure 2. Figure 2. UV-visible spectra of (a) RIT 62-Cu-MOF-1 and (b) RIT 62-Cu-MOF-2

UV-Visible Spectral studies: The UV-Visible spectrum of the Cu-MOFs are shown in Fig No.2. The RIT 62-Cu-MOF-1 showed three characteristic bands at and 733 nm . There was a slight increase in the wavelength of RIT 62-Cu-MOF-2 that showed bands at whereas a decreased band at 720 nm . It is evident from the graph that there was not much temperature effect on the absorption spectrum of both Cu-MOFs. Further increase in the temperature while synthesis of Cu-MOF was avoided due to the possibility of breakage of linker which is organic molecule. Hence only two different temperatures were monitored during the synthesis. [49].

FT-IR Spectral Analysis: Figure 3. inferes the FTIR spectrum of the both Cu-MOFs. In RIT 62-Cu-MOF-1, a broad for O-H str band was observed at , where as a fermi resoance band at 2917 was observed for the aldehyde C-H str along with a band at , a decreased wavenumber for the aldehyde streching due to the co-ordiantion band between the aldehyde carbonyl group and the copper metal oxide. Alkene C-H str was observed at . A similar peaks were observed in RIT 62-Cu-MOF-2.

Figure 3. FTIR spectrum of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2

Figure 3. Figure 3. FTIR spectrum of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2

XRD diffraction studies: The X-ray diffraction studies of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF2 were analyzed on a Bruker, Germany, fitted with D8-fine focus ceramic X-ray tube, source radiation ( ) at room temperature and the graphs are depicted in the Fig. 3. The RIT 62-Cu-MOF-1 showed peaks at values of and corresponding to the crystal planes at , and 023 respectively which are in agreeable to the literature (JCPDS card number 76-1393) For RIT 62-Cu-MOF-2 the values were observed at , corresponding to crystal plane at , respectively. The peak intensity increased in the RIT 62-Cu-MOF-2. However, many short shoulder peaks were absent I the RIT 62-Cu-MOF-2 in comparison to RIT 62-Cu-MOF-1. The crystallite size of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2 were calculated using Scherrer equation and were of respectively [51, 59, 60].

where K is crystallite shape constant ( 0.94 ), is full width at half maximum, is wavelength of X ray radiation ( ) and is glancing angle.

Figure 4. XRD patterns of of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2

Figure 4. Figure 4. XRD patterns of of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2

The surface morphology of the RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2 are shown in Fig no 5. The FESEM images of RIT 62-Cu-MOF-1 showed rough surface with round shape with average particle size between 150 nm to 200 nm . RIT 62-Cu-MOF-2 showed particle size between 120 nm to 200 nm . Both the images had non uniform particle size unevenly distributed throughout the surface.

Figure 5. FESEM images (a) RIT 62-Cu-MOF-1 (b) RIT 62-Cu-MOF-2 and histograms (a) RIT 62-Cu-MOF-1, (b) RIT 62-Cu-MOF-2

Figure 5. Figure 5. FESEM images (a) RIT 62-Cu-MOF-1 (b) RIT 62-Cu-MOF-2 and histograms (a) RIT 62-Cu-MOF-1, (b) RIT 62-Cu-MOF-2

Photoluminescence: Photoluminescent characteristics of are depicted in Fig. No. 6. A strong sharp absorption peak at and 506 nm were observed for RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2 respectively. A short bump was observed at 757 nm for both Cu-MOFs. Overall, there was no much difference in the PL spectra of both Cu MOFs.

Figure 6. Photoluminescence spectra of (a) RIT 62-Cu-MOF-1 (b) RIT 62-Cu-MOF-2

Optical properties: Band gap analysis: The UV-Visible absorption spectra were recorded using 210 plus UV-Visible absorption Spectrometer. Further, bandgap energy was calculated by Tauc's method. The graph was obtained by plotting versus . The band gap energy is obtained upon extrapolating the tangential line intersecting x axis at . RIT 62-Cu-MOF-1 showed the band gap energy of 2.76 eV whereas RIT 62-Cu-MOF-2 showed average band 2.03 eV . This indicates that RIT 62-Cu-MOF-2 showed better optical property compared to RIT 62-Cu-MOF1. A slight change in their individual band gaps or lattice distortion hybridization results in shifting of the energy level [50,51].

Figure 7. The energy band gaps of (a) RIT 62-Cu-MOF-1 (b) RIT 62-Cu-MOF-2

Figure 6. Figure 7. The energy band gaps of (a) RIT 62-Cu-MOF-1 (b) RIT 62-Cu-MOF-2

Figure 7 indicates the Tauc plots of the RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2. RIT 62-Cu-MOF1 showed the band gap energy of 2.76 eV whereas RIT 62-Cu-MOF-2 showed average band 2.03 eV . This indicates that RIT 62-Cu-MOF-2 showed better optical property compared to RIT 62-Cu-MOF-1.

Conclusion

The original version of this paper is available on https://www.scientific.net/EC.2.13.pdf

The focus of this work was to investigate the temperature effect employed during the synthesis of CuMOF and its effect on the optical properties of the Cu-MOFs. CU-MOFs were synthesized at two different temperatures at and . The synthesized Cu -MOFs were characterized by UVvisible spectra, FTIR and XRD. The XRD results infer that there was slight increase in the intensity of RIT 62-Cu-MOF-2. However, both cu-MOFs showed similar particle size between 150 to 25 onm with spherical shape randomly distributed on the surface. The Pl of RIT 62-Cu-MOF-1 and RIT 62-Cu-MOF-2 showed a strong peak at 505 nm . The bandgap energy of RIT-62-Cu-MOF-2 showed better optical property with average band gap energy as 2.03 eV when compared to the RIT 62-Cu-MOF-1 observed with bandgap energy at 2.76 eV . Thus, Temperature parameters play an important role in obtaining narrow band gap energy. However, in this work only temperature of to , further increase in temperature was avoided as the change of organic linker to decompose is high. Future studies include the study of other parameters such a solvent, solvent ration, stirring time etc., to enhance the optical properties of .

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Chapter 2

Waste Recycling

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 25-33

doi: 10.4028/p-erelbb

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

Submitted:
2022-07-29

Accepted:
2022-11-30

Online:
2023-05-16

Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

The original version of this paper is available on https://www.scientific.net/EC.2.25.pdf

Sinar Perbawani Abrina Anggraini , Mahfud , Sri Rachmania Juliastuti and Suprapto

Department of Chemical Engineering, Sepuluh Nopember Institute of Technology, Indonesia

spabrina74@gmail.com, mahfud@chem-eng.its.ac.id, juliaz30@chem-eng.its.ac.id, suprapto@chem-eng.its.ac.id

Keywords: microwave-assisted pyrolysis; coconut shell waste; size; power

Abstract

Coconut shell waste causes environmental pollution around the community. Therefore, it is necessary to have more optimal processing to produce valuable products using a microwaveassisted pyrolysis process. This study uses microwave-assisted pyrolysis (MAP) for the production of liquid smoke from coconut shells using different power and sizes , 3 mm ). The results of this study show that the highest yield for 300 W power at 2 mm size by , for 450 W power at 3 mm size by , for 600 W power size 3 mm by , while the optimal size for liquid smoke is 3 mm size by at 450 W power.

1. Introduction

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Indonesia is one of the countries with coconut plantation commodities. It has an area of around ha and can produce as much as tons. Almost of the site is smallholder plantations, growing of the total production in Indonesia [1]. Coconut is a folk plant used by the community in their lives [2]. The increase in coconut production also causes several waste problems caused, such as coconut shells, which cause environmental pollution and impact public health. Currently, coconut shell waste has not been optimally utilized. Coconut shells are generally used for handicrafts, as fuel, and to manufacture activated charcoal

Coconut shells have the potential to become liquid smoke. Liquid smoke can be used as a biopesticide because liquid smoke contains phenol compounds that act as antioxidants and acidic compounds that act as antibacterials. Coconut shell is classified as a hardwood type with a more lignin content of than cellulose , producing phenol compounds and acid compounds in the pyrolysis process [3]. The next problem is the appearance of pests on rice plants. Indonesia is one of the third countries after China and India to consume rice as a staple food [4]

The problem that arises with the presence of rice productivity is pests. Pests can harm farmers, especially with Indonesia's decreasing rice productivity. To avoid pests, farmers use chemical pesticides. This causes environmental pollution and public health, so biopesticides are needed to control pests in rice plants. One of the safe materials to use for biopesticides is liquid smoke because it comes from biomass materials. The liquid smoke resulting from the pyrolysis process contains phenol compounds of about [5]. Typically, liquid smoke can be produced using a conventional pyrolysis reactor. An effective pyrolysis process produces liquid smoke using a microwave [6]. A microwave absorbent is necessary to expand the heating rate in the pyrolysis process. The reactor temperature will stabilize with minimal energy input through microwave irradiation when solid residues are dropped directly into the heated absorbent. Activated carbon as an absorbent can help reduce the toxic content of harmful gas phase products [7]

Adding carbon and activated carbon is an excellent microwave absorber that shows a high capacity to absorb and convert microwave energy into heat. Anissa et al. stated that microwave technology could reduce the reaction time of pyrolysis and improve the quality of value-added products obtained from the biomass of pine wood saws [8]

The production cost of bio-oil and biochar from microwave catalytic pyrolysis can be decreased because catalyst combinations significantly improve catalytic performance. [9].

Microwaves can efficiently heat carbon materials (e.g., carbon, charcoal, activated carbon), generally being an excellent microwave absorb [10]. Recently, the microwave-assisted pyrolysis process used an absorber to help increase the heating rate. Energy will enter minimally through microwave irradiation so that the temperature in the reactor in the microwave will be more stable when solids residues mix with the absorber when heated

In pyrolysis, biomass heating will go through two simultaneous heating mechanisms, namely irradiation and microwave conduction, with increasing high temperatures of the absorber [11]. The heating of biomass will raise its temperature instantly continuously or semicontinuously through the reactor from the microwave. Previous studies have shown that microwave-assisted pyrolysis (MAP), classified as mid-level pyrolysis, can reach the level of fast microwave-assisted pyrolysis (fMAP) through heating using an absorber so that maximum results will be obtained with high-quality products [12]. It is possible to improve poor heating efficiency caused by low-loss raw materials by including a microwave absorber, a material that is amenable to microwave heating [13]. A microwave absorber is added to the material to speed up the heating process on pyrolysis [14]. The microwave will encounter intermolecular frictional force, producing heat [15]. A good absorber material is a material that has a high absorption of microwaves resulting in stability at high temperatures and high oxidation resistance [16]

Liquid smoke is produced by incomplete combustion involving the decomposition of polymer constituents into low molecular weight organic compounds due to the influence of heat, which includes oxidation, polymerization, and condensation reactions. The cooling medium used in the condenser is water that is flowed through an inlet pipe that comes out as the result of incomplete combustion and then flows through the condenser and condenses into the smoke distillate. Smoke particles have a diameter of . The density of the smoke can be determined by the proportion of solids and liquid particles in the gaseous medium. Liquid smoke is a mixture of wood smoke dispersion in water made by condensing liquid smoke from pyrolysis. The base material and the pyrolysis temperature influence the liquid smoke from this pyrolysis. Twelve components are found in the coconut shell's liquid smoke, mainly from the thermal degradation of wood carbohydrates, such as ketones of about , carbonyl, and acids of about , as well as furan and pyran derivatives of about . The liquid smoke of coconut shells contains 28 components derived from the thermal degradation of lignin. Those components are phenols , guaiacol and its derivatives , syringol and its derivatives and alkyl aryl ether [17]. The addition of magnetic ZnFe 2 O 4 will improve the efficiency of the pyrolysis process. It shows that the content of increased by , and the content of decreased by , and this shows that magnetic nanoparticles have good catalytic [7]. The purpose of this study is to determine the optimal size of raw materials and microwave power in the manufacture of liquid smoke using the microwave-assisted pyrolysis method

2. Materials and Methods

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Raw Material

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Coconut shells are obtained from the Dampit Malang area, East Java, Indonesia. Further cleaning is carried out and cut by , and 3 mm , then dried in the sun until completely dry. Another ingredient is activated carbon as an absorber used in the mixture of ingredients in the microwave.

