Spyro modelling

and steam cracking furnaces optimization

Fábio António Dias Santos

Thesis to obtain the Master of Science Degree in

Chemical Engineering

Supervisors: Professor Doctor Henrique Aníbal Santos de Matos

Engineer André Alexandre Bravo Ferreira Vilelas

Examination Committee

Chairperson: Professor Doctor Francisco Manuel da Silva Lemos

Supervisor: Professor Doctor Henrique Aníbal Santos de Matos
Members of the Committee: Engineer Jorge Miguel Campos Fernandes

November 2017
1
 You can get what you want
Just practice persistence
You’re the only person in control of your existence
So make every minute count
When in doubt
When they say you won’t amount
Shut them out
Show them what you’re all about
Live your life
Fall in love
Forget about your sorrow ‘cuz
Everything you have right now could be all gone tomorrow ‘cuz

- Snak the Ripper - Forgotten

2
3
 Acknowledgments
First of all, my sincere thanks to Professor Henrique Matos, for authorising me to do my
master thesis at Repsol Polímeros, Monte Feio. It was seven months, truly worth experience for
both my professional and personal life.

Also like to thanks Olefins Director Engineer André Vilelas and Steam Cracking Plant
Manager Jorge Fernandes for all the help to get me through this journey being by my side all the
time.

To all the olefins operation and process teams, who passed good moments with me, my
deepest thanks and I’m sure that I left good friends there. No matter the obstacles, they helped
me to rise my head and keep going. The kind of people I’ll love to work side by side further in my
career.

Finalmente, um enorme obrigado aos meus pais por todo o apoio que me deram ao longo
destes 6 anos da minha vida.

4
5
 Resumo

A produção de etileno e propileno a nível mundial, é maioritariamente realizada através

do processo de steam cracking. No corrente trabalho, modelaram-se fornalhas no software Spyro
Suite 7 de modo a afiná-lo de acordo com a realidade. Inicialmente, as matérias-primas
suscetíveis ao cracking térmico foram termodinâmicamente analisadas de modo a impor as
propriedades corretas no modelo. Relativamente as propriedades da nafta, a qual entra líquida
nas serpentinas, ocorre um erro de importação do ficheiro contendo as mesmas para o Spyro
que só poderá ser resolvido com o auxílio da empresa proprietária do software, a Technip. Para
as restantes matérias-primas que entram nas serpentinas no estado gasoso, as propriedades
contidas no modelo são adequadas. Após a convergência do modelo e o seu ‘‘tuning’’ de modo
a calcular os outside HTC factors reais, um indicador de performance (KPI) incluindo os desvios
entre o COT e os caudais de BFW e fuel gás obtidos pelo software e a realidade foi considerado.
Esse indicador provou que o modelo com os outside HTC factors diferentes de um é o mais
adequado à realidade uma vez que mostra os menores desvios. A possível renovação dos
‘’bancos’’ da convecção, que são autênticos permutadores de calor, levou a conclusões positivas
acerca de um balanço entre vapor de alta pressão (HPI) produzido e fuel gás consumido. Houve
um maior impacto no primeiro ‘’banco’’ da convecção designado por High Temperature
Convection (HTC) contendo este, o menor parâmetro dos outside HTC factors. Isso foi provado
também por uma análise económica simplificada. Com a designação de ‘’vapor de proteção’’, é
adicionado à fornalha com o intuito de proteger as serpentinas em caso de alguma falha
operacional e minimizar a formação de coque no HTC devido a cracking prematuro. Após uma
análise de sensibilidade relativa ao caudal desta alimentação, chegou-se a conclusão de que
este valor deve ser o máximo até ao máximo permitido pelas especificações impostas para as
serpentinas, mantendo a razão de vapor/hidrocarbonetos. Além destes estudos, muitos mais
poderão ser realizados agora que a Repsol tem em sua posse as fornalhas modeladas no
software Spyro Suite 7.

Palavras chave: Steam cracking, Spyro Suite 7, Propriedades termodinâmicas,

Outside HTC factors, vapor de proteção, KPI.

6
7
 Abstract

The ethylene and propylene production worldwide is mostly accomplished through the
steam cracking process. In the current work, furnaces have been modelled in Spyro Suite 7
software to perform the tuning to the reality conditions. Initially, the feedstocks susceptible to
thermal cracking were thermodynamically analysed in order to input the correct properties in the
model. Relatively to naphtha, which enters the coils in liquid state, an error in the file, containing
the right properties, import occurs and to perform Spyro simulations that problem must be fixed
by the company propriety, Technip. For the remaining feedstocks entering the coils in gaseous
state, the properties contained in the model are suitable. After the convergence of the model and
its tuning to calculate the real outside HTC factors, a performance indicator (KPI) including the
deviations between the COT and the BFW and fuel gas flow rates obtained by the software and
the reality was considered. This indicator proved that the deviations obtained by the reality model
were smaller than the normal convergence with the outside HTC factors equal to one. The
possibility of revamping the convection section banks, which are authentic heat exchangers, led
to a positive conclusion in the balance between high pressure steam (HPI) produced and fuel gas
consumed. There was a greater impact on the first bundle of the convection section (HTC) having
the lowest outside HTC factor. This was also proved by a simplified economic analysis. With the
designation of ‘’protection steam’’, is added to the furnace in order to protect the coils in case of
some operational failures and minimize coke formation at HTC bundle due to premature cracking.
After a sensitive analysis concerning the flow rate of this feedstock, it was concluded that this
value should be the highest allowed by the coils design specifications, maintaining the
steam/hydrocarbon ratio. In addition to these studies, many more can be realized now that Repsol
has their furnaces modelled in the software Spyro Suite 7.

Key words: Steam cracking, Spyro Suite 7, Thermodynamic properties, Outside HTC
factors, Protection steam, KPI.

8
9
Contents

Chapter 1 Introduction .............................................................................................. 18

1.1 Motivation ........................................................................................................... 18
1.2 Scope .................................................................................................................. 18
1.3 State of the art .................................................................................................... 19
1.4 Outline ................................................................................................................. 20

Chapter 2 Steam Cracking ........................................................................................ 21

2.1 Principles of Steam Cracking ........................................................................... 21
2.2 Process Description .......................................................................................... 24

Chapter 3 Spyro .......................................................................................................... 27

3.1 Framework of Spyro at Repsol ......................................................................... 28
3.2 Feedstocks ......................................................................................................... 29
3.2.1 Propane/Ethane............................................................................................. 29
3.2.2 Naphtha/Butane............................................................................................. 30
3.2.3 Boiler Feed Water.......................................................................................... 32
3.2.4 Dilution Steam ............................................................................................... 33
3.2.5 Fuel Gas ........................................................................................................ 34
3.2.6 Air .................................................................................................................. 35
3.3 Mixer .................................................................................................................... 35
3.4 Convection Section............................................................................................ 35
3.5 Steam Drum/Transfer line exchanger .............................................................. 37
3.6 Radiant Coil ........................................................................................................ 38
3.7 Radiant Box ........................................................................................................ 38
3.8 Product Exit ........................................................................................................ 39
3.9 How to obtain Spyro’s convergence ................................................................ 41

Chapter 4 Model Tuning ............................................................................................. 45

4.1 Outside HTC Factors Determination ................................................................ 46
4.2 Revamp Case-Study .......................................................................................... 50
4.3 Protection Steam................................................................................................ 53

Chapter 5 Conclusions............................................................................................... 55
5.1 Future Work ........................................................................................................ 56

References ................................................................................................................... 58

Appendix I .................................................................................................................... 60

Appendix II ................................................................................................................... 64

Appendix III .................................................................................................................. 66

10
Appendix IV .................................................................................................................. 69

Appendix V ................................................................................................................... 72

11
 List of Figures
Figure 1 - Steam ratio expressed in kilograms of steam per kilograms of hydrocarbon [12]. .... 22

Figure 2 - N-heptane cracking reaction steps (addapted by [16]). ............................................. 22

Figure 3 - Steam cracking process diagram ............................................................................... 24

Figure 4 - Cracking furnace scheme .......................................................................................... 25

Figure 5 - Furnace scheme at Repsol's site ............................................................................... 28

Figure 6 - Propane's feed characterization in Spyro .................................................................. 29

Figure 7 – Naphtha's feed characterization in Spyro .................................................................. 30

Figure 8 - Naphtha properties written in a txt file ........................................................................ 31

Figure 9 - Boiler feed water characterization in Spyro ............................................................... 32

Figure 10 - Mixer's representation in Spyro ................................................................................ 33

Figure 11 - Fuel's characterization in Spyro ............................................................................... 34

Figure 12 - Air's characterization in Spyro .................................................................................. 35

Figure 13 - ECO convection bank layout tab specification ......................................................... 36

Figure 14 - Steam drum model browser ..................................................................................... 37

Figure 15 - Flowsheet connection between TLX and steam drum ............................................. 37

Figure 16 - Cracking coils flowsheet .......................................................................................... 38

Figure 17 - Firebox radiant wall burner's specification ............................................................... 39

Figure 18 - Product exit specification tab ................................................................................... 40

