Complete utilization of waste pomegranate peels to produce

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Complete utilization of waste pomegranate peels to produce hydrocolloid, punicalagin rich phenolics and hard carbon electrode Sachin Talekar, Antonio Frank Patti, R. Vijayraghavan, and Amit Arora ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03452 • Publication Date (Web): 18 Oct 2018 Downloaded from http://pubs.acs.org on October 23, 2018

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ACS Sustainable Chemistry & Engineering

Complete utilization of waste pomegranate peels to produce hydrocolloid, punicalagin rich phenolics and hard carbon electrode Sachin Talekar †§, Antonio F. Patti‡, R. Vijayraghavan‡, Amit Arora⃰ §† †

IITB-Monash Research Academy, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

‡

School of Chemistry, Monash University, Wellington Road, Clayton, Victoria 3800, Australia §

Bioprocessing Laboratory, Centre for Technology Alternatives for Rural Areas

(CTARA), Indian Institute of Technology Bombay, Powai, Mumbai 400076, India

*Corresponding author. Dr. Amit Arora E-mail address: [email protected]

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Abstract This work demonstrates the complete utilization of waste pomegranate peels (WPP) to produce pectin, punicalagin rich phenolics, and a hard carbon electrode. The high yields of pectin (24.8%) and phenolics (11.9%) were obtained at optimal ultrasound (20 minultrasound time, 15 mL g-1-liquid: solid ratio) and cellulase treatment (55 U g-1-cellulase dosage, 4 h- treatment time) of WPP. The IR, 1H NMR, and TGA analysis showed that the recovered pectin was similar to commercial pectin. The recovered pectin had 68.5% degree of esterification, 146.5 kDa molecular weight, and 72% galacturonic acid content. A high content of valuable punicalagin (71.2% of total phenolics) occurred in the recovered phenolics. The WPP leftover (after pectin and phenolics recovery) was carbonized via pyrolysis and then impregnated with potassium hydroxide and heated in an inert atmosphere to obtain hard carbon (HC) to be employed as an electrode in electrochemical cells. The Raman spectroscopy, X-ray crystallography, and CHN analysis confirmed the formation of HC which was further characterized by scanning electron microscopy. During the electrochemical testing with sodium battery, the electrode fabricated with HC provided a constant charge-discharge cycle performance of 180 mA h g−1 at C/2 rate and nearly 100% columbic efficiency after 100 cycles using a Na-salt electrolyte. Keywords: Biorefinery, Complete biomass waste utilization, Green extraction, Enzymatic treatment, Value-added product recovery


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Introduction Over the last few years, the pomegranate industry has significantly expanded owing to the numerous health benefits of the pomegranate.1 The pomegranate processing industry produces 50-55% of the weight of the pomegranate as a waste in the form of waste pomegranate peels (WPP), disposal of which is a major environmental concern.2 Alternatively, such biomass waste can be valorized via an integrated process to obtain multiple marketable products and energy in transition to a future bio-economy.3-4 Such an integrated processing of biomass waste has advantages such as minimization of waste generated in industry, revenue diversification via marketing of multiple products, synergistic use of different processing technologies, sharing of manpower and equipment5, thus provides “win-win” solution to dispose biomass waste and increase profit.4-7 WPP constitute a spectrum of products which includes 1) phenolics (10-20%) that can impart multiple health benefits through their antioxidant potential8 2) pectin (20-25%) a commercial hydrocolloid, used as gelling, thickening, stabilizing, and encapsulating agent9-10 and 3) lignocellulosic matter (40-50%)1 which is used for production of materials and energy. However, most of the WPP processing technologies target only phenolics and generate 80-90% of WPP mass as a waste still to be disposed of. In addition, the extracted phenolics are standardized to the content of ellagic acid, a phenolic compound with less bioavailability and devoid of punicalagin, a key phenolic compound responsible for most of the pomegranate health benefits.11-12 A few reports present the extraction of punicalagin rich phenolics but employ non-food grade toxic organic solvents.13-14 Although the pectin extraction from WPP has been reported, most of the processes recover the only pectin and release the waste stream containing 70-80% of WPP mass still not utilized. Moreover, WPP pectin extraction employed mostly the traditional hot, aqueous acidic conditions9-10,