Research Methods

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This research began with the pyrolysis process using raw materials in the form of coconut shells. At first, the shells of raw materials that have been cleaned and ground vary ( ), and each variation of the impact was taken 50 grams to be mixed with an activated carbon absorber of . Then it was put in the microwave, with a power of ( watts) for as long as ( minutes). The process obtained the solid fraction in the form of charcoal, the heavy fraction in the form of Tar, and the light fraction in the form of smoke and methane gas. The light fraction would flow into the condensation pipe so that liquid smoke was obtained while the methane gas remained an uncondensed gas

Figure 1. Microwave-assisted pyrolysis device circuit scheme

Figure 1. Figure 1. Microwave-assisted pyrolysis device circuit scheme

3. Results and Discussion

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This research used the microwave-assisted pyrolysis method to make liquid smoke. The technique with microwave-assisted pyrolysis used an activated carbon absorber with a coconut shell size and heating time (5, 10, 15, 20, 25, 30 minutes), and power ( 300 watts, 450 watts, 600 watts). The analysis test used the gravimetric method to obtain density results from liquid smoke. The parameter used is the percentage yield. The data can be seen in Table 1 in the following observations:

3.1. Microwave-Assisted Pyrolysis Method against heating temperatures

Table 1. The relationship of liquid smoke to the heating temperature in the method microwave-assisted pyrolysis at 300 watts

No | Raw Material Size | Heating Temperature (°C) | Yield (%)
1 | 1 mm | 116 | 4.65
2 | 126 | 8.37
3 | 141 | 12.09
4 | 146 | 14.13
5 | 155 | 15.99
6 | 174 | 18.22
1 | 2 mm | 92 | 6.60
2 | 93 | 10.38
3 | 95 | 14.15
4 | 105 | 16.98
5 | 122 | 19.81
6 | 130 | 22.83
1 | 3 mm | 82 | 1.33
2 | 89 | 3.22
3 | 93 | 7.01
4 | 100 | 8.90
5 | 116 | 10.80
6 | 121 | 12.12

Figure 1. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method at 300 watts of power

Figure 2. Figure 1. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method at 300 watts of power

Figure 1. indicates that the higher the heating temperature, the higher the volume of liquid smoke produced. The difference in heating temperature will cause a break in the hydrocarbon chain from the polymer in the raw material. Subsequently, the yield of liquid smoke differs at each temperature change due to the power variance carried out in the pyrolysis process and the power used. This will affect the result of liquid smoke to the reaction temperature that is increasing, and the microwave power increases. It is because the random motion of the molecules gets more extensive with increasing temperature. The increasingly sizeable spontaneous movement of molecules leads to increasingly large collisions between molecules. As the heating temperature increases, the smoke emitted will increase, so the yield of liquid smoke will rise. A material size of 1 mm produces a faster and more liquid smoke yield than 2 mm and 3 mm . This is related to the surface area because the heat propagation rate is more rapid, producing more liquid smoke yields under stable condenser water conditions. Since microwaves can penetrate the material and store energy, heat can be generated from all parts of the material simultaneously, so microwave heating will take place quickly. In microwave heating, the temperature on the (bulk) part of the material is higher on the surface, and this can be seen in the results of liquid smoke that comes out first than Tar

Table 2. The relationship of liquid smoke yield to heating temperature in the method
Microwave-assisted pyrolysis at 450 watts

No | Raw Material Size | Heating Temperature (°C) | Yield (%)
1 | 1 mm | 98 | 1.86
2 | 118 | 3.72
3 | 138 | 5.58
4 | 154 | 9.30
5 | 168 | 11.16
6 | 184 | 21.20
1 | 2 mm | 104 | 5.64
2 | 118 | 9.40
3 | 133 | 16.92
4 | 146 | 22.56
5 | 151 | 24.44
6 | 173 | 27.82
1 | 3 mm | 112 | 9.51
2 | 133 | 15.21
3 | 143 | 19.02
4 | 153 | 22.82
5 | 163 | 26.62
6 | 176 | 28.52

Figure 2. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method based on 450 watts of power

Figure 3. Figure 2. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method based on 450 watts of power

Figure 2. shows that the higher the heating temperature, the higher the yield of liquid smoke produced is due to the greater the amount of smoke produced at high temperatures so that the smoke condensed into liquid smoke is more significant. It also affects the power used. The interaction of charged particles in the material with the electric field of electromagnetic radiation causes the materials to heat up. The heat generated from this interaction is mainly caused by two factors, namely polarity and electron movement. In polar molecules, such as water, the electric field of microwaves causes the formation of permanent dipoles, and it induces the dipole to rotate according to the electric field of the return ball.

The movement of these molecules generates frictions between molecules that rotate to produce heat. In solid materials, the interaction of charged particles with an electric field causes electrons to move freely. Because the electron cannot change the phase of the electric field, the movement of the electron will generate heat. In addition, because the wave will propagate in the heating chamber, the greater the volume of the heating chamber, the less the microwave power will be. As a result, microwave power is reduced, and the highest temperature (peak temperature) will be lower. A power of 450 watts will increase, and the temperature will be higher than the power of 300 watts. Because the microwave power will increase because the wave will spread to fill the heating chamber, resulting in a larger volume of the heating chamber so that the temperature will be higher.

Table 3. The relationship of liquid smoke yield to heating temperature in the method Microwave-assisted pyrolysis at 600 watts

No | Raw Material Size | Heating Temperature (°C) | Yield (%)
1 | 1 mm | 158 | 3.70
2 | 205 | 5.55
3 | 210 | 7.39
4 | 215 | 9.24
5 | 221 | 11.09
6 | 232 | 14.42
1 | 2 mm | 135 | 4.07
2 | 154 | 7.78
3 | 170 | 9.63
4 | 187 | 11.48
5 | 198 | 13.33
6 | 209 | 15.19
1 | 3 mm | 113 | 7.64
2 | 137 | 13.38
3 | 151 | 17.20
4 | 163 | 21.02
5 | 176 | 24.84
6 | 191 | 28.67

Figure 3. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method based on 600 watts of power

Figure 4. Figure 3. The relationship between liquid smoke yield to heating temperature using microwave-assisted pyrolysis method based on 600 watts of power

Figure 3. shows that the higher the heating temperature, the greater the yield of liquid smoke produced. This is as a result of microwave technology is a modern technology that makes thermal energy by rapid movement and rotation of polar molecules by rubbing against each other. Microwave irradiation induces a thermal, electric field, and other nonthermal effects in substances. Thermal effects convert electromagnetic energy into thermal energy to generate heat. The nonthermal effect causes rotation and polarization of dipole molecules, increasing the frequency of collisions between
molecules that generate heat through friction and heat transfer from the inside of the substance to the outside. The frictional force between the molecules produces heat. The forces increase the diffusion rate of internal water from the interior to the surface of the object. In addition, mechanical action and thermal effects increase the fluidity of water, which further accelerates movement

3.2. Microwave-Assisted Pyrolysis Method against particle size

Table 4. The relationship of particle size to yield (%) liquid smoke in power , and 600 W

No
Raw material
size (mm)
Power (Watt)

300
450
600

1
1 mm
18.22
21.20
14.42

2
2 mm
22.83
27.82
17.41

3
3 mm
12.12
31.95
30.58

Figure 4. Relationship of Particle Size to Liquid Smoke Yield At Power and 600 W

Figure 5. Figure 4. Relationship of Particle Size to Liquid Smoke Yield At Power and 600 W

Figure 4. shows that at a power of 300 watts, the larger the particle size, the less the volume produced. A material length of 1 mm shows a more decreased yield when compared to 2 mm and 3 mm , which increases throughout the heating time. The influence of microwave fire on the material results in a lower yield of liquid smoke. The larger the surface area, the lower the decomposition rate of organic compounds, and the damage to the constituents of the material decreases so that the liquid smoke produced will be less when compared to a larger particle size because it has a larger surface area. During the thermal decomposition process, particle size influences the surface area of heat transfer contact between the material and the heat source. The smaller the particle size, the smaller the heat transfer surface and will decrease the heat transfer rate to the material surface. The consequence will decrease the rate of decomposition in the material and reduce the efficiency of pyrolysis, especially in need of a short period of stay

While at a power of 450 watts, it is seen that the volume of liquid smoke continues to increase at a size of to 3 mm . The most significant liquid smoke yield is found at a length of 3 mm , which is . Because, at this size, with a power of 450 watts, it produced a higher temperature of compared to a capacity of 350 watts at . The compounds evaporate at that temperature. The yield of liquid smoke is increasing at high temperatures because the amount of liquid smoke produced at high temperatures is getting bigger so that the smoke condensed into liquid smoke is getting bigger. At this temperature, it gets a relatively large amount of heat intensity. The temperature in the condenser water is still stable, so the smoke in the coconut shell will be more decomposed and condensed into liquid smoke-the more significant the power in the microwave, the more temperature.

At a power of 600 Watts, it tends to go down more ( ) and 300 Watts and 450 Watts. It is because, in the process of hot propagation on the entire surface of the particles, charcoal is formed so that it produces less yield. At a smaller particle size, there will be a faster heating process and run out faster to produce outcomes so that the results are less. The higher the power at optimal conditions, the lower the temperature so that the friction force between the molecules is reduced because there is no longer a friction force that appears. Microwave radiation will also decrease so that it will reduce the desire of polar molecules to make movements, and this causes the heat that appears less to transfer thermal energy to water in the heated material.

4. Conclusions

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In this study, pyrolysis-assisted microwaves were processed based on material sizes and varying microwave power producing the highest yield at 300 Watts of power with a length of 2 mm of . A power of 400 Watt with a size of 3 mm resulted in , and a capacity of 600 watts with a length of 3 mm produced . While the optimal size for liquid smoke is a size of 3 mm by at a power of 450 Watt

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 35-41

doi: 10.4028/p-1z7h01

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

Submitted:
2022-07-29

Revised:
2022-10-28

Accepted:
2022-11-10

Online:
2023-05-16

Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

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Rafli Eghbal Haraki , Arenst Andreas Arie , Ratna Frida Susanti , Haryo Satriya Oktaviano , and Agung Nugroho .

Department of Chemical Engineering, Faculty of Industrial Technology, Universitas Pertamina, Jakarta, Indonesia

Chemical Engineering Department, Industrial Technology Faculty, 40141 Parahyangan Catholic University, Ciumbuleuit 94, Bandung, Indonesia

Research and Technology Innovation, PT. Pertamina (Persero), Jakarta, 12950, Indonesia

@student.universitaspertamina.ac.ad, arenst@unpar.ac.id, santi@unpar.ac.id, haryo.oktaviano@pertamina.com, agung.n@universitaspertamina.ac.id Corresponding Author: Agung Nugroho

Keywords: vetiver root waste, zinc oxide, impregnation, activated carbon, cyclic voltammetry, galvanostatic charge-discharge.

Abstract

The addition of zinc oxide ( ZnO ) as impregnation for activated carbon (AC) with the hydrothermal method has been performed in this research. Vetiver distillation waste has been used as a precursor for activated carbon synthesized with pyrolisis methods. Carbon is activated by a chemical process using KOH . Enhancement of amorph structure and function group by addition of zinc oxide has been characterized by Raman Spectroscopy, Fourier Transform Infra-Red (FT-IR), and X-Ray Diffraction (XRD). Furthermore, cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) has been done to show the electrochemical properties enhancement of the compared to pristine AC. At the current density of , the specific capacitance of VRW-ACM has a value of . After the impregnation process, the specific capacitance of VRW-ACM-ZnO has been improved by compared to VRW-ACM. The result showed that the activated carbon-based vetiver root waste impregnated with ZnO has the potential to be applied as supercapacitors electrodes.