Figure 19 - Full furnace flowsheet simulation ............................................................................. 41

Figure 20 - Spyro convergence advised fixed list ....................................................................... 42

Figure 21 - Cut fins and full fins (Repsol's case) ........................................................................ 46

Figure 22 - Outside HTC factors calculated by Spyro ................................................................ 47

Figure 23 - Tuning scheme for real outside HTC factors calculation ......................................... 48

Figure 24 - Revamp scheme by changing the outside HTC factors one by one to 1. ................ 50

12
13
 List of Tables

Table 1 - Steam cracking products [12]. ..................................................................................... 21

Table 2 - Enthalpy of formation of naphtha in gas and liquid phase .......................................... 31

Table 3 – Deviation from the ideal convergence of Spyro from real operating values. .............. 43

Table 4 - KPI indicator for normal convergence of the model. ................................................... 44

Table 5 - Outside HTC factors calculated by Spyro for furnace F1003. ..................................... 48

Table 6 - Real outside HTC factors for furnaces F1003 and F1006 ........................................... 49

Table 7 - Difference between the KPI's from the real and the ideal simulations. ....................... 49

Table 8 - % of deviation from the real case parameters of revamping cases ............................ 51

Table 9 - Earnings and expends from the revamp cases relative to the real case. .................... 52

Table 10 - Impact on adding or reducing the flow rate of ''protection steam''. ............................ 53

Table 11 - Earnings and expends of adding or reducing 1 metric tonne of ''protection steam''
relative to the real case. ...................................................................................................... 54

14
15
Nomenclature

COT – Coil outlet temperature

HTC – Heat transfer coefficient

TLX/TLE – Transfer line exchanger

ECO – Economizer (bundle)

HTC (bundle) – High Temperature Convection (bundle)

FPH/LTC – Feed Pre-Heater / Low Temperature Convection (bundle)

DSSH – Dilution Steam Super Heater (bundle)

HPSSH I and II – High Pressure Steam Super Heater I and II (bundle)

HPI – High pressure steam

BFW – Boiler feed water

VGO’s – Vacuum gas oils

HVGO’s – Heavy vacuum gas oils

KTI – Kinetics Technology International

PINA – Paraffins, iso-paraffins, naphtenes, aromatics

TBP – True boiling point

ASTM – American Society for Testing and Materials

CSTR – Continuous stirred-tank reactor

PFR – Plug flow reactor

DSR – Distributed series reactor

SMD – Symbolic model definition

F1003 – Furnace 3 at Sines Cracker

F1006 – Furnace 6 at Sines Cracker

HL/HV – Enthalpy of liquid/vapor

DL/DV – Density of liquid/vapor

16
VISL/VISV – Viscosity of liquid/vapor

TCL/TCV- Thermal conductivity of liquid/vapor

CPL/CPV – Heat capacity of liquid/vapor

LIQ – Liquid

VAP – Vapor

P/E – Propylene/ethylene ratio

F – Flow rate

T – Temperature

KPI – Key performance indicator

17
Chapter 1

Introduction

1.1 Motivation

European petrochemical plants are now changing, depending on economics, for lighter
feedstocks in order to reduce ethylene production costs. The steam cracking furnaces are the
heart of a Steam Cracker and represent a biggest energy consumer in the plant as fuel
consumption as well the major part of waste heat recovery in the furnaces convection section.

The changing type of the feedstocks, operating conditions and the plant load need a
systematic approach by Operations Management to fulfil the maximum benefit of the unit and the
maximum energy efficiency at every day.

1.2 Scope

The plant management has a detailed study and analysis of the energetic and process
status of the cracking furnaces with ideas and hypothetical modifications/projects that can lead to
an increased performance of the installed assets based on what-if scenarios assessment.
Therefore, the work developed on this dissertation was mainly the use of the licensed software
Spyro that provides a dedicated tool to model and simulate the cracking furnaces behaviour.

The main task was to converge the real furnaces data with the Spyro simulations and
evaluate the impact of all the performed plant changes which are part of the business optimization
every day.

This training period is also an opportunity to feel the industrial environment of a running
plant as give the contribution, asking questions “outside the box”, to increase the performance of
the units.

18
1.3 State of the art

Spyro was created in the late sixties with the objective of predicting olefin yields from
hydrocarbon pyrolysis. This program was a marriage between a mathematical and kinetic model
by the Professor Mario Dente and Eliseo Ranzi [1]. Since then, Spyro has been tuned and
validated not only in kinetic scheme but also in a full steam cracking simulation and optimization
tool.

For many years, the complexity of the radical reactions and mathematical scheme were
studied with a view to find practical methods characterizing all possible reactions (more than 6600
nowadays).

The ‘’pseudo steady state’’ assumption, which says that the rate of formation of a radical
must equal its rate of disappearance, resolved the problem with the overcoming the ‘stiff’ material
balance equations problem [2]. Predictions given by Spyro model were consistent with observed
data as long as changes in feedstocks, temperatures, steam dilution, etc.

To know the initial distribution of pyrolysis products, a Rice theory based on the formation
of radicals that by chain mechanism results in olefins production was created [3]. Along limited
number of isomerization and decomposition kinetic parameters, it became possible to predict the
primary products from decomposition of saturated species. Improving prediction of heavier
feedstocks, such as VGOs and HVGOs, pyrolysis product distributions, simplifications were made
in order to reduce the number of reactions and related kinetic parameters and also the number of
species to be considered. It’s well known that the heavier the feedstock is, more difficulties are
present in the mechanistic modelling and for that, correct feedstock characterization is necessary.
To improve the program, Technip, before known as KTI (Kinetics Technology International),
added new ways to characterize heavy feedstocks based on PINA, density, TBP or ASTM boiling
points.

In a way to reduce the convergence time, Spyro was reduced in sub-models, integrating
the Open Spyro model. Sub-models for entrance, section, nodes and exit of the cracking coil and
between the transfer line exchanger and the one before were attach to the existing ones like feed
and mixer. Broyden proposed a quasi-Newton method to solve this model which gave reliable
results as the original model [4].

With the appearance of larger computers and thermochemical kinetic theory and
experimental data, a model with the same mechanistic kinetic scheme for feedstocks from ethane
thought gasoils, became usable to solve booth simulation and optimization cases. That model
was called Equation-based Spyro [5].

A new distributive reaction-mixing synthesis model, d-RMix, incorporating ideal CSTR,

PFR and DSR models was applied for thermal cracking of ethane. The maximum amount of

19
ethylene per unit mass of ethane was obtained for the plug flow mode in isothermal and isobaric
operations with maximum temperature and minimum pressure allowed [6]. At that point, a
flowsheet package was ready for industrial uses.

Demanding more flexibility to Spyro, a symbolic model definition (SMD) module was
integrated. A language similar to the gPROMS one was adapted to the program to supply
information during the solution procedure, making easier to find possible errors inside the model
[7].

In ethane cracking a maximum ethylene yield of about 67 wt% was revealed by an

optimization with a linear-concave temperature profile between 1200 and 1300K [8]. That shape
of temperature profile also revealed that successive reactions of product ethylene to larger side-
products were minimized. In temperatures above 1300k, dehydrogenation reactions and H-
abstraction of ethylene became more important [7].

1.4 Outline

Firstly, a review of the most important principles and the description of steam cracking
more focussed in Repsol’s process is shown in chapter 2.

Chapter 3 describes all the models in Spyro Suite 7 from the feedstocks to the product
exit. Feedstocks are analysed from a thermodynamically point of view in order to input in Spyro.
All the important parameters from each model were explained finishing with an advised fix list to
converge the full simulation.

In chapter 4, the real outside HTC factors are found with the objective to have real
furnaces simulated in the model. Further, with the real furnaces converged in the model, two
sensitive analysis are made along with an economic evaluation for each one. The first is a
revamping case study were the outside HTC factors are changed to 1, one by one, comparing
the fuel gas and HPI flow rates with the real operation case. The second one is the analysis of
the impacts by adding one metric tonne of ‘’protection steam’’ reducing it in the dilution steam
flow rate.

Finally, chapter 5 summarises the conclusions on this work, referring what was achieved
and discussing possible future works.

20
Chapter 2

Steam Cracking

Steam cracking was first patented in 1913 and the first facilities appeared in the United
States in the years near 1920 [11]. Since then, became the main process for the production of
ethylene and propylene and other valuable petrochemicals. This chapter will be more focused in
the principles which are crucial for the process and its description based on Repsol’s plant.

2.1 Principles of Steam Cracking

Also known as pyrolysis, this process involves a breaking carbon-carbon or carbon-

hydrogen bond within hydrocarbon molecules in the presence of steam and high temperatures.
Ethylene and propylene are most valuable unsaturated molecules originated by this process
along with other olefins and diolefins [12].

