Co-processing renewables in a
hydrocracker
Understanding and controlling the impact on catalyst performance, yields, and product
properties is key to renewables co-processing in hydrocracking units
Peter Andreas Nymann and Pronit Lahiri
Topsoe
T
he demand for having part of the product slate
from refineries consisting of renewable materials is
increasing. Hydrotreating units have been the pri-
mary choice so far, but hydrocracking units are also quite
suitable and will be unavoidable in the future, especially
when processing more demanding second- and third-gen-
eration feedstocks.
Extensive pilot plant testing and a fundamental under-
standing of chemistry supported by industrial operation
from several units worldwide have put Topsoe in a position
to support refineries in this challenging effort. Topsoe has
been collaborating with refineries navigating through the
energy transition to reduce CO2 emissions originating from
the use of fossil-based feedstocks.
Renewable feedstock challenges
The world energy sector is going through an energy transi-
tion and looking for solutions to decarbonise energy produc-
tion. Part of this is facilitated by replacing fossil feedstocks
with renewable resources and treating these in the existing
refinery framework to produce fuels that are fully compat-
ible with the hydrocarbon fuels in the market today.
Processing of renewable feedstocks, like first-generation
feedstocks such as palm oil and other triglyceride-based
hydrocarbons, has therefore been widely applied in recent
years. Several projects constructing new standalone units
or revamping existing hydroprocessing units to either
co-process or solely process renewable feedstocks have
materialised.
Co-processing renewable feedstocks in hydrotreating
units is now well established, and refineries are looking for
more ways to include renewable feedstocks in their exist-
ing units. Furthermore, the increased demand for includ-
ing renewable feedstocks in the energy system and the
availability of renewable feedstocks directs the industry
to incorporate second- and third-generation renewable
feedstocks. This introduces new and more demanding
requirements to convert these challenging feedstocks into
on-spec fuels.
One way is to co-process renewables in hydrocracking
units. The hydrocracker has advantages and disadvan-
tages when it comes to co-processing renewables. If the
economic uplift from processing renewable feedstocks is
lower than that of normal hydrocracker feedstock, or the
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renewable feedstock should cause severe performance
deficits in the hydrocracker, co-processing in the hydro-
cracker might not be feasible.
Understanding the impact on the performance of the
hydrocracking unit when introducing new feedstock
types, such as first-, second- and third-generation renew-
able feedstocks, is therefore of utmost importance for
this evaluation.
Feedstocks and chemistry
In recent years, the most applied renewable feedstocks
in refinery units have been triglycerides. These typically
originate from what is referred to as virgin oils, more com-
monly known as first-generation feedstocks. More recently,
second-generation feedstocks like used cooking oil (UCO),
palm oil mill effluent (POME), and others have been con-
sidered. Second-generation renewable feedstocks are typi-
cally byproducts from the production of virgin oils. Going
forward, third-generation feedstocks like pyrolysis oils
derived from municipal sewage waste, byproducts from the
paper and pulp industry, wood, plastic, or tyres are being
investigated.
The triglycerides are characterised by consisting of three
glycerol chains with a typically even carbon number and
a backbone of propane connected by oxygen atoms (see
Figure 1). Hydrotreating reactions include saturation of
double bonds inside chains, breaking of triglyceride into pro-
pane from the backbone and paraffins from the side chains,
and the reaction of oxygen atoms with hydrogen, forming
water, CO or CO2. They occur readily over hydrotreating
catalysts and are well known in several hydroprocessing
units worldwide.
Many second- and third-generation feeds are more com-
plex than the first-generation feeds and hold more complex
molecules. Consequently, they result in a different boiling
range of the products as well as different properties. Unlike
the triglycerides that generate straight chained molecules
boiling in the distillate boiling range, the second- and third-
generation feedstocks contain ring structures with different
heteroatoms that need more hydrogenation and eventually
cracking to bring them into the transportation fuel boiling
range and to ensure that these products fulfil other product
specifications, such as cold flow properties and densities.
Hydrotreating of triglycerides requires significant
Catalysis 2023 25
 Triglyceride molecule
Better cetane index
O Paraffins Higher cloud point

H2C O
Backbone – O
Formation of CO, CO2 & H2O
propane Oxygen
HC O Higher H2 consumption
formation O
9 12

