energies

Article
Cleaner Fuel Production via Co-Processing of Vacuum Gas Oil
with Rapeseed Oil Using a Novel NiW/Acid-Modified
Phonolite Catalyst
Jakub Fratczak
˛ , Nikita Sharkov * , Hector De Paz Carmona , Zdeněk Tišler and Jose M. Hidalgo-Herrador

ORLEN UniCRE, a.s., Revoluční 1521/84, 400 01 Ústí nad Labem, Czech Republic; jakub.fratczak@unicre.cz (J.F.);
Hector.Carmona@unicre.cz (H.D.P.C.); Zdenek.Tisler@unicre.cz (Z.T.); jose.hidalgo@unicre.cz (J.M.H.-H.)
* Correspondence: nikita.sharkov@unicre.cz

Abstract: Clean biofuels are a helpful tool to comply with strict emission standards. The co-processing
approach seems to be a compromise solution, allowing the processing of partially bio-based feedstock
by utilizing existing units, overcoming the need for high investment in new infrastructures. We
performed a model co-processing experiment using vacuum gas oil (VGO) mixed with different
contents (0%, 30%, 50%, 70%, 90%, and 100%) of rapeseed oil (RSO), utilizing a nickel–tungsten
sulfide catalyst supported on acid-modified phonolite. The experiments were performed using a
fixed-bed flow reactor at 420 ◦ C, a hydrogen pressure of 18 MPa, and a weight hourly space velocity
(WHSV) of 3 h−1 . Surprisingly, the catalyst stayed active despite rising oxygen levels in the feedstock.





 In the liquid products, the raw diesel (180–360 ◦ C) and jet fuel (120–290 ◦ C) fraction concentrations
increased together with increasing RSO share in the feedstock. The sulfur content was lower than
Citation: Fratczak,
˛ J.; Sharkov, N.;
200 ppm for all the products collected using feedstocks with an RSO share of up to 50%. However,
De Paz Carmona, H.; Tišler, Z.;
Hidalgo-Herrador, J.M. Cleaner Fuel
for all the products gained from the feedstock with an RSO share of ≥50%, the sulfur level was
Production via Co-Processing of above the threshold of 200 ppm. The catalyst shifted its functionality from hydrodesulfurization to
Vacuum Gas Oil with Rapeseed Oil (hydro)decarboxylation when there was a higher ratio of RSO than VGO content in the feedstock,
Using a Novel NiW/Acid-Modified which seems to be confirmed by gas analysis where increased CO2 content was found after the
Phonolite Catalyst. Energies 2021, 14, change to feedstocks containing 50% or more RSO. According to the results, NiW/acid-modified
8497. https://doi.org/10.3390/ phonolite is a suitable catalyst for the processing of feedstocks with high triglyceride content.
en14248497

Keywords: co-processing; acid-modified phonolite; hybrid fuels; VGO; RSO

Academic Editor: Poul Alberg
Østergaard

Received: 29 October 2021

1. Introduction
Accepted: 9 December 2021
Published: 16 December 2021
In the European Union (EU), road (71.7%), aviation (13.9%), and marine (13.3%)
transport are responsible for almost 99% of the greenhouse gas (GHG) emissions of the
Publisher’s Note: MDPI stays neutral
transportation sector [1], primarily due to their heavy utilization of fossil fuels. Thus, there
with regard to jurisdictional claims in is much interest in the development of “clean” fuels. One promising strategy involves
published maps and institutional affil- the introduction of biofeedstock processing in refineries. However, traditional petroleum
iations. refineries have a well-developed infrastructure for crude oil processing and usually lack
newer units able to process biofeeds. To avoid huge investment costs, the co-processing of
bio-based starting materials with petroleum-derived feedstocks could offer a compromise
solution [2–4] for such refineries.
Copyright: © 2021 by the authors.
The co-processing approach can help to produce a hybrid (petroleum- and bio-derived)
Licensee MDPI, Basel, Switzerland.
fuel that reduces GHG emissions through biomass utilization. Because vacuum gas oil
This article is an open access article (VGO), the product from the vacuum distillation of atmospheric residue, is the most widely
distributed under the terms and used feedstock for cracking processes [5], it has been used as a petroleum-derived blending
conditions of the Creative Commons component for co-processing mixtures [6]. Vegetable oils, such as rapeseed oil (RSO), are
Attribution (CC BY) license (https:// also considered good candidates for fuel production due to their high triglyceride con-
creativecommons.org/licenses/by/ tent [7]. Several studies have investigated RSO content in co-processing feedstocks [8–10],
4.0/).

Energies 2021, 14, 8497. https://doi.org/10.3390/en14248497 https://www.mdpi.com/journal/energies

Energies 2021, 14, 8497 2 of 13

and it has been reported that the use of RSO can have a positive synergistic effect when co-
processed with VGO [11]. Thus, VGO and RSO, as respective petroleum- and bio-derived
fractions, appear to be suitable candidates for use in co-processing for the production of
cleaner fuels.
Furthermore, research by Doronin et al. [9] showed that the yields of the target
cracking products from vegetable oils do not reach the level of values obtained in the
processing of vacuum gas oil, a traditional cracking feedstock. This is primarily due to the
fatty acid composition of vegetable oils. The processing of vegetable oils under cracking
conditions is not entirely appropriate due to the high reactivity of the primary products
of thermal decomposition of the initial triglycerides of oils—C15–C18 olefins. In this
regard, the interest is mainly in the joint cracking of raw materials of plant and petroleum
origin [12–14]. The high reactivity of the primary products of thermal decomposition of the
starting triglycerides of vegetable oils can adversely affect both the quantity and quality of
cracking products. For this reason, it is advisable to carry out co-processing of vacuum gas
oil and vegetable oil.
In addition to the selection of raw materials for the joint conversion of vacuum gas oil
with vegetable oil under cracking conditions, the choice of a catalyst remains an important
aspect. The above-mentioned studies used catalytic hydrocracking, a process that aims
to reduce the boiling point of the feedstock, for co-processing. The most commonly used
catalysts for hydro-processing are based on Co–Mo [15] or Ni–Mo [16] sulfides. However,
these metal complexes favor the hydrodeoxygenation pathway for the removal of oxygen,
meaning that O2 and H2 are converted into water molecules during the process. Due to
the undesired hydrogen consumption related to water formation, other metals have been
studied, such as nickel–tungsten (NiW). In particular, it was reported that NiW catalysts
mostly favor the decarbonylation and decarboxylation pathways for oxygen removal,
thereby consuming far less hydrogen compared with hydrodeoxygenation [17]. Thus, NiW
catalysts appear to be more suitable for feedstocks with higher oxygen content and, thus,
an increased bio-derived fraction.
A wide variety of support materials (zeolites, alumina, silica–alumina, etc.) have
been used in the synthesis of NiW catalysts [18–20]. Nevertheless, other potential support
materials remain to be explored, one of which is phonolite. As an extrusive volcanic
rock, it is primarily composed of alkali feldspar and, being widespread in nature, is
easily accessible and cheap [21]. In its default form, phonolite is a solid non-porous
material. However, after simple acid treatment, it can be quickly transformed into a porous
material with a significant surface area, making it highly desirable as a catalyst support [22].
A comparative study of NiW catalysts supported on acid-modified phonolite (A-Ph), foam
zeolites, and alumina revealed that the NiW/A-Ph catalyst showed the highest activity
for cracking and oxygen removal. Moreover, the A-Ph-supported catalyst resulted in the
lowest carbonaceous deposits on the surface, which is significant as such deposits cause
deactivation [23]. In this study, we use the above-mentioned NiW/A-Ph catalyst to co-
process VGO with different RSO ratios (0, 30, 50, 70, 90, and 100 wt.%) using a temperature
of 420 ◦ C, 18 MPa of H2 with a 100 L/h flow rate, and a weight hourly space velocity
(WHSV) of 3 h−1 . In particular, we focus on evaluation of its suitability in terms of product
yield, oxygen removal pathways, and possible process-emissions savings.