Cracking reactions require high input of heat energy and high temperatures since they
are highly endothermic. Inside these extreme conditions, we have cracking temperatures
rounding 800 to 850ºC, residence times of 0.1 to 0.5 seconds and low pressures, slightly higher
than atmospheric one [12]. These extreme conditions are justified by the stability of the
hydrocarbons like for example, at temperatures near 815ºC ethylene start to be more stable than
ethane [10]. In the top of the stability career are coke and hydrogen. To reduce the amount of
coke which is a product of secondary reactions, residence times must be very low increasing the
yield of primary products like ethylene and propylene represented in table 1. Those short
residence times with very rapid cooling or quenching of the cracked products favours the yields
of the desired hydrocarbons [12].

Table 1 - Steam cracking products [12].

Primary Reactions Secondary Reactions

Ethylene C4 products
Propylene C5 products
Feedstocks/
Acetylene C6 products
Steam
Hydrogen Aromatics
Methane C7 products
Heavier products (coke,
-
etc.)

21
 These hydrocarbons are mainly produced by the primary reactions that prevail over
secondary ones due to the conditions said before and the reduced hydrocarbon partial pressure
by steam present on the system. Secondary products result from reactions where the number of
the molecules decrease, so decreasing the pressure favours the formations of the desirable ones.
Steam also reduces the partial pressure of high molecule-mass aromatics, reducing the tendency
to deposit and form coke in the radiation coils [12]. The amount of steam added to the hydrocarbon
feed depends on the feedstock used and is usually expressed in a ratio. Typical values of the
ratios are represented in figure 1.

Figure 1 - Steam ratio expressed in kilograms of steam per kilograms of hydrocarbon [12].

The chemistry of steam cracking (figure 2) is extremely complex since it includes primary
and secondary cracking of C-C bonds leading to hydrocarbons with shorter chains,
dehydrogenation reactions yielding unsaturated species and addition reactions leading to
formation of aromatics and coke. To have a clear vision of the chemistry of the steam cracking
process the scheme below show the cracking net of n-heptane.

Figure 2 N-heptane cracking reaction steps (addapted by [16]).

22
 Summing up, to have maximum ethylene and propylene production, the feedstocks must
be highly saturated, the coil outlet temperatures must be high, steam is required in the system
and the residence times must be low.

Varying those conditions, yields obtained from different feedstocks will be different, which
is represented in the Appendix I [12].

A variety of different feedstocks can be used in the steam cracking process starting from
the lightest like ethane and propane, passing through butanes and naphthas and finishing in the
heavy ones like diesel fuels and distillates which the costs are lower than the light ones.

Ethane, being associated with natural gas and commonly used in American and Middle
East steam crackers, is the feedstock that gives higher yields of ethylene and lower of propylene,
C4 hydrocarbons and aromatic gasolines. Naphtha is the main feedstocks used in the Europe
steam crackers as they supply a large range of products like 25 to 30% of ethylene, 13 e 17% of
propylene and about 20% of gasoline. The heavier feedstocks produce more fuel oil and les
ethylene then the lighter ones. The amount of each product depends on the severity of the
process. The propylene to ethylene mass ratio is the most common measure of severity among
the coil outlet temperature and others. When low-severity cracking conditions are present, the
P/E ratio is higher than the one in the high-severity conditions.

23
2.2 Process Description

Steam crackers (figure 3) are industrial facilities that can vary since the state of
feedstocks to the product specification products required as the end of the chain. They are usually
divided in three main zones with different equipment and functions. Starting with the hot zone
including the cracking furnaces, the quench exchanger and the columns of the hot separation
train, passing through the compression zone including a cracked gas compressor, dryers,
purification and separation columns and finishing with the cold zone comprising the cold box,
methanator, separation columns, C2 and C3 converters and the gasoline hydrogenation [12].

Figure 3 - Steam cracking process diagram

Starting in the storage area where the feedstocks are available, they are then pumped
and preheated by heat recovery from effluents of the unit and finally fed separately in the coils of
the furnace. The hydrocarbons enter the convection section where they are pre-heated with
dilution steam by the heat released from the flue gas burned at the radiation section where the
cracking reactions occur (figure 4).

24
 Figure 4 - Cracking furnace scheme (Drum instead of Pocket)

In the coils outlet, the effluent gas passes by an indirect quenching in the transfer line
exchangers (TLX or TLE) where high pressure steam (HPI) is generated and by a direct
quenching by injection of quench oil. These two brutal quench from temperatures of 830/860ºC
to 380-470ºC at TLE outlet and 200ºC after quench oil injection immediately stops the chemical
reactions and avoid formation of coke in the coils [13].

The heavier fractions, mainly fuel oil, are then separated by the bottom of the primary
fractionator tower going out through the top, gasoline and lighter fractions. The fuel oil can be
stored or can be used as quench oil in the effluent direct quench, after being cooled in heat
exchangers where feedstocks are pre-heated and steam generated. From the top leaves the gas
effluent which, with water, fed a scrubber. In here the water and heaviest gasoline condense
coming out from the bottom of the column going the last one to the hydrogenation section. The
remaining water, after removed the hydrocarbons left, becomes process steam by passing
through heat exchangers [13].

At this point finishes the hot zone of the process and starts the compression zone.

After the first two separations, the effluent gas is compressed by a centrifugal compressor
that generally is composed by five stages. In the inter-stages, the gas is cooled, which, by the
increase in pressure, leads to condensation of water and hydrocarbons. The liquid condensates
are separated from the gaseous phase in drums situated between the stages of the compressor.
Heavier hydrocarbons, mainly gasoline, from the first, second and third stages goes to the

25
hydrogenation section. From the last two stages, the condensates after being cooled, feed the
– +
deethanizer to separate the C2 from C3 fraction going the last one to the depropanizer.

To generate the amount of energy necessary for the compression a steam turbine is
necessary. That energy is provided from the high pressure steam (HPI) produced in the transfer
line exchanges (TLX) situated at the furnaces as mentioned before [10].

The effluent gas have acid compounds in his composition like hydrogen sulphide (H2S)
and carbon dioxide (CO2) which are removed in a washing tower situated between the fourth and
fifth stage of the compressor. Normally is a caustic washing scrubber where that compounds are
eliminated in the form of sodium sulphide, soluble in a soda caustic solution, and sodium
carbonate respectively [13].

Before entering the deethanizer the gas effluent is cooled and dried in order to remove
water, avoiding the risk of hydrate formation and water icing [13]. Starting at this point the cold
-
zone, by the top of the deethanizer leaves the C2 fraction containing acetylene (C2H2) that is
further converted to ethylene in adiabatic reactors. Another drying step is done to insure no water
to the rest of the process.

-
Now hydrogenated, C2 fraction, needs to be cooled to separate methane (CH4) liquid and
hydrogen (H2). With help of Joule-Thompson effect and cold fluids like methane, hydrogen and
ethylene, hydrogen is removed by condensations of methane. The hydrogen stream, before going
to the hydrogenation reactors, needs to suffer a removal of carbon monoxide (CO).

-
Methane and C2 fraction, with no hydrogen left, are separated in the demethanizer. From
the bottom comes out a mixture rich in ethylene and ethane and from the top methane which can
be used as fuel gas in the furnaces. Ethylene and ethane are separated in the C2 splitter. As said
before, ethylene is used as cold utility. The refrigeration is possible due to the Joule-Tompson
effect and a centrifugal compressor. The same happens to propylene supporting higher
temperatures than ethylene [12].

+
The C3 fraction from the deethanizer is the feed to the depropanizer. Here, C3 fraction is
separated from C4 and C5 fractions. The lighter passes through a hydrogenation reactor to convert
components like propyne and propadiene to propylene. Propylene is finally separated from
propane in the C3 splitter.

Finally, C4 is separated from C5 fraction in the debutanizer and the last following to the
gasoline hydrogenation. This C4 fraction is rich in butadiene which is a valuable product like
ethylene and propylene. The valuable products can be storage or can be used directly in other
processes like for example, Repsol’s case which the high and low density polyethylene plant has
as main feedstock the ethylene produced in the same site.

26
Chapter 3

Spyro

Used by almost all steam crackers in the world, Spyro main use is to predict the yields of
the products in the conditions implemented by the user. Besides that, it can be used for global
simulation of furnace along with the steam drum and the transfer line exchanger representing the
cracking itself. It is the main tool for the tuning of the furnace as well as for the study of revamping
cases viability.

This chapter shows the required tools to represent a furnace in the Spyro model and to
normally converge it in order to get viable results inside Repsol’s environment.

Repsol has 8 furnaces operating in Sines. A typical scheme of the Repsol’s furnaces is
shown in the figure 5. All feedstocks before entering the coils in the convection section are mixed
with steam, named “protection steam”. This steam protects the coils from thermal shocks caused
for example when the feedstocks flow became unstable or when the furnace goes down. That
protection steam comes from the dilution steam which is mixed with the hydrocarbon feed before
the feed preheater (FPH) and the dilution steam super heater (DSSH) banks. After the mixture’s
made, it enters the last bundle of the convention section, high temperature coil (HTC), and the
goes to the radiation section. In the economizer (ECO) bank the boiler feed water is pre-heated
and fed to the steam drum, where one liquid and one vapour phase are present. That liquid water
flows from the steam drum to the TLX where high pressure steam is generated by the cooling of
the effluent to stop the chemical reactions. The HPI goes back to the steam drum being then
superheated in the high pressure steam super heater banks (HPSSH I and II). Between these
two banks there is an injection of boiler feed water to control the final temperature of the HPI
leaving the furnace.

