free-h palm oil deoxygenation into green diesel …...volume-10, issue-2, february 2020 free-h 2...

Volume-10, Issue-2, February 2020

Free-H2 Palm Oil Deoxygenation into Green

Diesel-Grade Biofuel Via Fish Scale Derived Hydroxyapatite Catalyst

1,2Fouad Warid, 1,* Ismail Zainol, 2Nada Mutter, 1Nurulsaidah Rahim

1Department of Chemistry, Faculty of Science and Mathematics, University

Pendidikan Sultan Idris, Perak, Malaysia.

E-mail: [email protected]

2Department of Chemistry, Faculty of Science, University of Baghdad, Iraq.

Abstract

Wet impregnating methods have been developed to produce advanced hydroxyapatite binary SrO-Ag2O3/ HA Catalyst with improved physiochemical properties, modified surface morphology and chemistry. A catalyst (SrO-Ag2O3/ HA) for decarbonylation / decarboxylation was used to turn palm oil into green diesel. FESEM, FTIR, TGA, XRD, TPD-CO2, BET and TPD-NH3 have all been characteristics of the new catalyst. High catalytic activity depended largely on the hydroxyapatite and binary metallic systems' high and simple density of active sites that led to a greater synergy between the cycle of simultaneous decarbonization and decarboxylation of palm oil. The result showed a maximum range of 96% hydrocarbons and selection n-(C15+C17) of about 80% under optimal condition at 3% of the catalyst at 330°C, 3wt.% within 180min. The catalyst is robust with a high degree of reusability around 6 run. Keywords: Decarbonylation/Decarboxylation, Heterogeneous catalyst, Hydroxyapatite,Green diesel, Deoxygenation

Journal of Green Engineering, Vol. 10_2, 376–398. Alpha Publishers

This is an Open Access publication. © 2020 the Author(s). All rights reserved

mailto:[email protected]

377 Fouad Warid et al

1 Introduction

Recent advances in biofuels have been motivated by a number of geopolitical, economic and environmental concerns (e.g. global warming, reduced petroleum reserves, higher crude oil prices and a need for energy independence). In reaction, green fuels were viewed as a neutral carbon and sustainable unconventional for fossil fuel. Bio-oils, which can be obtained easily by biomass pyrolysis (thermal and catalytic cracking), in particular, have received much attention. Nonetheless, this method, which produces a variety of undesirable products (mainly oxygenates), requires an additional upgrade step because its significantly low selectivity. Over the years, many improvements have been made in biofuel production. The thermal and catalytic biomass pyrolysis, for instance, is a simple procedure to provide a variety of fuel-like bio-oils. This technique is however extremely indiscriminate and also yields many unwanted compounds primarily oxygenates that require further purification steps. [1]. The conversion of sustainable feeds like vegetable oils and fats (from animal) keen to Fatty Acid Methyl Esters (FAME) which is normally identified as biodiesel, however, can be accomplished with transesterification reactions [2]. Although the technology has been developed for relatively common business applications, the unfavourable cold flow characteristics and weak stores of FEMEs reduce biodiesel not as much of the ideal transport fuel in addition to the engine performance concerns. [3,4]. In particular, because of its high oxygen content, many of the constraints of biodiesel and bio-oils, including their lower temperatures in respect of traditional oil-driven fuels. Despite this, the main benefits of processing sustainable hydrocarbons such as gasoline, which are totally fungible with fossil fuel, were catalytic advances in which oxygen was extracted either as water (H2O) or carbon oxides (COX). It can't be overlooked whether these biofuels are fully compatible with the current substructure, as the latter characterizes expenditure of over $12 trillion in the United States alone. [5,6].

In this paper, the optimized OVAT analysis of deoxygenation through testing of different reaction parameters (such as reaction temperature, catalyst loading and reaction time) is an alternative method. The optimisation method with variation of OVAT was done in this analysis. The current study thus emphasizes the effect on the deoxygenation of palm oil from co loading of solid acid base catalysts (SrO-Ag2O3/ HA). XRD, FESEM-EDX, BET and TPD analyses were used to test the physicochemical properties of SrO-Ag2O3/ HA acid based catalysts. The GC-FID and GC-MS tests have been used to analyse the detailed study of the chemical composition and distribution of deoxidized liquid products. In addition, the modulation of the three reaction variables (i) reaction times, (ii) the reaction temperature and (iii) the catalyst concentration) assessed the optimization cycle in palm oil deoxygenation. SrO-Ag2O3/ HA Acid

Free-H2 Palm Oil Deoxygenation into Green Diesel-Grade Biofuel Via Fish Scale

Derived Hydroxyapatite Catalyst 378

Catalyst was also tested in terms of its recoverability and stability profile. The present work also will provide in-depth insight on the newly

understanding of DO of palm oil under inert reaction systems.