H2C O 3
Ole-sat gives higher H2 consumption
Olefins
Higher heat release

Figure 1 First-generation renewable feedstocks mainly consist of triglycerides that consist of a propane backbone linking
the paraffin chains with oxygen bonds. Breaking of the oxygen bonds will result in yields of paraffins, propane, and
oxygen-containing molecules like water, CO and CO2

amounts of hydrogen, and the reactions are highly exo-
thermic. The product will be boiling in the middle distillate
range and suitable for diesel. If jet fuel is needed, the lon-
ger normal paraffin chains need to be converted to lower
boiling material by either cracking or isomerisation. Normal
paraffins have low density and high cetane index, but also
high cloud point. Isomerisation provided by a hydrocrack-
ing catalyst is therefore sometimes needed to achieve cloud
point specifications.
Hydrotreating of aromatics and oxygen-containing ring
structures produce naphthenes with higher density and
boiling range than what is suitable for diesel. Selective
hydrocracking reactions involving ring opening will there-
fore be needed for processing these more demanding
second- and third-generation feedstocks to produce high
yields of high-quality jet and diesel products.
Overcoming operational challenges
Operational challenges are better overcome in hydrocrack-
ers. Considering the high content of oxygen in renewable
feeds, the H2 consumption associated with these reactions
is in the range of 300-500 Nm3/m3, which is orders of mag-
nitude greater than what is normally seen in hydrotreaters.
However, compared to hydrocrackers, the difference is less,
and the impact from processing in a hydrocracker would
Vegetable oil, 0% Vegetable oil, 5%
Feed C, Feed C,
Feed A,
3% Feed A,
36%
3%
36%
Planned throughput
Planned throughput
during fossil run,
co-processing run,
vol%
vol%
Feed B, Feed B,
61% 56%
Figure 2 Unit throughput was kept stable during the test
run processing typical feedstock for baseline comparison.
5 vol% of the feedstock was slowly replaced with vegetable
oil and then all unit operational parameters were kept stable
to evaluate performance during co-processing
therefore be less. Likewise, the associated heat release
originating from these reactions is also more in the same
order of magnitude as in hydrocrackers designed to handle
high temperature rises by having multiple beds.
Contaminants present in the renewable feeds pose a
challenge to the hydrotreaters, and significant amounts
of bulk catalysts need to be replaced to manage the con-
taminants. In hydrocrackers, the VGOs and HCGOs often
processed also have considerable amounts of contami-
nants, and hydrocrackers are therefore normally designed
to include volume for grading catalysts. They may therefore
allow greater quantities of renewables to be processed
without compromising catalyst cycle length.
Different types of renewable feeds may produce differ-
ent renewable products, and the fractionation section in
hydrocrackers makes it possible to separate these differ-
ent products. The products from renewables often require
more than hydrotreating, either to achieve better cold flow
properties by isomerisation or, in the case of second- and
third-generation feedstocks, hydrogenation of rings and
ring opening. Hydrocracking catalysts are multifunctional
and may be selected to include both isomerisation and
selective ring opening activity to ensure the fulfilment of all
required end-product properties.
Real-world examples
Several hydrocrackers worldwide are processing renewable
feedstocks. Some hydrocrackers are part of standalone units
comprising hydrotreating, isomerisation, and hydrocracking
sections, and others are conventional fossil fuel hydrocrack-
ers co-processing renewable feed batches. Topsoe has
supported refineries in preparing for and conducting test
runs, and the following discussion gives examples of the
observations from one of these test runs showing industrial
data supporting the theoretical basis previously discussed,
confirming learnings from pilot plant studies.
Test run co-processing vegetable oil in a European refinery
The refinery operates a single-stage once-through hydro-
cracking unit, designed for 80 wt% gross conversion of
various low-value gas oil streams to high-quality products.
The primary objective of the unit is to maximise middle dis-
tillate yield. In 2021, the refinery considered co-processing
bio-based vegetable oil feedstocks in the hydrocracking unit.