The heat transferred from the flue gas going out of from the radiation section at high
temperatures allows the required temperatures for the process side fluids. That steam produced
is then fed to a turbine to generate work, moving the centrifugal gas compressor being the two
coupled.

27
 Figure 5 - Furnace scheme at Repsol's site

3.1 Framework of Spyro at Repsol

Spyro was parameterized at Repsol by Technip, using the data sheets provided by the
Repsol company. It was built using furnaces model with both radiant and convection sections.
The Spyro implemented at Sines plant was almost able to work using coils geometry and
convection bundles by the data sheets available. To complete the model, some more data is
required to be inserted in order to carry out optimization and run some scenarios of operation like
for example, the burners placement in the walls. The data is obtained from the industrial available
datasheets recorder in the plant control room.

28
3.2 Feedstocks

For the cracking process, the feedstocks used are naphtha, butane, propane and ethane. The
choice of which one will be used in the process is made with an evaluation based on the product
yields obtained and their price in the market.

3.2.1 Propane/Ethane

Feedstocks need to be well defined for the start of the process. Spyro Suite 7 check the
vapour fraction in the process conditions by the properties inside the model. For propane and
ethane, the property table selected must be the gas feedstock with the initial conditions, namely
the vapour fraction should be set equal to 1. Composition of the feed must be defined with the
components and their weight or volume fractions as well as flow rate and inlet temperature with
the help of real data (figure 6). Pressure values of feed sources are not fixed, this allows Spyro
to calculate them by fixing the coil outlet pressure of the effluent generated by the centrifugal
compressor after the furnace.

Figure 6 - Propane's feed characterization in Spyro

Besides ethane being the most used feedstock for ethylene production, it is a product of
other common feedstocks. In Europe, mainly, this compound is recycled and continuous fed to
the furnace after being separated from ethylene in the C2 splitter. Ethane is the main feedstock
in the north of USA and Middle East because they extract it from the currently shale gas at lower
temperatures.

29
3.2.2 Naphtha/Butane

When detailed composition is not available to user, other ways of defining the feed are
included in Spyro like for naphtha, gasoil and air. That characterization can be made with a PINA
analysis, the specific gravity and the boiling curve percentages (figure 7). PINA analysis is made
in mass or volume and it appears as normal paraffins, iso-paraffins, naphtenes and aromatics
fractions. The boiling curve can be TBP, ASTM-D86 or ASTM-D2887 type according with the test
made to that feed. ASTM-D86 is the more common one because it can be determined in a
laboratory. In case of naphtha feed, the initial boiling point must be at temperature below 130ºC
and 95% vaporized point below 180ºC. The temperatures from these two points with the one from
50% vaporized are required in the curve characterization. The 95% point avoid adding additional
components due to very long tails in the ASTM data meaning that if the last 5% of the feed boils
over a wide temperature range Spyro feedstock characterization will not be skewed in favour of
the heavier components [9].

Figure 7 – Naphtha's feed characterization in Spyro

In Repsol case, naphtha enters the convection section at liquid state where is preheated
and vaporized. For that reason to describe the feed, properties like fraction, enthalpy, viscosity,
thermal conductivity and specific heat of booth liquid and vapour phase need to be calculated.

With the help of Aspen Hysys V8.4 a stream analysis was made with the intuition to have
the table including all the properties described before. After the analysis, the results can be
exported to excel not forgetting that the values of enthalpies given by Hysys tool comprises the
enthalpy of formation of the mixture called naphtha in the case study. The enthalpy of formation

30
need to be calculated in a way of deducting from the enthalpy of each state given by Hysys (table
2) [14]. To calculate the enthalpy of formation to naphtha liquid and gas, a weighted average of
the majority compounds present his composition provided by Repsol’s laboratory (appendix II).

Table 2 - Enthalpy of formation of naphtha in gas and liquid phase

Compound Fraction ΔHf(l) (KJ/mol) ΔHf(l) Mixture (Kcal/Kg)

n-pentane 0.327 -173.5
n-hexane 0.205 -198.7
-533.7
cicloheptane 0.174 -156.4
2Mpentane 0.294 -204.3
Compound Fraction ΔHf(g) (KJ/mol) ΔHf(g) Mixture (Kcal/Kg)
n-pentane 0,327 -146.8
n-hexane 0.205 -167.1
-476.7
cicloheptane 0.174 -124.8
2Mpentane 0.294 -174.3

Finally, with the correct properties (appendix III), a txt file (figure 8) is made and saved as
ppf. extension readable by Spyro Suite 7.

Figure 8 - Naphtha properties written in a txt file

In this txt file, begin (LIQ 1 VAP 0) and end (LIQ 0 VAP 1) vaporization points need to be
well defined as in the figure 8. The heattype equal to 2 indicates the presence of mixed vapour
and liquid properties, the spectype equal to 0 indicates tabulated properties and for last the zero

31
after unit means a system with metric units. The initials represent each property and the last letter
indicates the phase like for example, VISL means viscosity for the liquid.

At last that file is imported to the simulation and naphtha uses that properties in the
bundles before the high temperate convection (HTC) one. In this last one naphtha is already all
vaporized so the property table used is the same as for propane and ethane.

In a continuous basis, naphtha is mixed with a C5 fraction coming from gasoline before
entering the furnace. This fraction can be mixed or can continue in the gasoline if the market
indicates it always respecting the reid vapour pressure specification. Therefore, if the price of
naphtha is higher than the gasoline, the recycling compensates like the opposite if the price is
lower. Remind that the gasoline as final product have to be within specifications. That flow rate is
small comparing to naphtha so it is not necessary to add new properties only for C5 fraction.

The same procedure of adding properties to the model happens with butane.

3.2.3 Boiler Feed Water

As mention before, boiler feed water (BFW) is fed to the furnace to recover the heat from
the flue gases and produce high pressure steam (HPI). To define this stream, water/steam with
the fraction equal to 1 needs to be added and the property table selected must be the VDI steam
table (figure 9). Here Spyro calculates the flow rate of BFW needed for the process or the amount
of HPI produced with the conditions imputed in the model. As the steam drum working pressure
is fixed, the one for the BFW is calculated.

Figure 9 - Boiler feed water characterization in Spyro

32
 This boiler feed water comes from the deaerator and enters in the eight furnaces where
is preheated in the first bundles of the convection section feeding then the steam drum. That
saturated water from the steam drum is vaporized in the transfer line exchangers and then
superheated in the bundles called high pressure steam super heaters I and II (HPSSH I and II).

After this, high-pressure steam at 490ºC is available to move the turbine which is coupled
with the compressor. In other words, the shaft from the turbine is attached to the one from the
compressor so moving one moves the other. In revamped furnaces, boiler feed water is added
between the two bundles to control the final temperature of HPI [10]. The others are producing
HPI at lower temperatures.

There are other types of steam produced in different zones of the process with lower
pressure and temperature but the main is the one described above.

3.2.4 Dilution Steam

To reduce the partial pressure of the hydrocarbons that are exposed to cracking
conditions, dilution steam is added to the coils (chapter 2). Using the same properties and
composition as BFW, the only difference is that vapour fraction is one and besides the
temperature, the flow rate needs to be fixed. There are two ways, fixing normally in the stream or
fixing the inlet ratio of the mixer which receives the steam and the hydrocarbon feed (figure 10).

Figure 10 - Mixer's representation in Spyro

33
3.2.5 Fuel Gas

Fuel gas is composed mainly by methane and hydrogen (figure 11). When adding this
stream to que radiant box, detailed component list must be selected as well as the fractions of
each compound. PhysProp 298K are used as well as pressure and temperature fixed, letting the
model to calculate the flow rate based mostly in the coil outlet temperature and crossover
temperature of the flue gases.

Figure 11 - Fuel's characterization in Spyro

Methane and hydrogen are both formed by the pyrolysis reactions. Hydrogen atoms
formed by the decomposition of radicals at high temperatures, collide with hydrocarbon molecules
forming finally the molecule itself. The collision with two hydrogen atoms can occur but is less
probable due to small concentration of this species in the mixture. Methane is formed by the same
mechanism described before. A methyl radical is formed by decomposition of a propyl radical or
break of a C-C bond. To originate the molecule, hydrogen abstraction reactions of other molecules
occurs forming another radical and methane [10].

The majority of all fuel gas is supplied by the demethanizer which separates the methane
by the top of the column from the ethane and ethylene. The hydrogen produced is divided for the
hydrogenation of gasoline, C3’s and C2’s. The surplus is mixed with the methane and fed to the
furnaces or power plant.

34
3.2.6 Air

Air enters the furnace by negative pressure induced by the fans. Flow rate is calculated
by Spyro with the % of oxygen in the crossover, or at the flue gases leaving the furnace after
convection section assuming the complete combustion of the fuel gas. Air specification is used
along the PhysProp 298K and the relative humidity, temperature and pressure needs to be
inserted (figure 12).