2 Materials and Method

2.1 Materials

Fish scales hydroxyapatite (HA) were prepared from fish scales using thermal extraction method. Hydrochloric acid (HCl) and chlorosulphonic acid with 85.0–87.0% purity was purchased from J.T. Baker, USA. Sliver nitrate (Ag(NO₃)₂) with purity of 99.0% was purchased from R and M

(Malaysia) while Strontium nitrate Sr(NO₃)₂ with 99.99% purity was purchased from Sigma Aldrich (USA). The liquid products are both alkane and alkene standard n-(C8-C20) and 1-bromohexane used as internal standard for (GC) gas chromatograph analysis were purchased from Sigma Aldrich and used without further purification. N-Hexane (GC grade) with purity of 98% from USA Merck was used for dilution. The N2 gas, with 99.9% purity, was provided by local Malaysian company (Linde Sdn. Bhd). The feedstock in this study was used-palm oil obtained from local market.

2.2 Catalyst Preparation

The first step was purification of hydroxyapatite (HA) were done by mixing HA with 37% of HCl and the mixture were kept under ultrasonication for 3 hours at room temperature. The HA were participated by using NH3 dropwise till pH=11 and wishing the participated particles by using DI water till pH 7 and drying it at 100C for 24 h. the wet impregnation method were used to dope the Ag(NO₃)₂ and Sr(NO₃)₂ nitrate on HA were add dropwise and stirred at 30°C (room temperature) for 8h. then the blend was dehydrated for 24 h at 100°C. then the dried powder was calcine at 550 °C. The calcined powder was treated with chlorosulphonic acid at room temperature for 6h, the it was whished using DI water till pH7 and drying it and the catalyst ready for characterize and used for Dox reaction.

2.3 Catalyst Characterization

X-ray diffraction (XRD) research has been used to determine the dispersion state and chemical composition before and after the reaction of the modified HA catalysts. A Shimadzu diffractometer (XRD-6000 model)


was employed to analyse the XRD. The Brunauer–Emmett-Teller (BET) approach used the N2 adsorption / desorption analyser (Thermo-Finnigan Sorpmatic 1990 series) to identify the specific surface area and pore distribution of the catalysts. The Around 150°C, the catalysts were degassed overnight to eliminate surface moisture and external gases. In a vacuum chamber at −196 ° C, the adsorption and desorption of N2 is studied on the catalyst surfaces. In addition, the basicity and acidity of the catalysts were investigated using CO2 and NH3 as the probe molecules (TPD-CO2 and TPD-NH3) with temperature-programmed desorption. The study was conducted with a thermal conductivity detector (TCD) fitted Thermo Finnigan TPD / R / O 1100. The catalyst (freezing 0.05 g) was pre-treated for 30 minutes at 150 ° C with N2 gas flow. At ambient temperature, CO2was then exposed to the catalyst for sixty minutes so that CO2 was adsorbed into the air. N2 gas then flushed excess CO2. TCD was measured in the helium gas flux of (30 ml / min) 50 ° C to 900 ° C and the heat was sustained for 30 mins from simple sites of the catalyst. Similar steps were followed in the adsorption and desorption of NH3 as TPD-NH3 process. Images were collected on the JSM 7600F JEOL electron microscope, in the field of emission scanning microscopy (FESEM). EX-230BU, JEOL spectrometer for O, P, Ca, Zn and CO determination, was installed into the FESEM system. The chemical status of the representative HA catalyst Ag2O3 and SrO was analysed by an XPS and measured under ultra-high vacuum conditions (basic vacuum − 10−8 Pa) under room temperature using the microprobe PHI Quantera II.. Quantera II was used. The X-ray test was used for mg Ka radiation (hemplo= 1253.6 eV). The used catalyst was also differentiated by XRD, and thermogravimetry (TGA), simultaneous thermal analyser, measured the degree of coke formation. (TGA, Mettler Toledo 990). Thermo gravimetric analytics (TGA) (Pyris Diamond TG / DTA) was used for evaluating the level of coke / carbon deposition on the spent catalyst. At 15 ° C / min heating and an O2 atmosphere, samples were heated from 50 ° C to 1000 ° C. The metal liquidation in the green diesel was assessed after pre-treatment by digesting a sample (0,025 g) of 5% nitric acid with inductively plasma-atomic emission spectrometer (ICP-AES, Perkin–Elmer Emission spectrometer model Plasma 100).