2. Materials and Methods

2.1. Feedstock Analysis
As blending components, the commercial feedstocks VGO and RSO were used. RSO,
food grade vegetable oil, was obtained at a local market from the company ARO. Except
for when using pure VGO and RSO fractions, VGO was mixed with different shares of RSO
to create a series of feedstock blends. The blends had an RSO content of 30%, 50%, 70%,
and 90%, respectively. The feedstock characteristics are shown in Table 1.
Energies 2021, 14, 8497 3 of 13

Table 1. Elemental composition of all utilized materials, including density and water content.

Property VGO 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO
Density (15 ◦ C),
905.1 905.9 908.8 913.8 918.5 919.8
kg/m3
Carbon, % 85.3 84.0 82.6 81.6 78.5 77.7
Hydrogen, % 12.7 12.5 12.5 12.4 12.0 12.0
Sulfur, ppm 16,200 11,600 8607 3990 1714 1
Nitrogen, ppm 493.0 394.0 340.0 216.0 104.0 1.3
Water, ppm 119.7 157.6 221.6 243.2 276.9 289.3
Oxygen 1 , % - 2.28 3.98 5.56 9.30 10.27
1 Calculated by difference from the mass balance.

VGO, as an industrial stream, had a sulfur content of over 1.6%, while RSO, as a
vegetable oil, contained practically no sulfur (1.0 ppm). As expected, the oxygen and water
contents increase together with the increase in the RSO share in the feedstock blend. RSO
contains the oxygen, being its source in the elemental composition of the feedstock blends.
Removing water from the raw materials is one of the main parameters for obtaining high-
quality biofuels, since in the future any free water content in biodiesel fuel will encourage
biological growth in storage tanks, which could lead to corrosion of metals (iron, copper,
and others) and the formation of sludge. Ultimately, this leads to clogged fuel filters and
fuel lines, which in turn can damage a vehicle’s fuel injection systems.
The boiling curves of all used fractions and mixtures, which were obtained using
simulated distillation analysis, are shown in Figure 1.
For the pure RSO, simulated distillation (SIMDIS) results showed that the main
products were mono-, di-, and triglycerides at boiling temperatures above 420 ◦ C by a very
narrow distillation curve in the temperature range of 600–620 ◦ C. No free fatty acids were
found, as shown in Figure 1 (range of boiling temperatures: 340–420 ◦ C). When the RSO
was mixed with the VGO, the height of the distillation curve at temperatures over 600 ◦ C
varied depending on the respective contents of RSO and VGO in the blend.
2.2. Support Material and Catalyst Preparation
2.2.1. Support Preparation—A-Phonolite (A-Ph)
The material for the synthesis of the catalyst support, which is originally from the
Czech Republic, was supplied by the company Keramost. Phonolite sand with a size range
of 0.224–0.560 mm was sieved using Retsch AS300. Then, it was dried in an oven at 120 ◦ C
overnight. The next step was leaching in 3M hydrochloric acid at 80 ◦ C for four hours
(dealumination). The phonolite to acid ratio was 1:10 (g/mL). The obtained product was
filtered, washed with demineralized water, and again dried in an oven at 120 ◦ C overnight.
The prepared dried samples were then calcined at 500 ◦ C for six hours with a 1 ◦ C/min
temperature ramp in the air [23].

2.2.2. Catalyst Preparation—5Ni10W/A-Phonolite (NiW/A-Ph)

Acid-treated phonolite, using an aqueous solution of nickel nitrate and ammonium
meta-tungstate, was impregnated. The support material impregnated with 5 wt.% nickel
and 10 wt.% tungsten became a catalyst. The obtained catalyst was further calcined at
450 ◦ C for six hours with a 1 ◦ C/min temperature ramp in the air. A detailed description of
the step-by-step synthesis can be found in a recently published paper by Hidalgo et al. [24].
Energies 2021, 14, 8497
Energies 2021, 14, x FOR PEER REVIEW  4  of  14  4 of 13
 