Figure 12 - Air's characterization in Spyro

3.3 Mixer

At Repsol’s steam cracker, the mixers present are inline mixers. They are represented in
Spyro by normal mixers which can operate in isobaric or minimum pressure mode. In isobaric
mode all the inlet streams will have the same pressure and it can be fixed upstream or
downstream or even in the mixer (outlet pressure) (figure 10). In minimum pressure mode the
outlet pressure will be equal to the lowest of the inlet pressures fixing all the pressures, inlet and
outlet except one [9].

3.4 Convection Section

In the convection section, where the heat released by the combustion of fuel gas at the
radiation box, they are present banks for each fluid circulating in. To this section be used in Spyro,
the geometry and the number of rows for each bank must be set equal to the real furnaces so
that the results given can be correct.

35
 Starting by the top of the furnace to the bottom, there are the economizer (ECO), the feed
pre-heater (FPH or LTC), the dilution steam super heater (DSSH), the high pressure steam super
heater I and II (HPSSH I, HPSSH II) and finally the high temperature convection (HTC). The order
of the banks can vary from furnace to furnace but this is the most commonly one at Repsol’s
cracker (figure 5).

Inlet and outlet temperatures for the process fluid and flue gas estimations lead to a better
convergence behaviour. That values, as well as inlet and outlet pressures for the process fluid,
can be inserted in the bank data specification tab. Besides that, in the bank layout tab the process
inlet and outlet and the properties taken must be selected (figure 13).

Figure 13 - ECO convection bank layout tab specification

At last, in the row data tab are the specification parameters given by the data sheets like,
for example, the inside diameter and the number of pipes as well as the outside heat transfer
coefficient factor (see chapter IV).

With all correct parameters and estimations, convection section can be connected to the
radiation section, TLX and steam drum in order to simulate the full furnace.

36
3.5 Steam Drum/Transfer line exchanger

Being water the fluid in the steam drum and in the TLX shell side, the properties chosen
must be the VDI steam tables. In the first, working pressure and blowdown factor or blowdown
flowrate are fixed (figure 14) and in the TLX shell side the operation mode selected must be steam
drum boiler due to the connection between each other.

Figure 14 - Steam drum model browser

That connection can be represented like is shown in figure 15. From the hydrocarbons
side, in the tube tab must be specified the design parameters as well as adjustment factors which
reduce the gap between simulation and real values.

Figure 15 - Flowsheet connection between TLX and steam drum

37
3.6 Radiant Coil

This model represents the coils in the cracking conditions (figure 16). In the coil pipe
passes, design values and adjustment parameters are implemented giving only the user the
possibility to input variables in the coil inlet and outlet tabs.

Figure 16 - Cracking coils flowsheet

Known as coil outlet temperature (COT), this value can be fixed in the coil outlet tab if the
measuring device is in the same position where the coils leave the radiation zone. In Repsol case,
the measuring thermocouple is located after the coils outlet in the transfer line volume. This
adiabatic volume represents a reaction volume separating the radiant coil and the TLX where, if
the temperature level is high enough, chemical reactions can be calculated. The same happens
in the crossover volume between the convection sections and the radiant coil. P/E ratio can be
fixed in the transfer line volume besides being more correct to fix it in the effluent leaving the TLX.

3.7 Radiant Box

This model includes the radiation coil in order to obtain the fuel gas and air flowrate
needed for the reactions desired. For that, design values of the firebox must be implemented in
Spyro along with the pressure inside and the radiant fuel and air selected (figure 17). The excess
of air in the burners, which allows Spyro to calculate the oxygen percentage in the firebox, is fixed
by default. Another way to calculate the air flow rate is by fixing the same percentage in the flue
gas leaving the convection section.

38
 Figure 17 - Firebox radiant wall burner's specification

3.8 Product Exit

Leaving the TLX, the product exit can be used to fix or to specify initial estimates for flow
rates, temperatures, pressures and P/E severity. Another way to characterize it is selecting the
key component and fixing fractions or conversion (figure 18).

39
Figure 18 - Product exit specification tab

40
3.9 How to obtain Spyro’s convergence

Spyro can be simulated as full furnace (figure 19) with radiation coil, TLX with steam
drum, firebox and convection section models or only for yield simulations containing only the
radiation coil model.

Figure 19 - Full furnace flowsheet simulation

To obtain reliable results in both simulations, the advised list for normal convergence is
the same (figure 20). The operation values for the simulations are represented in appendix V.

41
 Figure 20 - Spyro convergence advised fixed list

The more unfixed estimation parameters imputed in Spyro, the better and faster the
convergence behaviour.

Starting with the process gas side, hydrocarbon and dilution steam flow rates and
temperatures need to be fixed (figure 6). Other way to fix dilution steam flow rate is by fixing the
dilution ration in mixer model where this compound is mixed with the hydrocarbons (figure 10).
The vapour fraction of the hydrocarbon feed must be verified along with the correct properties for
Spyro to perform the calculations. At last the pressure can be fixed at coil outlet, in transfer line
volume or in the product exit. Pressure drop for all junctions like mixer, coil inlet, outlet and more
must be fixed too. One of the cracking severity parameters must be fixed. It can be the coil outlet
temperature, key component conversion or the P/E ratio in the effluent (figure 18).

In the high-pressure steam side, BFW inlet temperature is fixed leaving the flow rate
unfixed (figure 9). Pressure can be fixed in the HPI effluent or in the steam drum along with the
blow down factor or flow rate, the heat loss fraction or enthalpy loss and external heat. If the TLX
shell side is connected to the steam drum the mode selected is steam drum operation and if it
works as BFW heater the mode selected is BFW heater operation. All the properties tables
selected are VDI steam tables and estimated pressures, flow rates and temperatures are
important for the convergence behaviour. If it is the case, BFW quench added to temperate the
HPI produced must have flow rate, temperature and pressure fixed and the mixer operates in
minimum pressure mode with only pressure drop fixed.

42
 In the firebox model, the pressure and the excess air for radiant wall burners are fixed
unfixing the flow rate of fuel gas and air. In the other way, temperature and pressure of both
compounds are fixed not forgetting to give proper estimate parameters for the flow rates.

The banks inside the convection section need to have all tuning parameters fixed and
unfixed real values for the inlet and outlet temperatures of the process and flue gas side.

With all parameters correctly imputed in Spyro and all connections made (appendix IV),
becomes possible to converge the full furnace simulation and compare the model output
calculations with real cases.

Values for the output of the model normal convergence are represented in table 3. The
output is different from reality, representing this simulation the ideal operating conditions. The
percentage of deviation was estimated by the equation 3.1.

(-./0123456)
%"#$%&'%() = ∗ 100 (3.1)
3456

A key performance indicator (KPI) including the sum of COT, BFW and fuel gas flow rates
percentage of deviation was defined to compare the normal convergence and the tuning results
described in the next chapter.

Table 3 – Deviation from the ideal convergence of Spyro from real operating values.

F1003 COT (ºC) BFW (kg/h) Fuel (kg/h)

Real 851.60 29616.29 3444.49
Spyro 838.00 28380.34 3018.03
% Deviation 1.60% 4.17% 12.38%
F1006 COT (ºC) BFW (kg/h) Fuel (kg/h)
Real 852.00 29764.43 3199.08
Spyro 836.00 27403.75 2961.49
% Deviation 1.88% 7.93% 7.43%

Besides the deviations shown in table 3, there are more like for example in temperatures
leaving the convection section bundles. That deviations became insignificant when the tuning to
the real furnace is made. The KPI indicator, for the normal convergence is shown in table 4.

43
 Table 4 - KPI indicator for normal convergence of the model.

F1003 COT (ºC) BFW (kg/h) Fuel (kg/h) KPI

% Deviation 1.60% 4.17% 12.38% 18.15%
F1006 COT (ºC) BFW (kg/h) Fuel (kg/h) KPI
% Deviation 1.88% 7.93% 7.43% 17.24%

44
Chapter 4

Model Tuning

The main task of this thesis was to evaluate all the feedstocks used for the steam cracking
at Repsol Polímeros situated in Sines as well as to converge all the real furnaces in Spyro
convection model. After the correct properties given by Aspen Hysys v8.4 for hydrocarbon
feedstocks entering the furnace in liquid state and the analysis made by Repsol laboratory
(appendix II), characterization in the Spyro model can be made. After the normal convergence,
the model had to be tuned to real condition operation values. To achieve this, the outside HTC
factors were calculated by the model by fixing operation values from a period of time where they
were constant (appendix V). Having all the furnaces converge to real operating values, the outside
HTC factors were fixed and then two sensitive analysis were made. First the hypothesis of
revamping bundles by changing the factors to 1, one by one and evaluate the gains and losses.
The second was to analyse the impact of adding or reducing 1 metric tonne of ‘’protection steam’’
in the hydrocarbon coils maintaining the ratio steam/hydrocarbons. In other words, if the 1 metric
tonne is reduced in the ‘’protection steam’’, one is added to the dilution steam.

A problem occurred in the furnaces with liquid feedstocks entering the convection section.
Spyro recognized the ppf. file but when the import was made the properties didn’t appear in the
model. With the help of Technip, Eng. André Vilelas and Eng. Jorge Fernandes, we reached the
conclusion that the problem was in the software installed in Repsol and for that reason the goals
were made only for the furnaces with propane as feedstock (F1003 and F1006).