Introduction

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Nowadays, the use of electric vehicles is increasing rapidly. This development is also in line with the rapid distribution of electrical energy. Public electric vehicle charging stations are increasingly needed all over the globe. However, many charging stations in developing countries still rely on fossil fuel resources. In the future, solar cell-based charging stations will become promising. Solar cell-based charging stations require storage devices with a large power density and fast chargedischarge times. Supercapacitors are considered suitable to answer these needs [1]. Supercapacitors have been widely developed as electrical energy storage. The advantages of supercapacitors are high life cycle, high specific power delivery, and fast charge-discharge compared to batteries. Supercapacitors have the drawback of small energy density. Increasing energy density can be done using electrode materials with high capacitance, and optimizing the supercapacitor structure [2]. Electrode materials are one of the main factors for determining the performance of supercapacitors and have become the focus of ongoing research. Activated carbon is the most widely studied to be used as a supercapacitor electrode material. Especially in developing environmentally friendly activated carbon materials, one of which is biomass-based. The highest specific capacitance value was recorded at from activated carbon-derived biomass [3]. Vetiver root waste is one of the biomasses that has the potential to be converted to activated carbon (AC) as electrode material due to its high cellulose ( ) and lignin ( ) content. Previous research shows the potential of activated carbon based on vetiver root waste to be applied as an electrode due to its high surface area of [4]. Of the many metal oxides used to improve the electrochemical performance of electrode materials, ZnO has attracted much researchers because it has large theoretical capacitance
values ( current density or ). ZnO is low in price, environmentally friendly, and easy to obtain. [5]. Previous studies by Li et al. obtained superior cyclic stability ( in 1000 cycles) with the ratio of . This study used vetiver root waste as a supercapacitor electrode with zinc oxide impregnation to utilize vetiver root waste. This study used characterization and electrochemical analysis such as FTIR, XRD, Raman Spectroscopy, CV, and GCD. Thus, this study is expected to produce materials with high specific capacitance so that they can become an alternative to supercapacitor electrode materials.

Material and Method

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Materials. Pottasium hydroxide (Merck), Zinc Oxide (ROFA Laboratory Centre), Sodium hydroxide (Merck), Sulphuric acid (Mallinckrodt), Nafion (Merck). All used regents were in analytic grade.

Synthesis of Activated Carbon. Vetiver root waste is obtained from the essential oil home industry in Garut, West Java, Indonesia. All other reagents were analytical grade, and the solution was prepared using double-distilled water. Vetiver root waste is cleaned with water to remove the impurities and dried in the oven at for 24 h . Dry vetiver root waste is ground with a ball mill and filtered with 100 mesh. The powdered material was pre-carbonized for 1 h at in a muffle furnace to produce pyrochar [7]. The pre-carbonized powder was mixed with KOH at a mass ratio for . The mixture was activated in to obtain the vetiver root waste-activated carbon at for 2 h .
Synthesis of Activated Carbon. The composite was synthesized with the hydrothermal method. ZnO solution was made by dissolving 0.05 g ZnO powder in 120 ml double distilled water. 0.1 g of pyrochar was dispersed in ZnO solution and stirred for 30 min . Then mixer was transferred into a Teflon-lined autoclave with a volume of 200 mL and heated for 4 h at . After multiple washing with double distilled water, composite was dried in the oven for 8 h at , and the sample was obtained.

Characterization. Functional groups were analyzed by FT-IR Thermo Scientific iS5 in wavelength. Crystal structures were characterized by X-Ray Diffraction Olympus BTX II Benchtop using Co-K radiation and scanning speed of . The defect of the material was determined by Raman spectra Horiba spectrometry (LabRAM HR Evolution Raman Microscope) at a wavelength of 532 nm and .

Electrochemical Measurement. Active material ( AC or ) as much as 1.6 mg were mixed with 0.5 ml of isopropanol and then sonicated for 15 min to form an ink. A ink was dropped to a glassy carbon electrode and coated with nafion. The complete method of the working electrode preparation can be seen in our previous report [8]. By using aqueous electrolyte M concentration, the three-electrode system was assembled with the reference electrode ( ), working electrode (glassy carbon), and counter electrode (Pt wire). Cyclic Voltammetry was measured within , and . GCD was measured within 0.5 to .

Result and Discussion.

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The FTIR result (Fig.1) identified the O-H stretching functional group at wavenumber . This group was identified due to the presence of KOH activators that have not disappeared even after intensive washing [9], [10]. The O-H stretching group is also indicated by phenol commonly found in activated carbon [11]. The stretching C-H group was identified at wavenumber , and the intensity in the C-H group was not very significant due to activation at high temperatures [12]. The stretching group was identified in wavenumber . This group also indicates the loss of the oxygen group due to high-temperature treatment [6]. For the VRW-ACM ZnO sample, the Zn-O group was not identified because the group was read on a wavenumber of . Another thing that explains the absence of is due to the low content of impregnation. At a ZnO : AC mass ratio of 0.5 grams, ZnO enters the pore and leaves no deposition on the surface, making it challenging to read FTIR [13].

Fig.1. FTIR test result for VRW-ACM and VRW-ACM ZnO

Fig.1. FTIR test result for VRW-ACM and VRW-ACM ZnO

Raman analysis (Fig.2a) showed the presence of bands at 1349 and indicating Dband and G-band. The defect degrees of activated carbon samples (VRW-ACM) and ZnOimpregnated activated carbon samples (VRW-ACM ZnO) were calculated by comparing the D-band and G-band intensities. The degree of defect of VRW-ACM and the VRW-ACM ZnO was calculated by comparing the D-band and G-band intensities as written in Fig.2. In the VRW-ACM ZnO sample, the value decreased compared to VRW-ACM. This result indicates that graphite carbon levels are higher after adding ZnO . The higher degree of graphitization can result from the catalytic graphitization process, which usually occurs in carbon pyrolysis in the presence of metal oxide [14]. In these cases, zinc oxide leads to the conversion of carbon structure into the ordered graphitic structure. This shows in the low value of VRM-ACM-ZnO compared to pristine VRM-ACM. These results correspond to previous tests comparing the impregnation of ZnO to activated carbon with commercial activated carbon increasing the crystallinity value [15]. In addition, there is no reaction to the impregnation of zinc oxide into activated carbon so that it does not damage the structure of the sample. The XRD result of activated carbon before and after ZnO impregnation can be seen in Fig.2b. The XRD pattern of VRW-ACM shows peaks at and , which is in agreement with the XRD pattern of carbon materials [16]. After ZnO impregnation, an unnoticeable peak can be seen in the result. This result indicates that ZnO is only impregnated in the carbon structure without entering into the structure of carbon. The similar result has also been observed in the previous research done by Aljeboree et al [17].

Fig.2. Raman Spectroscopy (a) and XRD analysis (b) result of VRW-ACM and VRW-ACM ZnO

Fig.2. Raman Spectroscopy (a) and XRD analysis (b) result of VRW-ACM and VRW-ACM ZnO

The sample VRW-ACM and VRW-ACM-ZnO was then analyzed by CV to see the electrochemical mechanism in the three-electrode system (Fig. 3). The CV curve of VRW-ACM shows a symmetrical curve in various scan rate, which indicates the EDLC mechanism (Fig. 3a). The curve also shows that there is no reduction or oxidation reaction, which agrees with the concept of the EDLC supercapacitor mechanism, which only occurs on surfaces [18]. The storage mechanism of EDLC is a reversible surface phenomenon involving the adsorption and desorption of ions from the electrolyte. After the impregnation of ZnO into the carbon structure, the shape of the curve changes, indicating the pseudocapacitance mechanism [19]. Further, at a scan rate of , the comparison of CV between before and after ZnO addition shows that VRM-ACM-ZnO has a more significant CV curve area (Fig. 3c). The large area of the CV curve might indicate the larger specific capacitance of VRW-ACM-ZnO compared to the pristine VRW-ACM sample.

Fig.3. CV test result for (a) VRW-ACM (b) VRW-ACM ZnO (c) comparison at scan rate

Fig.3. CV test result for (a) VRW-ACM (b) VRW-ACM ZnO (c) comparison at scan rate

GCD analysis was performed to quantify the specific capacitance of the as-synthesized material. Both samples show that the curve forms the same charge-discharge manner. The GCD result of pristine activated carbon (Fig. 4a) shows the symmetrical triangle that results from the EDLC mechanism [20]. This result differs from the GCD result of ZnO impregnated samples (Fig. 4b), which shows that the discharge time is longer than the charging time. The curvature at the end indicates a redox reaction between ZnO and electrolyte ions. This phenomenon shows the combined mechanism, namely EDLC on charge and pseudocapacitance on discharge [21]. Table 1 shows the calculated value of specific capacitance from GCD analysis. It can be seen that after adding ZnO, the specific capacitance of the materials increases all current densities.

Fig.4. GCD test result for (a) VRW-ACM, (b) VRW-ACM ZnO and (c) comparison at current density 1A/g

Fig.4. GCD test result for (a) VRW-ACM, (b) VRW-ACM ZnO and (c) comparison at current density 1A/g

Table 1. Capacitance for VRW-ACM and VRW-ACM ZnO

Sample | Current Density (A/g) | Specific Capacitance (F/g) | Increase of Capacitance
VRW-ACM | 0.5 | 277 | -
1 | 218 | -
2 | 186 | -
4 | 160 | -
VRW-ACM-ZnO | 0.5 | 400 | 44%
1 | 383 | 75%
2 | 314 | 66%
4 | 248 | 55%

The GCD cyclability test was carried out at current density to determine the retention of the VRW-ACM-ZnO material after being cycled 50 times (Fig.5). The result was reduced from 246 to after 50 cycles. In the 50 cycles, there is relatively good stability. An insignificant and still higher decline than VRW-ACM before impregnation proves that VRW-ACM ZnO has the potential to be used as an electrode for supercapacitors.

Fig.5. Cycle Performance of VRW-ACM ZnO

Fig.5. Cycle Performance of VRW-ACM ZnO

Conclusion

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Vetiver root waste left over from essential oil distillation can be a precursor to the manufacture of activated carbon by pyrolysis and hydrothermal pre-carbonization methods followed by activation with KOH . The FTIR, Raman, and XRD analysis show that zinc oxide impregnation was successfully carried into activated carbon. The decrease in defects in Raman analysis reflects the graphitization of carbon materials into the graphitic structure. The CV and GCD analysis showed an increase in specific capacitance in each sample. This result suggests that activated carbon material was successfully impregnated with zinc oxide and has the potential to be used as an electrode for supercapacitors.

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The original version of this paper is available on https://www.scientific.net/EC.2.35.pdf

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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-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 43-51

doi: 10.4028/p-5f6oj6

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

Submitted:
2022-08-12

Revised:
2022-09-20

Accepted:
2022-09-28

Online:
2023-05-16

Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

The original version of this paper is available on https://www.scientific.net/EC.2.43.pdf

Meta Fitri Rizkiana , Boy Arief Fachri , Syahrul Gunawan , Mohammad Nor , Iswahyono Iswahyono , Bekti Palupi , Istiqomah Rahmawati , Helda Wika Amini

Department of Chemical Engineering, Universitas Jember

Politeknik Negeri Jember

metafitririzkiana@unej.ac.id, fachri.teknik@unej.ac.id, syahrur150@gmail.com, muhammadnor169@gmail.com, iswahyono@polije.ac.id, bekti.palupi@unej.ac.id, iistiqomah.rahmawati@unej.ac.id, jheldawikaamini@unej.ac.id

Keywords: sugarcane bagasse, magnetic activated carbon, optimization, adsorption, ultrasound.

Abstract

This study focused on the optimization of methylene blue removal on a magnetic activated carbon from the carbon-rich agro-industrial residue, sugarcane bagasse, synthesized by microwave method. The adsorption process was assisted by ultrasound. The magnetic sugarcane bagasse activated carbon (MSB) was characterized by FTIR and SEM-EDX. Based on FTIR results, the functional groups found in magnetic sugarcane bagasse activated carbon are , and O . The SEM results show that MSB is porous with a rough surface. In addition, EDX data found the presence of three main elements, namely C, O, and Fe. Response Surface Methodology (RSM) BoxBehnken Design was applied to analyze the effects of three parameters, including adsorbent dosage , ultrasonic power , and contact time . The obtained optimum conditions of the adsorption process were the sonication power of 155.65 W , the adsorbent dosage of , and the sonication time of 57.81 minutes. The results indicated that the parameters of adsorbent dosage, ultrasonic power, and contact time influenced the response ( and methylene blue removal).

Introduction

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Organic dyes are one of the most significant pollutants in wastewater released by the textile and other manufacturing industries. Methylene blue (MB), a cationic dye, has been used widely in textile industries. However, it is challenging to remove MB from wastewater due to its complex structure. Untreated organic dyes create not only aesthetic problems but also have a negative impact on health, such as carcinogenesis, teratogenesis, and mutagenesis [1]. It is mandatory to use effective treatment methods to remove water contamination before releasing them into water streams. Different wastewater treatment methods are adopted for removing textile dyes, such as biological, chemical, physical, and hybrid treatments. Among several wastewater treatment methods, the adsorption process is a proper mechanism to remove dyes from wastewater. Purification or contaminants removal utilized adsorbent, small porous materials, which can attract target contaminants [2].