15

and recently the hydrothermal processing8 that may hydrolyze 3 ACS Paragon Plus Environment


punicalagin as it is sensitive to acidic and high-temperature conditions11 and thus is not synergistic for the recovery of punicalagin. The traditional hot, aqueous acidic conditions also generate acidic effluent requiring neutralization before disposal, cause corrosion as well as rapid wearing out of the equipment and undesirable breakdown of the pectin chain16. Therefore, a comprehensive green processing of WPP is required in order to not only recover pectin and punicalagin rich phenolics but also utilize WPP leftovers post recovery. Herein, we propose a strategy for complete utilization of WPP that integrates enzyme treatment of WPP to obtain pectin and punicalagin rich phenolics with the synthesis of carbon electrode material for energy storage devices via pyrolysis of remaining WPP mass (Figure 1). The key step is the treatment of WPP with the cell wall degrading enzyme cellulase. The cellulase breaks down the cell wall cellulose and releases pectin in the acid-free aqueous medium at low temperature.16 Therefore, it would also release punicalagin in intact form as a co-product due to cell wall degradation at mild conditions and the remaining WPP residue will be rich in lignin and hemicellulose (L-H). The cellulase treatment was optimized by the response surface methodology to achieve maximum pectin and phenolics recoveries. It has been recently shown that the biomass rich in

L-H is the best resource for the synthesis of bio-derived high-

performance hard carbon electrode materials.17 Therefore, in the following step, the biowastederived hard carbon electrode as an alternative to fossil-derived carbon electrode was synthesized by the pyrolysis carbonization of L-H rich WPP residue and tested in sodium battery. Thus, diverting the WPP from landfills and adhering to green chemistry principles.18 It also offers a distinct advantage over existing approaches which lose value present in biomass waste by its direct carbonization despite the presence of other natural products of high commercial value therein. Hence the complete conversion of WPP into value-added products via


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the proposed integrated process could eliminate environmental concerns with WPP disposal and substantially enhance the sustainability of WPP biomass use. Experimental Materials and preparation of WPP sample. The Cellulase from Trichoderma reesei (Celluclast® 1.5L, 700 U/g), commercial citrus pectin, punicalagin, ellagic acid, gallic acid, Folin-Ciocalteu reagent, D2O, etc., were obtained from Sigma Aldrich. The WPP of Wonderful variety were provided by a pomegranate processing company in Australia. The peels were oven dried for 24 h at 50°C, ground into powder (particle size 100 nm, and 10-100 nm). The samples were eluted at 40°C and 1.0 mL min-1 flow rate using aqueous solution (eluent) of 0.1 M NaNO3 and 0.1 M NaHCO3. The calibration curve (log molecular weight versus elution time) was established using PEG/PEO standards (Agilent) of molecular weights from 106-1,000,000 g mol-1. The filtered pectin samples (1 mg mL-1 in eluent) were injected onto the column and the molecular weight (MW) and polydispersity (PD) were determined by analyzing the data using EcoSec Analysis software. Analysis of phenolics. The ethanoic liquid phases containing phenolics obtained with the optimized extraction in triplicates were distilled to recycle the ethanol and then analyzed using an Agilent 1260 Infinity liquid chromatography system consisting of a Phenomenex Kinetex® 5 um C18 100Å column (250 mm × 4.6 mm) connected to a 6120 series quadrupole electrospray mass spectrometer as presented in previous work.8 The 10 uL of sample was injected (triplicate injections per sample) into the column and the phenolic compounds were separated under gradient elution at 30°C with two solvents (acetonitrile and water each containing 0.5% acetic 7 ACS Paragon Plus Environment


