Accepted Manuscript

Modelling and simulation of hydrotreating of palm oil components to obtain green

diesel

Meliza Plazas-González, Carlos Alberto Guerrero-Fajardo, José Ricardo Sodré

PII: S0959-6526(18)30607-3

DOI: 10.1016/j.jclepro.2018.02.275

Reference: JCLP 12222

To appear in: Journal of Cleaner Production

Received Date: 11 March 2017

Revised Date: 04 December 2017

Accepted Date: 24 February 2018

Please cite this article as: Meliza Plazas-González, Carlos Alberto Guerrero-Fajardo, José Ricardo
Sodré, Modelling and simulation of hydrotreating of palm oil components to obtain green diesel,
Journal of Cleaner Production (2018), doi: 10.1016/j.jclepro.2018.02.275

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 ACCEPTED MANUSCRIPT

MODELLING AND SIMULATION OF HYDROTREATING OF PALM OIL

COMPONENTS TO OBTAIN GREEN DIESEL

Meliza Plazas-González

Universidad Nacional de Colombia, Department of Chemical Engineering

Av. Carrera 14 # 127-25 – Cundinamarca 11001– Bogotá - Colombia

Phone: +57-1-3165000 ext 14509 E-mail: mbplazasg@unal.edu.co

Carlos Alberto Guerrero-Fajardo

Universidad Nacional de Colombia, Department of Chemical Engineering

Av. Carrera 14 # 127-25 – Cundinamarca 11001– Bogotá - Colombia

Phone: +57-1-757-2515 E-mail: caguerrerofa@unal.edu.co

José Ricardo Sodré

Pontifical Catholic University of Minas Gerais, Department of Mechanical Engineering

Av. Dom José Gaspar, 500 – CEP 30535-610 – Belo Horizonte – MG – Brazil

Phone: +55-31-3319-4911 Fax: +55-31-3319-4910 E-mail: ricardo@pucminas.br

 Corresponding author

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ABSTRACT

This work presents a model for hydrotreating of palm oil components to produce

green diesel. The main reactions of triglycerides and fat acids in the presence of a

NiMo/γAl2O3 catalyst are shown, especially cracking of triglycerides, hydrogenation,

decarboxylation, decarbonylation and fat acid reduction. These reactions were modelled

using Aspen Plus® 7.3 software, where an equilibrium reactor was used to predict the

reaction behavior. The influence of reactor pressure, temperature and H2/oil molar ratio

was analyzed. The results showed that the optimized conditions are obtained at average

pressure from 30 bar to 60 bar, temperature between 300C and 400C, and H2/oil molar

ratio of 20.1. In the separation system the operating conditions adopted were 40 bar,

200C in the first plate and 1.013 bar, 60C in the second plate, resulting in green diesel

purity of 97%. High levels of n-C18 and n-C16 production were attained, compared with

other methods.

Keywords: Hydrotreating; decarbonylation; decarboxylation; reduction; green diesel.

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1. INTRODUCTION

The continuous increase of energy consumption, together with increasingly strict

environmental regulation, make biofuels an attractive alternative to partially replace fossil

fuels (Charusiri et al., 2016). Three main routes are currently used to obtain biofuels from

natural triglycerides (Fig. 1). The first one is transesterification with an alcohol, normally

methanol, producing fatty acid methyl esters (FAME, biodiesel) and glycerin, using

homogeneous base catalysts (NaOH, for instance). Hydrocracking and selective

deoxygenation (SDO) of natural triglycerides are the other two alternative methods.

Cracking/hydrocracking is performed over acid catalysts, resulting in a liquid organic

product consisting of a blend of hydrocarbons (gasoline, kerosene and diesel oil) with

traces of short-chain oxygenated compounds, hydrocarbon gases (C3-C5) and coke. SDO

is a promising route to improve the natural triglycerides, performed by a hydrotreating

that implicates in three different reactions to produce hydrocarbons (green diesel) in the

range of diesel fuel (Kordulis, 2016).