100
VGO
90
30% RSO
80

Amount Distilled, wt.%
50% RSO
70 70% RSO
60 90% RSO
50 100% RSO
40
30
20
10
0
250 300 350 400 450 500 550 600 650
Temperature, °C  
Figure 
Figure1. 1.Simulated 
Simulateddistillation  (SIMDIS) 
distillation curves 
(SIMDIS) of  all 
curves ofthe 
all used  feedstock 
the used materials. 
feedstock VGO  is 
materials. VGOthe  is the
feedstock without added RSO; 30%, 50%, 70%, and 90% RSO are the blends containing 70%, 50%, 
feedstock without added RSO; 30%, 50%, 70%, and 90% RSO are the blends containing 70%, 50%, 30%,
30%,  and  10%  VGO,  respectively;  and  100%  RSO  is  pure  rapeseed  oil.  The  measurement  was 
and 10% VGO, respectively; and 100% RSO is pure rapeseed oil. The measurement was performed
performed according to ASTM D7169 [25]. 
according to ASTM D7169 [25].
The suitability of the newly synthetized NiW/A‐Ph catalyst was evaluated together 
The suitability of the newly synthetized NiW/A-Ph catalyst was evaluated together
with  a  commercially  available  NiW  catalyst  supported  on  amorphous  silica–alumina 
with a commercially available NiW catalyst supported on amorphous silica–alumina
(NiW/Comm.)  by  two  parallel  experiments.  Experiments  were  conducted  under  the 
(NiW/Comm.) by two parallel experiments. Experiments were conducted under
reaction conditions given for the commercial catalyst by the supplier (420 °C, 18 MPa H 2, 
the
reaction conditions given for the commercial catalyst by the supplier (420 ◦ C, 18 MPa H ,
WHSV = 3 h−1), and using the same reactor setup.  2
WHSV = 3 h−1 ), and using the same reactor setup.
2.3. Experimental Setup and Catalytic Tests 
2.3. Experimental Setup and Catalytic Tests
All experiments were carried out using a continuous‐flow reactor system MaR 1101 
All experiments were carried out using a continuous-flow reactor system MaR 1101
(universal hydrogenation device) utilizing NiW catalysts based on two different support 
(universal hydrogenation
materials.  The  device)
purpose  of  the  utilizingwas 
experiments  NiWthe 
catalysts based onof 
deoxygenation  two
RSO different support
with  the 
materials. The purpose of the experiments was the deoxygenation of
addition of VGO at various ratios. In total, two experiments were carried out with two RSO with the addition
of VGOsystems 
catalytic  at various
on ratios. In supports 
different  total, two(acid‐modified 
experiments were carried
phonolite  and out with two catalytic
silica–alumina) 
systems on different supports (acid-modified phonolite and silica–alumina) under the same
under the same conditions and using the same methodology. 
conditions and using the same methodology.
At the beginning, the reactor was loaded with 27 g of catalyst mixed with fine silicon 
At(54 
carbide  the mL) 
beginning, the reactor
to  improve  was loaded
the  mass  with
and  heat  27 g ofthrough 
transfer  catalyst mixed with fine
the  catalyst  bed. silicon
carbide (54 mL)
Subsequently,  the  to improve
reactor  was the mass andsealed 
hermetically  heat transfer through the
and  pressurized  catalyst
with  bed. Sub-
a  nitrogen 
sequently, the reactor was hermetically sealed and pressurized with a nitrogen pressure
pressure of 200 bar under an ambient temperature of 25 °C for a pressure test. Then, the 
of 200 bar under an ambient temperature of 25 ◦ C for a pressure test. Then, the reactor
reactor pressure was reduced to 45 bar using nitrogen at a selected 100 L/h gas flow rate. 
Heating 
pressurewas 
wasthen  started 
reduced to to 
45 350  °C  with 
bar using a  heating 
nitrogen at arate  of  30 100
selected °C/h. 
L/h After 
gas reaching 
flow rate.the 
Heating
was then started to 350 ◦ C with a heating rate of 30 ◦ C/h. After reaching the designated
designated temperature, the gas was switched to hydrogen at a selected 25 L/h flow rate 
and a pressure of 45 bar to flush out residual nitrogen. Subsequently, the hydrogen flow 
temperature, the gas was switched to hydrogen at a selected 25 L/h flow rate and a pressure
was increased to 100 L/h, and the injection of the sulfuring mixture (diesel + 2% DMDS) 
of 45 bar to flush out residual nitrogen. Subsequently, the hydrogen flow was increased
was begun. Simultaneous activation/sulfurization was carried out for 72 h. The pressure 
to 100 L/h, and the injection of the sulfuring mixture (diesel + 2% DMDS) was begun.
was set to 90 bar, and the temperature increased to 420 °C with a 30 °C/h gradient for 6 h. 
Simultaneous activation/sulfurization was carried out for 72 h. The pressure was set to
After the drying phase, the operational gas was switched to hydrogen with a 100 L/h flow 
90 bar, and the temperature increased to 420 ◦ C with a 30 ◦ C/h gradient for 6 h. After the
rate  and phase,
drying a  pressure  of  180  bar. gas
the operational To was
avoid  an  aggressive 
switched cracking 
to hydrogen reaction 
with a 100 L/hby  flow
a  freshly 
rate and a
activated catalyst, the temperature was reduced to 380 °C, and the feedstock injection at a 
pressure of 180 bar. To avoid an aggressive cracking reaction by a freshly activated catalyst,
flow rate of 81 g/h was started (WHSV = 3 h ◦
−1). The temperature was then increased slowly 
the temperature was reduced to 380 C, and the feedstock injection at a flow rate of 81 g/h
to the desired 420 °C with a heating rate of 10 °C/h. After reaching a reaction temperature 
was started (WHSV = 3 h−1 ). The temperature was then increased slowly to the desired
of 420 °C, the reactor was operated on pure vacuum gas oil for 72 h (stabilization). After 
420 ◦ C with a heating rate of 10 ◦ C/h. After reaching a reaction temperature of 420 ◦ C, the
the stabilization phase using VGO, the feedstock was immediately changed to a mixture 
reactor was operated on pure vacuum gas oil for 72 h (stabilization). After the stabilization
of vacuum gas oil with different shares of rapeseed oil. The reactor operated on each blend 
phase using VGO, the feedstock was immediately changed to a mixture of vacuum gas oil
with different shares of rapeseed oil. The reactor operated on each blend for 48 h. Liquid
 
samples were collected every 4 h from the start of the feedstock injection, and the outcome
Energies 2021, 14, 8497 5 of 13

gas was sampled every 24 h. At the end of the experiment, the heating was turned off,
and the operating gas was switched to nitrogen with a 100 L/h flow rate and a pressure of
180 bar. After cooling to 200 ◦ C, a xylene flush was started using a 200 g/h flow rate for
48 h. After the cleaning, the pressure was reduced to 0 bar and the reactor dried under a
100 L/h nitrogen flow rate for 6 h. After drying, the gas flow was switched off, and after
cooling to room temperature, the catalyst was recovered.

