Accepted Manuscript

Slow pyrolysis of chemically treated walnut shell for valuable products: Effect of
process parameters and in-depth product analysis

Shubhi Gupta, Goutam Kishore Gupta, Monoj Kumar Mondal

PII: S0360-5442(19)31102-8
DOI: https://doi.org/10.1016/j.energy.2019.05.214
Reference: EGY 15466

To appear in: Energy

Received Date: 15 March 2019

Revised Date: 7 May 2019
Accepted Date: 29 May 2019

Please cite this article as: Gupta S, Gupta GK, Mondal MK, Slow pyrolysis of chemically treated walnut
shell for valuable products: Effect of process parameters and in-depth product analysis, Energy (2019),
doi: https://doi.org/10.1016/j.energy.2019.05.214.

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 ACCEPTED MANUSCRIPT

Slow pyrolysis of chemically treated walnut shell for valuable products: Effect
of process parameters and in-depth product analysis
Shubhi Gupta, Goutam Kishore Gupta, Monoj Kumar Mondal*
Department of Chemical Engineering and Technology, Indian Institute of Technology (Banaras

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Hindu University), Varanasi 221005, Uttar Pradesh, India

Abstract

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Pyrolysis is important method to harness bio-energy from not easily degradable biomass to meet

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today’s energy requirement. The fixed bed slow pyrolysis of walnut shell was performed in

continuous inert atmosphere to find out the effect of process parameters like temperatures (300 -

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600°C), particle size (0.25 – 1.00 mm), and bed height (8 – 12 cm) on yield and product
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characteristics. Walnut shell was pretreated with phosphoric acid at different concentrations (0.2

- 0.8 M) to improve yield and properties of pyrolysis products by removing inorganics and
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solubilizing lignin-hemicellulose components of biomass. Pretreatment showed enhanced

biochar and bio-oil yield. Characterization of biochar was done using proximate, ultimate
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analyses, FTIR, XRD, SEM-EDX, etc. The physicochemical properties of liquid product such as
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viscosity, density, carbon residue, HHV and FTIR were determined. Pyrolytic gas composition
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was analyzed using GC-TCD and GC-FID. The properties of biochar inferred its utility as solid

fuel or in waste water treatment as it has high BET surface area. The properties of bio-oil
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disclose its utility as blend fuel or a source of different valuable chemicals. Presence of CH4, H2
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and CO in pyrolytic gas recommends good combustion behaviour. Thus above results describe

the bio-energy potential of walnut shell.

Keywords: Walnut shell; pretreatment; pyrolysis; characterizations.

*Corresponding author: Tel.: +91 9452196638; fax: +91 5422367098;

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E-mail address: [email protected]

1. Introduction

With growing industrialism and technology, fossil fuel reserves are depleting enormously day by

day. Fossil fuels, in addition to being a non-renewable energy source, releases toxic gases to the

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environment and increase the rate of global warming. Thus there is a need to search for a

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renewable, sustainable as well as an environment-friendly resource for the synthesis of energy

and chemicals. Use of biomass has proved to be an effective substitute for fossil fuels in the

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present scenario. Biomass takes in carbon as it grows and releases this carbon when used for

energy, resulting in a carbon-neutral cycle that does not increase the atmospheric concentration

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of greenhouse gases. In addition to it, biomass contains lesser amount of nitrogen and sulphur,
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thus resulting in lesser release of NOx and SOx after thermochemical treatment [1]. Several

transportation fuels can be produced from biomass, helping to alleviate the demand for
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petroleum products and improve the greenhouse gas emissions profile of the transportation
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sector.
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There are number of methods to extract energy from biomass like chemical, biochemical and

thermochemical. Fermentation and anaerobic digestion are the most common biochemical
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processes used for energy conversion. However, because of their lesser efficiency and more time

consumption, they are less preferred. Also, nitrifying-enriched activated sludge (NAS) biomass
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is being used in wastewater treatment that enhances the permeation and mitigates the fouling
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problem [2]. Combustion, gasification and pyrolysis are the most common thermochemical

processes to extract bio-energy from biomass [3]. Combustion is a high-temperature oxidation

process in which complete oxidation of biomass takes place and as a result, heat is produced in

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the form of energy. Through this process only around 10% of the energy can be extracted and it

is also a source of substantial pollution. Gasification is a partial oxidation process that converts

solid biomass into gaseous fuel. But it requires high temperature and expensive experimental set-

ups. Pyrolysis involves the thermal degradation of solid biomass into solid, gaseous and liquid

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products without any oxidizing agent, i.e. in an inert atmosphere at moderate temperature range

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[4, 5, 6]. The proportion of the three products depends upon the type of feedstock used as well as

the process conditions [7, 8]. Liquid product or pyrolytic oil consist of numerous oxygenated

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hydrocarbons belonging to alcohols, aldehydes, ketones, carboxylic acid, carbonyls, phenols,

ethers, esters, furans, sugars, etc., has high calorific value and can be upgraded [9].

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In comparison to coal and petroleum-based fuels, bio-oil-based transport fuels have low sulphur
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and aromatic content [10]. Solid char is a carbon-rich product that can be used as solid fuel

having higher heating value compared to most high rank coals [11, 12]. It also finds application
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as an effective adsorbent for waste stream purification, carbon sequestrate, as support in catalyst
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preparation [13] or in soil amendment [14]. Non condensable gases produced during pyrolysis is
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mixture of CO, CO2, CH4 and H2 signifies good combustion behavior and can be used in fuel

cells [15], gas turbines as combined heat and power cycle [16] and also to meet the energy
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requirement of pyrolysis process [17, 18].

There can be numerous feedstocks for pyrolysis process like agricultural residues, wood, green
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plants as well as waste from food processing industries but waste biomass with no economic
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value can be considered as the most suitable feedstock for pyrolysis process. Extensive work has

been done in field of bio-oil production and pyrolysis of biomass by utilizing number of biomass

feedstock. But walnut shell is still an unutilized feedstock in spite of its high carbon content and

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high calorific value along with wide stock production of walnut shell waste every year [19, 20].