Differently from biodiesel, green diesel is a fuel that requires the presence of a

catalyst and hydrogen (H2) to eliminate oxygen and obtain linear or branched paraffinic

hydrocarbons (Furimsky and Massoth, 1999). The oil can be processed individually or

co-processed in an oil stream or in vacuum gas oil. The conversion of triglycerides in the

presence of H2 involves complex reactions with parallel and/or consecutive stages,

including cracking, hydrogenation, decarboxylation, decarbonilation, reduction, alcohol

formation, cycling, and ester formation from the fatty acids (Sivasamy et al., 2009).

Figure 2 presents the possible route for hydrotreating of vegetable oils (Veriansyah et al.,

2012).

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To obtain green diesel, the pressurized oil load is blended with hydrogen and it is

sent to a catalytic hydro-deoxygenation process in an adiabatic reactor (RLE). In the

reactor, the oil saturates and releases oxygen. Oil conversion can be close to 100%, and

the reaction sub-products are propane, water and carbon dioxide. The outflow from the

RLE reactor is sent to a high-pressure separator to isolate the gaseous sub-products from

the liquid product that will be blended with hydrogen. Under high pressure and

temperature, the gas carbon chains are separated (CS-01). The liquid is sent to another

separation column (CS-02) under low temperature and pressure to separate any remaining

gas in the blend. The gas is introduced in a separator, normally an absorption selective

membrane to separate CO/CO2/H2), for purification of the hydrogen that will be re-

circulated. Green diesel production takes place at moderate reaction conditions, and it can

be included in the traditional layout of the existing oil refineries.

For the oil hydrotreating reactions it is necessary the utilization of a catalyst with

low-size particles to facilitate the contact between oil and hydrogen, to keep the flow

patterns and to attain isothermal conditions. The catalyst must be activated for adequate

operation. The most influential operating parameters are pressure and temperature, which

must be kept from 40 bar to 60 bar and from 200°C to 400°C, respectively (Guzman et

al., 2010). Another parameter of high relevance is hydrogen-to-oil ratio. Generally, the

oil amount is limited and the hydrogen amount is excessive, in order to extend the

molecular contact to obtain the desired compounds. Figure 3 presents an inflow and

outflow diagram for hydrotreating of palm oil. The inlet raw material are palm oil

triglycerides and hydrogen in excess, to obtain the liquid product with branched chains

of 15-18 carbon, a CO/CO2 gas stream and a hydrogen purge.

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This work aims to model the hydrotreating mechanism of palm oil to determine

the optimized conditions in terms of pressure, temperature and H2/oil molar ratio for green

diesel production. The Aspen Plus® 7.3 software was used in the investigation. Table 1

shows the fatty acids constitution of palm oil. Oleic acid is the component with the highest

amount in position sn-2 of the triglycerides, making a large availability of

monounsaturated fatty acids.

2. LITERATURE SURVEY

Among the biomass conversion processes into liquid fuels, hydrotreating is an

interesting alternative process to obtain a high-quality diesel fuel substitute (Stumborg et

al., 1996). Using hydrotreating, a conversion efficiency of triglycerides near 100% has

been reported for cotton oil with the application of a commercial catalyst, obtaining a fuel

with high cetane number (Sebos et al., 2009b). Arend et al. (2011) investigated the

production of diesel-like hydrocarbons using deoxygenation of oleic acid with hydrogen

(H2) in continuous gas phase at 380°C, and 5 g of a catalyst with 2 wt.% Pd/C. The authors

obtained a maximum selectivity of 28.5 mol% for the formation of heptadecane and

heptadecene. Sari et al. (2013) investigated the correlation of activity and catalyst

properties for green diesel production, and found that Pd/Si-C-4 and Pd/C catalysts

showed high conversion of oleic acid and exhibited the highest selectivity (31%) to n-

heptadecane (n-C17) in the absence of H2. However, a regenerative hydrotreating was

necessary to restore the catalytic activity and the desired product selectivity.