2.4. Analyses of Materials and Products

Gas and liquid products were analyzed using different techniques. Gaseous products
were analyzed using Agilent’s “Refinery Gas Analysis” method on an Agilent 7890A gas
chromatograph with three parallel channels, which has two thermal conductivity detectors for
CO, H2, N2, and CO2 determination, and a flame ionization detector for hydrocarbon detection.
The raw materials and the liquid products collected were analyzed by SIMDIS and
compared to evaluate the suitability of both catalysts. Two main fraction yields were
monitored in the liquid samples: jet fuel (120–290 ◦ C) and diesel fraction (180–360 ◦ C). The
method of a high-temperature simulated distillation (ASTM D7169 [25]) performed by gas
chromatography is used to determine the distribution of boiling points in the analyzed
sample, depending on the distilled amount at the particular temperature. Injected samples
with an initial boiling point above 35 ◦ C and an ending boiling point higher than 750 ◦ C
can be analyzed. Based on the analysis of the known hydrocarbon mixture, covering the
sample distillation range and carried out under the same conditions as the sample, the
boiling point time points are assigned from the calibration curve. Based on these data, the
distribution of boiling points in the sample is determined. An Agilent 7890 HT/SIMDIS
system was used. The column installed was DBHT-SIMD, 5 m, 0.53 mm, 0.15 µm. The
density at 15 ◦ C was determined using a semi-hydrometer KYOTO DA-645 from Kyoto
Electronics Manufacturing co. A FLASH 2000 Elemental Analyzer according to the ASTM
D5291 [26] was used to determine the carbon and hydrogen contents of the samples. Also,
the Trace SN Cube was used to determine the sulfur and nitrogen contents in products at
micro scale according to ASTM D5453 [27] and ASTM D4629 [28].
To assess the efficiency of hydrocracking reactions, the selectivity, conversion, and product
yield for the raw fractions of diesel and jet fuel were calculated using Equations (1)–(5) [29].

Feed>360 ◦ C − Product>360 ◦ C
Diesel Conversion = (1)
Feed>360 ◦ C

Product180–360 ◦ C − Feed180–360 ◦ C
Diesel Selectivity = (2)
Feed>360 ◦ C − Product>360 ◦ C

Feed>290 ◦ C − Product>290 ◦ C
Jet Fuel Conversion = (3)
Feed>290 ◦ C

Product120–290 ◦ C − Feed120–290 ◦ C
Jet Fuel Selectivity = (4)
Feed>290 ◦ C − Product>290 ◦ C

Fraction Yield = Fraction Conversion ∗ Fraction Selectivity (5)

3. Results and Discussion

The evaluation of results was focused on the catalyst’s efficiency in terms of conversion,
selectivity, and yields. The conversion, the same as the product yields, depended on the
type of feed (RSO and/or VGO) and on the properties of the catalyst, the severity of the
reaction, and the operating system used (reactor configuration, fluid dynamics, testing and
analysis methods). Also, the raw liquid fuel fractions and the average gaseous product
composition were controlled. Because two catalysts were used (commercial and research
laboratory materials), the oxygen removal pathways of the two types of tests (using
laboratory or commercial catalyst) are discussed. Both experiments were conducted under
the reaction conditions defined by the supplier of the commercial NiW/silica–alumina
Energies 2021, 14, 8497 6 of 13

catalyst. This research aimed to carry out an initial evaluation of the suitability of the novel
NiW catalyst supported on A-Ph. Thus, before proceeding to the results and discussion, it
must be mentioned that there is still room for and a need for optimization of the reaction
conditions for the phonolite-based catalyst.

3.1. Product Analysis

3.1.1. Liquid Product Quality
Brief characteristics of the liquid products are presented in Table 2. The first significant
difference between the liquids obtained by the utilization of both NiW catalysts is related
to their density. As can be seen from Table 2 and Figure 2, NiW/Comm. produces a much
lighter general liquid product compared with NiW/A-Ph, which suggests more aggressive
cracking. The lower density means lighter, smaller, or shorter-chain molecules instead of
the larger molecules present in the feedstock.

Table 2. Characteristics of the liquid products: elemental composition, H/C ratio, density, and water content of the products
collected by processing each feedstock blend.

Energies 2021, 14, x FOR PEER REVIEW  NiW/A-Ph 6  of 

 
Property VGO—Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO—End
Density (15 ◦ C),
867.68 851.90 849.18 845.58 837.62 834.08 872.62
(commercial and research laboratory materials), the oxygen removal pathways of the tw
kg/m3
Carbon, % 86.6 86.8types of tests (using laboratory or commercial catalyst) are discussed. Both experimen
86.4 87.0 86.2 86.7 87.4
Hydrogen, % 13.4 13.4were conducted under the reaction conditions defined by the supplier of the commerci
13.4 13.4 13.5 13.6 13.0
H/C Ratio 1.84 NiW/silica–alumina catalyst. This research aimed to carry out an initial evaluation of th
1.84 1.84 1.83 1.87 1.87 1.77
Sulfur, ppm 343.33 suitability of the novel NiW catalyst supported on A‐Ph. Thus, before proceeding to th
94.15 133.50 253.50 153.50 82.50 1454.50
Nitrogen, ppm 90.87 26.10 69.50
results and discussion,  137.50 be mentioned that there is still 
it must  74.35 30.00 333.00
room  for and a  need f
Water content, wt.% 0 0.2optimization of the reaction conditions for the phonolite‐based catalyst. 
2.5 4.1 6.2 8 0
NiW/Comm.
3.1. Product Analysis 
Density (15 ◦ C), 3.1.1. Liquid Product Quality 
834.90 814.53 814.39 815.00 812.62 809.59 849.97
kg/m3
Carbon, % 85.6 85.5 Brief  characteristics 
86.0 of 
85.9 the  liquid  products 
85.6 are  presented 
85.6 in  Table  2.  The  fir
86.8
Hydrogen, % 14.0 14.5significant difference between the liquids obtained by the utilization of both NiW catalys
14.4 14.2 14.6 14.2 13.3
H/C Ratio 1.95 is related to their density. As can be seen from Table 2 and Figure 2, NiW/Comm. produc
2.01 2.00 1.96 2.03 1.98 1.83
Sulfur, ppm 10.39
a much lighter general liquid product compared with NiW/A‐Ph, which suggests mo
18.10 45.90 28.10 16.00 2.51 19.95
Nitrogen, ppm 1.03 0.87aggressive cracking. The lower density means lighter, smaller, or shorter‐chain molecul
0.74 0.37 0.38 0.17 1.17
Water content, wt.% 0 1.1instead of the larger molecules present in the feedstock. 
3.9 5.8 7.9 10.1 0.2

VGO ‐ Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
880

860
Density, kg/m3

840

820

800
0 24 48 72 96 120 144 168 192 216 240 264 288 312 336 360
Time, h
NiW/A‐Ph NiW/Comm.