45
 4.1 Outside HTC Factors Determination

In a way to achieve the state of each bundle from the convection section an estimation of
the outside Heat Transfer Coefficient (HTC) factor was made. This outside HTC factor is related
with problems in the bundle coatings like corrosion and deposition of dirt present in the flue gas
which is drown by the negative pressure induced by the fan. Some of these bundles are
composed by fins (figure 21) to increase the heat transfer area. They are spaced between each
other and with the passing days, months and years of operation, dirt particles accumulate
between the fins which difficult the heat transfer from the flue gases. Notice that in bare tube,
deposition of dirt particles is more difficult to occur being the correction the main parameter in the
outside HTC factor.

Figure 21 - Cut fins and full fins (Repsol's case)

After the normal convergence of the model, temperatures of the process side and
temperature of the flue gas leaving the convection section must be fixed (appendix V). In this
case, operating values of the temperatures leaving the bundles have to be imputed in the model
and fixed, unfixing the outside heat transfer coefficient factors. After the simulation run of the full
furnace, Spyro gives the factors for each bundle (figure 22).

46
 Figure 22 - Outside HTC factors calculated by Spyro

In this task two obstacles appeared. First, the operation don´t have values of the process
temperature leaving the feed pre-heater (FPH) and dilution steam super heater (DSSH) bundles
due to the absence of local temperature indicators. To overcome this, a sensitive analysis was
made with this two factors ranging from 0.6 to 0.9 in both bundles. The boundaries of the gap
were chosen by typical values and having in account that these factors cannot be higher than 1
and lower than 0. The other obstacle was the fact that by fixing the temperature of the flue gas
leaving the convection section to the atmosphere, we cannot fix the amount of oxygen in this feed.
By fixing the two variables, Spyro delivers a message to the user saying that the model has one
additional variable fixed and cannot perform the run. Because the furnaces aren’t fully isolated,
parasite air enters through cracks between the burners and pipes with the housing due to the
negative pressure induced by the fans. However, the values of that percentage of oxygen given
by Spyro were not far of the real ones, the temperature of the leaving flue gas seems the variable
more important to fix in the outside HTC factors test. A detailed scheme to overcome this task is
represented in the figure 23.

47
 Figure 23 - Tuning scheme for real outside HTC factors calculation

Values of fuel gas and boiler feed water flow rates as well as COT, were compared to the
real operation ones to choose the outside HTC factors who minimize that differences between
the Spyro and the real ones (table 5). That deviation was estimated by the equation 3.1.

Table 5 - Outside HTC factors calculated by Spyro for furnace F1006.

DSSH/FPH Deviation HTC HPSSH-II HPSSH-I ECO

0.6/0.6 12.760% 0,907 1,124 0,887 0,985
0.6/0.7 12.768% 0,855 1,084 0,846 0,985
0.6/0.8 12.777% 0,807 1,048 0,809 0,985
0.6/0.9 12.785% 0,762 1,015 0,776 0,985
0.7/0.6 12.760% 0,888 1,109 0,872 0,985
0.7/0.7 12.771% 0,836 1,070 0,831 0,985
0.7/0.8 12.780% 0,788 1,034 0,795 0,985
0.7/0.9 12.788% 0,744 1,000 0,763 0,985
0.8/0.6 12.763% 0,872 1,097 0,859 0,985
0.8/0.7 12.773% 0,820 1,058 0,819 0,985
0.8/0.8 12.782% 0,773 1,022 0,784 0,985
0.8/0.9 12.790% 0,728 0,990 0,752 0,985
0.9/0.6 12.766% 0,858 1,086 0,848 0,985
0.9/0.7 12.776% 0,807 1,048 0,809 0,985
0.9/0.8 12.784% 0,759 1,013 0,774 0,985
0.9/0.9 12.792% 0,715 0,981 0,742 0,985

48
 Given the gap with the possible values for the outside HTC factors and analysed the sum
of the errors for the parameters related before, the factors chosen for furnace F1003 were 0.8 to
DSSH bank and 0.8 to FPH bank. By the same method, the outside HTC factors chosen for
furnace F1006 were 0.7 to DSSH and 0.9 to FPH banks. That factors along with the ones for the
other banks are represented in the table 6.

After the analysis was made and having in account the feasible values we can conclude
that the error differs in the third decimal digits (table 5). Note that some furnaces which had
recently revamps in the HPSSH I and II bundles have the outside HTC factors close to 1 like in
furnace F1006 for example.

Table 6 - Real outside HTC factors for furnaces F1003 and F1006

HTC HPSSH-II HPSSH-I DSSH FPH ECO

F1003 0.587 0.978 0.848 0,8 0,8 0.982
F1006 0.744 1.000 0.763 0,7 0,9 0.985

To compare the real tuning case with the normal convergence of the model with all
outside HTC factors equal to 1, the KPI used in chapter III was compared to the one calculated
to the real operation case (table 7). Besides the KPI indicator only includes COT, BFW and fuel
gas flow rates, the deviation in the temperatures leaving the bundles from the convection section
turn zero in the tuning case. The gap between the KPI’s with the total deviation including all these
parameters becomes larger and more significant.

Table 7 - Difference between the KPI's from the real and the ideal simulations.

F1003 COT (ºC) BFW (kg/h) Fuel (kg/h) KPI

% Deviation 1.60% 1.56% 7.69% 10.84%
F1006 COT (ºC) BFW (kg/h) Fuel (kg/h) KPI
% Deviation 1.76% 7.91% 4.65% 14.32%

49
 4.2 Revamp Case-Study

After the tuning of the Repsol’ cracking furnaces model using the simulation by Spyro, a
new problem was posed: What would be the benefits in a possible revamp of each bundle from
the convection section?

To achieve an answer to that question, the outside HTC factors were changed to 1, one
by one, maintaining all the others equal to the real furnace case (figure 24). Besides unfixing the
process outlet temperatures and fixing the real factors described in table 4, in this case in more
correct to fix the percentage of oxygen in the flue gas given by Spyro for the real simulation
instead of fixing the temperature of the flue gas leaving the furnace. By that, it is guaranteed that
no temperatures are fixed letting Spyro to calculate them.

Figure 24 - Revamp scheme by changing the outside HTC factors one by one to 1.

After this test, differences between fuel gas consumed and HPI produced from revamping
cases and real furnace where measured to see which bundle causes more impact. In the furnace
F1006, the case of revamping the high-pressure steam super heater II (HPSSH-II) bank has no
deviations corresponding to the real outside HTC factor described in table 8.

50
 Table 8 - % of deviation from the real case parameters of revamping cases

F1006 Fuel Gas (kg/h) HPI (kg/h)

Real Case 3049.514 31236.735

Revamp Case % Deviation
HTC=1 -1.744 -2.656
HPSSH-II =1 - -
HPSSH-I =1 0.352 -0.439
DSSH = 1 -0.347 -0.419
FPH = 1 -0.376 -0.453
ECO = 1 0.002 0.115
F1003 Fuel Gas (kg/h) HPI (kg/h)
Real Case 3179.729 33307.384
Revamp Case % Deviation
HTC=1 -4.674 -3.400
HPSSH-II =1 0.029 -0.055
HPSSH-I =1 0.210 -0.312
DSSH = 1 -0.328 -0.258
FPH = 1 -0.766 -0.978
ECO = 1 -0.004 0.133

In table 8 the deviation is calculated with the deviation between the revamped cases from
the real case (equation 4.1). The minus signal represents less consumption/production of the
revamped cases for both parameters respectively. With these values, it’s hard to take conclusions
from which bank causes more impact when revamped.

(-./0123456)
%"#$%&'%() = ∗ 100 (4.1)
3456

This test along with an economic evaluation make possible to conclude if a revamp to the
bundles is viable. That economic evaluation was made in a simple way comparing only the fuel
gas consumed and the high-pressure steam (HPI) produced prices. Values of €/kg for HPI
produced and €/kg for fuel gas consumed were taken for this task [15]. Summing up, the test was
made with the view to give the user the earnings or expends compared to the real case (table 9).
The values represent with minus signal represents losses.

51
 Table 9 - Earnings and expends from the revamp cases relative to the real case.

F1006 €/h €/day €/month

HTC=1 10.01 240.17 7205.11
HPSSH-II =1 - - -
HPSSH-I =1 -7.03 -168.65 -5059.47
DSSH = 1 -0.25 -6.01 -180.19
FPH = 1 -0.26 -6.17 -185.24
ECO = 1 0.95 22.80 683.92
F1003 €/h €/day €/month
HTC=1 14.45 346.75 10402.36
HPSSH-II =1 -0.78 -18.81 -564.25
HPSSH-I =1 -4.87 -116.94 -3508.30
DSSH = 1 -0.40 -9.68 -290.49
FPH = 1 -1.22 -29.26 -877.66
ECO = 1 1.24 29.66 889.89

Looking at both tables 8 and 9 it is possible to take conclusions about which bundle
revamp case causes more impact. Having the lowest real outside HTC factor in both furnaces
F1003 and F1006, it was expected to predict that the HTC bank was the one causing more impact.
This simple analysis gives Repsol the idea of a possible revamp case, which before being taken
further, more detailed studies have to be done. Notice that this was only a simple evaluation test
looking only for the furnace as the whole process. In the real steam cracking process, the HPI
produced is not sold and the fuel gas not bought. The first one feds the turbine to generate the
energy necessary to move the gas centrifugal compressor and the second one comes from the
demethanizer and from the hydrogen leftover from the hydrogenation section (chapter 2).