Applying hydrotreating of crude palm oil with Pd/C catalyst at 400°C, 40 bar, and

reaction time of 3 h, Kiatkittipong et al. (2013) obtained a diesel-like hydrocarbon yield

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of 51%. When gum containing phospholipid compounds was removed from the crude

palm oil, a diesel yield of 70% could be obtained at 1 h, being n-pentadecane and n-

heptadecane the main liquid products. Wang et al. (2014) reported the application of a

single-step hydrotreating to soybean oil to obtain 100% conversion to diesel-like alkanes,

being 85% isoalkane, using 8 wt.% Ni/SAPO-11 as catalyst. Hengst et al. (2015) achieved

a maximum selectivity toward C17- products n heptadecane and all heptadecene isomers

of 51 mol% at a conversion rate of 87 mol% for diesel fuel production using gas phase

deoxygenation of oleic acid over palladium containing acidic catalysts under solvent-free

conditions. Low reaction temperatures of 380°C and moderate weight hourly space

velocities of 1.9 h−1 were most suitable for highest C17 selectivity. The best overall result

was obtained with 1 wt.% Pd/Siral70 as catalyst, reaction temperature of 350°C, and H2

pressure of 15 bar.

Chen et al. (2016) applied hydrotreating over 10 wt.% Ni/HZSM-5 (Si/Al = 25)

at 280°C, with a H2 pressure of 0.8 MPa and a highly purified H2/oil molar ratio of 15 to

obtain a high selectivity of 88.2% C5–C18 liquid alkanes from fatty acid methyl esters.

The alkane fuels included 8% of gasoline alkane, 32.5% of jet alkane and 47.7% of diesel

alkane. The isomerization selectivity was 27.0%, while the conversion of fatty acid

methyl esters reached 85.1%. Green fuels were produced through the

hydrodeoxygenation of palmitic fat and its hydrolyzed product by using Pd/C as a catalyst

(Sousa et al., 2016). The process was proved to be efficient for hydrodeoxygenation with

conversions of up to 96% after 5 h of reaction, at 10 bar of H2 pressure and 300°C,

producing approximately 82% of the hydrocarbons in the jet fuel range and 98% of the

oil composition in the diesel fuel composition range. In an application of deoxygenation

to macaúba oil, a conversion of 85% was obtained using optimized conditions (Silva et

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al., 2016). Those figures related to green diesel production from hydrotreating are much

higher than those related to jet fuel production from the same route, for which the yield

was reported to be around 54% (Chu et al., 2017).

3. PROCESS MODELLING

To model palm oil hydrotreating, the Aspen Plus® 7.3 software was used to

simulate the main triglyceride reactions (triolein, tripalmitin, trilinolein and tristearin):

cracking, fatty acid hydrogenation, decabonilation, reduction, and alcohol formation from

fatty acids. The model used was Peng Robinson with RK-Aspen, as it accurately predicts

the behavior of gas-liquid equilibrium of triglycerides at high pressure. Tripalmitin,

trilinolein and tristearin compounds were included in the program because they are not

preliminary considered. The program only presents database for triolein. Table 2 presents

the properties of the compounds introduced in the program.

The triglycerides composition of the feed stream to the reactor is 37% triolein,

48.6% tripalmitin, 10% trilinolein and 4.4% tristearin, established from average values of

chemical analyses of palm oil. The initial flux of triglycerides informed to the program

was 2500 kg/h, with a H2/oil ratio of 20:1. The catalyst used in the hydrotreating model

was NiMo/γAl2O3, with an oil (kg/h)/catalyst (kg) ratio of 30:1 (Kordulis et al., 2016).

This catalyst performs reactions that produce paraffins of high interest for a diesel fuel

and, at high pressures, can also produce C16-C18 alcohols. Table 3 shows the reactions

present in the equilibrium reactor.

Those reactions modelled in an equilibrium reactor are adequate to the processes

involved, according to the literature (Guzman et al., 2010). The initial reactions present

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the triglycerides degradation, the hydrogenation reaction presents the double-bond

saturation, the decarboxylation and decabornilation reactions represent the production of

C17 and C15 carbon chains, the reduction reaction represents the formation of C18 and C16

carbon chains, and reactions 16 and 17 represent alcohol production.