Activated carbon is a part of carbon-based adsorbent. Biomass, biomass waste, or industrial waste as carbon sources of activated carbon were selected due to the availability of raw materials and simple fabrication methods. The surface area, the pore structure, the particle size of carbon, the surface acidity, and the functionality of activated carbon influenced the adsorption capacity and interaction between MB and activated carbon. Fabrication of activated carbon is divided into carbonization and activation, which generally utilize thermal activation or chemical activation to promote surface functionality [3]. As mentioned later, the fabrication of activated carbon is generally conducted at relatively high temperatures in conventional convective or conductive heating systems. More extended time to achieve the activation process is the disadvantage of conventional heating systems. There is also a significant risk of overheating, which leads to the complete combustion of activated
carbon[4]. Alternatively, microwave heating has the advantages of short heating time, low energy consumption, accurate temperature control, and small equipment size. Microwave-assisted activation can enhance the impregnation process [5].

The spent activated carbon has to be separated from the solutions. was used as a precursor to producing magnetic activated carbon. Combining iron oxide and activated carbon will generate magnetic separation by an external applied magnetic field [6]. Many researchers have tried mechanical aid such as ultrasound to improve adsorption capacity. The advantages of ultrasoundassisted adsorption are cavitation formation. The growth and collapse of cavities release energy. This energy is higher than conventional processes like heat or agitation. This cavitation is responsible for increasing the adsorbate mass transfer to the adsorbent's surface [7]. Ultrasound-assisted adsorption has been conducted to remove fenoterol [8], pyridine [9], dyes [10], heavy metal [11] [12], dinitrophenol [13], levofloxacin [7], and other contaminants. Many studies reported that ultrasound could improve adsorption efficiency and gained interest due to its advantages over batch adsorption [14]. Adsorption efficiency could be measured and analyzed by and % removal value. is related to how many milligrams of adsorbate are adsorbed by the adsorbents. % Removal is proportional to concentration reduction of final and initial concentration of methylene blue solution after the adsorption process.

This study aimed to evaluate the adsorption ability of magnetic sugarcane bagasse activated carbon (MSB) using the ultrasound-assisted adsorption method. This research focuses on how the process parameters, namely adsorbent dosage, contact time, and ultrasound power, affect the efficiency and adsorption capacity. The effects of the process conditions and the optimization of adsorption process were measured with Design Expert software under RSM. Response surface methodology (RSM) is a combination of mathematical and statistical methods to analyze various independent variables effects on a dependent variable. RSM can minimize the number of experiments including chemicals usage, time, cost, and expensive characterization [15].

Experimental Section

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Materials. The source of MSB was sugarcane bagasse that provided from local micro enterprises (Jember, Indonesian). Methylene blue was purchased from Merck (Germany). MB stock solution was prepared by dissolving appropriate amount of MB in deionized water. (Loba Chemie) was used for the precursor of magnetic activated carbon. All chemicals were reagent grade.
Preparation of MSB. Fabrication of MSB refers to previous studies from Jiang et al. [4] Sugarcane bagasse is washed with deionized water to remove dirt particles from the surface. After drying moisture content) it was screened to 80 mesh. MSB precursors were prepared by mixing SB and with a mass ratio of in a mortar for 20 minutes. Then, it was calcined for 150 seconds in a microwave oven with a microwave input power of 800 W , a frequency of 2450 MHz . When the calcination is complete, the calcined material is rinsed repeatedly with distilled water until it reaches a neutral pH and then dried. The composite obtained by this microwave heating method is referred to as Magnetic Sugarcane Bagasse Activated Carbon (MSB).
Characterization of MSB. The morphology and elemental composition of MSB were investigated using Scanning Electron Microscope-Energy Dispersive X-ray spectroscopy (SEM-EDX). The functional groups present in the adsorbents were analyzed using Fourier Transform Infrared (FTIR) spectroscopy within the range of .
Design expert software. In this study, three parameters were adsorbent dosage (A), ultrasonic power (B), and contact time (C). All the parameters were studied with three levels. Run data has been processed in Design Expert software using the BBD (Box-Behnken Design) method. BBD (BoxBehnken Design) was chosen to determine the unknown optimal point of the MB adsorption process by MSB. Table 1 shows the ranges of the experimental values of independent variables. Table 2 shows the adsorption results of MB in the 17 runs done. Equilibrium concentration and percent removal was set as the system response (dependent variable).

Table 1. Three-coded level for the variable process parameters used.

Terms | Design variables | Units | Coded levels
|  |  | -1 | 0 | 1
A | Adsorbent dosage | [mg/l] | 50 | 75 | 100
B | Power | [W] | 100 | 150 | 200
C | Contact time | [min] | 30 | 45 | 60

Ultrasound-assisted adsorption. The ultrasound-assisted adsorption was conducted in the erlenmeyer flask ( 250 ml ). The first experiment determined the optimum conditions (adsorbent dosage, contact time, and power). The operating range is: Adsorbent dosage ( ), contact/sonication time ( ), power ( Watt). The sample solution was centrifuged, and the effluent solutions was record with a UV-Vis (Ultra Violet-Visible) Spectrophotometer at a wavelength of 665 nm . The quantity of adsorbed dyes in each unit mass of the adsorbent ( ) was calculated by equation 1 .

represents the initial concentration of the dye in , and represents the equilibrium concentration of the dye in . V stands for the volume of the solutions (l), and W represents the mass in grams of the adsorbent. Percent removal was calculated by equation 2.

represents the initial concentration of the dye in and stands for concentration after time .

Results and Discussion

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Characterization of MSB.Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy (SEM-EDX).

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Magnetic Sugarcane Bagasse Activated Carbon (MSB) samples were characterized using SEM-EDX at the Integrated Laboratory of Diponegoro University. Fig. 1 shows the morphology of MSB at different magnifications. The MSB exhibits rough surface with small number of pores. Pore structure can affect the surface area of activated carbon. The smaller the resulting pore size, the larger the surface area obtained, so that activated carbon can optimally adsorb methylene blue. Characterization was performed using scanning electron microscopy coupled with X-ray spectroscopy via energy dispersive (EDX), which allows qualitative determination of chemical composition. The results show that the elements contained in the adsorbent are , and elements. The element Fe indicates that iron oxide compounds are effectively immobilized on activated carbon.

Fig. 1 SEM images of MSB with different magnification: a. 250; b. 500; c. 750; d. 1000

Fig. 1. SEM images of MSB with different magnification: a. 250; b. 500; c. 750; d. 1000

Fig. 2 a. EDX spectra of MSB; b. Magnetic response of MSB to an external magnetic field

Fig. 2. a. EDX spectra of MSB; b. Magnetic response of MSB to an external magnetic field

The immobilized iron oxide on activated carbon can be verified in Fig. 2b. MSB could be separated by an external magnetic field. Sugarcane bagasse or activated carbon do not attracted by the magnetic
field. However, using microwave-assisted activation and as precursor, activated carbon has magnetic response.

Fourier Transform Infrared Spectroscopy (FTIR). Fig. 3 shows the results of the FTIR spectrum of MSB. The broadband appears in the absorption area of , indicating the presence of an O-H (Hydroxyl) functional group [16]. The absorption peaks observed at correspond to the presence of the functional group of the aromatic ring. The band located in the is assigned to the presence of the stretching vibration [4]. The sharp peak appears in the absorption area of , indicating the presence of bending vibration of or [17]. The functional groups found in magnetic sugarcane bagasse activated carbon are , and .
RSM Approach and Statistical Analysis. Table 2 shows the 17 data which contain the process parameters and the response (qe and % removal). The responses varied between 1-3 mg/g for qe and for % removal. In this study, obtained R square value is equal to 0.9605 for qe and 0.9701 for % removal, near the value of 1. This shows the dye removal variability could be explained by the model [18]. The quadratic polynomial model was obtained for the responses:

which, A represents adsorbent dosage ( ); B stands for ultrasound power (Watt), and C represents contact time (minute).

Fig. 3 FTIR result of MSB

Fig. 3. FTIR result of MSB

The equation shows that increasing process parameters (MSB dosage, power, and contact time) promotes responses. Compared to the other two independent variables, the coefficient of the ultrasound power is the highest ( 0.5397 ), showing that ultrasound power has the most significant influence on the quantity of adsorbed dyes in each unit mass of the adsorbent (qe). In comparison, % removal is influenced by adsorbent dosage (8.53).

Table 2. Adsorption results (relationship of process parameters to the response

Run | A: Adsorbent Dosage [mg/l] | B: Power [Watt] | C: Time [min] | Qe [mg/g] | % Removal
1 | 75 | 150 | 45 | 2.29 | 17.19
2 | 100 | 150 | 60 | 2.96 | 29.63
3 | 75 | 200 | 30 | 2.85 | 21.34
4 | 75 | 150 | 45 | 2.35 | 17.65
5 | 50 | 150 | 60 | 3.35 | 16.73
6 | 75 | 100 | 60 | 2.35 | 17.65
7 | 100 | 200 | 45 | 2.78 | 27.79
8 | 75 | 150 | 45 | 1.86 | 13.96
9 | 100 | 100 | 45 | 2.73 | 27.33
10 | 100 | 150 | 30 | 3.06 | 30.55
11 | 75 | 150 | 45 | 2.11 | 15.81
12 | 50 | 200 | 45 | 3.25 | 16.27
13 | 75 | 150 | 45 | 2.29 | 17.19
14 | 50 | 100 | 45 | 1.50 | 7.51
15 | 75 | 200 | 60 | 3.15 | 23.64
16 | 75 | 100 | 30 | 1.12 | 8.43
17 | 50 | 150 | 30 | 1.32 | 6.59

The significance of the BBD model design was determined by variance analysis. Table 3 and Table 4 show the ANOVA results for MB adsorption. Based on the results of ANOVA, p-value ensures that the second order polynomial model is significant. A non-significant lack-of-fit test (low F -value and P -value ) indicates that the model is well validated for MB adsorption [19]. Three process parameters (A, B, C) were found to be significant. The parameters with p -value were assumed to be significant.

Table 3. ANOVA results for the BBD model of MB adsorption by MSB (response : qe)

Source | Sum of Squares | df | Mean Square | F-value | P-value |
Model | 7.09 | 9 | 0.7876 | 18.90 | 0.0004 | significant
A-Dosage | 0.5565 | 1 | 0.5565 | 13.35 | 0.0081 |
B-Power | 2.33 | 1 | 2.33 | 55.93 | 0.0001 |
C-Time | 1.51 | 1 | 1.51 | 36.16 | 0.0005 |
AB | 0.7276 | 1 | 0.7276 | 17.46 | 0.0041 |
AC | 1.12 | 1 | 1.12 | 26.96 | 0.0013 |
BC | 0.2128 | 1 | 0.2128 | 5.11 | 0.0583 |
A² | 0.4975 | 1 | 0.4975 | 11.94 | 0.0106 |
B² | 0.0074 | 1 | 0.0074 | 0.1775 | 0.6861 |
C² | 0.0890 | 1 | 0.0890 | 2.14 | 0.1872 |
Residual | 0.2917 | 7 | 0.0417 |  |  |
Lack of Fit | 0.1299 | 3 | 0.0433 | 1.07 | 0.4558 | not significant
Pure Error | 0.1619 | 4 | 0.0405 |  |  |
Cor Total | 7.38 | 16 |  |  |  |
Std. Dev. | 0.2041 |  | R² | 0.9605 |  |
Mean | 2.43 |  | Adjusted R² | 0.9097 |  |
C.V. % | 8.40 |  | Predicted R² | 0.6842 |  |

Table 4. ANOVA results for the BBD model of MB adsorption by MSB (response: % removal)

Source | Sum of Squares | df | Mean Square | F-value | p-value |
Model | 847.38 | 9 | 94.15 | 26.06 | 0.0001 | significant
A-Dosage | 581.41 | 1 | 581.41 | 160.94 | < 0.0001 |
B-Power | 98.84 | 1 | 98.84 | 27.36 | 0.0012 |
C-Time | 53.77 | 1 | 53.77 | 14.88 | 0.0062 |
AB | 17.22 | 1 | 17.22 | 4.77 | 0.0653 |
AC | 30.58 | 1 | 30.58 | 8.47 | 0.0227 |
BC | 11.97 | 1 | 11.97 | 3.31 | 0.1115 |
A² | 44.13 | 1 | 44.13 | 12.22 | 0.0101 |
B² | 0.0684 | 1 | 0.0684 | 0.0189 | 0.8944 |
C² | 6.87 | 1 | 6.87 | 1.90 | 0.2103 |
Residual | 25.29 | 7 | 3.61 |  |  |
Lack of Fit | 16.18 | 3 | 5.39 | 2.37 | 0.2116 | not significant
Pure Error | 9.10 | 4 | 2.28 |  |  |
Std. Dev. | 1.90 |  | R² | 0.9710 |  |
Mean | 18.54 |  | Adjusted R² | 0.9338 |  |
C.V. % | 10.25 |  | Predicted R² | 0.6870 |  |

The coefficient of variation (CV) has an acceptable limit between 0.5 and [14]. According to the results, C.V. % on qe response and C.V. % on % removal response . The lower the value, are more reproducible. The optimum conditions for MB on MSB were determined using this model, and the results are adsorbent dosage , ultrasound power 155.65 W , and contact time 57.81 min . The supposed adsorption capacity is and % removal .