2.4 Catalytic Deoxygenation of Palm Oil

As shown in Figure 1, the deoxygenation (DO) for palm oil was performed with a mechanically agitated semi-batch reactor of 250 ml. In virtually all the tests, palm oil (~100 g) and 0.5% WTC were put in the reactor and inert N2 gas was flushed into the reactor with the continuous mixture before the experiment was started. The purpose of this process was



to ensure that the O2 was absorbed before heat was extracted. To order to maintain a consistent removal of oxygen during a DO reaction, the mixture is purged continuously at an inert N2 (flux rate of 20cc per minute). The temperature rose over time, and this atmosphere was kept constants for 1 hour, in order to achieve the target temperature of 350°C. The condensation of condensable materials was allowed by using a cooler. For the study of liquid products, gas chromatography was applied along with flame ionization detection (GC-FID), infrared spectroscopy of Fourier-alpha, and gas chromatography–mass spectrometry (GC-MS).

2.5 Green Diesel Quantitative Analysis

A Shimadzu GC14B gas chromatograph (length 30 m= inner diameter: 0.32 mm per film thickness: 0.25 m) and a flame-ionization detector (FID) were used to test the liquid products quantitatively and the flame ionization detector (FID) was operated with a temperature of 300C. Prior to the yield study the GC grade n-hexane and 1μL aliquot of the sample was used to dilute the liquid items. The mixture was moved with a syringe to the GC base. The temperature of the injection was set at 250 C and nitrogen was used as carrier gas. Over 6 mins, the oven temperature was kept at 40 C. It was then elevated to 270 ° C (increased per minute by 7 ° C). The internal norm was 1-bromo hexane for quantitative analysis. The presence of saturated and unsaturated hydrocarbon fractions (C8–C20) was further established during pre-experimental studies of liquid product analysed by

GC‐MS. Through a study by GC-FID with a standard compound from commercially saturated hydrocarbons in the range of C8–C20 and commercially non-saturated nonene, these hydrocarbons were further identified. Figure 1 displays the typical hydrocarbon and deoxidized palm oil GC-FID chromatograms. Equation 1 has also been quantified with the total yield of hydrocarbons (X) called total saturated and unsaturated straight-chain carbon (C8-C20).


Figure 1 GC-FID chromatogram for hydrocarbon standard and deoxygenized palm

oil product.

where, X represents the hydrocarbon yield of unsaturated and saturated straight chains (%), no denotes the alkene’s area (C8–C20), ni represents the alkane’s area (C8–C20), and nz denotes the product area (total).

Additionally, hydrocarbon selectivity (Sc) (also referred to as carbon balance) was identified with the following equation:

where Scarbon refers to hydrocarbon selectivity (%), Co represents the desirable alkene’s area and Ci represents the desirable alkane’s area while no



denotes the alkene’s area (C8–C20) and ni represents the alkane’s area (C8–C20).

The measurements were performed in triplicates with 1-bromo-hexane strength (as the internal norm), with a standard deviation of less than 4, to check the degree to which the findings could be replicated. In the GAS chromatography-mass Spectrometry (GC-MS), in which the process was based on a SHIMADZU QP3050A tool, the DO for fluid products and qualitative characterization of palm oil were also used. The instrument consists of a non-polar column of DB-5HT (30 m x 0.25 mm x I.D μm) and a split inlet. After the application of n hexane grade and GC grade (more than 98% pure), the deoxygenated liquid products and palm oil diluted to 100 ppm. However, the verification of the fractional peaks of GC-MS spectrum was assisted by a study of the library of the NIST. It is worth noting that likelihood match greater than (or equal to) 95% was used to classify the most appropriate items. In order to determine organic compound production the following equation was used (namely, hydrocarbon

fractions, carboxylic acid, and alcohol):

3 Results and Discussion

Under scanning electron microscopy for raw HA, observed the HA is large irregular aggregates with a smooth surface. Dramatically change in the morphology of the surface after treated by HCl and chlorosulphonic acid appear the particles changed to cubic shape and irregular size as shown in figure 2. Sr and Ag accumulation on the catalyst within the synthesis stage led to metal agglomeration and change the surface which apparently looks like grains compact with cubic shapes. With small particles (about 2.9 μm) agglomerated on the catalyst surface between the metals and the support. EDX analysis used for all samples. it can be found all elements and determine their uniform distribution on the surface. Good standard for selecting the catalyst type required. Through the presence of improved elements. such as found of the elements Ag and Sr distribution on the HA surface in an excellent way. there are appear perfect of synthesis of samples by use combustion method. were found to be almost similar to the theoretical calculation [7–10].