Figure 4 presents the process flux diagram, where the operations for hydrotreating

of palm oil can be observed and the most important paths identified. The equipment used

in the process are:

 two storage tanks, one of them at high pressure, for hydrogen (TQ-02), and the other

one for palm oil (TQ-01);

 a packing bed reactor (RLE-01), where the catalyst is located and hydrogen and palm

oil are put in contact at 300°C and 40 bar;

 a high pressure, high temperature separation column (CS-01) that separates the gas

components, hydrogen, propane, carbon monoxide and carbon dioxide;

 a low pressure, low temperature separation column (CS-02) that depressurizes the

blend and volatilizes the gas for separation, obtaining hydrocarbons in the bottom,

mostly n-C16 and n-C18;

 a third column (CS-03) that separates hydrogen from the gas, especially from water

vapor.

For subsequent separation of the reaction products, three separation columns were

used to purify the product and obtain non-reacting hydrogen for recirculation. The first

separation column operates at high pressure and temperature to separate the volatiles.

After a sensibility analysis performed to determine the operation pressure and

temperature, it was decided to operate at 250°C and variable pressure to evaluate the

process efficiency.

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4. RESULTS AND DISCUSSION

4.1. Sensibility analysis of pressure, temperature and H2/oil ratio

To analyze the process parameters the initial temperature of 350°C was

considered, based on the literature (Guzman et al., 2010). The pressure was varied to

observe the production of the compounds of interest (n-C16 and n-C18). Figure 5 shows

the mass fraction variation of the compounds of interest and the sub-products as a function

of pressure. The mass fractions of n-C16 and n-C18 are increased with increasing pressure,

with preference to the reduction reactions of palmitic acid and stearic acid (Fig. 5). With

increasing pressure, the reactions 7, 8, 10 and 11 (Table 3) are not favored, reducing the

mass fractions of n-C15 and n-C17 (Fig. 5). The production of double-bond carbon chains

C17= and C18= are not favored with pressure increase either, and the production of

octadecan-1-ol and hexadecan-1-ol show low increase. At moderate pressures (30-40 bar)

the production of the compounds of interest is higher; thus, it was decided to operate at

40 bar, since, for higher pressures, no significant difference was noticed (Fig. 6).

Temperature influence in the system was analyzed in the range from 250°C to

450°C, at the pressure of 40 bar. With increasing temperature, the reduction reactions of

palmitic acid and stearic acid are affected, with reduced production of n-C16 and n-C18

(Fig. 7). On the other hand, the production of n-C17 and n-C15 is increased, favoring the

decarboxylation and decarbonilation reactions of palmitic and stearic acids. Alcohol

production is not favored with temperature increase (Fig. 8). It was decided to operate the

reactor at the temperature of 300°C for the forthcoming analyses, as it provides a desirable

production of the compounds of interest.

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The H2/oil ratio was varied from 10:1 to 25:1, at the pressure of 40 bar and

temperature of 300°C. Figure 9 shows that, with increasing H2/oil ratio, the production of

the compounds of interest, n-C16 and n-C18, are increased, benefiting from the reduction

reactions of palmitic acid and stearic acid. For low H2/oil ratio, the production of carbon

chains is significantly reduced. With 20:1 H2/oil ratio, hydrocarbons production is

improved and the compounds mass fraction shows little variation, making the green diesel

homogeneous along the process and attending the desirable characteristics. Increasing

H2/oil ratio slightly reduces the production of alcohol and double-bond compounds, C18=

and C16= (Fig. 10).

From the previous analysis (Figs. 5 to 10), it can be concluded that the indicated

operating conditions of the process to obtain green diesel with the desirable requirements

are average pressure from 30 bar to 60 bar, temperature from 300°C to 400°C, and H2/oil

molar ratio of 20:1.

4.2. Process analysis in the optimized operating range

Figure 11 shows the pressure effects on the top CS-01 column products, where the

gaseous products present are mainly propane, hydrogen, carbon dioxide and carbon

monoxide. Hydrogen mass fraction is increased with increasing pressure, but that is not

an indication that hydrogen is fully recovered as its mass flow rate show a slight decrease.

From these results it was chosen to operate with an average pressure of 40 bar, as, at this

condition, a considerable amount of hydrogen and propane is obtained.

