Gasification applications in existing

industrial and agricultural

infrastructures for production of
sustainable value-added products
Case Study 4: Gasification of RDF and integration into an
existing naphtha cracker

IEA Bioenergy: Task 33

December 2021
 Gasification applications in existing industrial and
agricultural infrastructures for production of sustainable
value-added products

Case study 4: Gasification of RDF and integration into an existing naphtha

cracker

Authors: Berend Vreugdenhil, Leonie Lucking

TNO

IEA Bioenergy: Task 33

December 2021

Copyright © 2021 IEA Bioenergy. All rights Reserved

Published by IEA Bioenergy

The IEA Bioenergy Technology Collaboration Programme (TCP) is organised under the auspices of the International Energy Agency (IEA) but is functionally and legally autonomous.
Views, findings and publications of the IEA Bioenergy TCP do not necessarily represent the views or policies of the IEA Secretariat or its individual member countries
Abstract
This report discusses the feasibility of using gasification technology to provide circular and
biobased feedstock to an existing naphtha cracker of a petrochemical plant. This approach is
different to a widely investigated approach of producing liquids to replace naphtha. This liquid
can be produced from biomass or from pure plastic waste streams, and after hydrotreating will
similar properties as naphtha. Gasification allows the usage of more complex mixed streams
(RDF), that produce a similar gas phase composition of olefins and aromatics, when compared
to the outlet of a naphtha steam cracking unit.
Operating on a complex mixture of biomass and plastics (RDF), means that a surplus of oxygen
is introduced to the recovery section after the naphtha cracker. This oxygen will end up in the
gas as CO and CO2 and for a naphtha cracker these components are generally not desired. Some
crackers can operate with CO, but in all cases the bulk of the CO2 needs to be removed. For
this to work we have integrated the gasifier with a CO2 removal technology that converts also
CO at the same time, reducing both the level of CO and CO2. The desk study is not meant to
provide the final solution but what it does show is that the feedstock base for naphtha crackers
can grow much more and also a big share of biogenic components can be introduced to the
product slate. Recycling of plastic is always suffering from losses, which means that fossil fuels
remain necessary, unless biogenic replacements can be found.
The vision of this route is that it will be supplemental to pyrolysis based routes, and that via
gasification of RDF the much needed addition of “lost carbon” is covered. This case study is not
meant to provide off the shelve designs for integration of gasification technology into naphtha
cracker settings. The aim of this case study is to show the potential and create awareness of
other strategies to create circular and biobased products in traditional refineries.

2
List of contents
Abstract ......................................................................................................... 2
Traditional naphtha cracking processes ................................................................. 4
Gasification processes ...................................................................................... 5

SEWGS technology ............................................................................................. 7

Comparing product slates .................................................................................. 8
Intergrating gasification into naphtha crackers ...................................................... 10
Case study Boundary settings ........................................................................... 11
Mass and energy balance ................................................................................. 11
Conclusion .................................................................................................. 14

Appendices .................................................................................................... 15

Appendix A Gas composition of gas going to the downstream processing of a naphtha cracker
.................................................................................................................. 15

Index of Tables ............................................................................................... 16

Index of Figures .............................................................................................. 16

Publication bibliography .................................................................................... 17

3
TRADITIONAL NAPHTHA CRACKING PROCESSES
There are various routes to produce the building blocks of plastics. Ethane crackers and naphtha
crackers are the most common technologies used. A naphtha cracker produces olefins and
aromatics, mostly ethylene, propylene and benzene. This is one of the reasons that our plastics
today are made from these building blocks. A traditional naphtha cracking process is a fully
integrated design where mass and energy balances are tuned rather precisely in order to
maximize product yield. Spallina et al. [1] wrote a paper on assessing different routes and in
his publication a nice representation is given for a naphtha cracker including the downstream
processing train. Impurities in the feedstock can have detrimental effects on the plant, therefor
there are rather strict requirements to the quality of naphtha, which are translated also to
naphtha replacements like pyrolysis oils.