acid) at 1.0 mL min-1 and monitored at wavelengths: 210 nm, 254 nm, 280 nm, 320 nm, 378 nm. Electrospray ionization mass spectrometer was used under following settings: 100-1200 Da mass range, 12 L min-1 drying gas at 350°C, 35 psi nebulizer pressure, 3000 V capillary voltage, and positive and negative operation mode. The gallic acid was quantified at 280 nm whereas ellagic acid and punicalagin were quantified at 378 nm using their calibration curves. Synthesis of hard carbon and electrochemical performance test. The hard carbon was synthesized from WPP residuals after pectin and phenolics recovery by following a previously reported route with slight modification.27 Briefly, WPP residuals were vacuum dried at 110°C, ground followed by 5 h pyrolysis at 1100°C with 5°C min-1 heating rate in a tubular furnace under 100 mL min-1 nitrogen supply. The carbon formed by pyrolysis was treated at 70°C with 3.5 M aqueous KOH solution for 2 h, washed at 60°C with 2 M aqueous HCl for 15 h, filtered followed by washing with DI water to pH 7. The obtained carbon was dried and heated for 3 h at 300°C with 5°C min-1 heating rate under 50 mL min-1 dry air supply in the tubular furnace, ground, treated again with 2 M aqueous HCl followed by washing with DI water to pH 7. The hard carbon was characterized using X-ray diffraction (XRD, Bruker D8 Advance diffractometer with a Cu-Ka X-ray wavelength = 0.154 nm), Raman spectrometry (jobin yovon hr 800 microraman), and scanning electron microscopy (FEI Magellan 400 XHR FEGSEM). The slurry was prepared by adding hard carbon derived from WPP residuals, carbon black (C-65, Timcal) and CMC (Sigma-Aldrich) binder into the water in 80:10:10 mass proportion, uniformly layered onto aluminum foil and the hard carbon electrode was prepared by drying the aluminum foil at 120°C in vacuum. The electrochemical test (conducted in triplicates) of the hard carbon electrode was performed by using it as working electrode in the 2032 coin-cell half-cell configuration consisting of the sodium foil reference electrode, a separator of borosilicate glass fiber, and electrolyte of Ethylene Carbonate: Propylene Carbonate (1:1) v/v containing 1M 8 ACS Paragon Plus Environment

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NaClO4. The cyclic performance was assessed on a battery cycler (Biologic VMP-2) at 20 ± 5 °C and 0.05 mV s-1 scanning rate.

Results and Discussion Pectin and phenolics recovery by cellulase treatment. The maximum amount of pectin and phenolics was obtained by optimizing cellulase treatment with the Box-Behnken experimental design (Table 1). The variables and response were processed by applying multiple regression analysis and related as quadratic polynomial equations:

( ) ( )

( )

(2) Where A= Ultrasound time, B = Liquid: solid ratio, C = Cellulase dosage and D = Cellulase treatment time As shown in ANOVA of responses (Table 2) the predictive models are significant as their pvalues are 50%), 146.5 kDa-MW and 1.46-PD, whereas pectin isolated with conventional acid method had lower DE (60.2%), MW (139.3 kDa) and PD (1.37). The cellulase and conventional method derived pectin contained 72% and 64-65% galacturonic acid, respectively. Since the galacturonic acid content of pectin used for food applications should not be less than 65%,40 the cellulase derived pectin is good for food applications. Analysis of phenolics. The HPLC chromatograms of cellulase and conventional method derived phenolics extracts are illustrated in Figure S1a-b. The ellagic acid, gallic acid, and punicalagin (α and β anomers) were found in cellulase and conventional method derived phenolics extracts. Despite the similar TPC, the amount ellagic acid, gallic acid, and punicalagin (α and β anomers) in both extracts differed significantly (Table 3). The punicalagin, an active ingredient of pomegranate phenolics, is highly bioavailable and converted into potent antioxidants ellagic acid and urolithins inside the body.41 The consumption of free ellagic acid reduces its ability to offer antioxidant potency to the body as the free ellagic acid is less water-soluble at physiological pH which decreases its bioavailability.8,