Figure 2 FESEM results for the synthesized catalyst. a) Ag2O3(1%)-SrO(5%)/HA,

b) Ag2O3(5%)-SrO(5%)/HA, c) Ag2O3(10%)-SrO(5%)/HA, d) Ag2O3(15%)-

SrO(5%)/HA, e) Ag2O3(20%)-SrO(5%)/HA and d) Ag2O3(25%)-SrO(5%)/HA

Figure 3 presents the X-ray powder diffractogram obtained for the prepared catalyst. The figure presents a set of diffraction patterns that corresponds to SrO, and HA structure. The patterns are well defined and very intense, suggesting a high crystalline samples. The 2θ :29, 33,35 and 56 which is refer to SrO (JCPDS file #6-520) Moreover, the 2θ= 25.89°, 31.69°,32.35°, 32.91°, 34.16°, 39.97°, 49.40°, 50.44°, 53.17° (ICDD 9-432), indicating the presence of calcium hydroxyapatite [11,12].

Figure 3 XRD profile of SrO/HA catalyst.

10 20 30 40 50 60 70

Inte

nsity

(a.u

)

2θ degree

Sr5/HA Sr10/HA Sr15/HASr20/HA Sr25/HA Sr30/HA

SrO

(a

)

(d)

(b

)

(e)

(c)

(f)



Figure 4 presents the X-ray powder diffractogram obtained for the prepared catalyst. The figure presents a set of diffraction patterns that corresponds to SrO, Ag2O3 and HA structure. The patterns are well defined and very intense, suggesting a high crystalline samples. The 2θ :29, 33,35 and 56 which is refer to SrO (JCPDS file #6-520) and the 2θ=28.8o, 34.2o, 38.1o, 44.0o, 50.9o, and 64.5o which is refer to Ag2O3 (JCPDS File No. 40-0909 [13]). Moreover, the 2θ= 25.89°, 31.69°,32.35°, 32.91°, 34.16°, 39.97°, 49.40°, 50.44°, 53.17° (ICDD 9-432), indicating the presence of calcium hydroxyapatite [11,12]. The crystal size was increased from 24nm to 40nm when increase the Ag doping present from 1 to 25 wt., % while keeping the Sr doping present constant at 5 wt., % this is due to the agglomeration this result was confirmed by BET and FESEM results. From Table 5.1 the total surface area and pore size were reduced from 89.40 to 60.58 m2/g and 0.24 to 0.21 this may be due to the agglomeration during the doping or because the centering during the calcination proses.

Figure 4 XRD patterns for the prepared bimetallic catalyst.

The helium flow as carrier gas has been used to develop temperature programmed desorption (TPD) patterns on all materials and their profiles are shown in Figure 5, the catalyst showing one of the desorption peaks on its profiles. Among all the modified samples, Ag2O3(20%)-SrO(5%)/HA has shown the highest amount of CO2 desorbed (985 µmol/g), with two characteristic desorption peak at 633 oC. The overall TPD-CO2 desorption trend is Ag2O3 (20%)-SrO(5%)/HA> Ag2O3 (1%)-SrO(5%)/HA> Ag2O3

5 25 45 65

Inte

nsity

(a.

u)

2θ degree

Ag1Sr5/HA

Ag5Sr5/HA

Ag10Sr5/HA

Ag15Sr5/HA

Ag20Sr5/HA

Ag25Sr5/HA

Ag2O3

HASrO


(5%)-SrO(5%)/HA> Ag2O3 (10%)-SrO(5%)/HA> Ag2O3 (25%)-SrO(5%)/HA

Once paired with the signals in Ag2O3 (20%)-SrO (5%)/HA, the CO2 desorption peak was difficult to detect and imperceptible, with a small degree of CO2 solubility of 135μmol / g. The lack of usable surface oxygen groups and active sites for HA adsorbing CO2 can be approved. Nevertheless the incorporation of Ag and Sr into HA products induced dramatic surface changes, formation of active sites and the production of functional groups of oxygen, for example carboxy, hydroxylic, carbonyl, lactones etc. This also increased the total gas desorbed from the surface when the oxygen comprising feature groups were exposed to heating at higher temperatures, which emitted CO and CO2. According to Vukcevic et al., lower temperature carboxyl groups produce CO2 (< 400 K) and higher lactones emit CO2. Whereas carbonyls, ethers, phenols, etc. are responsible for CO and CO2 decomposition.