Figure 2. The density of the products throughout the experiment performed using two catalysts  
Figure  2. (NiW/A-Ph,
The  density NiW/Comm.).
of  the  products 
Thethroughout 
experimentthe  experiment 
started performed 
by processing using  and
pure VGO, two then
catalysts 
there (NiW/A‐Ph, 
were
NiW/Comm.). The experiment started by processing pure VGO, and then there were five feedstock blend changes using 
five feedstock blend changes using 30%, 50%, 70%, 90%, and 100% RSO, respectively.
30%, 50%, 70%, 90%, and 100% RSO, respectively. 

Table  2.  Characteristics  of  the  liquid  products:  elemental  composition,  H/C  ratio,  density,  and  water  content  of  the 
products collected by processing each feedstock blend. 

NiW/A‐Ph 
Property  VGO—Start  30% RSO  50% RSO  70% RSO  90% RSO  100% RSO  VGO—End
Density (15 °C), kg/m   867.68 
3 851.90  849.18  845.58  837.62  834.08  872.62 
 Energies 2021, 14, x FOR PEER REVIEW  7  of 
 

Energies 2021, 14, 8497 7 of 13

Nitrogen, ppm  1.03  0.87  0.74  0.37  0.38  0.17  1.17 
Water content, wt.%  0  1.1  3.9  5.8  7.9  10.1  0.2 

Surprisingly, there are two there 

Surprisingly,  similar visible
are  trendsvisible 
two  similar  in terms of the
trends  density
in  terms  of liquid
of  the  density  of  liqu
products. The density of the liquid product gained from RSO-containing feedstock
products.  The  density  of  the  liquid  product  gained  from  RSO‐containing  pro- feedsto
cessed over NiW/Comm. decreases very slightly, with the mean value in the
processed over NiW/Comm. decreases very slightly, with the mean value in the range  range of
809–815 kg/m3 .809–815 
Meanwhile, the density of the liquid product produced from the RSO-
kg/m .  Meanwhile,  the  density  of  the  liquid  product  produced  from  the  RSO
3

containing material processed overprocessed 

containing material  the NiW/A-Ph catalyst significantly decreased with
over the NiW/A‐Ph catalyst significantly decreased  wi
increasing RSO increasing RSO content over time. In terms of fuel production, however, products gaine
content over time. In terms of fuel production, however, products gained
by 90–100% RSOby 90–100% RSO processing over the NiW/A‐Ph catalyst under the tested conditions ha
processing over the NiW/A-Ph catalyst under the tested conditions had a
density matching the restrictions of the European EN590 standard for diesel fuel, being in
a density matching the restrictions of the European EN590 standard for diesel fuel, bein
the range of 820–845 kg/m3 [30].
in the range of 820–845 kg/m 3 [30]. 

The density of the products increased when more RSO was included in the feedstock
The density of the products increased when more RSO was included in the feedsto
mixture. However,mixture. However, the H/C ratio was lower, indicating a lower content of saturated line
the H/C ratio was lower, indicating a lower content of saturated linear
paraffins. For the commercial catalyst, the VGO final test led to a product with a H/C rat
paraffins. For the commercial catalyst, the VGO final test led to a product with a H/C
ratio of 1.83, which waswhich 
of  1.83,  a lower was  a  lower 
number number  compared 
compared with 1.95 at with 
the1.95 
startat ofthe 
thestart  of  the  reactio
reaction,
indicating  a  deactivation  of  the  catalyst.  For  the  phonolite‐type 
indicating a deactivation of the catalyst. For the phonolite-type catalyst, the trend was catalyst,  the  trend  w
similar but with lower H/C ratio values, indicating a lower hydrogenation activity durin
similar but with lower H/C ratio values, indicating a lower hydrogenation activity during
the reaction compared with the reaction using the commercial catalyst. 
the reaction compared with the reaction using the commercial catalyst.
As can be seen As can be seen in Table 2, the sulfur and nitrogen removal was much more efficie
in Table 2, the sulfur and nitrogen removal was much more efficient
when the commercial catalyst was used. The heteroatom content of the liquid produc
when the commercial catalyst was used. The heteroatom content of the liquid products ob-
obtained by the commercial catalyst was in the range of 0–50 ppm for sulfur and 0.0–1.
tained by the commercial catalyst was in the range of 0–50 ppm for sulfur and 0.0–1.05 ppm
ppm  for  nitrogen,  respectively  (Table  2,  Figure  3).  In  the  case  of  the  research  cataly
for nitrogen, respectively (Table 2, Figure 3). In the case of the research catalyst NiW/A-Ph,
NiW/A‐Ph,  the  average  heteroatom  content  for  the  liquid  products  gained  wh
the average heteroatom content for the liquid products gained while processing RSO-
processing RSO‐containing blends was in the range of 80–255 ppm for sulfur and 25–1
containing blends was in the range of 80–255 ppm for sulfur and 25–140 ppm for nitrogen
ppm for nitrogen (Table 2, Figure 4). 
(Table 2, Figure 4).

VGO ‐ Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
50

40
Concentration, ppm

30

20

10

0
0 24 48 72 96 120 144 168 192 216 240 264 288 312 336 360
Time, h
Sulfur Nitrogen
 
Figure 3. The change in the heteroatom content (S, N) in the liquid products throughout the experi-
Figure 3. The change in the heteroatom content (S, N) in the liquid products throughout the experiment carried out using 
the NiW/Comm. catalyst 
ment carried out using the NiW/Comm. catalyst.
As can be seen in Figure 4, after the catalyst started processing RSO-containing feed,
the heteroatom removal continuously decreased with the higher RSO addition in the range
of 30–90% RSO. This is usually related to catalyst deactivation due to RSO addition (coking,
sulfur leaching, etc.). Lower sulfur content results were gained when pure RSO was
processed, which is surely related to the almost zero sulfur and nitrogen contents in the
RSO composition. On the contrary, when processing pure VGO, the content of heteroatoms
was quite high, which is due to the fact that the industrial raw material of VGO contains
a sufficiently high content of sulfur. Nevertheless, the increased sulfur content for the
products obtained from pure RSO processing suggests a sulfur leaching from the catalyst
bed to the liquid products. In addition, as mentioned, this result is probably related to the
  relatively short time (48 h) of processing for 100% RSO. The sulfur leaching, suggested
by the increased sulfur content in liquid products collected from RSO processing, would
surely lead to severe catalyst deactivation over time.
Energies 2021, 14, 8497 8 of 13
Energies 2021, 14, x FOR PEER REVIEW  8  of 
 

VGO ‐ Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
1400
1200

Concentration, ppm
1000
800
600
400
200
0
0 24 48 72 96 120 144 168 192 216 240 264 288 312 336 360
Time, h
Sulfur Nitrogen
 
Figure 4. The change in the heteroatom content (S, N) in the liquid products throughout the experiment carried out using 
Figure 4. The change in the heteroatom content (S, N) in the liquid products throughout the experi-
the NiW/A‐Ph catalyst. 
ment carried out using the NiW/A-Ph catalyst.