Fig. 4 shows the impacts of two variables: two dimensional contour. Fig. indicated the combined effects of adsorbent dosage-ultrasound power, dosage-time, and power-time. It can be concluded that both responses increase as the adsorbent dosage and contact time rises. The plot showed that the higher the adsorbent dosage, the greater the gain of Qe and % removal. A higher adsorbent dosage increases the availability of the adsorbent surface area, thereby increasing the removal of methylene blue.

Fig. 4. Contour plots for the effects of: a. dosage-power; b. dosage-time; c. power-time

Fig. 4. Contour plots for the effects of: a. dosage-power; b. dosage-time; c. power-time

Conclusions

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The morphology of MSB exhibits rough surface with small number of pores. The EDX results show that the elements contained in the adsorbent are , and elements. The functional groups found in magnetic sugarcane bagasse activated carbon are , and Fe O. The element Fe in SEM and FTIR results, at once magnetic response of MSB to an external magnetic field have proved that iron oxide compounds are effectively immobilized on activated carbon. The purpose of this study was to evaluate various process parameters on the adsorption capacity MB by MSB. Design expert software was used in this research to find out the optimum condition and analyze the effects of three parameters. The obtained optimum conditions of the adsorption process were the sonication power of 155.65 W , the adsorbent dosage of , and the sonication time of 57,81 minutes.

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The original version of this paper is available on https://www.scientific.net/EC.2.43.pdf

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 53-64

doi: 10.4028/p-1t2bpt

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

Submitted:
2022-08-12

Revised:
2022-09-12

Accepted:
2022-09-28

Online:
2023-05-16

LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

The original version of this paper is available on https://www.scientific.net/EC.2.53.pdf

Jenny N.M.Soetedjo , Michael Osborn , Lucas Adriel Setiawan , Farhan Azka Fadillah , Felicia Tjandra , Kevin Frendy Mulya , Nehemia Rariel E. , Tedi Hudaya

Department of Chemical Engineering, Parahyangan Catholic University, JI. Ciumbuleuit 94, Bandung, 40141, Indonesia

*Corresponding author: t.hudaya@unpar.ac.id, ªjenny.novianti@unpar.ac.id, michaelosborn7974@gmail.com, lucasadrielsetiawan@gmail.com, kevinfren97@gmail.com, nehemiaevan10@gmail.com

Keywords: LDPE, cracking, bentonite, waste to energy, plastic to oil, kerosene

Abstract

Plastic industry development has increased the amount of plastic waste, including LDPE plastic film, therefore LDPE waste processing becomes essential, such as thermal or catalytic cracking. Cracking is the breakdown of complex hydrocarbons into simple and commercial hydrocarbons ( ). The catalytic cracking is preferred due to lower temperatures, which is 200 instead of . In this study, catalyst selection, acid impregnation of catalyst, catalyst loading (wt%), -gas-purging, feed-to-solvent weight-ratio, temperature, and reaction time were studied to determine the most suitable process condition to obtain the highest liquid fraction. In this study, the catalytic cracking was conducted at 20 bar with kerosene as solvent, with and without -gas-purging at several temperatures ( 265 and ), solvent-to-feed weight-ratios ( and ), catalyst types (bentonite, and ZSM-5), catalyst loading ( ) ( ; ), and reaction time ( hours). The best results were with -gas-purging using -bentonite in (5:1) solvent-to-feed weight-ratio for 1 hour at produced of liquid fraction and without -gas-purging at produced of liquid fraction, indicating the possibility of -gas-purging exclusion in future studies. Additionally, this study has promoted bentonite as a potentially viable catalyst for LDPE plastic waste catalytic cracking.

Introduction

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Plastic pollution has become one of the world's major problems. A World Bank study found that the world's population generates 1.3 billion metric ton of waste every year, with plastic being one of the largest contributors [1]. Human life is closely related to the use and production of plastics and rapid population growth is a problem. As can be seen in the report "Evaluating Scenarios Toward Zero Plastic Pollution", the plastic production in 1950 was 2.3 million metric ton, which soared to 448 million metric ton in 2015 and is projected to reach up to 1.3 billion metric ton by 2040 [2]. The increase in plastic pollution occurred because of single-use culture, where plastic is often used once and then thrown away and is not managed properly. According to the publication by the United Nations Environment Program [3], it was found that of the world's plastic pollution consists of single-use plastics. Examples of single-use plastics include plastic wrap, plastic bottles, plastic bags, plastic straws, and plastic cutlery [3]. Single-use plastics are generally composed of LDPE (low density polyethylene) and it is estimated that the world's population use one to five trillion plastic bags [3,4].

There are many known methods for processing LDPE, such as land filling, incineration, mechanical recycling, and thermo-chemical processes. Landfilling is the most common waste management strategy in many countries. Plastic waste landfilling is not favoured today due to quantities of toxic chemicals and their potential for leaching at landfill sites into groundwater which is an environmental and potential health issue [5]. Incineration processing produces toxic gases that pollutes the environment [5]. Mechanical recycling of plastics processes plastics waste into secondary raw material or products, however mechanical recycling itself will lead to downcycling
of the plastic waste due to continual recycling. Plastics recycled this way will lose mechanical integrity that renders it unfit for application [5]. Thermo-chemical processes, such as cracking and gasification pose great potential due to its ability to upcycle the plastic waste. Gasification and cracking are similar, as they involve heating to produce short chain hydrocarbons, however gasification requires higher temperatures ( ) and cracking, thermal or catalytic, does not require such temperatures. The production of liquid products is an advantage of cracking, as gasification mainly produces gaseous products that also has less calorific value due to formation of and CO , whereas cracking does not suffer from that problem due to having a small amount of oxygen present. [5, 6]. Cracking is the breaking of complex hydrocarbon chains into simple hydrocarbons. Cracking works in conditions without oxygen to gas and liquid products as well as solid (char). Cracking reaction consists of two main mechanisms, which are primary cracking and secondary cracking. Primary cracking produces hydrocarbon products with short chains in the form of oil, gas, and char, while secondary cracking produces hydrocarbons with shorter and lighter chains than primary cracking [7]. A scheme of cracking reaction pathways can be seen in Fig. 1.

Fig. 1: Illustration of scheme of cracking reaction pathways [8]

Fig. 1. Illustration of scheme of cracking reaction pathways [8]

Thermal cracking is the breaking of complex hydrocarbon chains into simple hydrocarbons using heat. Thermal cracking generally produces hydrocarbon products that vary between . Thermal cracking is an endothermic process, the operating conditions of thermal cracking is usually in the range of . Catalytic cracking is the breaking of complex hydrocarbon chains into simple hydrocarbons with the aid of a catalyst. Catalytic cracking has an advantage over thermal cracking since it can be carried out at lower operating temperatures. Some studies states that catalytic cracking can already begin to take place at while thermal cracking at temperatures of to get a significant fraction [10]. Catalytic cracking is also more selective in contrast to thermal cracking which gives hydrocarbon products in the range of . Products obtained from the catalytic cracking have better quality, due to the increased levels of cyclic and aromatic components, hence have a better commercial value [5]. Catalytic cracking products are dependent on experiment temperature, catalyst used, catalyst loading ( ), the type of feed (plastic type), and reaction time [10].

Catalytic cracking using various catalysts has been conducted to determine the effect of ratio of the catalyst to the fraction of catalytic cracking products, in that lesser value of ratio yielded a greater gaseous product than liquid product due to greater amounts of the end chain cracking occurring [10, 12]. Acidity affects the type of cracking that occurs during primary cracking. Random cracking tends to occur at sites with moderate or weak acidity resulting in liquid products ( ), while high acid strength promotes end chain cracking resulting in gaseous products . Catalyst such as , and bentonite have been studied and it was found that these catalysts provide good liquid product fractions, however these studies were conducted using variations of a fixed-bed reactor system. ZSM-5 was found to be able to produce a large amount of liquid product ( ) at [13]. Although this process took 3 hours, produced a large amount of liquid product ( ) at [14]. Bentonite was also found to be able to produce a large amount of liquid product ( ) at [15].

Temperature also affects the fraction from the cracking process. At low temperatures, catalytic cracking tends to produce longer chain products, or waxy products, while increasing operating temperatures results in more cracking, i.e. short chain products [9]. However, the increase of operating temperature does not result in more liquid products. Cracking activity is increased at higher temperatures, therefore producing fractions with lower number of hydrocarbon chains.

According to other studies, it was found that if the operating temperature is too high, the gaseous fraction would increase and the liquid fraction would decrease [16]. This result is also supported by other studies, in which it was found that a decrease in the conversion of LDPE to liquid fraction after the temperature was raised, namely from the conversion result of to being raised above [17].

Reaction time was studied to examine the effect of time spent at a reaction temperature on cracking products. Previous studies on reaction time effect concluded that longer reaction time would increase the activity of secondary cracking, resulting in more short chain products where the gaseous fraction would increase and the liquid fraction would decrease [8]. Studies on cracking at a peak temperature of discovered a decrease of liquid products, with reaction time of 60 minutes yielded of liquid products and at reaction time of 90 minutes yielded of liquid products. The study in the same literature at lower temperatures of discovered similar results [8, 18].

A study on dissolution of LDPE in cyclohexane and liquid paraffin in thermal cracking of LDPE has determined that cracking using solvent has advantages over cracking without solvent. Cracking of dissolved LDPE was found to occur at much lower temperatures instead of 400 due to lower viscosities resulting in better mass and heat transfer [11]. Although numerous studies have been done in regards to catalytic cracking of LDPE, studies regarding the effects of dissolution of LDPE during catalytic cracking are scarce, resulting in few studies available.

Previous studies have been conducted in regards to catalytic cracking of LDPE waste. It was determined that catalytic cracking products are dependent on experiment temperature, catalyst used, catalyst loading (wt%), the type of feed (plastic type), and reaction time [10]. The aim of this study was to convert the waste plastics to oil fraction products for use as a hydrocarbon fuel oil and to discover options in cost reduction for catalytic cracking in a batch, pressurised autoclave reactor. Variations in this study include catalyst types (bentonite, and ZSM-5), the effect of acid impregnation of catalyst, catalyst loading (wt%) ( ), the effect of -gas-purging, solvent-to-feed weight-ratios ( and ), temperatures ( and ), and reaction time ( hours). The cracking reaction in this study was not carried out at temperatures due to concerns that higher temperatures would support the production of gas in large quantities and excessive evaporation of the solvent being used (kerosene normal boiling point starts at ) [19]. Variations such as -gas-purging prior to catalytic cracking has not been conducted, to the writer's knowledge, and the potential exclusion of -gas-purging prior to catalytic cracking would lead to further cost reduction, hence increasing its economic feasibility. Although the use of solvents during catalytic cracking has not been widely conducted, the use of solvent in catalytic cracking may lead to further reduction in temperature conditions due to better mass and heat transfer.