Figure 5TPD-CO2 profile of Ag2O3-SrO/HA catalyst.

The synthesized Catalyst TPD-NH3 profiles (Figure 6) also give an additional indication that the modified HA help includes acid sites. It was experiential to increase the number or quantity of acid sites in Ag%, and to suit the findings of TPD-NH3. Table 1 provides an overview of the cumulative NH3 desorbed from the soil. The findings of TPD-NH3 shown in Figure 6 explain a growth of acidic sites on the catalyst's surface. The main possibility of dissolving NH3 (1880 μmol / g) of outside the magnet catalyst is consistently Ag2O3 (20%)-SRO(5%)/HA. Figures 5 and 6 illustrate the correlation between acid and basic sites with an increase in iron content in all samples. The findings show that both acidic and basic

-100

900

1900

2900

3900

4900

5900

50 250 450 650 850 1050

TC

D s

igna

l (-

mV

)

Temperature (°C)

Ag1Sr5/HA Ag5Sr5/HA Ag10Sr5/HA

Ag20Sr5/HA Ag25Sr5/HA Ag30Sr5/HA

Free- Free-H2 Palm Oil Deoxygenation into Green Diesel-Grade Biofuel Via Fish

Scale Derived Hydroxyapatite Catalyst 386

materials were not likely to be generated and the previous deduction is followed by Ag2O3 (20%)- SrO (5%)/HA materials.

Figure 6 TPD- NH3 profile of Ag2O3-SrO/HA catalyst.

Table 1 physicochemical properties of Ag 2 O 3 -SrO/ HA catalysts

Catalyst XRD BET TPD-NH3 TPD-CO2

Crystallite

sizea

(nm)

Surface areab

(m2/g)

Pore

volumeb

(cc/g)

NH3 desorption

temperaturec (°C)

Amount of

NH3 adsorbed

c

(µmol/g)

CO2 desorption

temperatured

(°C)

Amount of CO2 adsorbedd

(µmol/g)

Ag1Sr5/HA 24 89.40 0.24 560 333 649 762

Ag5Sr5/HA 26 82.96 0.19 569 764 586 716

Ag10Sr5/HA 29 74.83 0.27 134/596 1305 579 684

Ag10Sr5/HA 30 72.61 0.26 216/550 1383 568 791

Ag20Sr5/HA 33 66.13 0.24 472 1880 550 985

Ag25Sr5/HA 40 60.58 0.21 185/790 503 342 536

aDetermined by using Debyee Scherrer equation. bBET surface area. cNH3 desorption peak for all catalysts.

-500

500

1500

2500

3500

4500

50 250 450 650 850 1050

TC

D s

igna

l (-

mV

)

Temperature (°C)

Ag1Sr5/HA Ag5Sr5/HAAg10Sr5/HA Ag20Sr5/HAAg25Sr5/HA Ag30Sr5/HA


3.1 Catalytic Performance Test

The catalytic deoxygenation of palm oil using Ag2O3-SrO/HA were investigated using 3 wt.% catalyst loading at 350 °C within 3 h reaction time under inert N2 flow condition. The reactivity of all the catalyst is shown in Figure 7. The results of the GC-FID analysis indicated that the deoxygenized liquid products were comprised of saturated and unsaturated hydrocarbon fractions, ranging between C8 and C20 in length. A blank experiment was performed using the same reaction conditions and parameters to establish the distribution of product of palm oil in the absence of catalyst. The liquid hydrocarbon yield in the blank experiment was low (3%), indicating that the inherent rate of deoxygenation of palm oil without catalyst is low. Liquid hydrocarbon yields were Ag2O3 (20%)-SrO(5%)/HA> Ag2O3 (1%)-SrO(5%)/HA> Ag2O3 (5%)-SrO(5%)/HA> Ag2O3 (10%)-SrO(5%)/HA> Ag2O3 (25%)-SrO(5%)/HA> ranked blank. Deoxygenation of Palm oil over Ag2O3 (20%)-SrO(5%)/HA catalyst resulted in higher hydrocarbon yield within the range of 25% than those obtained with CO2O3-ZnO/HA catalysts, which confirmed high efficiency of Ag2O3 (20%)-SrO(5%)/HA in converting majority of fatty acid chains in Palm oil to hydrocarbons. Notably, the hydrocarbon yield reduced when high dosage of Ag species is used. It is due to Ag-rich catalyst species favouring high extension of cracking reactions is yielding more gases and reducing the relative content of hydrocarbons in the liquid product [14]. Overall, the results showed that the deoxygenation activity was dominated by Ag2O3 (20%)-SrO(5%)/HA with highest hydrocarbon yield (93%) at the optimum conditions .