26 Catalysis 2023 www.digitalrefining.com

As a first preparation step, pilot plant tests were conducted
in the refinery’s research facility using Topsoe catalysts
installed in the industrial unit. Pilot plant results were anal-
ysed and interpreted in comparison with estimates made by
Topsoe. The refinery then decided to conduct a test run in
the hydrocracking unit using 5 vol% refined palm oil feed-
stock co-processed during normal operation (see Figure 2).
At operating conditions of the hydrocracking unit, the
hydrotreating of triglycerides in vegetable oil are relatively
easy reactions and are expected to occur over the first NiMo
pretreat catalyst bed (see Figure 3).
The weighted average bed temperatures (WABT) for
pretreat and cracking beds show that catalytic severity
was lower during the co-processing run. This is in line with
expectations due to the following factors:
 Effect over pretreat catalysts: Vegetable oil replaces
VGO feed. Pretreat reactions on triglyceride are easier com-
pared to HDS, HDN, and HDA reactions on VGO molecules
that are more complex.
 Effect over hydrocracking catalysts: Pretreat effluent
during co-processing has a higher number of C16-C18 mol-
ecules from triglyceride side chains. These boil in the distil-
late fraction. Hence, the true conversion over hydrocracking
catalysts is lower during co-processing compared to the
fossil run to achieve a similar UCO yield/gross conversion
(see Figure 4).
PTR WABT HC WABT
Fossil run Base Base
Co-processing run Base – 1°C ↓ Base – 1°C
Yield structure
Mass balance during both fossil and co-processing runs
closed well within the accepted tolerance for commercial
hydrocracking units (see Figure 5). Hence, the yield struc-
ture could be evaluated in more detail with a good degree
of confidence.
The following are salient points from the fossil and co-
processing runs:
 Hydrogen consumption: Co-processing vegetable oil
consumes additional hydrogen as expected and explained in
the previously discussed feedstocks and chemistry section.
 Diesel yield: Diesel yield is higher during the co-pro-
cessing run. This is an indication that C16 and C18 molecules
expected from the triglyceride side chain in the feed are
retained in the diesel fraction. See further discussion on the
2 wt%
Co-processing run
Fossil run
True conversion Gross conversion
Figure 4 Even at lower catalytic severity during
co-processing test run, higher gross conversion was
recorded, further validating the two factors mentioned in
WABT discussion above
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HC Bed 1 HC Bed 2
PTR Bed 2
PTR Bed 3
PTR Bed 1
HC Bed 1
HC Bed 2
PTR Bed 3
PTR Bed 2
Fossil run Co-processing run
PTR Bed 1 5˚C
Figure 3 The recorded temperatures show that almost all
reactions related to triglycerides in the vegetable oil occur
in the first pretreat bed during the co-processing run.
Thereafter, the temperature profile in the catalyst beds is
almost identical for fossil and co-processing runs
composition of diesel stream in the following product prop-
erties discussion.
 Unconverted oil (UCO) yield/gross conversion:
Vegetable oil replaces VGO in feed during the co-pro-
cessing run. Molecules in vegetable oil are relatively easy
to treat at hydrocracking unit conditions. Hence, the feed
during the co-processing run is relatively easy to process
compared to 100% VGO feed. Even at directionally lower
catalytic severity, UCO yield is lower, i.e., gross conversion
is higher during the co-processing run
 Off-gas make: Higher off-gas flows are recorded dur-
ing the co-processing run. As explained in the feedstocks
and chemistry section, C3 is expected from the triglycer-
ide backbone, and C1 is expected from the methanation
reaction. These are also consistent with higher C1 and C3
recorded in the treat gas composition during the co-pro-
cessing run.
Product properties
Vegetable oil feed has predominantly C16 and C18 chain
length side chains. These are expected to fully saturate to
n-paraffins and boil in the middle distillate product fraction.
The following plots compare chromatograms of distillate
samples recorded during the test run. The peaks in the
chromatograms are representative of the concentration of
molecules boiling at the specified temperature.
Following are the theoretical boiling points of isomers of
varying chain lengths:
Fossil run Co-processing run
5 wt%FF
Naphtha Kero Diesel UCO
Figure 5 Mass flows recorded during the test run as a
percentage of fresh feed processed
Catalysis 2023 27
 1.4 Biogenic carbon Fossil carbon
Biogenic carbon, 2%

1.2

1
Fossil run, Co-processing
kero product run, kero product
0.8
wt%

0.6

Fossil carbon,
0.4 98%

0.2 Figure 7 Result from ASTM D6866 test for distinguishing

0 run
100 150 200 250
Temp, ˚C
Kero product - 100% fossil run Kero product - 5% co-processing run
Figure 6 Chromatogram of kerosene product sample
drawn during the test run
Chain length Boiling point, °C
nC14 254
nC15 271
nC16 287
nC17 303
iC18 303
nC18 317
nC19 330
Product samples were also analysed for biogenic carbon
content by ASTM D6866. This is done by distinguishing
carbon isotopes from biogenic sources (containing well-
characterised amounts of carbon-14 isotope) against car-
bon from fossil sources (containing carbon-12 isotope and
carbon isotopes in kerosene sample drawn during the test
300
no carbon-14 isotope). In this application, the amount of
biogenic carbon in the product fractions can be directly
correlated to the relative amount of product resulting from
vegetable oil during co-processing.
Results from the biogenic carbon analyses in the prod-
uct fractions are discussed in conjunction with the product
chromatograms in Figures 6, 8 and 10.
Kerosene product
Interpreting a simulated distillation curve as a probability plot
is shown in Figure 6, where the temperature on the x-axis
refers to the average boiling point of lumps of material boil-
ing in 1°C intervals, making identification of different quanti-
ties of specific components possible. We can, for example,
infer from this chromatogram that there was a higher con-
centration of nC15 (BP 271°C) in the kerosene product dur-
ing the co-processing test run compared to the fossil run.
The presence of carbon sourced from vegetable oil during
co-processing is further validated by biogenic carbon analy-
ses showing a 2% carbon-14 isotope (see Figure 7).