Materials and Methodology

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Materials. LDPE was procured from collected LDPE waste in Parahyangan Catholic University, Bandung, Indonesia. Then, it was cut to roughly to fit the reactor. Kerosene was procured from CHEMICALPRO-SMT. Bentonite (purity of ) was procured from PT. Brataco. ZSM-5 (purity of 96.5-97.0 wt%) was procured from Sigma Aldrich. (purity of 99.5wt%) was procured from HiMedia Laboratories Pvt. Ltd. Acid impregnated catalysts were prepared by submerging ZSM-5, Bentonite, and in solution, heated for 1 hour with continuous stirring and then stored overnight at room temperature. It was then filtered and washed with distilled water until the pH was neutral and dried at for 6 hours.
Methodology. The reactor used for this work was a batch pressurised autoclave reactor in Parahyangan Catholic University, Bandung, Indonesia, illustrated in Fig. 2. A rubber seal was inserted into the top of the reactor to prevent leakage of the reactor during the experiments. Kerosene was then poured into the reactor according to the ratio desired. LDPE waste and the desired catalyst was fed to the reactor according to experiment variations. The reactor was then preheated to to melt the LDPE, based on the melting point of LDPE. A magnetic stirrer was also
placed inside the autoclave reactor and was turned on at the start of pre-heating to dissolve the LDPE feed. Then, if variations required purging process, purging with -gas was done to remove oxygen to create an oxygen free condition. Pressure inside the reactor was then increased to 20 bar to prevent excess evaporation of the kerosene solvent. Finally, the reactor temperature was increased according to temperature variations for the duration of the experiment variations.

Fig. 2: Illustration of batch pressurised autoclave reactor from Parahyangan Catholic University, Bandung, Indonesia

Fig. 2. Illustration of batch pressurised autoclave reactor from Parahyangan Catholic University, Bandung, Indonesia

Analysis

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The liquid product was collected and separated from the solid product using a Buchner funnel. The liquid product was then weighed to acquire the weight of the liquid product and liquid fraction was calculated based on Eq. 1. The separated solid product was then weighed to acquire the weight of the solid product and solid fraction was calculated based on Eq. 2. The gaseous product fraction was calculated based on Eq. 3.

Further analysis was conducted on the liquid product, such as calorific value analysis, viscosity analysis, density analysis, and GC-MS (Gas Chromatography - Mass Spectrometry) analysis. Analysis of liquid product density was conducted using a pycnometer and density was calculated based on Eq. 4. Analysis of liquid product viscosity was conducted using an Ostwald viscometer and a stopwatch to measure the flow time of the liquid product and viscosity was calculated based on Eq. 5. Calorific value analysis of liquid product was conducted using a bomb calorimeter from Bandung Institute of Technology, Bandung, Indonesia. GC-MS analysis of liquid product was conducted in Bandung Institute of Technology, Bandung, Indonesia.

Results and Discussion

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Effect of reaction time variations on catalytic cracking of LDPE. Fig. 3 showed that using ZSM at for two hours in this experiment gave the highest liquid fraction ( ) compared to one hour ( ) and a reaction time of three hours ( ). Fig. 3 also showed that reaction time of 3 hours yielded a slightly larger amount of gas product than the results of 1 hour and 2 hours of reaction time. This is due to increased activity of secondary cracking process on LDPE at longer reaction times, where the secondary cracking increased the production of gas products [7]. These results are also supported by various studies, where similar results were found [8, 18]. Although reaction time of two hours in this experiment gave the highest liquid fraction compared to a reaction time of one hour and a reaction time of three hours, however, the difference in the fraction of liquid products produced at one hour of reaction time when compared to the results of two hours of reaction time and three hours of reaction time was not much different. These results indicated that the one hour of reaction time was sufficient reaction time for LDPE catalytic cracking. One hour of reaction time is also considered to be more economical because the difference of liquid fraction between one hour of reaction time and two hours of reaction time is only .

Fig. 3: Product fraction using ZSM-5 (9wt%) at at various reaction time. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Fig. 3. Product fraction using ZSM-5 (9wt%) at at various reaction time. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Effect of catalyst loading (wt%) variations on catalytic cracking of LDPE. Fig. 4 showed the product fraction at using ZSM-5 catalyst at for 2 hours and 3 hours of reaction time. From Fig. 4 (a), the liquid product fraction from catalytic cracking of LDPE conducted for 3 hours using were similar. However, it can be seen from Fig. 4 (b) that the liquid product fraction from catalytic cracking of LDPE conducted for 2 hours using catalyst was , which was less than the liquid product fraction when using catalyst (60.1wt%). This result suggested that at least may be required to produce more liquid fraction. This is due to the increase in catalyst loading ( ) that would result in the increase of the liquid products due to increased amounts of active acid sites, where the cracking process occurs [20]. However, when viewed from the difference in liquid products fraction obtained from catalytic cracking conducted for 3 hours using , it is around and it can be said that there is no significant difference. Thus, the catalyst loading was enough to facilitate the LDPE cracking since catalytic action at active sites was within a cycle.

Fig. 4: Product fraction at using ZSM-5 at various catalyst loadings ( ) with reaction times variations as follows: (a) 3 hours; (b) 2 hours. ( - Liquid fraction; - Solid fraction; Gaseous fraction)

Fig. 4. Product fraction at using ZSM-5 at various catalyst loadings ( ) with reaction times variations as follows: (a) 3 hours; (b) 2 hours. ( - Liquid fraction; - Solid fraction; Gaseous fraction)

Effect of catalyst selection on catalytic cracking of LDPE. Fig. 5 showed that the most liquid product was obtained when ZSM-5 was used. However, the fraction of liquid products among the three types of catalysts can be said to be insignificant, this may be due to other catalyst characteristics aside from number of acid sites in the catalyst.

Fig. 5: Product fraction at using various catalyst with reaction times and catalyst variations as follows: (a) 3 hours, ; (b) 2 hours, . (- Liquid fraction; - Solid fraction; - Gaseous fraction)

Fig. 5. Product fraction at using various catalyst with reaction times and catalyst variations as follows: (a) 3 hours, ; (b) 2 hours, . (- Liquid fraction; - Solid fraction; - Gaseous fraction)

High fraction of liquid products using the ZSM-5 catalyst may be due to ZSM-5 has a high acidity level, ZSM-5 catalyst has Bronsted acid active centers which is the site of cracking as an donor. Bronsted acid is the site of cracking as an donor, which plays an important role in catalytic cracking. The catalyst functions at the initiation step of the cracking process of hydrocarbons, where in the initiation step, Bronsted acid site on the catalyst function to donate ions which forms carbenium ions, then in the propagation step there will be a breaking of the chain bonds ( -scission) which form a shorter carbenium ion and also a shorter alkenes [7, 13].

Table 1. Characteristics of ZSM-5, , bentonite catalysts [21, 22, 23].

Catalyst Properties | ZSM-5 | SiO₂ | Bentonite
Bronsted Acid Sites [μmol/g] | 201.0 | 3.6 | 10.2
Lewis Acid Sites [μmol/g] | 65.0 | 35.0 | 59.4
Pore Diameter [nm] | 4.2 | 3.5 | 7.0

Insignificant difference in the liquid product fraction could be due pore size, which would also affect the activity of cracking [23,24]. Characteristics of ZSM-5, , bentonite catalysts can be seen in Table 1. The pore size gives catalyst feature of shape selectivity, where only small enough molecules can enter the pores. Primary cracking is done in the macroporous surface and secondary cracking is continued in the micropores [20]. The carbon chains of the polymer that can enter the pores are carbon chains that are shorter or smaller than the pores of the catalyst, therefore not all of
the active acid centers in the catalyst could be accessed and make these insignificant differences from the results obtained from the three types of catalysts used in this study [21, 22, 23]. From Fig. 5, the most liquid product was obtained when ZSM-5 catalyst was used. However, considering that the fraction of the liquid product was not too different and bentonite was much cheaper, the use of bentonite catalyst from an economic point of view was more desirable.

Effect of Acid Impregnation of Catalyst on Catalytic Cracking of LDPE. Fig. 6 showed the liquid yield at , 2 hours of contact time, and catalyst at various catalyst acidity variations for , bentonite, and ZSM-5. At a temperature of after acidification of the catalyst, the yield obtained decreased significantly in (from to ), bentonite (from to ), and ZSM-5 (from to ). The decrease in the yield of liquid products could be due to the increase in the number of active acid centers after acid impregnation resulting in more cracking activity that cracked the liquid product into gas product [25]. Although acid impregnation would increase the cracking activity, it can be seen in Fig. 6 that the yield of liquid product decreased and gas products increased on each type of catalyst due to more cracking activity. Literatures from previous experiments support these results, where acid strength would affect the type of cracking that occurs during primary cracking. Random cracking would tend to occur at sites with moderate or weak acidity resulting in more liquid products ( ), while at sites with high acid strength would lead to end chain cracking which produces gas products . From these results, it can be concluded that the acid impregnated catalyst does not necessarily give better results in obtaining the desired liquid product.

Fig. 6: Product fraction at , 2 hours contact time, and catalyst at various catalyst acidity with catalyst variations as follows: (a) ; (b) ZSM-5; (c) Bentonite. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Fig. 6. Product fraction at , 2 hours contact time, and catalyst at various catalyst acidity with catalyst variations as follows: (a) ; (b) ZSM-5; (c) Bentonite. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Effect of -gas-purging variations on catalytic cracking of LDPE. Fig. 7 showed that at solvent-to-feed weight-ratios ( ), , and without -gas-purging, liquid product fraction was and at solvent-to-feed weight-ratios , and without -gas-purging liquid product fraction was . The results showed that -gas-purging resulted in a higher liquid product fraction (wt%) at . However, without -gas-purging resulted in a higher liquid product fraction (wt%) at . These results might indicate an interaction between purging and temperature and -gas-purging exclusion could be possible for LDPE catalytic cracking. This would increase the economic competitiveness of the catalytic cracking of LDPE waste.

Fig. 7: Product fraction using bentonite ( ) during -gas-purging variations with solvent-to-feed ratios and temperatures as follows: (a) ; (b) ; (c) ; (d) , . (- Liquid fraction; - Solid fraction; - Gaseous fraction)

Fig. 7. Product fraction using bentonite ( ) during -gas-purging variations with solvent-to-feed ratios and temperatures as follows: (a) ; (b) ; (c) ; (d) , . (- Liquid fraction; - Solid fraction; - Gaseous fraction)

Effect of temperature variations on catalytic cracking of LDPE. Fig. 8 showed that without -gas-purging at both solvent-to-feed weight-ratios liquid fraction ( ) at was higher compared to . This study also showed that at cracking produced higher liquid fraction compared to , which produced higher gaseous fraction compared to . These results are in line with previous studies, in which higher temperatures resulted in more cracking, hence more gaseous fraction [5, 9, 17, 18].

Fig. 8: Product fraction without -gas-purging using bentonite ( ) for 1 hour at various temperatures with solvent-to-feed weight-ratios as follows: (a) 4:1; (b) 5:1. ( - Liquid fraction; Solid fraction; - Gaseous fraction)

Fig. 8. Product fraction without -gas-purging using bentonite ( ) for 1 hour at various temperatures with solvent-to-feed weight-ratios as follows: (a) 4:1; (b) 5:1. ( - Liquid fraction; Solid fraction; - Gaseous fraction)

It can be concluded that catalytic cracking done without -gas-purging, catalytic cracking at was better. However, in this study, it was found that the solid product produced from the catalytic cracking was in the form of residue (feedstock that has not yet been cracked) and small amount of char. Other studies that conducted TGA analysis without solvent suggested that conversion at was low [15, 26].

Effect of solvent-to-feed weight-ratios variations on catalytic cracking of LDPE. Fig. 9 showed the liquid product fraction ( ) in the variation of the solvent-to-feed weight-ratio ( ) was greater due to the effect of LDPE dissolution in kerosene solvent. According to other studies, dissolving LDPE in a solvent causes lower viscosity of the feed resulting in better mass and heat
transfer, helping the cracking reaction [11, 27, 28]. Dissolving LDPE in light hydrocarbon solvents, in this study, kerosene was used, causes lower viscosity of the feed. This act is usually called visbreaking. Studies suggest that visbreaking helps suppress the production of char products through the hydrogen transfer process [29].

Fig. 9: Product fraction using bentonite ( ) for 1 hour at various solvent-to-feed weightratios at , and without -gas-purging. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Fig. 9. Product fraction using bentonite ( ) for 1 hour at various solvent-to-feed weightratios at , and without -gas-purging. ( - Liquid fraction; - Solid fraction; - Gaseous fraction)

Dissolution of LDPE is not commonly carried out, but studies on the dissolution of other types of plastics has been carried out. The effect of solvent on PS (polystyrene) cracking, in which the results showed that the ideal solvent-to-feed weight-ratio for PS cracking is . In this study, variations in solvent-to-feed weight-ratio ( ) and ( ), it was found that the variation of obtained better results.