Figure 7 a) hydrocarbon yield for Sr/HA single mantel system catalyst and b)

hydrocarbon yield of Ag2O3-SrO/HA bimetallic catalyst system.

Overall, mixed metal oxides system (Ag2O3-SrO) doped HA resulted in

significant improvement of the n-(C15+C17) selectivity than individual SrO doped HA. This suggests that all Ag2O3 (20%)-SrO(5%)/HA catalysts effectively functioned through large synergistic effect by incorporation of Sr and Ag [15]. It is assumed that the activation of oxygenated compound via deCOx reactions occurred over the strong acidic site catalyst considering a large formation of strong acid sites density (> 1880 µmol/g) was observed for all mixed metal oxides Ag2O3 (20%)-SrO(5%)/HA catalysts. Yet, excess of large strong acidic sites are practically inevitable and generally acknowledged to be the main reason of cracking of deoxygenized product to form light hydrocarbon fractions [16,17]. Evidently, Ag2O3 (20%)-SrO(5%)/HA catalyst with large strong acidic sites > 1880 µmol/g (see

0

5

10

15

20

25

30

35

40

45

Yiel

d (%

)

a

b


TPD-NH3, Table 1) resulted in highest of n-(C15,C17) fractions. It is important to mention that the great deCOx performance is associated with the high existence of weak acidic sites. TPD-NH3 results provided evidence that the ability of large weak acidic sites in Ag2O3 (20%)-SrO(5%)/HA was the key factor in promoting deCOx activity and rendered higher n-(C15+C17) selectivity (~75%). From GCMS results show that the screening result at the optimum condition for the bimetallic catalyst the Ag20Sr5/HA catalyst give the heist selectivity to the C8-C20 with the maximum hydrocarbons selectivity of 96% and a >4% of oxygenated compounds (figure 8)

Figure 8 the GCMS profile of Ag20Sr5/HA catalyst at the optimum conditions

3.2 Optimization Studies

The effect of catalyst loading from 0.5 to 5wt.% on the catalytic deoxygenation of Palm oil was investigated and results were depicted in Figure 8 a and b. It is evident that catalyst loading showed a volcano-shape curve with respect to deoxygenation activity. Low dosage catalyst loading (0.5 wt.%) exhibited the lowest deoxygenation activity. In contrast, the percentage of hydrocarbon increased with increasing catalyst loading up to 3 wt.% and further reduced as the loading exceeded 3 wt.%. The light fractions of (C15-C17) were observed significantly when 0.5 wt.% and 5 wt.% of catalyst were loaded (Figure 9 a and b). These results clearly demonstrated that low and excessive active sites of the catalysts apparently resulted in the consecutive stronger cracking processes, which then induced



the formation of gaseous or lighter products [18]. The effects of the residence time (30 min to 240 min) on deoxygenation activity were inspected and the outcomes shown in Figure 9 c and d. The deoxygenation activity increased with increase in residence time within 180 min and further increment in residence time led to reduction of hydrocarbon rich species. The reaction temperatures were studied from 270 to 400oC. The maximum deoxygenation activity was observed at reaction temperature of 330oC, 3 wt.% catalyst loading within 180 min (Figure e and fi). It is noteworthy to mention that the selectivity of n-(C15+n-C17) was the highest when reaction was run in low temperature (270oC), suggesting the occurrence of negligible thermal decomposition rate.

Figure 9 Deoxygenation optimization results. (a-b) are the effect of catalyst loading

wt.%, (c-d) time effect of deoxygenation reaction and (e-f) temperature effect on the

deoxygenation reaction using Ag2O3 (20%)-SrO(5%)/HA catalyst.

(a) (b)

(d) (c)

(e) (f)


3.3 Catalyst Reusability and Stability

The reusability and stability of the catalyst are advantageous for practical application in the refinery of green diesel under H2-free environment [19] which is shown in figure 10. The deoxygenation of palm oil was carried out six times at optimized reaction conditions. The catalyst was separated from the fresh cycle by simply washing with hexane to clean the active sites and it was dehydrated at 30°C (room temperature) and reused for the next cycle. Interestingly, the Ag2O3(20%)-SrO(5%)/HA catalyst appeared to offer high catalytic activity and outstanding activity maintenance for deoxygenation of palm oil. The high and steady deoxygenation activity was observed up to six reaction runs with 93 to 73% hydrocarbons yield. The ICP results shows low metals leaching from the catalyst support during the six run with the total metal leaching of Ag

2+ and

Sr2 were 71 ppm and 94 ppm, respectively.