Walnut shells are the most abundant, inexpensive and lignocellulosic waste available in India

with an annual production of around 25000 tons according to the Indian walnut market (2011). A

very few researches that are being done on walnut shell suggests high potential of walnut shell

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bio-oil as transportation fuel. Acikalm and Karaca (2017) [21] performed slow pyrolysis of

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walnut shell and showed that bio-oil produced through the process has high prospective to be

used as fuel for engines after up gradation or it can also be utilized as such without up gradation

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as low grade boiler fuel. Also biochar can be used as a valuable fuel having calorific value in the

range to that of bituminous coal.

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Kar (2011) [22] investigated the synergetic potential of copyrolysis of walnut shell with tar sand
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and showed that addition of tar sand increases the alkaline and aromatic content of the bio-oil.

Biochar produced from walnut shell had high adsorption potential for number of heavy metals
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and dyes. Ding et al., (2013) prepared a biosorbent from walnut shell which has high selectivity
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and affinity for cesium metal [23]. Similarly, Yang and Qiu (2010) showed that activated carbon
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produced via vacuum chemical activation of walnut shell can be effectively utilized for dyes

such as methylene blue from aqueous solution [24]. Preparation of carbon sieves from walnut
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shell is another interesting application area for walnut shell [25]. Also, Senneca et al. (2018) [26]

performed the slow pyrolysis of walnut shell at 600 °C in the presence of nitrogen and carbon di
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oxide. Kinetic study for biomass degradation was studied using the results from TGA. The char
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and tar samples were analyzed with GC-MS, elemental, TGA and SEM.

Present work aimed to convert the walnut shell into valuable products using pyrolysis. Prior to

the process, the suitability of walnut shell was checked using various characterizations

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(proximate, ultimate, high heating value (HHV) and thermogravimetric analysis (TGA)). The

effect of different process parameters like temperature, particle size and bed height on the

product distribution and its characteristics were investigated for their application in different

fields. Also, the effect of chemical (phosphoric acid) treatment of biomass on product yield and

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its quality was studied. Moreover, the optimum process conditions at which maximum liquid

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product yield obtained from slow pyrolysis of the walnut shell was also determined. Previous

researches lack such detailed study of all the three products from walnut shell pyrolysis at

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different process parameters. This work has massive involvement in this regard as such detailed

characterization study from walnut shell pyrolysis has not been performed earlier.

2. Materials and methods

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2.1. Raw material

Walnut shells were brought from the local market nearby Banaras Hindu University, Varanasi,
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India, washed with deionized water to remove impurities, and then oven dried at 105 oC until we
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get the constant weight of the sample. Walnut shells were then grinded in rotary mill and passed
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to sieves to produce four samples with size range 1.0mm<dp<0.71mm, 0.71mm<dp<0.6mm,

0.6mm<dp<0.42mm and 0.42mm<dp<0.25mm. Prepared samples were then stored in sample

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containers for pyrolysis experiments.

2.2. Pretreatment of biomass

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Phosphoric acid (H3PO4) was used for the pretreatment of walnut shell. Firstly stock solution of
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2M was prepared by adding 11.869 mL (density 1.685g/mL, 98% purity) H3PO4 solution with

deionized water to make up to 100mL of the solution. Then it was diluted with deionized water

to make 0.2, 0.4, 0.6 and 0.8M solutions required in the experiments. The 20g of walnut shell

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was mixed with 100 mL of desired concentration H3PO4 solution. Continuous mixing was done

in magnetic stirrer at 600 rpm for about 2 hours and mixture temperature was kept at 100 °C

during the mixing process. Then the biomass solution was filtered using filter paper to remove

excess acid and dried in the oven at 110 oC for 24 hours to lower down the moisture

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content (less than 10 wt%).

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2.3. Experimental setup and procedure

Pyrolysis of the walnut shell was conducted in fixed bed stainless steel tubular reactor externally

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heated by split tube furnace. The length of the reactor was 500 mm and internal and outer

diameter of the reactor was 44 mm and 40 mm respectively. The temperature inside the reactor

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was measured by thermocouple and PID (Proportional derivative controller) is fitted to control
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the reactor temperature. To determine the effect of parameters like temperature, particle size, and

bed height as well as biomass pretreatment on pyrolysis products, experiments were performed
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in different runs. 20 g of the sample with particle size 1.0mm<dp<0.71mm was fed to the fixed
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bed stainless steel reactor. Pyrolysis was performed in the inert gas atmosphere. Inert nitrogen
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gas was purged at a rate of 200 ml/min for 30 minutes and then the furnace was switched on until

the desired temperature (300-600 °C) was attained with the heating rate of 15oC/min. The
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residence time of 60 minutes was provided inside the reactor. Pyrolysis flow diagram of the

process is shown in Fig. 1.

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Pyrolysis liquid, gaseous and solid products were collected after 60 min of retention time. Bio-oil
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was condensed using ice cooled condenser and weighted. Biochar was collected using

compressed air supply and weighted. Gas yield was determined by subtracting the liquid and

biochar weight from the total sample weight. Then the above experiment was repeated in the

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same manner at optimum temperature to determine the effect of particle size and bed height as

well as optimum process conditions. Once the optimum process condition was determined then

acid pretreated biomass was pyrolysed at that optimum condition to analyze the effect of acid

leaching on product distribution as well as the quality of biochar and bio-oil. All the pyrolysis

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experiments were performed in triplicate and average values have been reported.