Sulfur removal As can be seen in Figure 4, after the catalyst started processing RSO‐containing fee

and nitrogen removal were very efficient when the commercial catalyst
was used. Nevertheless, even inremoval 
the  heteroatom  this case,continuously 
the catalyst needed
decreased to stabilize
with  the for a minimum
higher  of
RSO  addition  in  th
24 h after the feedstock blend change,This is usually related to catalyst deactivation due to RSO additio
range of 30–90% RSO. which is presented in Figure 3.
The most significant finding, however,Lower sulfur content results were gained when pure RS
(coking, sulfur leaching, etc.). is related to the possible hydrogen savings,
more concretelywas processed, which is surely related to the almost zero sulfur and nitrogen contents 
the oxygen removal pathways. As can be seen in Table 2, the water content
observed in thethe  RSO products
liquid composition.  On  the  contrary, 
is significantly higher when 
for theprocessing 
commercial pure 
NiW VGO,  the  content 
catalyst.
This suggests aheteroatoms was quite high, which is due to the fact that the industrial raw material 
more favorable hydrodeoxygenation pathway of oxygen removal, which
produces waterVGO  as ancontains 
effect ofa  sufficiently 
the reactionhigh  content and
of oxygen of  sulfur. Nevertheless, 
hydrogen. the  increased 
This seems to be sulfu
content for the products obtained from pure RSO processing suggests a sulfur leachin
proven by the lower hydrogen content in the outcome gas using the commercial catalyst
from the
(Figure 5). Besides the possibility
catalyst  bed 
of ato water–gas
the  liquid shift
products.  In  addition, 
reaction, which isas  mentioned, 
possibly takingthis  result 
probably related to the relatively short time (48 h) of processing for 100% RSO. The sulfu
place in all the experiments carried out, there is still a visible difference in the CO2 and H2 O
Energies 2021, 14, x FOR PEER REVIEW 
leaching, suggested by the increased sulfur content in liquid products collected from RS 9  of  1
  produced by NiW/Comm. in comparison with NiW/A-Ph. The expected water content is
processing, would surely lead to severe catalyst deactivation over time. 
higher when RSO is used, due to the deoxygenation of the triglycerides.
Sulfur  removal  and  nitrogen  removal  were  very  efficient  when  the  commerci
catalyst was used. Nevertheless, even in this case, the catalyst needed to stabilize for
100
minimum of 24 h after the feedstock blend change, which is presented in Figure 3. 
90
The most significant finding, however, is related to the possible hydrogen saving
80
Concentration, wt.%

more  concretely  the  oxygen  removal  pathways.  As  can  be  seen  in  Table  2,  the  wat
70 content observed in the liquid products is significantly higher for the commercial NiW
60 catalyst.  This  suggests  a  more  favorable  hydrodeoxygenation  pathway  of  oxyge
50 removal, which produces water as an effect of the reaction of oxygen and hydrogen. Th
40 seems  to  be  proven  by  the  lower  hydrogen  content  in  the  outcome  gas  using  th
30 commercial catalyst (Figure 5). Besides the possibility of a water–gas shift reaction, whic
20 is possibly taking place in all the experiments carried out, there is still a visible differen
10 in  the  CO2  and  H2O  produced  by  NiW/Comm.  in  comparison  with  NiW/A‐Ph. Th
0 expected  water  content  is  higher  when  RSO  is  used,  due  to  the  deoxygenation  of  th
VGO ‐ Start 30% RSO
triglycerides.  50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
Feedstock blend
3.1.2. Gaseous Product Quality 
Hydrogen Hydrogen Sulfide Alkanes Isoalkanes С5+ Carbon Monoxide Carbon Dioxide
NiW catalysts were used in this research to possibly improve the hydrogen saving
 
Figure 5. Composition of the maindecarbonylation 
by  enhanced  gaseous products collected for each feedstockpathways 
and  decarboxylation  blend processed using remova
of  oxygen 
Figure 5. Composition of the main gaseous products collected for each feedstock blend processed using the NiW/Comm. 
the NiW/Comm. producing CO and CO
catalyst. 2,  respectively. As can be seen in Figures 5 and 6, decarboxylatio
catalyst. 
and decarbonylation occurred for both tested catalysts. 
3.1.2. Gaseous Product Quality
100
NiW catalysts were used in this research to possibly improve the hydrogen savings
90
by enhanced decarbonylation and decarboxylation pathways of oxygen removal, produc-
80
ncentration, wt.%

  70
60
50
40
30
 Co
20
10
0
VGO ‐ Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
Energies 2021, 14, 8497 Feedstock blend 9 of 13

Hydrogen Hydrogen Sulfide Alkanes Isoalkanes С5+ Carbon Monoxide Carbon Dioxide

 
ing CO and CO2 , respectively. As can be seen in Figures 5 and 6, decarboxylation and
Figure 5. Composition of the main gaseous products collected for each feedstock blend processed using the NiW/Comm. 
catalyst.  decarbonylation occurred for both tested catalysts.

100
90
80
Concentration, wt.% 70
60
50
40
30
20
10
0
VGO ‐ Start 30% RSO 50% RSO 70% RSO 90% RSO 100% RSO VGO ‐ End
Feedstock blend
Hydrogen Hydrogen Sulfide Alkanes Isoalkanes С5+ Carbon Monoxide Carbon Dioxide