Figure 10 Reusability of Ag2O3 (20%)-SrO(5%)/HA catalyst toward straight chain

hydrocarbon and for 6 consecutive cycles.

Typically, deoxygenation catalyst is proned to be deactivated due to coke deposition. Therefore, the coke is deposited on the Ag2O3-SrO/HA spent catalyst were studied using TGA and the results showed in Figure 11. The coke formation was determined by the difference in weight loss between the spent catalyst and the fresh catalyst [20]. The spent catalyst were simply reactivated by hexane washing. The result displayed that both of the fresh and spent catalysts resulted in major weight loss within T=753°C and 200 to 500°C respectively. The weight loss at T= 350-499°C due to the oxidation of hard coke in the air [21]. In can be seen that both spent and fresh Ag2O3-SrO/HA catalyst favored hard coke formation. Hard coke typically formed at high temperature and contents lower H/C ratio[22].



Figure 11 TGA profile of fresh and spent catalyst under oxygen gas atmosphere

FTIR was applied to characterise the functional groups before and after

treatment with chlorosulphonic acid (Figure 12). In Ag2O3-SrO/HA-SO3Cl, the bands centred at 614 cm–1, which was credited to the stretching of the HA–S and the band at 1655 cm–1, which were recognized to the stretching of the Ca–S symmetric. and the peak around 1690 which is refer to PO4 group of the HA. moreover, the peak around 1300 cm-1 which is refer to the P of the HA. Furthermore, the relative absorption band intensity at 3314 cm–1, which matched the stretching vibration of the –OH group, was significantly enhanced, indicating plentiful oxygen-containing groups, which was favourable for the modification of the –SO3H groups. The catalyst showed an additional peak at 1000 cm–1, which was found in the sample with the Sulfonation treatment. This absorption could be ascribed to the S=O symmetric stretching [23,24], and demonstrated that the –SO3H groups had been successfully modified onto the HA–SO3H composites.

0

20

40

60

80

100

120

50 250 450 650 850 1050

wei

ght

lose

(wt)

Temp. C

fresh catalyst spent catalyst


Figure 12 FTIR profile of Ag2O3-SrO/HA catalyst

3.4 Comparison Study

Attraction has been paid to use carbon as a support due to its novel physicochemical properties. Transition metal doped activated carbon catalyst was exposed excellent green fuel production from edible and non-edible oil without presence of hydrogen. The comparison of Ag2O3-SrO supurted HA catalytic activity were compared with several similar studies (Table 2). Ag2O3-SrO/HA where applied to study the deoxygenation reaction of palm oil (Table 2) From this summary the Ag2O3-SrO/HA catalyst was the reactive catalyst with high hydrocarbon yield and selectivity to n-C15+C17 . The catalyst shows a high reusability up to six times will low coke formation and leaching. This is due to the presence of high acidity acitive sites with high surface area pore volume, which is favor criterias for deoxygenation reaction. Morover, the catalyst can be easyly to regenareated by recalcination, thus this catalyst reactivation is time efficient and highly economical.

300800130018002300280033003800

tra

nsm

itta

nce

weave leangth

Ag2O3-SrO/HA-SO3HCl Ag2O3-SrO/HA



Table 2 Types of catalyst used on deoxygenation reaction

Conclusion

This study undertook the conversion of triglycerides-based feeds into diesel-like fuel with Ag2O3(20%)-SrO(5%)/HA catalyst to provide an efficient deoxygenation reaction. The acid-base Ag2O3 (20%)-SrO(5%)/HA catalyst led to better deoxygenation activity because the highly acidic catalyst was neutralized. Furthermore, The Co2O3-ZnO/HA catalyst also has a multitude of strong basic and acid sites, and as a result, Ag content increase led to cracking pathway improvement. Regarding the level of Ag content, which was in the range of 1-20wt.%, deCOx activity benefitted the most from 3wt.% content (Ag2O3 (20%)-SrO(5%)/HA). Moreover, the investigation regarding the impact of reaction time, catalyst loading and reaction temperature revealed that the ideal deoxygenation condition with ~96% hydrocarbon yield and ~80% n-C15 selectivity at 180 min and temperature of 330°C.