In this study, it was found that there was a of loss of kerosene during the catalytic cracking. Further research regarding the use of another solvent with higher boiling point could be done to prevent evaporative losses or addition of a condenser system to prevent excessive losses of the solvent and volatile liquid.

Analysis results for catalytic cracking of LDPE for one hour at , without purging, using bentonite , and solvent-to-feed weight-ratio (5:1). This variation was chosen due to high liquid product fraction at a lower temperature variation, short reaction time and the use cheap bentonite catalyst. The density and the viscosity of the liquid fraction is and poise, which are similar to diesel, which are roughly and in the range of poise. It was also found that the liquid fraction has a calorific value of which is similar to diesel, which is in the range of [31]. GC-MS and peak components analysis can be seen in Table 2. which showed that cracking has occurred, shown by the presence of 1,2,3-trimethylbenzene and 1,3-dimethylbenzene, which are aromatic compounds reported in another study on catalytic cracking of LDPE plastic waste [32]. These compounds are uncommon in kerosene, which are mostly n -paraffins ( ) and/or iso-paraffins ( ) along with cycloparaffins, and alkyl derivatives ( ). These components in kerosene include cyclohexanes, octanes, nonanes, decanes [19]. However, to better differentiate the compounds found in the solvent and product, GC-MS analysis should also be conducted for the solvent.

Table 2. GC-MS peak components results of liquid product fraction using bentonite catalyst at for 1 hour, without purging, and solvent-to-feed weight-ratio (5:1). *LDPE cracking products

Peak | R.Time | Area% | Height% | A/H | Name
1 | 2.5 | 2.3 | 3.6 | 1.7 | Cyclohexane, methyl- (CAS) Methylcyclohexane
2 | 3.0 | 2.3 | 2.8 | 2.2 | Cyclohexane, 1,3-dimethyl-, cis-
3 | 3.2 | 3.2 | 4.8 | 1.7 | Octane (CAS) n-Octane
4 | 3.8 | 2.2 | 2.7 | 2.1 | Cyclohexane, 1,1,3-trimethyl- (CAS) 1,1,3 Trimethylcyclohexane
5 | 4.2 | 3.7 | 4.0 | 2.4 | Octane, 2-methyl- (CAS) 2-Methyloctane
6 | 4.4 | 2.3 | 2.7 | 2.3 | Octane, 3-methyl-
7 | 4.4 | 3.0 | 3.8 | 2.1 | *Benzene, 1,3-dimethyl-
8 | 4.9 | 7.3 | 10.3 | 1.8 | Hexane, 2,4-dimethyl-
9 | 5.7 | 4.5 | 4.2 | 2.8 | Nonane, 3-methyl- (CAS) 3-Methylnonane
10 | 6.3 | 5.8 | 2.3 | 6.4 | trans-2-Dodecen-1-ol, trifluoroacetate
11 | 6.5 | 4.2 | 4.1 | 2.7 | Nonane, 2-methyl- (CAS) 2-Methylnonane
12 | 6.6 | 2.1 | 2.1 | 2.5 | Nonane, 3-methyl- (CAS) 3-Methylnonane
13 | 7.3 | 6.2 | 5.2 | 3.0 | *Benzene, 1,2,3-trimethyl- (CAS) 1,2,3-Trimethylbenzene
14 | 7.4 | 9.1 | 10.7 | 2.2 | Dodecane (CAS) n-Dodecane
15 | 8.0 | 8.7 | 8.3 | 2.7 | Decane, 4-methyl-
16 | 8.2 | 5.5 | 4.3 | 3.3 | *Octadecane, 1-chloro- (CAS) 1-Chlorooctadecane
17 | 8.3 | 4.5 | 4.0 | 2.9 | Decane 4-cyclohexyl-, 4-cyclohexyl- (CAS)
18 | 9.2 | 4.8 | 4.9 | 2.5 | Decane, 2-methyl- (CAS) 2-Methyldecane
19 | 9.4 | 4.3 | 4.1 | 2.7 | Decane, 3-methyl-
20 | 10.3 | 14.2 | 11.4 | 3.2 | Tridecane (CAS) n-Tridecane

Concluding Remarks

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This study has provided new insight regarding the reduction of process costs, in that -gaspurging exclusion could be possible for LDPE catalytic cracking. This study concluded that the best process condition without using -gas-purging to achieve the highest liquid fraction was bentonite in (5:1) solvent-to-feed weight-ratio for 1 hour at produced of liquid fraction. Additionally, this study has promoted bentonite as a potentially viable catalyst for LDPE plastic waste catalytic cracking. However, research using higher temperatures ( ) may need to be conducted in order to increase conversion of LDPE. From this study, there was a of loss of kerosene during the catalytic cracking, therefore the next step of this study is to fit a condenser system to combat the potential losses volatile liquid products at higher temperatures and evaporative losses of the solvent used. Furthermore, further research regarding the use of another solvent should be done due to evaporation of kerosene and for further cost reduction. A study regarding the deactivation of bentonite needs to be considered in order to optimize the use of bentonite. GC-MS analysis of the solvent used should be done to better differentiate product composition and the solvent composition

References

The original version of this paper is available on https://www.scientific.net/EC.2.53.pdf

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N. Tangri and M. Wilson, "Waste Gasification & Pyrolysis: High Risk, Low Yield Processes for Waste Management A Technology Risk Analysis," no. March, 2017.

F. Gao, "Pyrolysis of Waste Plastics into Fuels," University of Canterbury, 2010.

J. A. Onwudili, N. Insura, and P. T. Williams, "Journal of Analytical and Applied Pyrolysis Composition of products from the pyrolysis of polyethylene and polystyrene in a closed batch reactor: Effects of temperature and residence time," vol. 86, pp. 293-303, 2009.

R. Miandad et al., "Catalytic pyrolysis of plastic waste: Moving toward pyrolysis based biorefineries," Front. Energy Res., vol. 7, no. MAR, pp. 1-17, 2019.

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G. S. Kumar, V. R. Kumar, and G. Madras, "Continuous distribution kinetics for the thermal degradation of LDPE in solution," J. Appl. Polym. Sci., vol. 84, no. 4, pp. 681-690, 2002.

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S. L. Wong, T. A. Tuan Abdullah, N. Ngadi, A. Ahmad, and I. M. Inuwa, "Parametric study on catalytic cracking of LDPE to liquid fuel over ZSM-5 zeolite," Energy Convers. Manag., vol. 122, pp. 428-438, 2016.

J. Shah, M. R. Jan, F. Mabood, and F. Jabeen, "Catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problems," Energy Convers. Manag., vol. 51, no. 12, pp. 2791-2801, 2010.

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-2/978-3-0364-1307-5

Engineering Chemistry, ISSN: 2813-6535, Vol. 2, pp 65-74

doi: 10.4028/p-kx6jk5

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

Submitted:
2022-12-10

Revised:
2023-03-14

Accepted:
2023-03-18

Online:
2023-05-16

Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

The original version of this paper is available on https://www.scientific.net/EC.2.65.pdf

Fatma Darkbira , Oussama Nehar , Fatima Zohra Chiboub Fellah Thierry Roisne and Abdelghani Chiboub Fellah

Laboratoire de Chimie Inorganique et Environnement, Université de Tlemcen, BP 119, 13000 Tlemcen, Algeria

Centre de Diffractometrie X, UMR 6226 CNRS, Unit Sciences Chimiques de Rennes, Universite de Rennes I, 263 Avenue du General Leclerc, 35042 Rennes, France

Laboratoire de Valorisation des Ressources en Eau, Équipe de chimie de coordination, Université de Tlemcen, BP 119, 13000 Tlemcen, Algeria

fatimadd@hotmail.fr, oussamanehar@gmail.com, cfatema@yahoo.fr, thierry.roisnel@univrennes1.fr, chibabghani@yahoo

*corresponding author

Keywords: Mononuclear copper complexes, X-ray molecular structure, Schiff base complexes, Photocatalysis, Organic dyes

Abstract

The titled mononuclear complex with the formally tetradentate schiff base ligand, [N,N'-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropan-2-ol] has been synthesized and characterized using IR spectroscopy and elemental analysis. Cristal structure has been determined by XR diffraction that reveals the pseudo octahedral complex geometry and the use of hydroxo bridges between two neighbor units to form a 1D coordination polymer. The use of this complex as a catalyst for the degradation of two textile dyes: crystal violet (CV) and methylene blue , in the presence of the appropriate amount of and a UV light source has given very good results with yields exceeding 90% after 50 minutes.

Introduction

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Condensation reactions between carbonyl compounds and diamines have provided one of the most important and widely studied classes of chelating ligands. Schiff bases derived from aromatic or aliphatic diamine and phenolic aldehydes have proved to be the source of tetradentate ligands [13] for many transition metal complexes [4-6].

Depending on the intended application and area of interest, the formulas and structures of Schiff base compounds change. Indeed, we find homometallic complexes with different nuclearities, which depending on the size of the desired active sites, can be formed either with transition metals [7-8], or with larger cations, generally lanthanides [9]. In addition, hetero-metallic complexes are very diverse. They essentially come from the association of a 3d element with a 4f element [10-12], an alkaline earth metal [13] or an alkali metal [14]. These complexes in general are very popular because of their numerous catalytic [15-16], magnetic [17-19], and biological [20-26] properties. Photocatalysis is a field of chemistry that deals with chemical reactions that occur in the presence of light and photocatalysts [27-30]. This technique is effective in wastewater treatment and has helped a lot to effectively degrade organic pollutants such as textile dyes, especially since this technique is environmentally friendly and cost-effective. Several studies have recently been conducted in this direction [31-34].

The main objective of our work is to study the catalytic efficiency of a mononuclear copper Schiff base complex on the degradation of two industrial textile dyes, crystal violet (CV) and methylene blue (MB). We are specifically interested in homogeneous photocatalysis including photo-Fenton [35]

In this paper, we report the synthesis of the complex resulting from the reaction of a symmetric Schiff base ligand namely '-bis(2-hydroxy-3-méthoxybenzylidene)-1,3-diaminopropan-2-ol,
with nitrate copper and the characterization by IR spectroscopy and elemental analysis. Single crystal XR diffraction is used to establish the structure of resulted Cu (II) complex unit and the chain obtained in polymer form. The same complex was used as a catalyst in the photodegradation of Crystal Violet (CV) and Methylene Blue (MB) dyes, the results are very promising.

Fig. 1 Structure of (a) Crystal violet, (b) Methylene blue

Fig. 1. Structure of (a) Crystal violet, (b) Methylene blue

Experimental Section

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Materials. All starting materials; o-vanillin, Copper nitrate, Triethylamine (NEt3) including solvents Methanol (MeOH), Dimethylformamide (DMF) and Acetonitrile were of reagent grade and were used without further purifications.

Synthesis. A mixture of 1,3-diaminopropan-2-ol ( ) and o-vanillin ( ) in Methanol (MeOH) was stirred for 30 min . Copper nitrate ( ) was added followed by an excess of NEt3 dissolved in MeOH. The resulting green solution was mixed for 3 hours. It was then filtered and left to evaporate at room temperature. After 24 hours single green crystals suitable for X-ray Diffraction were formed on the surface of the solution.

Physical measurements. IR spectra were recorded on Perkin Elmer spectrum two spectrometer in the range with the samples as KBr pellets. UV-vis measures were recorded on JENWAY 7300 spectrometer.
Crystallography. X-ray diffraction data of the single crystal were collected at 150 K on an APEXII Bruker-AXS diffractometer equipped with a CCD-LDI-APEX2 detector using a radiation type Mo . The structure was solved by a dual-space algorithm using the SHELXT program [36], and further refined by full-matrix least-squares methods based on using SHELXL [37]. A final refinement on unique reflections and 139 converging parameters at for 1536 reflections observed with .

Results and Discussion

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IR. The free ligand spectrum, shows a band at which is shifted to for the complex indicating the participation of this group in coordination to the metal ion [39]. The shift of the phenolic band from in the ligand to in LCu confirms its role in the complex formation [40]. The bands between 3477 and were attributed to ; 3054 to to and at to stretching.