Figure 1: Schematic lay-out of a naphtha cracker, including downstream processing stepsi

From this graph it becomes clear that most of the cleaning and downstream processing is done
to produce ethylene, propylene and Pygas (BTX) and the off gasses tend to be used as fuel gas
in the naphtha cracker. For this case study combination of a gasifier on RDF connected to the
outlet of the naphtha cracker will be investigated combined to SEWGS technology for removal
of CO and CO2.

4
GASIFICATION PROCESSES
The naphtha cracking process is a thermally driven process, where liquid naphtha is evaporated
and ran through series of tubes inside a furnace (see Figure 1). The tubes are heated via
external combustion of gas. This fuel gas is the off-gas of the naphtha process as can be seen
in Figure 1. In an oversimplified approach this would be called in indirectly heated gasification
process, where feedstock is externally heated to produce gas components. The term
gasification can have different meanings, but for sake of this case study the following definition
is used.

Gasification: The thermal conversion of a solid/liquid feedstock into a gas under mild
conditions.

The most common view of gasification is to produce synthesis gas. The production of CO and
H2 via gasification at high temperature, which in part is due to the fact that coal gasification
tends to go in that direction. However, gasification can also lead to producer gas. This is
produced in gasifiers that operate at lower temperature (mild condition) and a producer gas
consists of much more than CO and H2, with methane, ethylene etc in there as well. In fact
when evaluating the conditions used for naphtha cracking and RDF gasification, one will see
that these two process have many similarities.

The starting point for the RDF gasification in this case study is the indirect gasification
technology MILENA [2]. This technology is developed in the early 2000’s and was eventually put
into a joint venture with Synova. The technology operates under mild conditions, leaving many
of the gas phase constituents intact. In Figure 2 the schematic lay out of the gasifier is depicted.
The feedstock is fed to a vertical riser tube, which can operate between 600 – 850C. The bottom
of this riser can be fluidized using steam (or nitrogen, air or other gases) to enable the inflow
of hot bed material from the combustion zone. This hot material will convert the feedstock
into gas and from the feedstock sufficient gas volume is produced to transport solids and char
upwards in the riser. Exiting the riser tube creates a reduction in velocity, which will force the
solids to separate from the gas flow and the bed material and char will fall down and flow into
the combustion zone. This cyclic procedure allows for good temperature control and complete
conversion of feedstock. The internal design is such that no solid circulation needs to be forced
with for instance j-valves/l-valves, which are known to present complications during operation.

5
Figure 2: Schematic lay-out of the MILENA indirectly heated gasification reactor

Biomass gasification typically is performed at 750 – 850 C, but with plastics content the
temperature can or needs to be lowered. Lowering the temperature will limit the cracking of
biomass and would result in a few percent more char. However, for plastics the lower
temperature will limit the cracking (less methane and hydrogen) but still maintain a high
conversion to gas phase components (ethylene and benzene). The following graph is developed
to identify what is happening with plastic waste streams in the MILENA gasifier. In Figure 3 the
heating of plastics is shown on the x-axis, with chain length on the y-axis. The idea is that
plastics will go through a melting phase into what is known as the pyrolysis phase. In this
temperature window the main outlet is unsaturated long chained molecules (liquids), which
after upgrading can be used to replace naphtha. The end of the curve represents the high
temperature gasification and eventually combustion, where the feedstock is broken down into
the smallest of molecules. Syngas for the high temperature gasification approach and flue gas
(CO2 and H2O) for the combustion. The mild conditions, here referred to as low temperature
gasification (in fact cracking conditions) result in olefins and aromatics, which represents the
naphtha cracker output.

Low temperature gasification conditions can be considered as thermal cracking and produces
a very different gas compared to high temperature gasification. A gas containing the molecular
capital of the feedstock, such as ethylene, propylene and benzene.