No.

Catalyst Support

Reactio

n

Feed FFA (%)

Reaction condition

H/C (yield

%)

Selectivity (%)

Reusabilit

y

Coke (wt.%)

1. Ni-Ag/ACCFR

Coconut fibre residue

DO JCO 15.4 Catalyst loading: 5 wt.% Temperature: 350 °C

Time: 1 h under N2 flow

80 83 (n-C15+C17)

5 2.5

2. CaO-La2O3/AC

Walnut shell

DO WCO 18.4 Catalyst loading: 3 wt.% Temperature:

330°C, T ime: 3 h under N2 flow

72 82 (n-C15+C17)

6 2

3. Ag2O3-La2O3/ACnan

o

Walnut shell

DO WCO 18.4 Catalyst loading :1 wt.%

Temperature: 350 °C Time: 2 h under N2 flow

89 93 (n-C15+C17)

6 1.3

4. Pd/C, Pd Sebunit DO Lauric

acid

- 26 h, 300 °C:

0.075 ml/min reactant flow rate (WHSV 0.33h

−1),

15 bar Ag, 10

ml/min argon flow, 4.4 mol/l (solvent-free conditions).

80 55 (n-

C15+C17)

3 12.4

5 Ni NiCo

MWCNT

DO JCO 5 1h; 350 °C; partial vacuum condition

82 48 C17 5 4-5

6 MgO carbon DO Palm

oil

>1 430 °C, feed late

13.5 g/h., under atm pressure

65 12 (C17) 3 -


References

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[5]Alsultan, Abdulkreem, Asikin Mijan, and Yun Hin Taufiq-Yap, "Preparation of activated carbon from walnut shell doped la and Ca catalyst for biodiesel production from waste cooking oil", Materials Science Forum, vol. 840, pp. 348-352, 2016.

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Biographies

Fouad W. Mezaal obtained his Bachelor's degree in chemistry in the Faculty of Science from Dhi Qar University, Iraq. Then he received his Master's degree in physical chemistry in the Faculty of Science from Dhi Qar University, Iraq. He is doing his PhD in Department of Chemistry, Faculty of Science and Mathematics, University Pendidikan Sultan Idris, Malaysia. Till date, He has presented papers in three international conferences. He has two books on the practical experiments of physical chemistry and applied for a patent. He worked lecturer in the department of chemistry at the Faculty of Science, Dhi Qar University, Iraq. He has a total experience of 7 years in administration, teaching and research. He researched the laboratories of the Faculty of Science at the University of Baghdad, Iraq. He has investigations in renewable energy and preparing biofuels from biomass in new methods. His current field of research includes, reuse of oil waste in the production of biofuels and the preparation of catalysts from biowaste such as fish scales and bones.

Prof Dr. Ismail Zainol currently working as Professor in the Department of Chemistry, Faculty of Science and Mathematics, Sultan Idris Education


Derived Hydroxyapatite Catalyst 398 University, Malaysia. He completed his Bachelor of Science (Hons) in Chemistry at National University of Malaysia. Then he obtained his PhD in Polymer Science and Technology from University of Manchester Institute of Science and Technology, United Kingdom. His research interest includes polymer composite, biomaterials and biodiesel. He has total experience of 26 years in materials research and lead several national and international grants. He has total more than 50 research publications and 4 patents.

Nada M. Abbass obtained her Bachelor’s degree in chemistry in the Faculty of Science from University of Baghdad, Iraq. Then she received her Master's degree in Inorganic chemistry in the Faculty of Science from University of Baghdad, Iraq. Currently, working as an Assistant Professor at the Department of Chemistry in the Faculty of Science at the University of Baghdad, Iraq. She has seven research publications. She has membership in many professional bodies. Her current field of research includes synthesis of nanopolymers and the field of renewable energy.

Dr. Nurulsaidah Abdul Rahim obtained her bachelor degree in Chemical Sciences from University College of Science and Technology Malaysia. Then, she completed her Master of Science in Chemistry from National University of Malaysia. She did her PhD in polymer chemistry at Dublin City University, Ireland. Currently, working as Senior Lecturer at Department of Chemistry, Faculty of Science and Mathematics, Sultan Idris Education University, Malaysia. Her specialisation include polymer synthesis, polymer chemistry and chemistry education. Her current field research interest includes biomaterials, polymer chemistry and educational module

development.

free-h palm oil deoxygenation into green diesel …...volume-10, issue-2, february 2020 free-h 2...

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