The sensibility analysis is also applied to variation of temperature (Fig. 12). The

mass fraction of the recovered propane is observed to reduce with increasing temperature.

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This is due to the amount of other substances released in the column gas phase. Hydrogen

flow rate does not vary significantly with variation of the temperature. From these results,

it was chosen to operate at the temperature of 200°C.

For the column liquid phase, the pressure and temperature influence on the flow

stream was also analyzed (Figs. 13 and 14). It is noticed that pressure variation does not

significantly affect the amount of the compounds of interest, n-C18 y n-C16, especially

above 20 bar. Thus, pressure influence is more important in the gaseous stream of the

column (Fig. 11). Temperature variation has a significant influence on the mass fraction

of the components of interest and, for temperatures above 250°C, the mass flow rate of

those components is dramatically decreased. Therefore, the adoption of 40 bar, 200°C is

also a good practice for those components.

After separation, the bottom products of the first column (SC-01) are sent to a

second column (SC-02) that operates at ambient pressure (1.013 bar) and low

temperature. A sensibility analysis was carried out to verify the effects of temperature on

the composition of the outlet bottom stream, which includes the products of interest, n-

C18 and n-C16 (Fig. 15). Increasing temperature allows to obtain higher purity products

and higher recovery rate of the compounds. This is due to the higher water amount that

evaporates, resulting in a stream of higher purity. The recovery fraction of n-C18 is not

significantly affected by temperature, and the recovery fraction of n-C18 is slightly

reduced for temperatures over 60°C. With the selected operating conditions of 1 atm and

60°C recovery fractions of 99.2% and 98.3% are obtained for n-C18 and n-C16,

respectively.

The results from the present model indicates the possibility to obtain improved

results in comparison with those reported by Snare et al. (2008), where the conversion

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efficiency of fatty acids and saturated esters was around 96% for methyl oleate and 92%

for oleic acid. The catalyst used by those authors was Pd/C, and the process conditions

were 15 bar, 300C, for methyl oleate, and 21 bar, 330C, for oleic acid. The results from

the work by Veriansyah et al. (2012) for soybean oil hydrotreating reached a maximum

conversion efficiency of 92.9%, using a NiMo/γ-Al2O3 catalyst, obtaining a predominant

composition of n-C15 and n-C17 alkenes. The present model of palm oil hydrotreating

shows higher n-C18 and n-C16 production than the ones by Sari et al. (2013), Hengst et

al. (2015), Liu et al. (2015), Xin et al. (2016), Chen et al. (2016), and Kiatkittipong (2013),

due to the distillation process here applied. Similar production levels were achieved by

Wang et al. (2014), for hydrotreatment of soybean oil. Sousa et al. (2016) also report a

highly efficient process. The possibility to attain reduction of energy consumption by the

method here proposed is related to its operation in the pressure range from 30 bar to 60

bar, and temperature range from 300°C to 400°C, while other methods, like pyrolysis and

gasification, require higher pressures and temperatures above 400°C.

5. CONCLUSIONS

The investigation carried out on hydrotreating of palm oil to obtain green diesel

showed that low-pressure operating reaction considerably decreases the production of n-

C16 and n-C18, and produces high amounts of n-C15 and n-C17 chains. High temperatures

can decrease the production of n-C16 and n-C18, thus reducing the production of green

diesel. Increasing H2/oil ratio was shown to be favorable to the reduction reactions that

produce n-C16 and n-C18. The optimized operating conditions for the process was pressure

between 30 bar and 60 bar, temperature from 300°C to 400°C and H2/oil molar ratio of

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20:1. For the operating conditions chosen, the purity degree of the green diesel obtained

is 97%. The final product is composed by 52.9% n-C18, 44.2% n-C16, 1% H2O, 1% n-C17

and 0.7% n-C15.

6. ACKNOWLEDGMENTS

The authors thank CAPES, CNPq research project number 304114/2013-8,

FAPEMIG research projects number TEC PPM 000385-15 and TEQ APQ 00014-11, and

VALE/FAPEMIG research project number TEC RDP 00198-10 for the financial support

to this work.