6
Figure 3: Thermal cracking of plastic waste stream, graphical representation.

In the MILENA gasifier, RDF can be converted at mild conditions, allowing the olefins and
aromatics to remain intact. It also produces these molecules from the biomass in the feedstock
whilst maintaining a complete conversion of feedstock. This set of unique features makes it an
ideal technology to be used in waste management that allows biobased and circular products
to be produced and recovered.

SEWGS technology
The SEWGS technology (Sorption Enhanced Water-Gas-Shift) is a solid sorbent based separation
technology for the capture of CO2 from process gas. The system improves the capture by
converting CO of the process stream to H2 and CO2, which is then captured as well. The
technology has been proven on large scale for the application of steel production off gases (EU
2020 project STEPWISE [3]).

The system is a pressure swing adsorption unit consisting of several columns filled with sorbent.
The process gas is fed to a column where the CO2 is adsorbed shifting the equilibrium of the
WGS to produce H2 and CO2. The stream exiting the column is CO2 lean with a higher H2 content.
After the adsorption pure steam is added to remove as much gas from the void fraction of the
column during depressurization. To improve the purity of the products and the energy recovery,
the first part of the depressurization are pressure equalization steps. The product from the last
depressurization step, to reach the purge pressure, is part of the final CO2 product. Once the
purge pressure level is reached, low pressure steam is fed into the column to desorb CO2 and
regenerate the sorbent. To get back to adsorption pressure level, the column receives the
outlet from the pressure equalization steps followed by a repress with the CO2-lean product.
The steps are shown in Error! Reference source not found. with counter-current blowdown
and purge. To allow for continuous feed of process gas and pressure equalizations several
columns are needed.

7
Figure 4: SEWGS cycle with 3 pressure equalisation steps [4]

A model has been developed and verified within TNO [4-6] which models a continuous operation
of a cyclic PSA system for the SEWGS unit. This model is used to determine operation condition,
cycle design and column sizing.

For the application of SEWGS in this project, a first study was conducted under the assumption,
that the higher carbon molecules are inert to the sorbent and do not compromise its’
characteristics. There has been testing performed on the sorbent with higher molecules which
showed no changed behavior (internal communication). Furthermore COS is assumed to convert
to H2S and CO2 in the system.

COMPARING PRODUCT SLATES

An important reason for this case study is the extensive R&D undertaken by TNO in the past on
a broad range of feedstocks. With changing feedstock, the gas composition was also changing,
some unexpectedly into direction of olefins or aromatics. The excursion into the RDF and plastic
waste streams further supported the ideas that the technology of indirect gasification could
also be used in the production of chemicals. The following graphs are to illustrate the unique
effect the MILENA gasifier has on product output with varying feedstocks.

The three bars (Figure 5) represent the range from biomass to plastic waste. RDF is the mix and
is the focus of this case study. As can be seen the product slate shifts from an oxygen rich (CO
and CO2) product gas to an olefins rich product gas. The plastic waste clearly is interesting from
a naphtha standpoint, since this is starting to resemble more and more the existing gas outlet.
The RDF is chosen, since it represents part biogenic content and part circular content, which
means that when obtaining the olefins and aromatics from this gas, it resembles both and it
means that the plastics produced from this gas is partly circular and partly biobased. Secondly,
in a fully circular world, losses are unavoidable and addition of a sustainable component is
needed. Via de the RDF gasification route, this can be done in an easy manner.

8
Figure 5: Gas composition for three different feedstock tests. Gas shifts from syngas rich to olefins and
aromatics rich. All feedstocks have been tested on a 1 MWth Indirect gasifier

In order to relate the gas composition obtained with RDF to gas from a naphtha cracker the
following approach is chosen. The gas is translated into energy yields, which mean that CO2
and N2 automatically fall out of the graph. Especially CO2 is relevant in a later stage with
respect to the integration in a naphtha cracker process. Gas compositions from a naphtha
cracker are mentioned in literature [1] and this was taken as input to make a graph representing
the energy yield in the gas. In Figure 6 these energy concentrations are given for the gasification
case and the naphtha cracking case. It is interesting to see when gasifying RDF the cracker off
gas will have more methane, carbon monoxide and hydrogen as fuel gas. The yields in ethylene,
benzene and toluene deviate from traditional gas, but the yield in propylene and butadiene are
significantly lower. The integration of the RDF is described in the next chapter which involves
tar removal (OLGA) and CO/CO2 removal (SEWGS), providing some more details to the steps
considered in this case study.