42

The cellulase treatment was highly efficient for the

extraction of punicalagin being able to recover 8.48 g of punicalagin per 100 gDM of WPP which represents 71.2% of its total phenolics recovered. On the other hand, the conventional method extracted only 5.22 g of punicalagin per 100 gDM of WPP representing 42.4% of its total phenolics recovered, but the ellagic acid and gallic acid content of the conventional method derived phenolic extract was higher than that of cellulase derived phenolic extract (Table 3). This could be due to the punicalagin breakdown into ellagic and gallic acids by the high temperature and acidic conditions of the conventional method.13, 43 The punicalagin content of WPP has been reported to vary from 3.9-14.6 g per 100 gDM of WPP based on the pomegranate cultivar.44-45 The cellulase treatment of WPP of Wonderful cultivar presented in the current study recovers a 13 ACS Paragon Plus Environment


higher amount of punicalagin (8.48 g per 100 gDM) than that previously recovered by supercritical CO2 extraction (8 g per 100 gDM)46 and hydrothermal treatment (6.75 g per 100 gDM)8 of WPP of the Wonderful cultivar. This suggests that the cellulase treatment is better for extracting punicalagin - beneficial for human health. Synthesis and electrochemical performance test of hard carbon. The biomass waste is under continuous investigation as a renewable resource for the synthesis of sustainable bio-derived carbon electrode materials for battery applications.47 All of the approaches employ a direct thermochemical conversion of biomass waste to carbon materials, without considering the prior recovery of other value-added products present therewith. However, the present study demonstrates an integrated concept in which the value-added pectin and phenolics were first recovered from WPP biomass waste followed by carbonization of WPP residuals to hard carbon (HC) used as the electrode in energy storage devices. WPP residuals turn black after carbonization, indicating a successful transition to a carbon material. The CHN analysis indicated that the as-synthesized HC contains 97% C, 1% H, and 2% N. This leftover nitrogen even after the drying, washing, and annealing processes is most likely due to the proteins present in the WPP biomass.48 As shown in Figure 5a, the XRD analysis of HC derived from WPP residuals showed the appearance peaks of HC diffraction planes (002) and (100) located at 22° and 43°, respectively which confirms the formation of the HC.49 The SEM image in Figure 5b reveals the HC particles have irregular morphology with smooth surface and size less than 1 μm similar to commercially available HC50 and that synthesized from other biomass waste.48, 51 As shown in Figure 5c, the Raman spectrum of HC exhibit characteristic carbon D (corresponding to the carbon defect induction) and G (corresponding to the carbon atom vibration) bands at 1325 and 1594 cm-1, respectively.48 The D band : G band intensity ratio (2.9) is also in good agreement with that of commercial HC.52


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The Electrochemical performance of HC shown in Figure 6 was tested by HC| Na cell with electrolyte of Ethylene Carbonate: Propylene Carbonate (1:1) v/v containing 1M NaClO4. The cyclic voltammetry curves of HC from 0.01 to 2.5 V potential against Na/Na+ at 0.05 mV s-1 scanning rate are shown in Figure 6a. A broad peak of irreversible reduction appeared during first cycle is possibly because of the SEI layer.53 The insertion/extraction of sodium in HC as observed previously54 resulted in the appearance of two sharp redox peaks at about 0.1 V and 0.01 V. As can be seen in Figure 6b, at C/2 current density rate, a constant capacity of 180 mAhg-1 with 99% retention (excluded first cycle capacity) and almost 100% coulombic efficiency obtained after 100 cycles indicated an excellent cyclic performance of WPP derived HC electrode and followed the similar results of bio-derived HC electrode materials in sodium batteries17,

48, 54

. This result demonstrates that WPP residuals after the recovery of pectin and

phenolics can be carbonized to prepare a high-performance sodium battery electrode. The overall mass balance for the complete utilization of WPP is shown in Figure 7. After the ultrasound and cellulase treatment, 2.48 g pectin, 1.19 g phenolics containing 0.84 g punicalagin, and 3.53 g solid residue were recovered from of 10 g dw of WPP. Further carbonization of 3.53 g solid residue via pyrolysis followed by KOH activation resulted in the formation of 1.7 g hard carbon which was tested as carbon electrode in sodium battery. The process demonstrated in the present study not only provides a chance to recover value-added pectin and punicalagin rich phenolics from WPP but also broaden the remaining WPP residue for applications in batteries, thus allowing complete utilization of biomass waste in terms of sustainable standpoint. Such a process of hierarchical utilization of fruit waste biomass could be a viable option for fruit processing industries to improve their economics and diversify the product portfolio including value-added products and materials for energy storage devices. Acknowledgments 15 ACS Paragon Plus Environment