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3. Characterization and instruments used

Proximate analysis was carried out to determine moisture content, ash content and volatile matter

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in accordance to standard method ASTM D1037 (1991), ASTM D2017 (1998) and ISO 562

(1974) respectively. Fixed carbon was calculated by subtracting the sum of ash, moisture and

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volatile percentage from 100.The ultimate analysis was carried out to determine the elemental
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composition of the sample. It was performed through EURO-EA, EUROVECTOR instruments,

Italy. The higher heating value (HHV) indicates the energy content of the sample. It was
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calculated by using bomb calorimeter manufactured by Rajdhani scientific instts. Co., New Delhi
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(India). Thermogravimetric analysis of walnut shell was performed using SHIMADZU TGA-
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50H model with temperature range from ambient to 900 °C. The pH of the samples were

measured by systronics pH meter India. Fourier transform infrared analysis (FTIR) was carried
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out to determine the organic and inorganic functional groups present in the sample. It was

performed on Fourier transform spectrophotometer (Thermo electron corporation, USA) in range

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of 4000 - 400 cm-1 wave number. Scanning Electron Microscopy (SEM) was used to examine
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physiological and morphological changes occurred in biomass during pyrolysis. EDX was done

to determine the elemental composition of biochar. The model used was Evo 18 Research, Carl

Zeiss, Oxford Instruments (Germany). X-ray diffraction (XRD) was carried out to determine the

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crystalline structure of biochar samples. The XRD pattern was obtained by a diffraction unit

(RIGAKU MINIEX DMAX-B) with wavelength 1.54056 A, current 15 mA and 40 KV potential

difference. BET analysis was performed to determine the surface area and pore volume of the

biochar samples to have an idea about the adsorptive capacity of the samples. It was performed

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on micrometrics ASAP 2020 surface area and porosity analyzer. Viscosity measurement of bio-

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oil samples were carried out by Redwood Viscometer I.P. 70/46 Instrument No – 6084,

GALLENKAMP, British made. The water content was determined using Karl Fisher moisture

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titrator, model 1760, Esico International, Himachal Pradesh, India. Standard ASTM D 1298

method was used for the density measurement. The quantitative analysis of gases emitted from

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pyrolysis was done by gas-chromatography (GC) Nucon 5765 (India) with TCD and FID
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detector fitted with Porapak-Q column.

4. Results and discussion

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Raw walnut shell is abbreviated as RWS. Pretreated biomass is denoted by RWS-Y. Biochar and
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bio-oil obtained without pretreatment are labeled as BC-X and BO-X where X denotes
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temperature of pyrolysis. Pretreated biochar and bio-oil are denoted as BC-X-Y and BO-X-Y

where X denotes the pyrolysis temperature and Y denotes the concentration of acid used for
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pretreatment.

4.1. Thermogravimetric analysis of walnut shell

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Fig. 2 depicts the TG/DTG analysis of raw walnut shell biomass at constant heating rate of 15
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C/min from ambient temperature to 900 oC in continuous flow of nitrogen gas. 7.951 mg of

walnut shell was loaded for the TG analysis. TG analysis of the walnut shell provides its

pyrolysis behaviour and rate of mass loss. The TG curve shows initial mass loss till around 140

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C that is due to the release of extrinsic or intrinsic moisture and lighter lower volatile

compounds. Thereafter no degradation occurred till around 200 oC and then again degradation

started from 200 oC and it continued to degrade further up to 600 oC at which all the volatiles got

released into product. Depending upon this, pyrolysis of walnut shell can be divided into 3 zones

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where the first zone is simply moisture removal from the biomass. Second one starts from 200-

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280 oC which involves devolatilization of hemicellulosic components of biomass. Third zone

from 280-410 oC represents thermal decomposition of cellulosic constituents present in the

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walnut shell. Maximum devolatization occurred in the temperature range of 200 – 410 oC since

pyrolytic cracking as well as series of reaction occurs simultaneously [1]. Lignin is the third

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component in the biomass that is very difficult to degrade and it degrades in wider temperature
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range due to its heterogeneity. A small volatile fraction was observed till 600 oC but beyond 600
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C the release of volatiles was almost negligible. Thus it reveals that pyrolysis of walnut shell
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into various products can be done in the temperature range of 300 – 600 oC in an energy efficient
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manner [3].
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DTG curve of the biomass shows two peaks and a plane tailing section. A very small peak

around 105 oC is attributed to the the release of moisture from the sample. Two peaks are
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observed in the temperature range of 200 – 400 oC, the first peak represents the decomposition of

hemicelluloses whereas the second peak corresponds to the decomposition of cellulose

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components in biomass. Tailing section in the graph attributes to the thermal decomposition of
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lignin present in raw biomass which decomposes over a wide temperature range giving char

residue at the completion of reaction.

4.2. Pyrolysis of walnut shell in fixed bed system

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4.2.1. Effect of temperature

Temperature is the most important parameter affecting the yield and properties of pyrolysis

products. Temperature range 300-600 oC was selected for pyrolysis of walnut shell. The

selection was done based on thermogravimetric analysis of walnut shell and several other studies

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done on similar raw material which ensures that maximum decomposition occurs in temperature

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range of 350 to 600 oC [27, 28]. Increase in pyrolysis temperature increases the yield of bio-oil

and gas at the expense of low yield of biochar as shown in Fig. 3(a). At low temperature,

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biomass gets carbonized into biochar due to charring reactions which occurs at low temperature.

As temperature increases, de-volatilization reaction occurs releasing more volatiles thus leading

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to increase in the yield of bio-oil and gas. However, with further increase in temperature above
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500oC, volatiles undergoes several secondary cracking reactions like polymerization, de-

carbonylation, decarboxylation and reforming reactions leading to the increase in non-

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condensable gases with decrease in the yield of bio-oil [21]. Similar results were obtained by
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other researchers with similar feedstock [19, 21].