 
Figure 6. Composition of the main gaseous products collected for each feedstock blend processed
using the NiW/A-Ph catalyst.
Figure 6. Composition of the main gaseous products collected for each feedstock blend processed using the NiW/A‐Ph 
catalyst.  In the case of the water formation (deoxygenation) with the NiW/A-Ph catalyst,
decarbonylation was a more favorable way of oxygen removal (Table 2, Figure 6). The
In  the  case  of  the  water  formation  (deoxygenation)  with  the  NiW/A‐Ph  catalyst
composition of the gaseous product gained by using NiW/A-Ph seems to be less harmful to
decarbonylation  was  a  more favorable  way  of  oxygen  removal  (Table  2,  Figure 6).  Th
the environment, with less CO2 , H2 S, and cracking gases and a higher level of hydrocarbons
composition of the gaseous product gained by using NiW/A‐Ph seems to be less harmfu
compared with the gas produced by NiW/Comm.
to  the  environment,  with  less  CO2,  H2S,  and  cracking  gases  and  a  higher  level  o
In terms of cleaner fuel production and possible hydrogen savings, the best way for
hydrocarbons compared with the gas produced by NiW/Comm. 
oxygen removal seems to be decarbonylation, producing CO and H2 O as products. Mean-
In terms of cleaner fuel production and possible hydrogen savings, the best way fo
while, CO2 is aoxygen 
problematic emission
removal  seems gas, whereas
to  be  CO can be separated
decarbonylation,  producing from the outcome
CO  and  H2O  as  products
gas and be further processed to produce fuels or other chemicals. In light
Meanwhile, CO2  is a  problematic emission gas,  whereas  CO  can be  of the above-
separated from th
mentioned benefits, NiW/A-Ph looks very promising in comparison with NiW/Comm.
outcome gas and be further processed to produce fuels or other chemicals. In light of th
The NiW/Comm. catalyst prefers
above‐mentioned  hydrodeoxygenation
benefits,  NiW/A‐Ph  looks  and decarboxylation
very  promising  in reactions,
comparison  with
giving significantly more water and almost two times more CO2 compared with NiW/A-Ph
NiW/Comm. The NiW/Comm. catalyst prefers hydrodeoxygenation and decarboxylation
(Table 2, Figurereactions, giving significantly more water and almost two times more CO
5). 2 compared with

NiW/A‐Ph (Table 2, Figure 5). 
3.2. Conversion, Selectivity, and Yield for Raw Fuel Fractions
The conversion and selectivity for diesel and jet fuel fractions by using the NiW catalysts
is presented in Table 3. Generally, NiW/Comm. tests led to a better overall result in terms of
  conversion, selectivity, and yield compared with the tests performed using NiW/A-Ph. This
difference in activity was found for these specific reaction conditions. Nevertheless, both of
the catalysts were able to process the VGO and RSO, as well as their blends.
In the case of conversion and yield, the greatest difference between the tested catalysts
can be observed with pure VGO processing. The use of a pure industrial fraction of VGO
led to a lower efficiency in obtaining diesel and jet fuel fractions with the lowest overall
conversion of 33.6% and yield of 11.4% (jet fuel fraction). Taking into account that the VGO
presented different contents of hydrocarbons, sulfur, and nitrogen compounds, a change
in the general conversion was expected. Similar results were obtained by Chen et al. [31],
where an 80/20 heavy vacuum gas oil (HVGO)/canola oil blend was found to have product
yields of 36–40%, while pure HVGO had the lowest. Thus, they concluded that canola oil
is easier to crack than HVGO.
The RSO contains triglycerides, which react to produce free fatty acids by β-elimination
and cracking reactions. Subsequent fatty acid deoxygenation proceeds via decarboxyla-
tion/decarbonylation and produces hydrocarbons, which are then hydrocracked into
shorter molecules [32]. Furthermore, the RSO generates (after only the deoxygenation
pathway reaction) mainly C17 compounds, which are then hydrocracked into shorter
Energies 2021, 14, 8497 10 of 13

hydrocarbons. This reaction pathway directly affects the hydrocracking reaction of VGO,
which contains hydrocarbons from C16 to C31 (boiling range of 300–450 ◦ C). Therefore,
the addition of RSO increases the yield of jet fuel and diesel fractions, due to its initial
content generating mainly C17 hydrocarbons. Moreover, Rana et al. [16], when studying
the co-processing of used vegetable oil and light atmospheric gas oil, found that increasing
the content of used oil in the feed resulted in higher product yields. Thus, the final product
consisted mainly of diesel range hydrocarbons (60–90% yield) and a small amount of jet
fuel range hydrocarbons (10–35% yield).
The differences between catalyst efficiencies decrease over time, together with the
increase in the RSO content in the feedstock. The highest RSO share in the feedstock blend
also led to the highest overall raw fuel fraction yields, which is graphically presented in
Figures 7 and 8.

Table 3. Conversion, selectivity, and yield for raw fuel fractions (diesel, jet fuel) produced using both tested NiW catalysts
(NiW/A-Ph, NiW/Comm.).

NiW/A-Ph
Diesel Fraction Jet Fuel Fraction
Conversion (%) Selectivity (%) Yield (%) Conversion (%) Selectivity (%) Yield (%)
VGO 33.6 62.3 20.9 19.7 58.0 11.4
30% RSO 52.7 57.4 30.2 31.7 52.3 16.6
50% RSO 59.8 51.8 30.9 40.1 48.0 19.2
70% RSO 61.6 58.7 36.1 40.0 53.4 21.3
90% RSO 66.1 57.0 37.7 45.8 57.4 26.3
100% RSO 68.0 56.2 38.2 48.9 59.0 28.8
NiW/Comm.
Diesel fraction Jet Fuel fraction
Energies 2021, 14, x FOR PEER REVIEW 
Conversion (%) Selectivity (%) Yield (%) Conversion (%) Selectivity (%) 11  of  14 
Yield (%)
 
VGO 57.1 58.9 33.6 40.1 66.1 26.5
30% RSO 75.5 55.9 42.2 51.2 60.9 31.2
50% RSO 75.7 60.9
The  differences  46.1
between  51.0decrease  over  time, 
catalyst  efficiencies  67.8 together  with the 
34.5
70% RSO 77.3 59.4 45.9 52.9 62.9 33.2
increase in the RSO content in the feedstock. The highest RSO share in the feedstock blend 
90% RSO 78.5 60.0 47.1 54.2 64.4 34.9
also led to the highest overall raw fuel fraction yields, which is graphically presented in 
100% RSO 80.2 59.8 47.9 56.8 65.3 37.1
Figures 7 and 8. 

50
45
40
Diesel Fraction Yield, %

35
30
25
20
15
10
5
NiW/Comm. NiW/A‐Ph
0
0 10 20 30 40 50 60 70 80 90 100
RSO content in the feedstock, wt.%
 
Figure 7. Diesel fraction yield gained throughout the experiment using both tested NiW catalysts 
Figure 7. Diesel fraction yield gained throughout the experiment using both tested NiW catalysts
(NiW/A‐Ph, NiW/Comm.) depending on the RSO content in the processed feedstock blend. 
(NiW/A-Ph, NiW/Comm.) depending on the RSO content in the processed feedstock blend.