9
 40
Energy content of gas before separation (%)

35

30

25

20

15

10

RDF after SEWGS Naphtha gas

Figure 6: Energy content of gas produced by the conversion of RDF and removal of CO2 compared to the
gas produced by traditional naphtha crackers.

INTERGRATING GASIFICATION INTO NAPHTHA CRACKERS

In order to integrate the gasifier into the recovery section of a naphtha cracker, certain gas
cleaning is needed. The line-up considered in this case study is shown in Figure 7. The feedstock
RDF (1) is fed to the MILENA gasifier and converted into gas. The gas is cleaned using OLGA in
which tar components are removed and fed to the combustor of MILENA. The gas is subsequently
cooled to about 30 degrees, removing some of the impurities (HCl and NH3) after which the gas
is compressed to 12 bar. SEWGS technology is used to both convert CO as much as possible to
CO2 and H2 and at the same time capture the CO2. This will result in a stream (11) enriched
with H2, but still containing the olefins and aromatics from the gasification process. Second to
that there is a rather pure stream of CO2 (containing traces of H2S) produced from the
feedstock, which can be used for sequestration purposes and reduce the carbon footprint of
the installation significantly. The CO2 is also a possible source for utilization (CCUS). More
details on the numbers is given in the next chapter.

10
 4
190
1.2

-34.4 MW

3.0 MWel
-17.9 MW
7 8
880
1.3

400

400
12

12
775 500 92 30 30 399
1.3 1.3 1.2 1.2 12 11.7

11
MILENA

OLGA SEWGS
3
-11.4 MW

1.2
30
2

-1.9 MW

405
1.2
5.0 MW

400
12
1 6
9 10

Figure 7: RDF gasification line-up considered for integration with a traditional naphtha cracker

CASE STUDY BOUNDARY SETTINGS

This case study is meant to show the potential of integrating gasification in existing
petrochemical plants. The particular case study on mild conditions for the RDF gasification,
using the MILENA technology is based on a few assumptions.

1. Impurities relevant to naphtha cracker operators (oxygenates, NOx, etc) are not in the
product gas.
2. The final concentration of CO and CO2 is sufficiently low to be handled (either in the
existing system or by dilution) in the total naphtha cracker outlet gas flow.
3. SEWGS technology will not affect the olefins/aromatics content in the producer gas.
4. For the modelling work on SEWGS the hydrocarbons are considered inert.
5. No additional gas cleaning is included.
6. No dynamic simulation has been included to see how the addition of this particular gas
will affect the overall energy balance of the naphtha cracker operation / production
side of the naphtha cracker.

MASS AND ENERGY BALANCE

For the mass and energy balance the setup is shown in Figure 7. The flows in this system are
given in the following table. The mass balance has an error of 0.4%, which for this case study
is considered acceptable. The RDF input stream has a biogenic carbon content of 70% and 30%
is of plastic (fossil) origin. These numbers become very interesting when interpreting the mass
balance for this system.

Interpretation 1. Allocate all CO2 emissions from the process as biogenic first.
This feedstock contains 26588 kg/h of carbon, of which 7976 kg/h is of plastic origin (30%). In
the flue gas of MILENA is 8211 kg/h of carbon in the form of CO2 and from SEWGS we obtain
5482 kg/h of carbon in the form of CO2. This results in 13693 kg/h of carbon produced from the
system as CO2. Now we credit this to the biogenic content, which means that the remaining
product from the system contains 12895 kg/h of carbon in the gas to be recovered as products.
Which means that the products of this approach can be considered 61.8% circular and 38.2%
biobased. After correcting for 28% of the carbon present as CO and CH4, which will currently
be diverted to the naphtha furnace, the products obtained have 88% circular content and 12%

11
biogenic content. It is perhaps playing with numbers, but this shows that gasification can have
a major contribution to circular plastics, even with feedstocks that have a low plastic content.
Furthermore this route, since the CO2 is stored, contributes to net negative emissions.