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4.2.2. Effect of particle size

Fig. 3(b) shows the effect of particle size on the yield of solid, liquid and gaseous products.
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Particle size significantly affects the yield of pyrolysis products. With the increase in particle

size, the yield of biochar increases with a decrease in the yield of bio-oil and gas. As the particle
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size increases then the difference between surface temperature and core temperature increases
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leading to an increase in heat transfer resistance. Moreover, with the increase in particle size, it

can be difficult for the volatiles to escape out and thus it gets re-polymerized into more stable

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char leading to the increase in char yield [29]. Similar results were also obtained by many other

researchers [30, 31].

4.2.3. Effect of bed height

Bed height is another factor affecting pyrolysis products yield. Since the heating zone in split

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tube furnace was 15 cm, bed height variation from 8-12 cm was done. Increase in bed height

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provides resistance for escaping of volatile vapours. Thus the yield of biochar increases with the

formation of more stable and carbon-rich char due to increase in heat and mass transfer

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resistance while that of oil and gas yield (Fig. 3(c)) reduces due to re-condensation of volatiles

into stable char [29].

4.2.4. Effect of pretreatment

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Pretreatment of biomass with acid also has an incremental effect on the yield of biochar and bio-

oil. Acidic pretreatment removes all the inorganic metal content like most of the alkali and
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alkaline earth matter and solubilizes most of the lignin and hemicellulose component of the
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biomass and thus increase the relative concentration of cellulose [32]. Presence of the alkali and
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alkaline earth metals catalyze the secondary pyrolysis to form non-condensable gases. Thus

phosphoric acid pretreatment increased the yield of bio-oil and char by selective pyrolysis of
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cellulose. However, with the further increase in acid concentration beyond 0.6 M, it does not

further reduce the mineral concentration while the phosphoric acid concentration continues to
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build up due to its adsorption over biomass surface during pretreatment which can be shown in
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Fig. 3(d). This reduces the relative concentration of cellulose thus lowering the yield of bio-oil

and biochar.

4.3. Feedstock and solid product analysis

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4.3.1. Proximate analysis and heating value

The proximate analysis of raw walnut shell and its corresponding biochar at different pyrolysis

temperature is shown in Table.1. The fixed carbon content of raw walnut shell is 19.33% and its

volatile content is 71.52% which is same as published in other studies for similar raw material

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[19]. Pyrolysis process reduces the moisture and volatile content of the biomass resulting in

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different properties of pyrolytic char as compared to that of raw biomass.

Volatile content of the biochar decreases from 35.7% to 33.63% when pyrolysis temperature

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increases from 300oC to 400oC and it drops to 12.18% at a pyrolysis temperature of 600oC. Fixed

carbon shows a reverse pattern with that of volatile matter. The fixed carbon content of biochar

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is 56.62% at pyrolysis temperature 300oC and it increases to 59.59% at pyrolysis temperature
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400oC while it rises to 80.91% by pyrolysing at 600oC. This increase in fixed carbon content is

due to more and more volatiles released at higher pyrolysis temperature. Ash content of biochar
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increases with increasing pyrolysis temperature which indicates the increase in inorganic
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minerals in the biochar at higher pyrolysis temperature. Acidic pretreatment of biomass results in
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a decrease in ash content due to the removal of inorganic matters as well as a decrease in

moisture content for both raw biomass and biochar produced after pyrolysis. Fixed carbon and
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volatile matter increase after acid leaching. Thus the properties of biochar produced were

improved after pretreatment.

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The HHV shows the gross calorific value including the latent heat of vaporization of produced
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vapor product too. HHV value indicates the heat content of the solid and its potential to be used

as solid fuel. It can be seen that HHV of the char increases with increase in temperature. This is

because of the increase in carbon content due to more carbonization at a higher temperature. The

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heating value of char at 600oC is 30.966 MJ/Kg which is very close to pure carbon [33]. The

HHV of biochar after acidic pretreatment was increased as shown in Table 1 due to increase in

fixed carbon content and reduction in ash and moisture content leading to the improvement in the

fuel property of the biochar. The HHV can also be determined from proximate data. The

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following equation gives the heating value of the solid fuel by utilizing its fixed carbon(%),

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volatile matter(%) and ash(%) which comes to be very near to that obtained using bomb

calorimeter [34]:

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HHV (MJ/Kg) = 0.3536 FC + 0.1559 VM - 0.0078 ASH

4.3.2. Ultimate analysis

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Ultimate analysis of raw biomass and biochar produced at different pyrolysis temperature is
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shown in Table 2. It designates the stability of biochar. With increase in temperature, carbon

content increases in biochar with a decrease in oxygen, hydrogen and nitrogen content make the
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char more carbonaceous [35]. This is advantageous for being used as energy fuel as well as being
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applied in the soil as a carbon source. The increase in HHV of biochar was observed with
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increasing pyrolysis temperature because of the increased carbon content in the biochar that is

responsible for energy content in biochar [36]. Pyrolysis process favours the elimination of H
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and O over C. Thus O/C and H/C ratio reduces with increase in process temperature. O/C ratio

indicates the extent of deoxygenation over the extent of charring and H/C ratio tells about the
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aromaticity and resistance to microbial and chemical degradation. Biochar obtained after
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pretreatment has a higher percentage of carbon and lower amount of oxygen due to the removal

of inorganics and dehydration. Moreover, the content of hydrogen and nitrogen remains

unaffected.