40

35
tion Yield, %

30

25
 5
NiW/Comm. NiW/A‐Ph
0
0 10 20 30 40 50 60 70 80 90 100
RSO content in the feedstock, wt.%
Energies 2021, 14, 8497   11 of 13
Figure 7. Diesel fraction yield gained throughout the experiment using both tested NiW catalysts 
(NiW/A‐Ph, NiW/Comm.) depending on the RSO content in the processed feedstock blend. 

40

35

Jet Fuel fraction Yield, %
30

25

20

15

10

5
NiW/Comm. NiW/A‐Ph
0
0 10 20 30 40 50 60 70 80 90 100
RSO content in the feedstock, wt.%
 
Figure 8. Jet fuel fraction yield gained throughout the experiment using both tested NiW catalysts 
Figure 8. Jet fuel fraction yield gained throughout the experiment using both tested NiW catalysts
(NiW/A‐Ph, NiW/Comm.) depending on the RSO content in the processed feedstock blend. 
(NiW/A-Ph, NiW/Comm.) depending on the RSO content in the processed feedstock blend.

Regarding 
Regardingdiesel 
dieselfraction 
fractionyield 
yield(Figure 
(Figure7), 
7),the 
thedifferences 
differencesbetween 
betweenthe thetwo 
twotested 
tested NiW
NiW catalysts were rather constant throughout the experiment. Both catalysts showed the 
catalysts were rather constant throughout the experiment. Both catalysts showed the best
best results when pure RSO was the feedstock. This result could be related to the previous 
results when pure RSO was the feedstock. This result could be related to the previous
obtainment of linear paraffins by HDO, and their subsequent hydrocracking to diesel, jet 
obtainment of linear paraffins by HDO, and their subsequent hydrocracking to diesel, jet
fuel, and other products. The VGO contains not only linear paraffins but also other types 
fuel, and other products. The VGO contains not only linear paraffins but also other types
of hydrocarbons such as aromatic and naphtenes. In addition, the relatively short time of 
of hydrocarbons such as aromatic and naphtenes. In addition, the relatively short time
reaction  (48  h), 
of reaction (48even  when 
h), even having 
when a  feedstock 
having with  with
a feedstock sufficient  sulfur sulfur
sufficient content,  was  not 
content, was not
enough to cause loss of efficiency at the active sites (metal sulfides and loss of sulfur). It 
enough to cause loss of efficiency at the active sites (metal sulfides and loss of sulfur). It
would be expected to see severe deactivation due to sulfur leaching when processing RSO 
would be expected to see severe deactivation due to sulfur leaching when processing RSO
for a longer time. 
for a longer time.
Phonolite is a novel potential raw material for use as a catalyst support. With its acid 
Phonolite is a novel potential raw material for use as a catalyst support. With its
modification,  the  phonolite  acquires  porous  properties  with  a  significant  surface  area, 
acid modification, the phonolite acquires porous properties with a significant surface area,
becoming a cost-effective support material for catalyst preparation. Furthermore, the novel
application of phonolite as a new type of catalyst gives information about the effects of
  adding RSO on VGO processing. The experiment is aimed at future expansion of phonolite
application for further use in refinery operations, specifically for the co-processing of
feedstocks with a partial bio-origin. Therefore, this information is useful not only for
researchers but also for refineries.
It also needs to be mentioned that our work has some uniqueness in comparison
with the existing literature. There was no information about the use of phonolite-based
catalysts for processing bio-derived materials from other publications. Thus, this indicates
the novelty of our work.

4. Conclusions
Two catalysts (NiW/Comm. and NiW/A-Ph) were tested in the hydrocracking reac-
tion of RSO and/or VGO feedstocks. Both catalysts were active in the hydrocracking of the
feedstock mixtures, with the commercial catalyst being the most active in the production
of diesel and jet fuels. Moreover, tests on the NiW/Comm. catalyst led to better overall
results in terms of conversion, selectivity, and yield compared with tests performed using
NiW/A-Ph. However, the composition of the gaseous product obtained by NiW/A-Ph
appears to be less harmful to the environment as it contained less CO2 , H2 S, and cracking
gases and more hydrocarbons than the gas produced by the commercial catalyst. The
NiW/Comm. catalyst preferred hydrodeoxygenation and decarboxylation reactions, pro-
ducing significantly more water and almost double the amount of CO2 compared with
NiW/A-Ph. The best jet fuel and diesel fraction yields were found for the tests using pure
RSO. This study suggests the initial suitability of the NiW/A-Ph catalyst for processing
feedstocks with an increased oxygen content, showing a comparable result to a commer-
Energies 2021, 14, 8497 12 of 13

cial catalyst. Even despite the operation in possibly non-optimized reaction conditions,
the phonolite-based catalyst showed a comparable result to the NiW/Comm. catalyst.
Moreover, the NiW/A-Ph catalyst showed a better performance regarding possible hydro-
gen and emission savings, which is significant for cleaner fuel production in the future.
This study highlights the benefit of further optimization of the operating conditions for
phonolite-based catalysts. To conclude, the NiW/A-Ph catalyst is a promising candidate to
be utilized for the processing of oxygenated feedstocks with bio-origin.

Author Contributions: Conceptualization, J.F. and J.M.H.-H.; methodology, J.F., Z.T. and H.D.P.C.;
validation, J.F., J.M.H.-H., H.D.P.C. and Z.T.; data curation, J.F., Z.T. and J.M.H.-H.; visualization and
writing—original draft preparation, J.F. and N.S.; funding acquisition, J.F.; project administration, J.F.;
and writing—review and editing, J.F., N.S., J.M.H.-H. and H.D.P.C. All authors have read and agreed
to the published version of the manuscript.”
Funding: This publication is a result of a project that was funded by Ministry of Industry and Trade
of the Czech Republic, with institutional support for long-term conceptual development of research
organization. The result was achieved using the infrastructure included in the project Efficient Use of
Energy Resources Using Catalytic Processes (LM2018119), which has been financially supported by
MEYS within the targeted support of large infrastructures.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
List of abbreviations used in this paper:
A-Ph Acid-modified phonolite
ASTM American standard test method
Co–Mo Cobalt–molybdenum
DMDS Dimethyl disulfide
EU European Union
GHG Greenhouse gas
HDO Hydrodeoxygenation
Ni–Mo Nickel–molybdenum
NiW Nickel–tungsten
NiW/A-Ph. Nickel–tungsten catalyst supported on acid-modified phonolite
NiW/Comm. Commercial nickel–tungsten catalyst
RSO Rapeseed oil
SIMDIS Simulated distillation
VGO Vacuum gas oil
WHSV Weight hourly space velocity

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