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deoxygenation of oleic acid in continuous gas flow for the production of diesel-like

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palm oil at pilot plant scale. Catal. Today 156, 38-43.

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 Kordulis, C., Bourikas, K., Gousi, M., Kordouli, E., Lycourghiotis. A., 2016.

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like hydrocarbons from palmitic acid over HZSM-22 supported nickel phosphide

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nanocomposite silica-carbon supported palladium catalyst for decarboxylation of

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 Sebos, I., Matsoukas, A., Apostolopoulos, V., Papayannakos, N., 2009. Catalytic

hydroprocessing of cottonseed oil in petroleum diesel mixtures for production of

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diesel and jet fuel formulation from palm kernel fat over Pd/C. Fuel Proc. Technol.

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fuel improvement. Bioresour. Technol. 56, 13-8.

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Oh, S.-G., Kim, J., 2012. Production of renewable diesel by hydroprocessing of

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LIST OF FIGURE CAPTIONS

Figure 1- Main routes for treatment of natural triglycerides (Kordulis et al., 2016).

Figure 2- Possible routes of triglycerides reaction in hydrotreating of vegetable oils

(Veriansyah et al., 2012).

Figure 3- Inflow and outflow diagram of palm oil hydrotreating.

Figure 4- Process flux diagram for hydrotreating of palm oil to obtain renewable diesel.

Figure 5- Pressure effects on mass fraction and mass flow rate of products of interest (n-

C15…n-C18 and H2O).

Figure 6- Pressure effects on sub-products (C17=, C18=, CO, hexadecan-1-ol and

octadecan-1-ol) mass fraction.

Figure 7- Temperature effects on the mass fraction and mass flow rate of the products of

interest (n-C15…n-C18 and H2O).

Figure 8- Temperature effects on sub-products (octadecan-1-ol, hexadecan-1-ol, CO,

C17= and C18=) mass fraction.

Figure 9- Effects of H2/oil molar ratio in reactor inlet on the mass fraction and mass

flow rate of the products of interest (n-C15…n-C18 and H2O).

Figure 10- Effects of H2/oil molar ratio in reactor inlet on sub-products (octadecan-1-ol,

hexadecan-1-ol, CO, C17= and C18=) mass fraction.

Figure 11- Pressure effects on mass fraction and mass flow rate of the gas in the top of

the separation column SC-01.

Figure 12- Temperature effects on mass fraction and mass flow rate of the gas in the top

of the separation column SC-01.

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Figure 13- Pressure effects on mass fraction and mass flow rate of the products of

interest (n-C15…n-C18, H2O and propane) in the bottom part of the separation

column SC-01.

Figure 14- Temperature effects on mass fraction and mass flow rate of the products of

interest (n-C15…n-C18, H2O and propane) in the bottom part of the separation

column SC-01.

Figure 15- Temperature effects on mass fraction and recovery ratio of the products of

interest (n-C16 and n-C18) in the bottom stream of the separation column SC-

02.

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LIST OF TABLE CAPTIONS

Table 1- Composition of palm oil fatty acids.

Table 2- Properties of triglycerides introduced in the Aspen Plus 7.3® software (Guzman

et al., 2010).

Table 3- Reactions included in the simulation (Veriansyah et al., 2012).

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Table 1- Composition of palm oil fatty acids.

FATTY ACIDS COMPOSITION

Oleic 36-44%
Unsaturated
Linoleic 9-12%

Palmitic 39.3-47.5%
Saturated
Stearic 3.5-6%

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Table 2- Properties of triglycerides introduced in the Aspen Plus 7.3® software

(Guzman et al., 2010).

PROPERTY TRIPALMITIN TRILINOLEIN TRISTEARIN

Structure C51H98O6 C57H98O6 C57H110O6

Molecular weight 807.29 879.38 801.48

Boiling point (K) 722.717 687.1 727.77

Critical temperature (K) 801.044 757.54 800.149

Critical Pressure (bar) 4.585 4.33 4.168

Critical volume (cm3/mol) 3082.1 3292.7 3412.7

Acentric factor 1.7068 1.7593 1.7567

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Table 3- Reactions included in the simulation (Veriansyah et al., 2012).