1.8 Diesel product

Two of the most well-defined peaks can be seen in the
1.6
diesel chromatogram in Figure 8, corresponding to nC16
1.4 (BP 287°C) and nC18 (BP 317°C). The other two smaller
peaks correspond to nC15 (BP 271°C) and nC17 / iC18
1.2 (BP 303°C).
1
Biogenic carbon, 9%
wt%

Biogenic carbon Fossil carbon

0.8

0.6

0.4
Fossil run, Co-processing
diesel product run, diesel product
0.2

0
100 200 300 400
Temp, ˚C
Diesel product - 100% fossil run Diesel product - 5% co-processing run Fossil carbon,
91%

Figure 8 Chromatogram of diesel product sample drawn Figure 9 Result from ASTM D6866 for distinguishing
during the test run carbon isotopes in diesel sample drawn during the test run

28 Catalysis 2023 www.digitalrefining.com

 1.2
0.8
wt%
0.6
0.4
0.2
0
250 300 350 400 450 500 550
Temp, ˚C
UCO product - 100% fossil run UCO product - 5% co-processing run
Figure 10 Chromatogram of unconverted oil sample drawn
during the test run
Biogenic carbon analyses of diesel from fossil and co-
processing runs validated significant retention of vegetable
oil feed in diesel product fraction, as shown in Figure 9.
Unconverted oil
Unconverted oil product during both fossil and co-process-
ing runs appears to have similar boiling range distribution.
This is also validated by biogenic carbon analyses that show
no presence of carbon-14 isotope during co-processing
(see Figure 10).
The most significant UCO properties recorded during the
test run bear testimony to the lower true conversion over
the hydrocracking catalyst during co-processing. Typically,
it is seen that the UCO density and viscosity reduce with
increasing conversion severity (see Figure 11). The higher
density and higher viscosity of UCO during the co-process-
ing run are an indicator of lower conversion severity on the
VGO part during this operation.
Test Method Fossil run Co-processing run
SG 60/60°F D4052 0.870 0.872
Viscosity at
100°C, cSt D7042 5.903 6.247
Conclusions
Processing renewable feedstocks in existing refinery assets
is a strategy being used by many refiners globally to reduce
CO2 emissions originating from fossil-based feedstocks. In
addition to the local availability of renewable feedstocks,
another critical consideration has been to evaluate which
unit in an existing refinery is best suited for co-processing
biogenic feeds together with fossil-based feedstock.
Hydrotreaters are widely used, but hydrocracking units,
being one of the most versatile units in the refinery, are ide-
ally suited to co-process renewable feedstocks. They can
better overcome the operational challenges related to H2
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Biogenic carbon Fossil carbon
Co-processing
Fossil run,
UCO product run, UCO product
Figure 11 Result from ASTM D6866 for distinguishing
carbon isotopes in unconverted oil sample drawn during
the test run
600
consumption, temperature rises, and contaminants, as well
as separate the renewable products into different product
streams.
Hydrocracking catalyst options also provide the func-
tionality needed to make products with desired properties,
such as good cold flow properties or high degree of satu-
ration, as demonstrated with the recent industrial test run
co-processing 5 vol% vegetable oil in a hydrocracking unit
using Topsoe catalysts. The bulk catalysts already loaded in
the reactors were found adequate for co-processing mod-
erate quantities of renewable feedstock.
Most exothermic hydrotreating and hydrodeoxygen-
ation reactions occur in the first/grading bed. There was a
slight increase in exotherm in this bed, but this could eas-
ily be handled by reducing the reactor inlet temperature.
Thorough product analyses showed that the kero/jet prod-
uct stream had 2% biogenic carbon, and the diesel stream
had 9% biogenic carbon during the co-processing test run.
Most of these carbon molecules are n-paraffins, as noted
by chromatogram peaks.
Activity requirement during co-processing was lower
compared to normal operation, as noted by lower pretreat
WABT, as well as higher gross conversion during co-pro-
cessing, indicating feed during co-processing is easier to
treat compared to typical fossil-based VGO feed in this unit.
This test run has helped establish base-line performance
for processing biogenic feedstocks in commercial applica-
tions and validated estimates made by Topsoe based on
fundamental research. The hydrocracking unit will remain a
critical component of the renewable transition.
Peter Nymann is Senior Solution Specialist at Topsoe, involved in
technical service for hydrocrackers, hydrotreaters, and renewable units
worldwide. He graduated as a chemical engineer from Technical Uni-
versity of Denmark. Email: pan@topsoe.com
Pronit Lahiri is Principal Technical Service Engineer, Clean Fuels, at
Topsoe in Denmark, involved in technical sales and service, as well as
R&D for making estimates of catalyst performance and planning pilot
plant tests. He holds a BTech in chemical engineering from National
Institute of Technology in Jaipur, India. Email: prla@topsoe.com
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