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4.3.3. FTIR analysis

FTIR spectra of walnut shell and its corresponding biochar at different pyrolysis temperature is

shown the Fig. 4(a). The analysis provides information about various organic and inorganic

functional groups as well as about the chemical nature of the compound. The O-H stretching

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vibrations present between 3600 and 3100 cm-1 indicates the presence of phenols, alcohols, and

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carboxylic acid. The presence of this broadband with hydrogen bonding indicates that still, some

water remained present in the shell. The intensity of the peak decreases with the increase in the

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temperature and at 600oC, the peak almost disappears. C-H stretching bands present between

3000 and 2800 cm-1 and C-H deformation bands present between 1350 and 1475 cm-1 indicates

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the presence of alkanes. C=O carbonyl vibration with transmittance bands present between 1750
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and 1625 cm-1 indicates the presence of aldehydes, ketones, carboxylic acids. Bands present

between 1640 and 1550 cm-1 signifies the presence of amides. In the region between 1800 and
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900 cm-1 several bands are present that corresponds to different functional groups present in
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cellulose, hemicellulose, and lignin whose intensity depends on the proportion of the
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components. Peaks between 1575 and 1675 cm-1 show the presence of C=C stretching vibrations

that correspond to alkenes and aromatics. C-O stretching vibrations present between 1300 and
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1000 cm-1 in ethers and esters. An increase in pyrolysis temperature results in a decrease in the

intensity of many peaks. The absence of many peaks indicates that the char is mostly carbonized.
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The decrease is observed in bands due to carbonyl C=O groups, C-H aliphatic groups, C-O
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groups. There is an increase in the aromatic content with increase in temperature that is in

accordance with many authors [37, 38].

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Pretreated samples show same spectra as that of untreated samples as shown in Fig. 3(b). Thus it

because acid washing removes only ash content of the biomass while it has no significant effect

on the organic compounds during mild acid pretreatment. However, some of the organic

compounds decompose with an increase in the concentration of the acid which can be shown by

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the reduction in the peak intensity at higher acid concentration.

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4.3.4. XRD analysis

X-ray diffraction (XRD) is a unique technique in the determination of crystallinity of the

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material. XRD diffractogram for raw walnut shell, biochar produced at 500 and pretreated

biochar at optimum concentration is shown in Fig. 5. Two sharp and intense peaks were detected

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in the diffractogram of the walnut shell at a 2ϴ angle of around 18o and 22o, these peaks are
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assigned to a crystalline region of cellulose. Hemicellulose and lignin are generally amorphous in

nature. In the biochar obtained at 500 °C, peak at 22o decreases in intensity and becomes broader
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and peak at 18o disappears. This indicates that the decomposition of cellulose at 500 oC and some
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of the cellulose still remained at 500 oC while the cellulose completely decomposes at further
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higher temperature leaving the char fully amorphous. With an increase in temperature, the

crystallinity of the biochar reduces while its amorphous characteristics increase.

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Acid hydrolysis breaks down the crystalline structure of the cellulose and makes it more

available for degradation. This can be confirmed by the XRD pattern of the biochar obtained
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after pretreatment as shown in Fig. 5. The amorphous nature of biochar increases after acidic
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pretreatment of the biomass.

4.3.5. BET analysis

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BET surface area, average pore volume and average pore diameter of biochar samples are shown

in the Table 3. BET surface area and pore volume increase with temperature due to the formation

of more micropores at a higher temperature [39]. Thus the average pore diameter reduces from

14.504 to 2.744 nm as temperature increased from 300 to 600oC. BET surface area increases

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from 5.895 to 201.846 m2/g as the temperature rises from 300 to 600oC. A sharp increase in BET

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surface area is observed at 600 oC due to the release of pore blocking substances like ash and

release of volatiles which open up the pores making biochar more porous. Since inorganics are

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removed during acid pretreatment which further leads to the increase in surface area from

201.306 to 271.306 m2/g. Thus, it can be concluded from BET analysis that biochar obtained

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from pyrolysis has a high surface area to be effectively utilized as adsorbent and to be applied to
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the soil. Moreover, its effectiveness as an adsorbent increases with pretreatment which leads to

the high surface area and more microporous biochar.

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4.3.6. SEM/EDX analysis

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SEM EDX analysis was used to depict the surface morphology and structural properties of raw
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biomass and to analyze the change in morphology that occurs by applying pyrolysis at different

temperatures. SEM images of raw and pretreated biochar at different temperatures are shown in
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Fig. 6 and 7, respectively. SEM image of raw biomass material shows that it has a completely

fused structure having no pores. Pyrolysis process results in the development of some pores on
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the surface of biochar due to dehydration and precipitation reactions as well other cellulose
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degradation reactions that occur during pyrolysis which results in opening up the pores on the

surface of biochar. At 300oC, biochar surface shows very few pores but as the temperature

increases number of pores increases, reducing the size of individual pores. Though the changes

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are observed in surface morphologies of the biochar the original rough structure of biomass

retained during the pyrolysis process. This occurs due to reason that lignin only undergoes partial

degradation during pyrolysis process and thus some of the lignin still remained in the biochar

carrying the original structure of biomass material in the biochar. It can also be seen that some of

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the pores that are present in biochar at low temperature disappear at a higher temperature. This

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may be due to more releases of volatiles at a higher temperature. Due to its porous nature, many

researchers suggested the use of walnut shell biochar to be used as an adsorbent for removal of a

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large number of heavy metals and other components in wastewater treatment after certain

physical and chemical modifications [40]. In addition, pretreatment with phosphoric acid

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increased the number of pores in the biochar and enhanced the concentration of phosphorus in
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the biochar that can improve the soil fertility for better plant growth [14].

The EDX analysis of raw, pretreated walnut shell and its biochar is shown in Table 4. It is done
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to determine the elemental composition on the surface of the biochar. Biochar produced from
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pyrolysis has a mineral-rich composition consisting mainly of carbon, oxygen, and nitrogen in
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addition to the small proportion of other minerals like sodium, magnesium, potassium, iron,

calcium, etc as depicted in Table 4.

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Carbon content in biochar increases with increase in pyrolysis temperature due to a higher degree

of carbonization at a higher temperature while the oxygen content reduces due to a number of
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dehydration reactions at high temperature. Thus O/C ratio decreases with increase in pyrolysis
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temperature. EDX analysis shows that biochar is rich in nitrogen and other mineral content and

thus can be effectively utilized as a soil conditioner to enhance soil fertility. The SEM images of

pretreated biochar show that acid pretreatment opens up the pores making biochar more porous.