# STOICHIOMETRIC REACTION TYPE

1 Triolein + 3H2 ⇌ 3 oleic acid + propane

2 Tripalmitin +3H2 ⇌ 3 palmitic acid + propane

Initial reactions
3 Trilinolein +3H2 ⇌ 3 linoleic acid + propane

4 Tristearin +3H2 ⇌ 3 stearic acid + propane

5 Oleic acid +H2 ⇌ stearic acid

Hydrogenation
6 Linoleic acid +2H2 ⇌ stearic acid

7 Stearic acid ⇌ n – C17 + CO2

8 Palmitic acid ⇌ n – C15 + CO2 Decarboxilation

9 Oleic acid ⇌ C17 = +CO2

10 Stearic acid + H2 ⇌ n – C17 + CO + H2O

11 Palmitic acid + H2 ⇌ n – C15 + CO + H2O Decarbonilation

12 Oleic acid + H2 ⇌ C17 = +CO + H2O

13 Stearic acid + 3H2 ⇌ n – C18 + 2H2O

14 Palmitic acid + 3H2 ⇌ n – C16 + 2H2O Reduction

15 Oleic acid + 3H2 ⇌ C18 = +H2O

16 Stearic acid + 2H2 ⇌ octadecan-1-ol + H2O

Alcohol formation
17 Palmitic acid + 2H2 ⇌ hexadecan-1-ol + H2O

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PLANT OILS
ANIMAL FAT NATURAL
WASTE COOKING OIL TRIGLYCERIDES
ALGAE OIL

HYDROTREATING CRACKING TRANSESTERIFICATION

SDO - SELECTIVE HYDROCRACKING

DEOXIGENATION

GREEN DIESEL GREEN GASOLINE, BIODIESEL

C15-C18 ALKANES KEROSENE AND DIESEL
C15-C18 ALKANES

Figure 1- Main routes for treatment of natural triglycerides (Kordulis et al., 2016).

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Figure 2- Possible routes of triglycerides reaction in hydrotreating of vegetable oils

(Veriansyah et al., 2012).

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Figure 3- Inflow and outflow diagram of palm oil hydrotreating.

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Figure 4- Process flux diagram for hydrotreating of palm oil to obtain renewable diesel.

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0.70 70000
MASS FRACTION MASS FLOW RATE
n-C15 n-C15
0.60 n-C16 n-C16 60000

MASS FLOW RATE (kg/h)

n-C17 n-C17
0.50 n-C18 n-C18 50000
MASS FRACTION

H 2O H 2O

0.40 40000

0.30 30000

0.20 20000

0.10 10000

0.00 0

20 30 40 50 60 70 80 90
PRESSURE (bar)

Figure 5- Pressure effects on mass fraction and mass flow rate of products of interest (n-

C15…n-C18 and H2O).

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10-2

10-3

10-4
MASS FRACTION

-5
10

10-6
C17=
10-7 C18=
CO
10-8 HEXADECAN-1-OL
OCTADECAN-1-OL

10-9

10-10

20 30 40 50 60 70 80 90
PRESSURE (bar)

Figure 6- Pressure effects on sub-products (C17=, C18=, CO, hexadecan-1-ol and

octadecan-1-ol) mass fraction.

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0.70 70000
MASS FRACTION MASS FLOW RATE
n-C15 n-C15
0.60 n-C16 n-C16 60000

MASS FLOW RATE (kg/h)

n-C17 n-C17
0.50 n-C18 n-C18 50000
MASS FRACTION

H 2O H 2O

0.40 40000

0.30 30000

0.20 20000

0.10 10000

0.00 0

250 300 350 400 450

TEMPERATURE ( C)
O

Figure 7- Temperature effects on the mass fraction and mass flow rate of the products of

interest (n-C15…n-C18 and H2O).

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10-2

-3
10

-4
10
MASS FRACTION

-5
10

-6
10 C17=
C18=
10-7 CO
HEXADECAN-1-OL
10
-8 OCTADECAN-1-OL

10-9

10-10

250 300 350 400 450

TEMPERATURE (OC)

Figure 8- Temperature effects on sub-products (octadecan-1-ol, hexadecan-1-ol, CO,

C17= and C18=) mass fraction.