52
 4.3 Protection Steam

Another aspect that came out was the ‘’protection steam’’ flow rate, which is added to the
hydrocarbon feedstocks before entering the convection section of the furnaces. The steam is
controlled manually and don’t having flow rates in the control panel, this value doesn’t enter for
the calculi of the mass ratio steam/hydrocarbons. It is mixed with the hydrocarbon feedstocks to
protect the coils when occurring for example a shut down. If the furnaces go down, the
hydrocarbon flow rates stop automatically and the coils can be fragile be the thermic shock
increasing the probability to break. Ensuring that protection steam continue to flow into the coils,
that probability decreases exponentially.

The flow rate in all furnaces is about 1 metric tonne and that value comes by the difference
of the total dilution steam fed to each furnace and the sum of dilution steam entering the coils of
DSSH bundle given by the control panel. The impact of this steam was measured by a sensitive
analysis (table 10), increasing 1 metric tonne in the hydrocarbon coils before entering the FPH
and decreasing it in the dilution steam flow rate entering the DSSH bundle and vice versa.

Table 10 - Impact on adding or reducing the flow rate of ''protection steam''.

F1006 Fuel Gas (kg/h) HPI (kg/h)

Real Case 3049.51 31236.74
Protection Steam % Error
+ 1 ton/h 0.26 0.32
- 1 ton/h -0.24 -0.29
F1003 Fuel Gas (kg/h) HPI (kg/h)
Real Case 3179.73 33307.38
Protection Steam % Error
+ 1 ton/h 0.24 0.31
- 1 ton/h -0.20 -0.28

With the information from table 10, it isn’t easy to distinguish the most favourable case.
The minus signals indicate less consumption/production of fuel gas and HPI respectively. When
making the same economic analysis referred in the sub chapter before, the task becomes much
easier (table 11).

53
 Table 11 - Earnings and expends of adding or reducing 1 metric tonne of ''protection steam''
relative to the real case.

F1006 €/h €/day €/month

+ 1 ton/h 0.17 4.11 123.35
- 1 ton/h -0.16 -3.93 -117.92
F1003 €/h €/day €/month
+ 1 ton/h 0.42 10.11 303.33
- 1 ton/h -0.53 -12.72 -381.6

The results given by the economic evaluated indicates that the more steam used as
‘’protection steam’’, maintaining the mass ratio steam/hydrocarbons, the more HPI is produced
compensating more fuel consumed. In this economic evaluation, no impact calculation was done
by electricity generation lost at Power Plant and the extra feed to the Cracker. Being above the
DSSH bank, the FPH one in the favourable case has more flow rate circulating in the coils. To
pre-heat that hydrocarbons/’’protection steam’’ mixture, more fuel gas needs to be consumed
producing more high pressure steam.

Besides the protection criteria, the more steam into the coils, more flow rate passing in
the transfer line exchangers, more HPI produced. By feeding more high pressure steam to the
turbine, more power is available to rotate the compressor shaft. Of course, if you have more flow
rate in the coils you consume more fuel gas in the burners to achieve cracking temperatures. The
coils were design with a maximum flow rate allowed and Repsol Polímeros work in their maximum
to produce more HPI in the transfer line exchangers and generate more power to the compressor
insuring the protection of the coils and the facility to evaporate the liquid feedstocks in the FPH
bundle.

54
Chapter 5

Conclusions

In this work, a steam cracking simulation model called Spyro Suite 7 was used, which is
a necessary toll used by the majority of steam cracking producers worldwide. With the option of
yield prediction, using only the radiation coils model, it is a fundamental tool to predict which are
the required operational conditions to be taken in real time cases. It can be used to simulate the
full furnace models.

Before the convergence of the full furnace, a thermodynamic evaluation of the feedstocks
had to be made in order to characterize them properly in Spyro. For gaseous feedstocks it was
concluded that with the detailed mass or volume composition and selecting the gaseous feedstock
properties, the model was correct and ready to be connected to the others to perform the full
furnace simulations. Some difficulties were found with the feedstocks entering the furnace in liquid
phase. Spyro properties don’t describe well naphtha’s used at Repsol’s steam cracking. New
properties had to be added with the help of Aspen Hysys v8.4 and correctly written in a ppf. file
readable by Spyro. The ppf. file was recognized but the properties didn’t appear in the model
enabling to simulate furnaces with liquid feedstocks. Having all feedstocks thermodynamically
analysed, it was only possible to converge the furnaces (F1003 and F1006) using as feedstock
propane to the real operating conditions.

Englobing the corrosion and deposition of dirt particles in the fins of the bundles of the
convection section a factor designated as outside heat transfer coefficient factor was taken in
account (chapter 4.1). The chosen outside HTC factors for furnaces F1003 and F1006, besides
being in the gap of possible values, describes well the real state of each bank of the convection
section as well as the behaviour of the real time operating conditions. Being, the HTC bank, the
first bundle after the radiation box, it was expected to have the lowest outside HTC factor in both
furnaces. This is due to the first bank of the convection section being more able to suffer from dirt
deposition and corrosion than the higher ones. The real outside HTC factors from furnace F1006
were higher than the ones from F1003 as a result of suffering recently a revamp in the HPSSH I
and II banks and cleaning process in the others.

The main key performance indicator (KPI) containing the sum of the deviations from COT
and BFW and fuel gas flow rates between the simulations and the real case was used to prove
the convergence of the model to real operating values. The values of this parameter in the normal
convergence of the furnace was 18.15% and 17.24%, decreasing when the furnace in tuned to
the real operating values to 10.84% and 14.32% for furnaces F1003 and F1006 respectively.

55
 To study a possible revamp case of each bundle, a sensitive analysis was made to
calculate the savings in fuel gas and HPI flow rates. From those analyses, the high temperature
convection (HTC) bundle, being the one with the lowest outside HTC factor, represented the
highest savings when revamped. In other words, less HPI compensates less fuel consumed
turning it into profit. Besides the high temperature convection (HTC) bundle, the economizer
(ECO) bundle also represented profits when revamped. To take decisions in the remaining
bundles of the convection section, more detailed studies must be done to prevent having financial
losses. The economic evaluation was made in a simplified way, establishing the balance only in
the furnace and not for the whole process.

Furthermore, the ‘’protection steam’’ flow rate was taken into question. Maintaining the
mass ratio steam/hydrocarbons, another sensitive analysis was made by increasing/decreasing
one metric tonne per hour of ‘’protection steam’’ and by decreasing/increasing it in the dilution
steam. The benefits were analysed along with an economic evaluation like in the revamp case
study. The favourable scenario was reached when one metric tonne per hour was increased in
the ‘’protection steam’’ flow rate. The high-pressure steam produced compensates the higher
amount of fuel consumed, leading to a higher flow rate into the turbine generating more power to
the effluent centrifugal compressor. It indicates that working in the maximum flow rate allowed by
the specifications of the coils is the better scenario to operate.

To sum up, Repsol now has their furnaces F1003 and F1006 simulated in Spyro for other
studies and yield simulations. Relatively to the revamping cases, more detailed studies need to
be done to have all economic parameters and differences in the real operation and Spyro
parameters to decide further actions.

5.1 Future Work

To have all of Repsol’s furnaces simulated in Spyro and able to converge, the properties,
describing feedstock entering in the convection section in liquid state, import problem has to be
resolved internally with Technip’s help in a future study. When resolved, the furnace tuning
sequence is the same that the one described in chapter 4. For different liquid feedstocks, new
properties have to be simulated with Aspen Hysys v8.4 and written after in a new ppf. file readable
in Spyro.

A global economic evaluation must be made to prove the investment in a possible bank
revamp case in the convection section, as well a more detailed comparison between real case
and simulation case parameters.