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Inorganic mineral content decreases in the biochar. Most of the inorganic mineral concentration

is due to the presence of phosphorous in the biochar which gets adsorbed on the biomass surface

during pretreatment [41]. Phosphorous is an effective plant growth nutrient. So such

phosphorous enriched biochar can be effectively utilized as fertilizer for enhancing nutrient

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content in the soil and an effective adsorbent for removal of harmful impurities.

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4.3. Bio-oil analysis

4.3.1. Physical characterization of bio-oil

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Bio-oil obtained from pyrolysis of the walnut shell has a yield of about 40-45%. The various

physical properties of bio-oil obtained at 400 and 500oC along with pretreated bio-oil at 500oC

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and 0.6 M acid concentration is represented in the Table 5.
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Bio-oil has a high water content of about 33-36 % which is mainly due to the intrinsic water

content of the feedstock and some of the water formed during pyrolysis reactions and it can be
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minimized by carrying out pyrolysis at a higher temperature. Bio-oil obtained through pyrolysis
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is corrosive having pH in the range of 2.4-2.5 because of the presence of various carboxylic acids
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like acetic acids, formic acids, propionic acids, etc. Hence, it can create handling and storage

problems due to the corrosive nature. Pyrolytic bio-oil is higher in density and viscosity as
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compared to that of commercial diesel fuel [8, 9]. Increase in density is observed at higher

temperature due to the formation of various high molecular weight oligomeric compounds at
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high temperature. The viscosity of bio-oil is increased with increase in temperature because of
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the reduction in water content [42, 43]. Bio-oil is highly unstable and its constituents undergo

various aging reactions leading to the increase in its viscosity. Such aging reactions can be

minimized by keeping bio-oil at a cooler temperature. Carbon residue explains the percentage of

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unburnt carbon left after ignition. Its value ranges from 4-5 % for bio-oils but it is negligible for

diesel fuels. HHV of the bio-oil is about 40–50% that of the diesel fuel [9]. The lower heating

value of the oil is due to the presence of water content and oxygenated compounds but since the

increase in the temperature leads to the reduction in both water content as well as oxygenated

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compounds thus the heating value of bio-oil improves at a higher temperature.

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Acidic pretreatment resulted in slight variation in physical properties of bio-oil. pH of bio-oil

reduces from 2.39 to 2.14 after pretreatment at 500 °C-0.6 M phosphoric acid which may be due

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to the reduction of alkaline metals from the biomass. Since the water content of bio-oil increases

thus chemical reaction due to pretreating acid results in the production of water. However, with

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reference to water content viscosity of bio-oil must decrease but here viscosity of bio-oil
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increases from 30 to 37 cst. This is because of the additional polymerization of bio-oil after

acidic treatment. There is not much variation in density of bio-oil after phosphoric acid
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pretreatment. Calorific value of bio-oil was reduced to 19.07 MJ/kg which is in accordance with
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increased water content.

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Thus bio-oil obtained from either raw pyrolysis or pretreated pyrolysis needs to be upgraded for

its direct use in boilers or engines because of its corrosive nature, instability, large water content,
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high ignition delay, high viscosity and low calorific value. The upgradation can be done through

various techniques like catalytic cracking, hydroforming, etc. for its use in various fields.
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4.3.2. FTIR analysis

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FTIR spectra of untreated and acid pretreated bio-oil at 400 and 500 oC and different acid

concentration are shown in Fig. 8 (a) and (b), respectively. FTIR analysis of the bio-oil was done

to predict the functional groups present in the sample and gave an idea about the chemical

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composition of the sample. The IR spectra obtained for samples pyrolyzed at 400 and 500 oC are

more or less very similar.

O-H stretching vibrations present between 3600 and 3100 cm-1 indicates the presence of phenol,

alcohol, and water in the sample. The large intensity of the peak shows the abundance of water,

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alcoholic and phenolic content in the bio-oil. C-H stretching vibrations present between 3000-

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2800 cm-1 and C-H deformation vibrations present between1500-1440 cm-1 is related to the

presence of alkanes. Peaks between 1750 and 1625 cm-1 represent C=O stretching vibrations

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which shows the presence of ketones, aldehydes and carboxylic acid in the bio-oil sample. C=C

symmetric stretching vibrations present between 1675 and 1600 cm-1 is related to the presence of

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alkenes. C=C stretching vibrations present between 1600 and 1500 cm-1, C-H in-plane bending
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present in the region between 1150 and 1000 cm-1 and C-H out of plane bending in the region

between 900 and 650 cm-1 is indicative of the presence of various aromatic compounds in the
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sample. C-O stretching peaks present between 1300 and 1000 cm-1 shows the presence of ether
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and esters. The number of peaks present in the region between 700 and 900 cm-1represents the
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presence of monocyclic and polycyclic substituted aromatic compounds. FTIR analysis of acid

pretreated bio-oil shows narrowing of the peak near 3423 cm-1 indicating a reduction in the
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moisture content and increase in organic content in the bio-oil due to less intense dehydration

reactions on acid washing.