ST gratefully acknowledges the IITB-Monash Research Academy and TATA Chemicals, Pune, Maharashtra, India for providing the doctoral fellowship.

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j.; Zhang, W.-x., Biomass derived hard carbon used as a high performance anode material for sodium ion batteries. J. Mater. Chem. A 2014, 2 (32), 12733-12738, DOI 10.1039/C4TA02068E. Figure captions Figure 1 Schematic illustration of the biorefinery experimental scheme for the complete utilization of WPP. Figure 2 Surface response plots of the effect of (a) cellulase dosage and ultrasound time (b) cellulase treatment time and ultrasound time and (c) contour plots of the effect of cellulase treatment time and liquid:solid ratio on pectin and total phenolics yield. Figure 3 (a) IR (b) 1H NMR spectra (c) TGA of cellulase and conventional method derived WPP pectin compared to commercial pectin. The cellulase derived pectin was obtained at 20 minultrasound time, 15 mL g-1-liquid:solid ratio, 55 U g-1-cellulase dosage, and 4 h-cellulase treatment.



Figure 4

Influence of ultrasound time, liquid:solid ratio, cellulase dosage, and cellulase

treatment time on the degree of esterification, average molecular weight, and polydispersity of pectin obtained by proposed biorefinery scheme. While studying the influence of individual variable the other variables were kept constant at 20 minultrasound time, 15 mL g-1-liquid:solid ratio, 55 U g-1-cellulase dosage, and 4 h-cellulase treatment. Figure 5 Structural and morphological characterization of the hard carbon material a) X-ray diffraction pattern b) SEM image and c) Raman spectrum. Figure 6 Electrochemical performance of HC by HC|Na cell with organic electrolyte (a) Cyclic voltammetry performed at a scan rate of 0.05 mVs-1 (b) Charge-discharge cycling performance for 100 cycles at C/2 rate in the potential range of 0.01 to 2V vs Na/Na+. Figure 7 Overall mass balance flow chart of complete utilization of WPP.


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Figure 1



Figure 2a

Figure 2b

Figure 2c 26 ACS Paragon Plus Environment

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Figure 3a

Figure 3b 27 ACS Paragon Plus Environment


Figure 3c


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Figure 4



a

b

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c

Figure 5

Figure 6


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Figure 7



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Table 1 Box-Behnken response surface design with observed and predicted pectin and phenolics yields. Entry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

Ultrasound time (min)

10 20 20 20 20 20 10 20 20 30 20 10 30 20 20 30 10 20 20 20 30 20 10 10 30 20 20 30 20

Liquid:solid (mL/g)

25 25 15 15 15 15 15 15 15 15 15 15 5 15 25 15 5 5 5 5 15 5 15 15 25 25 15 15 25

Cellulase dosage (U/g)

Cellulase treatment time (h)

55 30 55 80 80 30 55 55 55 55 55 30 55 55 55 80 55 55 80 30 55 55 55 80 55 55 30 30 80

4 4 4 6 2 6 6 4 4 6 4 4 4 4 6 4 4 2 4 4 2 6 2 4 4 2 2 4 4

Pectin yield (%)

Exp. 10.1 9 24.8 25 20.1 19.5 18.5 25.3 24.7 21.6 24.6 8.3 18.5 25 18.5 22.2 10.9 10.4 20.5 10 15 18.5 7 19.2 13.2 6 5 15 16.8