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0.70 70000
MASS FRACTION MASS FLOW RATE
n-C15 n-C15
0.60 n-C16 n-C16 60000

MASS FLOW RATE (kg/h)

n-C17 n-C17
0.50 n-C18 n-C18 50000
MASS FRACTION

H 2O H 2O

0.40 40000

0.30 30000

0.20 20000

0.10 10000

0.00 0

5 10 15 20 25
H2/OIL MOLAR RATIO

Figure 9- Effects of H2/oil molar ratio in reactor inlet on the mass fraction and mass

flow rate of the products of interest (n-C15…n-C18 and H2O).

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10-3

10-4

10-5
MASS FRACTION

10-6
C17=
10-7 C18=
CO
-8
HEXADECAN-1-OL
10 OCTADECAN-1-OL

-9
10

-10
10

5 10 15 20 25
H2/OIL MOLAR RATIO

Figure 10- Effects of H2/oil molar ratio in reactor inlet on sub-products (octadecan-1-ol,

hexadecan-1-ol, CO, C17= and C18=) mass fraction.

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100 104

MASS FLOW RATE (kg/h)

10-1 103
MASS FRACTION

10-2 102
MASS FRACTION MASS FLOW RATE
H2 H2
CO2 CO2
10-3 CO CO 101
C 3H 8 C 3H 8

10-4 100

20 30 40 50 60 70 80
PRESSURE (bar)

Figure 11- Pressure effects on mass fraction and mass flow rate of the gas in the top of

the separation column SC-01.

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100 104

10-1

MASS FLOW RATE (kg/h)

103
MASS FRACTION

10-2
MASS FRACTION MASS FLOW RATE
102
H2 H2
10-3 CO2 CO2
CO CO
C 3H 8 C 3H 8
101
-4
10

10-5 100

50 100 150 200 250 300

TEMPERATURE (OC)

Figure 12- Temperature effects on mass fraction and mass flow rate of the gas in the top

of the separation column SC-01.

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100 105

MASS FLOW RATE (kg/h)

MASS FRACTION MASS FLOW RATE
n-C15 n-C15
MASS FRACTION

n-C16 n-C16
10-1 n-C17 n-C17 104
n-C18 n-C18
C 3H 8 C 3H 8
H 2O H 2O

10-2 103

10-3 102

20 30 40 50 60 70 80
PRESSURE (bar)

Figure 13- Pressure effects on mass fraction and mass flow rate of the products of

interest (n-C15…n-C18, H2O and propane) in the bottom part of the separation column

SC-01.

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100 105

MASS FRACTION MASS FLOW RATE

MASS FLOW RATE (kg/h)

n-C15 n-C15
n-C16 n-C16
MASS FRACTION

n-C17 n-C17
10-1 n-C18 n-C18
104
C 3H 8 C 3H 8
H 2O H 2O

10-2 103

10-3 102

50 100 150 200 250 300

TEMPERATURE (OC)

Figure 14- Temperature effects on mass fraction and mass flow rate of the products of

interest (n-C15…n-C18, H2O and propane) in the bottom part of the separation column

SC-01.

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0.60 99.5

RECOVERY RATIO (%)

MASS FRACTION

0.40 99.0
MASS FRACTION RECOVERY RATIO
n-C16 n-C16
n-C18 n-C18
H 2O
0.20 98.5

0.00 98.0

20 40 60 80 100
TEMPERATURE ( C)
O

Figure 15- Temperature effects on mass fraction and recovery ratio of the products of

interest (n-C16 and n-C18) in the bottom stream of the separation column SC-02.

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 Low-pressure operating reaction decreases the production of n-C16 and n-C18,

 Low-pressure operating reaction produces high amounts of n-C15 and n-C17 chains
 High temperatures can decrease the production of renewable diesel
 Increasing H2/oil ratio is favorable to produce n-C16 and n-C18
 The purity degree of renewable diesel was 97% with optimized operating conditions