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4.4. Gas analysis

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About 20-30% gas is produced during pyrolysis process. Syngas produced during slow pyrolysis

process is mainly composed of CO, CO2, CH4 and H2. Fig. 9(a) shows the variation of

concentration of different gases produced during pyrolysis with temperature. The yield and

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average composition of gas produced highly depend on pyrolytic temperature. These gases are

produced due to several reactions such as decarboxylation, dehydrogenation, decarbonylation,

deoxygenation that occurs during pyrolysis process. The rate of these reactions increases with

increase in temperature thus high yield of gas is obtained at high temperature at the expense of

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low yield of oil and char. CO and CO2 are the indicators of the presence of oxygen in the

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biomass and are generally produced due to decomposition and reforming of carbonyl (C=O) and

carboxylic group (COO). CH4 is produced during decomposition of methoxy (-O-CH3) and

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methylene (-CH2-) groups while H2 is produced due to cracking and dehydrogenation of heavier

hydrocarbons which mainly occur at higher temperature. CO and CO2 are mainly produced due

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to decomposition of hemicellulose and cellulose which occurs at low temperature while CH4 and
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H2 are produced due to lignin decomposition at high temperature [44, 45]. Release of CO and

CO2 showed opposite trend to that of CH4 and H2. With the increase in temperature CO and CO2
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concentration decreases while trend of H2 and CH4 production increases with temperature. At
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low temperature CO2 is the main product and H2 and CH4 are the main components of syngas at
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higher temperature. Decomposition starts from 300oC thus at this temperature very little

proportion of gases are formed. HHV of pyrolytic gases ranged from 2 to 6 MJ/m3 which
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represents a medium value for gas to be used as fuel. However, it was seen that heating value of

the gases increases with the increase in temperature as shown in Fig. 9(b). Pyrolytic gas
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produced by pyrolysis has a satisfactory level of combustible matter and energy content and thus
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is an appropriate candidate to be used as gaseous fuel after certain modifications.

5. Conclusion

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In this study, pyrolysis of waste walnut shell was carried out to produce solid biochar, liquid bio-

oil, and non-condensable gases and to determine the effect of type of feedstock and operating

conditions like temperature, particle size and bed height on the pyrolysis product yield and

properties. Feedstock selected for pyrolysis should have a high carbon content, low moisture, and

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ash content. Thus walnut shell is the most appropriate candidate having a fixed carbon content of

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21.33%. At 300oC, about 42.448% of the biochar is formed. The yield of bio-oil shows a

maximum with the temperature at 500oC while gas yield increases continuously with

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temperature. The yield of bio-oil decreases with increase in particle size due to increase in heat

and mass transfer resistance. Bed height also affects the pyrolysis process by providing

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resistance to the escaping vapours. Pretreatment of the walnut shell with H3PO4improves the
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yield of both biochar and bio-oil. Highly porous, carbon-rich and phosphorous enriched biochar

is obtained after pretreatment. It can be effectively utilized as fuel, as an adsorbent and can be
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applied in the soil as soil enhancer due to rich phosphorous content. Quality of bio-oil improves
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after pretreatment by lowering the proportion of oxygenated organic compounds which in turn
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increases its calorific value. This makes bio-oil to be either used as low-grade fuel or it can be

upgraded into high-grade transport fuel. Pretreatment of biomass with H3PO4 is the most
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inexpensive way to increase the efficiency of the pyrolysis process as well as to improve the

properties of the process. Thus it can be concluded that pyrolysis is the most effective way of
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converting the waste biomass having no use into economical energy-rich fuels, chemicals, and
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adsorbents. It helps to reduce the burden of continuously depleting fossil fuels.The only

challenge is to improve the yield as well as various properties like high viscosity, acidity,

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instability, low volatility etc. of pyrolytic oil by modifying process parameters and various

pretreating agents.

Acknowledgement

The authors are highly thankful to the department of Chemical Engineering and Technology and

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Central Instrument Facility Centre, Indian Institute of Technology (Banaras Hindu University),

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Varanasi, Uttar Pradesh, India for providing facilities to conduct the research work.

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List of tables:

Table 1 Proximate analysis of raw and pretreated walnut shell and corresponding biochar

obtained at different temperatures

Table 2 Ultimate analysis of raw walnut shell and biochar at different temperatures

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Table 3 BET surface area analysis of biochar

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Table 4 EDX analysis of raw walnut shell, biochar and pretreated biochar

Table 5 Physicochemical properties of bio-oil

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Figure captions:

Fig. 1 Flow diagram of the experimental process

Fig. 2 TG-DTG curve of raw walnut shell biomass

Fig. 3 Effect of variation of process parameters (a) temperature, (b) particle size, (c) bed height

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and (d) H3PO4 acid concentration on pyrolysis product yield

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Fig. 4 FTIR spectra of (a) raw walnut shell and its biochar at 300, 400, 500 and 600oC, (b) pre-

treated biochar obtained at 500oC and 0.2, 0.4, 0.6 and 0.8M acid concentration

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Fig. 5 XRD diffractogram of walnut shell, biochar at 500 oC and pre-treated biochar at 500oC

and 0.6 M acid concentration

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Fig. 6 SEM-EDX images of (a) raw walnut shell, (b) biochar at 300 oC, (c) biochar at 400 oC, (d)
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biochar at 500 oC and (e) biochar at 600 oC

Fig. 7 SEM-EDX images of biochar produced at 500 oC treated with (a) 0.2M H3PO4
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concentration, (b) 0.2 M H3PO4 concentration, (c) 0.4 M H3PO4 concentration and (d) 0.8 M
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H3PO4 concentration
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Fig. 8 FTIR spectra of (a) bio-oil at 400oC, 500oC, (b) bio-oil at 500oC treated with 0.2, 0.4, 0.6

and 0.8 M H3PO4 concentration

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Fig.9 Variation of (a) concentration and (b) HHV of pyrolytic gases with temperature
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Tables:

Table 1

Properties RWS RWS- BC-300oC BC-400 oC BC-500oC BC-600oC BC-500oC-

(Wt. %) 0.6 M 0.6 M

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Fixed carbon 19.33 21.59 56.62 59.59 74.52 80.91 76.22

Volatile matter 71.52 72.07 35.7 33.63 18.71 12.18 19.63

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Ash content 1.65 0.59 1.89 2.67 2.95 3.4 1.05

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Moisture content 7.5 6.15 5.79 4.11 3.82 3.51 2.71

Heating value 17.91 18.89 25.542 26.594 29.297 30.966 30.16

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(MJ/Kg) AN
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Table 2