Elemental analysis. [C19 H22 Cu1 N2 O6] calculated: C 52,10; H 5,06; N 6,40 and found: C 51,96; H 5,16 and N 6,33.

X-ray Crystal structure. The title complex is a molecule in which a copper atom is linked by six atoms; two nitrogen and four oxygen; forming an octahedral geometry as shown in Fig. 2. Interatomic distances and angles are given in table 3. Equatorial bonds and
(2.014(3) and 1,9529(19) respectively are clearly shorter than apical ones Cu -O14 and Cu -O15 ( 2,572(2) and respectively). The chelating angles observed around the metal are a little different from and . The angle O14 Cu1 O15 (174.93 ) deviates slightly from . This difference in bond lengths and angles around the copper valence indicates its pseudo-octahedral geometry. The four atoms of the equatorial plane are coplanar because of symmetry with a dihedral angle close to zero.
The cupric ion is out of a plane (N11O1N11O1) at a distance of . The distance N11-O1 (via Cu1) is equal to 3.9669 (2) Å. The significant elongation along the O14 ... O15 axis (5.280 (3) can be attributed to the Jahn-Teller effect. Except for hydrogen, all other atoms were anisotropically refined. No disorder was observed in the asymmetric unit; Fig. 2; where the whole atoms occupation is .

Fig. 2 DIAMOND plot of LCu asymmetric unit. Thermal ellipsoids are drawn at the 30% probability level.

Fig. 2. DIAMOND plot of LCu asymmetric unit. Thermal ellipsoids are drawn at the 30% probability level.

Table 1 Crystallographic data of LCu

Chemical formula
C₁₉H₂₂CuN₂O₆

Mr
437.92

Crystal system, space group
Orthorhombic, Pnma

Temperature (K)
150

a, b, c (Å)
10.5990 (6), 22.8447 (14), 7.3098 (3)

V (Å³)
1769.93 (16)

Z
4

Radiation type
Mo Kα

μ (mm⁻¹)
1.28

Crystal size (mm)
0.32 × 0.27 × 0.11

Data collection

Diffractometer
APEXII Bruker-AXS

Absorption correction
Multi-scan
[Sheldrick, G.M. (2014). SADABS Bruker AXS Inc., Madison, Wisconsin, USA]

Tmin, Tmax
0.743, 0.869

No. of measured, independent and
observed [I > 2σ(I)] reflections
7252, 2038, 1536

Rint
0.032

(sin θ/λ)max (Å⁻¹)
0.649

Refinement

R[F² > 2σ(F²)], wR(F²), S
0.041, 0.111, 1.03

No. of reflections
2038

No. of parameters
139

Δρmax, Δρmin (e Å⁻³)
1.18, −0.59

This material forms a one-dimensional zigzag chain where the cupric ion in each asymmetric unit is linked to the adjacent unit through the aliphatic alcohol oxygen of the diamine to form a linear chain (Fig. 3). The distance between two successive copper atoms is . Selected lengths and angles are presented in table 3, respectively.

Fig. 3 Diamond plot showing one chain of LCu.

Fig. 3. Diamond plot showing one chain of LCu.

Each chain consists of the previously described copper entities associated through intermolecular hydrogen bonds established between neighboring asymmetric units in addition to dative bonds forming also one-dimensional chains. These connections take place between the oxygen atom of water molecule O15 and the methoxy oxygen atom O8 through H15, then the oxygen atom of the alcohol O14 and the oxygen of water O15 through H14, see table 2.

Table 2 Hydrogen bonds geometry

Donor—H—Acceptor | D-H | H...A | D...A | D-H...A
O14 - H14 .... O15 | 0.78(6) | 2.08(7) | 2.800(5) | 153(7)
O15 - H15 .... O8 | 0.76(3) | 2.02(3) | 2.703(2) | 149(3)

Table 3 Selected bonds and angles ( )

Selected bonds | Selected angles
Cu1 | N11 | 2.014(3) Å | O1 | Cu1 | O1 | 174.94(9)
Cu1 | O1 | 1.9529(19) Å | O1 | Cu1 | N11 | 124.6(3)
N11 | C12 | 1.483(4) | O1 | C2 | C3 | 119.2
C7 | O8 | 1.364(3)Å | C5 | C4 | H4 | 109.5
C2 | C3 | 1.416(4) | O8 | C9 | H9C | 109.5
C9 | H9A | 0.9800 Å | H9A | C9 | H9C | 128.4(3)
O8 | C9 | 1.421(3) | N11 | C10 | C3 | 99(5)
O14 | H14 | 0.78(6) | C13 | O14 | H14 | 106(5)
C10 | N11 | 1.279(4) | H15 | O15 | H15 | 174.94(9)

Photocatalytic activity. With an aim to investigate the photo-catalytic capacity of the catalyst LCu in the degradation of industrial dyes, Crystal violet and methylene blue were used as substrates and optimization studies were conducted to determine the optimum degradation parameters.
As mentioned above in the paper, we worked with a photo-Fenton like process, as shown in figure 4. Charge transfer between metal (3d) and ligand through oxygen or nitrogen (2p) plays an important role in the mechanism of dye photo-degradation.

Fig. 4 Possible photo-catalytic mechanism for degradation of CV and MB dyes by LCu complex.

Fig. 4. Possible photo-catalytic mechanism for degradation of CV and MB dyes by LCu complex.

Crystal violet. A series of experiments were conducted to determine the optimum parameters for the degradation of crystal violet with LCu. To determine the optimal hydrogen peroxide quantity the degradation reaction of crystal violet ( 15 ppm ) was conducted with different volumes of with a catalyst concentration of 15 ppm in a total volume of a solution of 300 under UV radiation ( ) at room temperature. As it's shown in Fig. 5, the best results are obtained ( degradation) with a (volume) of equal to 1.5 ml after 30 min . Subsequently, the effect of catalyst quantity was studied in the same manner as before, while using the optimum volume previously determined. Fig. 6 shows that the best results are obtained with a catalyst concentration equal to 6 mg and 20 min of reaction time. However to confirm the synergic effect of UV radiation and hydrogen peroxide on the degradation process with the catalyst, two experiences were conducted one without the UV radiation and the other in the absence of , the degradation rates were and respectively. An additional experience was carried out in the same latter reaction conditions except UV wavelength was 365 nm and the results of this experiment showed no significant degradation only . Thus, the optimum parameters for the degradation of crystal violet with LCu are: 6 mg of catalyst, (3 %) and 20 min of reaction time.

Fig. 5 Effect of hydrogen peroxide quantity on the degradation of crystal violet ( 15 ppm ), catalyst , room temperature.

Fig. 5. Effect of hydrogen peroxide quantity on the degradation of crystal violet ( 15 ppm ), catalyst , room temperature.

Fig. 6 Catalyst concentration effect on the degradation of crystal violet at and room temperature.

Fig. 6. Catalyst concentration effect on the degradation of crystal violet at and room temperature.

Methylene blue. Similarly with the other dye in search of optimum degradation parameters experiments were carried out. Aiming to determine the optimal hydrogen peroxide quantity the degradation reaction of methylene blue ( 15 ppm ) was conducted with different volumes of with a catalyst concentration of 15 ppm in a total volume of a solution of under UV radiation ( ) at room temperature. Fig. 7, reveals that the best results are obtained ( degradation) with a volume of equal to 2.25 ml after 50 min of reaction. Afterward, an investigation of the catalyst quantity effect on the degradation reaction was carried what in similar reaction conditions, while using the optimum volume previously determined. Results are represented in Fig. 8. It's evident that the best results are obtained with catalyst concentration equal to 4.5 mg and 120 min of reaction time. The synergetic effect of UV radiation and hydrogen peroxide on the degradation process along the catalyst is visible (Fig. 8), we notice that degradation rates in the experiences without the UV radiation and the other in the absence of , were and respectively. Another experience was carried out in the same latter reaction conditions with a different UV wavelength ( ) and the results of this experiment showed no significant degradation of only . Hence, the optimum parameters for the degradation of crystal violet with LCu are: 4.5 mg of catalyst, and 2.25 ml of (3 %) in a relatively short reaction time.

Fig. 7 Effect of hydrogen peroxide quantity on the degradation of Methylene blue ( 15 ppm ), catalyst ( 15 ppm ), and room temperature..

Fig. 7. Effect of hydrogen peroxide quantity on the degradation of Methylene blue ( 15 ppm ), catalyst ( 15 ppm ), and room temperature..

Fig. 8 Catalyst concentration effect on the degradation of Methylene blue at and room temperature.

Fig. 8. Catalyst concentration effect on the degradation of Methylene blue at and room temperature.

The results obtained from optimization studies reveal that our copper complex indeed can successfully catalyze the degradation of CV and MB two dyes of different structures and different classes, our compound is as effective as other recently published Schiff base catalysts [35,41]. As a perspective, we plan to replace the UV lamp with sunlight if the gap energy of the catalyst is appropriate [42].
The results also highlight the capacity and potential of the complex making it an efficient candidate in the pool of similar catalytic agents for the degradation of industrial textile dyes.

Conclusion

The original version of this paper is available on https://www.scientific.net/EC.2.65.pdf

The complex LCu was synthesized and characterized using FT-IR and elemental analysis, single crystal of the complex were isolated, and its structure was later determined using XRD.
Catalytic efficiency of the LCu complex in the degradation of industrial textile dyes was investigated. The results of the photo-catalytic study experiments, prove that LCu possesses a significant photo-catalytic capacity in the degradation of crystal violet and methylene blue. The optimum parameters of the degradation reactions were determined for both of the dyes. The catalyst turned out to be very efficient while using very low quantities of hydrogen peroxide and fast acting with a short reaction time to achieve around to degradation. The sum of the results of this study reveal that LCu could be a very promising catalyst in the field of environment and the photodegradation of industrial dyes.

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Keywords Index

A

Activated Carbon Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

Adsorption Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

B

Bandgap Energy Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Bentonite LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

C

Copper Composites Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Copper Metal Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Cracking LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Cyclic Voltammetry Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

G

Galvanostatic Charge-discharge Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

I

Impregnation Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

K

Kerosene LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

L

Ldpe LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

M

Magnetic Activated Carbon Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Metal Organic Frameworks Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Microwave-assisted Pyrolysis; Coconut Shell Waste; Size; Power Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

Mofs Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Mononuclear Copper Complexes Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

N

Nano Metal Oxide Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

O

Optical Properties Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Optimization Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Organic Dyes Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

P

Photocatalysis Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Photoluminescence Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Plastic To Oil LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

R

Rit-62 Cu-mofs Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

S

Schiff Base Complexes Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Sugarcane Bagasse Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

U

Ultrasound Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

V

Vetiver Root Waste Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

W

Waste To Energy LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

X

X-ray Molecular Structure Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Z

Zinc Oxide Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

Authors Index

A

Adimule, V. Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works; Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Amini, H. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Anggraini, S. Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

Arie, A. Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

B

Batakurki, S. Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works; Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

D

Darkbira, F. Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

F

Fachri, B. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Fadillah, F. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Fellah, A. Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Fellah, F. Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

G

Gunawan, S. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

H

Haraki, R. Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

Hudaya, T. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

I

Iswahyono, I. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

J

Juliastuti, S. Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

K

Kamat, V. Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

M

Mahfud, M. Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

Manjunath, D. Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs

Mulya, K. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

N

Nagalakshmi, G. Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Nandeesh, I. Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works

Nehar, O. Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

Nehemia, E. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Nor, M. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Nugroho, A. Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

O

Oktaviano, H. Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

Osborn, M. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

P

Palupi, B. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

R

Rahmawati, I. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Rizkiana, M. Optimization of Methylene Blue Ultrasound-Assisted Adsorption onto Magnetic Sugarcane Bagasse Activated Carbon Using Response Surface Methodology

Roisnel, T. Study of the Degradation of Dyes by a Mononuclear Copper Complex Forming a Zigzag Chain

S

Setiawan, L. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Soetedjo, J. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Suprapto, S. Coconut Shell Liquid Smoke Production Quality from Size and Power Using Microwave-Assisted Pyrolysis

Susanti, R. Synthesis and Electrochemical Properties of ZnO/ Activated Carbon from Vetiver Distillation Waste

T

Tjandra, F. LDPE Film Waste Treatment into Liquid Fuel using Catalytic Cracking

Y

Yallur, B. Synthesis and Optical Properties of Copper Terephthalate Metal Organic Frame Works; Study of Temperature Effect on the Structure and Optical Properties of RIT-62 Cu-MOFs