Pred. 10.1 8.9 24.9 24.3 19.4 19.6 19.1 24.9 24.9 21.9 24.9 8.1 17.9 24.9 18.2 22.8 10.4 11.1 20.9 10.1 14.7 18.6 7.0 19.4 13.1 6.3 5.1 15.2 17.0

Total phenolics yield (%) Exp. 9 9.2 12 12.1 9.4 8.4 8.1 12.2 12 11 11.9 5.3 10.5 12.1 10.4 11.9 6.5 6 11.9 6 7.3 8.5 5.4 12 10.5 7 4.8 10.3 11.8

Pred. 9.2 9.2 12.0 12.1 9.4 8.3 8.0 12.0 12.0 11.1 12.0 5.2 10.3 12.0 10.4 11.9 6.5 5.9 12.0 6.2 7.5 8.6 5.4 11.9 10.5 6.9 4.8 10.3 11.8

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Table 2 ANOVA for quadratic model of the pectin and total phenolics recovery using cellulase treatment. Source

Sum of Squares

Model A-Ultrasound time B-Liquid:solid C-Cellulase dosage D-Cellulase treatment time AB AC AD BC BD CD A² B² C² D² Residual Lack of Fit Pure Error Cor Total

1162.07 82.69 19.25 270.75 281.30 5.06 3.42 6.00 1.82 4.84 23.04 159.10 326.06 82.44 117.30 4.10 3.79 0.3080 1166.17

Model A-Ultrasound time B-Liquid:solid C-Cellulase dosage D-Cellulase treatment time AB AC AD BC BD CD A² B² C² D² Residual Lack of Fit Pure Error Cor Total

173.10 19.25 6.02 52.50 28.83 1.56 6.50 0.2500 2.72 0.2025 0.2025 13.31 14.50 3.85 44.10 0.2445 0.1925 0.0520 173.34

df

Mean Square Pectin 14 83.00 1 82.69 1 19.25 1 270.75 1 281.30 1 5.06 1 3.42 1 6.00 1 1.82 1 4.84 1 23.04 1 159.10 1 326.06 1 82.44 1 117.30 14 0.2928 10 0.3791 4 0.0770 28 Total phenolics 14 12.36 1 19.25 1 6.02 1 52.50 1 28.83 1 1.56 1 6.50 1 0.2500 1 2.72 1 0.2025 1 0.2025 1 13.31 1 14.50 1 3.85 1 44.10 14 0.0175 10 0.0192 4 0.0130 28 33

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F-value

p-value

283.51 282.43 65.76 924.78 960.81 17.29 11.69 20.50 6.22 16.53 78.70 543.41 1113.70 281.58 400.65

< 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 0.0010 0.0042 0.0005 0.0257 0.0012 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001

significant

4.92

0.0691

not significant

707.97 1102.44 344.75 3006.18 1650.80 89.47 372.33 14.31 155.89 11.60 11.60 762.16 830.12 220.21 2525.27

< 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 0.0020 < 0.0001 0.0043 0.0043 < 0.0001 < 0.0001 < 0.0001 < 0.0001

significant

1.48

0.3758

not significant


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Table 3 Chemical composition of WPP phenolic extracts. The enzymatic extraction was done at optimal conditions: 20 min ultrasound time, 15 mL g-1 liquid: solid ratio, 55 U g-1 cellulase dosage, and 4 h cellulase treatment. Method Enzymatic extraction Conventional a

Total phenolics (g 100 g-1 db) 11.9 ± 0.2 12.3 ± 0.4

Punicalagin (g 100 g-1 db) 8.48 ± 0.05 (71.2%)a 5.22 ± 0.03 (42.4%)a

percentage of total phenolics


Ellagic acid (g 100 g-1 db) 1.67 ± 0.02 (14%)a 2.85 ± 0.01 (23.1%)a

Gallic acid (g 100 g-1 db) 0.38 ± 0.03 (3.2%)a 1.80 ± 0.01 (14.6%)a

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Abstract graphic Synopsis: Complete valorization of pomegranate waste was realized by producing pectin, punicalagin rich phenolics and hard carbon electrode.


Complete utilization of waste pomegranate peels to produce

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