Samples C (wt. %) H (wt. %) N (wt. %) O (wt. %) O/C H/C

RWS 46.653 5.804 1.649 47.543 0.76 1.49

BC-300 oC 56.570 5.265 1.541 36.624 0.49 1.12

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BC-400 oC 69.053 3.931 1.213 25.803 0.28 0.68

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BC-500 oC 77.969 3.217 1.121 17.693 0.17 0.50

BC-600 oC 81.265 2.535 - 16.2 0.15 0.37

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BC-500 oC 82.971 2.518 - 14.157 0.13 0.36
(0.6M)

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Table 3

BET surface area, SBET Average pore volume, Average pore diameter,
-3 3
2
VT * 10 (cm /g) Vavg (nm)
(m /g)
o
BC-300 C 5.895 1.329 14.504

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o
BC-400 C 10.129 1.411 10.831

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o
BC-500 C 81.487 7.983 7.287

o
202.846 21.916 2.744

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BC-600 C
o
BC-500 C 271.306 24.051 2.190
(0.6 M)

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Table 4
Eleme RSW BC- BC- BC- BC- BC- BC- BC- BC-
nts 300oC 400oC 500oC 600oC 500 °C 500 °C 500 °C 500 °C
0.2 M 0.4 M 0.6 M 0.8 M
C 45.72 47.29 50.63 52.16 60.78 52.47 53.36 60.90 66.11

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O 39.05 38.61 35.01 35.18 21.55 34.65 33.04 19.19 11.64
N 20.69 17.82 16.95 12.69 12.47 11.10 9.91 16.00 14.68

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Na 0.18 0.12 0.19 0.01 0.03 - - - -
Mg 0.21 0.13 0.13 0.01 0.06 - 0.02 0.02 0.06

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P - - - - - 1.26 3.02 3.51 6.59
Al 0.27 0.11 0.03 0.03 0.10 - - - -

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Si 0.17 0.16 0.01 0.09 0.07 0.06 0.04 0.04 0.10
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K 0.35 0.57 0.44 1.08 1.06 0.13 0.24 0.15 0.21
Ca 0.67 0.65 0.60 0.49 0.62 0.22 0.25 0.09 0.36
Fe 0.11 0.10 0.06 0.12 0.26 0.11 0.11 0.11 0.26
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Table.5

Properties BO - 400oC BO - 500oC BO - 500oC ASTM- ASTM-

0.6 M Grade G Grade D
Appearance Brownish Brownish Light - -
brownish
Water content (wt. %) 35.14 31.94 33.81 30 30

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pH 2.46 2.39 2.14 Report Report

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Density (kg/dm3) 1.074 1.094 1.196 1.1-1.3 1.1-1.3

Viscosity (cst) 26 30 37 125 125

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Ash content (wt. %) 0.27 0.34 0.28 0.25 0.15

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Carbon residue 3.96 5.4
AN 4.33 - -

HHV(MJ/kg) 18.94 21.53 19.07 15 15

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Figures:

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Fig. 1
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100 0.01

0.00
80
-0.01

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DTG curve
Mass loss %

DTG (%/ oC)

-0.02
60

-0.03

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40 TG curve
-0.04

-0.05

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20
-0.06

0 -0.07

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0 100 200 300 400 500 600 700 800 900
Temperature (oC)
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Fig. 2
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50 50
Biochar
Biooil
Gas
Char (%)

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40 40 Biooil (%)
Gas (%)
Yield (%)

% Yield
30 30

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20 20

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300 350 400 450 500 550 600 0.25-0.42 0.42-0.60 0.60-0.71 0.71-1.0

Temperature (oC) % Particle size (mm)

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(a) AN (b)

Gas
Biooil
50
Biochar Biochar
Biooil 100
Gas
80
M

40
Yield (%)

Yield (%)

60
D

40
30

20
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20 0
8 9 10 11 12 Untreated 0.2 M 0.4 M 0.6 M 0.8 M
Bed height (cm) Concentration (mol/L)
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(c) (d)
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Fig. 3

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BC 600
BC 500-0.8

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% Transmittance
% Transmittance

BC 500

RI
BC 500-0.6
BC 400

SC
BC 300 BC 500-0.4

U
AN
Walnut shell BC 500-0.2

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)
M

(a) (b)
D

Fig. 4
TE
CEP
AC

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PT
B C 5 0 0 - 0 .6 M

RI
Intensity (cps)

SC
BC 500

U
AN
W a ln u t s h e ll
M
D

0 10 20 30 40 50 60 70 80
2θ
TE

Fig. 5
C EP
AC

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(a)

PT
(b)

RI
U SC
(c)
AN
M

(d)
D
TE
EP

(e)
C
AC

Fig. 6

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(a)

PT
RI
(b)

U SC
AN
(c)
M
D
TE
EP

(d)
C
AC

Fig.7
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BO-500oC-0.8M
BO-500oC-0.6M
BO-500oC-0.4M
500
BO-500oC-0.2M
BO-500oC
BO-500oC
BO-400oC
400
160

% T ra n s m itta n c e
300
% Transm ittance

120

PT
200
80

RI
100
40

SC
0

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1) Wavenumber (cm-1)

U
(a) (b)
AN
Fig. 8
M
D
TE
C EP
AC

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PT
RI
SC
(a) (b)

Fig. 9

U
AN
M
D
TE
EP
C
AC

45
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Highlights:

• Walnut shell pyrolysis was performed at various process parameters.

• Pre-treatment with ortho-phosphoric acid improved the biochar yield.

• In-depth product characterizations were carried out using advanced analytical techniques.

PT
• The characteristics of bio-oil provided the fuel properties and can be upgraded as blend

RI
with conventional fuel.

• Biochar contained concentrated nutrient and has high BET surface area.

U SC
AN
M
D
TE
C EP
AC