Table 1: Carbon distribution by assuming all emissions to be of biogenic origin

Feedstock Flue gas CO2 Carbon Carbon in

RDF MILENA SEWGS in off gas product

Flow 74720 157998 45572 9525 10848 [kg/h]

C biogenic 18612 8211 5482 3870 1049 [kg/h]

C fossil 7976 0 0 0 7976 [kg/h]

8211 kg C/h in Flue

Gas MILENA
5482 kg C/h in
SEWGS
3870 kg C/h to
naphtha furnace
Feedstcok
RDF

70% 57%
38% 12%
30% 43% 62% 88%

Figure 8: Flow scheme on how the carbon distribution in the end product might end up, based upon a
simple accounting approach.

Interpretation 2. Allocate MILENA flue gas CO2 as biogenic carbon, the SEWGS CO2 as fossil
In this case the flue gas from MILENA is accredited to the biogenic content, but the CO2 in pure
form from SEWGS is considered to be of fossil origin, but can be used for sequestration. In that
case the products that can be recovered in the downstream processing of the naphtha cracker
are 80.7% biogenic in origin and 19.3% circular. Again after correction for the loss of CO and
CH4 in the product gas to the naphtha cracker furnace, the final product will contain 72%
biogenic content and 28% circular plastics. This route should be considered more or less climate
neutral and the product obtained in the downstream processing of the naphtha cracker has
more or less the same split in carbon as the original feedstock has.

The interesting part of this exercise is that the fact that the feedstock contains biomass, allows
the user of this process to maintain the claim that the end product is 100% circular, with over
10% or biogenic olefins/aromatics. If the feedstock had to be upgraded to very high quality
(high plastic content), then part of the emissions sources had to be allocated to plastic
molecules, reducing the overall circularity of the system. In thermochemical recycling of plastic
waste materials, there is always an energy penalty to pay. This approach shows that having
technology that can operate on both biomass and plastic waste streams, will have the highest
circularity numbers for the plastic waste, with less sorting needed.

12
The overall mass balance for the gasifier with gas cleaning is given in Table 2. For the final gas
composition of the flow number 11, the details are given in Appendix A.

Table 2: Mass flows for the proposed scheme depicted in Figure 7

Stream Type T [°C] P [bar] Flow [kg/h] Flow [Nm3/h]

1 RDF 20 1.3 74720

2 Steam-1 150 1.3 100 124

3 Air 174 1.3 143980 111774

4 Flue Gas 190 1.2 157998 113568

5 Bottom ash 700 2803

6 Scrubber water 30 24056

7 Steam-2 400 12 12869 15958

8 Rinse 400 12 5195 6549

9 Purge 400 1.4 12987 16371

10 CO2 gas 405 1.2 45572 42518

11 Cracker feed 399 11.7 20374 28017

Considering the mass balance the 300 MWth input MILENA gasifier operating on 1800 tpd of RDF
material can generate 260 tpd of hydrocarbons (C2  C7) with ethylene (142 tpd), benzene (55
tpd), propylene (55 tpd) and toluene (11 tpd) as the largest contributors.

13
CONCLUSION
Operating existing naphtha crackers on alternative fuels is typically looking at replacing
naphtha with a biogenic or circular alternative. A second solution is not looking at the naphtha,
but at the gas which is produced from naphtha cracking and upgraded in the downstream
section. This case study has shown that there is a large overlap in the gas obtained from RDF
gasification using the MILENA technology and that substantial amounts of olefins and aromatics
can be produced via this route.