56
57
References

[1] – ‘The history of Spyro Simulation Software’, www.spyrosuite.com/pyrotec/hystory/ ,

(online, Accessed: 2017-05-15)

[2] – M. Dente, E. Ranzi and A.G. Goossens, ‘Detailed Prediction of Olefin Yields from
Hydrocarbon Pyrolysis through a Fundamental Simulation Model (Spyro)’, in Computers &
Chemical Engineering, 1979

[3] – E. Ranzi, M. Dente, S. Plerucci and G. Blardl, ‘Initial Product Distributions from
Pyrolysis of Normal and Branched Paraffins’, in Industrial & Engineering Chemistry
Fundamentals, 1983

[4] – Marco W.M. van Goethem, Florian I. Kleinendorst, Cor van Keeuwen and Nils van
Velzen, ‘Equation-based Spyro Model and Solver for the Simulation of the Steam Cracking
Process’, in Computers & Chemical Engineering, 2001

[5] – Marco W.M. van Goethem, Florian I. Kleinendorst, Cor van Keeuwen, Nils van
Velzen, Mario Dente and Eliseo Ranzi, ‘Equation Based Spyro Model and Optimiser fo the
Modeling of the Steam Cracking Process’, 2002

[6] – M.W.M. Van Goethem, S. Barendregt, J. Grievink, J.A. Moulijn and P.J.T. Verheijen,
‘Towards Synthesis of an Optimal Thermal Cracking Reactor’, in Chemical Engineering Research
and Design, 2008

[7] – Marco W.M. van Goethem and Peter J.T. Verheijen, ‘Integration of Symbolic
Modelling within an Equation Based Flowsheet Package for Steam Pyrolysis’, in Simulation
Modelling Practice and Theory, 2013

[8] – Marco W.M. Van Goethem, Simon Barendregt, Johan Grievink, Peter J.T. Verheijen,
Mario Dente and Elisio Ranzi, ‘A Kinetic Modelling Study of Ethane Cracking for Optimal Ethylene
Yield’, in Chemical Engineering Research and Design, 2013

[9] – Pyrotec division of Technip Benelux BV, ‘Spyro Suite 7 Training manual’, Repsol
archive, 2017

[10] – Oliveira Gomes, ‘Considerações Gerais Sobre Pirólise’, Repsol archive, 2017

[11] – ‘Olefins Production: olefins by steam cracking’ ,

https://mol.hu/images/pdf/A_MOL_rol/tvk-
rol/tarsasagunkról_roviden/egyetemi_kapcsolatok/debreceni_egyetem/oktatasi_anyagok/bemut
atok/OLEFINS%20PRODUCTION.pdf , (online, Accessed: 2017-06-10)

58
 [12] – Heinz Zimmermann and Roland Walzi, ‘Ethylene’, in Ullmann’s encyclopedia of
industrial chemistry, 2012

[13] – António Almeida, ‘Descrição simplificada do processo’, Repsol archive, 2017

[14] – ‘Enthalpies of formation’, http://webbook.nist.gov/chemistry/ , (online, Accessed:

2017-08-09)

[15] – Jorge Fernandes, ‘Consumers prices’, Repsol archive, 2017

[16] – Ifp, ‘Petrochemicals Olefins and Aromatics, Repsol archive, 2017

59
Appendix I

The yields from all feedstocks cracking with various residence times are represented in
figures I.1, I.2, I.3, I.4, I.5, I.6, I.7.

Figure I. 1 - Yields from ethane cracking with different residence times

Figure I. 2 - Yields from propane cracking with various residence times.

60
Figure I. 3 - Yields from butane cracking with various residence times.

Figure I. 4 - Yields from low-severity naphtha cracking.

61
Figure I. 5 - Yields from medium-severity naphtha cracking.

Figure I. 6 - Yields from high-severity naphtha.

62
Figure I. 7 - Yields for atmospheric gas oil (AGO) and hydrocracker residue (HCR) cracking.

63
Appendix II

Analytical report from naphtha feedstock used in steam cracking (figure II.1).

Figure II. 1 - Naphtha analytical report

64
65
Appendix III

Naphtha properties table with the required parameters to be used in Spyro are represented in table III.1.

66
 Table III 1- Naphtha correct properties

Temperature Phase Phase Phase Mass Phase Phase Phase Mass Phase Phase Phase Phase Phase Phase
Fraction Fraction Enthalpy Mass Mass Density Viscosity Viscosity Thermal Thermal MassHeat MassHeat
(Vap) (Liq) (Vap) Enthalpy Density (Liq) (Vap) (cp) (Liq) (cp) Conductivity Conductivity Capacity Capacity
(kcal/kg) (Liq) (Vap) (kg/m3) (Vap) (Liq) (Vap) (Liq)
(kcal/kg) (kg/m3) (kcal/m.hr.C) (kcal/m.hr.C) (kcal/kgC) (kcal/kgC)
State 1 60 1 42.025 642.667 0.2428 0.0888 0.5406
State 2 65 1 44.746 637.544 0.2318 0.0875 0.5479
State 3 70 1 47.504 632.354 0.2215 0.0863 0.5552
State 4 75 1 50.299 627.092 0.2118 0.0850 0.5627
State 5 80 1 53.131 621.753 0.2027 0.0837 0.5702
State 6 85 1 56.001 616.331 0.1941 0.0824 0.5779
State 7 90 1 58.910 610.821 0.1859 0.0810 0.5858
State 8 95 1 61.859 605.214 0.1782 0.0797 0.5938
Bubble P 99.09 0 1 38.994 64.307 10.200 600.600 0.0083 0.1722 0.0177 0.0786 0.4831 0.6005
State 9 100 0.0532 0.9468 40.761 66.876 10.203 601.587 0.0083 0.1729 0.0177 0.0787 0.4836 0.6003
State 10 105 0.3102 0.6898 50.519 81.003 10.220 607.364 0.0084 0.1772 0.0180 0.0792 0.4866 0.5990
State 11 110 0.5136 0.4864 60.264 94.664 10.227 613.176 0.0085 0.1815 0.0182 0.0797 0.4894 0.5979
State 12 115 0.6751 0.3249 69.880 107.315 10.228 618.595 0.0085 0.1853 0.0185 0.0802 0.4922 0.5971
State 13 120 0.8065 0.1935 79.255 118.559 10.229 623.253 0.0086 0.1884 0.0188 0.0806 0.4950 0.5971
State 14 125 0.9178 0.0822 88.284 128.254 10.235 626.949 0.0087 0.1907 0.0191 0.0810 0.4979 0.5979
100%Vap 129.1 1.0000 0.0000 95.409 135.166 10.250 629.300 0.0087 0.1920 0.0194 0.0812 0.5004 0.5990
State 15 130 1 95.854 10.218 0.0088 0.0195 0.5013
State 16 135 1 98.372 10.055 0.0089 0.0199 0.5060
State 17 140 1 100.914 9.897 0.0090 0.0203 0.5108
State 18 145 1 103.480 9.745 0.0091 0.0208 0.5155
State 19 150 1 106.069 9.599 0.0092 0.0212 0.5202
State 20 155 1 108.682 9.458 0.0093 0.0217 0.5250
State 21 160 1 111.319 9.321 0.0094 0.0221 0.5296
State 22 165 1 113.979 9.189 0.0096 0.0226 0.5343
State 23 170 1 116.662 9.061 0.0097 0.0230 0.5390
State 24 175 1 119.368 8.937 0.0098 0.0235 0.5436
State 25 180 1 122.098 8.817 0.0099 0.0240 0.5482
State 26 185 1 124.851 8.701 0.0100 0.0244 0.5528

67
State 27 190 1 127.626 8.588 0.0101 0.0249 0.5574
State 28 195 1 130.424 8.478 0.0103 0.0254 0.5619
State 29 200 1 133.245 8.372 0.0104 0.0259 0.5664

68
Appendix IV

To correctly connect the models in Spyro flowsheet, arrows are used by clicking with the
right bottom from one box to another. There are 4 flowsheets in Spyro, the main flowsheet, the
radiant coils, the firebox, the TLX/TLE and the convection one (figure IV.1, .2, .3, .4).

Figure IV. 1 - Main flowsheet

Figure IV. 2 - Radiant coils flowsheet

69
Figure IV. 3 - TLX/TLE flowsheet

Figure IV. 4 - Firebox flowsheet

70
Figure IV. 5 - Convection model flowsheet

71
Appendix V

From the control room at Repsol, the operating values were collected and analysed. The
time interval was chosen considering that the operating values were almost constant. The
average value of a continuous operating day interval to all parameters essential to input in the
simulation and to be compared are represented in table v.1.

Table V.1 - Operation values average taken along this thesis

F1006 Average F1003 Average

Q Propane (kg/h) 18000 Q Propane (kg/h) 18872
Q Dilution steam (kg/h) 9962 Q Dilution steam (kg/h) 10384
Q Protection steam (kg/h) 1093 Q Protection steam (kg/h) 1584
Q BFW (kg/h) 29764 Q BFW (kg/h) 29721
Q BFW quench (kg/h) 4370 Q BFW quench (kg/h) 3947
Q Fuel (kg/h) 3199 Q Fuel (kg/h) 3445
COT (ºC) 854 COT (ºC) 852
Tout HTC (ºC) 659 Tout HTC (ºC) 629
P Steam Drum (bar.g) 106 P Steam Drum (bar.g) 106
Tin Propane (ºC) 48 Tin Propane (ºC) 48
T Flue gas (ºC) 237 T Flue gas (ºC) 227
T Crossover (ºC) 1177 T Crossover (ºC) 1123
Severity P/E 0,36 Severity P/E 0,39
Tin HPSSH II (ºC) 326 Tin HPSSH II (ºC) 329
T HPI (ºC) 489 T HPI (ºC) 490
Tout ECO (ºC) 268 Tout ECO (ºC) 277
Tout HPSSH I (ºC) 410

72