The case study showed that to maintain 100% recycling efficiency for the plastics, a certain
amount of biogenic residue is in fact crucial. This has a profound effect on recycling strategies,
where to date a lot of effort is put into separation of all the different plastics and biogenic
waste, with a rather low resulting recycling efficiency. Having technology that can operate on
the more complex mixtures will simplify the sorting strategy.

Policy measures will have a major impact on how these process can or need to develop. If the
focus is to generate as much circular materials from waste, the gasification route needs to be
supported with CO2 mechanisms favoring the sequestration of biogenic carbon. This will in itself
also reduce the need of mechanical recycling, since residual paper/wood in the RDF is not an
issue but a very attractive outcome. Secondly, the reduction in mechanical recycling steps,
with all associated losses, also opens up a much larger potential of feed streams for the
gasification process.

14
Appendices
Appendix A Gas composition of gas going to the downstream
processing of a naphtha cracker
Syngas after SEWGS (11)

CO [mol%] 1.2%

H2 [mol%] 42.2%

CO2 [mol%] 0.6%

O2 [mol%] 0.0%

CH4 [mol%] 22.3%

N2 [mol%] 1.9%

Ar [mol%] 0.0%

C2H2 [mol%] 0.2%

C2H4 [mol%] 15.8%

C2H6 [mol%] 1.8%

C3H6 [mol%] 1.8%

C4Hy [mol%] 0.4%

C5Hy [mol%] 0.0%

C6H6 [mol%] 2.2%

C7H8 [mol%] 0.4%

H2S [ppm] 1.3

COS [ppm] 0.0

15
Index of Tables
Table 1: Carbon distribution by assuming all emissions to be of biogenic origin................. 12
Table 2: Mass flows for the proposed scheme depicted in Figure 7 ................................ 13

Index of Figures
Figure 1: Schematic lay-out of a naphtha cracker, including downstream processing stepsi ....4
Figure 2: Schematic lay-out of the MILENA indirectly heated gasification reactor ................6
Figure 3: Thermal cracking of plastic waste stream, graphical representation. ...................7
Figure 4: SEWGS cycle with 3 pressure equalisation steps [4] ......................................... 8
Figure 5: Gas composition for three different feedstock tests. Gas shifts from syngas rich to
olefins and aromatics rich. All feedstocks have been tested on a 1 MWth Indirect gasifier .....9
Figure 6: Energy content of gas produced by the conversion of RDF and removal of CO2 compared
to the gas produced by traditional naphtha crackers. ................................................ 10
Figure 7: RDF gasification line-up considered for integration with a traditional naphtha cracker
.................................................................................................................. 11
Figure 8: Flow scheme on how the carbon distribution in the end product might end up, based
upon a simple accounting approach. ..................................................................... 12

16
Publication bibliography
1. Spallina, V., et al., Techno-economic assessment of different routes for olefins production through
the oxidative coupling of methane (OCM): Advances in benchmark technologies, Energy Conversion
and Management, 2017. 154: p.244-261.

2. Meijden, C.M., Development of the MILENA gasification technology for the production of Bio-SNG,
Thesis Technische Universiteit Eindhoven 2010.

3. Van Dijk, H.A.J., et al., Stepwise project: Sorption-enhanced water-gas shift technology to reduce
carbon footprint in the iron and steel industry. Johnson Matthey Technology Review, 2018. 62(4):
p. 395-402.

4. Boon, J., et al., High-temperature pressure swing adsorption cycle design for sorption-enhanced
water–gas shift. Chemical Engineering Science, 2015. 122: p. 219-231.

5. Boon, J., et al., Isotherm model for high-temperature, high-pressure adsorption of CO2 and H2O
on K-promoted hydrotalcite. Chemical Engineering Journal, 2014. 248: p. 406-414.

6. Reijers, R., et al., SEWGS process cycle optimization. Energy Procedia, 2011. 4: p. 1155-1161.